JPS62175941A - Optical recording reading method - Google Patents

Abstract

PURPOSE:To obtain an optical record image having excellent stability and high quality by irradiating radiations for polymn. to an optical recording medium having a recording layer contg. the monomolecular film of a polydiacetylene deriv. compd. or the cumulative film thereof and >=1 kinds of two specific compds. to discolor the irradiated part of the recording layer according to recording information and irradiating reading light of a short wavelength on the recording layer to read the recording information. CONSTITUTION:This method has a stage for irradiating UV rays, then 800-900nm IR rays to the optical recording medium having the recording layer contg. the monomolecular film of the polydiacetylene deriv. compd. or the cumulative film thereof and >=1 kinds of compds expressed by formula (1) and (2) to discolor the irradiated part of the recording layer and stage for irradiating 550-750nm visible light to the discolored part of the recording layer to read the recording information. In formulas, R<1>-R<3> respectively denote aryl groups which may independently have substituents, R<4>, R<5> denote arylene groups which may have the substituent to form a conjugated double bond system with adjacent two -CH=CH- group, R<6> denotes hydrogen or an aryl group which may have a substituent and A denotes an anion residue.

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.

(Prior Art) Optical disks have recently 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
Able to efficiently organize and manage documents, etc. in the office. Various types of recording media have been considered for this optical disk, but those using organic materials are attracting attention 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-output laser such as an argon laser, laser recording is only possible when a small, relatively low-output semiconductor laser (wavelength 800-900 nm) is used. 6 I have confirmed that it is not possible. 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 Nos. 59-40648, 40649, and 40650 disclose organic coatings containing a polymethylene compound having a specific structure with good thermal stability, and these organic coatings are suitable for use in the radiation wavelength region of semiconductor lasers. The patent discloses that it is possible to perform so-called heat mode recording in which pits are formed using laser energy because the laser absorbs radiation and generates heat. However, when performing recording by forming physical pits 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. In addition to requiring sufficient care, it is particularly difficult to perform high-density, high-sensitivity, and high-speed optical writing and to read the written records with good granularity.

Furthermore, 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. This method was not necessarily suitable for high-density recording, as the absorbance and reflectance of light differed depending on the location, and the degree of chemical reaction varied depending on the location.

[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, high-intensity reading.

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

[Means for solving problems]

That is, the optical recording reading method of the present invention comprises a monomolecular film or a cumulative film thereof of a diacetylene derivative compound having at least a hydrophilic site and a hydrophobic site, and a compound represented by the following general formula (1) or (2). A step of irradiating an optical recording medium having a recording layer containing one or more of It is characterized by comprising a step of irradiating visible light of 550 to 750 nm to the discolored portion of the recording layer to read recorded information.

General formula (1) General formula (2) to R1-Gll=CIl-R4-CIIJ:ll-R3
(2) (In the formula, Hl, R2, and R3 each independently represent an aryl group that may have a substituent, and R4 and R5 represent two adjacent -(:ll=[l;II- represents an arylene group that may have a substituent that forms a conjugated double bond system with the group, R6 represents hydrogen or an aryl group that may have a substituent, and 8 represents an anion residue.) The diacetylene derivative compound having both a hydrophilic site and a hydrophobic site (hereinafter abbreviated as DA compound) contained in the optical recording medium used in the method of the present invention refers to the -CEC functional group in the C: in the adjacent molecule. It is a compound capable of a 1.4-addition polymerization reaction between groups, and is 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 (CH2) 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) (hereinafter referred to as a polymethylene compound) used in the present invention has an absorption peak in a wavelength range of 750 r+m or more, and is sensitive to infrared light of this wavelength. It is a compound that generates heat.

To explain this polymethylene compound salt more specifically, in general formulas (1) and (2), R1, R2 and R
3 each independently represents an aryl group such as a phenyl group or a naphthyl group which may have a substituent.

Examples of the substituent include substituted amino groups such as dimethylamino, diethylamino, dipropylamino, dibutylamino, diphenylamino, phenylbenzylamino, and phenylethylamino, and morpholino.

Examples include cyclic amino groups such as piperidinyl and pyrrolidino, and alkoxy groups such as methoxy, ethoxy and butoxy.

