JP2662475B2 - Optical recording medium, method for reproducing recorded data on optical recording medium, and apparatus for reproducing recorded data on optical recording medium - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical recording medium for reproducing information or recording / reproducing information with light, in particular, laser light such as a semiconductor laser, and more particularly to a card-shaped optical recording medium (hereinafter referred to as an optical card) which is convenient to carry. ).

[0002]

2. Description of the Related Art In recent years, as information has been advanced in society, information recording media for recording or reproducing optical information, such as optical disks, optical cards, and optical tapes, have been used as means for efficiently handling a large amount of various information at high speed and efficiently. Many information recording / reproducing devices have been proposed. Some of the information record carriers can convert binarized information into a change in the intensity of reflected light depending on the presence or absence of a pit and detect the change.

As a recording medium based on a change in optical reflectance, a so-called heat mode recording material is used in which a recording layer is irradiated with an energy beam such as a laser beam in the form of a spot to change the state of a part of the recording layer for recording. Has been proposed.
These recording materials do not require a development process after writing information, and can be read directly after writing, so-called DRAW [direct read after write (direct read after write)].
e)] Medium, capable of high-density recording, and additionally writable.

[0004] Among such optical recording media, optical cards which are particularly excellent in portability, can record a large amount of information, and have higher security than magnetic cards have been actively studied in recent years.

[0005] In an optical information recording / reproducing apparatus, there is a method in which tracking tracks such as grooves and light-shielding portions are formed at predetermined intervals on the surface of a substrate of a medium for track servo of writing / reading. is there.

In this system, the tracking track serves as a guide for the recording laser beam and / or the reproducing laser beam, so that the accuracy of the laser beam following the information recording track is improved, and a substrate having no conventional tracking track can be used. Higher-speed access is possible than the optical recording medium used.

FIG. 3 is a schematic plan view showing the recording format of the optical card. In FIG. 3, a plurality of information recording tracks 33 are arranged on the optical card 11, and the information recording tracks are separated from each other by tracking tracks 32 for track servo of reproduction light or recording light.
A recording area 34 including a plurality of the information recording tracks is provided on the optical card 11, and information is recorded in the form of pits 31 by the recording light on the information recording tracks in this area. Arrow A indicates the optical card 1 during recording / reproduction.
1 is the moving direction.

FIG. 4 is a schematic block diagram of an optical card recording / reproducing apparatus.

In FIG. 4, the optical card 11 includes a driving means 46.
Thereby, the recording and / or reproducing beam 47 can reciprocate in the direction A parallel to the track groove 2. On the other hand, light from a light source 45 such as a semiconductor laser in the optical head 41 is condensed by a lens system 42 and irradiates the information recording track 33 of the optical card as recording light and / or reproduction light. Thus, the recording light is applied to the recording layer 3 on the information recording track.
The reproduction light is reflected by the recording layer 3 again, passes through the lens system 42, is separated from the light from the light source by the beam splitter 43, and enters the photodetector 44. An electric signal corresponding to the recorded information is output. Thus, the information recording track 3 is moved by the relative movement of the optical card 11 with respect to the reproducing beam.
When the reproduction of one track No. 3 is completed, the optical head 41 moves and performs tracking servo in a direction (not shown) perpendicular to the track of the optical card to detect another information recording track 33. Next, the optical card is driven in the reverse direction to reproduce information similarly.

In the conventional optical card, for example, as shown in FIG. 2, a recording layer 3 is formed on a surface of a substrate including a track groove forming region of a transparent substrate 5 having a track groove 2 serving as a tracking track on the surface. Are bonded together with an adhesive layer 4 interposed therebetween.

The recording and reproduction of information is performed by irradiating a laser beam through the transparent substrate 5, and the tracking of the laser beam is performed by measuring the phase difference and the amplitude difference between the track groove 2 corresponding to the tracking track and the reflected light from the information recording track. I use it.

When the recording light used for recording information on such an optical card is applied to the recording layer 3 of the optical card driven by the driving means, the recording layer responds to this light and optically responds. The intensity is selected so as to form a detectable change (pit), and the reproducing beam is a laser beam whose intensity is reduced to such an extent that the recording layer 3 does not change when irradiated on the recording layer 3.

In the conventional optical card, since the adhesive layer is in close contact with the recording layer, a change in the state of the recording layer due to the recording light is suppressed, and the recording sensitivity is low. Therefore, it has been necessary to use a high-intensity laser or to reduce the recording speed of the optical card for recording on the conventional optical card.

On the other hand, when reproducing information recorded on an optical card, US Pat. No. 4,189,735 (JP-A-54-126)
No. 005), it is preferable to increase the reproduction light intensity in order to improve the S / N ratio of the signal to be read.

However, since the reproduction of the optical card is normally performed by reciprocating the optical card with respect to the reproduction laser beam, the reproduction of one of the information recording tracks is completed as described above, and the reproduction of the other information recording tracks is completed. When moving on to playback,
With the reversal of the moving direction of the optical card, there is a point in time at which the relative moving speed of the optical card relative to the reproduction light decreases and the relative speed becomes zero. The recording layer in the stop, inversion, and inversion areas 21 is irradiated with the reproduction light for a long time, and as a result, the recording layer material is degraded by light or heat to lower the reflectivity, or the reproduction light easily causes writing. There was a problem. For example, when the reflectivity of the recording layer in the stop / reverse area decreases, the laser beam cannot be tracked in this area, and the information track for recording or reproduction cannot be detected. Also, the focusing of the reproduction light performed by the reflected light of the reproduction light cannot be performed. That is, the optical card in which the reflectance of the stoppage of the optical card and the reversal area is lowered cannot be reproduced.

Therefore, in the conventional optical card, the power of the reproducing laser beam cannot be increased so much that a signal having a satisfactory high S / N ratio cannot be reproduced.

As a means for solving such a problem, the present applicant has disclosed in European Patent Publication No. 259151 a non-recordable optical member having a reflectance equal to that of a recording area in a margin portion other than the recording area. The method of providing is disclosed.

However, in this method, it is difficult to select a member that maintains the same amount of reflected light in the recording region and the other region, and AT (auto tracking) is deviated due to discontinuity of the amount of reflected light at the boundary between the two, and AF is not performed. (Autofocus) There is a disadvantage that a malfunction such as a deviation is likely to occur.

Further, as is generally known, there is a method of adding a stabilizer having an effect of suppressing thermal deterioration between recording layers. However, in this method, a decrease in the reflectivity in the stop reversal area 21 can be suppressed to some extent, but the recording sensitivity in the recording area 34 also decreases, and there is a problem in that an increase in the recording speed is hindered.

In addition, the addition of the stabilizer could not significantly improve the intensity of the reproduction light in consideration of a decrease in reflectivity in the stop reversal region and writing.

Further, in order to improve the recording sensitivity of the recording area, the present applicant discloses in EP-A-280531 a method of laminating a film coating layer on a recording area on an organic optical recording layer without using an adhesive layer. I have. As a result, the area where the film coating layer is not provided has a close contact structure, so that the recording sensitivity is lowered, and the deterioration of the recording layer due to the reproduction light can be prevented in the stop and inversion area of the optical card. However, this configuration also prevents the deterioration of the recording layer in the stop / reverse region when the reproduction light intensity is increased, particularly, the decrease in reflectance due to heat accumulation of the reproduction light due to the close contact of the adhesive layer having a low temperature diffusivity. Was not enough.

[0022]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and the present invention has excellent recording sensitivity and high SN ratio by using a high-intensity reproducing beam. It is an object of the present invention to provide an optical recording medium capable of reproducing a signal. It is another object of the present invention to provide an optical recording medium in which the recording layer does not deteriorate in the stop reversal area even when a high-intensity reproducing beam is used.

Another object of the present invention is to provide a reproducing method and a reproducing apparatus for an optical recording medium in which the recording layer is not deteriorated in the stop inversion area even when a high-intensity reproducing beam is used.

Still another object of the present invention is to provide a method for reproducing an optical recording medium capable of reproducing a signal having a high SN ratio.

Still another object of the present invention is to provide an optical recording medium reproducing apparatus capable of reproducing a signal having a high SN ratio.

Another object of the present invention is to provide an optical recording medium which is excellent in recording sensitivity and has uniform sensitivity and reflectivity in a recording area.

[0027]

That is, the optical recording medium of the present invention has a substrate and a recording layer formed on the surface of the substrate, and the recording layer is provided on the surface of the recording layer which is not opposed to the substrate. It is characterized by comprising a recording auxiliary layer covering the recording area of the recording layer and a recording suppressing layer covering the recording layer not covered with the recording auxiliary layer.

Further, the optical recording medium of the present invention has a substrate having stripe-shaped tracks on the surface, and a recording layer formed on the surface of the substrate, and has a recording layer formed on the surface of the recording layer not facing the substrate. An optical recording medium comprising a recording auxiliary layer covering a recording area of the recording layer and a recording suppressing layer covering a recording layer outside the recording area, wherein the optical recording medium is provided with recording and / or reproducing light. The recording and / or reproduction of data is performed by the relative reciprocating movement of the recording medium, and the recording layer area outside the recording area of the medium is an area for tracking servo track access of recording and / or reproduction light and auto focus. And the irradiation area of the reproduction light when the moving direction of the medium is reversed.

