JP3124076B2 - Optical information recording medium and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical information recording medium containing a phthalocyanine dye perchlorate or periodate in a light absorbing layer and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, for a dye-based write-once optical disk, in order to optimize recording characteristics and reproduction characteristics, a light absorbing layer material is mainly composed of an indodicarbocyanine-based dye and a Ni complex or an aminium salt. A system to which a light stabilizer such as a nitroso compound has been added has been used. However, these systems do not have sufficient weather resistance, in particular, stability against light, and therefore, improvements are desired. Therefore, metal complexes of phthalocyanine dyes, which have long been considered to be excellent in light and heat stability, have been regarded as promising as light absorbing layer materials.

With respect to metal complexes of phthalocyanine dyes (including naphthalocyanine dyes, the same applies hereinafter in the present specification), a central metal and a central metal are used in order to enhance solvent solubility and improve coating properties by spin coating. Detailed studies have been made on changes in properties due to differences in compounds, introduced functional groups, and the like, and many patent applications have been filed. However, up to now, there has been almost no study on improving the easiness of recording formation using a phthalocyanine dye, particularly on reducing the recording power.

[0004]

In the case of a dye-based write-once optical disk, the maximum reflectance (Rtop) after recording must be about the same as that of a commercially available ROM-type CD, and light absorption at a recording / reproducing laser wavelength is required. The absorption efficiency of the layer, ie the absorbance, cannot be increased more than necessary.

[0005] In the case of the conventional indodicarbocyanine-based material, since it is relatively easy to generate heat by decomposition, recording was possible with a minimum absorbance of about 6 to 10 mW. Because of its stability, it was not possible to record even with a laser beam of about 10 mW at the same absorbance as that of the indodicarbocyanine system. This is exactly the same for a conventionally known phthalocyanine-based material having improved solvent solubility during spin coating.

[0006]

In order to reduce the power at the time of recording of a phthalocyanine-based material, as in the case of indodicarbocyanine-based material, a part or all of the material is exothermicly decomposed below 300 ° C. You need to do that. As one means for achieving this, it has been found that it is extremely effective to treat a phthalocyanine-based material with perchloric acid or periodic acid to form a salt with these acids, and have reached the present invention.

As another means for achieving the above object, (a) a phthalocyanine dye or a salt of a phthalocyanine dye with perchloric acid or periodate,
_{^{Wherein: R + · XO 4 - (}} R + is an organic cation, X is Cl or I) was found to be a method of adding a halogenated peroxide salts of organic substance represented by is effective.

[0008] The addition amount of the relative said (A) and (B), based on the amount of phthalocyanine dye or its perchlorate or periodate, R ⁺ · XO ₄ ^- amount 1 to 300 weight %, Preferably 5 to 100% by weight. If it is less than 1% by weight, the desired effect cannot be obtained.
On the other hand, if the content is more than 300% by weight, the dye is diluted and cannot be recorded. R ⁺ · XO ₄ ^- Examples of tetraethyl ammonium perchlorate, tetrapropylammonium perchlorate, tetra n- butylammonium perchlorate, tetraethylammonium perfluoro iodide, tetrapropylammonium par iodide, tetra-n- butylammonium par Aodai de And tetra-n-butylammonium perchlorate is particularly preferred. That is, R ⁺ · XO ₄ ^- is
A halogenated peroxide of a nitrogen alkylated compound such as a tetraalkylammonium perchlorate as described above may be used, or an IRG-003 (manufactured by Nippon Kayaku Co., Ltd.)
It may be an aminium compound that stabilizes a dye. Further, a cyanine dye having a methine chain such as indodicarbocyanine perchlorate may be used.

The resin material of the reflection auxiliary layer may be any resin material as long as it can be spin-coated as a solution, but the condition of complex refractive index n _E ≦ 1.6 must be satisfied. In order to further increase the reflectance and lower the recording power, it is more preferable to use a resin having a complex refractive index n _E ≦ 1.5. The material that can be used for this purpose, polyterpene resin (n _E = 1.38) fluorinated resin (n _E = 1.4) siloxane-based resin (n _E = 1.41) oligo styrene resin (n _E = 1.59) and the like weathering Although it has excellent properties and is useful, any material other than the above materials may be used as long as it satisfies the above-mentioned conditions. As a solvent for dissolving these, commonly used ketone-based, alcohol-based, keto-alcohol-based and cellosolve-based solvents or those obtained by perchlorinating them can be used.

