Title of Invention

OPTICAL INFORMATION RECORDING MEDIUM AND RECORDING METHOD THEREOF

Abstract To provide an optical information recording medium including a pigment appropriate for high-density and high-speed optical recording by the blue laser light of 350 to 500 nm and especially around 400 nm (for example, 405 run), enabling recording at low power, suppressing thermal affect of recording to the optical recording layer, and assuring a reflection ratio or modulation degree by the change of a refraction index n and an attenuation coefficient k; and to provide a recording method thereof. Instead of the recording based on the optical phase difference obtained by a change A n of the refraction index n of the pigment as in the conventional method, a pigment capable of performing recording based on the change ?k of the attenuation coefficient k has been obtained. Recording may be performed mainly by the change Ak of the attenuation coefficient k. It is preferable to use a recording wavelength which is at the side of longer wavelength than the absorption peak of the absorption spectrum for the laser beam of the aforementioned pigment. However, the invention is not to be limited to this and characterized in recording performed by the change of the attenuation coefficient of the pigment against the recording wavelength.
Full Text Technical Field
This invention relates to a postscript (write once) type
optical information recording medium and to the recording method
thereof. In particular, this invention relates to an optical
information recording medium which is capable of writing
information by means of a semiconductor laser such as a laser
beam having a wavelength of 350-500nm (blue laser, a blue laser
beam) and to the recording method thereof.
Background Art
Nowadays, many efforts have been conducted trying to
develop an optical information recording medium of postscript
type which is designed to use a blue laser beam having a wavelength
in the vicinity of 350-500nm (for example, around 405nm) which
is shorter in wavelength than that conventionally employed. In
this optical information recording medium, an organic dye
compound is employed for creating an optical recording layer.
As the organic dye compound absorbs laser beam, the organic dye
compound is decomposed (e.g. thermal decomposition) or denatured,
thereby bringing about a change in optical properties of the laser
beam of recording or regenerating wavelength. This change is
then picked up respectively as a modulation factor, thereby
making it possible to perform the recording as well as the
regeneration.

In conformity with recent trend to increase the density and
the velocity of recording, a laser beam of shorter wavelength
zone is now increasingly employed in the recording. As the laser
beam to be employed is getting shorter in wavelength, the optical
recording layer is required to be formed increasingly thinner.
Therefore, the development of the optical information recording
medium is now being advanced especially attaching importance to
the selection of dyes having a higher refractive index.
Namely, it has been practiced to secure the modulation factor
by taking advantage of the optical phase difference that can be
generated due to a change in refractive index at the recording
or regenerating wavelength.
A general structure of an optical information recording
medium 1 which is capable of recording and regenerating
information by means of a blue laser beam will be explained with
reference to FIG. 15.
FIG. 15 illustrates an enlarged cross-sectional view of a
main portion of a disc-like optical information recording medium
1. More specifically, FIG. 15 is a cross-sectional view of the
optical information recording medium 1 as it is sectioned
diametrally. Namely, FIG. 15 schematically shows a
cross-section of the optical information recording medium 1 as
it is sectioned perpendicular to the surface provided with a
pre-groove 7 and also perpendicular to the direction of the
pre-groove 7. This optical information recording medium 1
comprises a light-transmitting substrate 2, an optical recording
layer 3 (light-absorptive layer) formed on the substrate 2, a
light-reflecting layer 4 formed on the optical recording layer
3, and a protective layer 5 (adhesive layer) formed on the
light-reflecting layer 4 . By the way, under some circumstances ,

a dummy layer 6 having a predetermined thickness may be laminated
on the top of the protective layer 5 so as to make the optical
information recording medium 1 have a predetermined thickness
which is required by the specification.
The substrate 2 is provided in advance with a pre-groove 7
which is formed spirally. On both sides of this pre-groove 7,
there are located lands 8 constituting the regions other than
the pre-groove 7.
As shown in FIG. 15, as a laser beam (recording beam) 9 is
irradiated onto the optical information recording medium 1 from
the light-transmitting substrate 2 (incident layer) side, the
optical recording layer 3 is caused to generate heat (or absorb
heat) as the energy of the laser beam 9 is absorbed by the optical
recording layer 3, thereby forming a recording pit 10 through
the thermal decomposition of the optical recording layer 3.
By the way, the substrate 2 is contacted, through a first
boundary layer (or interface) 11, with the optical recording
layer 3.
The optical recording layer 3 is contacted, through a second
boundary layer 12, with the light-reflecting layer 4.
The light-reflecting layer 4 is contacted, through a third
boundary layer 13, with the protective layer 5.
The protective layer 5 is contacted, through a fourth
boundary layer 14, with the dummy substrate 6.
The light-transmitting substrate 2 can be generally formed
using a resin having a high transparency exhibiting a refractive
index ranging from about 1.5 to 1.7 to a laser beam and being
excellent in impact resistance. For example, the
light-transmitting substrate 2 can be formed using a
polycarbonate plate, an acrylic plate, an epoxy resin plate, etc.

It is also possible to use a glass plate as the light-transmitting
substrate 2.
The optical recording layer 3 deposited on the substrate 2
is formed of a layer made of a light-absorptive substance (a
light-absorbing substance) containing a dyestuf f . This optical
recording layer 3 is caused to generate heat as it is irradiated
with a laser beam 9 , thereby bring about the thermal decomposition,
the heat generation, the absorption of heat, melting, sublimation,
deformation or denaturing. This optical recording layer 3 can
be formed, for example, by uniformly coating an azo-based dye,
a cyanine dye, etc., which has been dissolved in a solvent, on
the surface of substrate 2 by means of spin-coating method, etc.
With respect to the materials to be employed for forming the
optical recording layer 3, although it is possible to employ any
kind of optical recording materials, it is more preferable to
employ a photoabsorptive organic dye.
The light-reflecting layer 4 is formed of a metal film which
is high in heat conductivity and light reflectance, and can be
created by the deposition of gold, silver, copper, aluminum, or
an alloy comprising any of these metals by means of vapor
deposition method, sputtering method, etc.
The protective layer 5 can be formed, as in the case of the
substrate 2, by making use of a resin which is excellent in impact
resistance and adhesion. For example, the protective layer 5
can be formed by coating an ultraviolet-curing resin on the
light-reflecting layer 4 by means of spin-coating method followed
by the curing of the coated layer through the irradiation of
ultraviolet rays thereto.
The dummy layer 6 can be formed by making use of the same
kinds of materials as those of the substrate 2, thereby securing

a predetermined thickness (about 1.2mm) of the optical
information recording medium.
Further, FIG. 16 is an enlarged cross-sectional view
illustrating, as in the case of FIG. 15, a main portion of a
disc-like optical information recording medium 20 of another type
using a blue laser beam. In this case, the optical information
recording medium 20 comprises a light-transmitting substrate 2
having a thickness of 1.1mm, a light-reflecting layer 4 formed
on the substrate 2, an optical recording layer 3
(light-absorptive layer) formed on the light-reflecting layer
4, a protective layer 5 formed on the optical recording layer
3, an adhesive layer 21 formed on the protective layer 5, and
a cover layer 22 having a thickness of 0.1mm and formed on the
adhesive layer 21.
The substrate 2 is provided in advance with a pre-groove 7
which is formed spirally. On both sides of this pre-groove 7,
there are located lands 8 constituting the regions other than
the pre-groove 7.
By the way, if a boundary layer between the substrate 2 and
the optical recording layer 3 satisfies a low reflectance and,
furthermore, if the light reflected from the optical recording
layer 3 is sufficient enough, the provision of light-reflecting
layer 4 may not be required.
As shown in FIG. 16, as a laser beam (recording beam) 9 is
irradiated onto the optical information recording medium 20 from
the light-transmitting incident layer (the cover layer 22) side,
the optical recording layer 3 is caused to generate heat (or
absorb heat) as the energy of the laser beam 9 is absorbed by
the optical recording layer 3, thereby forming a recording pit
10 through the thermal decomposition of the optical recording

layer 3.
By the way, the substrate 2 is contacted, through a first
boundary layer 23, with the light-reflecting layer 4.
The light-reflecting layer 4 is contacted, through a second
boundary layer 24, with the optical recording layer 3.
The optical recording layer 3 is contacted, through a third
boundary layer 25, with the protective layer 5.
The protective layer 5 is contacted, through a fourth
boundary layer 26, with the adhesive layer 21.
The adhesive layer 21 is contacted, through a fifth boundary
layer 27, with the cover layer 22.
In the optical information recording medium 1 or the optical
information recording medium 20, which are constructed as
described above, the laser beam 9 is irradiated onto the recording
film of the optical recording layer 3 through the transparent
substrate 2 or through the cover layer 22, and the energy of this
beam is converted into a thermal energy, thereby bring about the
generation of heat causing thermal decomposition, i.e. heating,
melting, sublimation, or decomposition, thus creating a
recording pit 10. By making use of this recording pit 10, the
contrast that can be created due to the reflectance of light at
the recorded portion or unrecorded portion is read out as an
electric signal (modulation factor).
As described above, in the optical information recording
medium 1 or the optical information recording medium 20, the
recording pit 10 is created mainly through the change in
refractive index that can be caused due to the thermal
decomposition of an organic dye compound as the laser beam 9 is
irradiated onto the optical recording layer 3 formed of the
organic color dye compound.

