JPS6353732A - Optical recording method - Google Patents

Abstract

PURPOSE:To permit ternary recording by 2 kinds of dots by projecting light of controlled exposures to an optical recording medium having a recording layer contg. a polydiacetylene deriv. compd. and specific compd. to discolor the exposed parts, thereby forming the pits consisting of recesses. CONSTITUTION:The light of the exposures controlled according to recording information is projected to the optical recording medium having the recording layer 2 contg. the polydiacetylene deriv. compd. and >=1 kinds of the compd. expressed by the formula [I], [II] or [III] to discolor the exposed parts 3a, 3b of the exposure Q1 and to form the pits consisting of the recesses in the exposed parts of the exposure Q2. (Q1<Q2). In the formulas, R<1> and R<2> denote a hydrogen atom or alkyl group, cyclic alkyl group, allyl group, aralkyl group or aryl group, R<3> and R<4> denote a hydrogen or halogen atom. Z1 and Z2 denote an atomic group necessary for completing a nitrogenous heterocycle and A1 and A2 denote a bivalent hydrocarbon group for forming a 5-membered or 6-membered ring. High-density recording by the ternary recording is thereby permitted with a sheet of the recording medium.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to an optical recording method using an optical recording medium, and in particular, enables a combination of color change recording and pit recording, that is, ternary recording, on one optical disc. The present invention relates to an optical recording method that enables high-density, high-sensitivity optical recording even when using a low-output semiconductor laser, and is advantageous in terms of energy saving.

(Prior Art) Recently, optical recording media such as optical disks, optical tapes, and optical cards (hereinafter collectively referred to as optical disks) have been attracting attention as central players in office automation. For example, optical discs can record and store a large amount of documents, documents, etc. on a single disc, so they can be used to organize documents, etc. in the office.
It has the advantage that management can be carried out efficiently.

The recording layer used in such optical disc technology can store high density information using optically detectable small (eg 1 micron) dots in the form of spiral or circular tracks.

A typical disk used in this optical disk technology is one in which a recording layer made of a material sensitive to laser is provided on a substrate. To write information on this disc, a laser beam focused on the laser sensitive layer (recording layer) is scanned, dots are formed only on the surface irradiated with the laser beam, and the dots are shaped into a spiral or circular shape depending on the recorded information. Form in the form of a track. That is, the laser sensitive layer is capable of absorbing laser energy to form optically detectable dots. For example, in the heat mode recording method, the laser-sensitive layer absorbs thermal energy and can form dots consisting of small recesses (pits) at that location by evaporation or melting. In another beat mode recording method, absorption of the applied laser energy can form a dot of optically detectable discoloration at that location.

Information recorded on this optical disk is detected by scanning a laser along a track and reading optical changes in areas where dots are formed and areas where dots are not formed. For example, when a disk is used that does not have a recording layer on the reflective surface of the substrate, a laser is scanned along a track and the energy reflected by the disk is monitored by a photodetector. At this time, in the case of pit recording, the output of the photodetector decreases in areas where pits are not formed, while in areas where pits are formed, the laser beam is sufficiently reflected by the underlying reflective surface and the photodetector output is reduced. output becomes larger.

Various types of recording layers for such optical discs have been studied, including those mainly using inorganic materials such as metal thin films such as aluminum evaporated films, bismuth thin films, tellurium oxide thin films, and chalcogenide amorphous glass films. However, recently, organic materials have been attracting attention due to their cost and ease of manufacture.

On the other hand, since the conventional heat mode method performs binary recording of whether dots are formed or not, there is a limit to the ability to perform higher density recording.

[Problem that the invention seeks to solve]

The present invention has been made to solve the problems of the prior art, and by forming the recording layer of an optical recording medium by combining a cyanine dye and a diacetylene derivative compound, it is possible to record a change in color with a single optical disc. In other words, it is possible to perform three-value recording using two types of dots, and even when using a low-output semiconductor laser, color change recording and pit recording can be performed at the same high speed. It has been completed by discovering.

An object of the present invention is to provide an optical recording method that enables three-value recording using two types of dots on one disc.

Another object of the present invention is to provide an optical recording method that enables optical writing using a small, lightweight, and low-output semiconductor laser and also enables high-speed recording.

Still another object of the present invention is to provide an optical recording method that allows recording at higher density and higher sensitivity.