That is, one object of the present invention is to provide (1)
An optical information recording medium having a light absorbing layer made of an organic thin film, wherein the light absorbing layer is made of a phthalocyanine dye perchlorate or periodate. To provide.

Here, the phthalocyanine dye is a general term of a dye compound having a phthalocyanine skeleton represented by the following general formula 1 in the structural formula, and also includes naphthalocyanine. In the formula, M represents a central metal, but Cu, Co or Ni is particularly preferred.

Embedded image

Another object of the present invention is to provide (2) a method wherein the salt of the phthalocyanine dye is a perchlorate of a copper complex of 4,4 ', 4 ", 4""-tetra (monohydroxyethylsulfonylamide) phthalocyanine. Another object of the present invention is to provide the optical information recording medium according to the above (1), which is a periodate.

Still another object of the present invention is (3) an optical information recording medium having a light absorbing layer comprising an organic thin film,
The light absorbing layer, (b) perchlorate or periodate of phthalocyanine dyes or phthalocyanine dyes, and (b) _{^{formula: R + · XO 4 - (}} R + is an organic cation, X is Cl or An optical information recording medium comprising a mixture of an organic halogenated peroxide salt represented by I). .

Another object of the present invention is to provide (4) the phthalocyanine-based dye which is a copper complex of 4,4 ', 4 ", 4""-tetra (monohydroxyethylsulfonylamide) phthalocyanine and the organic halogen compound. It is an object of the present invention to provide the optical information recording medium according to the above (3), wherein the hydrogenated peroxide salt is tetra-n-butylammonium perchlorate or tetra-n-butylammonium periodate.

Still another object of the present invention is to provide (5) a light-absorbing layer made of a dye on a substrate having a light-transmitting and spirally formed pregroove, and further comprising a metal film formed thereon. In the production of an optical information recording medium, further comprising providing a protective layer made of a resin layer thereon, a perchlorate or a periodate of a phthalocyanine dye is provided. An object of the present invention is to provide a method for producing an optical information recording medium, characterized by applying a coating liquid comprising a spin coating method.

Still another object of the present invention is to provide (6) a method wherein the perchlorate or periodate of the phthalocyanine dye is 4,4 ', 4 ", 4""-tetra (monohydroxyethylsulfonylamide) ) It is an object of the present invention to provide the production method according to the above (5), which is a perchlorate or a periodate of a phthalocyanine copper complex.

Still another object of the present invention is to provide (7) a light-absorbing layer made of a dye on a substrate having a light-transmitting and spirally formed pregroove, and further comprising a metal film on the light-absorbing layer. In the production of an optical information recording medium, which comprises providing a reflective layer made of a phthalocyanine dye and a protective layer made of a resin layer on the reflective layer, (a) a perchlorinated phthalocyanine dye or a phthalocyanine dye is used. acid salt or periodic acid salt, and (b) _{^{formula: R + · XO 4 - (}} R
⁺ Is an organic cation; and X is an organic halide peroxide salt represented by Cl or I). It is to be.

Still another object of the present invention is to provide (8) the phthalocyanine dye of the above (a), which is 4,4 ', 4 ",
4 ""-tetra (monohydroxyethylsulfonylamide) phthalocyanine copper complex, wherein the organic halogenated peroxide salt of (b) is tetra-n-butylammonium perchlorate or tetra-n-butylammonium periodate The object of the present invention is to provide a production method according to the above (7).

Still another object of the present invention is to provide (9) a light-absorbing layer made of a dye on a substrate having a light-transmitting and spirally formed pregroove, and further having a complex refraction thereon. Provide a reflection auxiliary layer made of a low-refractive-index resin having a real number part n _E of n _E ≦ 1.6, further provide a reflective layer made of a metal film thereon, and further provide a protective layer made of a resin layer thereon. In the production of the optical information recording medium consisting of, in forming the light absorbing layer and the reflection auxiliary layer, a light absorbing layer forming coating solution comprising a perchlorate or periodate of a phthalocyanine dye, and a low refractive index resin It is an object of the present invention to provide a method for producing an optical information recording medium, characterized in that a coating liquid for forming a reflection auxiliary layer is applied by a spin coating method.