As a result, the optical constant and decomposition behavior
of the organic color dye compound to be employed in the optical
recording layer 3 are now important factors in order to create
excellent recording pit.
Therefore, the organic color dye compound to be employed in
the optical recording layer 3 is now required to be selected from
those which are excellent in optical properties and in
decomposition behavior to blue laser wavelength. Namely, with
the view of securing excellent recording/regenerating properties
even in the blue laser wavelength zone, there has been tried to
enhance the reflectance of the optical recording layer 3 when
it is not yet recorded and to cause a large change in refractive
index as the organic dye compound is thermally decomposed by the
irradiation of laser beam (thereby making it possible to secure
a large modulation factor).
The change of refractive index "n" and of the extinction
coefficient "k" of the organic dye compound employed as the
optical recording layer 3 due to the absorption of laser beam
9 by the organic dye compound will be explained in reference to
FIG. 17.
FIG. 17 is a graph showing the relationship between the
wavelength of the laser beam 9 and the refractive index "n" and
the relationship between the wavelength of the laser beam 9 and
the extinction coefficient "k". As the organic dye compound
employed is thermally decomposed, the molecular bond is destroyed,
resulting in the decrease of refractive index "n" after recording
and hence resulting in the decrease of reflectance "R" .
Therefore, there has been conventionally tried to increase the
magnitude of change "Δn" in refractive index "n" to thereby secure
a sufficient magnitude of the change "AR" in reflectance, thus

securing a modulation factor between the recording pit 10 and
other portions of the optical recording layer 3 and making it
possible to perform regenerable recording.
Further, the graph describing the extinction coefficient "k"
is substantially the same as the graph describing the absorbency
to the laser beam 9 of the dye, so that it is generally practiced
to make the wavelength on the long wavelength side of this
absorption peak (recording wavelength) the same as the wavelength
of recording' beam (laser beam 9). Namely, since the graph of
refractive index "n" indicates the absorption peak on the long
wavelength side of the graph of the extinction coefficient "k",
it is possible to secure a large magnitude of change "Δn" in
refractive index "n" at this recording wavelength.
On the other hand, it is well known that, as in the case of
the refractive index "n", the extinction coefficient "k" is
caused to decrease after recording at the same recording
wavelength due to the destruction of molecular bond of the organic
dye compound as a result of thermal decomposition of the organic
dye compound. As the extinction coefficient "k" is decreased,
the reflectance "R" is caused to increase. Namely, the change
"Δk" of the extinction coefficient "k" acts to decrease the
magnitude of change "AR" in the reflectance "R" due to the change
"Δn" in refractive index "n" . Namely, the absolute value of "AR"
can be derived as a magnitude corresponding to (An-Ak).
Therefore, according to the prior art, the interest of
development of optical information recording medium is focused
to find a way to increase the "Δn" as much as possible in order
to secure a desired level of modulation factor and to select a
dye exhibiting as small magnitude of "Δk" as possible.
Actually however, no one has succeeded as yet to obtain a

suitable dye which is useful as a coloring material of the optical
recording layer 3 with respect to the laser beam 9 having a
recording wavelength within the range of 350-500nm (for example,
around 405nm).
As described above, the coloring material is required to
exhibit a suitable extinction coefficient "k" (absorption
coefficient) and a large refractive index "n" so as to secure
a sufficient contrast before and after the recording. Therefore,
the coloring material has been selected such that the
recording/regenerating wavelength can be located at the skirts
of the long wavelength side of absorption peak of absorption
spectrum of dye, thus designing the optical recording layer 3
so as to secure a large magnitude of change "Δn" in refractive
index "n" .
Further, as for the properties demanded of the organic
compound, the behavior of decomposition thereof is required to
be suitably selected in addition to the aforementioned optical
properties to the blue laser beam wavelength. However, the
materials having an optical property indicating a refractive
index "n" which is comparable to that of the conventional CD-R
or DVD-R in this short wavelength zone is extremely limited in
kinds. Namely, in order to bring the absorption band of an
organic compound close to the wavelength of blue laser beam, the
molecular skeleton of the organic compound is required to be
minimized or the conjugated system of the organic compound is
required to be shortened. However, when the structure of the
organic compound is adjusted in this manner, it will invite the
decrease of the extinction coefficient "k" or the decrease of
the refractive index "n".
As for the method of overcoming these problems, there have

been recently reported possibilities of improving the optical
properties of organic compound through the utilization of
interaction between molecules such as association instead of
utilizing the optical properties of the simple substance of dye
molecule. However, no one has succeeded as yet to realize
satisfactory recording properties by making use of such a method.
Meanwhile, if a high-speed recording is to be performed by
making use of the optical information recording medium 1 or the
optical information recording medium 20, it is required to
perform a predetermined recording in a shorter period of time
than that required in the conventional speed of recording or low
speed recording. Therefore, the recording power is required to
be increased, thus increasing a quantity of heat or a quantity
of heat per unit time at the optical recording layer 3 on the
occasion of the recording. As a result, the problem of thermal
strain tends to become more prominent, thus giving rise to the
generation of non-uniformity of recording pits 10. Further,
since there is a limit in increasing the output power of
semiconductor laser for emitting the laser beam 9, it is now
demanded to develop a dyestuff having such a high sensitivity
that can be coped with a high-speed recording.
As described above, since an organic dye compound is employed
in the optical recording layer 3 in the cases of the optical
information recording mediums 1 and 20, the development of
optical information recording medium is mainly directed to a
dyestuff which is capable of exhibiting high refractive index
to the laser beam 9 of short wavelength side.
Namely, as long as the conventional postscript type optical
information recording medium using an organic dye compound is
concerned, only the organic compounds which are capable of

exhibiting a large refractive index and a relatively small
extinction coefficient (0.05-0.07) to a recording/regenerating
wavelength are enabled to be employed in viewpoints of securing
modulation factor and reflectance.
Since there are known at present a large number of organic
dye compounds having an absorption band which is close to the
blue laser wavelength, the extinction coefficient "k" thereof
can be controlled. However, since these organic dye compounds
fail to have a large refractive index "n" , the dye compound layer
is required to have a certain degree of film thickness in order
to obtain modulation factor securing a sufficient optical phase
difference of the recording portion (recording pit 10).
However, since the organic compound is incapable of
exhibiting a large absorption power to the recording beam, it
is impossible to make thinner the film thickness of the organic
compound film. Therefore, it is required to employ a substrate
2 having a deep trench (since the film of organic compound is
formed by means of spin-coating, the increase of film thickness
of the organic compound film is achieved by depositing the organic
compound in a deep trench) . In this case however, it is very
difficult to fabricate a substrate 2 having a deep trench, giving
rise to the deterioration in quality of the optical information
recording medium.
Additionally, since the recording medium where blue laser
beam is employed is demanded to execute a high-density recording,
the physical track pitch is required to be formed narrow. As
a result, when a laser beam of high output such as blue laser
beam is employed, the heat generated on the occasion of the

decomposition of dye compound is liable to be accumulated, thus
enabling the heat generated on the occasion of the decomposition
of dye compound to easily transmit to the neighboring tracks and
hence raising the problem that the properties of the recording
medium will be deteriorated.
As described above, the recording medium using a blue laser
wavelength zone where the refractive index of dyestuff (organic
dye compound) cannot be easily enhanced is accompanied with the
problem that it is difficult to enable the recording medium to
exhibit excellent recording properties in the conventional
recording to be effected through the phase change of the change
of refractive index "n".
Patent document 1: JP-A 2003-223740 (KOKAI)
Patent document 2: JP-A 2003-331465 (KOKAI)
Patent document 3: JP-A 2004-142131 (KOKAI)
Patent document 4: JP-A 2004-216714 (KOKAI)
Disclosure of Invention
Problems to be Solved by the Invention:
The present invention has been accomplished in view of the
aforementioned problems and hence, an object of the present
invention is to provide an optical information recording medium
comprising a dyestuff, which is suited for optical recording of
high density and high speed by means of a novel recording system
using a recording wavelength of 350-400nm, in particular, around

400nm (for example, 405nm) , the recording system being different
from the conventional recording system. Another object of the
present invention is to provide a recording method of such an
optical information recording medium.
Further, further objects of the present invention are to
provide an optical information recording medium which is capable
of performing the recording by making use of a blue laser beam
without necessitating to increase the film thickness of dyestuff
of the optical recording layer and to provide a recording method
thereof.
Further, further objects of the present invention are to
provide an optical information recording medium which is capable
of performing the recording with low power and suppressing the
thermal influence that may be caused due to the recording onto
the optical recording layer and to provide a recording method
thereof.
Further, further objects of the present invention are to
provide an optical information recording medium which is capable
of performing the recording with a wavelength located on the long
wavelength side of the absorption peak and which capable of
expecting the synergistic effects to secure the reflectance and
modulation factor that can be derived from the synergistic
effects to be obtained from the change of extinction coefficient
"k" or from the change of refractive index "n" and of extinction
coefficient "k". A further object of the present invention is
to provide a recording method of such an optical information
recording medium.

