JP2002342993A - Method of manufacturing optical information recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing an optical information recording medium which is large in modulation degree and has stable recording and reproducing characteristics. SOLUTION: The method of manufacturing the optical information recording medium, which has a recording layer containing a solvent soluble organic compound having an absorption maximum at a wavelength of 300 to 450 nm and having >=0.07 of absorbance of a dye solid film at a recording laser wavelength on a substrate surface, a light reflecting layer and a substrate in this order and performs recording and reproducing with light of 380 to 500 nm in wavelength at a track pitch of 300 to 600 nm and a groove depth of 40 to 150 nm, has a recording layer forming process step of forming the recording layer on the substrate surface and a light reflecting layer forming process step of forming the light reflecting layer on the surface of the recording layer and is provided with an annealing process step of regulating the temperature between 10 and 40 deg.C and maintaining the temperature for 1 to 12 hours between the recording layer forming process and the light reflecting layer forming process.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an optical information recording medium,
In particular, the present invention relates to a method for manufacturing a write-once optical information recording medium in a heat mode.

[0002]

2. Description of the Related Art Conventionally, an optical information recording medium (optical disk) on which information can be recorded only once by a laser beam has been known. This optical disc is a write-once CD (so-called CD-
R), a typical structure of which comprises a transparent disc-shaped substrate, a recording layer made of an organic dye, a light reflection layer made of a metal such as gold, and a protective layer (cover layer) made of a resin in this order. It is a laminate. The recording of information on the CD-R is performed by irradiating the CD-R with near-infrared laser light (usually a laser light having a wavelength around 780 nm), and the irradiated portion of the recording layer emits the light. The temperature is locally increased by absorption, and information is recorded by changing the optical characteristics of the portion due to a physical or chemical change (for example, generation of pits). On the other hand, when reading (reproducing) information, a laser beam having the same wavelength as that of the recording laser beam is also used as a CD-R.
The recording is performed by detecting a difference in reflectance between a portion where the optical characteristics of the recording layer have changed (recorded portion) and a portion where the optical characteristics have not changed (unrecorded portion).

In recent years, an optical information recording medium having a higher recording density has been demanded. In response to such demands, write-once digital versatile discs (so-called DVD-R)
Has been proposed (for example, "Nikkei New Media" separate volume "DVD", published in 1995). This DVD-R is a transparent disk-shaped guide groove (pre-groove) for tracking the laser beam to be irradiated, which is formed with a narrow groove width of half or less (0.74 to 0.8 μm) of the CD-R. A structure in which two disks each having a recording layer containing an organic dye, a light reflection layer, and a protective layer laminated in this order on a substrate are usually laminated with the recording layer inside.
Alternatively, the disk has a structure in which a disk-shaped protective substrate having the same shape as the disk is bonded with the recording layer inside. Recording and reproduction of information on the DVD-R is performed by irradiating a visible laser beam (normally, a laser beam having a wavelength in a range of 630 nm to 680 nm).
Higher density recording is possible than CD-R.

[0004] Recently, networks such as the Internet and high-definition TVs have rapidly become widespread. Also, HDT
V (High Definition Televis)
ion) is about to start broadcasting. Under such circumstances, there is a need for a large-capacity recording medium capable of simply and inexpensively recording image information. At present, DVD-Rs play a sufficient role as large-capacity recording media, but demands for large-capacity and high-density are increasing, and it is also necessary to develop recording media that can meet these requirements. . For this reason, a recording medium having a larger capacity capable of performing high-density recording with light having a shorter wavelength than that of the DVD-R is being developed.

For example, JP-A-4-74690, JP-A-7-304256, JP-A-7-304257
JP-A-8-127174 and JP-A-11-53
758, 11-334204, 11-
334205, 11-334206, 11-334207, JP-A-2000-43423
JP 2000-108513, JP 2000-108513
-113504, 2000-149320, 2000-158818, and 200
Japanese Patent Application Laid-Open No. 0-228028 discloses that in an optical information recording medium having a recording layer containing an organic dye, information is recorded and reproduced by irradiating a laser beam having a wavelength of 530 nm or less from the recording layer side to the light reflecting layer side. Is disclosed. In these methods, an optical disk having a recording layer containing a porphyrin compound, an azo dye, a metal azo dye, a quinophthalone dye, a trimethine cyanine dye, a dicyanovinylphenyl skeleton dye, a coumarin compound, a naphthalocyanine compound, and the like, Blue (wavelength 4
30 nm, 488 nm) or bluish green (wavelength 515 nm)
The recording and reproduction of information are performed by irradiating the laser light.

