JPH06243506A - Optical recording medium - Google Patents

Abstract

PURPOSE:To obtain a high reliability optical recording medium by controlling the relation among the thickness and hardening shrinkage of a protective layer and those of a printing part to a specified condition range. CONSTITUTION:A recording layer 3 contg. at least an org. dye, a metal layer 4, one or more protective layers 5 and a single- or multilayered printing part 6 are successively laminated and directly contacted on a transparent substrate 2. The protective layers 5 and the printing part 6 are formed so as to satisfy SIGMAAiBi+SIGMACjDj<3 (mum) [where Ai is the thickness (mum) of the protective layers 5, Bi is the hardening shrinkage (-) of the protective layers 5, Cj is the thickness (mum) of the printing part 6 and Dj is the hardening shrinkage (-) of the printing part 6].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical recording medium, and more particularly to a writable organic dye optical recording medium.

[0002]

2. Description of the Related Art Conventionally, as an optical recording medium, recorded information, and prepits or pregrooves for tracking for reproducing the recorded information, a substrate made of translucent polycarbonate or the like by using a means such as a press in advance. Au, A on the surface on which the pits are formed
A reflective layer made of a metal film such as 1 is formed, and a protective layer made of a photo-curable resin is further formed on the reflective layer, and the read-only light is label-printed with the photo-curable ink on the protective layer. The recording medium has been put to practical use as a compact disc (CD). This CD contains music, images, data,
It is widely used for the purpose of storing and reproducing programs. The specifications for recording and reproducing signals of this CD are C
It is defined as the D standard, and playback devices that comply with this standard are widely used as CD players.

On the other hand, it has been noted that a write-once type optical recording medium satisfying the CD standard (so-called CD-Recordable) can be reproduced by a commercially available CD player which is widely used. This recordable CD (CD-
R) is an optical recording medium in which an organic dye recording layer, a metal reflection layer and a protective layer are laminated on a transparent substrate, and examples thereof include Nikkei Electronics (No. 465, issued January 23, 1989, p. 107), It is disclosed in JP-A-2-132657, JP-A-2-147286, JP-A-2-168448 and the like.

This CD-R is known as an optical recording medium capable of recording information as a signal by changing the organic dye recording layer by laser light emitted from the transparent substrate side.
This recording / reproducing signal can obtain a high reflectance and brightness by the metal reflection layer, and can be reproduced by a CD player. A protective layer is provided on the reflective layer in order to prevent the dye recording layer and the metallic reflective layer from being damaged. Further, a label is printed on the protective layer to show the disc specifications and the like. The printing portion on which the label is printed is not only for decoration but also for clearly indicating recorded contents, disc specifications and the like, and is essential for practical use.

Regarding the protective layer and the printing section of the optical recording medium, JP-A-2-7249 and the like describe that both the protective layer and the printing section are screen-printed in order to simplify the manufacturing process. There is. Moreover, JP-A-3-40
239 describes that the mechanical strength and durability of the protective layer are improved by stacking the first printed layer and the second printed layer on the protective layer. However, in these known techniques, although there are characteristics in the manufacturing method or the layer structure, the conditions of the printing section and the protective layer including the influence of the printing section are not shown at all. This is a conventional compact disc (C
In D), the write-once medium, the magneto-optical recording medium, etc., the printing section does not affect the recording characteristics of the medium, and it is conceivable that no particular attention was required.

On the other hand, the conditions for the protective layer used for the CD-R are, for example, Japanese Patent Laid-Open No. 232130/1993 and Japanese Patent Laid-Open No.
232131 and Japanese Patent Laid-Open No. 3-232132 specify the hardness, expansion coefficient, and shrinkage ratio of the protective layer, but these also show the conditions of the printed portion and the protective layer including the influence of the printed portion. Absent.

[0007]

DISCLOSURE OF THE INVENTION The inventors of the present invention have a structure in which a recording layer containing an organic dye, a metal reflection layer, a protective layer, and a printing portion are sequentially laminated on a transparent substrate, and satisfy the CD standard. A detailed study of a recordable optical recording medium (CD-R) capable of obtaining a recording / reproducing signal that
The fact that the media surprisingly has a protective layer in which the printed part can influence the media properties, in particular:
It was found that there is an unexpected phenomenon that the medium characteristics after the heat cycle test and the high temperature and high humidity test are adversely affected. This is considered to be a phenomenon peculiar to the CD-R medium, which occurs because the medium has an organic dye / metal interface that does not necessarily have good adhesion. CD-R
In the medium, it has been attempted to provide two or more protective layers and to provide the outermost layer as the scratch-resistant protective layer in order to improve the scratch resistance of the surface. It has been found that the deterioration of is extremely remarkable.

The present invention has a structure in which a recording layer containing an organic dye, a metal reflection layer, a protective layer and a printing portion are sequentially laminated on a transparent substrate, and a recording / reproducing signal satisfying the CD standard can be obtained. In a recordable optical recording medium (CD-R) that can be recorded, a medium in which a recording / reproducing signal does not change from the initial state even after a weathering test such as a heat cycle test and a high temperature and high humidity test for a long period of time, that is, reliability is extremely It is an object of the present invention to provide an optical recording medium having a protective layer and a printing section which are highly expensive and are suitable for practical use.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned objects, and as a result, in the protective layer and the printed portion, the relationship between the respective film thickness and the curing shrinkage ratio is within a specific condition range. By controlling to 1, the optical recording medium with extremely high reliability was completed for the first time. That is, the present invention is
On the transparent substrate, a recording layer containing at least an organic dye, and a metal layer provided directly on the recording layer,
A protective layer (i = 1,2, ─────) consisting of one or more layers provided in direct contact with this metal layer, and a printing section (j = 1,1 consisting of one or more layers provided in direct contact with this protective layer).
2, ─────)), the protective layer has a film thickness of Ai (μm) and curing shrinkage of Bi (−).
And the film thickness of the printed portion is Cj (μm) and the curing shrinkage is D
An optical recording medium characterized by satisfying formula (1) and [Equation 2], where j (−)

[0010]

## EQU2 ## ΣAiBi + ΣCjDj <3 (μm) (1)

Preferably, the protective layer comprises two or more layers (i
= 2, 3, 4, 5), and the outermost layer thereof is a scratch-resistant protective layer.

