JPH01297293A - Optical recording medium - Google Patents

Abstract

PURPOSE:To obtain an optical recording medium having practically superior characteristics, by providing an organic thin film layer containing at least one kind of specific phthalocyanine compounds on a substrate. CONSTITUTION:An organic thin film layer containing at least one kind of phthalocyanine compounds shown by a formula is provided on a substrate. In the formula, rings A1-A4 independently represent benzene ring and naphthalene ring ; M represents Al, Ga, In, Si Ge, Sn, or transition metals ; Z represents oxygen atom, halogen atom, hydroxyl, OR5, SR5, OSiR6R7R8, or OGeR6R7R8 ; Y represents hydrogen atom, oxygen atom, halogen atom, hydroxyl OR5, SR5, OSiR6R7R8, or OGeR6R7R8 ; R1-R4 independently represents aromatic heterocyclic residue which may have substituent ; p and q represent the number of the substituents Y or Z, which is 0 or 1; and k, l, m, n independently represent integers 0-2, but all of them cannot represent 0 at the same time.

Description

[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention relates to an optical recording medium that can be additionally recorded using a focused beam of a semiconductor laser. It relates to optical recording media used for recording various information such as external memory, 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 rely on thin film formation in a vacuum, such as vacuum evaporation or sputtering.Furthermore, the high thermal conductivity of the recording layer limits the recording density, and they also contain toxic substances such as tellurium. Since substances 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. 112793/1983)
, phthalocyanine dye (US Pat. No. 4,298,975), naphthalocyanine dye (US Pat. No. 4,492,75)
A recording medium having a recording layer made of an organic dye having absorption in the semiconductor laser oscillation wavelength region has been proposed in Japanese Patent Publication No. 0). However, the recording media using organic dyes that have been proposed so far do not have sufficient characteristics in terms of durability and reflectance, or have poor solubility in solvents, making it difficult to apply economically advantageous coatings. This method has the disadvantage that a thin film formation method based on this method cannot be applied.

(Problems to be Solved by the Invention) The present invention improves various drawbacks of conventional recording media using organic dyes, and provides an optical recording medium that has practically excellent characteristics2 and is also economically advantageous. It is something to do.

[Structure of the invention]

(Means for Solving the Problems) The present invention provides an information recording medium that performs recording by causing a state change by high-density energy irradiation such as a laser beam. It is an optical recording medium having an organic thin film layer containing at least one kind of compound.

[In the formula, rings A and ~A4 each independently represent a benzene ring and a naphthalene ring.

M represents Al, Ga, In, Si, Ga, Sn or a transition metal.

Z is an oxygen atom, a halogen atom, a hydroxyl group, ORs: SR
s , OS iRb Rt Re , or QQ e
Represents R6R7R6.

Y is a hydrogen atom, an oxygen atom, a halogen atom, a hydroxyl group, O
Rs, SRs, O3tRb Rt R1, or 0
Represents GeRh Rt Rs.

R8 to R4 each independently represent an aromatic heterocyclic residue which may have a substituent.

R2 represents a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkyl group, or a cycloalkyl group.

R6, Rt, and RI are a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group, a cycloalkyl group,
Represents any one of an alkoxy group, a monoloxy group, a siloxy group, a germaniumoxy group, or a polyether group.

p and q represent the number of substituents Y or Z.

0 or 1.

k, 1. m and n each independently represent an integer from 0 to 2, but they are never O at the same time. ]R, -
R, specifically, is a pyridyl group.

Butylpyridyl group, ethoxypyridyl group, quinoxalyl group, phthalazinyl group, butylquinoxalyl group.

dichlorotriazinyl group, dimethoxytriazinyl group,
dibutylaminotriazinyl group, dibutoxytriazinyl group, dihydroxyethoxytriazinyl group, distearyloxytriazinyl group, dianilinotriazinyl group, ditoluidinotriazinyl group.

Dibutylanilinotriazinyl group, benzothiazolyl group, chlorobenzothiazolyl group, butylbenzothiazolyl group, methoxybenzothiazolyl group, carbazolyl group, benzoxacylyl group, indolyl group.

Examples include, but are not limited to, a benzimidazolyl group and a benzothiophenyl group.

Specifically, R7 is a methyl group or an ethyl group.

Propyl group, butyl group, stearyl group, ethoxyethyl group, hydroxyethyl group, butoxyethyl group.

Examples include, but are not limited to, chloroethyl group, diethylaminoethyl group, phenyl group, butylphenyl group, butoxyphenyl group, and cyclohexyl group.

R,,R? , Re specifically includes a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a stearyl group, an ethoxyethyl group, a hydroxyethyl group,
Butoxyethyl group, chloroethyl group.

Diethylaminoethyl group, phenyl group, butylphenyl group, butoxyphenyl group, cyclohexyl group.

Examples include, but are not limited to, a trimethylsiloxy group, a triphenylgermaniumoxy group, a polyoxyethylene group, and a butoxypolyoxyethylene group.