[0006] On the other hand, a phase change optical disk is known as a DVD, which is a GeSbTe as a recording layer.
The recording layer is instantaneously heated with a laser beam to change its phase from a crystalline state to an amorphous state.
This is a method of recording and reproducing using a reflectance changed by a phase change. Recently, a DVR system for performing recording and reproduction using a blue-violet laser using this phase-change type DVD has been announced ("ISOM2000", pp. 210-211). This system has achieved certain results for the issue of high density.

In the production of such an optical disk, a recording layer is formed by applying a recording layer coating solution to a substrate surface, and a light reflecting layer is laminated thereon by sputtering a metal such as gold or silver. Further, it is performed by providing a substrate. Alternatively, a light reflection layer is laminated on the substrate surface, a recording layer is formed thereon, and a protective layer (cover layer) is further laminated thereon. When laminating the light reflecting layer or the cover layer on the recording layer, if the light reflecting layer is formed with the recording layer coating liquid remaining, the solvent remains, and this is particularly the case when irradiating a short-wavelength laser. There has been a problem that the degree of modulation deteriorates and stable recording and reproduction cannot be performed.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and has as its object to achieve the following objects. That is, an object of the present invention is to provide a method for manufacturing an optical information recording medium having a large degree of modulation and having stable recording and reproducing characteristics.

[0009]

Means for solving the above problems are as follows. That is, <1> a recording layer containing a solvent-soluble organic compound having an absorption maximum from 300 nm to 450 nm on the substrate surface and having an absorbance of 0.07 or more at the recording laser wavelength of the dye solid film, and a light reflection layer. , A substrate in this order, the track pitch is 300 to 600 nm, and the groove depth is 40 nm to 1 nm.
What is claimed is: 1. A method for manufacturing an optical information recording medium for recording and reproducing with light having a wavelength of 380 to 500 nm at 50 nm, comprising: a recording layer forming step of forming the recording layer on a substrate surface; and a light reflecting layer on the surface of the recording layer. Forming a light reflecting layer to be formed, wherein the temperature is set to 10 ° C. or more and less than 40 ° C. between the recording layer forming step and the reflecting layer sputtering step;
A method for manufacturing an optical information recording medium, comprising an annealing step for holding time.

<2> A light reflecting layer and 300
a recording layer containing a solvent-soluble organic compound having an absorption maximum at from 450 nm to 450 nm and an absorbance of the dye solid film at the recording laser wavelength of 0.07 or more, and a cover layer in this order. A method for producing an optical information recording medium for recording / reproducing with light having a wavelength of 400 nm, a groove depth of 40 nm to 150 nm, and a wavelength of 380 to 500 nm,
A light reflecting layer forming step of forming a light reflecting layer on the substrate surface, a recording layer forming step of forming a recording layer on the surface of the reflecting layer, and a cover layer forming step of forming a cover layer on the surface of the recording layer. A temperature between 10 ° C. and less than 40 ° C. between the recording layer forming step and the cover layer forming step;
A method for manufacturing an optical information recording medium, comprising an annealing step of holding for up to 12 hours. <3> The method for producing an optical information recording medium according to <1> or <2>, wherein the solvent-soluble organic compound is phthalocyanine.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an embodiment of a method for manufacturing an optical information recording medium according to the present invention will be described. First, an optical information recording medium obtained by the manufacturing method of the present invention will be described. According to the first aspect, the optical information recording medium has a recording layer, a light reflection layer, and a substrate in this order on a substrate surface, and has other layers as necessary. Hereinafter, the substrate and each layer will be described.

<Substrate> As the substrate, various materials used as substrate materials for conventional optical information recording media can be arbitrarily selected and used. Specific examples include glass; acrylic resins such as polycarbonate and polymethyl methacrylate; vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymer; epoxy resins; amorphous polyolefin; polyester; If desired, these may be used in combination. Among the above materials, polycarbonate and amorphous polyolefin are preferable, and polycarbonate is particularly preferable, in terms of moisture resistance, dimensional stability, low cost, and the like. Further, the thickness of the substrate is preferably set to 0.5 to 1.4 mm.

A guide groove for tracking or an unevenness (pre-groove) representing information such as an address signal is formed on the substrate. C to achieve higher recording density
It is preferable to use a substrate on which pre-grooves with a narrower track pitch are formed as compared with a DR or a DVD-R. The track pitch of the pre-groove is 300-600
μm. The pregroove depth (groove depth)
It is in the range of 40 to 150 nm.

On the surface of the substrate on which the light reflecting layer described later is provided, for the purpose of improving the flatness and the adhesive strength,
It is preferable to form an undercoat layer. Examples of the material for the undercoat layer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleic anhydride copolymer, polyvinyl alcohol, N-methylolacrylamide, styrene / vinyltoluene copolymer, and chlorinated copolymer. High molecular substances such as sulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, polyethylene, polypropylene, and polycarbonate; silane coupling Surface modifiers such as agents. The undercoat layer is prepared by dissolving or dispersing the above materials in an appropriate solvent to prepare a coating solution, and then applying the coating solution by spin coating, dip coating,
It can be formed by applying to the substrate surface by an application method such as extrusion coating. The thickness of the undercoat layer is generally in the range of 0.005 to 20 μm, preferably in the range of 0.01 to 10 μm.