Means for Solving the Problems:
Namely, according to the present invention, it has been taken
notice of performing the recording based mainly on an optical
phase difference to be brought about by the change "Δk" of the
extinction coefficient "k" of dyestuff and not based on an optical
phase difference to be brought about by the change "Δn" in
refractive index "n" of dyestuff as conventionally conducted.
Thus, the present invention is based on the finding of possibility
of obtaining a dyestuff which is useful in carrying out the
aforementioned recording, wherein the recording is performed
mainly based on the change "Δk" of the extinction coefficient
"k" of dyestuff.
Namely, it is designed to form a recording pit on the
unrecorded optical recording layer formed of an organic dye
compound by making use of the color change of the organic dye
composition of optical recording layer as a result of recording.
More specifically, there is employed a dyestuff whose main
absorption band (absorption peak) before recording is located
on the short wavelength side relative to the
recording/regenerating wavelength and which can be colored or
discolored (absorption) at the recording/regenerating
wavelength zone after the irradiation of laser beam. More
preferably, there is employed a dyestuff whose color can be
thickened as it is irradiated with laser beam as compared with
the color thereof before the irradiation of the laser beam.

FIG. 1 is a graph showing a recording system of the present
invention and illustrating a relationship between the wavelength
of the laser beam 9 and the refractive index "n" and the
relationship between the wavelength of the laser beam 9 and the
extinction coefficient "k", wherein a dyestuff useful in the
present invention is employed. As seen from this graph, while
the refractive index "n" was caused to decrease, the extinction
coefficient "k" was caused to increase as a result of recording
at the recording wavelength. According to this novel recording
system, it has been taken notice of the facts that the magnitude
of decrease "Δn" of refractive index "n" becomes smaller and the
magnitude of change (increment) "Δk" of the extinction
coefficient ™k" becomes larger. At the same time, it has been
found possible to obtain such a dyestuff which is useful in this
recording system. It has been also found possible to suppress
to a possible extent the influence of the generation of heat that
has been a problem involved in the conventional recording system
where a change of refractive index due to thermal decomposition
are utilized.
As a result of extensive studies made by the present
inventors, it has been succeeded to find out an optical recording
layer exhibiting excellent recording/regenerating properties
that can be manifested through the coloring (increase in
concentration) or discoloration of the optical recording layer
while enabling to retain mainly the composition of an organic
dye compound and by making use of recording/regenerating beam
of high output and of short wavelength such as blue laser beam.

This indicates that it is possible to secure a sufficient optical
phase difference through a quantity of change "Δk" of the
extinction coefficient "k" of dyestuff that can be brought about
by the recording and also possible to minimize the influence of
heat generation through the suppression, as much as possible,
of the change "Δn" in refractive index that may be caused to occur
due to the thermal decomposition of the organic dye compound.
Namely, it is now possible to decrease the reflectance "R"
by increasing the extinction coefficient "k", thus making it
possible to derive a sufficient degree of change "AR" in
reflectance which is required for securing the modulation factor.
Moreover, due to the decrease of refractive index "n", the
reflectance "R" can be also decreased, thus making it possible
to further increase the change "AR" in combination with the change
"Δk" of the extinction coefficient "k". Namely, it is now
possible to obtain the absolute value of "AR" as a quantity
corresponding to a value of (Ak+An).
Therefore, it is now possible to perform the recording
through the change of the extinction coefficient "k" and not
through the employment of a dyestuff exhibiting a high refractive
index as conventionally conducted. Moreover, if the decrease
of the change "Δn" is confined to a predetermined level which
is smaller than the conventional level, the generation of heat
due to the thermal decomposition of the organic dye composition
can be suppressed correspondingly. Therefore, it is now
possible to secure the change "AR" of reflectance "R" to be caused
by the change "Δn" in addition to the change "Δk", thus making

it possible to realize efficient recording through synergistic
effects to be derived from the refractive index "n" and the
extinction coefficient "k". Namely, the recording power may be
of a lower level as compared with the conventional level and the
recording with lower power is effective in enhancing the
reliability of the recording of high density and high speed
especially.
Thus, according to a first aspect of the present invention,
there is provided an optical information recording medium
comprising a light-transmitting substrate, and an optical
recording layer ..containing a light-absorbing substance
constituted by a dyestuff which is capable of absorbing laser
beam, wherein an optically readable information is recorded
through an irradiation of the laser beam onto the optical
recording layer. In this optical information recording medium,
a wavelength on the long wavelength side of the absorption peak
of the absorption spectrum of the dyestuff to the laser beam is
preferably employed as a recording wavelength. However, this
invention is not limited to such a kind of optical information
recording medium but may be an optical information recording
medium which is characterized in that the aforementioned
recording can be performed through the change of extinction
coefficient of the dyestuff relative to the recording wavelength.
According to a second aspect of the present invention, there
is provided an optical information recording medium comprising
a light-transmitting substrate, and an optical recording layer
containing a light-absorbing substance constituted by a dyestuff

which is capable of absorbing laser beam, wherein an optically
readable information is recorded in the optical recording layer
through an irradiation of the laser beam onto the optical
recording layer, this optical information recording medium being
featured in that the dyestuff is enabled to not so greatly change
in refractive index but enabled to greatly change in extinction
coefficient as a result of the recording, thereby making it
possible to record the information through the change of
extinction coefficient.
The extinction coefficient of the dyestuff may be 0.25 or
less before the recording.
The extinction coefficient of the dyestuff may be such that
it is enabled to change at a ratio of not less than 30% as a result
of the recording as compared with that before the recording.
The refractive index of the dyestuff may be confined to the
range of 1.5 to 2.0 before the recording.
The refractive index of the dyestuff may be such that it is
enabled to change at a ratio of not more than 10% as a result
of the recording as compared with that before the recording.
According to a third aspect of the present invention, there
is provided an optical information recording medium comprising
a light-transmitting substrate, and an optical recording layer
containing a light-absorbing substance constituted by a dyestuff
which is capable of absorbing laser beam (especially, an organic
dyestuff) wherein an optically readable information is recorded
through an irradiation of the laser beam onto the optical
recording layer, wherein the optical recording layer is enabled

to form an isomer due to the light created by an irradiation of
the laser beam thereto and due to the heat generated by the
absorption of the laser beam. Preferably, this optical
information recording medium is characterized in that the isomer
is enabled to form a-polarized structure which is unbalanced in
electric charge as it is irradiated with the laser beam, this
polarized structure being designed to be orientated by an
electrostatic interaction, thereby making it possible to record
the information.
The organic dyestuf f may comprise a compound whose absorption
peak is enabled to shift to the long wavelength side as a result
of the recording.
The organic dyestuff may be enabled to change in extinction
coefficient as the aforementioned polarized structure is
orientated.
According to a fourth aspect of the present invention, there
is provided an optical information recording medium comprising
a light-transmitting substrate, and an optical recording layer
containing a light-absorbing substance constituted by a dyestuff
which is capable of absorbing laser beam, wherein an optically
readable information is recorded through an irradiation of the
laser beam onto the optical recording layer, this optical
information recording medium being featured in that a wavelength
on the long wavelength side of the absorption peak of the
absorption spectrum of the dyestuff to the laser beam is employed
as a recording wavelength and that the recording is performed
through the change of extinction coefficient of the dyestuff

relative to the recording wavelength.
According to a fifth aspect of the present invention, there
is provided an optical information recording medium comprising
a light-transmitting substrate, and an optical recording layer
containing an organic dyestuff which is capable of absorbing
laser beam, wherein an optically readable information is recorded
through an irradiation of the laser beam onto the optical
recording layer, this optical information recording medium being
featured in that the optical recording layer is enabled to record
the information at a wavelength ranging from 350 to 500nm and
contains an organic dye compound having reversible optical
properties.
An oxidation preventive layer may be disposed on one side
of and close to the optical recording layer, the oxidation
preventive layer containing at least one kind of compound
selected from the group consisting of hindered amine (HALS) -based
compound, a phenolic compound, an amine-based compound, a
phosphate-based compound and an organosulfur-based compound.
Further, the optical recording layer may contain an oxidation
preventing agent comprising at least one kind of compound
selected from the group consisting of hindered amine (HALS) -based
compound, a phenolic compound, an amine-based compound, a
phosphate-based compound and an organosulfur-based compound.
The optical recording layer may further contain a rust
preventive formed of a benzotriazole-based compound or a
benzothiazole-based compound.
The aforementioned substrate may be provided with trenches

