JP2001353966A - Optical information recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical information recording medium, during a long term storage of which a photo-deterioration can be prevented from developing and, in addition, neither recording function nor reproducing function are impaired. SOLUTION: In the optical information recording medium, by which the recording of information is executed by partially changing the optical characteristics of a recording layer through the irradiation of laser beam over the recording layer, which is formed on a substrate and includes organic coloring matters, the recording layer includes, as a stabilizer for stabilizing the organic coloring matter, a metal phthalocyanine, which has a degradation starting temperature higher than that of the organic coloring matter and a maximum absorption peak absorption curve in an absorption spectrum, which intersects with the maximum peak absorption curve of the organic coloring matter at a longer wavelength side.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a CD-R, a DV
The present invention relates to a write-once optical information recording medium on which information can be recorded and reproduced by a laser beam such as a DR, and more particularly to an optical information recording medium having improved light fastness after recording information.

[0002]

2. Description of the Related Art In general, a CD-R (compact disk-recordable) is used as an optical information recording medium for recording and reproducing data such as characters, figures and the like, images, videos and sounds.
This CD-R has a wavelength of 770-830.
It is composed of an optical disk capable of recording and reproducing information in response to a laser beam of nm.

[0003] Recently, a DVD-ROM capable of high-density recording and reproduction by using a red laser beam having a shorter wavelength than the laser beam used for the CD-R, for example, 620 to 690 nm.
R (digital video disk-recordable or digital versatile disk-recordable) and the like have been used as media for the next generation.

In these write-once optical information recording media such as CD-R and DVD-R, the recording layer containing an organic dye such as a cyanine dye is irradiated with laser light to partially change the optical characteristics of the recording layer. To record information by forming pits.

[0005] The cyanine-based dyes are excellent in that a method of high productivity such as spin coating can be applied, and that they have low thermal conductivity, so that they can be locally heated. Attention has been paid to its high absorption and reflection properties.

However, cyanine dyes are not sufficiently light-resistant to sunlight, and have a problem of light deterioration during long-term storage.

Therefore, conventionally, as a countermeasure, a stabilizing radical is added to a main component of a cyanine dye having an absorption characteristic in a semiconductor laser oscillation wavelength region, or a bond between a cyanine dye cation and a quencher anion. Addition of the body is performed.

That is, the addition of a stabilizing radical to the main component of the cyanine dye or the addition of a conjugate of the cyanine dye cation and the quencher anion produces singlet oxygen generated by sunlight which causes the cyanine dye to fade. The light resistance of the recording layer containing a cyanine dye of CD-R or DVD-R is improved by changing the oxidizing action to triplet oxygen having a milder oxidizing action.

Conventionally, for example, Japanese Patent Application Laid-Open No. 7-1965
JP-A-88-110, and the addition of an aminium salt to an organic dye, or the addition of a nickel dithiol metal complex to an organic dye as disclosed in JP-A-57-11090, the photodegradation of the dye. There is also known a method of preventing the occurrence of light and improving the light resistance of the optical disk. A compound added to an organic dye for improving the light resistance of an optical disk is generally called a light stabilizer.

[0010]

The improvement of the light resistance of optical disks such as CD-Rs and DVD-Rs can be roughly classified into the following two types.

1) Improve the light fastness of an optical disc on which no information is recorded. In this case, even if the optical disc has information recorded thereon, the improvement of the light resistance of a portion not involved in recording (unrecorded portion) is included.

2) Improve the light resistance of the optical disk after recording information. In this case, light deterioration of the shape of the formed pit is mainly included.

Here, since most of the purpose of using the CD-R or DVD-R lies in the long-term storage of the written information, the light resistance of the optical disk after the information is recorded rather than before the information is recorded is improved. The significance of that is greater.

However, in the conventional method using a light stabilizer, although the effect of improving the light fastness of an unrecorded portion of an optical disc is recognized, the effect of improving the light fastness after information recording is hardly obtained. can not see.

That is, generally, in an optical information medium based on heat mode recording, a very high temperature is applied to the periphery during recording, that is, when pits are formed.

However, since the conventional light stabilizer has a decomposition initiation temperature lower than that of the organic dye in the recording layer, the light stabilizer is decomposed and lost at the periphery of the pit.
The closer to the pit, the more easily the light deteriorates.

That is, the pits are enlarged by light irradiation with sunlight or the like after information recording, which causes deterioration in light resistance of the optical disk after recording.

The deterioration of the optical disk after recording the information is as follows.
It appears more remarkably in DVD-R than in CD-R.

That is, when the pits are optically deteriorated in the CD-R and the DVD-R and the pits are enlarged by the same size, the pits of the DVD-R having smaller pits are larger than those of the CD-R. This is because the DVD-R has a larger pit enlargement ratio.

Accordingly, a first object of the present invention is to provide an optical information recording medium which can prevent light deterioration during storage for a long period of time and which does not impair the recording and reproducing functions.