<Recording Layer> The recording layer is formed on the light reflection layer, and can record and reproduce information with a laser beam having a wavelength of 380 to 500 nm, has an absorption maximum at 300 to 450 nm, and has a recording laser wavelength. It contains an organic solvent-soluble compound having an absorbance of 0.07 or more. The “recording laser wavelength” refers to the wavelength of the laser that irradiates the optical recording medium, and in the case of DVD, 635 nm and 650 nm.
In the case of m and DVR, it is 405 nm. The “absorbance” refers to the organic solvent-soluble compound (A) or (B)
Is the quantity representing the degree of light absorption in the amorphous film state, and is given by the absorbance A = log ₁₀ (I ₀ / I) when the light intensity changes from I _{0 to} I by absorption.

The organic solvent-soluble compound is preferably contained in the recording layer in an amount of 50 to 100% by mass, more preferably 70 to 100% by mass. When the amount is less than 50% by mass, the absorption is reduced, and the recording characteristics may not be obtained.

The organic solvent-soluble compound is preferably a phthalocyanine compound, a porphyrin compound, a triazole compound, an aminobutadiene compound, a cyanine compound or the like, and at least one of these is preferable. , Sulfonamide-substituted, sulfomoyl-substituted, and sulfonic acid-substituted ones.

Also, JP-A-4-74690, JP-A-8-127174, JP-A-11-53758, JP-A-11-334204, and JP-A-11-33420.
No. 5, No. 11-334206, No. 11-33
No. 4,207, JP-A-2000-43423, JP-A-2000-108513, and JP-A-2000-1
A dye described in US Pat. No. 5,818,818 can be used in combination. Furthermore, it is not limited to the above dyes, such as triazole compounds, triazine compounds, cyanine compounds, merocyanine compounds, aminobutadiene compounds, phthalocyanine compounds, cinnamic acid compounds, viologen compounds, azo compounds, oxonol benzoxazole compounds, benzotriazole compounds and the like. Organic compounds are also preferably used. Among these compounds, a cyanine compound, an aminobutadiene compound, a benzotriazole compound, and a phthalocyanine compound are particularly preferable.

<Light Reflecting Layer> The light reflecting layer is made of a light reflecting substance having a high reflectance to laser light. The reflectance is 70% or more. Light reflective substances having high reflectivity include Mg, Se, Y, Ti, Zr, Hf,
V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe,
Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, A
g, Au, Zn, Cd, Al, Ga, In, Si, G
Metals such as e, Te, Pb, Po, Sn, Bi, etc. and semimetals or stainless steel can be mentioned. These light reflective substances may be used alone, or may be used in combination of two or more kinds or as an alloy. Among these, preferred are Cr, Ni, Pt, Cu,
Ag, Au, Al and stainless steel. Particularly preferred are Au, Ag, Al and alloys thereof, and most preferred are Au, Ag and alloys thereof.

<Adhesive Layer> The adhesive layer is an optional layer formed to improve the adhesion between the recording layer and a cover layer described later. As a material forming the adhesive layer, a photocurable resin is preferable, and among them, a material having a small curing shrinkage is preferable in order to prevent the disk from warping. Examples of such a photo-curable resin include UV-curable resins (UV-curable adhesives) such as “SD-640” and “SD-347” manufactured by Dainippon Ink and Chemicals, Inc. Also,
The thickness of the adhesive layer is from 1 to 1000 to give elasticity.
The range of μm is preferred, the range of 5 to 500 μm is more preferred, and the range of 10 to 100 μm is particularly preferred.

Other examples of the material for forming the adhesive layer will be described.
The material is a resin curable by radiation irradiation,
A resin having two or more radiation-functional double bonds in the molecule, such as acrylates, acrylamides,
Examples include methacrylates, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. Preferably, it is a bifunctional or more functional acrylate compound or methacrylate compound.

Specific examples of bifunctional compounds include ethylene glycol diacrylate, propylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and neopentyl glycol. Diacrylate, tripropylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, butanediol dimethacrylate, hexanediol dimethacrylate,
Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, tripropylene glycol dimethacrylate, and the like can be used in which acrylic acid and methacrylic acid are added to an aliphatic diol represented by, for example. it can.

Polyether acrylates and polyether methacrylates obtained by adding acrylic acid and methacrylic acid to polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and polyester polyols obtained from known dibasic acids and glycols Polyester acrylates and polyester methacrylates obtained by adding acrylic acid and methacrylic acid can also be used. Furthermore, a polyurethane acrylate or polyurethane methacrylate obtained by adding acrylic acid or methacrylic acid to a known polyurethane obtained by reacting a polyol or a diol with a polyisocyanate may be used.