about 400nm in track pitch, each trench having a width of about
220-270nm and a depth of about 55-80nm.
According to a sixth aspect of the present invention, there
is provided an optical information recording medium comprising
a light-transmitting substrate, and an optical recording layer
containing a light-absorbing substance constituted by a dyestuff
which is capable of absorbing laser beam, wherein an optically
readable information is recorded through an irradiation of the
laser beam onto the optical recording layer, this optical
information recording medium being featured in that the dyestuff
is constituted by a dye compound represented by a chemical
structure shown in FIG. 2.
The dyestuff may be constituted by a dye compound represented
by a chemical structure shown in FIG. 3.
The dyestuff may be constituted by a dye compound represented
by a chemical structure shown in FIG. 4.
The dyestuff may be constituted by a dye compound represented
by a chemical structure shown in FIG. 5.
By the way, the expression of "aryl group or heterocyclic
structure" in FIGs. 2 and 6 is intended to include, in its concept,
"aryl group or heterocyclic structure" and hence may be expressed
as "aryl group or heterocyclic structure". Likewise, the
expression of "having hydrogen atom or a substituent group" in
FIG. 3 is intended to include, in its concept, "having hydrogen
atom and a substituent group" and hence may be expressed as
"having hydrogen atom and a substituent group".
According to a seventh aspect of the present invention, there

is provided an optical information recording medium comprising
a light-transmitting substrate, and an optical recording layer
containing a light-absorbing substance constituted by a dyestuf f
which is capable of absorbing laser beam, wherein an optically
readable information is recorded through an irradiation of the
laser beam onto the optical recording layer, this optical
information recording medium being featured in that the dyestuff
is constituted by a dye compound represented by a chemical
structure shown in FIG. 6.
The dyestuf f may be constituted by a dye compound represented
by a chemical structure shown in FIG. 7.
The dyestuf f may be constituted by a dye compound represented
by a chemical structure shown in FIG. 8.
The wavelength located on the long wavelength side of the
absorption peak of the absorption spectrum of the dyestuff to
the laser beam may be employed as a recording wavelength.
According to a eighth aspect of the present invention, there
is provided a recording method of an optical information
recording medium comprising a light-transmitting substrate, and
an optical recording layer containing a light-absorbing
substance constituted by a dyestuff which is capable of absorbing
laser beam, wherein an optically readable information is recorded
through an irradiation of the laser beam onto the optical
recording layer, this recording method of the optical information
recording medium being featured in that a wavelength on the long
wavelength side of the absorption peak of the absorption spectrum
of the dyestuff to the laser beam is employed as a recording

wavelength and that the recording is performed through the change
of extinction coefficient of the dyestuff relative to the
recording wavelength.
The optical information recording medium may include a
light-reflecting layer which is capable of reflecting the laser
beam.
The change of refractive index of the dyestuff relative to
the aforementioned recording wavelength may be combined with the
change of the extinction coefficient, thereby making it possible
to perform the aforementioned recording by making use of these
changes.
The dyestuff may be selected from those whose extinction
coefficient is enabled to greatly change at the aforementioned
recording wavelength.
The dyestuff may be selected from those whose extinction
coefficient is enabled to greatly increase at the aforementioned
recording wavelength.
The dyestuff may be selected from those which can be
isomerized as it is irradiated with the laser beam.
The aforementioned recording wavelength may be confined to
the range of 350nm to 500nm.
The aforementioned recording wavelength may be confined to
405nm.
By the way, each of the aforementioned limiting constituent
features described subsequent to each of main inventions may be
adopted as limiting constituent features in any of other main
inventions described above. For example, the light-reflecting

layer may be included in any of the main inventions described
above.
Effects of the Invention:
According to the optical information recording medium and
the recording method thereof, it is possible to perform optical
recording not through a large magnitude of change of dyestuff
as conventionally conducted but through the change of extinction
coefficient "k" of the dyestuff as represented by the dye
compounds having chemical structures as shown in FIGs. 2 and 6
or as shown in FIGs. 3-5 and FIGs. 7 and 8 for instance. Further,
for this reason, it is now possible to perform excellent optical
recording by making use of blue laser and to perform the optical
recording with low power since the dyestuff is not required to
be heated to the decomposition temperature of the dyestuff. As
a result, it is now possible to perform the optical recording
at high sensitivity and high density, while securing the
reliability and stability of the recording. In the conventional
recording system where a thermal decomposition reaction of
dyestuff is utilized, a large quantity of heat is generated at
the time of the decomposition. Whereas in the case of the
recording system as proposed by the present invention, wherein
the structural change of dyestuff such as the tautomerization
of dyestuff is utilized or the orientation of a polarized
structure unbalanced in electric charge that can be effected
through an electrostatic interaction is utilized, the generation

of heat is suppressed, thus making it possible to minimize the
transmission of heat to neighboring tracks (the problem that has
been raised on the occasion of forming a recording pit) and to
obtain an optical information recording medium having excellent
recording properties.
Namely, in the case of the present invention, as the light
and heat are applied to the optical recording layer on the
occasion of recording through the irradiation of laser beam, the
orientation of the dyestuff (organic dye compound) is caused to
change in the optical recording layer, thereby increasing the
absorption of laser beam by the dyestuff (due to the increase
of the extinction coefficient "k") in the recording region at
the recording/regenerating wavelength. As a result, the
reflectance "R" is caused to decrease, thus securing the
modulation.
Furthermore, since the recording is performed through the
change of absorption to be caused by the orientation of dyestuff
without generating the decomposition such as the thermal
decomposition of the dyestuff, the generation of heat on the
occasion of recording can be minimized. Namely, in the case of
the prior art, the magnitude of change of the refractive index
"n" through the decomposition of dyestuff has been a key.
Whereas, in the case of the present invention, a key is not how
to thermally decompose the dyestuff but how to change the
absorbance of the dyestuff through the decomposition thereof or
how to enlarge the change of reflectance "R" of dyestuff.
Therefore the dyestuff, according to the present invention, is

not necessarily required to be decomposed and the recording of
information can be performed with low power.
Specifically, the dyestuff is irradiated with laser beam to
isomerize the dyestuff or to generate an electrostatic
interaction or the association among the dye molecules, thereby
lowering the refractive index "n" and increasing the extinction
coefficient "k". Preferably, an organic dye material exhibiting
associating properties is employed in order to obtain excellent
recording properties. By the way, when an organic dye material
having a plurality of associating structures in the molecule
thereof is employed, it is possible to expect further improved
properties therefrom. Especially, since it is possible to
sufficiently secure the dyestuff that has been isomerized, it
is possible to obtain a dyestuff which is improved in desirable
recording properties . Especially, a material having a plurality
of isomerized structures in the molecule thereof (for example,
materials shown in FIGs. 6 and 8) is expected to exhibit greatly
improved properties.
Further, according to the present invention, since the
organic compound layer (optical recording layer) is not
restricted with regard to the refractive index "n" thereof, the
organic compound layer is no longer required to have the light
absorbing properties at all, so that it is no longer required
such a severe restriction as conventionally required with regard
to the optical constant.
Especially, according to the first, the second, the fourth
and the fifth aspects of the invention, not only the decrease

of the reflectance "R" due to the increase of the extinction
coefficient "k" but also the decrease of the reflectance "R" due
to the decrease of the refractive index "n" can be synergistically
secured as a modulation factor, thereby making it possible to
realize a more efficient recording as compared with the
conventional recording.
Especially, according to the third aspect of the invention,
since the organic dyestuff is enabled to form a polarized
structure which is unbalanced in electric charge as it is
irradiated with the laser beam, and this polarized structure is
designed to be orientated by an electrostatic interaction to
thereby make it possible to perform the recording, it is now
possible to minimize, without generating a large magnitude of
heat due to the recording that has been experienced in the
conventional recording system, the transmission of heat to the
neighboring track which has been a problem to be solved on the
occasion of forming a recording pit, thereby making it possible
to realize an efficient recording.
Especially, according to the sixth aspect of the invention,
it is now possible to form an optical recording layer by making
use of a dye compound having a relatively simple structure,
enabling to perform more efficient recording as compared with
the conventional recording.
Especially, according to the seventh aspect of the invention,
since a dye compound having a plurality of tautomeric structures
in the molecule thereof, it is now possible to further improve
the optical properties and to perform stable recording.