A second object of the present invention is to provide an optical information recording medium which reduces the absorbed energy of sunlight in the dye after recording information in the heat mode to prevent its deterioration.

A third object of the present invention is to provide a DVD-
An object of the present invention is to provide an optical information recording medium to which the conventional method for manufacturing R can be applied almost without any major change.

[0023]

According to the optical information recording medium of the present invention, the recording layer containing an organic dye formed on a substrate is irradiated with a laser beam to partially change the optical characteristics of the recording layer. In an optical information recording medium for performing information recording, the decomposition start temperature is higher than that of the organic dye as a stabilizer for stabilizing the organic dye in the recording layer, and a maximum absorption peak absorption curve in an absorption spectrum. Contains a metal phthalocyanine crossing the maximum peak absorption curve of the organic dye on the long wavelength side.

Here, the metal phthalocyanine is an organic dye containing a metal or a metal ion whose maximum absorption wavelength is appropriately controlled, and the metal includes a transition metal or a typical metal.

The above metal phthalocyanine is represented by the following general formula (Chemical Formula 1).

[0026]

Embedded image However, in (Chemical Formula 1), M represents a metal or a metal ion, for example, Mg, Ca, Ti, Cr, Mn, F
e, Co, V (VO), Ni, Cu, Zn, AlCl, S
wherein at least one member of the group consisting of iCl2, Si (OH) 2 and the like is included, R represents a substituent, for example, a substituted or unsubstituted alkyl group, alkylalkoxyl group, alkylamino group, alkylsulfonamide group, nitro group, Group, a halogen atom, a hydrogen atom, represents a substituent selected from the group of a halogenated alkyl group, etc., at the site where the substituent can be introduced, even if all are the same type of substituent,
It doesn't have to be.

Here, the mixing ratio of the organic dye to the metal phthalocyanine is preferably from 0.01 to 50 parts by weight, more preferably from 0.1 to 20 parts by weight, based on 100 parts by weight of the former.

If the content of the metal phthalocyanine is less than 0.01 part by weight, the effect of suppressing the fading deterioration of the organic dye due to sunlight may not be clearly exhibited,
When the amount is more than the weight part, the concentration of the organic dye is diluted, so that the reproducing power becomes high or the reflectance becomes too high, which is not preferable in some cases.

The substrate can be made of glass or translucent plastics such as epoxy resin, methacrylic resin, polycarbonate resin, polyester resin, polyvinyl chloride resin and polyolefin resin.
In addition, a track groove or a pit may be formed in advance on this substrate, or a substrate having a configuration necessary for generating an address signal may be used.

The recording layer is capable of forming pits by laser irradiation, includes a single layer or a plurality of dye layers, and has a refractive index and a refractive index for adjusting optical properties of an optical information recording medium. For example, those provided with an enhanced layer made of a resin material with adjusted film thickness, further include a substrate and a dye layer, and a case where a plurality of dye layers are provided with an intermediate layer therebetween or on the dye layer, These are generic names.

Further, the organic dye is characterized in that the absorbance at the recording wavelength of the laser beam is larger than that of the metal phthalocyanine.

Further, the recording wavelength of the laser light is characterized in that the maximum absorption peak absorption curve in the absorption spectrum is on a shorter wavelength side than the wavelength crossing the maximum peak absorption curve of the organic dye.

The organic dye is a cyanine dye,
It contains an azo metal compound dye or the like, and the recording laser light has a wavelength of 65
When it is near 0 nm, it includes trimethine dyes such as indodicarbocyanine and benzoindodicarbocyanine having three carbon atoms constituting the methine chain, and also includes those organic dyes singly or as a mixture.

The cyanine dye is a compound represented by the general formula (Formula 2).

[0035]

Embedded image [Where A represents any of the following general formulas (Chemical Formula 3) to (Chemical Formula 6);

Embedded image

Embedded image

Embedded image

Embedded image A ′ represents any of the following general formulas (Formula 7) to (Formula 10),

