JPS61162385A - Optical information-recording medium - Google Patents

Abstract

PURPOSE:to obtain an optical information-recording medium capable of recording and reproduction by long wavelength rays from a semiconductor laser or the like having excellent preservability and less deteriorated on reproduction, by incorporating a specified manganese phthalocyanine into a recording layer and specifying the thickness of the layer. CONSTITUTION:The recording layer is capable of recording information therein by inducing an optical change by irradiation with laser light, and comprises a manganese phthalocyanine of the formula, wherein each of R1-R4, which may be the same or different, is hydrogen or halogen, and each of (l), (m), (n), and (s) is an integer of 1-4. The recording layer is preferably provided by vacuum deposition, which include simultaneous co-deposition and mixed co-deposition. It is necessary that the thickness of the recording layer is 500-2,500Angstrom . In addition to the recording layer 2 provided on a base 1, a ground layer 3 and a protective layer 3 are provided, as required.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to an optical information recording medium suitable for writing and recording using a laser, particularly a semiconductor laser.

[Prior art]

2. Description of the Related Art Conventionally, information recording and reproducing apparatuses are known that record and reproduce information by irradiating a rotating disk-shaped information recording medium with a laser beam. As an information recording medium used in this type of information recording device, one in which a recording layer made of a low melting point metal or a low melting point metal and a dielectric is provided on a substrate has been proposed. However, these have drawbacks such as poor storage stability, low resolution, low recording density, and difficult manufacturing conditions, resulting in high cost.

Therefore, as a result of various studies, the inventor of the present invention, Tsutomu, found that when a thin dye film was provided on the substrate, a recording medium with improved writing sensitivity and reflectance and a high reading S/N ratio could be obtained, and he proposed it. are doing. However, at present, such recording media still lack sufficient stability against light and heat, and storage stability against reproduction light after recording.

〔the purpose〕

The present invention has been made in view of the above problems, and its purpose is to provide an optical information recording medium that is capable of recording and reproducing using long wavelength light such as a semiconductor laser, has excellent storage stability, and has little reproduction deterioration. be.

〔composition〕

As a result of various studies on the prior art, the inventor of the present invention found that manganese 7 of the following general formula CI'' is used as a constituent component of the recording layer.
Using talocyanine, the thickness of the recording layer is increased to 500X~
It was discovered that the above object could be achieved by specifying the range of 2500X, leading to the completion of the present invention.

General formula [■] However, R1 to circles may be the same or different and each represents hydrogen or halogen, and t1m%n and e each represent an integer from 1 to 4.

The optical information recording medium of the present invention basically has a recording layer containing manganese phthalocyanine of the above general formula (1) on a substrate. Furthermore, if necessary, a subbing layer may be provided between the substrate and the recording layer, or a protective layer may be provided on the recording layer. Further, the recording medium thus constructed can also be used in a sandwich structure.

The recording layer in the present invention is capable of causing some optical change by irradiation with laser light and recording information based on the change, and the recording layer contains the compound of the above general formula [I]. is necessary. Further, in forming the recording layer, two or more compounds of the above general formula [■] can be used in combination.

Furthermore, the compound of the above general formula [I] can be used with other dyes such as phthalocyanine dyes, tetrahydrocholine dyes, dioxazine dyes, triphetchazine dyes, phenanthrene dyes, cyanine (merocyanine) dyes, anthraquinone (indans) dyes, etc. ) dyes, xanthine dyes, triphenylmethane dyes, croconium dyes,
Beryllium dyes, azulene dyes, metals or metal compounds, such as H, Sn.

Te, Bi, At, Sunts, ToOB, EInO1A
+, Cd, etc. may be mixed and dispersed or laminated. Furthermore, the manganese phthalocyanine of the present invention can be mixed and dispersed in various polymeric materials such as ionomer resins, polyamide resins, vinyl resins, natural polymers, silicones, liquid rubbers, or silane coupling agents. Alternatively, it may be used together with stabilizers, dispersants, flame retardants, lubricants, antistatic agents, surfactants, plasticizers, etc. for the purpose of improving properties.