R4 and R5 represent an arylene group that may have a substituent that forms a conjugated double bond system with two adjacent 10H═CH- groups such as p-ferene and l4-naphthylene; Here, substituents include halogen atoms such as chlorine, bromine, and iodine, alkyl groups such as methyl and ethyl, methoxy,
Examples include alkoxy groups such as nidoxy. R6 represents hydrogen or a 7-aryl group such as a phenyl group or a naphthyl group which may have a substituent. Examples of the substituent include the same as those exemplified for R1 to R3. It will be done. Tsuru ±7 ion residues, for example BF? , c+op cp3co? , P
F? , halogen atoms such as B'RI♀, cts machine,
CH, SO, F.

e ee eC2H1S
03, C3) (7SO3, C4HgSO3, C5Hl,
SO3, C6H13SO3, ICH2SO? Alkyl sulfone compounds such as -CH2SopC
+(Tsukasa+H2SO9'l-Which benzenesulfonic acid compound,%3SCH2SO9,%35CH2CH250!
.

Moe 5 (CH2) 65 Moe, . 03SCH2C) 12-0
-IH2CH2SOp, and other alkyldisulfonic acid compounds. Specific examples of this polymethylene compound are illustrated below.

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d l) Engineering Q 〆165'9 3ζpu
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e'8g3 5 et al.
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De B 6
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0 ri0
8 Mori 2F The optical recording medium used in the present invention contains 1) the compound described in r and the polymethylene compound, and the compound alone or in a mixed state with the polymethylene compound has a monomolecular weight. The optical recording medium has a recording layer forming a cumulative layer thereof, and specific configurations of the optical recording medium include the following embodiments.

(1) One having a recording layer consisting of a mixed monomolecular film of the D-formula compound 16 and the polymethylene compound 17 or an accumulation thereof 11Q (a schematic cross-sectional view is shown in FIG. 2).

(2) One having a recording layer consisting of two layers: a layer consisting of one single molecule of formula D compound 16 or a cumulative film thereof, and a radiation absorbing layer 18 containing polymethylene compound 17 (two-layer separation system, A schematic cross-sectional view is shown in Figure 3).

(3) One or more layers of the A layer 19 consisting of a monomolecular film of the D formula compound 16 or a cumulative film thereof, and the polymethylene compound 17
8 layers 20 consisting of a monomolecular film or a cumulative film thereof containing
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 Di system, the layer consisting of a monomolecular film of a DA compound or a cumulative film thereof and the radiation absorbing layer 18 or eight layers 20 containing a polymethylene compound are stacked in any order. may be located on the surface side of the recording layer, and various protective layers may be provided on the recording layer configured in this way, if necessary.

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.

D on the substrate or on the layer containing the polymethylene compound.
To form a monomolecular film or a monomolecular cumulative film of a compound of the formula, for example, 1. The Langmuir-Prodgett method (hereinafter abbreviated as LB method) developed by Langmuir et al. is used. The LB method is a molecule with a structure that has a parent wood group and a hydrophobic group in the molecule, and when the balance between the two (balance of amphiphilicity) is maintained appropriately, this molecule has a parent wood group on the water surface. This is a method of creating a monomolecular film or an accumulated film of monomolecular layers by utilizing the fact that the monomolecular layer is directed downward. A monolayer on the water surface has the characteristics of a two-dimensional system. When the molecules are sparsely dispersed, the two-dimensional ideal gas equation, ■A=kT, holds between the area per molecule A and the surface pressure ■, resulting in a "gas film".Here, k is Boltzmann's constant, and T is the 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 is formed on the surface of a substrate such as glass. Can be transferred layer by layer.

Using this method, a monomolecular film or a monomolecular cumulative film of the compound of formula D is produced, for example, as follows. First, a compound of formula D is dissolved in a solvent such as chloroform, and this is spread on an aqueous phase to form a spread layer in which these compounds are spread into a film. Next, to prevent this developed layer from freely diffusing on the water phase and spreading too much, a partition plate (or float) is provided to limit the area of the developed layer and control the aggregation state of the D crystal compound. Obtain a surface pressure ■ proportional to . By moving this partition plate, the developed area is reduced to control the state of aggregation of the film material, and the surface pressure is gradually increased to create a surface pressure suitable for producing a cumulative film.
can be set. By vertically moving a clean substrate or a substrate on which a layer containing a polymethylene compound is formed on the surface while maintaining this surface pressure, a DA crystal compound monomolecular film is formed on the substrate or a layer containing a polymethylene compound. transferred to the top. 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 addition to the above-mentioned vertical dipping method, methods such as a horizontal deposition method and a rotating cylinder method can be used to transfer the monomolecular film onto a substrate. 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 monomolecular layer is formed on the substrate in which the parent group of the DΔ crystal compound faces the substrate in the first layer. .