The method of reproducing an optical recording medium according to the present invention comprises a substrate having stripe-shaped tracks on a surface thereof, a recording layer formed on the surface of the substrate, and a recording layer formed on the surface of the substrate which is not opposed to the substrate. On the surface, a recording auxiliary layer covering the recording area of the recording layer and a recording suppression layer covering the recording layer outside the recording area are provided, and encoded data is recorded on the recording layer. A method of reproducing recorded data on an optical recording medium, comprising: reciprocating the optical recording medium relative to reproduction light in a direction parallel to the track, and scanning the track with the reproduction light. The reversal of the moving direction of the optical recording medium is performed when the reproduction light is irradiating the recording layer area outside the recording area.

Further, a method of reproducing recorded data on an optical recording medium according to the present invention comprises a substrate having stripe-shaped tracks on the surface and a recording layer formed on the surface of the substrate. A recording area coated with an auxiliary layer and having an optically detectable change in the recording layer in response to a recording beam having a predetermined intensity; and a recording area covered with a recording suppression layer. And a low-sensitivity area having low sensitivity and reproducing the recorded data of an optical recording medium having coded data recorded on the recording layer using a reproducing beam having a predetermined intensity. Therefore, the reproducing beam does not cause a change in the recording layer of the recording area while the optical recording medium is moving at a predetermined speed with respect to the reproducing beam, and Relative displacement between the optical recording medium and the reproducing beam In a state where there is no movement, a change occurs in the recording layer in the recording area, and when there is no relative movement between the optical recording medium and the reproducing beam, recording in the low sensitivity area is performed. It is characterized by having a certain strength without causing a change in the layer.

[0031]

The data reproducing apparatus of the present invention has a substrate having stripe-shaped tracks on the surface and a recording layer formed on the surface of the substrate, and the recording layer is covered with a recording auxiliary layer. A recording area which produces an optically detectable change in the recording layer in response to a recording beam having a predetermined intensity; and a low sensitivity which is coated with a recording suppression layer and has a lower sensitivity than the recording area. And a device for irradiating the optical recording medium with a reproducing beam, the device comprising: an optical recording medium having an area and coded data recorded on the recording layer; A driving unit for relatively reciprocating the recording medium and the reproducing beam in a direction parallel to the track; and a reproducing beam for irradiating the optical recording medium is driven at a constant speed by the optical recording medium. The recording layer of the recording area In the optical recording medium and in the state where there is no relative movement between the optical recording medium and the reproducing beam, the recording layer in the recording area is changed, and In a state in which there is no relative movement between the medium and the reproducing beam, the intensity is set to a constant intensity that does not cause a change in the recording layer in the low sensitivity area.

[0033]

Next, the present invention will be described in detail with reference to the drawings.

FIG. 1 is a schematic view of an embodiment of the optical card 11 according to the present invention, and FIG. 1A is a cross-sectional view of the optical card 11 in a direction parallel to the track groove 2.

In FIG. 1A, reference numeral 5 denotes a transparent substrate having a track groove formed on the surface, 3 denotes a reflective recording layer formed on the surface of the substrate 5, and 6 denotes a recording area of the recording layer 3. Reference numeral 34 denotes a recording auxiliary layer laminated on the recording layer 34, and reference numeral 7 denotes a recording suppressing layer laminated on the recording layer outside the recording area.

FIG. 1B is a plan view of the optical card 11.
Denotes an information recording track 32 is a track groove. Also, 3
Reference numeral 4 denotes a recording area, on which data is recorded on an information recording track of the recording area.

Further, 4 is an adhesive layer and 1 is a protective substrate.

FIG. 1C shows the optical card 11 in FIG.
It is a schematic sectional drawing when cut | disconnected by the BC line of (a).

In the present invention, the recording auxiliary layer 34 refers to a change which occurs in the recording layer due to irradiation of a recording beam when data is recorded on the recording layer, for example, does not prevent deformation, decolorization, sublimation, etc. Those having a function of accelerating are preferred.

As a recording auxiliary layer that does not hinder the change that occurs in the recording layer, the recording layer differs depending on what kind of change is made in the recording layer. For example, the recording layer may be deformed. When recording is performed, a material that does not hinder the deformation and does not adversely affect the recording layer, for example, a polymer compound having rubber elasticity is used.

Specifically, a high molecular compound having a hardness of 2 or more and 70 or less, particularly 3 or more and 60 or less, furthermore 5 or more and 40 or less based on ASTM D2240 (spring type hardness test A type: JIS K6301) is preferably used. .

As the recording auxiliary layer for promoting the change, for example, a material which does not diffuse the heat generated in the recording layer from the recording layer and can effectively utilize the heat for generating the change in the recording layer is preferable. For example, a material having a low temperature diffusivity (thermal conductivity / heat capacity),
× 10 ⁻³ cm ² / s or less, especially 1 × 10 ⁻⁴ to 1 × 10 ⁻³
A material of cm ² / s is preferable, and when recording is performed by deformation of the recording layer, a material that does not suppress the above-described deformation of the recording layer is also preferable. It is preferable that such a material be appropriately selected from, for example, silicone rubber, urethane rubber, styrene and butadiene rubber. In particular, silicone rubber does not suppress deformation of the recording layer and does not cause decomposition or the like due to heat generated in the recording layer at a low temperature diffusivity. It can be suitably used as an auxiliary layer.

The recording auxiliary layer has a thickness of 0.1 to
50 μm, particularly preferably 0.5 to 10 μm.

The material used for the recording auxiliary layer is preferably a material that can be formed on the recording layer by coating. That is, according to the coating, it can be formed accurately on the recording area of the recording layer, and the recording sensitivity in the recording area can be made uniform. Further, unevenness in recording sensitivity and unevenness in reflectance do not occur with respect to bending which is likely to occur in a portable optical recording medium.

Specific examples of such a material include an ultraviolet-curable silicone rubber and a thermosetting silicone rubber. These materials are applied on a recording layer and then cured by a predetermined method. Thereby, a recording auxiliary layer can be formed.

Further, a resin film may be used as the recording auxiliary layer. In this case, deformation of the recording layer due to recording is not suppressed by forming a micro air layer between the recording layer and the resin film by laminating a resin film on the recording layer without an adhesive layer, and The heat utilization efficiency is improved, and the recording sensitivity of the recording area can be improved.
Examples of the resin film that can be used here include, for example, an acrylic resin, a polyester resin, a polycarbonate resin, a vinyl resin, a polysulfone resin, a polyimide resin, a polyacetal resin, a polyolefin resin, a polyamide resin, a vinylidene resin, a cellulose derivative, or a derivative thereof. Copolymer vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, vinyl acetate-acrylate copolymer, styrene-butadiene copolymer film and Silicone rubber formed into a sheet shape can be used.

Of these, silicone rubber and polyester resin formed on the sheet, especially polyethylene terephthalate, are preferred.

The thickness of the resin film is preferably 0.05 to 100 μm, particularly preferably 0.1 to 50 μm.

Next, the recording suppression layer of the present invention changes the intensity of the energy beam required to cause some change (for example, reflectance) in the recording layer outside the recording area of the optical card. It is intended to make the recording layer area 35 outside the recording area lower in sensitivity than the recording area so that the intensity of the energy beam required to generate the energy beam is higher than the intensity of the energy beam. A material that does not decrease the temperature is preferably used, and specifically, for example, a material having a high temperature diffusivity capable of diffusing heat causing deterioration of the recording layer without accumulating the heat in the recording layer.
Here, the material having a high temperature diffusivity is preferably at least larger than a normal resin material, for example, more than 1 × 10 ⁻³ cm ² / s, particularly 1 × 10 ^{−2 to 2} cm ² / s.
Further, at 1 × 10 ^{−2 to} 1 cm ² / s, ordinary resin is 1 × 10 ^−3.
Those that are at least one digit larger than cm ² / s are preferably used.

As such a material, for example, SiO ₂ , T
iO ₂ , Si ₃ N ₄ , Al ₂ O ₃ , ZnO, AlN, ZnS
And metal such as Al, Ag, and Au. Further, a resin adhesive or the like in which metal particles or inorganic dielectric particles such as alumina are dispersed to improve the temperature diffusivity can be used. In this case, the recording suppressing layer 7 and the adhesive layer 4 shown in FIG. Can be changed.

In the present invention, the recording suppression layer is made of Si ₃
When a material having a large temperature diffusivity such as N ₄ or metal is used,
Since the sensitivity of the region 35 can be further reduced, the intensity of the reproduction light can be further increased, and an optical card capable of reproducing a signal having an excellent S / N ratio can be obtained, which is preferable. The relationship between the optical recording medium of the present invention and the intensity of the reproduction light will be described later.

The thickness of the recording suppressing layer of the present invention varies depending on the material to be used, but is preferably about 0.01 to 50 μm. In particular, in the case of a metal or inorganic dielectric, about 0.01 to 1 μm provides sufficient recording layer sensitivity. The suppression effect is obtained.