Especially, according to the fourth and the eighth aspects
of the invention, not only the decrease of the reflectance "R"
due to the increase of the extinction coefficient "k" but also
the decrease of the reflectance "R" due to the decrease of the
refractive index "n" can be secured as a modulation factor, it
is now possible to perform the recording with a lower power as
compared with that employed in the conventional recording.
Brief Description of Accompanying Drawings
FIG. 1 shows a graph showing the relationship between the
wavelength of the laser beam 9 and the refractive index "n" and
the relationship between the wavelength of the laser beam 9 and
the extinction coefficient "k" in the optical recording layer
3 to be employed in the present invention;
FIG. 2 shows a general formula of a tautomeric organic dye
compound or an organic dye compound (especially, an amine
compound) having associating properties to be employed in the
present invention;
FIG. 3 shows a general formula of one example of a
heterocyclic compound (one of tautomeric structures or one of
structures having associating properties) to be utilized in the
present invention;
FIG. 4 shows a chemical structure of a preferable compound
which is useful as an organic dye material to be employed in the
optical recording layer 3 of the present invention or as a
dyestuff to be employed in the following examples;
FIG. 5 shows a chemical structure of another preferable
compound which is useful as an organic dye material to be employed

in the optical recording layer 3 of the present invention;
FIG. . 6 shows a general formula of a dyestuff having a
plurality of tautomeric structures or a plurality of associating
structures in its molecule, which is designed to be employed as
an organic dyestuff of the present invention;
FIG. 7 shows a general formula of one example of the compound
having a plurality of tautomeric structures or a plurality of
associating structures in its molecule;
FIG. 8 shows a general formula of another example of the
compound having a plurality of tautomeric structures or a
plurality of associating structures in its molecule;
FIG. 9 shows a chemical formula of an oxacyanine dye employed
in a comparative example;
FIG. 10 shows a table illustrating the results assessed of
the recording properties of one example and one comparative
example;
FIG. 11 shows a table illustrating the optical constants
before and after the recording of a recording pit 10 in one example,
i.e. a magnitude of the change "A" in refractive index "n" as
well as in extinction coefficient "k" in the optical recording
layer 3 of the disc employed in the example;
FIG. 12 is a graph illustrating the influence of the "Δn"
and the "Δk" on the modulation factor (reflectance) in each of
the discs which were fabricated in the same manner as one example,
wherein the film thickness of the optical information recording
medium 1 created by making use of the dyestuff shown in FIG. 4
was variously changed;
FIG. 13 is a graph illustrating the change of reflectance
relative to the refractive index "n";
FIG. 14 is a graph illustrating the change of reflectance

relative to the extinction coefficient "k";
FIG. 15 is an enlarged cross-sectional view illustrating a
main portion of a disc-like optical information recording medium
1 wherein a blue laser beam is to be employed;
FIG. 16 is an enlarged cross-sectional view illustrating a
main portion of a disc-like optical information recording medium
2 0 of another type wherein a blue laser beam is to be employed;
FIG. 17 is a graph showing the relationship between the
wavelength of the laser beam 9 and the refractive index "n" and
the relationship between the wavelength of the laser beam 9 and
the extinction coefficient "k".
FIG. 18 is a diagram illustrating a process wherein the
optical recording layer 3 containing an amine compound as one
of the organic dye materials of the present invention changes
from its basic structure to a polarized structure (quinoid
structure) and then to an orientated structure;
FIG. 19 shows a table illustrating the refractive index "n",
the extinction coefficient "k" and the modulation factor, before
and after the recording, of various kinds of optical information
recording mediums which were prepared in the same manner as one
example by making use of each of the organic dye compounds
represented by the general formula shown in FIG. 2; and
FIG. 20 is a graph illustrating the ranges of the extinction
coefficient "k" and of the change "Δk" of the extinction
coefficient "k" which were required for satisfying the modulation
factor of not less than 35% as stipulated by the standard, these
results being obtained using various kinds of optical information
recording mediums which were prepared in the same manner as one
example by making use of each of the organic dye compounds

represented by the general formula shown in FIG. 2.
Best Mode for Carrying Out the Invention
According to the present invention, since not only the
decrease of the reflectance "R" due to the increase of the
extinction coefficient "k" but also the decrease of the
reflectance "R" due to the decrease of the refractive index "n"
can be secured as a modulation factor, it is now possible to
perform the recording with a laser beam having a wavelength
ranging from 350nm to 500nm. Further, since the recording layer
contains an organic dye compound having a reversible optical
property, i.e. since a dye compound having a structure
represented by that shown in FIG. 2 or FIG. 6, it is now possible
to obtain an optical information recording medium which is
capable of performing more efficient recording as compared with
the conventional optical information recording medium and to
realize the recording method thereof in the recording especially
by making use of blue laser beam.
Next, the optical information recording medium and the
recording method thereof according to various embodiments of the
present invention will be explained with reference to FIGs. 2
to 20. In FIGs. 15 to 17, the same portions are identified by
the same reference symbols, thereby omitting the detailed
explanation thereof.
FIG. 2 shows a general formula of an isomerizable organic
dye compound or an organic dye compound (especially, an amine
compound) having associating properties to be employed in the

present invention.
By the way, as for the ring constituting the residual group
of the aromatic ring of the ring "B" in the general formula, it
may preferably be constituted by a substituted or unsubstituted
carbocyclic aromatic ring or a substituted or unsubstituted
heterocyclic aromatic ring.
As for a preferable form of the heterocyclic compound
according to. the present invention, it is possible to employ a
compound represented by the general formula shown in FIG. 3 , which
represents one of the isomerizable structure or one of the
structures having associating properties.
Namely, FIG. 3 shows one example of the heterocyclic compound
(one of the isomerizable structure or one of the structures having
associating properties) to be utilized in the present invention.
This compound has an isomerizable structure or may constitute
a tautomeric body or may be a structure having associating
properties or orientating properties to be caused by an
electrostatic interaction.
By the way, as for the preferable examples of the substituent
groups to be provided by Rx, R2, R3 and R4 in the formula, they
include halogen atom, nitro group, cyano group, hydroxyl group,
mercapto group, carboxylic group, substituted or unsubstituted
alkyl group, substituted or unsubstituted amide group,
substituted or unsubstituted aralkyl group, substituted or
unsubstituted aromatic ring group, substituted or unsubstituted
alkoxy group, substituted or unsubstituted aralkyloxy group,
substituted or unsubstituted aryloxy group, substituted or

unsubstituted alkylthio group, substituted or unsubstituted
aralkylthio group, substituted or unsubstituted arylthio group,
substituted or unsubstituted amino group, substituted or
unsubstituted acyl group, substituted or unsubstituted acyloxy
group, substituted or unsubstituted alkoxycarbonyl group,
substituted or unsubstituted aralkyloxycarbonyl group,
substituted or unsubstituted aryloxycarbonyl group, substituted
or unsubstituted alkenyloxycarbonyl group, substituted or
unsubstituted aminocarbonyl group, substituted or unsubstituted
alkenyl group, substituted or unsubstituted alkenyloxy group,
substituted or unsubstituted alkenylthio group, substituted or
unsubstituted heteroaryl group, substituted or unsubstituted
heteroaryloxy group, substituted or unsubstituted
heteroaryloxycarbonyl group, substituted or unsubstituted
heteroarylthio group and substituted or unsubstituted
metallocenyl group.
Among them, if the organic dyestuff has a substituent group
consisting of amide group, preferably alkylamide, it may become
more reactable by the light and heat to be provided by the laser
beam, so that an isomer is more liable to be formed and that the
organic dyestuff can be more easily orientated by the change in
association thereof through an electrostatic action.
FIG. 4 shows a chemical structure of a preferable compound
which is useful as a dye (organic dyestuff) to be employed in
the optical recording layer of the present invention. This
dyestuff is employed in the examples as explained below.
FIG. 5 shows a chemical structure of another preferable
compound which is useful as an organic dyestuff to be employed

in the optical recording layer of the present invention.
As for the structure of the organic dye compound having more
excellent properties according to the present invention, it may
be a structure having in its molecule a plurality of isomerizable
structures or a plurality of associating structures.
FIG. 6 shows a general formula of a dyestuff having a
plurality of isomerizable structures or a plurality of
associating structures in its molecule. By the way, B, C and
X in the formula may become identical with each other. A material
having a plurality of tautomeric structures or a plurality of
associating structures in its dye molecule is expected to exhibit
improved properties especially as the optical recording layer
3 or as an optical information recording medium 1 or 20.
FIG. 7 shows a general formula of one example of the compound
having a plurality of tautomeric structures or a plurality of
associating structures in its dye molecule.
By the way, as for the preferable examples of the substituent
groups to be provided by Rx, R2, R3 and R4 in the formula, they
include, as in the case of the compound shown in FIG. 3, halogen
atom, nitro group, cyano group, hydroxyl group, mercapto group,
carboxylic group, substituted or unsubstituted alkyl group,
substituted or unsubstituted aralkyl group, substituted or
unsubstituted amide group, substituted or unsubstituted aromatic
ring group, substituted or unsubstituted alkoxy group,
substituted or unsubstituted aralkyloxy group, substituted or
unsubstituted aryloxy group, substituted or unsubstituted
alkylthio group, substituted or unsubstituted aralkylthio group,
substituted or unsubstituted arylthio group, substituted or