Embedded image

Embedded image

Embedded image

Embedded image A and A 'may be the same or different (provided that D1 and D2 are each a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group, a halogen atom, a carboxyl group,
Alkoxycarbonyl group, alkylcarboxyl group, alkylhydroxyl group, aralkyl group, alkenyl group,
Alkylamide group, alkylamino group, alkylsulfonamide group, alkylcarbamoyl group, alkylsulfamoyl group, alkylsulfonyl group, phenyl group, cyano group, ester group, sulfone group, acyl group, allyl group,
Aryl group, aryloxy group, alkylthio group, arylthio group, phenylazo group, pyridinoazo group, alkylcarbonylamino group, sulfonamide group, amino group,
Represents a substituent selected from the group consisting of an alkylsulfone group, a thiocyano group, a mercapto group, a chlorosulfone group, an alkylazomethine group, an alkylaminosulfone group, a vinyl group and a nitro group; P and q are the number of substituents, each of which represents one or more integers. ), R and R ′ are a substituted or unsubstituted alkyl group, carboxyl group, alkoxycarbonyl group, alkylcarboxyl group, alkoxyl group, alkylhydroxyl group, aralkyl group, alkenyl group, alkylamide group, alkylamino group, alkylsulfone Amide group, alkylcarbamoyl group, alkylsulfamoyl group, hydroxyl group, halogen atom, alkylalkoxyl group, alkyl halide group, alkylsulfonyl group,
Represents a substituent selected from the group consisting of an alkylcarboxyl group or an alkylsulfonyl group bonded to a metal ion or an alkyl group, a phenyl group, a benzyl group and an alkylphenyl group, and may be the same or different, and X-
Halogen atom, PF6-, SbF6-, H3PO4, perchloric acid, borofluoric acid, benzenesulfonic acid, toluenesulfonic acid, alkylsulfonic acid, benzenecarboxylic acid, alkylcarboxylic acid, trifluoromethylcarboxylic acid, periodic acid And an anion selected from the group of SCN- anions, and B represents 0, 1, 2 or 3. In order to manufacture the optical information recording medium of the present invention, a dye solution in which the organic dye is dissolved together with the metal phthalocyanine is prepared, and the dye solution is applied on the substrate.

When the organic dye is a cyanine dye, the dye solution may be a fluorinated solvent such as chloroform, dichloroethane, fluorinated alcohol, methyl ethyl ketone, dimethylformamide, methanol, toluene, cyclohexanone, acetylacetone, diacetone alcohol. , Cellosolves such as methyl cellosolve, dioxane and the like.

In this case, the concentration of the cyanine dye and the metal phthalocyanine derivative contained in the dye solution is preferably 5 g / l to 30 g / l.

In order to apply the dye solution to the substrate, a spin coating method can be used. In this case, the thickness of the coating layer after drying may be the same as the thickness conventionally used.

Further, other compounds such as an antioxidant, an ultraviolet absorber, a peroxide decomposer, and a superoxide quencher may be used in combination with the metal phthalocyanine.

In the optical information recording medium of the present invention, a reflective layer may be provided in addition to the above-mentioned recording layer, and a protective layer is provided on the reflective layer, and a protective layer is provided on the laser beam incident side of the substrate. Also includes those having a layer.

The reflective layer may be formed of a metal film such as Au, Al, Ag, Cu, Pt, each of these and other alloys formed by vapor deposition or sputtering, or an alloy to which a trace component other than these is added. A high-reflectance material film such as a UV-curable resin solution can be used as a protective layer to protect the optical information recording medium and improve light resistance. A coating layer applied and cured by the method described above can be used.

An optical disk having at least the above recording layer may be bonded to an optical disk having another similar configuration or another configuration, or may be bonded with the substrate itself facing.

Materials and methods for this bonding include an ultraviolet curable resin, a cationic curable resin, a double-sided pressure-sensitive adhesive sheet, a hot melt method, a spin coating method, a dispensing method (extrusion method), a screen printing method, and a roll coating method. A method can be used.

As the above-mentioned cyanine dyes, those having 3 methine carbon atoms can be used. In this case, recording and reproduction can be performed by a laser in a wavelength range of 620 to 690 nm, and the invention can be applied to DVD-R.

The mechanism of photobleaching of cyanine dyes are not yet clear, but the dye ^{(1 D)} is the singlet excited absorbs light ^{(1 D *).} Then, this becomes an excited triplet ( ³ D ^* ) due to intersystem crossing, energy is transferred to oxygen ( ³ O ₂ ), and oxygen becomes a singlet ( ¹ O ₂ ). This singlet oxygen is active and degrades the ground state dye.

[0046] However, optical oxygenation degradation of cyanine dyes are not considered to be due only to the singlet oxygen, oxygen anion radicals _- believed to be due to (O 2 ^·).

That is, ¹ O ₂ receives electrons from the dye to form O ₂ ^−. O ₂ ⁻ . Attacks and decomposes the dye. If there is moisture, it is possible that the hydroxyl radical (HO.) Attacks. In general, these ¹ O ₂ , O ₂ ⁻ , HO and the like are collectively called active oxygen.

The dye in the excited singlet state is itself in an activated state with high energy and is unstable.
Therefore, it is considered that the excited singlet dye is attacked and decomposed by not only active oxygen but also oxygen in a triplet state.

From the above, it is considered that a compound having a function of stabilizing an excited singlet dye or active oxygen has an effect of preventing photodeterioration of the dye.

In addition to having a metal atom at the center, metal phthalocyanine has a characteristic structure in which a π-electron cloud is spread over the entire molecule, and an excited singlet dye or singlet oxygen (Literature: Boris D. et al. Rinters, JA
m. Chem. Soc. , 1990 , p8064), which facilitates exchange of energy and electrons, stabilizes the excited singlet dye and active oxygen, and has the effect of preventing photodegradation of the dye.