The recording auxiliary layer and the recording suppression layer according to the present invention are used as recording areas 3 due to the interference effect of these layers.
It is preferable to select a material whose refractive indexes are close to each other so that the reflectances of the recording area 4 and the area 35 outside the recording area do not greatly differ from each other. -Dispersion of metal particles of vinyl acetate copolymer.

Further, when a reflective material such as metal is used as the recording suppressing layer, the structure shown in FIG. 1A, that is, the recording suppressing layer 7 is used so that the reflectivity of the recording area 34 and the area 35 outside the recording area do not greatly differ. Can be laminated so as to cover not only the region 35 but also the recording auxiliary layer 6.

FIG. 5A is a schematic sectional view of another embodiment of the optical card according to the present invention, in which a recording suppressing layer and a recording auxiliary layer are laminated in respective regions.

Next, as the transparent substrate 5 of the optical recording medium of the present invention, a transparent substrate which is less inconvenient in optical recording / reproducing is preferable.
Polycarbonate resins, vinyl resins, polysulfone resins, polyimide resins, polyacetal resins, polyolefin resins, polyamide resins, cellulose derivatives, and the like can be used.

For forming the track groove 2 on the transparent substrate,
When the transparent substrate is a thermoplastic resin, a method of thermally transferring a stamper mold by a method such as injection molding or hot press forming at a temperature equal to or higher than the melting point, or applying a photocurable resin composition on the transparent substrate Then, the stamper mold is brought into close contact with the photocurable resin composition by irradiating ultraviolet rays or the like to cure the photocurable resin composition.

In the case of the thermal transfer method, the track groove portion and the transparent substrate are the same, whereas in the case of the optical transfer method,
The track groove is bonded to the transparent base member instead of being the same. Alternatively, separately from the stamper-type transfer method, a resist film is formed on a transparent base material having a light-transmitting thin film having a desired thickness which can be etched, and the resist film is exposed through a photomask having a track groove pattern and developed. Then, a resist pattern is formed, and the thin film is etched using the resist pattern as a mask to form a track portion on the transparent substrate.

The transparent substrate 5 may be subjected to a pretreatment for improving adhesiveness, such as a corona discharge treatment, a plasma treatment, a primer treatment, and an ozone treatment, if necessary.

As the protective substrate 1, any material that can be used as an ordinary card base material can be used. Specifically, polyvinyl chloride, a fluorine-substituted ethylene polymer, a vinyl chloride-vinyl acetate copolymer , Acrylic polymers such as polyvinylidene chloride, polymethyl methacrylate,
Polystyrene, polyvinyl butyral, acetyl cellulose, styrene-butadiene copolymer, polyethylene,
Polypropylene, polycarbonate, epoxy, acrylonitrile-butadiene-styrene copolymer and the like are used.

In some cases, metal sheets such as iron, stainless steel, aluminum, tin, copper, and zinc, synthetic paper, paper,
A wide variety of materials can be used depending on the application, such as fiber reinforced plastics, composites of metal powders such as magnetic substances and plastics, and ceramics. Of course, a material used for a transparent substrate may be used.

The optical recording layer 3 has a wavelength near the light source used,
For example, when the wavelength of the energy beam for reproduction is 650 nm or more, particularly 700 to 900 nm, it is preferable that the difference between the reflectance of the bit or the like as the recording portion and the reflectance of the unrecorded portion is large. In order to be absorbed, it is necessary to have absorption in the above wavelength range.

It is preferable that the energy required to cause a change in reflectance by irradiation of the recording energy beam be small. Further, it is preferable that the reflectivity of the recorded portion (bit or the like) and the unrecorded portion hardly change by the energy beam for reproduction.

An organic thin film whose optical property can be changed optically by an energy beam can be continuously applied by a solution or a dispersion system, and is preferable for mass production.

For example, anthraquinone derivatives (hereinafter referred to as having an indathrene skeleton), dioxazine compounds and derivatives thereof, triphenodithiazine compounds, phenanthrene derivatives, cyanine compounds, merocyanine compounds, pyrylium compounds, xanthene compounds, Examples include phenylmethane compounds, croconium dyes, azo dyes, crocones, azines, indigoids, methine dyes, polymethine dyes, azulenes, squarium derivatives, sulfur dyes, and metal dithiolate complexes.

The present invention is particularly effective for an optical recording medium using the following cationic dye in the recording layer.

The cationic dyes are listed below.

A polymethine dye represented by the general formula (I).

[0070]

[Outside 1] In the formula, A, B, D and E each represent a group selected from a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a styryl and a heterocyclic group. r ₁ ′ and r ₂ ′ are hydrogen atoms,
Alkyl group, cyclic alkyl group, alkenyl group, aralkyl group and aryl

[0071]

Wherein k is 0 or 1, 1 is 0, 1
Or 2 with X Represents an anion.

The aralkyl group, aryl group, styryl group and heterocyclic group in A, B, D, E, r ₁ ′ and r ₂ ′ may be substituted.

A dye represented by formula (II):

[0074]

[Outside 3]

[0075]

Wherein A, B, D, E and X Is as defined above, and r₁~ R_Five
Is a hydrogen atom, halogen atom, alkyl group or aryl
Represents a group. Y is required to complete a 5- or 6-membered ring
A divalent residue having an atomic group is shown. m and n are 0, 1 or
Is 2.

A dye represented by formula (III):

[0077]

[Outside 5]

[0078]

Where A, B, D, E, r_Two, R_Three, Y and X Is the same as above
Righteous. A dye represented by the general formula (IV).

[0079]

[Outside 7] In the formula, A, B, D, E, r ₁ , r ₂ , r ₃ , r ₄ , m and n are as defined above.

[0080]

[Outside 8]

An azulenium dye represented by formula (V), (VI) or (VII).

[0082]

[Outside 9]

Here, R _{1 to} R ₇ represent a hydrogen atom, a halogen atom (a chlorine atom, a bromine atom, an iodine atom) or a monovalent organic residue. The monovalent organic residue can be selected from a wide range.

R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R
_A substituted or unsubstituted condensed ring may be formed by at least one of combinations of ₄ and R ₅ , R ₅ and R _6, and R ₆ and R ₇ . The condensed ring is a 5-, 6-, or 7-membered condensed ring, and includes an aromatic ring (benzene, naphthalene, chlorobenzene, bromobenzene, methylbenzene, ethylbenzene, methoxybenzene, ethoxybenzene, etc.),
Heterocycles (furan ring, benzofuran ring, pyrrole ring, thiophene ring, pyridine ring, quinoline ring, thiazole ring, etc.) and aliphatic rings (dimethylene, trimethylene, tetramethylene, etc.)

[0085]

[Outside 10] X Represents an anion as defined above. F represents a divalent organic residue linked by a double bond
You. Specific examples of the present invention containing such F are represented by the following general formula:
List those represented by (1) to (12)

[0086]

[Outside 11] Where Q in the formula Is the following azurenium salt nucleus
And Q in the formula The right side except F indicates F.

[0087]

[Outside 12] R ₁ ′ to R ₇ ′ have the same meanings as R _{1 to} R ₇ .

[0088]

[Outside 13] Q And the azurenium salt nucleus represented by the formula (3)
May be symmetrical with the azulene salt nucleus on the right side of
It may be asymmetric.

[0089]

[Outside 14] In the formula, M represents a group of nonmetal atoms necessary to complete the nitrogen-containing heterocyclic ring.

[0090]

[Outside 15] In the formula, R ₁₀ represents a substituted or unsubstituted aryl group or a cationic group thereof. P represents an integer from 1 to 8. q is 1 or 2.

[0091]

[Outside 16] In the formula, R ₁₁ represents a heterocyclic group or a cationic group thereof.

[0092]

[Outside 17] In the formula, R ₁₂ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group.

[0093]

[Outside 18]

[0094]

[Outside 19] In the formula, Z ₂ represents an optionally substituted pyran, thiapiran, selenapyran, telluropyran, benzopyran, benzothiapyran, benzoselenapyran, benzotellopyran, naphthopyran, naphthothiapyran or naphthoselenapyran, an atom group necessary for completing naphthotellopyran. Is shown.

L represents a sulfur atom, an oxygen atom or a selenium atom, a tellurium atom.

R ₁₃ and R ₁₄ represent a hydrogen atom, an alkoxyl group, a substituted or unsubstituted aryl group, an alkenyl group or a heterocyclic group.

In addition, as a suitable dye, general (VII)
Dyes represented by I), (IX), (X) and (XI).

[0098]

[Outside 20]

The above formulas (VIII), (IX),
In (X) and (XI), L ₁ and L ₂ represent a sulfur atom, an oxygen atom, a selenium atom or a tellurium atom, and Z ₁ represents an optionally substituted pyrylium, thiopyrylium, selenapyrylium, telluropyrylium, benzopyri Group of atoms necessary to complete ium, benzothiopyrylium, benzoselenapyrylium, benzotelluropyrylium, naphthopyrylium, naphthothiopyrylium, naphthoselenapyrylium or naphthoterropyrilium, Z ₂ may be substituted Pyran, thiopyran, selenapyran, tellropyran,
The benzopyran, benzothiopyran, benzoselenapyran, benzotelluropyran, naphthopyran, naphthothiopyran, naphthoselenapyran, or a group of atoms necessary to complete naphthotellopyran are shown. S is 0 or 1. R ₁₅ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. (The same as r ₁ ′ and r ₂ ′ described above for r ₃ ′ to r ₇ ′.)