Still another object of the present invention is to provide an optical recording method that has excellent stability and can obtain high-quality optically recorded images.

[Means for Solving the Problems] That is, the optical recording method of the present invention comprises a polydiacetylene derivative compound and the following general formula [I], [11] or [I
I! ] An optical recording medium having a recording layer containing one or more compounds represented by is irradiated with light whose exposure amount is controlled according to the recorded information, and the exposed area of the exposure NQ+ is discolored,
The exposure part of the exposure Ji Q2 is characterized by having a step of forming a pit consisting of a concave part (however, Q+ < Q2).

General formula [I] General formula [■ General formula [111] % formula % (In the above formula, R1 and R2 are a hydrogen atom, a substituted or unsubstituted alkyl group, a cyclic alkyl group, an allyl group, a substituted or unsubstituted alkyl group, It represents a substituted aralkyl group or a substituted or unsubstituted aryl group, and R3 and R4 represent a hydrogen atom or a halogen atom.

Zl and z2 represent an atomic group necessary to complete a substituted or unsubstituted nitrogen-containing heterocycle, and ^1 and 82 are divalent hydrocarbons forming a substituted or unsubstituted 5- or 6-membered ring. represents a group, M represents a cation, and x represents an anion.

The diacetylene derivative compound (hereinafter abbreviated as compound D) contained in the optical recording medium used in the method of the present invention is expressed by the following general formula % (where R and R' are polar groups; An alkyl group, a cyclohexyl group, etc., which may be substituted with a group.

a saturated aliphatic hydrogen group such as; may be substituted with a polar group,
An olefinic hydrocarbon group such as a vinyl group or a propenyl group; or an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, or an alkylphenyl group, which may be substituted with a polar group; is, for example, a carboxyl group or a metal or amine salt thereof, a sulfonic acid group or a metal or amine salt thereof, a sulfamide group, an amide group, an amino group, an imino group, a hydroxy group, an oxyamino group, a diazonium group, a guanidine group, and a dorazine group. , phosphoric acid group, silicic acid group, aluminate group, nitrile group, thioalcohol group, nitro group and halogen atom. ) and their polymers.

On the other hand, the compound represented by the general formula [I], [■] or [III] used in the present invention (hereinafter abbreviated as cyanine dye) has an absorption peak in a wavelength range of 750 r+m or more, and It is a compound that generates heat when exposed to infrared light.

To explain this cyanine dye more specifically, in the general formulas [I], [■co and [II], R1 and R2
is an alkyl group (e.g., methyl group, ethyl group, n-propyl group, 1so-propyl group, n-butyl group, 5e
c-butyl group, 1so-butyl group, t-butyl group, n-
amyl group, t-amyl group, n-hexyl group, n-octyl group, t-octyl group, etc.), substituted alkyl groups (e.g. 2- and droxyethyl groups, 3-hydroxypropyl groups,
4-hydroxybutyl group, 2-acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-sulfatepropyl group , 4-sulfatebutyl group, N-(methylsulfonyl)-rubamylmethyl group, 3-(acetylsulfamyl)propyl group, 4-(acetylsulfamyl)butyl group, etc.), cyclic alkyl group (e.g. cyclohexyl group, etc.), allyl group (CH2”CH-CI(2-),
Aralkyl groups (e.g. benzyl group, phenethyl group, α
-naphthylmethyl group, β-naphthylmethyl group, etc.), substituted aralkyl group (e.g., carboxybenzyl group, sulfobenzyl group, hydroxybenzyl group, etc.), aryl group (e.g., phenyl group, etc.), or substituted aryl group (e.g., phenyl group, etc.)
For example, carboxyphenyl group, sulfophenyl group, hydroxyphenyl group, etc.). In particular, in the present invention, among these organic residues, hydrophobic ones are preferred.

R3 and R4 represent a hydrogen atom or a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.).