The optical recording medium of the present invention will be described in more detail below with reference to FIGS. 1 and 2. FIG. 1 is a sectional view showing an example of the structure of the optical recording medium of the present invention, and FIG. 2 is a sectional view showing another example of the structure of the optical recording medium of the present invention. The optical recording medium 1 of the present invention comprises a transparent substrate 2, a recording layer 3, a metal layer 4, a protective layer 5 and a printing section 6, and a substrate protective layer may be provided under the transparent substrate as needed for the purpose of improving the characteristics. It may be provided, an intermediate layer may be provided between the transparent substrate 2 and the recording layer 3, and an intermediate layer or the like may be provided between the recording layer 3 and the metal layer 4.

Therefore, in the medium of the present invention satisfying the formula (1), that is, in the protective layer 5 and the printing portion 6, the sum of the products of the respective film thickness and the curing shrinkage, that is, the protective layer 5 and the printing portion due to the curing shrinkage. The optical recording medium 1 in which the maximum fluctuation of 6 was less than 3 μm did not undergo peeling at the interface between the dye recording layer and the gold reflecting layer even after a durability test, and showed good signal and mechanical characteristics. . However, the medium which does not satisfy the formula (1), that is, the optical recording medium 1 in which the maximum variation of the protective layer 5 and the printing portion 6 due to curing shrinkage is 3 μm or more, is the interface between the dye layer and the metal reflection layer after the durability test. Therefore, the object of the present invention cannot be achieved because the signal property or mechanical property deteriorates as the value exceeds the CD standard value.

The protective layer 5 of the present invention is a layer that uniformly covers the entire region where the recording layer 3 and the metal layer 4 laminated on the transparent substrate 1 overlap, or a region where information is recorded uniformly over the entire surface. It is a layer to cover. The latter is intended to include a case where a bar code, a prepit, or the like is formed on the metal layer and medium information is recorded.

The printing portion 6 of the present invention is a layer formed on a part of the area where the recording layer 3 and the metal layer 4 overlap each other on the protective layer 5, or an area where information is recorded on the protective layer 5. Is a layer formed in a part of.

The protective layer 5 of the present invention may have a structure of two or more layers (first protective layer 5a, second protective layer 5b, ...) As described above. For example, in the case of two layers, the first protective layer 5a is formed on the metal layer, the thickness of the first protective layer 5a is A1, and the curing shrinkage of the first protective layer 5a is B1. Second protective layer that is the outermost layer (for example, scratch-resistant protective layer) 5
b is formed on the first protective layer 5a, and the second protective layer 5a
The film thickness of b is A2, and the curing shrinkage of the second protective layer 5b is B2.
And The same applies to the case of three or more layers. In order to improve the scratch resistance of the surface, a structure in which two or more layers are provided and a scratch-resistant protective layer is provided as the outermost layer is preferable.

The printing unit 6 of the present invention may have a structure of two or more layers (first printing unit 6a, second printing unit 6b, ...) As described above. For example, in the case of two layers, the first printing portion 6a is formed on the protective layer 5, the thickness of the first printing portion 6a is C1, and the curing shrinkage of the first printing portion 6a is D1. The second printing portion 6b is at least laminated on the first printing portion 6a, and the film thickness of the second printing portion 6b is C2.
The curing shrinkage of is D2. The same applies to the case of three or more layers.

In the present invention, there is no particular critical upper limit to the number of protective layers and the number of layers in the printing section, but in practice, each is about 5 layers at the maximum. The film thickness described in the present invention is measured by a stylus type surface roughness meter (for example, SLOAN).
It is a value (μm) measured by TECHNOROGY Dektak II) or the like.

The curing shrinkage described in the present invention is a value (-) obtained by comparing the volume before curing and the volume after curing and dividing the reduced volume by the volume before curing, more specifically, It is a value (−) obtained by measuring the volume before curing and the volume after curing for each of the material such as the resin forming the protective layer and the material forming the printing portion, and dividing the reduced volume by the volume before curing. .

The transparent substrate 2 used in the present invention is preferably made of a highly transparent material having a refractive index of 1.4 to 1.6 with respect to light in order to record and read signals. It is desirable that the light transmittance is 85% or more and the optical anisotropy is small. A preferable example is a substrate using a thermoplastic resin such as an acrylic resin, a polycarbonate resin, a polyamide resin, a vinyl chloride resin, or a polyolefin resin. Among these, acrylic resin, polycarbonate resin, and polyolefin resin injection-molded resin substrates are used from the viewpoints of mechanical strength of the substrate, ease of providing guide grooves and reproduction-only signals, and economical efficiency. A polycarbonate-based resin substrate is particularly preferable.

The shape of these transparent substrates 2 may be plate-like, film-like, circular or card-like. Of course, the surface of the transparent substrate 2 may have a guide groove for indicating a recording position, a pit for indicating a recording position, a pit for partially reproducing information, or the like. Such guide grooves and pits are preferably provided when the substrate is made by injection molding or casting, but they are also provided by applying an ultraviolet curable resin on the substrate and overlapping it with a stamper for ultraviolet exposure. it can.