Conventionally used light stabilizers, for example,
The aminium salt represented by the following general formula (Chemical Formula 11) is considered to have the same effect as metal phthalocyanine. However, in the case of metal phthalocyanine, the structure of the metal phthalocyanine is strong against light. The effect of prevention can be exhibited.

[0052]

Embedded image Here, since the metal phthalocyanine is selected to have a decomposition initiation temperature higher than that of the organic dye, the metal phthalocyanine remains without being decomposed around the pit after information recording, thereby recording information. It is possible to minimize the light deterioration of the later pits and to improve the so-called light resistance after information recording.

[0053]

As described above, according to the present invention, the recording layer containing the organic dye formed on the substrate is irradiated with laser light to partially change the optical characteristics of the recording layer to record information. In the optical information recording medium, the decomposition start temperature is higher than the organic dye as a stabilizer for stabilizing the organic dye in the recording layer, and the maximum absorption peak absorption curve in the absorption spectrum is the organic dye. Metal phthalocyanine that intersects the longest wavelength with the maximum peak absorption curve of the compound, the excited dye and active oxygen are stabilized by this metal phthalocyanine, and the degradation of the target dye due to photooxygenation can be prevented. Therefore, the following effects are obtained.

1) The optical information recording medium can be prevented from light deterioration during storage for a long period of time, and the recording and reproducing functions are not impaired.

2) After the information is recorded in the heat mode, the absorbed energy of sunlight in the target dye can be reduced to prevent its deterioration.

3) The conventional method of manufacturing a DVD-R can be almost applied without major changes.

[0057]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the optical recording medium according to the present invention will be described below in detail with reference to the accompanying drawings.

In the optical recording medium of the following embodiment, a polycarbonate substrate is used as a substrate, and a cyanine dye belonging to an indolenine cyanine dye is used as an organic dye of a recording layer.

The metal phthalocyanine contained in the recording layer has a structure represented by the above general formula (Formula 1).

Further, these cyanine dyes may be used alone or in combination, and the metal phthalocyanine may be used alone or in combination of the specific compounds belonging to the above general formula (Chemical Formula 1). A plurality of each specific compound is used across the general formula.

The recording layer is formed on a polycarbonate substrate by spin coating using a solution of the cyanine dye and the metal phthalocyanine derivative.

Then, a reflective layer of Au or Ag is provided on the recording layer by sputtering, and a polycarbonate substrate having the same structure is bonded on the reflective layer with an adhesive layer made of an ultraviolet curable resin by spin coating.
A laminated DVD-R optical disk is obtained.

Next, a synthesis example of the metal phthalocyanine used in this embodiment will be described.

[Synthesis Example 1] Diethylation of 3-aminophthalonitrile was described in the literature (author; Eusebio Juaristi, J. Daniel).
Reyna, Magazine Name: Tetrahedron Letter, Volume 25, 33
No. 3521-524) to obtain white crystals.

Melting point: 118 ° C., elemental analysis: C ₁₂ H ₁₃ N ₃ ; (calculated value) C: 72.34%, H: 6.58%, N: 21.0
9%, (actual value) C: 72.39%, H: 6.60%,
N: 21.00% 3.99 g of 3-diethylaminophthalonitrile represented by the following formula (Chem. 12) synthesized by the above synthesis method (2 /
100 mol), 0.99 g of manganese chloride tetrahydrate (0.
5/100 mol), 1,8-diazabicyclo [5,4,
0] -7-undecene (hereinafter referred to as DBU) 4.57 g
(3/100 mol), 1-pentanol (bp 13
(7.5 ° C.) 20 g was stirred at 130 ° C. for 6 hours, and after cooling, the solvent was distilled off by steam distillation. The precipitated dye was separated by suction, filtered and dried at 60 ° C. overnight.

Crude yield 1.75 g. The crude crystals were washed with methanol to obtain purple crystals. Yield 1.70 g. The absorption spectrum was as shown in FIG. 1, and the maximum absorption peak was λmax = 870 nm.

[0079] Weigh out 3.000 mg of the purple crystals and measure them with a thermogravimetric analyzer (Rigaku Thermal Analyzer T).
G-8110) at a heating rate of 20 ° C./min., The decomposition start temperature was 298.8 ° C.

[0068]

Embedded image [Synthesis Example 2] Except for 0.99 g of manganese chloride tetrahydrate,
The same operation as in Synthesis Example 1 was carried out except that 0.79 g (0.5 / 100 mol) of vanadium chloride was used, to obtain dark purple crystals.
Yield 1.50 g. FIG. 2 shows the absorption spectrum, and the maximum absorption peak was λmax = 834 nm. The decomposition onset temperature was 342.7 ° C.

