JPS62162253A - Optical recording and reading method - Google Patents

Abstract

PURPOSE:To miniaturize a device and to carry out high-speed and high- resolution recording and reproduction by using radiation for writing on an optical recording medium having a recording layer consisting of the built-up film of a diacetylene derivative compd. and contg. a specified diene compd. salt, and using the light having a shorter wavelength than the radiation for reading. CONSTITUTION:A soln. obtained by adding >= kind of compd. shown by the general formula (1) or (2) to a diacetylene derivative compd. (DA compd.) is used, and the monomolecular film or the built-up film of the DA compd. is formed on a substrate or a layer contg. a diene compd. salt by the Langmuir- Blodgett's technique to obtain an optical recording medium. UV rays of 254nm are irradiated on the optical recording medium to polymerize the DA compd. in the recording layer, and the recording layer is converted into a blue film. A semiconductor laser 2 radiating IR rays in the region of wavelength in the range 800-900nm is used as an information writing means. Meanwhile, a semi conductor laser or a light emitting diode 10 radiating visible radiation in the region of wavelength in the range 550-750nm is used as an information reading means.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an optical recording/reading method for an optical recording medium containing a diacetylene derivative compound. The present invention relates to an optical record reading method using visible light of 550 to 750 nm as a reading means.

[Conventional technology]

Recently, optical discs have been attracting attention as a central player in office automation. Optical discs can store large amounts of documents, literature, etc. on a single disc, so
Organize and manage documents, etc. in the office efficiently. Various types of recording media have been considered for this optical disc, but those using organic materials are the most preferred because of their cost and ease of manufacture.

Diacetylene derivative compounds are known as organic materials for such recording media. Focusing on the thermochromic properties of these compounds, a recording technology for use as laser recording media was disclosed in Japanese Patent Application Laid-Open No. 147807/1983. There is. However, this specification does not mention what kind of laser was used or should be used, and merely states that recording was performed using a laser.

The present inventors investigated laser recording of this diacetylene derivative compound using various lasers, and found that although thermochromic recording is possible using a large, high-power laser such as an argon laser, It has been confirmed that laser recording cannot be performed when a low-output semiconductor laser (wavelength: 800 to 900 nm) is used. However, for a practical recording medium such as an optical disk, it is required that optical writing is possible using a small, low-output semiconductor laser, and reading can be performed using a light emitting diode or a small laser.

On the other hand, JP-A-59-84248 and JP-A-84249 disclose an organic coating containing a salt of a diene compound having a specific structure with good thermal stability. It is disclosed that since the laser absorbs radiation and generates heat, it is possible to perform so-called heat mode recording in which pits are formed using laser energy. However, when recording is performed by forming physical bits on the surface of a recording medium, it is necessary to ensure that the initial surface of the recording medium is sufficiently smooth and at the same time that the surface of the recording medium is not scratched even after recording. Sufficient care is required, and in particular,
It has been relatively difficult to perform high-density, high-sensitivity, and high-speed optical writing and to read the written records with high precision.

In addition, the recording layer of these recording media is made up of microcrystals of diacetylene derivative compounds or salts of diene compounds dispersed in a binder, and the orientation of these compounds within the recording layer is random, so the locations vary. Due to this, phenomena such as differences in light absorption and reflectance and differences in the degree of chemical reactions occur, and it cannot be said that high-density recording is necessarily achieved.

[Problem that the invention seeks to solve]

The present invention has been made in order to solve the problems of the prior art, and the purpose of the present invention is to enable optical writing using a small and lightweight semiconductor laser, and to read data by light irradiation with a small and lightweight visible light emitter. The object of the present invention is to provide an optical recording reading method that enables the following.

Another object of the present invention is to provide an optical recording/reading method that enables high-density, high-sensitivity, high-speed recording, and high-speed, highly accurate reading.

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

(Means for Solving the Problems) That is, the optical recording and reading method of the present invention comprises a monomolecular film of a diacetylene derivative compound having at least a hydrophilic site and a hydrophobic site or an accumulation thereof 11i, and the following general formula ( An optical recording medium having a recording layer containing one or more of the compounds represented by 1) or (2) is irradiated with ultraviolet rays, and then irradiated with infrared rays of 800 to 900 nm depending on the recorded information to improve the quality of the recording layer. A step of discoloring the irradiated part,
It is characterized by comprising the step of irradiating the discolored portion of the recording layer with visible light of 550 to 750 nm to read recorded information.