Zl and Z2 are substituted or unsubstituted heterocycles, for example, thiazole series nuclei (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4.5-diphenylthiazole, 4-(2-
chenyl)-thiazole, etc.), benzothiazole series nuclei (e.g. benzothiazole, 5-chlorobenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5
-bromobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5゜6-cymethoxybenzothiazole, 5,6-cyoxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6- hydroxybenzothiazole, 4.5.6.7-titrahydroxybenzothiazole, etc.), naphthothiazole series nuclei (e.g. naphtho(2,1-d)thiazole, naphtho(1,2-d)thiazole, 5-methoxynaphtho (1,2-d)thiazole, 5-ethoxynaphtho(1,2-d)thiazole, 8
-methoxynaphtho(2,1-d]thiazole, 7-methoxynaphtho(2,1-d)thiazole, etc.), thionaphthene(7,6-d)thiazole series nuclei (e.g. 7-medoxythionaphthene(7, 6-d) thiazole), oxazole series nuclei (e.g. 4-methyloxazole,
5-methyloxazole, 4-phenyloxazole,
4,5-diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole, 5-phenyloxazole), benzoxazole series nuclei (e.g. benzoxazole, 5-chloropenzoxazole, 5
-Methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5.6-dimethylbenzoxazole, 5-methoxybenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc. ), naphthoxazole series nuclei (e.g. naphtho(2,1-d)oxazole, naphtho(1,2-d)
)oxazole, etc.), selenazole series nuclei (e.g. 4-methylselenazole, 4-phenylselenazole, etc.), penzoselenal series nuclei (e.g. benzoselenazole, 5-chlorobenzoselenazole, 5-methylbenzoselenazole) , 5.6-dimethylbenzoselenazole, 5-methoxybenzoselenazole, 5-methyl-
6-methoxybenzoselenazole, 5,6-cyoxymethylenebenzoselenazole, 5-hydroxybenzoselenazole, 4°5,6,7-titrahydroxybenzoselenazole, etc.), naphthoselenazole series nuclei (e.g. naphthoselenazole), (2,1,d) selenazole, naphtho(1,2
-d) selenazole), thiazoline series nuclei (e.g. thiazoline, 4-methylthiazoline, 4-hydroxymethyl-4-methylthiazoline, 4,4-bis-hydroxymethylthiazoline, etc.), oxazoline series nuclei (e.g. oxazoline), Selenazoline series nuclei (e.g. selenazoline), 2-quinoline series nuclei (e.g. quinoline, 6-methylquinoline, 6-chloroquinoline, 6-medoxyquinoline, 6-nitoxyquinoline, 6-hydroxyquinoline), 4-quinoline series nuclei Nuclei (e.g. quinoline,
6-medoxyquinoline, 7-methylquinoline, 8-methylquinoline), 1-isoquinoline series nuclei (e.g. isoquinoline, 3,4-dihydroxyisoquinoline), 3-
Nuclei of the isoquinoline series (e.g. 3-isoquinoline), 3
, 3-dialkylindolenine series (e.g. 3,3
-dimethylindolenine, 3.3-dimethyl-5-chloroindolenine, 3.3.5-trimethylindolenine, 3,3゜7-trimethylindolenine), pyridine series nuclei (e.g. pyridine, 5-methyl and lysine), benzimidazole series nuclei (e.g. 1-ethyl-5,6
-dichlorobenzimidazole, 1-hydroxyethyl-5,6-dichlorobenzimidazole, 1-ethyl-
5-chlorobenzimidazole, 1-ethyl-5,6-
Dibromobenzimidazole, 1-ethyl-5-phenylbenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-ethyl-5-cyanobenzimidazole, 1-(β-acetoxyethyl)-5-cyanobenzimidazole, 1 -ethyl-5-chloro-6-cyanobenzimidazole, 1-ethyl-5-fluoro-6
-cyanobenzimidazole, 1-ethyl-5-acetylbenzimidazole, 1-ethyl-5-carboxybenzimidazole, 1-ethyl-5-ethoxycarborubenzimidazole, 1-ethyl-5-sulfamylbenzimidazole, 1-ethyl-5-N-ethylsulfamylbenzimidazole, 1-ethyl-5,6-difluorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-ethyl-5-ethylsulfonylbenzimidazole, 1-Ethyl-5-methylsulfonylbenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole,! -Ethyl 5-
Trifluoromethylsulfonylbenzimidazole, 1
-ethyl-5-trifluoromethylsulfinylbenzimidazole, etc.).

A1 and A2 are substituted or unsubstituted 5- or 6-membered ring-forming hydrocarbon groups (e.g. -CH2.CH
2-, etc.), and these 5- or 6-membered rings may be fused with a benzene ring, a naphthalene ring, etc.