[Synthesis Example 3] Manganese chloride tetrahydrate 0.9
Except for 9 g, 1.19 g of nickel chloride hexahydrate (0.5 g
/ 100 mol), except that dark green crystals were obtained. Yield 1.14 g. The absorption spectrum is shown in FIG. 3, where the maximum absorption peak is λ
max = 778 nm. Decomposition start temperature is 314.2
° C.

[Synthesis Example 4] Manganese chloride tetrahydrate 0.9
Except for 9 g, 1.19 g of cobalt chloride hexahydrate (0.5
/ 100 mol), except that dark green crystals were obtained. Yield 0.99 g. The absorption spectrum is shown in FIG. 4, where the maximum absorption peak is λ
max = 776 nm. Decomposition start temperature is 356.0
° C.

[Synthesis Example 5] 4-Diethylaminophthalonitrile represented by the following formula (Formula 13) was synthesized in the same manner as in Synthesis Example 1. Melting point 118 [deg.] C. 3.99 g (2/1) of 4-diethylaminophthalonitrile synthesized by the above synthesis method
00 mol), 0.99 g of manganese chloride tetrahydrate (0.5
/ 100 mol), DBU 4.57 g (3/100 mol),
20 g of 1-pentanol was stirred at 130 ° C. for 6 hours, and after cooling, the solvent was distilled off by steam distillation. Wash well with water, then with methanol,
Drying at 60 ° C. overnight yielded dark purple crystals. Yield 1.45
g. The decomposition onset temperature was 323.3 ° C. FIG. 5 shows the absorption spectrum.

[0072]

Embedded image Synthesis Example 6 Synthesis Example 1 except for using 4.54 g (2/100 mol) of 3-di-n-propylaminophthalonitrile represented by the following formula (Chemical Formula 14) except for 3-diethylaminophthalonitrile. In the same manner as described above, dark green crystals were obtained. Yield 1.23g. The decomposition onset temperature was 300.9 ° C. FIG. 6 shows the absorption spectrum.

[0073]

Embedded image [Synthesis Example 7] Synthesis Example 1 except for using 5.10 g (2/100 mol) of 3-di-n-butylaminophthalonitrile represented by the following formula (Chemical Formula 15) except for 3-diethylaminophthalonitrile. And green crystals were obtained. Yield 2.33 g. The decomposition onset temperature was 299.1 ° C.
FIG. 7 shows the absorption spectrum.

[0074]

Embedded image [Synthesis Example 8] The same procedure as in Synthesis Example 1 was carried out except that 4.54 g (2/100 mol) of 3-diisopropylaminophthalonitrile represented by the following formula (Formula 16) was used, except for 3-diethylaminophthalonitrile. Thus, dark purple crystals were obtained.
Yield 1.55 g. The decomposition onset temperature was 321.7 ° C. FIG. 8 shows the absorption spectrum.

[0075]

Embedded image [Synthesis Example 9] Except for using 3-diethylaminophthalonitrile, the same as Synthesis Example 1 except that 4.28 g (2/100 mol) of 3--3-pentoxyphthalonitrile represented by the following formula (Formula 17) was used. To obtain dark green crystals. Yield 2.14 g. The decomposition onset temperature was 344.2 ° C. FIG. 9 shows the absorption spectrum.

[0076]

Embedded image [Synthesis Example 10] Except for 3-diethylaminophthalonitrile, 4.85 g of 3-2,4-dimethyl-3-pentoxyphthalonitrile represented by the following formula (Formula 18) (2/10
0 mol) in the same manner as in Synthesis Example 1 to obtain dark green crystals. Yield 1.57 g. Decomposition start temperature is 307.
5 ° C. FIG. 10 shows the absorption spectrum.

[0077]

Embedded image [Synthesis Example 11] Except for 3-diethylaminophthalonitrile, 2,3-dicyano- represented by the following formula (Formula 19)
4.51 g of N, N-diethylbenzenesulfonamide
(2/100 mol) was carried out in the same manner as in Synthesis Example 1 to obtain dark green crystals. Yield 0.77g. The decomposition onset temperature was 311.1 ° C. FIG. 11 shows the absorption spectrum.

[0078]

Embedded image [Synthesis Example 12] Except for using 3-diethylaminophthalonitrile, the same procedure as in Synthesis Example 1 was carried out except that 3.46 g (2/100 mol) of 3-nitrophthalonitrile represented by the following formula (Formula 20) was used. Dark green crystals were obtained. Yield 0.98
g. The decomposition onset temperature was 330.6 ° C. FIG. 12 shows the absorption spectrum.

[0079]

Embedded image Next, examples of the optical recording medium of the present invention using the metal phthalocyanines synthesized in Synthesis Examples 1 to 12 will be described.