Also, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F
And acrylic acid to these alkylene oxide adducts,
Methacrylic acid-added products and isocyanuric acid alkylene oxide-modified diacrylates, isocyanuric acid alkylene oxide-modified dimethacrylates, tricyclodecane dimethanol diacrylates, and those having a cyclic structure such as tricyclodecane dimethanol dimethacrylate are also used. Can be.

As the radiation, an electron beam and an ultraviolet ray can be used. When ultraviolet rays are used, it is necessary to add a photopolymerization initiator to the following compounds. An aromatic ketone is used as a photopolymerization initiator. Aromatic ketones produce, but are not particularly limited to, the emission spectrum of mercury lamps commonly used as ultraviolet light sources.
Those having a relatively large absorption coefficient at a wavelength of 254, 313, 865 nm are preferred. Representative examples include acetophenone, benzophenone, benzoin ethyl ether, benzyl methyl ketal, benzyl ethyl ketal, benzoin isobutyl ketone, hydroxydimethyl phenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-2 diethoxyacetophenone, and Mich.
Ler's ketone and various aromatic ketones can be used. The mixing ratio of the aromatic ketone is as follows: Compound (a) 1
0.5 to 20 parts by weight, preferably 2 to 100 parts by weight
15 parts by weight, more preferably 3 to 10 parts by weight.
An ultraviolet curable adhesive to which a photoinitiator has been added in advance is commercially available, and it may be used.
A mercury lamp is used as the ultraviolet light source. Mercury lamp 2
0.3 m / min speed using a 0-200 W / cm lamp
Used at 20 m / min. Generally, the distance between the substrate and the mercury lamp is preferably 1 to 30 cm.

A scanning system is used as an electron beam accelerator.
A double scanning method or a curtain beam method can be adopted, but a curtain beam method which is relatively inexpensive and can provide a large output is preferable. As electron beam characteristics,
The acceleration voltage is 100 to 1000 kV, preferably 150 to
300 kV and an absorbed dose of 0.5 to 20 Mra
d, preferably 1 to 10 Mrad. Acceleration voltage is 1
In the case of 0 kV or less, the amount of transmitted energy is insufficient and
If it exceeds 00 kV, the energy efficiency used for polymerization decreases, which is not preferable in terms of cost.

Next, a second embodiment of the optical information recording medium will be described. The optical information recording medium of the second aspect has a light reflecting layer, a recording layer, and a cover layer in this order on a substrate surface, and has other layers as necessary. The optical information recording medium of this embodiment has a track pitch of 100 to 400 nm.
, And having a cover layer, is different from the first embodiment, and otherwise is the same as the first embodiment.
Therefore, only the cover layer will be described.

<Cover Layer> The cover layer is formed in order to prevent moisture from entering the inside of the optical information recording medium, and is not particularly limited as long as it is a transparent material, but is preferably polycarbonate, cellulose triacetate or the like. Preferably, 2
A material having a moisture absorption of 5% or less at 3 ° C. and 50% RH. Note that “transparent” means that the recording light and the reproduction light
It means that it is transparent enough to transmit the light (transmittance: 90% or more).

In the above optical information recording medium, a dielectric layer or a light transmitting layer can be formed between the light reflecting layer and the recording layer according to the characteristics of the recording layer. For example, a light transmissive layer for improving adhesion to the recording layer may be provided, and when a phase change type recording layer is provided, a dielectric layer for heat dissipation may be provided. As the dielectric layer, Zn, Si, Ti, Te,
It is preferable to use a material composed of nitride, oxide, carbide, sulfide such as Sn, Mo, Ge, etc., and ZnS-Si
It may be something like O ₂ . As the light transmission layer,
Any material can be used as long as it has a transmittance of 90% or more at the laser wavelength.

The dielectric layer or the light transmitting layer can be formed by a conventionally known method. The thickness of the dielectric layer is preferably 1 to 100 nm, and the thickness of the light transmitting layer is preferably 2 to 50 nm.

[Method of Manufacturing Optical Information Recording Medium] Next, the manufacturing method of the present invention for manufacturing the above optical information recording medium will be described in detail. First, a method for manufacturing the optical information recording medium according to the first aspect will be described.

<Recording Layer Forming Step> The recording layer is prepared by dissolving a recording material such as the above-described dye (organic solvent-soluble compound or the like) in a suitable solvent together with a binder or the like to prepare a recording layer coating solution. The recording layer is formed by applying a coating solution for the recording layer on the light reflection layer formed on the surface of the substrate to form a coating film and then drying the coating film. The concentration of the recording substance in the recording layer coating solution is generally in the range of 0.01 to 15% by mass, preferably 0.1 to 15% by mass.
10 to 10% by mass, more preferably 0.5 to 5% by mass
, Most preferably in the range of 0.5 to 3% by mass. Further, as a method for dissolving the recording material or the like, a method such as ultrasonic treatment, despar, a homogenizer, and heating can be applied.