General formula (1) (wherein R1 represents an alkyl group, a phenyl group which may have a substituent, or a styryl group, and R2 and R6 are
Represents an arylene group that may have a substituent that forms a military double bond system with two adjacent -CH=CH- groups,
R3 and R7 represent a phenyl group or a naphthyl group which may have a substituent, R4 represents an alkoxy group, R5 represents an alkyl group, and A represents an anionic residue. ) The diacetylene derivative compound having both a hydrophilic site and a hydrophobic site (hereinafter abbreviated as D-formula compound) contained in the optical recording medium used in the method of the present invention means that c= c - in adjacent molecules. CE is a compound capable of 1.4-addition polymerization reaction between functional groups, typically represented by the following general formula (% formula %) (wherein, X is a hydrophilic group forming a hydrophilic site,
m and n represent integers. ) Compounds represented by:

Examples of the hydrophilic group X in the above compound include a carboxyl group, an amino group, a hydroxy group, a nitrile group,
Examples include a thioalcohol group, an imino group, a sulfonic acid group, a sulfinyl group, or a metal or amine salt thereof.

The alkyl group represented by +1 (Gl+2) forming a hydrophobic site is preferably a long-chain alkyl group having 1 to 30 carbon atoms. Further, m+n is preferably an integer of 30 or less.

On the other hand, the compound represented by the general formula (1) or (2) used in the present invention (hereinafter abbreviated as diene compound salt)
is a compound that has an absorption peak in a wavelength range of 750 nm or more and generates heat when exposed to infrared light of this wavelength.

To explain this diene compound salt more specifically, in general formulas (1) and (2), R1 is an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, or phenyl which may have a substituent. or styryl group. Here, the substituents include methoxy, ethoxy,
Examples include alkoxy groups such as butoxy, halogen atoms such as chlorine, bromine, and iodine, alkyl groups such as methyl, ethyl, propyl, and isopropyl, and nitro groups. R2 and R
6 represents an arylene group which may have a substituent that forms a conjugated double bond system with two adjacent -CH=CH- groups, such as p-phenylene and 1,4-naphthylene. Examples of the substituent include halogen atoms such as chlorine, bromine and iodine, alkyl groups such as methyl and ethyl, and alkoxy groups such as methoxy and ethoxy.

R3 and R7 represent a phenyl group or a naphthyl group which may have a substituent. Examples of substituents include substituted amine groups such as dimethylamino, diethylamino, dipropylamino, dibutylamino, diphenylamino, phenylamino, phenylbenzylamine, and phenylethylamino, cyclic amino groups such as morpholino, piperidinyl, and pyrrolidino, methoxy, ethoxy, Examples include alkoxy groups such as butoxy. R4 represents an alkoxy group such as methoxy, ethoxy or butoxy. R5 represents an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl or hexyl. A is an anionic residue, such as BF2, c+9, c
F3clf, PFp, prosecution, P, c+sop, 0113
5g, C2) (,SO?C3H75O?C4H95O
? c5H,,5ope C6H13S03, CH3CHClSO3, Cl
CH2CH2SO3, CH3eOCX.

6H3>C11-503, ICH2S03, )I2
SR1c+ (c method C112s method, 0C112CH2S0
3, C035CH2SOP, eO3SCH2CH2SM, eO3SCH2G112CH7(:)12C82CI
l, Sg, θ03SCH2C:I+, -0-(:l
Specific examples of l2CH2503 and this diene compound are illustrated below.

The optical recording medium used in the present invention contains the OA compound and the diene compound salt, and the OA compound forms a monomolecular film or a cumulative film thereof alone or in a mixed state with the diene compound salt. The optical recording medium has a recording layer, and the specific structure of the optical recording medium is as shown below.

(+) To D: One having a recording layer consisting of a mixed monomolecular film of compound 16 and diene compound salt I7 or a cumulative film thereof (a schematic cross-sectional view is shown in FIG. 2).

(2) A recording layer consisting of two layers: a layer consisting of a monomolecular film of DA compound 16 or a cumulative film thereof, and a radiation absorbing layer 18 containing diene compound salt 17 (two-layer separation system, third A schematic cross-sectional view is shown in the figure).