[0100]

[21] k, n, M, r₁', R_Two', R₁, Y, Z , X Is before
It is synonymous with the statement. Abbreviations in the above general formula will be described in more detail.

A, B, D and E each represent a hydrogen atom or an alkyl group (for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, iso-butyl group) , T-butyl group, n-amyl group, t-amyl group, n-hexyl group, n-octyl group,
t-octyl group), and other alkyl groups,
For example, a substituted alkyl group (for example, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 2-acetoxyethyl group, carboxymethyl group,
-Carboxyethyl group, 3-carboxypropyl group, 2
-Sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-sulfatepropyl group, 4-sulfatebutyl group, N- (methylsulfonyl) -carbamylmethyl group, 3- (acetylsulfamyl) propyl Group,
4- (acetylsulfamyl) butyl group and other cyclic alkyl groups (eg, cyclohexyl group), alkenyl groups (vinyl, propenyl, pthenyl, pentenyl, hexenyl, heptenyl, octenyl, dodecynyl) , Prenyl group, etc.), aralkyl group (for example,
Benzyl group, phenethyl group, α-naphthylmethyl group, β
-Naphthylmethyl group) and substituted aralkyl groups (for example, carboxybenzyl group, sulfobenzyl group, hydroxybenzyl group, etc.). Further, R ₁ , R ₂ ,
R ₃ , R ₄ and R ₅ represent a substituted or unsubstituted aryl group (for example, phenyl, naphthyl, tolyl, xylyl, methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, ethoxyphenyl, dimethylamino) Phenyl group, diethylaminophenyl group, dipropylaminophenyl group, dibenzylaminophenyl group,
A substituted or unsubstituted heterocyclic group (eg, pyridyl group, quinolyl group, lepidyl group, methylpyridyl group, furyl group, thienyl group, indolyl group, pyrrole group, carbazolyl group, N-ethylcarba) Zolyl group) or substituted or unsubstituted styryl group (for example, styryl group, methoxystyryl group, dimethoxystyryl group, trimethoxystyryl group, ethoxystyryl group, dimethylaminostyryl group, diethylaminostyryl group, dipropylaminostyryl group , A dibenzylaminostyryl group, a diphenylaminostyryl group,
2,2-diphenylvinyl group, 2-phenyl-2-methylvinyl group, 2- (dimethylaminophenyl) -2-phenylvinyl group, 2- (diethylaminophenyl) -2
-Phenylvinyl group, 2- (diethylaminophenyl)
-2-phenylvinyl group, 2- (dibenzylaminophenyl) -2-phenylvinyl group, 2,2-di (diethylaminophenyl) vinyl group, 2,2-di (methoxyphenyl) vinyl group, 2,2- Di (ethoxyphenyl) vinyl group, 2- (dimethylaminophenyl) -2-methylvinyl group, 2- (diethylaminophenyl) -2-ethylvinyl group and the like.

R ₁ ', r ₂ ', r ₃ ', r ₄ ' r ₅ ', r ₆ ,
r ₇ ′ represents a hydrogen atom or an alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group,
n-butyl group, sec-butyl group, iso-butyl group,
t-butyl group, n-amyl group, t-amyl group, n-hexyl group, n-octyl group, t-octyl group, etc.), and further another alkyl group such as a substituted alkyl group.
(E.g., 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-acetoxyethyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 2-sulfoethyl,
3-sulfopropyl group, 4-sulfobutyl group, 3-sulfopropyl group, 4-sulfobutyl group, N-
(Methylsulfonyl) -carbamylmethyl group, 3- (acetylsulfamyl) propyl group, 4- (acetylsulfamyl) butyl group and the like, cyclic alkyl group (for example,
Alkenyl group (eg, cyclohexyl group), alkenyl group (eg, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, dodecynyl group, prenyl group), aralkyl group (eg, benzyl group, phenethyl group, α- Naphthylmethyl group, β-naphthylmethyl group, etc.) and substituted aralkyl groups (eg, carboxybenzyl group, sulfobenzyl group, hydroxybenzyl group, etc.). Further, R ₁ , R ₂ , R ₃ , R ₄ and R ₅
Is a substituted or unsubstituted aryl group (for example, phenyl group, naphthyl group, tolyl group, xylyl group, methoxyphenyl group, dimethoxyphenyl group, trimethoxyphenyl group, ethoxyphenyl group, dimethylaminophenyl group,
A diethylaminophenyl group, a dipropylaminophenyl group, a dibenzylaminophenyl group, a diphenylaminophenyl group, etc.), r ₁ , r ₂ , r ₃ , r ₄ and r ₅ are a hydrogen atom, a halogen atom (a chlorine atom, a bromine atom, Iodine atom, etc.), alkyl group (methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-amyl, n
-Hexyl, n-octyl, 2-ethylhexyl, t-
Octyl, etc.), alkoxy groups (methoxy, ethoxy,
A substituted or unsubstituted aryl group (phenyl, tolyl, xylyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, chlorophenyl, nitrophenyl, dimethylaminophenyl, α-
Naphthyl, β-naphthyl, etc.). Y is a divalent hydrocarbon group, for example _{-CH 2 -CH 2 -, - (} CH 2) 3 -,

[0103]

[Outside 22] -CH = CH-,

[0104]

[Outside 23] And the 5- or 6-membered ring may be condensed with a benzene ring, a naphthalene ring or the like.

R _{1 to} R ₇ and R ₁ 'to R ₇ ' each represent a hydrogen atom,
Halogen atoms (chlorine, bromine, iodine, etc.)
In addition, an alkyl group (methyl, ethyl, n-propyl,
Isopropyl, n-butyl, t-butyl, n-amyl,
n-hexyl, n-octyl, 2-ethylhexyl, t
-Octyl, etc.), alkoxy groups (methoxy, ethoxy, propoxy, butoxy, etc.), substituted or unsubstituted aryl groups (phenyl, tolyl, xylyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, chlorophenyl, nitrophenyl, dimethylaminophenyl,
α-naphthyl, β-naphthyl, etc.) and substituted or unsubstituted aralkyl groups (benzyl, 2-phenylethyl,
-Phenyl-1-methylethyl, bromobenzyl, 2-
Bromophenylethyl, methylbenzyl, methoxybenzyl, nitrobenzyl), acyl group (acetyl, propionyl, butyryl, valeryl, benzoyl, trioil, naphthoyl, phthaloyl, furoyl, etc.), substituted or unsubstituted amino group (amino, dimethylamino, diethylamino) , Dipropylamino, acetylamino, benzoylamino, etc.), substituted or unsubstituted styryl groups (styryl, dimethylaminostyryl, diethylaminostyryl, dipropylaminostyryl, methoxystyryl, ethoxystyryl, methylstyryl, etc.), nitro group, hydroxy group , A carboxyl group, a cyano group, or a substituted or unsubstituted arylazo group (phenylazo, α-naphthylazo, β-naphthylazo, dimethylaminophenylazo, chlorophenyl Luazo, nitrophenylazo,
Methoxyphenylazo, tolylazo, etc.).

Further, R ₁ ′ to R ₇ ′ may form a condensed ring similarly to R _{1 to} R ₇ .

R ₈ represents a hydrogen atom, a nitro group, a cyano group,
Represents an alkyl group (eg, methyl, ether, propyl, butyl) or an aryl group (eg, phenyl, tolyl, xylyl).

R ₉ is an alkyl group (methyl, ethyl, propyl, butyl, etc.), a substituted alkyl group (2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 3
-Hydroxypropyl, 3-methoxypropyl, 3-ethoxypropyl, 3-chloropropyl, 3-bromopropyl, 3-carboxypropyl, etc., cyclic alkyl groups (cyclohexyl, cyclopropyl), allyl, aralkyl groups (benzyl, -Phenylethyl, 3-phenylpropyl, 4-phenylbutyl, α-naphthylmethyl,
β-naphthylmethyl), substituted aralkyl groups (methylbenzyl, ethylbenzyl, dimethylbenzyl, trimethylbenzyl, chlorobenzyl, promobenzyl, etc.), aryl groups (phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl) or substituted aryl Represents a group (chlorophenyl, dichlorophenyl, trichlorophenyl, ethylphenyl, methoxyphenyl, dimethoxyphenyl, aminophenyl, nitrophenyl, hydroxyphenyl, etc.).