X is a chloride ion, bromide ion, iodide ion,
Perchlorate ion, benzenesulfonate ion, P-
p represents an anion such as toluene sulfonate ion, methyl sulfate ion, ethyl sulfate ion, propyl sulfate ion, etc., and p represents an anion group in which R1 and/or R2 itself is an anion group, such as -503♀0503", -C00e,
S@NH-,-so,'%-co-1-so2! %-
It does not exist when 5o2- is included.枦 represents cations such as hydrogen cations, sodium cations, ammonium cations, potassium cations, pyridium cations, and the like.

Next, representative examples of the cyanine dye used in the present invention are listed below, and for convenience, they are expressed in the form of a betaine structure of general formula [I] or [m]. However, in the preparation of these dyes, mixtures of dyes in betaine or salt form are obtained and are therefore used as mixtures.

Specific examples of general formulas [I] and [II] are (1) to (33
) is the general formula [■ As a specific example of (34) to (47)
are listed.

Oe (7) oe (8) 0゜ct ct (23)
. e(24)
Oe The cyanine dyes (1) to (47) above can be used alone or in combination of two or more.

The optical recording medium used in the present invention contains the above-mentioned DA compound and the above-mentioned cyanine dye, and may have any of a -layer mixed system, a two-layer separation system, or a multilayer laminated system.

Here, a -layer mixed system is one consisting of a mixed layer of a DA compound and a cyanine dye, and a two-layer separation system is one in which a layer containing a D^ compound and a layer containing a cyanine dye are separately laminated. Furthermore, a multi-layer laminated system does not include the above-mentioned two-layer separated system in which one or more layers containing a D^ compound and one or more layers containing a cyanine dye are laminated in a predetermined number and order. Refers to each component.

A typical configuration of the optical recording medium used in the present invention is shown in Figure 1 (A
) and shown in FIG. 1(B). In FIG. 1(A), a recording layer 2 of a -layer mixed system is provided on a substrate 1,
In FIG. 1(B), a recording layer 2 of a two-layer separation system, that is, a recording layer 2 consisting of a layer 2a containing a DA compound and a layer 2b containing a cyanine dye, is provided on a substrate 1.

To form the recording layer 2, typically, in the case of a -layer mixed system, a coating solution is prepared by mixing a fine crystal powder of a DA compound and a cyanine dye in a suitable volatile solvent, and then A coating solution is applied onto the substrate 1, and in the case of a two-layer separation system or a multilayer laminated system, a coating solution containing a fine crystal powder of the D^ compound and a coating solution containing a cyanine dye are separately prepared. ,
These may be applied to the substrate 1 in a predetermined order.

As the substrate 1 of the optical recording medium used in the present invention, glass,
Various supporting materials such as plastic plates such as acrylic resin, plastic films such as polyester, paper, and metal can be used, but when recording by irradiating radiation from the substrate side, recording radiation of a specific wavelength is used. Use something that allows the lines to pass through.

- The solvent of the coating liquid used to form the recording layer of the layer mixture system is selected as appropriate depending on the type of binder used and the type of DA compound and cyanine dye, but generally alcohol such as methanol, ethanol, isopropanol, etc. Ketones such as acetone, methyl ethyl ketone, and cyclohexanone: N.

Ketones such as N-dimethylformamide, ■, N-dimethylacetamide; Sulfoxides such as dimethyl sulfoxide; Ethers such as tetrahydrofuran, dioxane, ethylene glycol monomethyl ether; Esters such as methyl acetate, ethyl acetate, butyl acetate; Chloroform , methylene chloride, dichloroethylene, carbon tetrachloride,
Aliphatic halogenated hydrocarbons such as trichlorethylene;
Benzene, toluene, xylene, monochlorobenzene,
Examples include aromatic hydrocarbons such as dichlorobenzene.

In addition, suitable solvents for cyanine dyes as solvents for coating solutions used to form two-layer separated systems or multilayer laminated systems include various solvents similar to those used to form the above-mentioned single-layer mixed systems. .

Suitable dispersion media for the DA compound include aliphatic hydrocarbons such as n-hexane, n-hebutane, n-octane, and cyclohexane.

However, since DA compounds are highly crystalline compounds, -
Even if it is first dissolved in a solvent and this solution is applied onto a substrate, recrystallization proceeds during the drying process to obtain dalein. Therefore, not only a dispersion but also a solution of the DA compound may be used. As the solvent in this case, the same solvents as those mentioned above as solvents for cyanine dyes can be used.