The recording layer 3 used in the present invention is mainly composed of an organic dye, and specific examples thereof include macrocyclic azaannulene dyes (phthalocyanine dyes, naphthalocyanine dyes, porphyrin dyes, etc.), polymethine dyes (cyanine). Dye, merocyanine dye, styryl dye,
Squarylium dyes, etc.), anthraquinone dyes, azurenium dyes, azo dyes and the like. Of these, phthalocyanine dyes and cyanine dyes are preferable. In particular, in order to sufficiently obtain the effects of the present invention, a phthalocyanine dye having high light resistance and durability is desirable. The content of the organic dye in the recording layer 3 is 30% or more, preferably 60%
That is all. The dye used is not limited to a single dye, but may be a mixture of a plurality of dyes. Further, it may be composed of two or more dye layers. Further, the recording layer may be formed substantially by only the dye.

When the recording layer 3 is produced, other organic dyes such as substituted phthalocyanines, substituted naphthalocyanines, substituted porphyrin dyes, cyanine dyes, dithiol metal complexes and anthraquinone dyes are further added to improve recording characteristics. Or metallocene or other organometallic complex or nitrocellulosic, ethylcellulose, acrylic resin, polystyrene resin, urethane resin or other resins and leveling agents, defoaming agents and the like within the range that does not impair the effects of the present invention You can also

The recording layer 3 is usually prepared by spin coating,
The film can be formed by means of dip coating, spray coating, roll coating or the like, but the spin coat method is preferable from the viewpoint of ease of film formation. A solvent that does not damage the substrate 2 when the dye is formed by spin coating, for example, in a polycarbonate substrate, aliphatic or alicyclic hydrocarbons such as hexane, heptane, octane, decane, cyclohexane, and methylcyclohexane. System, non-polar solvents such as ether systems such as diethyl ether, dibutyl ether and diisopropyl ether, and alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, allyl alcohol and methyl cellosolve. The dye may be dissolved in a polar polar solvent and coated.

In the present invention, the thickness of the recording layer 3 containing the dye is usually about 30 to 500 nm,
It is more preferably about 250 nm. As the material of the metal layer (reflection layer) 4 used in the present invention, Au, Al, A
A metal such as g, Pt, Pd, Ni, Cu, a metal alloy, a metal compound, or the like is used. 70% reflectance, the standard for CD
To achieve the above, among these, Au or A
A metal film mainly composed of an alloy containing u is desirable. As the method for producing the metal layer 4, means such as vapor deposition, sputtering, ion plating, spin coating, spray coating and the like are used.

In the present invention, the thickness of the metal layer 4 is usually about 30 to 500 nm, more preferably about 50 to 200 nm. As a material for the protective layer 5 used in the present invention, an acrylic resin, a polycarbonate resin, an ultraviolet curable resin, an electron beam curable resin, a polysiloxane resin, or the like is used, and a resin excellent in impact resistance is selected. The protective layer 5 is generally obtained by applying a monomer and an oligomer, which can be polymerized into a polymer, and then performing a crosslinking reaction. The material is not limited to an organic compound, and may be a mixed component of an organic compound and an inorganic compound, or an inorganic material may be formed by a method such as a sputtering method or a vapor deposition method.

When it is obtained as an organic polymer by a crosslinking reaction, a small amount of a reaction initiator and a reaction catalyst are added to a mixture of monomers and oligomers of a polymerizable organic compound having at least one reactive acryloyl group in the molecule. The method of applying a liquid mixture of these and crosslinking by irradiating with an ultraviolet ray or an electron beam is advantageous from the viewpoint of workability.

However, the method of cross-linking is not limited to this, and like epoxy resins and urethane resins,
It may be one which advances crosslinking by heat, or one which advances polymerization by moisture in the air like a dialkoxysilane coupling agent. The main chain and side chains of the cross-linked product thus obtained may be saturated or unsaturated hydrocarbons or may contain cyclic compounds such as melamine and bisphenol. Further, in the middle of the main chain or side chain of this crosslinked product, polyether containing one or more ether bonds, polyester containing ester bonds, polyurethane containing urethane bonds, ionomer containing ionic bonds, polyamide containing amide bonds, sulfone Other bonds exemplified by polysulfone having a bond and polysulfide having a sulfide bond may be included. It may be a copolymer compound containing two or more of these bonds.

Further, in order to improve the moisture resistance of these crosslinked products, a side chain may contain fluorocarbon, or an epoxy resin may be contained in order to prevent deterioration due to hydrogen halide. Further, in order to improve the adhesion with the reflective layer 4, the side chain may contain a hydroxyl group, a carboxyl group, an acryl group, an amino group, a vinyl acetate group, or the like, and the main chain or the side chain may have an ionic group. May be included.

In forming the protective layer 5, a solvent and a diluent may be included in addition to the resin and its reaction agent, reaction initiator and the like during coating in order to improve the coating property. Further, a leveling agent, an antifoaming agent, a plasticizer, an antioxidant, an antistatic agent, etc. may be contained for the purpose of stabilizing the coating film and improving characteristics such as smoothness. Further, matting or coloring may be carried out with a filler, a pigment or a dye, if necessary. The protective layer 5 can be formed by a method such as spin coating, dip coating, spray coating, roll coating, or screen printing, but from the viewpoint of ease of film formation, the spin coating method or the screen coating method is used. The printing method is preferred.

The thickness of the protective layer is generally 0.1 μm to 10 μm.
It is in the range of 0 μm. In the present invention, the protective layer 5
Has a thickness of 3 to 30 μm, more preferably 5 to 20 μm. Curing shrinkage of the protective layer is usually 20% or less,
It is preferably 5% or less. As mentioned above, the outermost layer of the protective layer is preferably a scratch-resistant protective layer. The scratch-resistant protective layer, materials, additives, described in the protective layer,
Although the manufacturing method, film thickness, and shrinkage ratio conditions can be applied, a high hardness material containing an organic or inorganic filler is preferable from the viewpoint of scratch resistance.