(3) One or more layers of A layer 19 consisting of a monomolecular film of DA compound 16 or a cumulative film thereof, and 8 layers 20 consisting of a monomolecular film or a cumulative film thereof containing diene compound salt I7
Those having a recording layer formed by laminating one or more layers of (
Peter's cumulative membrane system, a schematic cross-sectional view is shown in Figure 4).

In addition, in the two-layer separation system and the Peter cumulative membrane system, D
The layer consisting of a monomolecular film of compound A or a cumulative film thereof and the radiation absorbing layer 18 or 8 layer 20 containing a diene compound salt may be stacked in any order, and either one may be located on the surface side of the recording layer. If necessary, various protective layers may be provided on the recording layer configured in this manner.

As the substrate 15 of the optical recording medium used in the present invention, various supporting materials such as glass, a plastic plate such as acrylic resin, a plastic film such as polyester, paper, and metal can be used. When recording is performed using a recording medium, one that transmits recording radiation of a specific wavelength is used.

To form a monomolecular film or a monomolecular cumulative film of a compound D on a substrate or a layer containing a diene compound salt, for example, the Langmuir-Prodgett method (hereinafter referred to as the LB method) developed by Langmuir et al. ) is used. In the LB method, when a molecule has a parent wood group and a hydrophobic group in its molecule, and the balance between the two (amphipathic balance) is maintained appropriately, this molecule is placed on the water surface and below the parent wood group. This is a method of creating a monomolecular film or a film consisting of an accumulation of monomolecular layers by utilizing the fact that the layer becomes a single layer toward the target.

A monolayer on the water surface has the characteristics of a two-dimensional system. When the molecules are sparsely dispersed, the area per molecule A and the surface pressure ■
The two-dimensional ideal gas seven-body equation, nA=kT, holds true between the two, resulting in a "gas film". Here, k is Boltzmann's constant and T is absolute temperature. If A is made sufficiently small, the intermolecular interaction becomes strong, resulting in a two-dimensional solid "condensed film (or solid film)". The condensed film can be transferred layer by layer to the surface of a substrate such as glass.

Using this method, a monomolecular film or a monomolecular cumulative film of the D^ compound is produced, for example, as follows. Mai'D
A gold octoxide compound is dissolved in a solvent such as loloform and spread on an aqueous phase to form a spread layer in which these compounds are spread in the form of a film. Next, to prevent this spread layer from spreading freely on the water phase and spreading too much, a partition plate (or float) is provided to limit the area of the spread layer and control the aggregation state of the compound to D. Obtain a surface pressure n proportional to . By moving this partition plate, the development area is reduced and the state of collection of the membrane material is controlled.
By gradually increasing the surface pressure, it is possible to set a surface pressure n suitable for producing a cumulative film. By vertically moving a clean substrate or a substrate with a diene compound salt-containing layer formed on the surface while maintaining this surface pressure, a monomolecular film of the DA compound is formed on the substrate or a layer containing the diene compound salt. The layer is then transferred to the top layer. A monomolecular layer film is produced in this manner, and a monomolecular layer cumulative film having a desired degree of accumulation is formed by repeating the above-described operations.

In order to transfer the monomolecular film to the substrate E, in addition to the above-mentioned vertical dipping method, methods such as a horizontal deposition method and a rotating cylinder method can be employed. The horizontal deposition method is a method in which the substrate is brought into horizontal contact with the water surface and transferred, and the rotating cylinder method is a method in which a cylindrical substrate is rotated on the water surface to transfer a monomolecular layer onto the surface of the substrate. In the vertical immersion method described above, when a substrate with a hydrophilic surface is lifted out of water in a direction transverse to the water surface, a first monomolecular layer of the hydrophilic groups of the DA compound facing the substrate is formed on the substrate.

As the substrate is moved up and down, one layer of monomolecular film is deposited with each step. Since the direction of the film-forming molecules is reversed between the pulling process and the dipping process, according to this method, a Y-shaped film is formed between each layer in which the parent wood group and the parent wood group and the hydrophobic group and the hydrophobic group face each other.

On the other hand, the horizontal deposition method is a method in which the substrate is brought into horizontal contact with the water surface and transferred, and a monomolecular layer of the DA compound with the hydrophobic group facing the substrate is formed on the substrate. In this method, there is no change in the orientation of the molecules of the compound toward D even if they are accumulated, and an X-type film is formed in which the hydrophobic groups face the substrate side in all layers. On the other hand, a cumulative film in which all the layers have parent groups facing the substrate is called a Z-type film.