Note that a binder made of natural or synthetic polymer may be added to each coating liquid as appropriate in order to improve the adhesion with the substrate 1 or with other layers. Furthermore, various additives may be added to improve the stability and quality of the recording layer 2.

Application of such a coating liquid to the substrate 1 can be performed by a spinner rotation coating method, a dip coating method, a spray coating method,
Peed coating method, wire bar coating method,
Techniques such as a blade coating method, a roller coach ink method, and a curtain coating method are used.

When the recording layer 2 is a single-layer mixed type, the film thickness is suitably in the range of about 400 to 2-2, and particularly preferably in the range of 1,000 to 5,000. In addition, in the case of two layers m-+, the thickness of each layer is suitable to be about 200 to 1 scale, especially 200 to 1 scale.
A range of 5,000 people is preferred. Furthermore, in the case of a multilayer laminated system, the total thickness of the layers containing individual DA compounds and the total thickness of the layers containing individual cyanine dyes are both 10
Approximately 0 to 1 u pass through.

In particular, a range of 200 to 5,000 people is preferred.

The blending ratio of the D compound and the cyanine dye in the recording layer 2 is preferably about 1715 to 15/I, and optimally about 1/I.
It is lO~10/l.

Note that various protective layers may be provided on the recording layer 2 configured as described above, if necessary. Note that the method of the present invention can be carried out regardless of the order in which the layers are laminated in the case of a two-layer separation system or a multilayer laminated system.

The optical recording method of the present invention can be carried out using an optical recording medium configured in this manner.

In this optical recording medium, by applying light to the DA compound (excluding the polymer), the absorption wavelength of the recording layer changes and the apparent color changes. That is, the DA compound (excluding the polymer) is initially almost colorless and transparent, but upon irradiation with ultraviolet rays, it polymerizes and changes into a polydiacetylene derivative compound. This polymerization occurs only by irradiation with ultraviolet light and not by the application of other physical energy such as heat. As a result of this polymerization, it has a maximum absorption wavelength in the range of 620 to 60 nm, and its color changes from blue to dark. This change in hue due to polymerization is an irreversible change;
- The recording layer that has changed to a blue or dark color does not return to a colorless transparent film.

Further, the recording layer containing the polydiacetylene derivative compound and the cyanine dye, which has changed its color from blue to dark, generates heat at a temperature corresponding to the exposure amount of the irradiated light. that time,
If the recording layer 2 is not melted and the polydiacetylene derivative compound is heated to about 50° C. or higher, the exposed area of the recording layer will have a maximum absorption wavelength of about 540 nm and turn into a red film. do. Note that this change to a red film is also an irreversible change.

Further, when the exposure amount is increased and the exposure amount exceeds a certain limit, the exposed portion of the recording layer melts.

The optical recording method of the present invention performs recording by utilizing the characteristics obtained by the combination of the compound and the cyanine dye. This recording method will be explained in detail below.

As the semiconductor laser used in the method of the present invention, it is particularly suitable to use a GaAs junction laser with an output wavelength of 800 to 850 nm.

When carrying out the optical recording method of the present invention, when using an optical recording medium having an optical recording layer composed of a D^ compound (excluding polymers) and a cyanine dye, first, the recording layer is Irradiates the entire area with ultraviolet light. By this irradiation with ultraviolet rays, the 0^ compound (excluding the polymer) in the recording layer is polymerized and changed into a polydiacetylene derivative compound, and the recording layer changes color into a blue to dark-colored film. (Of course, O
This operation is not required for those having a recording layer using a polydiacetylene derivative compound as the A compound. ) On the other hand, the recorded information is converted into an optical signal by a semiconductor laser via a control circuit. This optical signal passes through an optical system and is placed, for example, on an optical recording medium mounting means, and is placed at a predetermined position on a synchronously rotating disc-shaped optical recording medium having a single-layer mixed recording layer (see FIG. 2). The image is formed as shown in A). The imaging position is the recording layer 2 of the optical recording medium.

The exposure amount at imaging points (parts) 3a and 3b is approximately 50°C for polydiacetylene derivative compound for color change recording.
(Q+) is heated to a temperature that is sufficient to keep the recording layer 2 at a temperature that does not melt the recording layer 2, and the amount (Q2) is controlled to be sufficient to melt the recording layer 2 for pit recording ( However, Q+ < 02).