As the substrate is moved up and down, one layer of monolayer is deposited with each step. Since the direction of the unformed 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 D crystal 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 crystal compound even when the layers 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 directions of the hydrophilic groups and hydrophobic groups described above toward the substrate are in principle, 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 monolayer or mixed monolayer M 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 amphipathic balance of at least one compound is maintained, a monomolecular layer will be formed on the water surface, and the other compounds will be sandwiched between the amphipathic compounds, resulting in a well-ordered molecular layer as a whole. A monolayer is formed.

Therefore, a recording layer consisting of a mixed monomolecular film of a D crystal compound and a polymethylene compound or a mixed monomolecular cumulative 11q is obtained by dissolving the D crystal compound and the polymethylene compound in a solvent such as chloroform, and spreading this on an aqueous phase. A developed layer is formed by developing these compounds into a film, and then L
It can be formed by method B.

On the other hand, in order to form a layer containing a polymethylene compound, a typical method can be adopted in which the polymethylene compound is dissolved in a suitable volatile solvent to prepare a coating liquid, and then the coating liquid is applied. In order to improve the adhesion to the substrate and a layer consisting of a monomolecular film of a D crystal compound or a cumulative film thereof, the coating liquid contains:
Various binders made of natural or synthetic polymers may be added as appropriate. 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 valmitate, 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, and polyvinylpyrrolidone: styrene-butadiene copolymer, styrene-
Acrylonitrile copolymer, styrene-butadiene
Copolymer resins such as acrylonitrile copolymer and vinyl chloride-vinyl acetate copolymer; acrylic resins such as polymethyl methacrylate, polymethyl acrylate, polyacrylic acid, polymethacrylic acid, polyacrylamide, and polyaxolonitrile; polyesters such as polyethylene terephthalate class; poly(4,4'-isobropylidene 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'-5e
c-butylidene diphenylene carbonate), poly(
Polyarylate resins such as 4,4'-isopropylidene diphenylene carbonate blocked oxyethylene; polyamides; polyimides; epoxy resins;
Phenol resins; and polyolefins such as polyethylene, polypropylene, and chlorinated polyethylene can be used.

Suitable solvents for polymethylene compounds include alcohols such as methanol, ethanol, and impropatol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aliphatic nitriles such as niacetonitrile; chloroform, methylene chloride, dichloroethylene, and tetrachloride. Examples include carbon, aliphatic halogenated hydrocarbons such as trichloroethylene, and methylene chloride and acetonitrile are particularly preferred.

The coating solution 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 coach ink method, curtain coating method, etc. is used.

Further, the layer containing the polymethylene compound may be a monomolecular film or a cumulative film thereof, similar to a layer consisting of a monomolecular film of a DA compound or a cumulative film thereof. However, since polymethylene compounds are not amphiphilic substances, LB alone
Depending on the method, it is not possible to form a monomolecular film. However, organic polymers with an appropriate amphipathic balance, such as higher fatty acids such as stearic acid and aragidic acid, can be mixed and used as carrier molecules in any ratio to produce LB.
By applying the method, a mixed monomolecular film or a mixed monomolecular cumulative film containing a polymethylene compound can be formed.

When the recording layer is composed of a mixed monomolecular film of a D-type compound and a polymethylene compound or a cumulative film thereof, it is practically preferable that the film thickness has a cumulative degree of up to about 4 ec.

In the case of a two-layer separation system, the thickness of the monomolecular film of the crystalline compound or its cumulative film is preferably up to about 4 ec, and the thickness of the polymethylene compound-containing layer is preferably a monomolecular film or a cumulative film thereof. Or, if it is formed as a cumulative film, the cumulative degree is up to about 2ec, and if it is formed as a non-monolayer film, it is about 100 to 1p, especially in the range of 200 to 5000 people. preferable.

In the case of a hetero-cumulative film system, there are two or more bonding surfaces between the A layer 19 and the 8 layers 20, and the cumulative degree of the monomolecular film including the A layer 19 and the 8 layers 20 is up to about 4ec for practical use. It is preferable.

In the optical recording/reading method of the present invention, in the recording medium provided with the above-mentioned grooves for recording and reproduction, first, the D-type compound in the recording layer is polymerized.