From the viewpoint of workability, the material of the printing portion 6 used in the present invention is a mixture of a monomer and an oligomer of a polymerizable organic compound having at least one reactive acryloyl group in the molecule, a reaction initiator and a reaction catalyst. Is preferable, and an acrylic curable ink which is a liquid ink in which coloring such as coloring and matting is adjusted by adding a small amount of a pigment, a dye or a filler. In addition, a leveling agent, a defoaming agent, a plasticizer, an antioxidant, an antistatic agent and the like may be contained in the ink in order to improve properties such as printability, stability and smoothness. This ink is usually applied to the protective film 5 by screen printing or offset printing.
After printing on the surface, the printed portion 6 is formed by crosslinking by irradiation with ultraviolet rays or electron beams. The film thickness of the printed portion is generally in the range of 1 μm to 100 μm. In the present invention, the film thickness of the printing portion 6 is preferably 3 to 20 μm. The curing shrinkage of the printed part is usually 20% or less,
% Or less is preferable.

As a method of recording information on the optical recording medium 1 of the present invention, for example, the optical recording medium 1 is subjected to a constant linear velocity (preferably 1 to 10 m / sec, particularly preferably 1.2 to 2.8 m / sec).
It is performed by irradiating the bottom of the guide groove with a laser beam from the transparent substrate 2 side while forming a pit for reproduction in the recording layer 3 on the guide groove to record a signal while rotating the recording layer 3 on the recording layer 3 on the transparent groove. As the signal, it is preferable to record an EFM signal of CD standard (pit length recording) in order to obtain the effect of the present invention. Generally, a semiconductor laser beam having an oscillation wavelength in the range of 600 nm to 900 nm is used as the recording light. The optical recording medium 1 uses a semiconductor laser having an oscillation wavelength of 785 nm and has a linear velocity of 1.4 m / sec.
Recording can be performed with the following laser power, and further with a laser power of 15 mW or less at a linear velocity of 2.8 m / sec.

In the pits, the transparent substrate 2 and / or the recording layer 3 are melted, evaporated, sublimated, deformed or altered by the organic dye contained in the transparent substrate 2 and / or the recording layer 3 absorbing the laser light to generate heat. Changes such as a convex shape, a wavy shape, or a concave shape between and, and a change occurs in the recording layer 3,
The recording layer 3 and the metal layer 4 may be changed. To reproduce information, for example, the semiconductor substrate is irradiated with semiconductor laser light from the transparent substrate 2 with a laser power that does not change the recording layer 3 while rotating the optical recording medium 1 on which information is recorded at a constant linear velocity that is the same as or more than twice the above. Then, the information can be reproduced by detecting the reflected light.

The characteristics of the recorded reproduction signal are evaluated by the jitter indicating the variation of the recording signal in the case of the EFM signal of the CD standard and the block error rate (BLER) indicating the error rate of the EFM signal. The jitter value showing good characteristics is less than 30 ns, and the BLER value is less than 220 cps, preferably less than 30 cps. In addition, as a method for testing the reliability of the optical recording medium 1 of the present invention, a heat cycle test (IEC Publicat
ion 68-2-38: ZAD test), high temperature and high humidity test or light resistance test (sunshine carbon arc lamp weather resistance test JI
SB 7753) and the like. Even if you do these tests,
The reliability of the optical recording medium 1 is indicated when the jitter of the signal characteristics, the BLER and the like and the warp amount of the mechanical characteristics show good values and do not change.

As a method for testing the scratch resistance of the optical recording medium 1 of the present invention, the surface is scratched with a commercially available scratch tester capable of sweeping diamond needles with a predetermined load (for example, scratch tester CSR-01 manufactured by Lesca), A method of observing the degree of scratches with a magnifying glass is used.

[0037]

According to the findings of the present inventors, in a weather resistance test such as a heat cycle test or a high temperature and high humidity test,
From the portion where the printed portion and the protective layer are laminated, the recording characteristics are deteriorated, and further, when the protective layer is laminated in two layers for preventing scratches, the effect of distortion of the printed portion is likely to appear on the recording film, There is a problem that the recording signal cannot be read from the beginning. According to the findings of the inventors of the present invention, the above-mentioned phenomenon is apt to cause the peeling of the interface between the dye recording layer and the metal reflection layer from the structure of the CD-R medium, and the protection layer and the printing portion. Distortion is probably caused by the mutual influence on the recording layer.

Therefore, in the medium of the present invention satisfying the formula (1), that is, in the protective layer 5 and the printing section 6, the sum of the products of the respective film thickness and the curing shrinkage, that is, the protective layer 5 and the printing section due to the curing shrinkage. In the optical recording medium 1 in which the maximum fluctuation of 6 was less than 3 μm, the peeling of the interface between the dye recording layer and the metal reflective layer did not substantially progress even after a long-term durability test, and both the signal characteristics and the mechanical characteristics were improved. It shows a good value.

[0039]

EXAMPLES The present invention will be specifically described below with reference to examples, but these are merely examples of embodiments and do not limit the technical scope of the present invention defined in Article 70 of the Act. There is no. This is because an invention for which a patent is to be obtained should be grasped only from the description in the claims.

Example 1 Pd-tetra-having a bis (isopropyl) methoxy group at the α-position on one of the four benzene rings of the phthalocyanine ring.
A 3.5 wt% dibutyl ether solution of a phthalocyanine dye in which 4 chloro molecules are introduced into (bisisopropylmethoxy) phthalocyanine on average is used as a spiral groove (guide groove; spacing 1.6 μm, width 0.6 μm, depth 0). (0.07 μm) in an area (recording area) with a diameter of 44.7 to 118.0 mm and an outer diameter of 120 mm and a thickness of 1.2 mm.
1200 rpm on polycarbonate injection molded substrate
After spin coating at rpm, it was dried at 70 ° C. for 2 hours. The film thickness of this recording layer was 120 nm. Next, 80 nm of Au was sputtered on this recording layer to form a metal reflective layer. Furthermore, on this metal layer, ultraviolet curable resin SD-1
7 (manufactured by Dainippon Ink and Chemicals, Inc.) was spin-coated and then irradiated with ultraviolet rays to cure. Thickness 5μm Curing shrinkage 1
A 2% first protective layer was formed. Furthermore, the UV curable resin DICURE SSD medium (manufactured by Dainippon Ink and Chemicals, Inc.) within a diameter range of 40 to 119 mm on the first protective layer.
Was screen-printed and then irradiated with ultraviolet rays to be cured. A second protective layer (scratch-resistant protective layer) having a thickness of 8 μm and curing shrinkage of 10% was formed.