In order to change the exposure amount at the imaging point in this way, a method may be used such as changing the intensity of the semiconductor laser, changing the laser irradiation time, or using these in combination. Note that when performing irradiation with two types of exposure doses, the above control may be performed using one semiconductor laser, or multiple semiconductor lasers that can obtain different exposure doses may be used. .

The cyanine dye present at the imaging points (sites) 3a and 3b absorbs this laser beam 4 and generates heat.

Here, the imaging point 3a that received the above-mentioned exposure amount of Q+ is
As the polydiacetylene derivative compound is heated by the heat generated by the cyanine dye, the color changes to red, resulting in a dot 5a consisting of a discolored area that can be distinguished from the blue or dark color of the unexposed area as shown in FIG. 2(B). In addition, in an optical recording medium having a recording layer consisting only of an OA compound, the polydiacetylene derivative compound has no sensitivity to a laser with a wavelength of 800 to 85 Qnm, so when a semiconductor laser with this wavelength is used, , optical recording was impossible due to discoloration.

On the other hand, the imaging point 3b that received the exposure amount of Q2 mentioned above melts due to the heat generated by the cyanine dye, and as shown in Fig. 2 (B
), a pit consisting of a recess 5b is formed.

In this case, since the recording layer 2 of the optical recording medium used in the present invention is composed of a combination of cyanine dye and a polydiacetylene derivative compound as described above, in other words, the presence of the polydiacetylene derivative compound makes it possible to record The energy required to melt the layer can be significantly reduced, and pit formation by cyanine dyes is greatly promoted.

In this way, the discolored portion 5a is formed on the recording layer 2 according to the input information.
Optical recording using two different types of dots, ie, ternary recording, is carried out using dots having two different shapes, ie, the pits 5b and 5b. Moreover, since the optical recording medium used in the present invention has high sensitivity to both color change recording and pit recording, such ternary recording can be performed at high speed.

The case where an optical recording medium having a layer-mixed recording layer is used has been described above, but when a two-layer separation system as shown in FIG. 1(B) is used, the imaging points 3a, 3b is the third
As shown in Figure (A), a layer 2b containing cyanine dye is formed. When the laser 4 is irradiated in this way, the cyanine dye generates heat according to the exposure m Q+ and Q2 of the image forming points 3a and 3b according to the recorded information, and as shown in FIG. A dot 5a or a pit 5b consisting of a recess is formed.

The two types of dots recorded in the above manner can be read both at once or only one of them, as desired.

In the above example, a disk-shaped disk (optical disk) was used as the optical recording medium, but of course, depending on the type of substrate that supports the recording layer containing the D^ compound and cyanine dye, it may be possible to use an optical tape, an optical disk, etc. Cards can also be used.

〔Effect of the invention〕

The effects of the optical recording method of the present invention are listed below.

(+) Since a combination of cyanine dye and polydiacetylene derivative compound is used in the recording layer, discoloration recording and pit recording can be performed as desired on one recording medium using a small and lightweight semiconductor laser. can be done. That is, high-density recording by ternary recording is possible with one recording medium. Moreover, the recording layer has high sensitivity in both color change recording and pit recording, and high-speed recording is possible.

(2) Since the recording layer is formed uniformly and with good surface properties, it is possible to perform optical recording with excellent stability and high quality.

(3) Optical recording using an inexpensive recording medium having a highly homogeneous, large-area recording layer becomes possible.

〔Example〕

Hereinafter, the present invention will be explained in more detail based on examples.

Example 1 General formula (:12 H2S-c=ccmiC-C3H,6
1 part by weight of fine crystal powder of a diacetylene derivative compound represented by -C0OH and 15 parts by weight of the cyanine dye represented by the dye Al1L5 were added to 20 parts by weight of methylene chloride, and the mixture was sufficiently stirred to prepare a coating solution. .

Next, a glass disk substrate (thickness 1.5 mm, diameter 200 mm) was attached to a spinner coater, and after dropping a small amount of the coating liquid onto the center of the disk substrate, the spinner was applied at a predetermined rotation speed for a predetermined time. The thickness of the coating film after drying on the substrate is 500 mm and 1000 mm.
Optical recording media for 2000 people and 2000 people were created, respectively.

Each of the optical recording media obtained in this way was first given 25
The recording layer was uniformly and sufficiently irradiated with 4 nm ultraviolet rays to turn the recording layer into a blue film.

