JPH0474691A - Addition-writing optical disk corresponding to compact disk or compact disk-rom - Google Patents

Abstract

PURPOSE:To perform a recording regeneration in a wavelength ranging 770 - 810nm by selecting a recording film of an addition-writing optical disk consisting of a transparent substrate, a recording film, and a reflecting film out of specific phthalocyanine dyes. CONSTITUTION:In an addition-writing optical disk consisting of a transparent substrate, a recording film, and a reflecting film for recording compact disk format or compact disk ROM format signals, the recording film is selected out of phthalocyanine dyes. As a film forming method, a dry process, such as vacuum deposition and sputtering method, can be used. As a material for the reflecting film, a metal, such as gold, silver, copper, and aluminum; a metallic oxide, such as MgO and ZnO; and a nitride, such as SiN4 and AlN can be used. As a film forming method, a dry process is preferably used. As the disk substrate, a material having a light transmittance of 85% or more in writing and reading signals and a small optical anisotropy is used; for example, a glass or a thermosetting resin, such as an acrylic resin, is used.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to an optical disc on which information is recorded and reproduced using laser light.

More specifically, the present invention relates to a write-once optical disc compatible with a compact disc (CD) or a compact disc-ROM (CD-ROM).

(Prior Art) Among information recording media using focused laser light, CDs are widely used for reproducing music such as audio, and CD-ROMs are widely used as ROMs for computers.

Such CDs and CD-ROMs usually have CD7. A pit array having an i-mant signal is formed during injection molding, aluminum or gold is deposited thereon as a reflective film by layering or sputtering, and a protective layer is further coated.

A reproduction laser beam (780 nm semiconductor laser beam) is irradiated from the back side of the substrate of the optical disk thus prepared, and each signal is read from the change in reflectance due to the unevenness of the pits, thereby reproducing information.

However, since such CDs and CD-ROMs are only for reproduction and cannot record information, they have the inconvenience of not having an editing function unlike write-once optical discs or rewritable magneto-optical discs.

On the other hand, write-once optical disks or magneto-optical disks with editing functions are made of chalcokenite compounds such as Te,
Recording films made of rare earth metal compounds or organic dyes such as cyanine and naphthalocyanine have been put into practical use.

However, these optical discs have a reflectance from the substrate surface of 30 to 40%, and the reflectance from the substrate surface does not reach the 70% or higher level listed in the Red Book, the current international standard for CDs. However, there is a problem in that the signal cannot be reproduced by a CD or CD-ROM reproducing device as it is.

In order to solve these problems, a reflective film such as gold is provided on a recording film such as cyanine, and the reflectance of the substrate surface is 70%.
Optical discs and methods have been proposed that ensure the above, record CD format or CD-ROM format signals in 780nrn, and read out the information with a CD or CD-RO to 1 playback device.

The recording film material for such write-once optical discs compatible with CDs and CD-ROMs must absorb and reflect at a delicate ratio to the laser wavelength of the pickup of the CD or CD-ROM drive device. The usable range of pink amplifier laser wavelengths stipulated in Even with optical discs compatible with CDs, the reflectance is less than 70% at 770 nm, and there is insufficient recording sensitivity at 810 nm, so the current situation is that they do not accurately meet the Red Book standards. It is.

(Problems to be Solved by the Invention) The present invention solves the drawbacks of conventional CDs or CD-ROMs that have write-once functions and editing functions, and
The object of the present invention is to provide an optical disc that is compliant with the Red Book and that realizes stable optical characteristics in the wavelength range of 100 nm and is completely recordable and reproducible in this wavelength range.

[Structure of the invention]

(Means for Solving the Problems) As a result of intensive studies in order to solve the drawbacks of conventional CDs or CD-ROMs having write-once and editing functions, the present invention has developed a recording film made of a specific phthalocyanine compound on a substrate. The inventors have discovered that a write-once optical disc compatible with CDs having various excellent properties has led to the present invention.