The rotating cylinder method is a method in which a cylindrical substrate is rotated on the water surface to transfer a monomolecular layer onto the surface of the substrate.

The method of transferring the monomolecular layer onto the substrate is not limited to these methods, and when using a large-area substrate, a method of extruding the substrate from a substrate roll into an aqueous phase may also be adopted.

Furthermore, the orientation of the aforementioned parent wood group and hydrophobic group toward the substrate is a general rule, and can be changed by surface treatment of the substrate, etc.

Details of these monomolecular film transfer operations are already known and are described, for example, in "New Experimental Chemistry Course 18 Interfaces and Colloids", pages 498-507, published by Maruzen.

In addition, a so-called mixed monomolecular film or mixed monomolecular cumulative film composed of two or more compounds can also be obtained by the same method as described above. At this time, it is sufficient that at least one of the two or more compounds constituting the mixed monomolecular film or the mixed monomolecular cumulative film has both a hydrophilic site and a hydrophobic site,
Not all compounds are necessarily required to have both a hydrophilic site and a hydrophobic group in a hydrophobic portion. In other words, if the amphiphilic balance is maintained in at least one compound, a monomolecular layer will be formed on the water surface, and the other compounds will be sandwiched between the amphipathic compounds, resulting in a molecularly ordered structure as a whole. A monolayer is formed.

Therefore, a recording layer consisting of a mixed monomolecular film or a mixed monomolecular cumulative film of the compound D and the diene compound salt is prepared by dissolving the compound D and the diene compound salt in a solvent such as chloroform, and dissolving this in the aqueous phase -L. It is possible to form a developed layer in which these compounds are developed into a film shape, and then to form a developed layer by the LB method in the same manner as described above.

On the other hand, in order to form a layer containing a diene compound salt, a typical method can be adopted in which a diene compound salt is dissolved in a suitable volatile solvent to prepare a coating liquid, and then the coating liquid is applied. Various binders made of natural or synthetic polymers may be appropriately added to the coating liquid in order to improve the adhesion of the monomolecular film of the compound or the layer formed by the cumulative film thereof to the substrate or D.

Furthermore, various additives may be added to improve the stability and quality of this layer.

Suitable binders can be selected from a wide variety of resins. Specifically, cellulose esters such as nitrocellulose, cellulose phosphate, cellulose sulfate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose myristate, cellulose palmitate, cellulose acetate propionate, cellulose acetate butyrate: methylcellulose, ethylcellulose Cellulose ethers such as , propyl cellulose, butyl cellulose; polystyrene, polyvinyl chloride, polyvinyl acetate,
Vinyl resins such as polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyvinylpyrrolidone; copolymer resins such as styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer; polymethyl Acrylic resins such as methacrylate, polymethyl acrylate, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyacrylonitrile; polyesters such as polyethylene terephthalate: poly(4,4'-isopropylidene diphenylene-1,4- cyclohexylene dimethylene carbonate), poly(ethylenedioxy-3)
, 3'-phenylene thiocarbonate), poly(4,4
'-isopropylidene diphenylene carbonate coated terephthalate), poly(4,4'-isopropylidene diphenylene carbonate), poly(4,4'-5ec
-butylidene diphenylene carbonate), poly(4
,4'-isopropylidene diphenylene carbonate-
Polyarylate resins such as (block-oxyethylene); polyamides; polyimides; epoxy resins; phenolic resins; and polyolefins such as polyethylene, polypropylene, and chlorinated polyethylene can be used.

Suitable solvents for diene compound salts include alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aliphatic nitriles such as acetonitrile; chloroform, methylene chloride, dichloroethylene, and Carbon chloride, aliphatic halogenated hydrocarbons such as trichlorethylene; etc.; and the like, methylene chloride and acetonitrile are particularly preferred.

The coating liquid obtained in this way can be applied by spinner rotation coating method, dip coating method, spray coating method, pea coating method, wire bar coating method, blade coating method, roller coating method, curtain coating method, etc. law is used.