Next, a semiconductor laser with a wavelength of 830 nm whose laser output can be varied (R Ota Kani 10 mW, laser beam diameter = 1 scale, irradiation time: 200 ns) was applied to each optical recording medium having this blue film recording layer. / 1 dot) was irradiated according to manual information, and the optical recording of the present invention was carried out. Note that when a pit recording command was given, the laser output was 8 mW, and when a color change recording command was given, the laser output was 4 mW.

The evaluation of the recording results is shown in Table 1. The evaluation is based on a comprehensive evaluation of the sensitivity, resolution, and contrast ratio between recorded and non-recorded areas for recording both pits and discoloration, with particularly good results being ◎, and good results being unable to record O1 or Bad items were marked as ×.

Example 2 A mixed solution containing 1 part by weight of diacetylene derivative compound, 10 parts by weight of cyanine dye, and 20 parts by weight of methylene chloride was used as a coating liquid, and the same method as in Example 1 was carried out. An optical recording medium was created.

Each of the optical recording media obtained in this way was first given 25
After uniformly and sufficiently irradiating the recording layer with 4 nm ultraviolet rays to turn the recording layer into a blue film, optical recording was carried out in the same manner as in Example 1, and this was evaluated. Table 1 shows the evaluation of the recorded results.

Example 3 A mixed solution containing 1 part by weight of the diacetylene derivative compound, 5 parts by weight of the cyanine dye, and 12 parts by weight of methylene chloride was used as a coating liquid, and the same method as in Example 1 was carried out. An optical recording medium was created.

Each of the optical recording media obtained in this way was first given 25
After uniformly and sufficiently irradiating the recording layer with 4n111 ultraviolet rays to turn the recording layer into a blue film, optical recording was carried out in the same manner as in Example 1, and this was evaluated. Table 1 shows the evaluation of the recorded results.

Example 4 A mixed solution containing 1 part by weight of diacetylene derivative compound, 1 part by weight of cyanine dye, and 4 parts by weight of methylene chloride was used as a coating liquid, and the same method as in Example 1 was carried out. An optical recording medium was created.

Each of the optical recording media obtained in this way was first given 25
After uniformly and sufficiently irradiating the recording layer with 4 nm ultraviolet rays to turn the recording layer into a blue film, optical recording was carried out in the same manner as in Example 1, and this was evaluated. Table 1 shows the evaluation of the recorded results.

Example 5 A mixed solution containing 5 parts by weight of diacetylene derivative compound, 1 part by weight of cyanine dye, and 12 parts by weight of methylene chloride was used as a coating liquid, and the same method as in Example 1 was carried out. An optical recording medium was created.

Each of the optical recording media obtained in this way was first given 25
After uniformly and sufficiently irradiating the recording layer with 4 nm ultraviolet rays to turn the recording layer into a blue film, optical recording was carried out in the same manner as in Example 1, and this was evaluated. Table 1 shows the evaluation of the recorded results.

Example 6 A mixed solution containing 10 parts by weight of the diacetylene derivative compound, 1 part by weight of the cyanine dye, and 20 parts by weight of methylene chloride was used as a coating liquid, and the same method as in Example 1 was carried out. An optical recording medium was created.

Each of the optical recording media obtained in this way was first given 25
After uniformly and sufficiently irradiating the recording layer with 4 nm ultraviolet rays to turn the recording layer into a blue film, optical recording was carried out in the same manner as in Example 1, and this was evaluated. Table 1 shows the evaluation of the recorded results.

Example 7 A mixed solution containing 15 parts by weight of diacetylene derivative compound, 1 part by weight of cyanine dye, and 30 parts by weight of methylene chloride was used as a coating liquid, and the same method as in Example 1 was carried out. Created a light self-recording medium.

Each of the optical recording media obtained in this way was first given 25
After uniformly and sufficiently irradiating the recording layer with 4r++++ ultraviolet rays to turn the recording layer into a blue film, optical recording was carried out in the same manner as in Example 1, and this was evaluated. Table 1 shows the evaluation of the recorded results.

Example 8 General formula Cl2H2S-CmiC-CmiC-CeH+6-G
In place of the diacetylene derivative compound represented by o leaves, the general formula C8H, FuC:C-CmiC-C2H, -(:00
An optical recording medium was prepared in the same manner as in Example 4, except that the compound represented by No. 11 was used.