Example 1 Trimethine cyanine dye represented by the following formula (Formula 21) (NK-4270; manufactured by Japan Photographic Dye Laboratories, lmax = 546 nm, decomposition start temperature 29)
(3.6 ° C.) 90 parts by weight and 10 parts by weight of the 3-diethylamino derivative of manganese phthalocyanine synthesized in Synthesis Example 1 were dissolved in 15 g / l of tetrafluoropropanol, and the solution was applied to a thickness of 0.6 by a spin coating method.
It was applied to a polycarbonate disk having a thickness of 120 mm and an outer diameter (diameter) of 120 mm to form a recording layer comprising a photosensitive dye film having a thickness of 40 nm.

On this recording layer, 11 mm
A film thickness of 8 is formed on the entire surface of the 7 mmφ region by sputtering.
An Au film having a thickness of 0 nm was formed to form a reflective layer.

Further, an ultraviolet curable resin S
D-211 (manufactured by Dainippon Ink and Chemicals, Inc.) was spin-coated, and the coating film was cured by irradiating ultraviolet rays to a thickness of 5 μm.
m of the protective film was formed.

Further, an ultraviolet curable resin SD is formed on the protective film of the substrate and the recording layer on which the protective film is not formed.
After dropping -318 (manufactured by Dainippon Ink and Chemicals, Inc.), another substrate similar to the above is placed thereon, and the resin is diffused in the gap by a spin coating method. The substrate was laminated by forming an adhesive layer of resin having a thickness of 25 μm in a region of 32 mmφ to 120 mmφ of the substrate from the beginning, thereby forming a bonded optical disk.

The optical disk manufactured as described above includes
Recording was performed at a linear velocity of 3.5 m / sec with a DDU-1000 (recording machine of Pulstec) having a laser wavelength of 635 nm, and a time interval analyzer / T manufactured by Yokogawa Electric Corporation was used.
The jitter ratio (%) was measured by A-320.

[0086] DVD Specification f
or Read-Only DISC standard,
Data to Clock Jitter is a channel bit rate = 26.6 Mbps.
(38.23 nsec) is used as a reference clock to standardize the deviation value σ of the binarized data edge signal.

With respect to the evaluation criteria for jitter, the minimum pit length is set to 0.4 μm, and EFM signal modulation is performed at a linear velocity of 3.5 m / sec. Further, in order to prevent the signal from being erroneously demodulated (decoded) when standardized by a clock, the limit is 8%, and it is preferable that the limit is 8% or less, that is, 8% at most.

In order to check the light fastness of the recorded portion (recording portion light fastness), the optical disc on which the above recording was performed was subjected to a weather o-meter (irradiation light amount: 50,000 lux / hour) manufactured by Atlas Electric Co. for 20 hours. , Or for 40 hours, and the jitter ratio of the written portion was measured in the same manner.

Further, in order to check the light fastness (light fastness of the unrecorded portion) of the unrecorded portion, a new recording was performed on the optical disc exposed as described above, and the jitter ratio of the portion was similarly measured. .

The results of the above measurements are shown in the table of FIG.
These embodiments are examples of an optical disk for DVD-R. Both the post-exposure jitter (archival jitter) of the portion recorded before exposure and the jitter (shelf jitter) of the portion recorded after exposure are not high. It can be seen that both the light resistance of the unrecorded portion and that of the unrecorded portion are good.

[0090]

Embedded image [Example 2] A bonded optical disk was prepared in the same manner as in Example 1 except that a 3-diethylamino derivative of vanadyl phthalocyanine was used instead of the 3-diethylamino derivative of manganese phthalocyanine. This is shown in the table of FIG.

Example 3 A bonded optical disk was produced in the same manner as in Example 1 except that the 3-diethylamino derivative of nickel phthalocyanine was used instead of the 3-diethylamino derivative of manganese phthalocyanine, and the jitter was measured. The results obtained are shown in the table of FIG.

Example 4 A bonded optical disk was prepared in the same manner as in Example 1 except that the 3-diethylamino derivative of cobalt phthalocyanine was used instead of the 3-diethylamino derivative of manganese phthalocyanine, and the jitter was measured. The results obtained are shown in the table of FIG.

Example 5 A bonded optical disk was prepared in the same manner as in Example 1 except that the 4-diethylamino derivative of manganese phthalocyanine was used instead of the 3-diethylamino derivative of manganese phthalocyanine, and the jitter was measured. The results obtained are shown in the table of FIG.

Example 6 A laminated optical disk was produced in the same manner as in Example 1, except that the 3-di-n-propylamino derivative of manganese phthalocyanine was used instead of the 3-diethylamino derivative of manganese phthalocyanine. The result of measuring the jitter is shown in the table of FIG.

Example 7 A laminated optical disk was produced in the same manner as in Example 1, except that the 3-di-n-butylamino derivative of manganese phthalocyanine was used instead of the 3-diethylamino derivative of manganese phthalocyanine. The result of measuring the jitter is shown in the table of FIG.