-a The compound represented by formula [I] is 1, for example, the following - general formula t
n), (III), or (IV) general formula (II)
H7J General formula (III) HN (in the formula + A+-a + R+-4+ and, R
, m, n are.

It has the same meaning as in General 2N). It can be easily produced by heating an indoline compound, nitrile compound, or acid anhydride represented by the following formula and a metal compound in the presence or absence of a common organic solvent. When the acid anhydride represented by general formula (IV) is used as a raw material, ammonia gas or urea is used. In some cases, it may be preferable to use a catalyst such as ammonium molybdate, tributylamine, cyclohexylamine, or diazabicycloundecene.

-C Among the compounds represented by formula [I], those having a substituent on the central metal are described in Reference 1 M, B, enney et.
al, :J, Am, CheIIl, Soc,,
106.7404-7410 (1984).

Further, the compound represented by the general formula [I] is synthesized using mono- to tetraaminophthalocyanine or naphthalocyanine as an intermediate, and then synthesized with this intermediate.

It can also be produced by dehydrohalogenation reaction with an aromatic heterocyclic compound having an active halogen.

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, thermal Plastic resin or epoxy resin.

Examples include substrates using thermosetting resins such as allyl resins. Among these, the above-mentioned thermoplastic resins are preferred because of their ease of molding and ease of providing guide grooves, address signals, etc., and acrylic resins and polycarbonate resins are particularly preferred from their optical and mechanical properties. The thickness of these substrates is not particularly limited and may be plate-like or film-like. In addition, the shape may be two circles or a card shape,
There is no particular limit to its size.

Further, the substrate in the present invention usually has guide grooves for position control during recording and reading, and unevenness for preformatting such as address signals and various marks.
These irregularities are preferably provided using a stamper or the like when molding (injection, compression, etc.) the thermoplastic resin as described above.

In the optical recording medium of the present invention, a recording layer containing a phthalocyanine compound is fixed on a substrate.

For example, thin films can be made using methods such as vacuum evaporation, sputtering, ion plate method, and LB method (Langmuir-Blodgett method), but these methods require complicated operations and are inferior in terms of productivity. The most preferred method is When the recording layer is formed by a coating method, the phthalocyanine compounds used in the present invention are alcohols, ketones, amides, sulfoxides, ethers, and esters.

It is applied by dispersing or dissolving it in ordinary organic solvents such as aliphatic halogenated hydrocarbons and aromatic hydrocarbons.

Moreover, at this time, a polymer binder may be added as necessary. Examples of polymer binders include vinyl chloride resins, acrylic resins, polyester resins, polyamide resins, polycarbonate resins, epoxy resins, methacrylic resins, vinyl acetate resins, nitrocellulose, and phenolic resins, as well as thermoplastic resins or thermosetting resins. Can be used. The ratio of the polymer binder to the phthalocyanine compound represented by the general formula [I] 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 represented by the general formula [I]. Examples of pigments that can be used in combination are already known.

Aromatic or unsaturated aliphatic diamine metal complexes, aromatic or unsaturated aliphatic dithiol metal complexes, phthalocyanine complexes, naphthalocyanine complexes, squalium dyes, naphthoquinone complexes, anthraquinone dyes, polymethine dyes, etc. can give.

The recording layer containing the phthalocyanine compound represented by the general formula [I] formed on the substrate has a thickness of 10 pm or less,
Preferably it is 500 to 2 μm. After applying again,
Chloroform, tetrahydrofuran.

By exposure to vapors of organic solvents such as toluene,
In some cases, the absorption wavelength of the thin film shifts to longer wavelengths, and the sensitivity to light in the oscillation wavelength range of the semiconductor laser can be significantly improved.

In addition, in order to protect these recording layers, A12o3.
sio! A protective layer may be provided by depositing an inorganic compound such as 1sto or SnO. 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 above layer provided on the substrate with laser light focused to about 1 μm, preferably semiconductor laser light. The area irradiated with laser light.

This is done by reading the difference in reflectance between a portion of the recording layer where a thermal state change such as decomposition, evaporation, or melting due to absorption of laser energy has occurred and a portion where no such change has 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 preferred in terms of cost and size. As a semiconductor laser, the center wavelength is 830 parts m,
Lasers of 780 r+m and shorter wavelengths can be used.

(Example) The present invention will be explained in more detail with reference to Examples.

The present invention is not limited to the following examples.

Note that 9 parts in the two examples represent parts by weight.

Synthesis Example 1 Synthesis of Compound (a) To 20 parts of n-amyl alcohol, 2.2 parts of nitrile having the following structure, 0.5 part of acetylacetone vanadium, and 1.0 part of diazabicycloundecene were added.
The mixture was heated and stirred at 30 to 135°C for 5 hours, cooled, filtered, washed with methanol, and then washed with water.

After drying, 1.8 parts of compound (a) was obtained.

Synthesis Example 2 Synthesis of Compound (b) To 20 parts of n-amyl alcohol, 2.6 parts of nitrile having the following structure, 0.3 parts of cuprous chloride, and 2.0 parts of diazabicycloundecene were added, The mixture was heated and stirred at 130 to 135°C for 4 hours, cooled, and then filtered.