The present invention provides a write-once optical disc comprising a transparent substrate/recording film/reflection film and recording compact disc format or compact disc ROM format signals, in which the recording film is selected from phthalocyanine dyes represented by the following general formula [1]. A write-once type that is compatible with a compact disc or a compact disc-ROM, and is characterized in that

Y' to Y4 each independently represent a halogen atom, 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 a substituent. Acyl group that may have one, heterocyclic residue that may have a substituent, nitro group, cyano group, sulfonic acid group, carboxylic acid group, -OR irises -SR2-COORI-
N=N-R1-N=CHR'.

M represents a metal that may have a substituent Z or R2,
Z is a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, an acyl group that may have a substituent, a hydroxyl group,
An alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, or ) O-Ge-R".

Here, R', R'', and R' may be the same or different, and may have a hydrogen atom, an alkyl group that may have a W substituent, or a substituent. It represents a good aryl group, a cycloalkyl group which may have a substituent, an acyl group which may have a substituent, or a polyether group, and is a 4- to 7-membered two selected from R1 and R2R3. It may form a ring, and in that case, it may be a heterocycle further containing a heteroatom such as a nitrogen atom.

1'--1', , m' to m', n are each X
' to X', Yl -Y', represents the number of substituents of Z.

To explain in more detail the substituents of the general formula [1] and R1, R2R3, halogen atoms include chlorine, bromine, iodine, fluorine, etc., and alkyl groups that may have substituents include methyl group, N-butyl group, t
er t-butyl group, stearyl group, trichloromethyl group, 2-methoxyethyl group, N,N-dimethylaminopropyl group, N,N-dibutylaminopropyl group, 2
(N-piperazino)ethyl group, aryl groups which may have substituents include phenyl group, chlorophenyl group, tolyl group, naphthyl group, anthryl group, dimethylaminophenyl group, hydroxyphenyl group, diethylaminonaphthyl group, hydroxynaphthyl group Examples of the cycloalkyl group that may have a substituent include a cyclohexyl group and a cyclobutyl group; examples of the acyl group that may have a substituent include an acetyl group and a trifluoroacetyl group; and examples of the polyether group include diethylene glycol. Monoethyl group, triethylene glycol monobutyl group, heterocyclic residues which may have substituents include pyridyl group, furyl group, thiazolyl group, piperazinyl group, morpholinyl group, triazinyl group, etc. It is not limited to.

Typical examples of the phthalocyanine compounds represented by the general formula [1] used in the present invention include phthalocyanine compounds (a) to (k) shown below, but the compounds are not limited to these. do not have.

(c) (e) (f) (st+ta-025 (g) As a method for forming such a recording film, a dry process such as a vacuum evaporation method or a sputtering method can also be used.

It is also possible to use a wet process, such as a spin-coating method, a dip method, a roll-coating method, or an LB (Langmuir-Prodgett) method.

If the recording film material is soluble in general-purpose organic solvents, such as alcohol-based, ketone-based, cellosolve-based, halogenated hydrocarbon-based, and fluorocarbon-based solvents, the film can be formed by the spin code method for productivity reasons. (j) is desirable.

In this way, when forming a film by a so-called coating method, a polymer binder may be added as necessary. Examples of the polymer binder include vinyl chloride resin, acrylic resin, polyester resin, polyamide resin, polycarbonate resin, epoxy resin, methacrylic resin, vinyl acetate resin, nitrocellulose, and phenol resin.

When using a polymer binder, the ratio of the polymer binder to the dye is preferably 10% by weight or less.

Further, there is no particular restriction on the thickness of the recording film of the present invention, and the optimum film thickness also varies depending on the compound type, but is preferably 500 to 3,000, and the optimum film thickness range is 1,000 to 2,500.

Materials for the reflective film include metals such as gold, silver, copper, platinum, aluminum, cobalt, tin, and MgO.

Metal oxides such as ZnO1SnO1, SiN4, AIN,
Examples include nitrides such as TiN, but gold is most suitable because it has a high absolute reflectance and excellent stability.