Further, after UV-curing resin DICURE SSD582 (manufactured by Dainippon Ink and Chemicals, Inc.) was screen-printed on the portion on the second protective layer, it was irradiated with UV rays to be cured. A printed portion having a thickness of 10 μm and curing shrinkage of 10% was formed. The optical recording medium produced in this way was then provided with an optical disc recording device DDU-1000 (Pulstec Industrial Co., Ltd., laser wavelength 781 nm) and an EFM signal encoder (K
EF by changing the laser power in the range of 4 to 10 mW at a linear velocity of 1.3 m / sec using ENWOOD Co., Ltd.
The M modulated signal was recorded.

Next, a commercially available CD player (YAMAHA
The recorded signal was read using CDX-1050). Best error when recording laser power is 7mW
Rate and jitter were obtained, BLER was less than 20, pit jitter was 22 ns, and almost no distortion was observed in the waveform of the recording signal, and extremely good recording and reading could be performed. A scotch mending tape 810 was attached to the protective layer and the printing portion of this optical recording medium, and a peeling test was conducted, but peeling was not observed. This medium,
When ZAD test was conducted, BLER after 30 cycles
Both jitter and CD satisfied the CD standard without change.

When this medium was subjected to a high temperature and high humidity test at 80 ° C. and 85% RH, both BLER and jitter after 1000 hours did not change and satisfied the CD standard. This medium,
When a light resistance test (JIS B7753) was conducted, it was 10
Both BLER and jitter after 00 hours did not change and satisfied the CD standard. The maximum amount of warp of this medium is ± 0.3 in the initial stage.
It was less than ± 0.3 degrees after each endurance test and was good. When the surface of the medium on the protective layer side was scratched using a scratch tester CSR-01 manufactured by Lesca, scratches were hardly observed even when a load of 0.6 Kg / cm 2 was applied. The results are shown in Table 1.

Example 2 Pd-tetra-having a bis (isopropyl) methoxy group at the α-position on one of the four benzene rings of the phthalocyanine ring
A 3.5 wt% dibutyl ether solution of a phthalocyanine dye obtained by introducing an average of 3 bromine molecules into (bisisopropylmethoxy) phthalocyanine was placed on the same polycarbonate injection-molded substrate used in Example 1 at a rotation speed of 1200 rpm. After spin-coating at 70 ° C., it was dried at 70 ° C. for 2 hours. The film thickness of this recording layer was 120 nm.
Next, 80 nm of Au was sputtered on this recording layer to form a metal reflective layer. Further, an ultraviolet curable resin SD-17 (manufactured by Dainippon Ink and Chemicals, Inc.) was spin-coated on the metal layer and then irradiated with ultraviolet rays to be cured. A first protective layer having a thickness of 5 μm and curing shrinkage of 12% was formed. Further, an ultraviolet curable resin die cure SSD medium was offset-printed in a diameter range of 40 to 119 mm on the first protective layer, and then the ultraviolet curable resin was irradiated and cured. A second protective layer (scratch-resistant protective layer) having a thickness of 6 μm and curing shrinkage of 10% was formed. In addition, UV curable resin DICURE SS is applied on the second protective layer.
D583 (manufactured by Dainippon Ink and Chemicals, Inc.) was offset-printed and then irradiated with ultraviolet rays to be cured. A first printed portion having a thickness of 6 μm and curing shrinkage of 10% was formed. In addition, UV curable resin DICURE SSD582
Was offset-printed and then irradiated with ultraviolet rays to be cured. A second printed portion having a thickness of 6 μm and curing shrinkage of 10% was formed.

The optical recording medium thus prepared was processed in the same manner as in Example 1 at a linear velocity of 1.3 m / sec for 4 to 10 minutes.
When the EFM signal was recorded by changing the laser power in the range of mW and the reproduction characteristics were evaluated, the best error rate and jitter were obtained when the recording laser power was 6.5 mW, and the BLER was Less than 20, pit jitter is 20 ns
In addition, almost no distortion was observed in the waveform of the recording signal, and extremely good recording and reading could be performed.

A scotch mending tape 810 was attached to the protective layer and the printing portion of this optical recording medium, and a peeling test was conducted, but no peeling was observed. This medium is ZA
When the D test was conducted, both the BLER and the jitter after 30 cycles did not change and satisfied the CD standard. When this medium was subjected to a high temperature and high humidity test at 80 ° C. and 85% RH,
After 1000 hours, BLER and jitter were both unchanged C
Satisfies the D standard.

This medium was tested for light resistance (JIS B775.
When 3) was performed, both BLER and jitter after 1000 hours did not change and satisfied the CD standard. The maximum warp amount of this medium was less than ± 0.3 degrees at the initial stage, and was good, not exceeding ± 0.3 degrees after any endurance test. The surface of the protective layer side of this medium is scratched by a scratch tester CSR-01
When scratched by using, scratches were scarcely observed even with a load of 0.6 kg / cm 2. The results are shown in Table 1.
Shown in.