Solvents for preparing the coating solution for the recording layer include esters such as butyl acetate, ethyl lactate and cellosolve acetate; methyl ethyl ketone, cyclohexanone, and the like.
Ketones such as methyl isobutyl ketone; dichloromethane,
Chlorinated hydrocarbons such as 1,2-dichloroethane and chloroform; amides such as dimethylformamide; hydrocarbons such as methylcyclohexane; ethers such as tetrahydrofuran, ethyl ether and dioxane; ethanol, n-propanol, isopropanol and n-butanol diacetone Alcohols such as alcohols; fluorinated solvents such as 2,2,3,3-tetrafluoropropanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and propylene glycol monomethyl ether;

The above solvents can be used alone or in combination of two or more in consideration of the solubility of the recording material used. Antioxidant, UV in coating solution
Various additives such as an absorbent, a plasticizer, and a lubricant may be added according to the purpose.

When a binder is used, examples of the binder include natural organic polymers such as gelatin, cellulose derivatives, dextran, rosin, and rubber; and hydrocarbon resins such as polyethylene, polypropylene, polystyrene, and polyisobutylene. ; Polyvinyl chloride, polyvinylidene chloride,
Vinyl resins such as polyvinyl chloride / polyvinyl acetate copolymer; acrylic resins such as polymethyl acrylate and polymethyl methacrylate; polyvinyl alcohol, chlorinated polyethylene, epoxy resin, butyral resin, rubber derivatives, phenol / formaldehyde resin And other synthetic organic polymers such as precondensates of thermosetting resins. When using a binder as the material of the recording layer,
The amount of the binder used is generally in the range of 0.01 times to 50 times (mass ratio) the recording substance, and preferably 0.1 to 50 times.
It is in the range of 1 to 5 times (mass ratio). The concentration of the recording substance in the coating solution thus prepared is generally 0.01%.
It is in the range of 10 to 10% by mass, preferably in the range of 0.1 to 5% by mass.

Examples of the coating method include a spray method, a spin coating method, a dip method, a roll coating method, a blade coating method, a doctor roll method, and a screen printing method. The recording layer may be a single layer or a multilayer. The thickness of the recording layer is generally in the range of 20 to 500 nm,
Preferably it is in the range of 30 to 300 nm, more preferably in the range of 50 to 100 nm. The application temperature is not particularly limited as long as it is 23 to 50 ° C, but is preferably 24 to 40 ° C, more preferably 25 to 37 ° C.

For viscosity control, the coating temperature is 23 to 50 ° C.
Is more preferable, the range of 24-40 degreeC is more preferable, and the range of 25-37 degreeC is further more preferable. Irradiation of ultraviolet rays to the coating film is preferably performed using a pulsed light irradiator (preferably, a UV irradiator) to prevent the disk from warping. The pulse interval is preferably less than msec,
μsec or less is more preferable. The irradiation light amount of one pulse is not particularly limited, but is preferably 3 kW / cm ² or less.
kW / cm ² or less is more preferable. The number of irradiations is not particularly limited, but is preferably 20 times or less, more preferably 10 times or less.

The recording layer may contain various anti-fading agents in order to improve the light resistance of the recording layer. Generally, a singlet oxygen quencher is used as an anti-fading agent. As a singlet oxygen quencher,
Those described in publications such as already known patent specifications can be used. A specific example thereof is disclosed in
Nos. 75693, 59-81194, 60
18387, 60-19586, 6
Nos. 0-19587, 60-35054, 60-36190, 60-36191,
Nos. 60-44554, 60-44555, 60-44389, 60-44390, 60-54892, and 60-47069.
JP, JP-A-63-209959, JP-A-4-25
Nos. 492, JP-B1-38680 and JP-A-6-26028, and German Patent 3503.
No. 99, and the Chemical Society of Japan, October 1992, p. 1141, and the like.

The amount of the anti-fading agent such as the singlet oxygen quencher is usually in the range of 0.1 to 50% by mass, preferably 0.1 to 50% by mass, based on the amount of the compound to be recorded.
The range is 5 to 45% by mass, more preferably 3 to 40% by mass, and particularly preferably 5 to 25% by mass.

<Light Reflecting Layer Forming Step> The light reflecting layer can be formed on the substrate by vapor deposition, sputtering or ion plating of the above-mentioned light reflecting substance. The thickness of the light reflecting layer is generally 10 to 300 nm.
And preferably in the range of 50 to 200 nm.