Further, the layer containing the diene compound salt may be a monomolecular film or a cumulative film thereof, similar to the layer D consisting of a monomolecular film of the compound or a cumulative film thereof. However, since the diene compound salt is not an amphipathic substance, a monomolecular film cannot be formed using the LB method alone. However, if the LB method is applied by using organic polymers with an appropriately balanced amphipathic property, such as higher fatty acids such as stearic acid and aragidic acid, as carrier molecules in any ratio, diene compounds can be produced. Mixed monolayers or mixed monolayer cumulative films containing salts can be formed.

When the recording layer is composed of a mixed monomolecular film of a compound and a diene compound salt or a cumulative film thereof, it is practically preferable that the film thickness is up to about 4 ec.

In addition, in the case of a two-layer separation system, the thickness of the monomolecular film of the compound D or its cumulative film is preferably one with a cumulative degree of up to about 4 ec, and II5! of the diene compound salt-containing layer. As for the thickness, when it is formed as a monomolecular film or a cumulative film thereof, the cumulative degree is up to about 2ec, and when it is formed as a non-monolayer film, it is 5100 to 1μ.
m, particularly preferably in the range of 200 to 5000 people.

Hetero! 1′! In the case of a membrane system, there are two or more bonding surfaces between the A layer 19 and the 8 layers 20, and it is practically preferable that the cumulative degree of the monomolecular film of the A layer 19 and the 8 layers 20 is about 4ec. .

In the optical recording/reading method of the present invention, in the recording medium configured as described above which is used for recording and reproduction, a compound is first polymerized to D in the recording layer.

That is, the compound D is initially almost colorless and transparent, but when the entire recording layer is irradiated with ultraviolet rays, it polymerizes and changes into a polydiacetylene derivative compound. This polymerization occurs by irradiation with ultraviolet rays, etc., and cannot occur simply by applying thermal energy. As a result of this polymerization, the recording layer has a 620 to 66
The maximum absorption wavelength is at 0 nm, and the color changes from blue to dark. This change in hue due to polymerization is an irreversible change, and once the recording layer changes from blue to dark, it does not return to a colorless transparent film. In this way, first, the DA compound in the recording layer is polymerized and changed into a polydiacetylene derivative compound, thereby turning the entire recording layer blue or dark in color.

When this polydiacetylene derivative compound that has changed from blue to dark color is heated to about 50°C or higher, it changes to about 540 nm.
It has a maximum absorption wavelength at , and the color changes to red. This change is also an irreversible change.

The optical record reading method of the present invention performs optical writing and optical record reading using the color changing properties of such polydiacetylene derivative compounds.Hereinafter, the optical record reading method of the present invention will be described in detail. .

FIG. 1 is a schematic diagram showing an example of an optical recording/reproducing apparatus used to implement the optical recording/reading method of the present invention. This optical recording and reproducing apparatus includes an optical recording medium mounting means (not shown) for setting the optical recording medium 1 at a predetermined position, an information writing means for writing information to the optical recording medium, and an information writing means for writing information to the optical recording medium. It consists of an information reading means for reading recorded information. The information writing means is 80
A semiconductor laser 2 that emits ultraviolet light with a wavelength within the range of 0 to 900 nm, a control circuit 3 that controls oscillation of the semiconductor laser 2 according to input information, and an optical system (collimating lens 4, tichroic mirror 5, reflector 6, It consists of a wavelength plate 7 and an objective lens 8). As the semiconductor laser 2, GaAs with an output wavelength of 820 to 840 nm is used.
Welding laser, such as IILP-1500 (trade name,
Newly manufactured by Hitachi, output wavelength 830nm, maximum output 10mW
) is preferably used.

On the other hand, the information reading means is controlled by a drive circuit 9 and includes a semiconductor laser or light emitting diode that emits visible light with a wavelength in the range of 550 to 750 nm. A photodetector 12 connected to the IO1 output circuit 11 and an optical pickup optical system (optical system Although most of the optical system is shared with the optical system for the information writing means, it is composed of a collimating lens 13 and a polarizing beam splitter 14 as unique components.

The semiconductor laser 10 is one that emits visible light with a wavelength in the range of 650 to 750 nm, for example, GaAlAs.
It is preferable to use a PN junction laser, and the light-emitting diode IO is one that emits visible light in the wavelength range of 550 to 750 nm, such as GaAIP, G
Preferably, junction diodes such as aP, GaAIAS, etc. are used.