Still another object of the present invention is to provide (10) a light-absorbing layer made of a dye on a substrate having a light-transmitting and spirally formed pregroove, and further having a complex refractive index thereon. Since the real part n _E is provided with a reflection auxiliary layer made of a low refractive index resin of n _E ≦ 1.6, a reflection layer made of a metal film is further provided thereon, and a protection layer made of a resin layer is further provided thereon. In the method for manufacturing an optical information recording medium, when forming the light absorbing layer, (a) a phthalocyanine dye or a perchlorate or a periodate of a phthalocyanine dye, and (b) a formula: R ⁺ .XO ₄ ^- (R ⁺ is an organic cation, X is Cl or I), characterized in that applying the coating solution consisting of a mixture of organic halide peroxide salt, represented by the spin coating method, the above (9) wherein The manufacturing method of It is to be.

Still another object of the present invention is to provide (11) the phthalocyanine dye of the above (A), which is 4,4 ', 4 ",
4 ""-tetra (monohydroxyethylsulfonylamide) phthalocyanine copper complex, wherein the organic halogenated peroxide salt of (b) is tetra-n-butylammonium perchlorate or tetra-n-butylammonium periodate It is another object of the present invention to provide an optical information recording medium according to the above (9).

Still another object of the present invention is (12) any one of the above (5) to (11), wherein the light absorbing layer has a decomposition point or a heating point of 300 ° C. or less. To provide a method for manufacturing an optical information recording medium.

[0023]

As described above, the phthalocyanine dye is converted to a salt of perchloric acid or periodate, or the dye or its perchlorate or periodate is replaced with a halogenated peroxide salt of an organic substance. 10mW by adding
With the following relatively low laser power, the laser-irradiated portion can be heated to about 300 ° C by absorption of the phthalocyanine dye itself. At this time, the irradiation part, these ClO ₄ ^- ion or IO ₄ ^- by exothermic decomposition of ions, the temperature was further raised, phthalocyanine finally laser irradiation part, an exothermic decomposition. This portion can be read out as recording pits during reproduction.

[0024]

[Example 1] 0.5 μm width, 160 nm depth, 1.6 μm pitch
m with a spiral pre-groove formed thickness of 1.2
mm, an outer diameter of 120 mm, and an inner diameter of 15 mm were molded by an injection molding method.

As light absorbers, 4,4 ', 4 ", 4""
0.4 g of a tetra (monohydroxyethylsulfonylamide) phthalocyanine Cu complex treated with perchloric acid to form a perchlorate was dissolved in 10 ml of isopropyl alcohol to form a solution.

This solution was spin-coated on the above polycarbonate substrate.

Further, a fluorine-based coating resin (n _E = 1.4) is provided as a reflection auxiliary layer on the dyed substrate by a spin coating method, and an Au layer 500 is further formed thereon.
nm is provided by a sputtering method, an ultraviolet curable resin is applied on the Au layer by a spin coating method, and is irradiated with UV light.
Cured.

The optical disk manufactured in this manner was subjected to EFM at 9 mW by a 780 nm semiconductor laser by a recording device for optical disk (DDU-1000, manufactured by Pulstec).
When the signal was recorded and reproduced at 0.5 mW, a good eye pattern was obtained. When a signal of 450 kHz was recorded by the same machine, the C / N ratio was 50 dB, while
Rtop was 65%.

FIG. 1 shows a chart of the temperature versus weight loss and heat generation of the material used for recording at this time.

The above-mentioned copper phthalocyanine perchlorate is synthesized by adding perchloric acid to a 4,4 ′, 4 ″, 4 ″ ″-tetra (monohydroxyethylsulfonylamide) phthalocyanine Cu complex in ethyl acetate, After treatment for 3 hours at room temperature, the product was recrystallized in cold water.

The salt after the final washing was stored in a vacuum dryer, and after drying, the yield was determined and used as a sample for analysis of the bound acid component.

4,4 ′, 4 ″, 4 ″ ″ obtained by the above method
0.4 g of a perchlorate of a tetra (monohydroxyethylsulfonylamide) phthalocyanine Cu complex was dissolved in 10 ml of isopropyl alcohol to prepare a spin coating solution.

[0033]

Embodiment 2 On the same substrate as in Embodiment 1, 4, 4 ',
A solution obtained by dissolving 0.36 g of 4 ″, 4 ″ ″-tetra (monohydroxyethylsulfonylamide) phthalocyanine Cu complex and 0.04 g of tetra-n-butylammonium perchlorate in 10 ml of isopropyl alcohol was prepared by spin coating. Applied.