In some cases, an organic high-reflection film may also be used.

The method for forming such a reflective film is most preferably a dry process, such as a vacuum evaporation method or a sputtering method, but is not limited thereto.

Further, an overcoat layer may be provided on the reflective film to protect the film from chemical deterioration (for example, oxidation, water absorption, etc.) and physical deterioration (for example, scratches, scratches, etc.).

The overcoat layer is generally formed using an ultraviolet curable resin, but is not limited thereto.

The disc format is CD or CD-RO after information is recorded.
CD or CD-
ROM standards (Red Book) and R-CD standards (
It is preferable to comply with the Orange Book).

Further, the disk substrate used in the present invention preferably has a light transmittance of 85% or more for writing and reading signals, and has small optical anisotropy.

For example, thermal Examples include substrates made of thermosetting resins such as plastic resins, epoxy resins, and allyl resins. Among these, those made of thermoplastic resin are preferable due to ease of molding and ease of providing signals such as guide grooves, and more preferably those made of acrylic resin or polycarbonate resin from the viewpoint of optical properties, mechanical properties, and cost. Particularly preferred.

In addition, guide grooves etc. can be provided using a stamper etc. when molding thermoplastic resin (injection molding, compression molding), or so-called 2P using photopolymer resin.
The method by method is preferred.

(Examples) The present invention will be specifically explained below using Examples, but the present invention is not limited to the following Examples.

(Synthesis Example 1) (Vanadyl phthalocyanine tetrachlorosulfonic acid) 4 g of vanadyl phthalocyanine was gradually added to 36 g of chlorosulfonic acid to form a complete solution, and the temperature was raised to 1
The mixture was heated and stirred at 00 to 105°C for 4 hours.

After cooling to 90°C, thionyl chloride Log is 90~
The mixture was added dropwise while maintaining the temperature at 95°C, and the mixture was further heated and stirred at 90 to 95°C for 2 hours. After cooling the reaction solution, it was cooled with dry ice and poured into 500 g of appropriately crushed ice. 4.5 g of phthalocyanine tetrachlorosulfonic acid chloride powder was obtained.

(Synthesis of phthalocyanine compound (b)) Methanol 20
Add 14.5 g of di-N-octylamine to 0a+1,
After cooling to 0°C in a water bath, 4. vanadyl phthalocyanine tetrachlorosulfonic acid chloride synthesized previously.
5g was added gradually. After stirring at room temperature for 1 hour, the temperature was raised,
The mixture was perfused for 2 hours. After the reaction solution was cooled, it was poured into a 10% by weight aqueous sodium carbonate solution 21 with vigorous stirring, and the resulting Harz-like precipitate was collected by filtration, dissolved in 500 ml of benzene, and then washed with water in a separatory funnel until it became neutral. did. After drying with magnesium sulfate, N-hexane was added dropwise to the benzene solution.
The precipitate precipitated by reprecipitation is collected by filtration, washed with hexane, and dried to obtain a crude product of phthalocyanine compound (b) 2.
Obtained 0g. Purification was performed using a silica gel column with a mixed solvent of chloroform/methanol 20:1.

(Synthesis Example 2) (Synthesis of Phthalocyanine Compound (C)) Changing vanadylphuclocyanine in (Synthesis Example 1) to hydroxyaluminum phthalocyanine, the same procedure as in (Synthesis Example 1) was carried out, and aluminum phthalocyanine tetrasulfon 4.0 g of acid chloride powder was obtained.

A solution of 20 g of N,N-diethylaminopropylamine in 200 ml of methanol was cooled in a water bath, and aluminum phthalocyanine tetrasulfonic acid chloride was added.4.
0 g was added gradually. After stirring at room temperature for 1 hour, the mixture was heated and refluxed for 2 hours. After cooling the reaction solution, add 10% aqueous sodium carbonate solution 2. filtrate the precipitate,
After thorough washing, it is dried to form a phthalocyanine compound (C
) was obtained.