R ₁₀ is a substituted or unsubstituted aryl group (phenyl, tolyl, xylyl, biphenyl, α-naphthyl, β-naphthyl, anthralyl, pyrenyl, methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, ethoxyphenyl, diethoxyphenyl , Chlorophenyl, dichlorophenyl, trichlorophenyl, bromophenyl, dibromophenyl, tripromophenyl,
Ethylphenyl, diethylphenyl, nitrophenyl,
Aminophenyl, dimethylaminophenyl, diethylaminophenyl, dibenzylaminophenyl, dipropylaminophenyl, morpholinophenyl, piperidinylphenyl, piperazinophenyl, diphenylaminophenyl, acetylaminophenyl, benzoylaminophenyl, acetylphenyl, benzoylphenyl , Cyanophenyl, etc.) R ₁₁ represents a monovalent heterocyclic group derived from a heterocyclic ring such as furan, thiophene, benzofuran, thionaphthene, dibenzofuran, carbazole, phenothiazine, phenoxazine, pyridine and the like.

R ₁₂ is a hydrogen atom, an alkyl group (methyl, ethyl, propyl, butyl, etc.) or a substituted or unsubstituted aryl group (phenyl, tolyl, xylyl, biphenyl, ethylphenyl, chlorophenyl, methoxyphenyl, ethoxyphenyl, nitrophenyl Phenyl, aminophenyl, dimethylaminophenyl, diethylaminophenyl, acetylaminophenyl, α-naphthyl, β-naphthyl, anthralyl, pyrenyl and the like).

R ₁₃ and R ₁₄ are a hydrogen atom, an alkyl group (eg, methyl, ethyl, propyl, butyl), an alkoxyl group (eg, methoxy, ethoxy, propoxy, ethoxyethyl, methoxyethyl), and an aryl group (phenyl, tolyl, xylyl). , Chlorophenyl, biphenyl, methoxyphenyl, etc.), substituted or unsubstituted styryl groups (such as styryl, P-methylstyryl, O-chlorostyryl, P-methoxystyryl), substituted or unsubstituted 4-phenyl-1,3-butadienyl Group (4-phenyl 1,3-butadienyl, 4- (P-methylphenyl)-
1,3-butadienyl and the like, or a substituted or unsubstituted heterocyclic group (quinolyl, pyridyl, carbazolyl, furyl and the like).

M is pyridine, thiazole, benzothiazole, naphthothiazole, oxazole, benzoxazole, naphthoxazole, imidazole, benzimidazole, naphthoimidazole, 2-quinoline, 4-quinoline,
A group of atoms necessary to complete a nitrogen-containing heterocyclic ring such as quinoline, isoquinoline, or indole. Halogen atom (chlorine atom, bromine atom, iodine atom, etc.), alkyl group (methyl, ethyl, propyl, butyl, etc.), aryl group (Phenyl, tolyl, xylyl, etc.) and aralkyl (benzyl, P-tolylmethyl, etc.).

R ₁ ′ to r ₇ ′ are a hydrogen atom, a substituted or unsubstituted alkyl group (methyl, ethyl, propyl, isopropyl, butyl, t-butyl, amyl, isoamyl, hexyl, octyl, nonyl, dodecyl, methoxyethyl , Hydroxyethyl, carboxypropyl, etc.), substituted or unsubstituted aryl groups (phenyl, α-naphthyl, β-naphthyl, tolyl, xylyl, biphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl,
Dimethoxyphenyl, hydroxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, nitrophenyl, diethylaminophenyl, dimethylaminophenyl, dibenzylaminophenyl, etc.), a substituted or unsubstituted aralkyl group (benzyl,
Phenethyl, 3-phenylpropyl, methoxybenzyl, methylbenzyl, chlorobenzyl, etc.).

[0114]

Where k and s are 0 or 1, 1, m and n are 0, 1 or 2.
is there. X Is an anion, chloride ion, bromide ion
, Iodide ion, perchlorate ion, benzene sulfone
Honacetate ion, P-toluenesulfonate ion,
Tyl sulfate ion, ethyl sulfate ion, propyl sulfate
Salt ion, tetrafluoroborate ion, tetrafe
Nylborate ion, hexafluorophosphate ion,
Benzenesulfinate ion, acetate ion, trif
Luoro acetate ion, propion acetate ion, benzoic acid
Ion, oxalate ion, succinate ion,
Lonate ion, oleate ion, stearate
Ion, citrate ion, monohydrogen diphosphate ion,
Dihydrogen monophosphate ion, pentachlorostannate ion
, Chlorosulfonate ion, fluorosulfonate
Ion, trifluoromethanesulfonate ion,
Safluoroantimonate ion, molybdate ion
, Tungstate ion, titanate ion, jill
Represents citrate ions and the like.

The organic thin film containing such a dye is applied by a known coating method. For example, methods such as dip coating, spray coating, spinner coating, bar coating, roll coating, blade coating, and curtain coating can be used. The thickness of the thin film is generally 500-2000.
Å, preferably around 1000 °. In particular, the thickness is small from the viewpoint of recording sensitivity, and it is desirable to increase the thickness from the viewpoint of the S / N ratio of reproduction. The optimum film thickness differs depending on the type of dye.

Further, in order to prevent deterioration of the optical recording layer due to irradiation of light for reproduction, a stabilizer may be mixed with these dyes. For example, the stabilizer is selected from the following,
The selection is made in consideration of the compatibility with the dye and the solvent. The addition amount can be from several weight% to 50 weight% with respect to the dye, but if the addition amount is small, the effect as a stabilizer cannot be seen so much.
When added in excess of 0% by weight, a decrease in sensitivity is observed due to a decrease in the absolute amount of the heat mode recording material. Therefore, the content is preferably 10% by weight to 30% by weight based on the dye. Especially,
Those having a high effect without deterioration in sensitivity are around 20% by weight.

As such a stabilizer, various metal chelate compounds, in particular, Zn, Cu, Ni, Cr, Co, Mn,
A polydentate ligand having Pd or Zr as a central metal, for example, N ₄ ,
A tetradentate ligand such as N ₂ O ₂ , N ₂ S ₂ , S ₄ , O ₂ S ₂ , O ₄ or a tridentate ligand such as N ₂ O, NO ₂ , NS ₂ , O ₃ , NOS; Other ligands such as water, ammonia, halogens, phosphines, amines, arsine, olefins, etc., or two tetradentate forms of two bidentate ligands N ₂ , NO, O ₂ , S ₂ , bis Cyclopentagenenyl ligand, cyclopentagenyl-tropyrinium ligand system, or a combination of the above, etc., as well as various aromatic amines and diamines,
Nitrogen-containing aromatics and onium salts thereof, for example, aminium salts, diimonium salts, pyridinium salts, imidazolinium salts, quinolinium salts and the like. Further, pyrylium salt or the like, which is an oxygen-containing aromatic salt, may be used. It is also possible to use a combination of two or more of these quenchers, and the composition is appropriately determined in consideration of the coating properties of the dye composition, the stability of the coating film, optical characteristics (reflectance and transmittance), recording sensitivity, and the like. The ratio can be changed.

In addition to the dyes described above as materials used for the recording layer of the optical recording medium of the present invention, for example, the following formula (X)
Photochromic materials represented by spiropyran-based dyes shown in II),

[0119]

[Outside 25] Tb-Fe, Gd-Fe, Dy-Fe, Tb-Fe-C
Amorphous magneto-optical recording materials such as o, Gd-Fe-Co, Gd-Tb-Fe can also be used.

Next, the adhesive constituting the adhesive layer 4 is as shown in FIG.
As shown in (a), since the optical recording layer 3 is covered with the recording auxiliary layer 6 and the recording suppression layer 7, a wide range can be used. For example, vinyl acetate, vinyl acetate acrylic, vinyl acetate copolymer, vinyl acetate emulsion, acrylic, acrylate, acrylic copolymer,
Ethylene, ethylene vinyl acetate, ethylene vinyl acetate copolymer, polyethylene, methylene chloride, polyamide, polyamide-amine, polyimide, urea, epoxy, epoxy urethane, epoxy acrylate, urethane acrylate , Polyester,
Chloroprene, chloroprene rubber, nitrile, nitrile rubber, urethane, vinyl urethane, polyurethane, olefin, cyanoacrylate, alkyl acrylate, vinyl chloride, phonol, S
BR (styrene butadiene rubber), polyol, silica-alumina, synthetic rubber, emulsion, oligoester, cellulose, formaldehyde, ultraviolet curable, organic solvent, styrene butadiene freon T
A system etc. can be used. At the time of bonding, materials requiring energy such as heat, light, and an electron beam are also effective as long as the energy does not deteriorate the function of the optical recording material.

Next, a method and apparatus for reproducing recorded data on an optical recording medium according to the present invention will be described.