unsubstituted amino group, substituted or unsubstituted acyl
group, substituted or unsubstituted acyloxy group, substituted
or unsubstituted alkoxycarbonyl group, substituted or
unsubstituted aralkyloxycarbonyl group, substituted or
unsubstituted aryloxycarbonyl group, substituted or
unsubstituted alkenyloxycarbonyl group, substituted or
unsubstituted aminocarbonyl group, substituted or unsubstituted
alkenyl group, substituted or unsubstituted alkenyloxy group,
substituted or unsubstituted alkenylthio group, substituted or
unsubstituted heteroaryl group, substituted or unsubstituted
heteroaryloxy group, substituted or unsubstituted
heteroaryloxycarbonyl group, substituted or unsubstituted
heteroarylthio group and substituted or unsubstituted
metallocenyl group.
Among them, if the organic dyestuff has a substituent group
consisting of amide group, preferably alkylamide, it may become
more reactable by the light and heat to be provided by the laser
beam, so that an isomer is more liable to be formed and that the
organic dyestuff can be more easily orientated by the change in
association thereof through an electrostatic action.
FIG. 8 shows a general formula of another example of the
compound having a plurality of tautomeric structures or a
plurality of associating structures in its dye molecule.
FIG. 18 is a diagram illustrating a process wherein the
optical recording layer 3 containing an amine compound changes
from its basic structure to a polarized structure (quinoid
structure) and then to an orientated structure. The optical

recording layer 3 containing an amine compound having the
aforementioned associating properties is designed to generate,
. as it is irradiated with laser beam, an unbalanced electric charge
(polarization) in the dye molecule as the amine compound is
reacted with light and heat, thereby creating an isomer as shown
in FIG. 18.
Due to this unbalanced electric charge, a reversible change
in structure, of dyestuff is taken place at a portion of the
recording layer which has been irradiated with the laser beam
in distinction from a portion of the recording layer which has
not been irradiated with the laser beam, thus providing a
tautomeric change to the recording layer, thereby making it
possible to perform the recording.
Further, if there is existed an amine compound having
associating properties, an electrostatic interaction is
permitted to take place due to this unbalanced electric charge.
As a result, due to the association to be effected by this
electrostatic interaction, a change in orientation is caused to
occur in the recording layer, thereby making it possible to
perform the recording.
Furthermore, if there is existed an amine compound having
associating properties, the molecule of the dyestuf f is optically
excited by the irradiation of laser beam and hence this irradiated
portion is caused to change into a quinoid structure, thereby
making it possible to perform the recording.
These states mentioned above can be confirmed, for example,
by observing the absorption spectrums obtained before and after

the recording. For example, when the absorption peak of
absorption spectrum after the recording is found shifted to the
long wavelength side as compared with the absorption spectrum
of optical recording layer before the recording, it can be said
that the isomerization or the change in orientation has taken
place.
Further, whether or not the molecular composition (the kind
and the number of atoms constituting the molecule) of an organic
dye compound is retained without generating the decomposition
of the organic dye compound can be confirmed by the analysis of
the peak of each component by means of GC-MS system or a
high-performance liquid chromatography for instance. For
example, if the peaks obtained before and after the irradiation
of laser beam are the same with each other, it can be that the
molecular composition of an organic dye compound is retained
without being decomposed.
Although representative methods to confirm the
compositional state of an organic dye compound have been
discussed above, it is also possible to employ other confirmation
methods.
Since the aforementioned amine compound having associating
properties is liable to easily react with water or oxygen because
of its nature, i.e. the associating properties thereof, the
quinoid structure to be derived therefrom is very unstable so
that it is required to take some measures to retain as much as
possible the state of quinoid structure thus converted.
Therefore, in order to definitely retain the quinoid

structure or stabilize the recorded portion, it may be advisable
to incorporate various kinds of additives.
For example, a dehydration type additive such as carbodiimide
may be suitably employed as such an additive. Further, a quencher
may be mixed as a light stabilizer into the dye composition.
Further, in order to prevent the optical recording layer 3
from being deteriorated by water or oxygen, an auxiliary layer
should preferably be deposited on one of the surfaces of the
optical recording layer, which is opposite to the surface where
the light-reflecting layer is to be formed, thereby preventing
the penetration of water and oxygen into the optical recording
layer.
More specifically, an oxidation inhibitor should preferably
be incorporated into the optical recording layer 3, specific
examples of the oxidation inhibitor comprising at least one kind
of compound selected from the group consisting of a hindered amine
(HALS)-based compound, a phenolic compound, an amine-based
compound, a phosphate-based compound and an organosulfur-based
compound.
Alternatively, an oxidation inhibiting film comprising any
of these compounds may be disposed on one side of and close to
the optical recording layer 3.
Further, the optical recording layer'3 may further comprise
a rust preventive formed of a benzotriazole-based compound or
a benzothiazole-based compound.
Examples

Next, the examples of the present invention will be explained
together with comparative examples.
(Examples)
The amine compound shown in FIG. 4 was dissolved in TFP
(tetrafluoropropanol: 2,2,3,3-tetrafluoro-1-propanol) to
prepare a coating solution having a concentration of 18g/L.
The organic dye compound having associating properties to
be employed in the present invention is generally poor in
solubility. It was found however that, when TFP
(tetrafluoropropanol: 2,2,3,3-tetrafluoro-1-propanol) was
employed as a solvent, it was possible to obtain an optical
recording layer 3 which could be easily transformed into a quinoid
structure through a change in association. By means of
spin-coating method, this coating solution was then coated on
the surface of a disc-like polycarbonate substrate 2 (120mm in
outer diameter, and 0.6mm in thickness) having a continuous
guiding groove (pre-groove 7) having a depth of 7 5nm and a half
width of 220nm. Then, the resultant layer was dried for 30
minutes at a temperature of 80° C to obtain the optical recording
layer 3 having an average dye film thickness of 70nm.
The guiding groove (pre-groove 7) was formed at a track pitch
of about 4 00nm. In order to suppress the expansion of the
recording pit 10, this guiding groove should preferably be formed
such that the width thereof is as wide as possible and the depth
thereof is as shallow as possible. Specifically, the width of

the guiding groove should preferably be confined within the range
of 220-270nm and the depth of the guiding groove should preferably
be confined within the range of 55-80nm. Further, the average
film thickness of an optical recording layer 3 should preferably
be confined within the range of 40-80nm and the leveling value
of the optical recording layer 3 should preferably be confined
within the range of 0.35-0.45.
Then, silver (Ag) was sputtered onto the surface of this
optical recording layer 3 to form a light-reflecting layer 4
having a thickness of 120nm.
Furthermore, an ultraviolet curing resin (SD-318; Dainippon
Ink Chemical Industries) was spin-coated on the surface of the
light reflection layer 4 and irradiated with ultraviolet rays
to cure the resin to form a protective layer 5.
An ultraviolet-curing resin adhesive was coated on the
surface of this protective layer 5 and then a dummy substrate
6 formed of the same material and the same configuration (0.6mm
in thickness and 120mm in outer diameter) as those of the
substrate 2 was adhered on the surface of this protective layer
5. Subsequently, the adhesive was irradiated with ultraviolet
rays to cure the adhesive, thus manufacturing a postscript type
optical information recording medium 1.
Further, an optical information recording medium 1 was
fabricated as a comparative example in the same manner as the
aforementioned example except that the oxacyanine dye shown in
FIG. 9 was employed.
FIG. 10 shows a table illustrating the results of assessment
of recording properties of each of the aforementioned example
and comparative example.

As apparent from FIG. 10, according to the example, it was
possible to perform the recording with a recording power of about
a half of that required in the comparative example. With respect
to the reflectance and the modulation factor, values of almost
the same level were obtained in both of these examples.
It will be recognized that SbER (Simulated bit Error Rate)
which corresponds to jitter (jitter of signal) and PRSNR (Partial
Response Signal to Noise Ratio) which corresponds to noise to
regenerating signals were both deteriorated in the comparative
example as compared with those of the example.
FIG. 11 shows a table illustrating the optical constants
before and after the recording of a recording pit 10, i.e. a
magnitude of the change "Δk" in refractive index "n" as well as
in extinction coefficient "k" in the optical recording layer 3
of the disc employed in the example. It will be seen from the
results shown in FIG. 1 that, as a result of the recording, the
refractive index "n" was decreased and the extinction coefficient
"k" was increased. This indicates that the portion of recording
pit was thickened in color as compared with the unrecorded
portion.
FIG. 12 is a graph illustrating the influence of the "Δn"
and the "Δk" on the modulation factor (reflectance) in each of
the discs which were fabricated in the same manner as the
aforementioned example, wherein the film thickness of the optical
information recording medium 1 created by making use of the
dyestuff shown in FIG. 4 was variously changed. As shown in FIG.
12, as far as the contribution to the modulation factor is
concerned, the "Δk" is greater than the "Δn" in contrast to that
can be obtained from the conventional organic dyestuff.
It will be assumed from these results that about 80% of the