Example 8 A laminated optical disk was prepared in the same manner as in Example 1 except that the 3-diethylamino derivative of manganese phthalocyanine was used instead of the 3-diethylamino derivative of manganese phthalocyanine. The measurement results are shown in the table of FIG.

Example 9 A laminated optical disk was prepared in the same manner as in Example 1 except that the 3-diethylamino derivative of manganese phthalocyanine was replaced by a 3-3-pentoxy derivative of manganese phthalocyanine. Are shown in the table of FIG.

Example 10 In Example 1, 3-2,4-dimethyl-3 of manganese phthalocyanine was used instead of the 3-diethylamino derivative of manganese phthalocyanine.
A bonding optical disk was prepared in the same manner except that a pentoxy derivative was used, and the results of measuring jitter are shown in the table of FIG.

Example 11 A laminated optical disk was prepared in the same manner as in Example 1, except that a 3-N, N-diethylsulfonamide derivative of manganese phthalocyanine was used instead of the 3-diethylamino derivative of manganese phthalocyanine. The result of measuring the jitter is shown in the table of FIG.

Example 12 A bonded optical disk was prepared in the same manner as in Example 1 except that a 3-nitro derivative of manganese phthalocyanine was used instead of the 3-diethylamino derivative of manganese phthalocyanine, and jitter was measured. The results obtained are shown in the table of FIG.

Example 13 In Example 1, instead of 10 parts by weight of the 3-diethylamino derivative of manganese phthalocyanine, 5 parts by weight of the 3-diethylamino derivative of manganese phthalocyanine was replaced by NI represented by the following formula (formula 22).
R-403 (manufactured by Nippon Carlit Co., Ltd., decomposition start temperature 26)
(5.4 ° C.) A laminated optical disk was prepared in the same manner except that 5 parts by weight were used, and the results of measuring jitter are shown in the table of FIG.

[0102]

Embedded image Next, a comparative example will be described.

Comparative Example 1 A laminated optical disk was prepared in the same manner as in Example 1 except that no metal phthalocyanine was used, and the results of measuring the jitter are shown in the table of FIG.

This comparative example is an example of an optical disk for DVD-R, but since metal phthalocyanine was not used, both archival jitter and shelf jitter were high, and both the light resistance of the recorded portion and the unrecorded portion were poor. You can see that.

Comparative Example 2 A laminated optical disk was obtained in the same manner as in Example 1, except that NIR-403 (manufactured by Nippon Carlit Co.) represented by the above formula (Formula 22) was used instead of the metal phthalocyanine derivative. And the results of measuring jitter are shown in the table of FIG.

This is an example using a conventional light stabilizer without using metal phthalocyanine. The shelf jitter is improved as compared with Comparative Example 1, and the light resistance of the unrecorded portion is improved. However, archival jitter is high,
It can be seen that the light resistance of the recording portion has hardly been improved.

This is considered to be because the decomposition temperature of this conventional light stabilizer was lower than that of the target dye, NK-4270.

Comparative Example 3 In Example 1, FO represented by the following formula (Formula 23) was used instead of metal phthalocyanine.
M-1405 (manufactured by Wako Pure Chemical, decomposition start temperature 206.5)
(° C.) was used to produce a bonded optical disk in the same manner, and the jitter was measured. The results are shown in the table of FIG.

This is an example in which a metal phthalocyanine is not used and a conventional light stabilizer is used. The shelf jitter is improved as compared with Comparative Example 1, and the light resistance of the unrecorded portion is improved. However, archival jitter is high,
It can be seen that the light resistance of the recording portion has hardly been improved.

This is presumably because the decomposition temperature of this conventional light stabilizer was lower than that of the target dye, NK-4270.

[0111]

Embedded image From these results and other factors described above, the metal phthalocyanine represented by the general formula (Formula 1) has a function of effectively preventing the cyanine dye from being discolored by light irradiation. In particular, it is excellent in the function of improving light resistance after recording.

[Brief description of the drawings]

FIG. 1 is an absorption spectrum diagram of a manganese phthalocyanine derivative synthesized in Synthesis Example 1 used for an optical information recording medium according to the present invention.

FIG. 2 is an absorption spectrum diagram of a vanadyl phthalocyanine derivative synthesized in Synthesis Example 2 used for an optical information recording medium according to the present invention.

FIG. 3 is an absorption spectrum diagram of a nickel phthalocyanine derivative synthesized in Synthesis Example 3 used for an optical information recording medium according to the present invention.

FIG. 4 is an absorption spectrum diagram of a cobalt phthalocyanine derivative synthesized in Synthesis Example 4 used for an optical information recording medium according to the present invention.

FIG. 5 is an absorption spectrum diagram of a manganese phthalocyanine derivative synthesized in Synthesis Example 5 used for an optical information recording medium according to the present invention.