Purification was performed in the same manner as in (Synthesis Example 1).

(Synthesis Example 3) (Synthesis of Phthalocyanine Compound (e)) The N,N-diethylaminopropylamine of (Synthesis Example 2) was
Instead of N-butylaminopropylamine, (Synthesis Example 2
) to obtain 3.5 g of crude hydroxyaluminum phthalocyanine tetrasulfonic acid (N,N-di-N-butylaminopropyl)amide. Dissolve 3.0 g of the crude product in 100 ml of sufficiently dehydrated pyridine, and add 2.0 g of chlorodiphenylphosphine at 30°C or less.
g was added dropwise. After stirring at room temperature for 1 hour, the mixture was heated and refluxed for 2 hours.

After cooling the reaction solution, it was poured into 2.0 g of ice water with vigorous stirring, and the precipitate was collected by filtration, thoroughly washed with water, and dried to obtain 3.3 g of crude phthalocyanine compound (e). Purification was performed using a silica gel column with a mixed solvent of chloroform/methanol 5:2.

(Synthesis Example 4) (Synthesis of phthalocyanine compound (f)) Sulfuric acid 10 prepared by adjusting 2 g of chlorogallium phthalocyanine to 100% by weight
6.5 g of 2-chloroacetamide after dissolving in 0 g;
Add 2.0g of paraformaldehyde and raise the temperature to 90~
The mixture was heated and stirred at 100° C. for 4 hours. After cooling the reaction solution, add ice water 2. A composition of tetra(2-chloroacetamido)methyl chlorogallium phthalocyanine is obtained by injecting the precipitate into OL, filtering the precipitate, thoroughly washing it, and drying it in a vacuum dryer. I got 2.2g.

A solution of N,N-diethylaminopropylamine Log added to 100ml of methanol was cooled in a water bath, and tetra(
2.0 g of a composition of 2-chloroacetamido)methyl chlorogallium phthalocyanine was slowly added. After stirring at room temperature for 1 hour, the mixture was heated and refluxed for 2 hours. After cooling the reaction solution, it was filtered to remove insoluble materials, and the filtrate was mixed with a 10% by weight aqueous sodium carbonate solution.2. The precipitate precipitated was collected by filtration and added to a methanol/water (1:1) solution. Washed with OL. After drying, extract the methanol soluble content using Soxhlet, remove the solvent, and obtain the phthalocyanine compound (f).
1.0 g was obtained.

(Synthesis Example 5) (Synthesis of phthalocyanine compound (k)) The composition of phthalocyanine compound (k) was obtained by changing the chlorogallium phthalocyanine to tetraphenylthiophthalocyanine (Synthesis Example 4) in the same manner as in (Synthesis Example 4). 0.8 g of the product was obtained. Further purification was performed using chloroform using a silica gel column.

Example 1 Ethoxyethanol of a phthalocyanine compound represented by compound (b) was placed on a polycarbonate resin substrate with a thickness of 1.2 mm, an outer diameter of 120 mm, and an inner diameter of 15 mm, having a spiral guide groove with a depth of 800 people and a pitch of 1.6 μm. 2.0 of
Create a wt% solution and use a spin coater to coat it with a film thickness of 12%.
The film was deposited on 00 people.

Next, gold was applied to a thickness of 800 mm on the coating film thus obtained.
The film was formed manually by vacuum evaporation. Further, a protective layer was provided thereon using an ultraviolet curable resin to prepare an optical disc.

The reflection spectrum of the optical disc prepared in this way is in the wavelength range of 770 to 810 nm, and the reflectance to AI is 8.
It is 0% or more, which fully satisfies the CD standard.

Further, when an EMF-CD format signal was recorded on this optical disk using a semiconductor laser with a wavelength of 780 nm at a linear velocity of 1.3 m/sec and a recording power of 9 mW, recording was possible.

The recorded pit rows had a length of 0.9 to 3.3 μm and an interval of 0.9 to 3.3 μm.