After washing with methanol, washing with water and drying, the compound (
b) 1.6 parts were obtained.

Synthesis Example 3 Synthesis of Compound (c) To 30 parts of n-amyl alcohol, 4.2 parts of nitrile having the following structure, 0.3 parts of 1i chloride, and 2.0 parts of diazabicycloundecene were added. ~135℃
The mixture was heated and stirred for 5 hours, cooled, and then filtered.

After washing with methanol, washing with water and drying, the compound (
c) 3.1 parts were obtained.

Synthesis Example 4 Synthesis of Compound (d) 1 part nitrile used in Synthesis Example 1 to 20 parts quinoline
．． 1 part, 0.9 part of 2,3-dicyanonaphthalene, and 2.0 parts of silicon tetrachloride were added, heated and stirred at 180 to 200°C for 4 hours, cooled for 2 hours, filtered, washed with methanol, and dried. A crude product was obtained. The obtained crude product was dissolved in concentrated sulfuric acid 1
After dissolving in 1,000 parts of ice water, the resulting precipitate was filtered and washed with water, added to 300 parts of aqueous ammonia, and dissolved in 1,000 parts of ice water.
After boiling for an hour, it was filtered, washed with water, and dried. 1.0 parts of the obtained dry product was added to 20 parts of pyridine and 10 parts of tri-n-butylamine and stirred, and further 5.0 parts of trimethylchlorosilane was added and stirred at room temperature for 18 hours to obtain 2 reaction solutions. Ta.

The obtained reaction solution was poured into 1000 parts of ice water, and the precipitate was filtered off, washed with water, washed with a methanol/water (171 weight ratio) mixed solution, and dried to obtain 0.8 parts of compound (d). Ta.

Ω (%'z%N(H2C), niw', vs(csxbN
(ζshiHH).

Example 1 Pyrex (Corning Glass Work
A phthalocyanine compound (manufactured by S company, product name) is coated on a substrate made of
a) After dropping a solution consisting of 2.5 parts and 97.5 parts of chloroform, the substrate was rotated at a speed of 30 Orpm for 15 seconds.

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

The recording layer of the obtained recording medium had a thickness of 900 nm, a maximum absorption wavelength of 785 nm, and a reflectance of 27% for light with a wavelength of 830 ns+.

Mount the obtained recording medium on the turntable.

While rotating the turntable at 1800 rpm.

5 mW of 830 nm laser focused at 1.0 μm.

Recording was performed with irradiation at 8 MHz.

When the surface of the recorded optical recording medium was observed using a scanning electron microscope, the formation of clear pits was observed. Further, this optical recording medium has a wavelength of 830 nm.

When a laser beam of 0.4 mW was irradiated and nine reflected lights were detected, the C/N ratio was 52 dB.

Example 2 After dropping a solution consisting of 2.0 parts of phthalocyanine compound (b) and 98.0 parts of ethyl cellosolve onto a polycarbonate resin substrate, the substrate was heated at a speed of 800 rpm for 2 hours.
Rotate for 0 seconds and dry at 80°C for 30 minutes under reduced pressure.
Obtained a recording medium.

The recording layer of the obtained recording medium had a thickness of 650 nm, a maximum absorption wavelength of 825n+e, and a reflectance of 29% for light with a wavelength of 830n+.

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 51 dB.

Examples 3 to 11 Phthalocyanine compounds (c) to (j) were coated on a Pyrex substrate by the same method as in Example 1 and dried to obtain a recording medium.

The maximum absorption wavelength of the recording layer of the obtained recording medium and 830
Table 1 shows the reflectance for light with a wavelength of nn+ and the results of recording and reproducing the same as in Example 1 on this recording medium.

(Left below) Table 1 3c 830nm 292 45dB4
d 810 36 53 5 e 740 23 45 6 f 770 35 52 7 g 785 32 50 8 h 820 33 50 9 i 830 30 48 [Effects of the Invention] The optical recording medium of the present invention has the above structure.
It is chemically and 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] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, rings A_1 to A_4 each independently represent a benzene ring and a naphthalene ring. M represents Al, Ga, In, Si, Ge, Sn or a transition metal. Z is an oxygen atom, a halogen atom, a hydroxyl group, OR_5, S
R_5, OSiR_6R_7R_8, or OGeR_
Represents 6R_7R_8. Y is a hydrogen atom, an oxygen atom, a halogen atom, a hydroxyl group, O
Represents R_5, SR_5, OSiR_6R_7R_8, or OGeR_6R_7R_8. R_1 to R_4 each independently represent an aromatic heterocyclic residue which may have a substituent. R_5 represents a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group, or a cycloalkyl group. R_6, R_7, and R_8 are any one of a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group, a cycloalkyl group, an alkoxy group, an aryloxy group, a siloxy group, a germaniumoxy group, or a polyether group represents. p and q represent the number of substituents Y or Z, and are 0 or 1. k, l, m, and n each independently represent an integer of 0 to 2, but they are never 0 at the same time. ]