Example 3 Pd-tetra-having a bis (isopropyl) methoxy group at the α-position on one of the four benzene rings of the phthalocyanine ring
A 3.5 wt% dibutyl ether solution of a phthalocyanine dye obtained by introducing an average of 3 bromine molecules into (bisisopropylmethoxy) phthalocyanine was placed on the same polycarbonate injection-molded substrate used in Example 1 at a rotation speed of 1200 rpm. After spin-coating at 70 ° C., it was dried at 70 ° C. for 2 hours. The film thickness of this recording layer was 120 nm.
Next, 80 nm of Au was sputtered on this recording layer to form a metal reflective layer. Further, an ultraviolet curable resin SD-17 (manufactured by Dainippon Ink and Chemicals, Inc.) was spin-coated on the metal layer and then irradiated with ultraviolet rays to be cured. A protective layer having a thickness of 5 μm and curing shrinkage of 12% was formed. Further, after UV-curing resin die cure SSD158 was screen-printed on the portion on the protective layer, it was irradiated with UV rays to be cured. Thickness 12μ
A printed portion with 10% cure shrinkage was formed.

The optical recording medium thus prepared was processed in the same manner as in Example 1 for 4 to 10 at a linear velocity of 1.3 m / sec.
When the EFM signal was recorded by changing the laser power in the range of mW and the reproduction characteristics were evaluated, the best error rate and jitter were obtained when the recording laser power was 6.5 mW, and the BLER was Less than 20, pit jitter is 20 ns
In addition, almost no distortion was observed in the waveform of the recording signal, and extremely good recording and reading could be performed.

A scotch mending tape 810 was attached to the protective layer and the printing portion of this optical recording medium and a peeling test was conducted, but peeling was not observed. This medium is ZA
When the D test was conducted, both the BLER and the jitter after 30 cycles did not change and satisfied the CD standard. When this medium was subjected to a high temperature and high humidity test at 80 ° C. and 85% RH,
After 1000 hours, BLER and jitter were both unchanged C
Satisfies the D standard.

This medium was tested for light resistance (JIS B775.
When 3) was performed, both BLER and jitter after 1000 hours did not change and satisfied the CD standard. The maximum warp amount of this medium was less than ± 0.3 degrees at the initial stage, and was good, not exceeding ± 0.3 degrees after any endurance test. The results are shown in Table 1.
Shown in. Example 4 Pd-tetra-having a bis (isopropyl) methoxy group at the α-position on one of the four benzene rings of the phthalocyanine ring
A 3.5 wt% dibutyl ether solution of a phthalocyanine dye obtained by introducing an average of 3 bromine molecules into (bisisopropylmethoxy) phthalocyanine was placed on the same polycarbonate injection-molded substrate used in Example 1 at a rotation speed of 1200 rpm. After spin-coating at 70 ° C., it was dried at 70 ° C. for 2 hours. The film thickness of this recording layer was 120 nm.
Next, 80 nm of Au was sputtered on this recording layer to form a metal reflective layer. Further, an ultraviolet curable resin SD-17 (manufactured by Dainippon Ink and Chemicals, Inc.) was spin-coated on the metal layer and then irradiated with ultraviolet rays to be cured. A protective layer having a thickness of 5 μm and curing shrinkage of 12% was formed. Further, after UV-curing resin die cure SSD583 was screen-printed on the portion on the protective layer, it was irradiated with UV rays to be cured. Thickness 10μ
A first printed portion having m curing shrinkage of 10% was formed. In addition, UV curable resin die cure SSD on the first printed part
582 was screen-printed and then irradiated with ultraviolet rays to be cured. A second printed portion having a thickness of 10 μm and curing shrinkage of 10% was formed. Example 1 was added to the optical recording medium thus manufactured.
The EFM signal was recorded by changing the laser power in the range of 4 to 10 mW at a linear velocity of 1.3 m / sec in the same manner as described above, and the reproduction characteristics were evaluated. The recording laser power was 6.5 m.
When W, the best error rate and jitter are obtained, and BL
ER is less than 20, pit jitter is 20 ns,
Moreover, almost no distortion was observed in the waveform of the recording signal, and extremely good recording and reading could be performed.

A scotch mending tape 810 was attached to the protective layer and the printing portion of this optical recording medium and a peeling test was conducted, but peeling was not observed. This medium is ZA
When the D test was performed, the BLER and the jitter after 30 cycles were almost unchanged and satisfied the CD standard. When this medium was subjected to a high temperature and high humidity test at 80 ° C. and 85% RH, both BLER and jitter after 1000 hours hardly changed and satisfied the CD standard.

This medium was tested for light resistance (JIS B775.
When 3) was performed, both BLER and jitter after 1000 hours hardly changed and satisfied the CD standard. The maximum warp amount of this medium was less than ± 0.3 degrees at the initial stage, and was good, not exceeding ± 0.3 degrees after any endurance test. The results are shown in Table 1.

Comparative Example 1 Pd-tetra-having a bis (isopropyl) methoxy group at the α-position on one of the four benzene rings of the phthalocyanine ring.
A 3.5 wt% dibutyl ether solution of a phthalocyanine dye obtained by introducing an average of 4 chloro molecules per molecule into (bisisopropylmethoxy) phthalocyanine was placed on the same polycarbonate injection-molded substrate used in Example 1 at a rotation speed of 1200 rpm. After spin-coating at 70 ° C, it was dried at 70 ° C for 2 hours. The film thickness of this recording layer was 120 nm.
Next, 80 nm of Au was sputtered on this recording layer to form a metal reflective layer. Further, an ultraviolet curable resin SD-17 (manufactured by Dainippon Ink and Chemicals, Inc.) was spin-coated on the metal layer and then irradiated with ultraviolet rays to be cured. A first protective layer having a thickness of 8 μm and curing shrinkage of 12% was formed. Further, an ultraviolet curable resin die cure SSD medium was screen-printed on the first protective layer in a diameter range of 40 to 119 mm, and then irradiated with ultraviolet rays to be cured. A second protective layer having a thickness of 12 μm and curing shrinkage of 10% was formed. Further, after UV-curing resin die cure SSD582 was screen-printed on the portion on the second protective layer, it was irradiated with UV rays to be cured. A printed portion having a thickness of 12 μm and curing shrinkage of 10% was formed.