The human power information is converted into an optical signal by the semiconductor laser 2 via the control circuit 3. This optical signal passes through an optical system, is placed on the optical recording medium mounting means, and is imaged at a predetermined position of the optical recording medium having a blue to dark color recording layer that rotates synchronously. The image forming position is the recording layer when the optical recording medium is a single-layer mixed type, and is the radiation absorption layer containing a diene compound salt when the optical recording medium is a two-layer separated type. The polyacetylene derivative compound present at the imaging point (site) does not absorb the laser beam of this wavelength, but the diene compound salt absorbs this laser beam and generates heat. The heat generated by the diene compound salt is transmitted to the adjacent polyacetylene derivative compound, causing the polydiacetylene derivative compound to turn red. In this way, optical writing is performed by changing the color of the recording area on the recording layer in accordance with the manual information.

On the other hand, optical record reading is carried out using low power continuous wave light emitted from a semiconductor laser or light emitting diode IO emitting visible light at a trench wavelength of 550-750 nm. This reading light has a low output and a wavelength outside the infrared region, so it does not cause the diene compound salt to generate heat. Therefore, no recording is performed during reading using this reading light. The reading light is imaged on the surface of the recording layer of the optical recording medium 1 and reflected, or the reflectance of this reading light is different between recorded areas (discolored areas) and non-discolored areas, so this reflected light By applying the light to the light receiving surface of the photodetector 12 through the optical pickup optical system, it is converted into an electric signal, and the recording is reproduced and read via the output circuit 11.

In the above example, the optical recording medium is a disc-shaped tisf (
Although an optical disc) was used, optical tapes, optical cards, etc. can also be used depending on the type of substrate that supports the recording layer containing the polydiacetylene derivative compound and diene compound salt.

(Effect of the invention) The effects of the optical recording/reading method of the present invention are listed below.

(1) Since the recording layer contains a diene compound salt that absorbs infrared rays with a wavelength in the range of 800 to 900 nm,
Optical writing can be performed using a small and lightweight semiconductor laser that emits infrared rays in the range of 00 to 900 nm, and
It can be read using a small and lightweight semiconductor laser or light emitting diode that emits visible light in the wavelength range of 750 nm.

(2) As the optical recording medium, at least the compound in the recording layer is formed as a (mixed) monomolecular film or a cumulative film thereof, and has a high density and a high degree of order. Homogeneous optical writing and reading can be performed.

(3) Since the recording and reproducing method utilizes changes in the hue of the recording layer due to light irradiation, high-speed, high-density, and highly sensitive optical writing can be performed, and high-speed and highly accurate optical reading can be performed.

(4) In particular, it is formed as a Peter film having two or more bonding surfaces of a thermosensitive color-changing layer made of a D-type compound formed as a monomolecular film or a cumulative film thereof, and a radiation absorption layer made of a diene compound salt. When an optical recording medium is used, the heat transfer efficiency within the optical recording medium is extremely high, so highly sensitive optical writing can be performed.

〔Example〕

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

Example 1 General formula c12H7, -CE (nee CEC-CoH,6-
A solution prepared by dissolving 1 part by weight of a diacetylene derivative compound represented by CO leaf and 1 part by weight of a diene compound salt represented by the above compound/al in chloroform at a concentration of IxlO-3 mol/1 was prepared at a pH of 6.5. The mixture was developed on an aqueous phase having a cadmium chloride concentration of 1×10 −3 mol/1. After evaporating the solvent chloroform, the surface pressure was reduced to 20 dyne/
cm, and while keeping the temperature constant, gently raise and lower the glass substrate, which has been sufficiently washed and has a hydrophilic surface, in the direction across the water surface at a vertical speed of 1.0 cm/min to separate the elevated compounds and diene compounds. A mixed monomolecular film with a salt was transferred onto a substrate, and an optical recording medium was prepared in which mixed monomolecular cumulative films of 11 mixed monomolecular molecules, 21st layers, 41st layers, and 81st layers were formed on the substrate.

These optical recording media are uniformly and sufficiently irradiated with 254 nm ultraviolet rays to polymerize the D-type compound in the recording layer and turn the recording layer into a blue film. Therefore, recording was performed under the following recording conditions.