In the present invention, an annealing step is provided between the recording layer forming step and the light reflecting layer forming step.
Hereinafter, the annealing step will be described. Note that the annealing step is preferably performed immediately after the recording layer forming step is performed.

<Annealing Step> In this step, the substrate on which the recording layer has been formed as described above is heated to a temperature of 10 ° C. or higher.
The temperature is kept below 0 ° C. and this temperature is maintained for 1 to 12 hours. Then, by this step, the degree of modulation of the optical information recording medium can be increased. This is presumably because the solvent remained when the sputtering was performed after the recording layer forming step was performed, and this solvent was gasified, particularly when short-wavelength laser irradiation was performed, and a large hole was formed, thereby increasing the degree of modulation. That is, the modulation degree can be increased by appropriately controlling the amount of the residual solvent.

The temperature in the annealing step is preferably 15 to 35 ° C., more preferably 20 to 30 ° C.
° C. The time is preferably 1 to 10 hours, more preferably 1 to 8 hours.

In this step, if the temperature is lower than 10 ° C.,
The solvent content increases, and the pits may be too large than desired. When the temperature is 40 ° C. or higher, the solvent content decreases, sufficient sensitivity cannot be obtained, and the degree of modulation decreases. .

If the holding time of the temperature in the annealing step is less than 1 hour, the performance of the recording layer becomes unstable because the amorphous film of the recording layer is not stable, and if the holding time exceeds 12 hours, the amorphous recording layer is deteriorated and the performance is deteriorated. descend.

Next, a method of manufacturing the optical information recording medium according to the second embodiment will be described. The manufacturing method is based on the first method described above.
In addition to the “recording layer forming step” and the “light reflecting layer forming step” described in the method for manufacturing an optical information recording medium according to the aspect, a cover layer forming step is provided.

<Cover Layer Forming Step> The cover layer is prepared by dissolving the photocurable resin constituting the adhesive layer in an appropriate solvent to prepare a coating solution, and then applying the coating solution on the recording layer at a predetermined temperature. To form a coating film, and, for example, a cellulose triacetate film (T
AC film) and laminated TAC
It is formed by irradiating light from above the film to cure the coating film. The TAC film preferably contains an ultraviolet absorber. The thickness of the cover layer is 0.01 to
0.2 mm, preferably 0.03 to 0.1
mm, more preferably 0.05 to 0.095 mm
Range.

In the method for manufacturing an optical information recording medium according to the second aspect, an annealing step is provided between the recording layer forming step and the cover layer forming step. The annealing step is the same as the annealing step described in the method for manufacturing the optical information recording medium of the first embodiment.

[0049]

(Examples 1 to 7) 0.6 mm in thickness and 12 in diameter
Injection-molded polycarbonate resin having a 0 mm spiral group (groove depth, track pitch shown in Table 1 below) (Teijin Corporation polycarbonate product Panlite A)
D5503) Orazole GN (phthalocyanine absorbance 0.07 Ciba Specialty Chemical Co., Ltd.) was mixed with 2,2,3,3-tetrafluoropropanol at 2% on the surface having the group of substrates, and ultrasonication was performed for 2 hours. The recording layer coating solution thus dissolved was applied by a spin coating method at a temperature of 23 ° C. and 50% RH while changing the rotation speed from 300 rpm to 4000 rpm to form a recording layer. After that, for each example, it is stored under the conditions shown in Table 1 (temperature, time; defined as annealing conditions).
g was sputtered to a thickness of 100 nm to form a light reflecting layer, and a UV-curable adhesive (SD-640, manufactured by Dainippon Ink and Chemicals, Inc.) was used for 40
The coating was performed at 100 ° C. by spin coating at 100 to 300 rpm, the polycarbonate substrate (0.6 mm) was overlapped, and then the adhesive was spread over the entire surface while changing from 300 rpm to 4000 rpm. And cured to produce a sample.

[0050]

[Table 1]

(Examples 8 to 14) Injection-molded polycarbonate resin having a spiral group (groove depth, track pitch shown in Table 1) having a thickness of 1.2 mm and a diameter of 120 mm (polycarbonate trade name Panlite A manufactured by Teijin Limited)
D5503) A light reflecting layer having a thickness of 100 nm is formed by sputtering Ag on a surface having a group of substrates, and thereafter, isolazole GN (phthalocyanine having an absorbance of 0. 0).
07 Ciba Specialty Chemicals)
2,3,3, -Tetrafluoropropanol was mixed with 2% and subjected to ultrasonication for 2 hours to dissolve the recording layer coating solution. The rotation speed was changed from 300 rpm to 4000 rpm by spin coating.
m, and the recording layer was formed by applying under conditions of 23 ° C. and 50% RH. After that, for each example, it is stored under the conditions shown in Table 1 (temperature, time; defined as annealing conditions).
And then use a UV-curable adhesive (Dainippon Ink and Chemicals S
D-347) by spin coating at 100 to 300 r.
pm, and a polycarbonate sheet (Pure Ace Teijin Co., Ltd., 70 micron thickness) is overlaid to form a cover layer, and then the adhesive is spread over the entire surface while changing from 300 rpm to 4000 rpm. And cured to produce a sample.