Each of the optical recording media obtained in this way was first given 25
After uniformly and sufficiently irradiating the recording layer with 4 nm ultraviolet rays to turn the recording layer into a blue film, optical recording was carried out in the same manner as in Example 1, and this was evaluated. Table 2 shows the evaluation of the recorded results.

Examples 9 to 12 Dye A was used instead of cyanine dye represented by dye J/L5.
Optical recording media were prepared in the same manner as in Example 8, except that cyanine dyes represented by IEL+2.20.31.38 were used. Each of these optical recording media was first uniformly and sufficiently irradiated with 254 nm ultraviolet rays to form a blue film in the recording layer, and then optical recording was performed in the same manner as in Example 1 and evaluated. Table 2 shows the evaluation of the recorded results.

Example 13 1 part by weight of a cyanine dye represented by dye A6 was dissolved in 10 parts by weight of dichloromethane to prepare a coating liquid A.

Apart from this, Cl2H2SCmiC-CF(neeC3)1
．． 1 part by weight of fine crystal powder of a diacetylene derivative compound represented by 6-(:OOH) was added to 210 parts by weight of benzene, and the mixture was sufficiently stirred to prepare a coating liquid B.

Next, a glass disk substrate (thickness 1.5 mm, diameter 200 mm) was mounted on a spinner coater, and after first dropping a small amount of the coating liquid A onto the center of the disk substrate, it was heated at a predetermined number of rotations. Apply by rotating the spinner for an amount of time.
It was dried at room temperature to form a layer containing cyanine dye on the substrate. Next, the substrate on which the layer containing the cyanine dye has been formed is mounted on the spinner coating machine again, and the coating liquid B is applied to the center of the surface of the layer containing the cyanine dye on the disk substrate formed previously.
After dropping a small amount of the solution, the coating was applied by rotating a spinner at a predetermined number of rotations for a predetermined period of time, dried at room temperature, and a layer containing a DA compound was laminated on the layer containing a cyanine dye to form a recording layer.

The film thicknesses of the layer containing the cyanine dye and the layer containing the D-type compound were varied as shown in Table 3.
25 types of optical recording media, numbered 3-1 to 13-25, were obtained.

Each of the optical recording media obtained in this way was first given 25
The recording layer was uniformly and sufficiently irradiated with 4 nm ultraviolet rays to turn the recording layer into a blue film.

Next, optical recording was performed on each optical recording medium having the blue recording layer in the same manner as in Example 1, and the results were evaluated. Table 4 shows the evaluation of the recorded results.

Table 4

[Brief explanation of drawings]

FIG. 1(A) and FIG. 1CB) are schematic cross-sectional views illustrating one aspect of the configuration of an optical recording medium used in the method of the present invention, and FIG.
Figure (A) and Figure 2 (B) and Figure 3 (A) and Figure 3
Figure (B) is a schematic cross-sectional view of an optical recording medium showing the optical recording process of the present invention. 1: Substrate 2: Recording layer 2a: Layer containing D^ compound 2b Layer containing dianine dye 3a, 3b = exposure area 4: laser beam 5a: discoloration area 5b = bit

Claims (1)

[Scope of Claims] 1) A polydiacetylene derivative compound and the following general formula [
An optical recording medium having a recording layer containing one or more of the compounds represented by I ], [II] or [III] is irradiated with light whose exposure amount is controlled according to recorded information, and the exposure amount Q_1
A process of discoloring the exposed area of and forming a pit consisting of a concave part in the exposed area of the exposure amount Q_2 (however, Q_1 < Q_2
). General formula [I] ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ General formula [III] ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ ▲Mathematical formulas, chemical formulas, There are tables, etc. ▼ (In the above formula, R^1 and R^2 are hydrogen atoms, substituted or unsubstituted alkyl groups, cyclic alkyl groups, allyl groups, substituted or unsubstituted aralkyl groups, or substituted or unsubstituted aralkyl groups. represents an aryl group, R^3 and R^4 represent a hydrogen atom or a halogen atom. Z_1 and Z_2 represent an atomic group necessary to complete a substituted or unsubstituted nitrogen-containing heterocycle, and A_1 and A_2 represents a substituted or unsubstituted divalent hydrocarbon group forming a 5- or 6-membered ring, M^■ represents a cation, and X^
■ indicates an anion. )