Next, in the same manner as in Example 1, a reflection auxiliary layer, an Au layer, and an ultraviolet curable resin layer were provided. When the optical disk thus manufactured was recorded at 9.8 mW and reproduced at 0.5 mW using the same recorder as in Example 1, a good eye pattern was obtained. When a signal of 450 kHz was recorded, the C / N ratio was 52 dB. At this time, Rtop was 68%.

FIG. 2 is a chart showing the temperature versus mass loss and heat value of the material used for recording at this time.

[0036]

Comparative Example On the same substrate as in Examples 1 and 2, a Cu complex of 4,4 ', 4 ", 4""-tetra (monohydroxyethylsulfonylamide) phthalocyanine was used as a light absorbing agent. In the same manner as in No. 2, coating was performed by spin coating. Further, in the same manner as in Examples 1 and 2, a reflection auxiliary layer, an Au layer, and an ultraviolet curable resin layer were provided. When the optical disk produced in this manner was recorded at a maximum of 13 mW and reproduced at 0.5 mW using the same recorder as in Examples 1 and 2, no reproduced waveform was obtained and there was no recorded trace. Was.

FIG. 3 is a chart showing the temperature versus mass loss and heat value of the material used for recording at this time.

[0038]

As described above, the optical information recording medium of the present invention has both excellent preservability and excellent recording characteristics, and has extremely improved reliability as compared with the conventional optical information recording medium. Further, since the optical information recording medium of the present invention can record at 10 mW or less, it can be easily recorded by a relatively inexpensive and commercially available recorder using a semiconductor laser.

[Brief description of the drawings]

FIG. 1 is a chart of temperature versus mass loss and heat value of a photosensitive material in an example of an optical information recording medium of the present invention.

FIG. 2 is a chart of temperature versus mass loss and heat value of a photosensitive material in another example of the optical information recording medium of the present invention.

FIG. 3 is a chart showing the relationship between temperature and mass loss and heat value of a photosensitive material in a conventional optical information recording medium.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-63-270765 (JP, A) JP-A-63-132091 (JP, A) JP-A-62-216795 (JP, A) JP-A-3-3 100066 (JP, A) JP-A No. 1-40382 (JP, A) JP-A No. 1-40383 (JP, A) JP-A No. 60-133275 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/26 G11B 7/24 G11B 7/26

Claims (4)

(57) [Claims] 1. An optical information recording medium having a light absorbing layer made of an organic thin film, wherein the light absorbing layer is made of a phthalocyanine dye perchlorate or periodate. Optical information recording medium. 2. A light-absorbing layer made of a dye is provided on a substrate having a light-transmitting and spirally formed pregroove, and a reflective layer made of a metal film is further provided thereon, and further provided thereon. In the production of an optical information recording medium comprising a protective layer comprising a resin layer, in forming the light absorbing layer, a coating solution comprising a perchlorate or a periodate of a phthalocyanine dye is applied by spin coating. A method for manufacturing an optical information recording medium. 3. A light-absorbing layer made of a dye is provided on a substrate having a light-transmitting and spirally formed pregroove, and a reflective layer made of a metal film is further provided thereon, and further provided thereon. In the production of the optical information recording medium comprising the provision of a protective layer composed of a resin layer, the formation of the light absorbing layer includes the steps of: (a) a phthalocyanine dye or a perchlorate or a periodate of the phthalocyanine dye; B)
_{^{Wherein: R + · XO 4 - (}} R + is an organic cation, X is Cl or I) and characterized by applying the coating solution consisting of a mixture of organic halide peroxide salt, represented by the spin coating method Manufacturing method of an optical information recording medium. 4. has translucency, on the substrate on which pre-grooves are formed in a spiral shape, a light absorbing layer made of the dye formed, more complex refractive index real part n _E thereon, n _E ≦ 1.
6, a reflective auxiliary layer made of a low refractive index resin is provided, a reflective layer made of a metal film is further provided thereon, and a protective layer made of a resin layer is further provided thereon. In forming the light absorption layer and the reflection auxiliary layer, a light absorption layer formation coating liquid composed of a perchlorate or a periodate of a phthalocyanine dye, and a reflection auxiliary layer formation coating liquid composed of a low refractive index resin, Respectively,
A method for producing an optical information recording medium, wherein the method is applied by a spin coating method.