Next, this signal is processed using a commercially available CD player at a linear velocity of 1
．． When reproduction was performed at a speed of 3 m/sec and a reproduction output of 0.5 mW, the signal obtained was good and at a level sufficient for a CD player.

Example 2 Ethoxyethanol of a phthalocyanine compound represented by compound (C) was placed on a polycarbonate resin substrate with a thickness of 1.2 mm, an outer diameter of 120 mm, and an inner diameter of 15 mm, having a spiral guide groove with a depth of 800 people and a pitch of 1.6 μm. 2.0 of
Create a wt% solution and use a spin coater to make a film with a thickness of 110%.
The film was deposited on 0 people.

Next, gold was applied to a thickness of 800 mm on the coating film thus obtained.
The film was formed manually by vacuum evaporation. Further, a protective layer was provided thereon using an ultraviolet curable resin to prepare an optical disc.

The reflection spectrum of the optical disk prepared in this way has a reflectance of 85% with respect to AI in the wavelength range of 770 to 810 nm.
% or more, which fully satisfies the CD standard.

In addition, using this optical disk, a semiconductor laser with a wavelength of 780 nm was used to generate 9 mW at a linear velocity of 1.3 m/sec.
When an EMF-CD format signal was recorded with a recording power of , recording was possible.

The recorded pit rows had a length of 0.9 to 3.3 μm and an interval of 0.9 to 3.3 μm.

Next, this signal is processed using a commercially available CD player at a linear velocity of 1
．． When the signal was reproduced at a speed of 3 m/sec and a reproduction output of 0.5 mW, the signal obtained was good and at a level sufficient for a CD player.

Example 3 A phthalocyanine compound represented by compound (e) of ethoxyethanol was deposited on a polycarbonate resin substrate with a thickness of 1.2 mm, an outer diameter of 120 mm, and an inner diameter of 15 mm, having a spiral guide groove with a depth of 800 people and a pitch of 1.6 μm. Create a 2.0% by weight solution and use a spin coater to coat it with a film thickness of 130%.
The film was deposited on 0 people.

Next, gold was applied to a thickness of 800 mm on the coating film thus obtained.
The film was formed manually by vacuum evaporation. Further, a protective layer was provided thereon using an ultraviolet curable resin to prepare an optical disc.

The reflection spectrum of the optical disk prepared in this way has a reflectance of 82% with respect to AI in the wavelength range of 770 to 810 nm.
% or more, which fully satisfies the CD standard.

In addition, using this optical disk, a semiconductor laser with a wavelength of 780 nm was used to generate 9 mW at a linear velocity of 1.3 m/sec.
When an EMF-CD format signal was recorded with a recording power of , recording was possible.

The recorded pit rows had a length of 0.9 to 3.3 μm and an interval of 0.9 to 3.3 μm.

Next, this signal is processed using a commercially available CD player at a linear velocity of 1.
When reproduction was performed at 3 m/sec and a reproduction output of 0.5 mW, the obtained signal was good and at a level sufficient for a CD player.

Example 4 A phthalocyanine compound represented by compound (f) of ethoxyethanol was deposited on a polycarbonate resin substrate with a thickness of 1.2 mm, an outer diameter of 120 mm, and an inner diameter of 15 mm, having a spiral guide groove with a depth of 800 and a pitch of 1.6 μm. Create a 2.0% by weight solution and coat it with a film thickness of 120% using a spin coater.
The film was deposited on 0 people.

Next, gold was applied to a thickness of 800 mm on the coating film thus obtained.
The film was formed manually by vacuum evaporation. Further, a protective layer was provided thereon using an ultraviolet curable resin to prepare an optical disc.

The reflection spectrum of the optical disc prepared in this way has a reflectance of 78% with respect to AI in the wavelength range of 770 to 810 nm.
% or more, which fully satisfies the CD standard.