The optical recording medium thus prepared was processed in the same manner as in Example 1 at a linear velocity of 1.3 m / sec for 4 to 10 minutes.
When the EFM signal was recorded by changing the laser power in the range of mW and the reproduction characteristics were evaluated, the recording laser power was 7
Best error rate and jitter at mW, B
The LER was 50 cps, and the pit jitter was 26 ns.

A scotch mending tape 810 was attached to the protective layer and the printing portion of this optical recording medium, and a peeling test was conducted, but no peeling was observed. This medium is called Z
When the AD test was performed, after 5 cycles, peeling had progressed from the dye recording layer and the Au metal layer in the recording area corresponding to the printed portion. BLER exceeded 220 cps, and jitter was greater than 40 ns.

This medium was subjected to a high temperature and high humidity test at 80 ° C. and 85% RH. After 100 hours, the dye recording layer and Au in the recording area corresponding to the portion where the first printing portion and the second printing portion overlapped each other. Peeling was progressing from the metal layer. BLER is 22
Over 0 cps, the jitter was greater than 40 ns. The maximum amount of warp of this medium is +0.12 degrees at the beginning,
After any of the durability tests, it was greatly deformed to +0.3 degrees or more and was put to an end. The results are shown in Table 1.

Comparative Example 2 Pd-tetra-having a bis (isopropyl) methoxy group at the α-position on one of the four benzene rings of the phthalocyanine ring.
A 3.5 wt% dibutyl ether solution of a phthalocyanine dye obtained by introducing an average of 3 bromine molecules into (bisisopropylmethoxy) phthalocyanine was placed on the same polycarbonate injection-molded substrate used in Example 1 at a rotation speed of 1200 rpm. After spin-coating at 70 ° C., it was dried at 70 ° C. for 2 hours. The film thickness of this recording layer was 120 nm.
Next, 80 nm of Au was sputtered on this recording layer to form a metal reflective layer. Further, an ultraviolet curable resin SD-17 (manufactured by Dainippon Ink and Chemicals, Inc.) was spin-coated on the metal layer and then irradiated with ultraviolet rays to be cured. A first protective layer having a thickness of 8 μm and curing shrinkage of 12% was formed. Further, an ultraviolet curable resin die cure SSD medium was screen-printed on the first protective layer in a diameter range of 40 to 119 mm, and then irradiated with ultraviolet rays to be cured. A second protective layer having a thickness of 10 μm and curing shrinkage of 10% was formed. Further, after UV-curing resin die cure SSD583 was screen-printed on the portion on the second protective layer, it was irradiated with UV rays to be cured. A first printed portion having a thickness of 10 μm and curing shrinkage of 10% was formed. In addition, UV curable resin DICURE SSD582
Was screen-printed and then irradiated with ultraviolet rays to be cured. A second printed portion having a thickness of 10 μm and curing shrinkage of 10% was formed.

The optical recording medium thus prepared was processed in the same manner as in Example 1 at a linear velocity of 1.3 m / sec for 4 to 10 minutes.
When the EFM signal was recorded by changing the laser power in the range of mW and the reproduction characteristics were evaluated, the best error rate and jitter were obtained when the recording laser power was 6.5 mW, and the BLER was 120 cps, pit jitter is 32
It was ns. A scotch mending tape 810 was attached to the protective layer and the printing portion of this optical recording medium, and a peeling test was conducted, but peeling was not observed. This medium is called Z
When the AD test was performed, after 5 cycles, peeling was progressing from the dye recording layer and the Au metal layer in the recording area corresponding to the overlapping portion of the first printing portion and the second printing portion. BLER exceeded 220 cps, and jitter was greater than 40 ns.

This medium was subjected to a high temperature and high humidity test at 80 ° C. and 85% RH. After 100 hours, the dye recording layer in the recording area corresponding to the overlapping portion of the first printing portion and the second printing portion and Au were recorded. Peeling was progressing from the metal layer. BLER is 22
Over 0 cps, the jitter was greater than 40 ns. The maximum amount of warp of this medium was +0.1 degrees at the initial stage, and after any endurance test, it deformed to +0.3 degrees or more and ended. The results are shown in Table 1.

Comparative Example 3 Pd-tetra-having a bis (isopropyl) methoxy group at the α-position on one of the four benzene rings of the phthalocyanine ring.
A 3.5 wt% dibutyl ether solution of a phthalocyanine dye obtained by introducing an average of 3 bromine molecules into (bisisopropylmethoxy) phthalocyanine was placed on the same polycarbonate injection-molded substrate used in Example 1 at a rotation speed of 1200 rpm. After spin-coating at 70 ° C., it was dried at 70 ° C. for 2 hours. The film thickness of this recording layer was 120 nm.
Next, 80 nm of Au was sputtered on this recording layer to form a metal reflective layer. Further, an ultraviolet curable resin SD-17 (manufactured by Dainippon Ink and Chemicals, Inc.) was spin-coated on the metal layer and then irradiated with ultraviolet rays to be cured. A protective layer having a thickness of 10 μm and curing shrinkage of 12% was formed. Further, after UV-curing resin die cure SSD158 was screen-printed on the portion on the protective layer, it was irradiated with UV rays to be cured. Thickness 20
A printed portion having a μm curing shrinkage of 10% was formed.

The optical recording medium thus prepared was processed in the same manner as in Example 1 for 4 to 10 at a linear velocity of 1.3 m / sec.
When the EFM signal was recorded by changing the laser power in the range of mW and the reproduction characteristics were evaluated, the best error rate and jitter were obtained when the recording laser power was 6.5 mW, and the BLER was Less than 20, pit jitter is 22 ns
In addition, almost no distortion was observed in the waveform of the recording signal, and extremely good recording and reading could be performed.