As a method for forming the recording layer, vapor deposition, CVN, snottering, etc. can be used. Vacuum deposition methods are particularly preferred, including simultaneous co-deposition methods and mixed co-deposition methods. Further, the thickness of the recording layer needs to be in the range of 5001 to 2500 mm.

Further, regarding the undercoat layer and the protective layer provided as necessary on the recording layer in the present invention, the undercoat layer is (a) for improving adhesion, (b) as a barrier for water or gas, and (C) for the recording layer. improvement in storage stability, (d) improvement in reflectance, (el
) It is used for the purposes of protecting the substrate from solvents, (f) forming pregrooves, etc.

(For the purpose of al, moderate amounts of polymeric materials such as ionomer resins, polyamide resins, vinyl resins, natural polymers, silicones, liquid rubbers, etc., and silane coupling agents can be used, (1111), (C
) In addition to the above polymer materials, inorganic compounds such as MgF2.5iO1T102,
Metals or metalloids such as iN, SiN, etc.
cu s s s n 1. cr % G e s s
elAg-At5Au etc. can be used, (
(For the purpose of (11), metals such as At, Ag, etc. or organic thin films with metallic luster such as methine dyes, xanthine dyes, etc. can be used, and (8)
As fl, ultraviolet curable resins, thermosetting resins, and thermoplastic resins can be used. In addition, the protective layer may be scratched,
It is provided for the purpose of protecting the recording layer from dust, dirt, etc., improving the storage stability of the recording layer, and improving the reflectance, and the same material as the undercoat layer can be used as the material.

Next, a configuration example of the optical information recording medium of the present invention will be explained with reference to the drawings.

As shown in FIG. 1, the optical information recording medium of the present invention basically comprises a substrate 1 and a recording layer 2 containing the manganese phthalocyanine of the present invention. Further, the recording layer may be laminated with other layers such as a reflective layer.

Furthermore, as shown in FIGS. 2 to 4, a subbing layer 3 and a protective layer 4 are further provided, and at least one of the layers is doped with the compound of the general formula CI) of the present invention. Good too. Further, stabilizers, dispersants, flame retardants, lubricants, antistatic agents, surfactants, plasticizers, etc. may be contained in the undercoat layer and the W-retaining layer. In addition, the thickness of the undercoat layer is 0.1 to 30
[mu]m is preferably in the range of 0.2 to 10 [mu]m, and the thickness of the protective layer is preferably at least 0.f [mu]m, preferably at least 50 [mu]m.

Furthermore, as another configuration of the optical information recording medium according to the present invention, two recording media having the same configuration as shown in FIGS. It may be a so-called air sandwich structure in which it is placed inside and sealed, or it may be a so-called tight sandwich structure (bonded structure) in which it is bonded via a bonding wire.

The substrate in the present invention must be transparent to the laser beam used when writing and recording is performed from the substrate side, and does not need to be transparent when writing is performed from the recording gIn.

As the substrate, plastics such as glass, polyester, acrylic resin, polyamide, polyolefin resin, phenol resin, epoxy resin, polyimide, metal, ceramics, etc. can be used.

〔Example〕

The present invention will be further explained below with reference to Examples along with Comparative Examples, but the present invention is not limited thereto.

Example 1 Polymethyl methacrylate (thickness 1.211g11) (
PMMA) Manganese Phthalocyanine 11x1 on JIl
A recording medium was fabricated by vacuum deposition under 0-''1' orr to form a recording layer with a thickness of 1370×.

A semiconductor laser beam with a wavelength of 790 nm was applied to this recording medium from the substrate side at a recording frequency of 0.5 MH7 and a linear velocity of 1.5 m/8.
eC1 recording, information was written and reproduced at a power of 4 mW, and its spectrum analysis (scanning filter bandwidth 30
When the C/N was measured, 45 dB was obtained.

On the other hand, a recording medium produced in the same manner was heated at 60°C and 90 q
When the C/N was measured after being left for 1000 hours under the conditions of 6R, H, 43 dB was obtained. Furthermore, no change was observed in the eye-to-turn of the reproduced signal after 1,000,000 readings at the reproduction optical power of 〇 and amw.