modulation factor was derived from the effects of the "Δk".
Because of this reason, the recording can be suitably
performed by the increase in magnitude of change "Δk" of
extinction coefficient that can be derived from the recording
rather than the increase in magnitude of change "Δn" of refractive
index.
When calculated from the ratio of contribution to be obtained
from FIG. 12, if it is desired to achieve a modulation factor
of up to 0.45 for instance, the "Δn" is required to be 0.052 (an
increase of 94%), whereas the "Δk" is required to be 0.009 (an
increase of 22%). More specifically, Δn=0.335 or Δk=0.055 is
required.
FIG. 13 is a graph illustrating the change of reflectance
relative to the refractive index "n". When it is desired to
obtain a sufficient modulation factor (for example, a standard
value of 0.35) by making use of only the refractive index "n",
it is required to realize a change of about 1.55-1.9 as the range
of change in refractive index as shown by the dot-and-dash line
shown in FIG. 13. As a matter of fact however, as shown in the
graph of FIG. 11, a change of only 0.055 was permitted as the
"Δn" and hence the value of this change is confined to a very
narrow region (as indicated in FIG. 13 by a two dots-and-dash
line) as shown in FIG. 13, thus making it impossible to obtain
a sufficient change in reflectance.
FIG. 14 is a graph illustrating the change of reflectance
relative to the extinction coefficient "k" . When it is desired
to obtain a sufficient modulation factor (for example, 0.35) by
making use of only the extinction coefficient "k", it is required
to realize a change of about 0.15-0.22 as the range of change
in extinction coefficient "k" as shown by the dot-and-dash line

shown in FIG. 14. As a matter of fact however, as shown in the
graph of FIG. 11, a change of 0.05 was permitted as the "Δk" and
hence this change indicates a value of a very wide region (as
indicated in FIG. 13 by a two dots-and-dash line) as shown in
FIG. 13 in contrast to the case of refractive index "n", thus
making it possible to obtain a sufficient change in reflectance
by making use of only the "Δk".
In FIG. 14, the range of value required (as the range of
Ak) for the recording by making use of only the "Δk" (shown by
the dot-and-dash line shown in FIG. 14) is shifted to a smaller
value than the actual range of change (shown by the two
dots-and-dash line in FIG. 14). The reason for this is that,
as a tendency of the change of reflectance relative to the "Δk",
the rising gradient of reflectance tends to become higher as the
"Δk" becomes smaller, so that the range of value required for
the recording by making use of only the "Δk" is shown therein
as a preferable range. In practical use, the range of "Δk" may
be set to any optional zone.
FIG. 19 shows a table illustrating the refractive index "n",
the extinction coefficient "k" and the modulation factor, before
and after the recording, of various kinds of optical information
recording mediums which were prepared in the same manner as the
aforementioned example by making use of each of the organic dye
compounds represented by the general formula shown in FIG. 2.
In FIG. 19, the existence or absence of ferrocene group as
indicated in the organic dye compound shown in FIG. 5 is indicated
in each of the organic dye compounds.
FIG. 20 is a graph illustrating the ranges of the extinction
coefficient "k" and of the change "Δk" of the extinction
coefficient "k" which were required for satisfying the modulation

factor of not less than 35% as stipulated by the standard, these
results being obtained using various kinds of optical information
recording mediums which were prepared in the same manner as the
aforementioned example by making use of each of the organic dye
compounds represented by the general formula shown in FIG. 2.
With respect to the change of refractive index "n" and the
change of extinction coefficient "k" before and after the
recording according to the present invention, it will be
recognized that the refractive index "n" falling within the range
of 1.7 to 1.9 before the recording was caused to change by only
a magnitude of at most 0.1 or less than 0.1 after the recording
as shown in FIG. 19. Whereas, the extinction coefficient "k"
which was 0.22 before the recording was caused to change by a
magnitude of not less than 0.74 after the recording as shown in
FIG. 20.
With regard to the range of extinction coefficient "k" (0.22
or less) which is indicated by an arrow in FIG. 20 and the range
of change "Δk" (0.074 or more), they were derived, as described
above, as the conditions for securing not less than 35% as a
standard value of modulation factor in the optical information
recording medium of the present invention.
By the way, it is preferable to take the error of measurement
into consideration in evaluating the aforementioned results.
Namely, it is preferable to take into account a measuring error
of ±5%-±10% with respect to the values obtained in the measurement.
In that case, the refractive index "n" falling within the range
of 1.5 to 2.0 before the recording may be caused to change by
10% or less (the result obtained is re-calculated according to
the ratio) after the recording, and the extinction coefficient
"k" which has been 0.25 or less before the recording may be caused

to change by 30% or more (the result obtained is re-calculated
according to the ratio) after the recording.
By the way, the present invention has been accomplished
expecting the change of reflectance that can be derived from the
change of the extinction coefficient "k" and also expecting a
synergistic effect of the change of reflectance that can be
derived from the change of the extinction coefficient "k" and
also from the' change of the refractive index "n" as the dye
compounds represented by the chemical structures shown in FIGs.
2 and 6 or by the chemical structures shown in FIGs. 3 to 5 and
FIGs. 7 and 8 are employed as a dyestuf f of the optical recording
layer. Further, the present invention has been accomplished
expecting the change of reflectance that can be brought about
by the change of the extinction coefficient "k", preferably, by
an increase of the extinction coefficient "k". Further, when
a dyestuf f which is also capable of greatly changing (decreasing)
the refractive index "n" is employed, it is possible to obtain
further preferable optical properties. In this case however,
it is more preferable if these changes can be caused to generate
without inviting the decomposition of the dyestuff.

WE CLAIM:
1. An optical information recording medium comprising:
a light-transmitting substrate with trenches in the surface; and
an optical recording layer containing a light-absorbing substance constituted by a
dyestuff which is capable of absorbing laser beam, wherein an optically readable
information is recorded in the optical recording layer through an irradiation of the laser
beam onto the optical recording layer and by taking advantage of the discoloration of the
dyestuff while retaining the molecular composition of the dyestuff, said dyestuff having
the following chemical formula (2):

wherein R1, R2, R3 and R4 are individually hydrogen atom or a substituent group.
2. The optical information recording medium as claimed in claim 1, wherein the
optically readable information is recorded in the optical recording layer by taking
advantage of the change in extinction coefficient of the dyestuff.
3. The optical information recording medium as claimed in claim 2,wherein the
dyestuff is selected from those which are capable of being isomerized as a result of the
irradiation of laser beam thereto.
4. The optical information recording medium as claimed in claim 2, wherein the
extinction coefficient is designed to be increased as a result of the irradiation of laser
beam thereto as compared with that before the irradiation of laser beam.

5. The optical information recording medium as claimed in claim 2, wherein a
wavelength on the long wavelength side of the absorption peak of the absorption
spectrum of the dyestuff to the laser beam is employed as a recording wavelength and the
recording is performed through the change of extinction coefficient of the dyestuff
relative to the recording wavelength.
6. The optical information recording medium as claimed in claim 5, wherein the
change of refractive index of the dyestuff relative to the recording wavelength is
combined with the change of the extinction coefficient, thereby making it possible to
perform the recording by making use of these changes.
7. The optical information recording medium as claimed in claim 6, wherein the
refractive index of the dyestuff is confined to the range of 1.5 to 2.0 before the recording.
8. The optical information recording medium as claimed in claim 6, wherein the
refractive index of the dyestuff is enabled to change at a ratio of not more than 10% as a
result of the recording as compared with that before the recording.
9. The optical information recording medium as claimed in claim 5, wherein the
recording wavelength is confined within the range of 350 nm to 500 nm.
10. The optical information recording medium as claimed in claim 9, wherein the
recording wavelength is confined to 405 nm.
11. The optical information recording medium as claimed in claim 2, wherein the
extinction coefficient of the dyestuff is 0.25 or less before the recording.
12. The optical information recording medium as claimed in claim 2, wherein the
extinction coefficient of the dyestuff is enabled to change at a ratio of not less than 30%
as a result of the recording as compared with that before the recording.

13. The optical information recording medium as claimed in claim 1, wherein the
dyestuff is designed to be thickened in color as a result of the irradiation of laser beam
thereto as compared with that before the irradiation of laser beam.
14. The optical information recording medium as claimed in claim 1, wherein the
optical recording layer is enabled to form an isomer due to the light created by an
irradiation of the laser beam thereto and due to the heat generated by the absorption of the
laser beam, thereby enabling to perform the recording of the information.
15. The optical information recording medium as claimed in claim 14, wherein the
isomer is enabled to form a polarized structure which is unbalanced in electric charge as
it is irradiated with the laser beam, this polarized structure being designed to be
orientated by an electrostatic interaction, thereby making it possible to record the
information.
16. The optical information recording medium as claimed in claim 15, wherein the
dyestuff is enabled to change in extinction coefficient as the polarized structure is
orientated.
17. The optical information recording medium as claimed in claim 1, wherein me
optical recording layer is enabled to record the information at a wavelength ranging from
350 to 500 nm and the dyestuff is an organic dye compound having reversible optical
properties.
18. The optical information recording medium as claimed in claim 1, wherein the
dyestuff comprises a compound which is capable of changing the absorption peak to the
long wavelength side as a result of the recording.
19. The optical information recording medium as claimed in claim 1, which further
comprises a light-reflecting layer which is capable of reflecting the laser beam.