<Embodiment 15> A thickness of 1.2 mm and a diameter of 12
Ag was placed on a surface having a group of injection-molded polycarbonate resin (Polylite AD5503, manufactured by Teijin Limited) having a 0 mm spiral group (depth 100 nm, width 0.11 μm, track pitch 0.3 nm). A light reflecting layer having a thickness of 100 nm is formed by sputtering, and then a dielectric layer having a thickness of 90 nm is formed by sputtering a ZnS-SiO ₂ film, and FOM-56
1 (phthalocyanine absorbance 0.1, manufactured by Wako Pure Chemical Industries, Ltd.) was mixed with 2% dibutyl ether and subjected to ultrasonication for 2 hours.
23 ° C while changing from 0 rpm to 4000 rpm
The coating was performed under the condition of 50% RH. Thereafter, the film is stored at 25 ° C. for 1 hour, and then a SiO ₂ film is sputtered to form a light transmitting film having a thickness of 90 nm. A polycarbonate sheet (Pure Ace Teijin Co., Ltd., 80 μm thick) coated with benzotriazole was applied at 100 to 300 rpm to form a cover layer.
After that, the adhesive was spread over the entire surface while changing the speed from 300 rpm to 4000 rpm, and was then cured by irradiating ultraviolet rays with a UV irradiation lamp in a pulsed manner to produce a sample.

<Example 16> Thickness: 1.2 mm, diameter: 12
Ag was placed on a surface having a group of injection-molded polycarbonate resin (polycarbonate trade name, Panlite AD5503 manufactured by Teijin Limited) having a spiral group of 0 mm (depth 100 nm, width 0.11 μm, track pitch 0.3 nm). A light reflecting layer having a thickness of 100 nm is formed by sputtering, then a ZnS-SiO ₂ film is formed by sputtering to form a dielectric layer having a thickness of 90 nm, and aminobutadiene (absorbance 0.08) is added to 2,2. , 3,3, -Tetrafluoropropanol mixed with 2% and subjected to ultrasonic wave for 2 hours to dissolve the recording layer coating solution at a temperature of 23 ° C. and 50% RH while changing the rotation speed from 300 rpm to 4000 rpm by spin coating. This was applied to form a recording layer. Thereafter, the film is stored at 25 ° C. for 1 hour, and then a SiO ₂ film is sputtered to form a light-transmitting film having a thickness of 90 nm, and a UV-curable adhesive (SD-347 manufactured by Dainippon Ink and Chemicals, Inc.) is spin-coated. Is applied at 100 to 300 rpm, and a polycarbonate sheet (Pure Ace Teijin Co., Ltd., 80 μm thick) to which benzotriazole is added is laminated to form a cover layer, and then from 300 rpm to 4000 rpm.
After the adhesive was spread over the entire surface while changing to m, a pulse was irradiated with ultraviolet light from a UV irradiation lamp to be cured, thereby producing a sample.

(Comparative Example 1) Annealing conditions were set at a temperature of 8 ° C.
Except for 1 hour, a sample was prepared in the same manner as in Examples 1 to 7.

(Comparative Example 2) The annealing conditions were set to a temperature of 40
A sample was prepared in the same manner as in Examples 1 to 7, except that the temperature was changed to 1 hour.

(Comparative Example 3) The annealing condition was changed to a temperature of 25.
A sample was prepared in the same manner as in Examples 1 to 7, except that the temperature was 13 ° C. and 13 hours.

(Comparative Example 4) The annealing conditions were set at a temperature of 8 ° C.
Samples were prepared in the same manner as in Examples 8 to 14, except that the time was changed to 1 hour.

(Comparative Example 5) The annealing condition was changed to a temperature of 82.
A sample was prepared in the same manner as in Examples 8 to 14 except that the temperature was changed to 1 hour at 1 ° C.

(Comparative Example 6) The annealing conditions were set to 25
A sample was prepared in the same manner as in Examples 8 to 14, except that the temperature was 13 ° C. and 13 hours.