The spectral characteristics of this recording layer are shown in FIG. 5, and the relationship between the thickness of the recording layer and the spectral characteristics is shown in FIG. The results shown in Figure 6 were obtained by simulation based on the measured values of the film thickness, transmittance, and reflectance of several samples with different film thicknesses of the manganese phthalocyanine recording layer at a wavelength λ = 790 nm. The optical constants were estimated and used to simulate the relationship between film thickness, transmittance, and reflectance.

Example 2 A recording medium was produced by forming a recording layer with a thickness of 1150 Å in the same manner as in Example 1 except that manganese (hexadecafluoro7-thalocyanine) was used instead of manganese phthalocyanine in Example 1.

Example 3 Manganese phthalocyanine and a compound represented by the following general formula (1) were co-deposited at a composition of 1:1 on a PMMA substrate with a thickness of 1.2 mm to form a recording layer with a thickness of 900 H to produce a recording medium. did.

Example 4 A 1,2-dichloroethane solution of the compound of the following general formula (2) was applied on a PMMA substrate with a thickness of 1.2 layers using a spinner to form a first recording layer with a thickness of 500^. A recording medium was manufactured by forming a second recording layer by vacuum-depositing manganese phthalocyanine to a thickness of 300H.

CH! IC Horse Comparison Example 1 Te is evaporated onto a PMMA substrate with a thickness of 1.2 mm to a thickness of 4 mm.
A recording layer of 50A was formed.

Comparative Example 2 A recording layer having a thickness of 500 Å was formed by vacuum-depositing the compound of general formula (1) on an I'MMA substrate having a thickness of 1.2 mm.

Comparative Example 3 A recording layer having a thickness of 500 Å was formed by applying the compound of the general formula (2) using a spinner onto a PMMA substrate having a thickness of 1.2 Å.

Comparative Example 4 Manganese phthalocyanine was deposited in the same manner as in Example 1 to form a recording layer with a thickness of 400 Å.

Comparative Example 5 Manganese phthalocyanine was deposited in the same manner as in Example 1 to form a recording layer with a thickness of 3000 Å.

The C/N of the information recording medium produced as described in the above Examples and Comparative Examples was measured in the same manner as in Example 1, and the results are summarized in the table below.

Example (mw) c/N (aB)
C/N (dB) Example 1 4 4
5 45 Comparative Example 1 2.5
44 Membrane deterioration, inability to track 2 2.3
54 453 2.3
56 4044.5 Unwritable 54.5 [Effect] According to the optical information recording medium of the present invention, it is possible to form pits in a good shape that allows recording with high sensitivity even using a long wavelength laser (semiconductor laser). You can get a high quality can.
Advantages such as a recording medium having high stability against heat and light, excellent storage stability, and little reproduction deterioration can be obtained.

[Brief explanation of the drawing]

1 to 4 are cross-sectional views showing the structure of the optical information recording medium of the present invention, FIG. 5 is a diagram showing the spectral characteristics of the recording layer according to the present invention, and FIG. 6 is a diagram showing the spectral characteristics of the recording layer according to the present invention. FIG. 3 is a diagram showing the relationship between layer thickness and spectral characteristics. DESCRIPTION OF SYMBOLS 1... Substrate, 2... Recording layer, 3... Undercoat layer, 4...
...Protective layer. Patent applicant Rico Co., Ltd. - Figure 5 Laser light wavelength (Tlm)

Claims (1)

[Claims] An optical information recording medium comprising a recording layer provided directly or via an undercoat layer on a substrate, and further provided with a protective layer thereon as required, wherein the recording layer contains the general formula ▲mathematical formula , chemical formulas, tables, etc.▼ (In the formula, R_1 to R_4 may be the same or different and each represents hydrogen or halogen, and l, m, n, and s each represent an integer from 1 to 4. 1. An optical information recording medium characterized in that it contains manganese phthalocyanine represented by the following formula and has a film thickness of 500 to 2,500 Å.