That is, the compound of formula 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. Information writing means is 800
A semiconductor laser 2 that emits ultraviolet light with a wavelength within the range of ~900 nm, a control circuit 3 that controls the oscillation of the semiconductor laser 2 according to human input information, and an optical system (collimating lens 4, dichroic mirror 5, reflector 6, wavelength plate) 7) and an objective lens 8). The semiconductor laser 2 is a GaA laser with an output wavelength of 8zO to 84Qt+n+.
A welding laser of
mb) 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 10 that emits visible light with a wavelength in the range of 550 to 750 nm, and an output circuit 1.
A photodetector 1z connected to the photodetector 1z and an optical pickup optical system (most of the optical system is shared with the optical system for the information writing means, but it has a collimating lens 13 and a polarizing beam splitter 14 as unique ones). )
It consists of

The semiconductor laser 10 is one that emits visible light with a wavelength in the range of 650 to 750 nm, for example, a GaAl8s laser.
It is preferable to use an N-junction laser, and the light emitting diode 10 is one that emits visible light with a wavelength in the range of 550 to 750 nm, such as GaAIP, G
It is preferred to use junction diodes for aP, GaAl8S, etc.

The input 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 an optical recording medium mounting means, and is imaged at a predetermined position on an optical recording medium having a blue to dark-colored recording layer that rotates synchronously. The image formation position is the recording layer if the optical recording medium is a single-layer mixed type, or the radiation absorption layer containing a polymethylene compound if the optical recording medium is a two-layer type. The polyacetylene derivative compound present in the image-forming part) does not absorb the laser beam of this wavelength, but the polymethylene compound absorbs this laser beam and generates heat. The heat generated by this polymethylene compound is transmitted to the adjacent polyacetylene derivative compound,
The polydiacetylene derivative compound turns red. In this way, optical writing is performed by changing the color of the recording area on the recording layer in response to human effort or 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 with a wavelength in the range 550-75Qn+n. This reading light has a low output and a wavelength outside the infrared region, so it does not cause the polymethylene compound to generate heat. Therefore, no recording is performed during reading using this reading light. The reading light is
An image is formed on the surface of the recording layer of the optical recording medium 1 and reflected, but since the reflectance of this reading light differs between recorded areas (discolored areas) and non-recorded areas, this reflected light is transferred to an optical pickup optical system. By applying the light to the light-receiving surface of the photodetector 12 through the photodetector 12, it is converted into an electrical signal, and the recorded data is read and reproduced via the output circuit 11.

In the above example, the optical recording medium is a disc-shaped disk (
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 the polymethylene compound.

(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 polymethylene compound 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 of 800 to 9000 I; Also 55
Reading is possible with a small and lightweight semiconductor laser or light emitting diode that emits visible light with a wavelength in the range of 0 to 750 nm.

(2) As the optical recording medium, at least the D 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, high-grained optical reading can be performed.

(4) In particular, light formed as a Peter membrane having two or more bonding surfaces of a thermosensitive color-changing layer made of an OA compound and a radiation absorption layer made of a polymethylene compound, each formed as a monomolecular film or a cumulative film thereof. When a 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 Cl2H2S-Cmic-c=c-c8H,6-c
A solution in which 1 part by weight of a diacetylene derivative compound represented by ooH and 1 part by weight of a polymethylene compound represented by the above-mentioned compound A14 were dissolved in chloroform at a concentration of 1×10 = mol/l was prepared when p'#1 was 6.5. It was developed on an aqueous phase with a cadmium chloride concentration of 1×lO−3 mol/1. After removing the solvent chloroform by evaporation, the surface pressure was increased for 20dy.
ne/cm, and while keeping it constant, gently raise and lower the glass substrate, which has been thoroughly washed and has a clean surface with a hydrophilic surface, in the direction across the water surface at a vertical speed of 1.0 cm/min to form a compound of formula D. A mixed monomolecular film of and a polymethylene compound was transferred onto a substrate, and the mixed monomolecular film, 21 layers, and 41
An optical recording medium was prepared in which a mixed monomolecular cumulative film of 81 layers was formed on a 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 scale 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. I was disappointed. 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 the 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 marked as ◎, while a good result was marked as O1 recording or a poor correspondence was marked as ×. Also, record reading is
Evaluation was made by measuring the carrier-to-noise ratio (GlN 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 manual information, and the following was done. Recording was performed under the recording conditions, and the recording was read in the same manner as in Example 1.

Semiconductor laser (NLP-7802, newly manufactured by Hitachi) Laser wavelength: 800 nm Laser beam diameter: 1 laser beam output 3 mW, Laser beam irradiation time per 1 bit: 00 ns Record evaluation is based on actual h'fs example 1 The evaluation was conducted using the same criteria and the evaluation results are shown in Table 1.

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-
Heterostructure), prototype) Laser wavelength: 950 nm Comparative example 2: Xenon gas laser, laser wavelength: 7
52r+m Comparative Example 3 An optical recording medium was produced in the same manner as in Example 1 except that the polymethylene compound was not 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.