Comparative Example 7 A thickness of 0.6 mm and a diameter of 120
Injection molded polycarbonate resin having a spiral group of mm (groove depth, track pitch shown in Table 1) (Panlite AD55 manufactured by Teijin Limited)
03) Orazole GN (phthalocyanine absorbance 0.07 ciba Specialty Chemical Co., Ltd.) was mixed with 2,2,3,3-tetrafluoropropanol at 2% on the surface having the group of substrates, and ultrasonication was performed for 2 hours. The recording layer coating solution thus dissolved was applied by a spin coating method at a temperature of 23 ° C. and 50% RH while changing the rotation speed from 300 rpm to 4000 rpm to form a recording layer.
Thereafter, Ag was sputtered to a thickness of 100 nm to form a light reflecting layer, and a UV-curable adhesive (SD-64 manufactured by Dainippon Ink and Chemicals, Inc.) was used.
0) at 40 ° C. for 100 to 300 r by spin coating.
pm, and the polycarbonate substrate (0.6 mm) was overlapped. Then, the adhesive was spread over the entire surface while changing from 300 rpm to 4000 rpm, and then cured by irradiating ultraviolet rays with a UV irradiation lamp to prepare a sample. .

(Comparative Example 8) Thickness 1.2 mm, diameter 120
Ag was placed on a surface having a group of injection-molded polycarbonate resin (polycarbonate trade name, Panlite AD5503, manufactured by Teijin Limited) having a spiral group (depth: 100 nm, width: 0.11 μm, track pitch: 0.3 nm). A light reflecting layer having a thickness of 100 nm is formed by sputtering, and then a dielectric layer having a thickness of 90 nm is formed by sputtering a ZnS-SiO ₂ film, and FOM-56
1 (phthalocyanine absorbance 0.1, manufactured by Wako Pure Chemical Industries, Ltd.) was mixed with 2% dibutyl ether and subjected to ultrasonication for 2 hours.
23 ° C while changing from 0 rpm to 4000 rpm
The coating was performed under the condition of 50% RH. Thereafter, an SiO ₂ film is sputtered to form a light transmitting film having a thickness of 90 nm, and then a UV curing adhesive (SD-34 manufactured by Dainippon Ink and Chemicals, Inc.)
7) is applied at 100 to 300 rpm by a spin coating method, and a polycarbonate sheet (Pure Ace Teijin Co., Ltd., 80 micron thickness) is added and benzotriazole is added, and then the adhesive is spread over the entire surface while changing from 300 rpm to 4000 rpm. After that, a pulse was irradiated with ultraviolet light from a UV irradiation lamp to be cured, thereby preparing a sample.

The above Examples 1 to 16 and Comparative Examples 1 to 8
The 3T-14T signal was recorded on the sample obtained by using DDU-1000 (manufactured by Pulstec) equipped with a 405 nm laser, and the overall degree of modulation was measured. Table 1 shows the results. From Table 1, it can be seen that in Examples 1 to 16 in which the above annealing step was performed, the degree of modulation was large, but the annealing step was not performed, or the temperature was 10
In Comparative Examples 1 to 8 in which the annealing conditions were not higher than 40 ° C. and lower than 40 ° C. for 1 to 12 hours, the degree of modulation was small.

[0063]

According to the present invention, it is possible to provide a method of manufacturing an optical information recording medium having a large degree of modulation and having stable recording and reproducing characteristics.

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Claims (3)

[Claims] 1. The method according to claim 1, wherein the substrate surface has a thickness of 300 nm to 450 nm.
A recording layer containing a solvent-soluble organic compound having an absorption maximum of 0.07 or more at the recording laser wavelength, a light reflecting layer, and a substrate in this order, and the track pitch is 300-600nm, groove depth 40n
A method for producing an optical information recording medium for recording and reproducing with light having a wavelength of 380 to 500 nm and a wavelength of 380 to 500 nm, comprising: a recording layer forming step of forming the recording layer on a substrate surface; and light reflection on the surface of the recording layer. A light reflection layer forming step of forming a layer, between the recording layer formation step and the light reflection layer formation step,
The temperature is 10 ° C. or more and less than 40 ° C., and the temperature is 1 to 1
A method for manufacturing an optical information recording medium, comprising an annealing step of holding for 2 hours. 2. A light-reflecting layer on a substrate surface, and a recording layer containing a solvent-soluble organic compound having an absorption maximum from 300 nm to 450 nm and having an absorbance of a dye solid film of 0.07 or more at a recording laser wavelength. , A cover layer in this order, a track pitch of 100 to 400 nm, and a groove depth of 40.
A method for manufacturing an optical information recording medium for recording and reproducing with light having a wavelength of 380 to 500 nm and a wavelength of 380 to 500 nm, comprising: a light reflection layer forming step of forming a light reflection layer on a substrate surface; and recording on the surface of the reflection layer. A recording layer forming step of forming a layer, and a cover layer forming step of forming a cover layer on the surface of the recording layer, wherein a temperature of 10 ° C. or higher is provided between the recording layer forming step and the cover layer forming step. A method for producing an optical information recording medium, comprising an annealing step of maintaining the temperature at less than 40 ° C. for 1 to 12 hours. 3. The method for producing an optical information recording medium according to claim 1, wherein the solvent-soluble organic compound is phthalocyanine.