Semiconductor laser (IILP-1500, manufactured by Hitachi)
Laser wavelength: 830 nm Laser beam diameter: 1 μm Laser output: 3 mW, laser beam irradiation time per bit: 00 ns When the laser beam is irradiated onto the surface of a blue optical recording medium, the irradiated area changes color to red, and recording is performed. Ta. To read the records, a semiconductor laser with a wavelength of 680 nm and an output of 1 mW was used as a reading light source, and its reflected light was received by a photodetector (PN junction photodiode).

Evaluation of record writing was carried out as follows. The recording density was determined by measuring the optical density of the recording (red) area. The resolution and sensitivity were determined by observing the correspondence between the recorded image and the laser beam diameter using a microscope, and a very good result was rated ◎, a good result was rated ○, and a case where recording was not possible or the correspondence was poor was rated ×. Also, record reading is
Evaluation was made by measuring the carrier noise ratio (C/N ratio). The evaluation results are shown in Table 1.

Example 2 After uniformly and sufficiently irradiating the three types of optical recording media created in Example 1 with 254 nm ultraviolet rays to make the recording layer a blue film, the laser used for recording was changed according to the input information, and the following was performed. Recording was performed under the recording conditions, and the recording was read in the same manner as in Example 1.

Semiconductor laser () ILP-7802, newly manufactured by Hitachi)
Laser wavelength: 800 nm Laser beam diameter: 2 1 μm Laser output: 3+nW Laser beam irradiation time per 1 bit: 00 ns Recording was evaluated using the same criteria as in Example 1, and the evaluation results are shown in Table 1. Ta.

Example 3, Comparative Example 1.2 Recording and reading were carried out under the same conditions as in Example 1, except that the lasers used for recording were changed to the following ones, and the evaluation results are shown in Table 1. It was shown to.

Example 3: Semiconductor laser (Ga-As laser (W-
Heterostructure), prototype) Laser wavelength: 890 nm Comparative example 1: Semiconductor laser (Ga-As laser (W-
Hezoro structure), prototype) Laser wavelength: 950 nm Comparative example 2: Xenon gas laser, laser wavelength: 7
52 nm Comparative Example 3 An optical recording medium was produced in the same manner as in Example 1, except that no diene compound salt was used. After forming the recording layer of this optical recording medium into a blue film, recording and reading were performed under the conditions of Example 1 and Comparative Example 1.2, respectively. The recording was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Table 1 Example 4 General 2〇, 2H7, -CEC-C:C-C3) 1.6-
In place of the DA compound represented by GO leaves, the general formula C
8H,7-C: A monomolecular film recording medium with a cumulative degree of 21 was prepared in the same manner as in Example 1, except that a compound was used for D represented by C-C=C-C, H4-C0OH. Created. Recording was performed on and read from this recording medium under the same conditions as in Example 1. The evaluation results are shown in Table 2.

Examples 5 to 9 The same procedure as in Example 4 was carried out, except that the diene compound salts represented by compounds A3, 8, I2.15 and 20 were used instead of the diene compound salts represented by compounds A and 1. An optical recording medium was created.

Recording was written and read on and from these optical recording media under the same conditions as in Example 1. The evaluation results are shown in Table 2.

Table 2 Example 10 Compound Notification A coating solution obtained by dissolving 1 part by weight of the diene compound a represented by 1 in 4 parts by weight of methylene chloride was applied to a glass disk substrate (thickness 1
, 5mm in diameter, 200mm in diameter), applied by rotating a spinner at a specified rotation speed for a specified time, dried at room temperature, and the thickness of the coating film after drying on the substrate was 20mm.
A large number of samples for 0 and 1000 subjects were prepared.

Next, the general formula C,2H2,, -CI-CmiC-C3H
A monomolecular cumulative film of a DA compound represented by , 6-CO0I+ was transferred onto a diene compound salt layer on a substrate by the same method as in Example 1, and a monomolecular film, 5 layers, 21 layers,
and a recording medium in which a monomolecular cumulative film of 41 layers was formed was prepared. After the recording layers of these optical recording media were made into blue-jet copies, recording was written and read under the same conditions as in Example 1. The recording was evaluated in the same manner as in Example 1, and the results are shown in Table 3.