20. The optical information recording medium as claimed in claim 1, wherein the
dyestuff is an organic dye and an oxidation preventive layer is disposed on one side of
and close to the optical recording layer, the oxidation preventive layer containing at least
one compound selected from the group consisting of a hindered amine (HALS)-based
compound, a phenolic compound, an amine-based compound, a phosphate-based
compound and an organosulfur-based compound.
21. The optical information recording medium as claimed in claim 1, wherein the
optical recording layer contain an oxidation preventing agent comprising at least one
compound selected from the group consisting of hindered amine (HALS)-based
compound, a phenolic compound, an amine-based compound, a phosphate-based
compound and an organosulfur-based compound.
22. The optical information recording medium as claimed in claim 1, wherein the
optical recording layer contains a rust preventive formed of a benzotriazole-based
compound or a benzothiazole-based compound.
23. The optical information recording medium as claimed in claim 1, wherein the
substrate is provided with trenches about 400 nm in track pitch, each trench having a
width of about 220-270 nm and a depth of about 55-80 nm.
24. An optical information recording medium comprising:
a light-transmitting substrate; and
an optical recording layer containing a light-absorbing substance constituted by a dyestuff which is capable of absorbing laser beam, wherein an optically readable
information is recorded through an irradiation of the laser beam onto the optical
recording layer and by taking advantage of the discoloration of the dyestuff while
retaining the molecular composition of the dyestuff, wherein said dyestuff is a dye
compound represented by the following chemical formula (3):


25. An optical information recording medium comprising:
a light-transmitting substrate; and
an optical recording layer containing a light-absorbing substance constituted by a
dyestuff which is capable of absorbing laser beam, wherein an optically readable
information is recorded through an irradiation of the laser beam onto the optical
recording layer and by taking advantage of the discoloration of the dyestuff while
retaining the molecular composition of the dyestuff, wherein said dyestuff is a dye
compound represented by the following chemical formula (4):

26. An optical information recording medium comprising:
a light-transmitting substrate; and
an optical recording layer containing a light-absorbing substance constituted by a
dyestuff which is capable of absorbing laser beam, wherein an optically readable
information is recorded in the optical recording layer through an irradiation of the laser
beam onto the optical recording layer and by taking advantage of the discoloration of the

dyestuff while retaining the molecular composition of the dyestuff, the optical
information recording medium being characterized in that a dye compound represented
by the following chemical structure (5) is employed as the dyestuff:

wherein "A" is a substituted or unsubstituted aryl group or a heterocyclic group; R1,
R2, R3 and R4 are individually hydrogen atom, a substituted or unsubstituted alkyl group,
a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group;
"B" and "C" are individually a residue of aromatic ring; and "X" is a substituted or
unsubstituted linking group.
27. The optical information recording medium as claimed in claim 26, wherein the
dye compound represented by the chemical formula (5) is a dye compound represented
by the following chemical formula (6):

wherein R1, R2, R3 and R4 are individually hydrogen atom or a substituent group.

28. The optical information recording medium as claimed in claim 26, wherein the
dye compound represented by the chemical formula (5) is a dye compound represented
by the following chemical formula (7):

29. A recording method of optical information recording medium as claimed in any
one of claim 1, 24, or 26, the recording method being featured in that a wavelength on the
long wavelength side of the absorption peak of the absorption spectrum of the dyestuff to
the laser beam is employed as a recording wavelength and that the recording is performed
through the change of extinction coefficient of the dyestuff relative to the recording
wavelength.
30. The recording method as claimed in claim 29, wherein the recording wavelength
is confined within the range of 350 nm to 500 nm.
31. The recording method as claimed in claim 29, wherein the recording wavelength
is confined to 405 nm.


ABSTRACT

OPTICAL INFORMATION RECORDING MEDIUM
AND RECORDING METHOD THEREOF
To provide an optical information recording medium including a pigment
appropriate for high-density and high-speed optical recording by the blue laser light of
350 to 500 nm and especially around 400 nm (for example, 405 run), enabling recording
at low power, suppressing thermal affect of recording to the optical recording layer, and
assuring a reflection ratio or modulation degree by the change of a refraction index n and
an attenuation coefficient k; and to provide a recording method thereof.
Instead of the recording based on the optical phase difference obtained by a
change A n of the refraction index n of the pigment as in the conventional method, a
pigment capable of performing recording based on the change ?k of the attenuation
coefficient k has been obtained. Recording may be performed mainly by the change Ak of
the attenuation coefficient k. It is preferable to use a recording wavelength which is at the
side of longer wavelength than the absorption peak of the absorption spectrum for the
laser beam of the aforementioned pigment. However, the invention is not to be limited to
this and characterized in recording performed by the change of the attenuation coefficient
of the pigment against the recording wavelength.

Documents:

01249-kolnp-2007-abstract.pdf

01249-kolnp-2007-assignment.pdf

01249-kolnp-2007-claims.pdf

01249-kolnp-2007-correspondence others 1.1.pdf

01249-kolnp-2007-correspondence others 1.2.pdf

01249-kolnp-2007-correspondence others.pdf

01249-kolnp-2007-description complete.pdf

01249-kolnp-2007-drawings.pdf

01249-kolnp-2007-form 1.pdf

01249-kolnp-2007-form 18.pdf

01249-kolnp-2007-form 3 1.1.pdf

01249-kolnp-2007-form 3.pdf

01249-kolnp-2007-form 5.pdf

01249-kolnp-2007-international publication.pdf

01249-kolnp-2007-pct request.pdf

01249-kolnp-2007-priority document.pdf

1249-KOLNP-2007-(13-09-2011)-CORRESPONDENCE.pdf

1249-KOLNP-2007-(13-09-2011)-ENGLISH TRANSLATION.pdf

1249-KOLNP-2007-(14-11-2011)-CORRESPONDENCE.pdf

1249-KOLNP-2007-(14-11-2011)-FORM 3.pdf

1249-KOLNP-2007-(30-12-2011)-CORRESPONDENCE.pdf

1249-KOLNP-2007-ASSIGNMENT.pdf

1249-KOLNP-2007-CORRESPONDENCE.pdf

1249-KOLNP-2007-EXAMINATION REPORT.pdf

1249-KOLNP-2007-FORM 18.pdf

1249-KOLNP-2007-FORM 3.pdf

1249-KOLNP-2007-FORM 5.pdf

1249-KOLNP-2007-GPA.pdf

1249-KOLNP-2007-GRANTED-ABSTRACT.pdf

1249-KOLNP-2007-GRANTED-CLAIMS.pdf

1249-KOLNP-2007-GRANTED-DESCRIPTION (COMPLETE).pdf

1249-KOLNP-2007-GRANTED-DRAWINGS.pdf

1249-KOLNP-2007-GRANTED-FORM 1.pdf

1249-KOLNP-2007-GRANTED-FORM 2.pdf

1249-KOLNP-2007-GRANTED-SPECIFICATION.pdf

1249-KOLNP-2007-OTHERS.pdf

1249-KOLNP-2007-REPLY TO EXAMINATION REPORT.pdf

1249-KOLNP-2007-TRANSLATED COPY OF PRIORITY DOCUMENT.pdf

abstract-01249-kolnp-2007.jpg


Patent Number 254933
Indian Patent Application Number 1249/KOLNP/2007
PG Journal Number 02/2013
Publication Date 11-Jan-2013
Grant Date 07-Jan-2013
Date of Filing 10-Apr-2007
Name of Patentee TAIYO YUDEN CO., LTD.
Applicant Address 16-20, UENO 6-CHOME, TAITO-KU, TOKYO
Inventors:
# Inventor's Name Inventor's Address
1 IDA KEIICHI C/O TAIYO YUDEN CO., LTD., 16-20, UENO 6-CHOME, TAITO-KU, TOKYO 110-0005
2 MORISHITA, DAISUKE C/O TAIYO YUDEN CO., LTD., 16-20, UENO 6-CHOME, TAITO-KU, TOKYO 110-0005
PCT International Classification Number B41M 5/26
PCT International Application Number PCT/JP2005/018112
PCT International Filing date 2005-09-30
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2004-382052 2004-12-28 Japan
2 2004-287209 2004-09-30 Japan
3 2004-287210 2004-09-30 Japan
4 2004-382051 2004-12-28 Japan
5 2004-382053 2004-12-28 Japan