A scotch mending tape 810 was attached to the protective layer and the printing portion of this optical recording medium, and a peeling test was conducted, but peeling was not observed. This medium is ZA
When the D test was performed, after 5 cycles, peeling had progressed from the dye recording layer and the Au metal layer in the recording area corresponding to the printed portion. BLER exceeds 220 cps and jitter is 4
It became larger than 0 ns. This medium, 80 ℃ 85% R
When the high temperature and high humidity test of H was performed, after 100 hours, the change of the signal in the recording area corresponding to the printing portion was progressing. B
The LER was over 220 cps, and the jitter was over 40 ns. The maximum warp amount of this medium is −0.
The value was 01 degree, which was good at less than ± 0.3 degree after any endurance test. The results are shown in Table 1.

Comparative Example 4 Pd-tetra-having a bis (isopropyl) methoxy group at the α-position on one of the four benzene rings of the phthalocyanine ring.
A 3.5 wt% dibutyl ether solution of a phthalocyanine dye obtained by introducing an average of 3 bromine molecules into (bisisopropylmethoxy) phthalocyanine was placed on the same polycarbonate injection-molded substrate used in Example 1 at a rotation speed of 1200 rpm. After spin-coating at 70 ° C, it was dried at 70 ° C for 2 hours. The film thickness of this recording layer was 120 nm.
Next, 80 nm of Au was sputtered on this recording layer to form a metal reflective layer. Further, an ultraviolet curable resin SD-17 (manufactured by Dainippon Ink and Chemicals, Inc.) was spin-coated on the metal layer and then irradiated with ultraviolet rays to be cured. A protective layer having a thickness of 8 μm and curing shrinkage of 12% was formed. Further, after UV-curing resin die cure SSD583 was screen-printed on the portion on the protective layer, it was irradiated with UV rays to be cured. Thickness 12μ
A first printed portion having m curing shrinkage of 10% was formed. In addition, UV curable resin die cure SSD on the first printed part
582 was screen-printed and then irradiated with ultraviolet rays to be cured. A second printed portion having a thickness of 12 μm and curing shrinkage of 10% was formed. Example 1 was added to the optical recording medium thus manufactured.
When the EFM signal was recorded by changing the laser power in the range of 4 to 10 mW at a linear velocity of 1.3 m / sec in the same manner as described above and the reproduction characteristics were evaluated, the recording laser power was 6.5 m.
When W, the best error rate and jitter are obtained, and BL
ER is less than 20, pit jitter is 21 ns,
Moreover, almost no distortion was observed in the waveform of the recording signal, and extremely good recording and reading could be performed.

A scotch mending tape 810 was attached to the protective layer and the printing portion of this optical recording medium and a peeling test was conducted, but peeling was not observed. This medium is ZA
When the D test was performed, after 5 cycles, peeling was progressing from the dye recording layer and the Au metal layer in the recording area corresponding to the portion where the first printed portion and the second printed portion overlap. BLER is 2
The jitter was greater than 40 ns and exceeded 20 cps. When this medium was subjected to a high temperature and high humidity test at 80 ° C. and 85% RH, after 100 hours, a change in the signal in the recording area corresponding to the printing portion had progressed. BLER is 220 cps
And the jitter became larger than 40 ns. The maximum warp amount of this medium was −0.02 degrees at the initial stage, and was good at less than ± 0.3 degrees after any endurance test. The results are shown in Table 1.
Shown in.

[0066]

[Table 1]

[0067]

As is apparent from the examples and Table 1, in the present invention, a long-term weather resistance test is performed by setting the respective film thicknesses and curing shrinkage percentages in the protective layer and the printing part within appropriate conditions. It must be said that it is marvelous that the storage stability of information can be ensured even if the above procedure is performed. That is, according to the present invention, for the first time, having a protective layer and a printing portion that are practical,
Moreover, it is possible to obtain an optical recording medium having extremely high reliability.

The optical recording medium manufactured under the conditions of the present invention has the above-mentioned effects and effects, and therefore must be stored for a long period of time such as storage of medical diagnosis data and photographs, and storage of official documents. Suitable for recorded information media that do not Also,
It can be used without special storage conditions like the widely used read-only CD, so it can be used for various purposes (Photo-CD, storage of music and data, small volume publication C
D-ROM, etc.) is expected.

[Brief description of drawings]

FIG. 1 is a sectional view showing an example of the configuration of an optical recording medium according to the present invention.

FIG. 2 is a sectional view showing another example of the configuration of the optical recording medium of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Optical recording medium 2 Transparent substrate 3 Recording layer 4 Metal layer (reflection layer) 5 Protective layer 5a 1st protective layer 5b 2nd protective layer 6 Printing part 6a 1st printing part 6b 2nd printing part

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location B41M 5/26

Claims (2)

[Claims] 1. A protective layer comprising, on a transparent substrate, a recording layer containing at least an organic dye, a metal layer provided in direct contact with the recording layer, and one or more layers provided in direct contact with the metal layer. In an optical recording medium comprising (i = 1,2, ─────) and a printing section (j = 1,2, ─────) consisting of one or more layers provided directly in contact with this protective layer. , The thickness of the protective layer is Ai (μm), and the curing shrinkage is Bi.
(-), The film thickness of the printed portion is Cj (μm), and the curing shrinkage is Dj.
An optical recording medium characterized by satisfying formula (1) and [Equation 1] when (-). ## EQU1 ## ΣAiBi + ΣCjDj <3 (μm) (1) 2. The protective layer comprises two or more layers (i = 2, 3,
4. The optical recording medium according to claim 1, wherein the optical recording medium is composed of 4,5, and the outermost layer is a scratch-resistant protective layer.