The reproduction of data recorded in a coded state on the information recording track in the recording area of the optical recording medium of the present invention is reproduced by a reproducing apparatus as shown in FIG. That is, the apparatus includes a driving unit 46 for reciprocating the optical recording medium 11 in the direction A with respect to the reproduction light 47, an emission system for emitting the reproduction light, and an optical system for detecting reflected light from the optical recording medium, and a focus of the reproduction light. An optical head 41 having a reproduction light drive system for performing servo, radial servo, and the like is provided.
Then, the optical recording medium of the present invention is driven in a predetermined direction at a predetermined speed by the driving system 46, whereby the reproduction light scans the information recording track 33 to reproduce data.
When the reproduction of one track is completed, the optical head is driven in the direction traversing the track, and the track servo is further performed to allow the reproduced light to access another information recording track.
Next, the data of this track is reproduced by driving the optical recording medium in the direction opposite to the above by the driving system. Further, in the reproduction of the data of the optical recording medium of the present invention, the movement speed of the optical recording medium with respect to the reproduction light is reduced and stopped with the reversal of the moving direction of the optical recording medium. It is preferably performed when the recording layer is in a recording layer area 35 other than the above. That is, since the sensitivity of this area is reduced with respect to the reproduction light, the recording layer is not deteriorated by the reproduction light even when the relative sensitivity of the optical recording medium is increased due to the decrease and the stop of the moving speed.

The direction of movement of the optical card of the present invention can be reversed by, for example, detecting the amount of movement of the optical head relative to the optical card or detecting the information pits recorded on the information recording track, so that the reproduction light is reflected in the area 35. Detecting the entry, the control system 48 reverses the drive direction of the drive means.

Next, the relationship between the optical recording medium of the present invention and the intensity of the reproduction light will be described. In the optical recording medium of the present invention, the sensitivity of the recording layer area 35 outside the recording area is greatly reduced by the recording suppression layer, so that a high-intensity reproduction light can be used, and a higher S / N ratio can be obtained. This makes it possible to perform signal reproduction.

That is, a conventional optical card having a high sensitivity,
For example, as shown in FIG. 7, the energy required to cause a change in the recording layer at the time of driving and stopping at the recording speed of the optical card in which the entire optical recording layer is covered with the film coating layer 71 and the position of the optical card. FIG. 8 shows the relationship with. In FIG. 8, the solid line shows the amount of energy required to change the recording layer at each position of the recording layer of the optical card when the optical card is stopped, and the broken line changes the recording layer in the recording area when the optical card is driven. Shows the amount of energy (power of the laser beam) required for the laser beam. As shown in FIG. 8, in the conventional optical card, the recording layer is changed by the irradiation of the laser beam having the intensity b or more during driving, and the recording layer is changed by the energy not less than a when stopped. Must be performed with an energy less than a in order to prevent a change in the recording layer in the stop reversal area at the end of the optical card. In contrast,
In the optical card according to the present invention, as shown in FIGS. 9 and 10, the recording layer area 35 outside the recording area is changed in the recording layer for the first time by a laser beam having an intensity of c or more.
Therefore, a high intensity laser beam having an intensity of a or more and less than c (in the case of FIG. 9) and a light intensity of b or more and less than b (in the case of FIG. 10) can be used as a laser beam for reproducing the optical card. The S / N signal can be reproduced.

In the present invention, no change in the recording layer is defined as follows.

I) When stopped: The decrease in the reflectance of the recording layer when the laser beam is continuously irradiated for 180 seconds is within 5%.

II) At the time of driving: a decrease in reflectance due to repetitive reproduction of 5000 passes is within 2%.

[0129]

The present invention will be specifically described below with reference to examples.

[Example 1] Thickness: 0.4 mm, length: 85 m
m, pitch 1 on 54 mm wide polycarbonate sheet
A stripe-shaped guide groove pattern having a groove width of 2 μm, a groove width of 3 μm, and a groove depth of 3000 ° was thermally transferred using a stamper type (compression method) to obtain a transparent substrate 5. On this substrate, a polymethine-based dye represented by the following structural formula [I] and a stabilizer represented by the following structural formula [II] are mixed at a ratio of 3: 1 and dissolved in a diacetone alcohol solvent to form a gravure roll coater. About 1000 ° C.

[0131]

[Outside 26]

Next, an ultraviolet-curable silicone rubber (trade name: TUV6000; manufactured by Toshiba Silicone Co., Ltd.) was applied to the recording layer 34 with a thickness of about 79.6 mm × 30 mm using a gravure roll coater only on the recording area 34. 10 μm
And then cured by irradiating ultraviolet rays to form a recording auxiliary layer 6 having a temperature diffusivity of 4.3 × 10 ⁻⁴ cm ² / S hardness 25.

On the other hand, an ethylene-vinyl acetate hot melt adhesive (trade name: Evaflex-EV210 Mitsui
DuPont Co., Ltd.) mixed with alumina beads having a particle size of 20 μm (trade name: CB-A20S; manufactured by Showa Titanium) at a weight ratio of 1: 1 to form a sheet having a thickness of 50 μm and a recording suppressing layer / adhesive layer. A hot melt adhesive sheet functioning as was prepared. And through this adhesive sheet,
Transparent substrate 5 and protective substrate (polycarbonate, thickness 0.3
mm), and the hot melt adhesive sheet covers the recording layer outside the recording area. An optical card whose cross section is shown in FIG. The hot melt adhesive sheet has a temperature diffusivity of 1.3 × 10 ⁻² cm ² / s.

To examine the recording sensitivity of this optical card,
The laser power at which stable recording was possible in the recording area 34 was measured. The results are shown in Table (1). still,
Here, the recording condition is that the laser beam moving speed is (a) 60
mm / s (b) 400 mm / s The spot diameter is 3.0 μm. Table 1 shows the results.

The stable recording means the recording contrast in the present invention.

[0136]

[Outside 27] R ₁ : RF output level of the non-recording portion, R ₂ : RF output level of the recording portion) is 0.6 or more.

When reproducing information, the recorded information must not be destroyed. Therefore, I) when the beam is stopped, II) when the beam is moving (400 m
(m / s), the power of the reproduction light was examined to the extent that the information was not destroyed. It should be noted that not destroying information is defined as follows. I) When stopped: The rate of decrease in reflectance due to continuous irradiation for 180 seconds is within 5%. II) During movement: The decrease in reflectance due to repeated reproduction of 5000 passes is within 2%. That is, this is synonymous with no change in the recording layer.

The result is shown in FIG.

That is, the recording area 34 of the optical card of the first embodiment.
In (2), when there is no relative movement between the optical card and the reproduction light [(I): solid line portion], a change occurs in the recording layer with a laser beam of 0.1 mW, and the relative position between the optical card and the reproduction light is changed. When there is any movement [(II): dotted line], the recording layer is changed by a laser beam of 0.8 mW. On the other hand, in the recording layer area 35 outside the recording area, when there is no relative movement between the optical card and the reproduction light, the recording layer is changed by the laser beam of 0.6 mW.

However, in this embodiment, an optical card evaluation device (manufactured by Canon) equipped with a semiconductor laser beam having a wavelength of 830 nm was used for evaluation of the optical card.

Example 2 Casting sheet (0.4 mm thick) of polymethyl methacrylate (PMMA)
Photo-curing resin (trade name: 30X, manufactured by Three Bond Co., Ltd.)
717), a guide groove having a pitch of 12 μm, a groove width of 3 μm, and a groove depth of 3000 ° was transferred by the 2P method to obtain a transparent substrate 5. A recording layer was formed on this substrate in the same manner as in Example 1. Further, a thermosetting silicone rubber (trade name: TSE3033; manufactured by Toshiba Silicone Co., Ltd.) is applied to a thickness of 0.75 μm only on the recording area 34 of the recording layer, and 100
Cured at 1 ° C. for 1 hour, temperature diffusivity 4.1 × 10 ^-4 cm ²
/ S and a recording auxiliary layer 6 having a hardness of 30 were formed. Next, Al is vapor-deposited to a thickness of about 500 ° so as to cover the recording auxiliary layer 6 and the recording layer outside the recording area not covered with the recording auxiliary layer 6, and has a temperature diffusivity of 9.4 × 10 ^−1. A recording suppression layer 7 of cm ² / s was formed. And this substrate and the protection substrate (P
An MMA casting sheet (thickness: 0.3 mm) was bonded using an ultraviolet curable adhesive (trade name: Three Bond 3000, manufactured by Three Bond Co., Ltd.).
An optical card shown in (a) was produced.

The optical card obtained here was evaluated in the same manner as in Example 1. The results are shown in Table 1 and FIG.

Comparative Example 1 After forming a recording layer in the same manner as in Example 1, a recording auxiliary layer (trade name: TUV600, manufactured by Toshiba Silicone Co., Ltd.) was formed not only in the recording area but also in the inversion area.
0) was formed into a film having a thickness of about 10 μm using a gravure roll coater, and bonded to a protective substrate using a hot melt adhesive (trade name: Evaflex EV250, manufactured by DuPont Mitsui) to obtain an optical card.

The optical card thus obtained was evaluated in the same manner as in Example 1, and the results are shown in Table 1 and FIG.

Comparative Example 2 After forming a recording layer in the same manner as in Example 1, without forming a recording auxiliary layer and a recording suppressing layer, the temperature diffusivity was 6.6 × 10 ⁻⁴ cm ² / s. An optical card was obtained by laminating the protective substrate with a hot-melt adhesive (Hirodine 7580).

The optical card thus obtained was used in Example 1
The results are shown in Table 1 and FIG. 12 (b).