FIG. 6 is an absorption spectrum diagram of a manganese phthalocyanine derivative synthesized in Synthesis Example 6 used for an optical information recording medium according to the present invention.

FIG. 7 is an absorption spectrum diagram of a manganese phthalocyanine derivative synthesized in Synthesis Example 7 used in an optical information recording medium according to the present invention.

FIG. 8 is an absorption spectrum diagram of a manganese phthalocyanine derivative synthesized in Synthesis Example 8 used for an optical information recording medium according to the present invention.

FIG. 9 is an absorption spectrum diagram of a manganese phthalocyanine derivative synthesized in Synthesis Example 9 used in the optical information recording medium according to the present invention.

FIG. 10 is an absorption spectrum diagram of a manganese phthalocyanine derivative synthesized in Synthesis Example 10 used for an optical information recording medium according to the present invention.

FIG. 11 is an absorption spectrum diagram of a manganese phthalocyanine derivative synthesized in Synthesis Example 11 used for an optical information recording medium according to the present invention.

FIG. 12 is an absorption spectrum diagram of a manganese phthalocyanine derivative synthesized in Synthesis Example 12 used for an optical information recording medium according to the present invention.

FIG. 13 is a table showing characteristics of an optical information recording medium according to an embodiment of the present invention and a comparative example.

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[Procedure amendment]

[Submission date] March 30, 2001 (2001.3.3)
0)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0065

[Correction method] Change

[Correction contents]

Melting point: 104 ° C., Elemental analysis: C12H13N3; (calculated value) C: 72.34%, H: 6.58%, N: 21.0
9%, (actual value) C: 72.39%, H: 6.60%,
N: 21.00% 3.99 g of 3-diethylaminophthalonitrile represented by the following formula (Chem. 12) synthesized by the above synthesis method (2 /
100 mol), 0.99 g of manganese chloride tetrahydrate (0.
5/100 mol), 1,8-diazabicyclo [5,4,
0] -7-undecene (hereinafter referred to as DBU) 4.57 g
(3/100 mol), 1-pentanol (bp 13
(7.5 ° C.) 20 g was stirred at 130 ° C. for 6 hours, and after cooling, the solvent was distilled off by steam distillation. The precipitated dye was separated by suction, filtered and dried at 60 ° C. overnight.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0071

[Correction method] Change

[Correction contents]

[Synthesis Example 5] 4-Diethylaminophthalonitrile represented by the following formula (Formula 13) was synthesized in the same manner as in Synthesis Example 1. 103 ° C. 3.99 g (2/1) of 4-diethylaminophthalonitrile synthesized by the above synthesis method
00 mol), 0.99 g of manganese chloride tetrahydrate (0.5
/ 100 mol), DBU 4.57 g (3/100 mol),
20 g of 1-pentanol was stirred at 130 ° C. for 6 hours, and after cooling, the solvent was distilled off by steam distillation. Wash well with water, then with methanol,
Drying at 60 ° C. overnight yielded dark purple crystals. Yield 1.45
g. The decomposition onset temperature was 323.3 ° C. FIG. 5 shows the absorption spectrum.

Continued on the front page (72) Inventor Mamoru Uchida 6-16-20 Ueno, Taito-ku, Tokyo Taiyo Denki Co., Ltd. (72) Isao Okitsu 6-16-20 Ueno, Taito-ku, Tokyo Taiyo Denki Stock Inside the company (72) Inventor Satoshi Nagaya 6-16-20 Ueno, Taito-ku, Tokyo Taiyo Denki Co., Ltd. (72) Inventor Yoshikazu Takagishi 6-16-20 Ueno, Taito-ku, Tokyo Taiyo Denki Co., Ltd. F term (reference) 2H111 EA03 EA12 EA40 EA48 FB43 FB45 GA07 5D029 JA04 JC03

Claims (5)

[Claims] An optical information recording medium for recording information by irradiating a laser beam to a recording layer containing an organic dye formed on a substrate to partially change the optical characteristics of the recording layer, The recording layer has a decomposition start temperature higher than that of the organic dye as a stabilizer for stabilizing the organic dye, and the maximum absorption peak absorption curve in the absorption spectrum is longer than the maximum peak absorption curve of the organic dye. An optical information recording medium characterized by containing a metal phthalocyanine that intersects with the above. 2. The optical information recording medium according to claim 1, wherein the organic dye has a higher absorbance at a recording wavelength of the laser light than the metal phthalocyanine. 3. The recording wavelength of the laser light, wherein a maximum absorption peak absorption curve in the absorption spectrum is on a shorter wavelength side than a wavelength crossing the maximum absorption curve of the organic dye. The optical information recording medium according to the above. 4. The optical information recording medium according to claim 1, wherein the organic dye is a cyanine dye. 5. The optical information recording medium according to claim 4, wherein the cyanine dye has three methine carbon atoms.