Table 3 Example 11 General 2〇, 2H,, -C: C-C=C-CoH, 6-C
IxlO compound in chloroform to D represented by o leaf
A solution dissolved at a concentration of 1 mol/1 was developed on an aqueous phase with a pH of 6.5 and a cadmium chloride concentration of 1XIo-3 mol/1. After removing the solvent chloroform, increase the surface pressure to 20 dyne/cm, keep it constant, thoroughly clean it, and prepare a glass substrate with a hydrophilic surface (already composed of a monomolecular film containing diene compound salts). (including cases where an accumulated film etc. has been formed) is gently moved up and down a predetermined number of times at a vertical speed of 1.0 cm/min in the direction across the water surface (a drying step is carried out in the middle), and the compound is transferred to D. The monomolecular film was transferred onto a substrate to form a monomolecular film or a monomolecular cumulative film.

Compound Notification A solution of 1 part by weight of the diene compound salt represented by 1 and 2 parts by weight of araxic acid dissolved in chloroform at a concentration of 1 x 10-3 mol/1 was prepared with a pl+ of 6.5 and a concentration of cadmium chloride of 1XIO-3. Developed on a mol/l aqueous phase. After removing the solvent chloroform, the surface pressure was reduced to 2
While keeping the 0 dync/cm high and constant, the glass substrate is sufficiently cleaned and the surface is hydrophilic (already DA
(including cases where a cumulative film composed of a monomolecular film of a compound is formed) is moved at a vertical speed of 1.
The monomolecular film containing the diene compound salt was transferred onto the substrate by gently moving it up and down a predetermined number of times at 0 cm/min (with a drying step in between) to form a monomolecular film or a monomolecular cumulative film.

Based on the above-mentioned process for producing a monomolecular film of compound D and a monomolecular film containing diene compound salts, eight types of hetero-cumulative films were produced on a glass substrate by appropriately combining these operations. did. Table 4 shows the Betero cumulative 11!2 (optical recording medium) thus produced. In addition, symbols indicating the structure of the recording layer of the optical recording medium,
The meanings of the numbers are illustrated below.

■G /20PL/60DA/20PL glass substrate (G
), a monomolecular cumulative film containing diene compound salts with a cumulative degree of 20 → D with a cumulative degree of 60 → a monomolecular cumulative film of the compound → diene with a cumulative degree of 20.

■G/IOX (2PL/6DA) A laminated combination of a monomolecular cumulative film containing diene compound salts with a cumulative degree of 2 and a monomolecular cumulative film of a DA compound with a cumulative degree of 6 on a glass substrate (G), A recording medium constructed by repeating 10 times and stacking layers.

After the recording layer of these optical recording media was made into a blue film, recording was written and read under the same conditions as in Example 1. The recording was evaluated in the same manner as in Example 1, and the results are shown in Table 4.

Table 4

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing an example of a recording device used in the optical recording/reading method of the present invention. 2 to 4 are schematic cross-sectional views illustrating the structure of an optical recording medium used in the method of the present invention. 1: Optical recording medium 2: Semiconductor laser 3: Control circuit 4: Collimating lens 5: Dichroic mirror 6: Reflector plate 7: Wave plate 8: Objective lens 9: Drive circuit 1 Semiconductor laser or light emitting diode 11: Output circuit 12 Nif Detector 13: Collimating lens 14: Polarizing beam splitter 15: Substrate 11i Diacetylene derivative compound 17, diene compound salt 18 Diacetylene compound salt impregnated layer 19: A layer 20: B layer 2I: Organic carrier molecule

Claims (1)

[Scope of Claims] 1) A monomolecular film or a cumulative film of a diacetylene derivative compound having at least a hydrophilic site and a hydrophobic site, and one or more compounds represented by the following general formula (1) or (2). A step of irradiating an optical recording medium having a recording layer containing ultraviolet rays with ultraviolet rays and then irradiating infrared rays of 800 to 900 nm according to recorded information to discolor the irradiated portion of the recording layer, and discoloring the recording layer. 1. A method for reading an optical record, comprising the step of reading recorded information by irradiating visible light of 550 to 750 nm. General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) General formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (In the formula, R^1 represents an alkyl group or a substituent. Represents a phenyl group or styryl group that may have R^2 and R^
6 represents an arylene group which may have a substituent that forms a conjugated double bond system with two adjacent -CH=CH- groups, and R^3 and R^7 have a substituent. R^4 represents an alkoxy group, R^5 represents an alkyl group, and A represents an anionic residue. )