Here, the power at the time of reproducing the information is within a range where the information is not destroyed, that is, b and c in FIGS.
Must be less than the smaller of On the other hand, considering the reproduction characteristics such as C / N, it is preferable that the reproduction power is as large as possible, and the reproduction light can be increased to 0.6 mW in Example 1 and less than 0.7 mW in Example 2.

In the optical card of Comparative Example 1, when the reproduction was repeated 5000 times with the reproduction light power of 0.5 mW, the reflectivity of the stop / reverse area 21 was reduced by about 10%.

[0149]

[Table 1]

Example 3 An optical card was produced in the same manner as in Example 1, except that a cyanine dye having the following structural formula (III) was used instead of the polymethine dye.

[0151]

[Outside 28]

The optical card was evaluated in the same manner as in Example 1. The results are shown in Table 2 and FIG.

Comparative Example 3 A recording auxiliary layer was formed in the recording area and the stop / reverse area of the recording layer in Example 3, and a hot melt adhesive (manufactured by Du Pont-Mitsui, trade name: Evaflex EV250) was applied. An optical card was prepared by bonding the optical card to a protective substrate. Table 2 and FIG.
(B).

Comparative Example 4 In Comparative Example 3, an optical card was produced by bonding the recording layer directly to a protective substrate via a hot melt adhesive without forming a recording auxiliary layer, and evaluated. The results are shown in Table 2 and FIG.

[0155]

[Table 2]

Example 4 In Example 2, instead of silicone rubber, a polyethylene terephthalate film having a thickness of 5 μm was laminated as a recording auxiliary layer on the recording area of the recording layer without adhering to the recording layer. An optical card was manufactured in the same manner as in Example 2 except that Si ₃ N ₄ having a temperature diffusivity of 7.29 × 10 ⁻² cm ² / s was formed in place of Al to a thickness of 1 μm. As a result, the energy of the laser beam required for performing the recording with the contrast of 0.6 or more in the recording area is as follows when the transport speed of the optical card is 60 mm / s.
1.8 mW at ec, 3.0 m at 400 mm / sec
W.

On the other hand, the reproduction light intensities required to cause a change in the recording area and the recording layer outside the recording area when the optical card is stopped are 0.06 mW and 0.7 mW, respectively.
When the reproducing light was moved at 400 mm / s with respect to the optical card, the reproducing light intensity required to cause a change in the recording layer in the recording area was 0.5 mW. As a result, the intensity of the reproduction light of this optical card could be increased to 0.06 or more and less than 0.5 mW.

K and s are 0 or 1, l, m and n are 0,
1 or 2.

[Reference Example 1] The transparent substrate 5 is 85 m long.
m, width 54 mm, thickness 0.4 mm, using a stamper to thermally transfer by 3 μm width, pitch 12
diacetone in which a polymethine dye represented by the following structural formula [I] and a stabilizer represented by the following structural formula [IV] are mixed at a ratio of 3: 1 on which a stripe-shaped guide groove of μm is formed. The alcohol solution was applied to a thickness of about 1000 ° using a gravure roll coater.

[0160]

[Outside 29]

A UV-curable silicone rubber (trade name: TUV6000, manufactured by Toshiba Silicone Co., Ltd.) is applied only to the recording area 34 above the recording layer by a gravure roll coater for about 1 hour.
The composition was applied to a thickness of 0 μm and cured by irradiating ultraviolet rays to form a recording auxiliary layer. An ethylene vinyl acetate hot melt adhesive (manufactured by Du Pont-Mitsui Polychemicals, trade name: Evaflex 150) having a temperature diffusivity of 4 × 10 ⁻⁴ cm ² / s was applied on the transparent substrate thus obtained with a bar coater. An optical card having a cross section shown in FIG. 14A was obtained by applying the film to a thickness of about 50 μm and thermocompression bonding with a polycarbonate protective substrate having a thickness of 0.3 mm.

In order to examine the recording sensitivity of this optical card, recording was performed under the three conditions shown in Table 3 below with a laser power of 3.5 mW and a spot diameter of 3.0 μm, and the recording contrast (RF of the recording portion relative to the unrecorded portion). Output level). Table 4 shows the results.

[0163]

[Table 3]

As a guide for estimating the likelihood of deterioration of the optical recording layer outside the recording area when the card is stopped, a laser (laser power: 0.2 mW, spot diameter: 3.0 μm) under the same conditions as the laser beam used for reproduction is used as a guide. When the same position in the area 35 is continuously irradiated, the reflectance is 5% from the initial value.
The time until the drop (reproduction light deterioration time) was measured. Table 5 shows the results.

[Reference Example 2] Transparent substrate 5 having a length of 85 m
A casting sheet with a guide groove of PMMA, m, 54 mm in width and 0.4 mm in thickness was used. The recording layer shown in Reference Example 1 was formed on this substrate. A thermosetting silicone rubber (manufactured by Toshiba Silicone, trade name:
TSE3033) was applied with a bar coater to a thickness of about 10 μm, and then heated and cured at 80 ° C. for 2 hours so that the recording auxiliary layer was in contact only with the recording area. This substrate and a protection substrate having a thickness of 0.3 mm made of PMMA were put through a polyester adhesive sheet (manufactured by Toray Industries, trade name: Chemit R-99HV) having a temperature diffusivity of 8.1 × 10 ⁻⁴ cm ² / s. An optical card was obtained by thermocompression bonding.

The recording sensitivity and the reproduction light deterioration time of this optical card were measured in the same manner as in Reference Example 1. Tables 4 and 5 show the results.

Reference Example 3 A polycarbonate extruded plate (85 mm long, 54 mm wide, 0.4 mm thick) was coated with a photocurable resin (manufactured by Nippon Kayaku, Inc., trade name: INC118), 3 μm in width and 12 μm in pitch. Was transferred to obtain a transparent substrate 5. After providing an optical recording layer on this substrate in the same manner as in Reference Example 1, an ethylene-vinyl acetate hot melt adhesive sheet (manufactured by Hirodyne Co., trade name:
(Hirodine 7580, thickness 50 μm) was temporarily fixed so as to cover a place outside the pit formation recording area. Further, an ultraviolet-curable silicone rubber (trade name: TUV6000, manufactured by Toshiba Silicone Co., Ltd.) is applied to one surface of a protective substrate made of polycarbonate having a thickness of 0.3 mm and has a thickness of 50 μm, which is slightly wider than the recording area, and ultraviolet rays are applied. Irradiation was performed to form a film, and these were adhered by thermally laminating a transparent substrate and a protective substrate to obtain an optical card shown in FIG. 14B.

The properties of the optical card thus obtained were evaluated in the same manner as in Reference Example 1. Tables 4 and 5 show the results.

Comparative Example 5 After forming an optical recording layer in the same manner as in Reference Example 1, a recording auxiliary layer (trade name: TUV6000, manufactured by Toshiba Silicone Co., Ltd., thickness: 10) was formed on the entire area of the recording layer.
μm) was formed in the same manner as in Reference Example 1 to produce an optical card shown in FIG.

The optical card thus obtained was evaluated in the same manner as in Reference Example 1. Tables 4 and 5 show the results.
Shown in As shown here, the recording sensitivity is the same as that of the first embodiment, but the reproduction light deterioration time is extremely shortened, and the deterioration of the recording layer in the stop and inversion areas proceeds rapidly.

[Comparative Example 6] An ethylene-vinyl acetate hot melt adhesive (manufactured by Mitsui DuPont Polychemicals, trade name: Evaflex 150) without forming a recording auxiliary layer after forming a recording layer as in Reference Example 1. Is formed to a thickness of about 50 μm.
An optical card was obtained by thermal lamination with a 3 mm thick polycarbonate protective substrate.

The optical card thus obtained was evaluated in the same manner as in Reference Example 1. The results are shown in Tables 4 and 5.

[0173]

[Table 4]

[0174]

As described above, according to the present invention, since the sensitivity of the recording area is improved, information can be recorded even when the optical card is driven at a high speed, and in the recording layer area outside the recording area. In addition, since the sensitivity is lowered by the recording suppression layer, the relative speed of the optical card with respect to the reproduction light is reduced due to the reversal of the moving direction of the optical card, and the recording layer in the stop / reverse area of the optical card due to the reproduction light when stopped The change can be prevented, and the reliability of the optical card can be improved without changing the recording / reproducing device.

Further, according to the present invention, the sensitivity of the recording layer area outside the recording area is reduced, so that the maximum light intensity can be set higher than that of the conventional optical card.
The signal of the ratio can be reproduced.

Further, according to the present invention, there is no difference in reflectivity between the recording area and the recording layer area outside the recording area, and the occurrence of AT deviation and AF deviation can be suppressed.

Further, according to the present invention, the recording auxiliary layer can be formed by a normal printing technique, and the recording auxiliary layer can be accurately formed on the recording area of the recording layer. Further, by coating and forming a recording auxiliary layer, an optical recording medium having a uniform recording sensitivity can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an optical card according to the present invention. (A) is a sectional view of a direction parallel to a track groove of the optical card according to the present invention. (B) is a plan view of the optical card according to the present invention. (C) is a cross-sectional view of the optical card according to the present invention in a direction crossing a track groove.