In addition, using this optical disk, a semiconductor laser with a wavelength of 780 nm was used to generate 9 mW at a linear velocity of 1.3 m/sec.
When an EMF-CD format signal was recorded with a recording power of , recording was possible.

The recorded pit rows had a length of 0.9 to 3.3 μm and an interval of 0.9 to 3.3 μm.

Next, this signal is processed using a commercially available CD player at a linear velocity of 1.
When the signal was reproduced at a speed of 3 m/sec and a reproduction output of 0.5 mW, the obtained signal was good and at a level sufficient for a commercially available CD player.

Example 5 A naphthalocyanine compound represented by compound (k) was coated with cyclohexene 1 on a polycarbonate resin substrate with a thickness of 1.2 mm, an outer diameter of 120 mm, and an inner diameter of 15 mm, which had spiral guide grooves with a depth of 800 people and a pitch of 1.6 μm. .0% by weight
Films were formed on 150 people using a spin coater using a solution.

Next, gold was applied to a thickness of 800 mm on the thus obtained laminated film.
The film was formed manually by vacuum evaporation. Further, a protective layer was provided thereon using an ultraviolet curable resin to prepare an optical disc.

The reflection spectrum of the optical disk prepared in this way has a reflectance of 85% with respect to AI in the wavelength range of 770 to 810 nm.
% or more, which fully satisfies the CD standard.

In addition, using this optical disk, a semiconductor laser with a wavelength of 780 nm was used to generate 9 mW at a linear velocity of 1.3 m/sec.
When an EMF-CD format signal was recorded with a recording power of , recording was possible.

The recorded pit rows had a length of 0.9 to 3.3 μm and an interval of 0.9 to 363 μm.

Next, this signal is processed using a commercially available CD player at a linear velocity of 1.
When reproduction was performed at a speed of 3 m/sec and a reproduction output of 0.5 mW, the obtained signal was good and at a level sufficient for a CD player.

(Effect of the invention) By creating an optical disc according to the configuration of the present invention,
It is possible to provide a write-once optical disc that is compatible with CDs or CD-ROMs and has a write-once editing function.

Claims (1)

[Claims] 1. Comprised of a transparent substrate/recording film/reflection film, compact disc format or compact disc-RO
A write-once optical disc for recording M format signals, the recording film being selected from phthalocyanine dyes represented by the following general formula [1], which is compatible with compact discs or compact disc-ROM. General formula [1] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X^1 to X^4 are each independently, ▲ There are mathematical formulas, chemical formulas, tables, etc. There is ▼. Y^1 to Y^4 each independently represent a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, Acyl group which may have a substituent, heterocyclic residue which may have a substituent, nitro group, cyano group, sulfonic acid group, carboxylic acid group, -OR^1, -SR^2, - COOR
^1, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -NHCOR^1, -N=N-R^1, -N=CHR^1. M represents a metal that may have a substituent Z or H_2, and Z is
Hydrogen atoms, oxygen atoms, halogen atoms, alkyl groups that may have substituents, aryl groups that may have substituents, acyl groups that may have substituents, hydroxyl groups, and alkyl groups that may have substituents. an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylthio group that may have a substituent, an arylthio group that may have a substituent, or ▲Mathematical formula, chemical formula, table, etc. There are ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼. Here, R^1, R^2, and R^3 may be the same or different, and each has a hydrogen atom, an alkyl group that may have a substituent, or a substituent. represents an aryl group that may have a substituent, a cycloalkyl group that may have a substituent, an acyl group that may have a substituent, or a polyether group, and from R^1, R^2, R^3 The selected two may form a 4- to 7-membered ring, and in this case, it may be a heterocyclic ring further containing a heteroatom such as a nitrogen atom. l^1~l^4, m^1~m^4, n are each X^1
~X^4, Y^1~Y^4, represents the number of substituents of Z. l
^1~l^4 each independently represent an integer from 0 to 4,
They cannot all become 0 at the same time. m^1 to m^4 each independently represent an integer from 0 to 4. n represents an integer of 0 to 2. ]