Example 4 General formula: 12 H2,, -c=c-c=c-c8)11
Example 1 except that the compound D represented by the general formula c8H,, -c=c-c=c-C2H4-COOH was used instead of the compound compound for D represented by 6-colo.
A recording medium with a monomolecular film accumulation degree of 21 was prepared in the same manner as described above. 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 8 Instead of the polymethylene compound represented by the compound layer 14,
Optical recording media were prepared in the same manner as in Example 4, except that polymethylene compounds represented by compounds J/Ll, 5.18, and 26 were used, respectively. 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 9 A coating solution obtained by dissolving 1 part by weight of a polymethylene compound represented by compound/L14 in 4 parts by weight of methylene chloride was
After dropping a small amount onto the center of a glass disk substrate (thickness 1.5 mm, diameter 200 mm) attached to a spinner coating machine, apply by rotating the spinner at a predetermined rotation speed for a predetermined time, dry at room temperature, The thickness of the coating film after drying on the substrate is 3
A large number of samples for 00 and 3000 people were prepared.

Next, the general formula C, 2H7,, -C Mi (nee CE (nee C
A monomolecular film M4nQ of the compound D represented by 8H,6-C0OH was transferred onto the polymethylene compound layer on the substrate by the same method as in Example 1, and 7 layers, 41 layers, 1
Optical recording media each having a layer and a monomolecular cumulative film formed of 201 layers were prepared. 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 evaluation of the record is
It was carried out in the same manner as in Example 1, and the results are shown in Table 3.

Table 3 Actual h's Example 1〇 General 2C, 2H2S-(,: c-c= c-c8H,
A solution of a compound of formula D represented by 6-GOOI+ in chloroform at a concentration of 1×10−:′1 mol/1 was prepared with a pl+ of 6.5 and a cadmium chloride concentration of lXl0−.
3 moles/! was developed on the aqueous phase. 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 polymethylene compounds). (including cases where an accumulated film etc. is formed) at a vertical speed of 1.0 cm7 in the direction across the water surface.
The monomolecular film of the compound of formula D was transferred onto the substrate by gently raising and lowering it a predetermined number of times (drying step was performed in the middle) to form a monomolecular film or a single monomolecular stack.

Polymethylene compound 1Iff represented by compound Sui 14
i part and 2 parts by weight of araxic acid in chloroform 1×10
- A solution dissolved at a concentration of 3 mol/1 has a pl+ of 6.5
and the cadmium chloride concentration is 1×l0−3 mol/! was developed on the aqueous phase. After removing the solvent chloroform, increase the surface pressure to 20 dync/cm and keep it constant, thoroughly clean the glass substrate with a hydrophilic surface (already a cumulative film composed of a monomolecular film of an OA compound). etc.) in the direction across the water surface at a vertical speed of 1.0 cm/min.
A monomolecular film containing a polymethylene compound was transferred onto a substrate to form a monomolecular film or a monomolecular cumulative film.

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

■G/20PM/6008/20PM On a glass substrate (G), a monomolecular cumulative film containing polymethylene compounds with a cumulative degree of 2o → one single molecule cumulative sample of a D type compound with a cumulative degree of 60 → A recording medium constructed by laminating in this order a monomolecular cumulative film containing polymethylene compounds.

■G/lOx (2PM/6DA) glass substrate (
G) A recording medium configured by stacking a stacked combination of a monomolecular cumulative film containing a polymethylene compound with a cumulative degree of 2 and a monomolecular cumulative film of a DΔ compound with a cumulative degree of 6 repeated 10 times. .

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.

[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. 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 IO: Semiconductor laser or light emitting diode 11: Output circuit 12: Photodetector 13: Collimating lens 14: Polarizing beam splitter 15 : Substrate 16: Diacetylene derivative compound 17: Polymethylene compound 8: Polymethylene compound-containing layer 19: A layer 20: B layer 21: 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 and then irradiating infrared rays of 800 to 900 nm according to recorded information to discolor the irradiated area of the recording layer; An optical record reading method comprising the step of irradiating visible light of 550 to 750 nm to a discolored portion to read recorded information. 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, R^2, R^ 3 represents an aryl group that may each independently have a substituent, and R^4 and R^5 are substituents that form a conjugated double bond system with two adjacent -CH=CH- groups. represents an arylene group which may have a substituent, R^6 represents hydrogen or an aryl group which may have a substituent, and A represents an anion residue.)