FIG. 2 is a schematic view showing a conventional optical card. (A) is a sectional view of a conventional optical card in a direction parallel to a track groove. (B) is a cross-sectional view of a conventional optical card in a direction crossing a track groove.

FIG. 3 is a schematic plan view showing a recording format of a general optical card.

FIG. 4 is a schematic configuration diagram of a general optical card recording / reproducing apparatus.

FIG. 5 is a schematic sectional view showing another embodiment of the optical card according to the present invention.

FIG. 6 is a schematic sectional view showing a recording / reproducing apparatus for an optical card according to the present invention.

FIG. 7 is a sectional view of a conventional optical card with improved recording sensitivity.

FIG. 8 is a graph showing energy sensitivity when driving and stopping a conventional optical card.

FIG. 9 is a graph showing energy sensitivity at the time of driving and at the time of stopping according to an embodiment of the optical card of the present invention.

FIG. 10 is a graph showing energy sensitivity at the time of driving and at the time of stopping in another embodiment of the optical card of the present invention.

FIG. 11 is a graph showing energy sensitivity when the optical card of the embodiment is driven and when it is stopped. (A) Example 1 (b) Example 2

FIG. 12 is a graph showing energy sensitivity when the optical card of the comparative example is driven and stopped. (A) Comparative example 1 (b) Comparative example 2

FIG. 13 is a graph showing energy sensitivity when the optical card is driven and when it is stopped. (A) Example 3 (b) Comparative example 3 (c) Comparative example 4

FIG. 14 is a cross-sectional view in a direction parallel to a track groove of the optical card of the reference example. (A) Reference example 1 (b) Reference example 3

[Description of Signs] 1 Protective substrate 2 Track groove 3 Recording layer 4 Adhesive layer 5 Transparent substrate 6 Recording auxiliary layer 7 Recording suppression layer 11 Optical card 21 Stop / reverse area 31 Pit 32 Tracking track 33 Information recording track 34 Recording area 35 Recording Recording layer area outside area 41 Optical head 42 Lens system 43 Beam splitter 44 Photodetector 45 Light source 46 Driving means 47 Reproducing beam 48 Control means 71 Film coating layer

Continuation of front page (56) References JP-A-63-209041 (JP, A) JP-A-64-19541 (JP, A) JP-A-64-19542 (JP, A)

Claims (20)

(57) [Claims] A recording auxiliary layer for covering a recording region of the recording layer on a surface of the recording layer formed on the surface of the substrate that does not face the substrate; An optical recording medium comprising a recording suppression layer covering a recording layer not covered with the recording auxiliary layer. 2. The optical recording medium according to claim 1, wherein said optical recording medium is an optical card.
Optical recording medium. 3. A polymer in which the recording auxiliary layer has rubber elasticity.
2. The optical recording medium according to claim 1, which is a coating film of a compound. 4. The optical recording medium according to claim 3 , wherein said recording auxiliary layer contains at least one polymer compound selected from silicone rubber, urethane rubber, styrene rubber and butadiene rubber. 5. The optical recording medium according to claim 4 , wherein said recording auxiliary layer is a cured film of an ultraviolet curable silicone rubber or a thermosetting silicone rubber. 6. A substrate having a stripe-shaped track on the surface, and a recording layer formed on the surface of the substrate,
An optical recording medium comprising a recording auxiliary layer covering a recording area of the recording layer on a surface of the recording layer not facing the substrate and a recording suppression layer covering a recording layer outside the recording area, In the optical recording medium, data recording and / or reproduction is performed by reciprocating movement relative to recording and / or reproduction light, and a recording layer area outside the recording area of the medium is used for recording and / or reproduction light. An optical recording medium, which is an area for tracking servo track access and auto focus, and an irradiation area of reproduction light when the moving direction of the medium is reversed. 7. The optical recording medium according to claim 6, wherein said optical recording medium is an optical card.
Optical recording medium. 8. The recording layer outside the recording area, wherein the recording suppression layer is
The recording in a state where there is no relative movement between the
The sensitivity of the recording layer outside the area to the reproduction light is determined by
In a state where there is a relative movement between the recording layer and the reproduction light
Lower than the sensitivity of the recording layer of the recording area to the reproduction light.
The optical recording medium according to claim 6, wherein the optical recording medium is used. 9. The recording suppression layer having a temperature diffusivity of 1 × 10
^-3 cm ² The optical recording medium according to claim 6, which is larger than / s. 10. The recording suppression layer has a temperature diffusivity of 1 × 10
^-2 cm ² / S ~ 2cm ² 10. The optical recording of claim 9, wherein
Medium. 11. The recording suppression layer has a temperature diffusivity of 1 × 10.
^-2 ~ 1cm ² 11. The optical recording medium according to claim 10, wherein the ratio is / s. 12. A substrate having a stripe-shaped track on a surface thereof, and a recording layer formed on the surface of the substrate, wherein a recording area of the recording layer is provided on a surface of the recording layer not facing the substrate. And a recording suppression layer for covering a recording layer outside the recording area, and a method for reproducing recorded data of an optical recording medium in which coded data is recorded on the recording layer. In the step of reciprocating the optical recording medium relative to the reproduction light in a direction parallel to the track and scanning the track with the reproduction light, the optical recording medium is moved in the moving direction of the optical recording medium. A method for reproducing recorded data on an optical recording medium, wherein the inversion is performed while the reproduction light is irradiating the recording layer area outside the recording area. 13. The recording outside the recording area, wherein the recording suppressing layer
The recording in a state where there is no relative movement between the layer and the reproduction light
The sensitivity of the recording layer outside the area to the reproduction light is determined by
In a state where there is a relative movement between the recording layer and the reproduction light
Lower than the sensitivity of the recording layer of the recording area to the reproduction light.
13. The reproducing method according to claim 12, wherein the reproducing method is performed. 14. The optical recording medium according to claim 14, wherein said optical recording medium is an optical card.
12. A method for reproducing an optical recording medium according to 12 . 15. A recording medium having a predetermined strength, comprising: a substrate having stripe-shaped tracks on the surface; and a recording layer formed on the surface of the substrate, wherein the recording layer is covered with a recording auxiliary layer. recording region by responding to the beam produce an optically detectable change in the recording layer and; coated with a recording inhibition layer, and a low sensitivity low sensitivity area as compared to the recording area, and the A reproduction video having a predetermined intensity is recorded on an optical recording medium in which coded data is recorded on a recording layer.
A reproducing method using the optical recording medium, wherein the reproducing beam is provided on the recording layer of the recording area while the optical recording medium is moving at a predetermined speed with respect to the reproducing beam. raw changes in the
The optical recording medium and the reproducing beam
And causing a change in the recording layer of the recording area in a state where there is no relative movement with respect to the optical recording medium.
An optical recording device having a constant intensity that does not cause a change in the recording layer in the low-sensitivity region when there is no relative movement with the reproducing beam. A method for reproducing recorded data on a medium. 16. The recording control layer according to claim 1, wherein said recording suppression layer comprises a recording area outside said recording area.
Without relative movement between the layer and the read beam
The sensitivity of the recording layer in the low-sensitivity area to the reproducing beam.
Relative to the recording layer in the recording area and the reproduction beam.
The playback video of the recording layer of the recording area in a state where there is motion.
16. The sensitivity is lower than the sensitivity to the
How to play. 17. The optical recording medium according to claim 17, wherein said optical recording medium is an optical card.
16 playback methods. 18. A substrate having a stripe-shaped track on the surface , and a recording layer formed on the surface of the substrate.
The recording layer has a predetermined strength covered with a recording auxiliary layer.
Optically detectable on the recording layer in response to the recording beam
A recording area which produces an effective change; and a recording area covered with a recording suppression layer, which has a higher sensitivity than the recording area.
A low-sensitivity area, and coded data is recorded on the recording layer.
A reproducing apparatus for recording data on an optical recording medium, means for irradiating reproducing beam on the optical recording medium, and light
A driving unit for relatively reciprocating the recording medium and the reproducing beam in a direction parallel to the track; and a reproducing beam for irradiating the optical recording medium is driven at a constant speed by the optical recording medium. In the state where
No change occurs in the recording layer of the recording area,
No relative movement between the recording medium and the reproducing beam
In the state, a change occurs in the recording layer of the recording area.
And than, and relative shift between the optical recording medium and the reproducing beam
When there is no movement, the recording layer in the low-sensitivity area changes.
Set to a certain intensity that does not cause
A data reproducing apparatus for an optical recording medium, comprising: 19. The optical recording medium is an optical card.
18 data reproducing apparatus . 20. The optical recording medium according to claim 1, wherein the optical recording medium is
Relative movement between the recording layer outside the recording area and the reproduction light.
The reproduction light of the recording layer in the low-sensitivity area in the absence of
Sensitivity relative to the recording layer in the recording area and the reproduction light.
Reproduction of the recording layer of the recording area in a state where there is a large movement
Is configured to be less sensitive to light
19. The data reproducing apparatus according to claim 18, wherein: