JPS62132688A - Information-recording medium - Google Patents

Abstract

PURPOSE:To obtain an information-recording medium capable of recording and erasing information, by laminating, or incorporating in mixture, a light- absorbing material comprising a croconic methine compound of a specified formula. CONSTITUTION:A croconic methine compound of formula I or II is laminated or incorporated as a light-absorbing material to produce an information- recording medium capable of recording and erasing information. In the formulas, each of R1 and R2 is a substd. or unsubstd. alkyl, cycloalkyl, allyl, substd. or unsubstd. aralkyl or substd. or unsubstd. aryl, each of Z1 and Z2 is a non-metallic atomic group necessary for completing a substd. or unsubstd. heterocyclic ring, each of m and n is 0 or 1, M<+> is a cation and X<-> is an anion. The information- recording medium is capable of recording and erasing information at high speed and in high density by heating a specified region thereof to a specified temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Industrial Application Field The present invention allows information to be reversibly recorded and erased by heating.
Regarding information recording media that can be recorded and erased using optical means for heating, specifically, high-performance lasers that effectively absorb visible and near-infrared wavelength light and convert it into thermal energy. It relates to density recording and erasable information recording media.

(2) Prior Art Conventionally, photochromic materials, thermochromic materials, magnetic recording materials, and the like are known as reversibly erasable and repeatedly usable information recording materials. For example, organic compounds such as spiropyran and inorganic compounds such as silver halide dispersed in a glass-like matrix are examples of substances exhibiting four chromic properties, but these have the disadvantage that recorded information cannot be stably fixed. Furthermore, various organic and inorganic coloring materials are known as thermochromic materials, but like photochromic materials, they are difficult to fix. Chalcogenide-based glass castles, which utilize the phase change between crystalline and amorphous, are recently used as thermal recording materials to replace thermochromy, and are thermal substances made of low-molecular fatty acids, their amides, esters, or ammonium salts dissolved in thermoplastic polymers. System using change (Unexamined Japanese Patent Publication No. 1983-
11714.0) etc. have been proposed. However, chalcogenide glass is expensive because the recording layer is created by vapor deposition. Furthermore, films in which low-molecular substances are dissolved in thermoplastic polymers perform recording and erasing using slight temperature differences, and are currently not in practical use.

Needless to say, magnetic recording does not directly obtain visible images, but must be combined with other systems in order to handle it as image information.

(3) Problems to be Solved by the Invention The object of the present invention is to provide a device for recording, erasing, and displaying information that solves the drawbacks of conventional information recording devices using the information recording medium. shall be.

(4) Means for Solving the Problems The information recording, erasing and display device of the present invention is equipped with a combination of an information recording body and an optical means for recording on this information recording body, The recording medium is made of a mixture or lamination of a heat-sensitive material that becomes uniformly transparent or opaque when heated to a specific temperature and cooled, and a material that absorbs the wavelength of the light source. It is characterized by being able to display information by heating it. Furthermore, in the present invention,
As the material that absorbs the wavelength of the light source, a compound having azulenium salt extraction is used.

The information recording medium according to the present invention is made of a heat-sensitive material that becomes uniformly transparent or opaque when heated to a specific temperature and cooled, and has absorption characteristics in the visible and near-infrared wavelength regions, and effectively absorbs light. The information recording medium is made by mixing or laminating a light absorbing material that converts into thermal energy, and has the property of being able to record and erase information at high speed and high density by heating a specific range to a specific temperature.

Typical croconic methine compounds are:
It can be represented by the following general formula [I] [ml or [III].

General formula [] In the formula, R1 and R2 are an alkyl group (e.g., methyl group, ethyl group, n-propyl group, 15O-propyl group,
n-butyl group, 5ec-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-hydroxyethyl group, 3-hydroxypropyl group, 4- Hydroxybutyl group, 2-acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 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-(acetotylsulfamyl)butyl group, etc.), cyclic alkyl group (e.g. cyclohexyl group, etc.), allyl group (CH2= CH-
CH2-:)t Aralkyl group (e.g. benzyl group,
phenethyl group, 3-phenylpropyl 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 a substituted aryl group (e.g., carboxyphenyl group, sulfophenyl group, hydroxyphenyl group, etc.). In particular, in the present invention, among these organic residues, hydrophobic ones are preferred.

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-simethoxybenzothiazole, 5,6-cyoxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6- hydroxybenzothiazole, 4,5,6,7-titrahydrobenzothiazole, etc.), naphthothiazole series nuclei (e.g. naph)
(2,1-d)thiazole, natuto(1,2-d)thiazole, 5-methoxynaph)(1,2-d)thiazole, 5-methoxynaphtho(l,2-d)thiazole, 8
-methoxynaphtho(2,1-d)thiazole, 7-medoxynaph)(2,1-d)thiazole, etc.), thionaphthene(7,6-d)thiazole series nuclei (e.g. 7-medoxynaph)(2,1-d)thiazole, etc.
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-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5.6
-dimethylbenzoxazole, 5-methoxybenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.), naphthoxazole series nuclei (e.g. naph) [2,1-d)oxazole , Naft (1,
2-d) Oxazole, etc.), selenazole series nuclei (
For example, 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazole series nuclei (for example,
benzoselenazole, 5-chlorobenzoselenazole,
5-methylbenzoselenazole, 5,6-dimethylbenzoselenazole, 5-methoxybenzoselenazole, 5
-Methyl-6-medoxybenzoselenazole, 5,6-
cyoxymethylenebenzoselenazole, 5-hydroxybenzoselenazole, 4,5,6,7-titrahydrobenzoselenazole, etc.), naphthoselenazole series nuclei (e.g., natto(2,1-d)selenazole, naphthoselenazole, etc.), (1,2-d) selenazole), thiazoline series nuclei (
For example, 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 (e.g., quinoline, 6-medoxyquinoline, 7-methylquinoline, 8-methylquinoline), 1-isoquinoline series nuclei (e.g., isoquinoline, 3,4-dihydroisoquinoline) , 3-isoquinoline series nuclei (e.g. inquinoline), 3.3-dialkylindolenine series nuclei (e.g. 3,3-dimethylindolenine, 3,3-dimethyl-5-chloroindolenine, 3.3 .5-) dimethylindolenine, 3゜3.7-dimethylindolenine),
Nuclei of the pyridine series (e.g. pyridine, 5-methylpyridine), nuclei of the benzimidazole series (e.g. l-ethyl-5,6-dichlorobenzimidazole, 1-hydroxyethyl-5,6-dichlorobenzimidazole, 1
-ethyl-5-chlorobenzimidazole, 1-ethyl-5,6-dibromobenzimidazole, l-ethyl-
5-phenylbenzimidazole, ■-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-dithyl-5-acetylhenzimidazole, l-ethyl-5 -carboxybenzimidazole, 1-ethyl-5-ethoxycarbonylbenzimidazole, l-ethyl-5-sulfamylbenzimidazole, l-ethyl-5-N-
Ethylsulfamylbenzimidazole, l-ethyl-
5,6-difluorobenzimidazole, 1-ethyl-
5,6-dichlorobenzimidazole, l-ethyl-5
-ethylsulfonylbenzimidazole, 1-ethyl-
5-methylsulfonylbenzimidazole, l-ethyl-5-trifluoromethylbenzimidazole, l-ethyl-5-trifluoromethylsulfonylbenzimidazole, l-ethyl-5-trifluoromethylsulfinylbenzimidazole, etc.) Represents the necessary nonmetallic atomic group.

xe is chloride ion, bromide ion, iodide ion, perchlorate ion, benzenesulfonate ion, P
-1 luenesulfonate ion, methyl sulfate ion,
Represents an anion such as ethyl sulfate ion, propyl sulfate ion, etc.
, -cooe, 5O2ONH-1-so2-Ne-c
Mutokini containing o-1-3O2-NO-802- does not exist. M* represents a cation such as a hydrogen cation, sodium cation, ammonium cation, potassium cation, or pyridium cation. m and n are
0 or 1.

General formula [ml In the formula, R1 and R2 represent an alkyl group such as methyl, ethyl, propyl, butyl. Further, R1 and R2 can also form a ring such as morpholino, piperidino, or pyrrolidinyl together with the nitrogen atom. R3, R4, R5 and R6 are hydrogen atoms, halogen atoms (chlorine atom, bromine atom, iodine atom), alkyl groups (methyl, ethyl, propyl, butyl, etc.), alkoxy groups (methoxy, ethoxy,
(propoxy, butoxy, etc.) or hydroxy group.

Furthermore, R3 and R4 can be combined to form a benzene ring, and R3 and R4 can be combined with R5 and R6, respectively, to form a benzene ring.

The croconic methine compound used in the present invention is used as a compound since a mixture of compounds in the form of betaine or salt can be obtained.

Specific examples of the croconic methine compound used in the present invention are listed below, and for convenience, they are represented by a betaine structure.

Examples of compounds represented by the general formula [I] and [nl (2)
) θ (3)e (4) θ (5) θ (7) O(8)
○(9)
○(11)
θ(13)
θ(15) θ(1
6) θ(17)
e(19)
e(20)
θ(21)
e(2B) (
)n (27) θ The above general formula [I
Example of Compound Represented by II] Next, a synthesis example of a typical polygonic metine compound used in the present invention will be shown.

Synthesis Example 1 (Above Exemplified Compound No. 29) Croconic Acid 1
．． After heating a mixture of 20 g (0,00845 mol), 5.06 g (0,0169 mol) of quinaldine ethiosite, and 50 mfL of n-butanol to 110°C, 4 mfL of pyridine was added, and the mixture was heated to 110-116°C. 1 in C
The reaction was allowed to proceed for 0 minutes. Next, 4mM of triethylamine was added, and after stirring at the same temperature for 5 minutes, the mixture was left to cool to obtain a precipitated dye. After filtering the precipitated dye, it was washed with n-butanol and tetrahydrofuran in sequence, and then dried under reduced pressure. As a result, the yield was 2.1g (
A purified dye was obtained with a yield of 55%. The absorption characteristics of this dye in dimethyl sulfoxide are shown in FIG. The input maX was 845 nm.

Synthesis Example 2 (Above Exemplified Compound No. 35) 10.6 of N,N-dimethyl-m-aminephenol was added to a three-necked flask.
G,! = 180 mM of n-butanol was added and stirred to form a solution. Next, 5.0g of croconic acid and 50mM of benzene
was added and heated. The reaction was carried out for 1 hour while distilling off water at a liquid temperature of 90-100'C. After cooling, the precipitate was filtered and washed with 40 ml of n-butanol.
Heat filtration with 200mM methyl celerol three times,
Finally, the mixture was heated and filtered with 200 ml of T I-IF and then dried to obtain 6.3 g of the target product (yield: 47%). The solution characteristics in dimethylformamide solution are shown in FIG. Enter m
ax was 818 nm.

By laminating at least a heat-sensitive material and a light-absorbing material as described above or forming an information recording body having an IJ2 alloy, recording light is efficiently absorbed and converted into heat energy, and the heat-sensitive material made of a mixed polymer is brought into a phase-separated state. It is possible to effectively heat above the temperature. Furthermore, the phase separation state can be fixed by cooling from the heated phase separation state, and the fixed phase separation state can be returned to the original compatible state by heating to above the separation temperature and cooling. I can do it.

As is clear from the above description, the information recording medium of the present invention uses a combination of stable polymers without material change, such as conventional thermochromic substances or low-molecular substances in a polymer matrix. The number of times the erasure can be repeated can be significantly increased. Furthermore, it is not necessary to control delicate temperature differences, and a recording device can be easily configured by controlling heating and cooling times that exceed phase separation. Furthermore, by using a compact and low-cost semiconductor laser, it has become possible to record with high sensitivity and high density.

In addition, when displaying recorded information, a car using the above-mentioned light-absorbing material that does not have absorption in the visible region makes it possible to display unrecorded parts transparently and with a high contrast ratio. It is also possible to project and display or detect and reproduce the image. For example, it is possible to form an information recording medium in which the transmittance of the unrecorded portion to the visible region is 50% or more, particularly 75% or more.

FIG. 3 is a cross-sectional view of one embodiment of the information recording medium constituting the present invention.

This information recording body (1) is made by laminating a mixture of the above-mentioned heat-sensitive material 3 and a material 4 that absorbs a recording light source on a base material 2 such as glass or plastic in the shape of a disk, sheet, or belt. It is formed. Film thickness is 0.011Lm~10
00 pm, preferably 1#Lm to 200g, m is suitable.

In another embodiment, the information recording body (2) is formed by sequentially laminating a material 4 that absorbs a recording light source and a heat-sensitive material 3 on a base material 2. Furthermore, as in the embodiment of the information recording medium (3), a heat-sensitive material 3 and a material 4 absorbing the recording light source may be sequentially laminated on the base material 2. Information recording bodies (2) and (3)
) The film thickness of the heat-sensitive material 3 is 0.01 to '1000 ILm
, preferably 1#1. m to 200 g, m is suitable.

The film thickness of the material 4 that absorbs the recording light source may be a film thickness that can sufficiently absorb the recording light source light and convert optical energy into thermal energy, but it is preferably about o, otg to 10 g.

As described above, the heat-sensitive material 3 includes a copolymer and a polymer blend system that are compatible in a low temperature range and undergo phase separation in a high temperature range.

For example, the copolymer is obtained by copolymerization or alternating copolymerization of vinylidene cyanide or vinylidene fluoride with other vinyl compounds, vinylidene compounds, or dienes. Other vinyl compounds, vinylidene compounds, and dienes include styrene, dichlorostyrene, acrylic acid and its esters, methacrylic acid and its esters, vinyl alcohol and its esters, vinyl chloride, vinylidene chloride, butadiene, chlorobutadiene, isobutylene, anhydrous Examples include maleic acid, acrylonitrile, methyl vinyl ketone, vinyl isobutyl ether, etc. After polymerization, it is also possible to chemically modify part or all of the ester compound such as hydrolysis.

In addition, as polymer blend systems, polynystyl, polyamide, polyacrylate, polymethacrylate, polystyrene, silicone resin, polyvinyl chloride, vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-acrylonitrile copolymer, polycaprolactone, ethylene-vinyl acetate Copolymer, polycarbonate)) 1! Examples include bare rubber, polyvinylidene fluoride, polyvinylidene cyanide, fluororesin, and the above-mentioned copolymers, and two or more types of polymers can be selectively mixed and used. When these polymer combinations are heated to 100 to 200°C, depending on the blend ratio, phase separation occurs, and although there are differences in degree, light scattering is observed and the area becomes opaque compared to areas that are not heated. do.

In order to apply the polymer, it is better to make the polymer soluble in an organic solvent. For example, JP-A-59-135257
Vinylidene fluoride-based copolymers soluble in organic solvents, such as a copolymer of vinylidene fluoride and hexafluoroacetone as shown in (1) or a copolymer of vinylidene fluoride and trifluoroethylene, are preferably used.

The material that absorbs the recording light source must be selected appropriately depending on the wavelength of the light source used. For example, when using a semiconductor laser, a material that absorbs near infrared light, particularly long wavelength light of 700 nm or more, is suitable. It is.

These information recording bodies (1), (2), and (3) are a method of recording information in an opaque state with the heat-sensitive material 3 completely transparent; There is a way to record it as a transparent state.

Hereinafter, one specific example of the present invention will be described with reference to the drawings.

FIG. 4 is a schematic diagram of the main parts of a recording, erasing, and display device to which the present invention is applied.

Reference numeral 10 denotes a vertical device exterior box, and 20 denotes a display image viewing window formed with a large opening on the front surface of the exterior box, and generally has a transparent plate 3 such as a glass plate stretched over it. Further, 40 is the aforementioned information recording body, which is an endless belt type stretched between a driving pulley (or roller) 50 and a driven pulley (or roller) 60, which are horizontally installed in the upper and lower parts of the outer box. Hereinafter, this information recording body will be referred to as a belt. This bell) 40 is rotationally driven in the direction of the arrow by the rotation of the drive pulley.
40 passes through the display image viewing window 20 in the direction of the arrow. Then, 70080 is placed in contact with the back side of the center area on the slack side of the belt at a slight distance from -c.
A pair of tension rollers 90 are an erasing section, and the image formed on a sheet is moved to the erasing section 9 according to the need for erasing.
Cleared at 0. The image can be erased by heating the sheet and then adjusting the cooling rate.

The heating means used for erasing uses a heater, a light source, etc., and controls heating and cooling.

It is also possible to perform partial erasing by using an erasing unit 90' that heats and adjusts the cooling rate using an optical device of 100 as an erasing means.

Reference numeral 100 denotes an optical device that exposes the outer surface of the belt tensioned portion between the tension rollers 70 and 80 to a light image using a light source such as a semiconductor laser.

The main body of the optical device 100 is of a light beam scanning type, which generates a modulated light beam L corresponding to time-series electric pixel signals output from an electronic computer, etc., and directs the beam L in the belt width direction. This is used as a main scan, and the surface movement of the belt is used as a sub-scan to expose the belt surface to a light image.

With the above configuration, the belt 40 passes through the optical device 100 during its rotation process, whereby the information recording medium on the belt is heated and changes from a transparent state to an opaque state, thereby making the information to be displayed visible. Next, the cloudy recording section moves to within the range of the image viewing window 20 and once stops, so that an image is displayed on the window 20. After a predetermined period of time has elapsed, or by pressing a button to command the belt to rotate again) 40
rotates again, the cloudy part on the belt surface is erased by the erasing section 90, and this belt is used repeatedly for the next image display.

In addition, as another specific example to which the present invention is applied, it can be used for an optical disc on which information can be recorded and erased.

Information recording bodies used in optical disk technology store high-density information by forming optically detectable small (for example, about 1 LL) pits in the form of spiral or circular tracks, which are formed in a small information recording layer provided on a base. can be recorded. To write information on such a disk, a focused laser is scanned over the surface of the information recording layer, and only the surface irradiated with this laser beam forms pits, and these pits are formed in the form of a spiral or circular track. do. The information recording layer is laser
It can absorb energy and form optically detectable pits. For example, in the heat mode recording method, laser energy irradiated to the information recording layer is absorbed and converted into thermal energy, changing the information recording layer from a transparent state to an opaque state and forming pits. Further, the opaque portion can be returned to a transparent state by heating with a heating element of the laser beam 1 and cooling slowly. By forming pits, optically detectable transmittance difference 9 reflectance difference,
Creates a refractive index difference.

Information recorded on this optical disk is detected by scanning a laser along a track and reading optical changes in areas where pits are formed and areas where pits are not formed. For example, a laser is scanned along a track and the energy reflected by the disk is monitored by a photodetector. When no pits are formed, the output of the photodetector decreases, while when pits are formed, the laser beam is sufficiently reflected by the underlying reflective surface and the output of the photodetector increases.

Next, the present invention will be explained by examples, but the present invention is not limited thereto in any way.

Example 1 As a heat-sensitive material, 50 parts by weight of vinylidene fluoride and hexafluoroacetone copolymer resin and 50 parts by weight of polymethyl methacrylate resin were dissolved in a methyl ethyl ketone solution.
Furthermore, the light-absorbing material, the above compound No. (22), was added to 25
Parts by weight were added and mixed. This mixed solution was applied to a polyethylene terephthalate belt until the dry film thickness was 70p.
An information recording body was created so that it would be L.

The information recording body thus prepared was mounted on the display device shown in FIG. 4, and was suspended and driven to repeatedly display images. A semiconductor laser with an oscillation wavelength of 780 nm was used as an optical means.

A sufficient contrast ratio between the recorded area (opaque state) and the unrecorded area (transparent state) was obtained, and image recognition was possible. Furthermore, the visible area (400~
When the transmittance at 700 nm) was measured, the results shown in Table 1 were obtained.

Table 1 Transmittance (%) Unrecorded area 90 Recorded area 12 Furthermore, even if the image display was repeated too many times, a good image display could be performed.

Comparative Example 1 A comparative information recording medium was prepared in exactly the same manner as in Example 1, except that the light-absorbing material (compound No. (29)) used in Example 1 was removed.

Image display was repeatedly performed on this information recording body in the same manner as in Example 1, but no opaque state was observed. The transmittance of the unrecorded area was 92%.

Even when comparing the transmittance of Example 1 and Comparative Example 1, it was found that there was almost no change in the transmittance and it was possible to display images without any problems even if light absorbing material compound No. (29) was mixed. .

Examples 2-7 Compound No. of Example 1, (29) The aforementioned compound No., (3), (12), (24).

Instead of each compound (32), (35), and (38), it was applied to a polyethylene terephthalate substrate in the same manner as in Example 1 so that the dry film thickness was 70 mm.
An information recording medium was prepared and each compound was prepared in Examples 2 to 7.
And so.

Example 1 The information recording bodies of Examples 2 to 7 thus created were
Images were displayed using the same method as above, and all images could be displayed. Further, the transmittance was measured in the same manner as in Example 1, and the results shown in Table 2 were obtained.

Table 2 Examples Compound Transmittance (%) No.
Unrecorded area Recorded area Example 8 The above compound No., (
10 parts by weight of the compound (29) was added and mixed. This mixed solution was applied onto a disc-shaped aluminum vapor-deposited glass plate having a diameter of 20 cm to obtain an information recording medium with a dry film thickness of 2,500 mm.

The information recording medium created in this way was mounted on a turntable, and while rotating the turntable, a semiconductor laser (oscillation wavelength 78
0 nm) was scanned in a track shape on the surface of the information recording layer to perform recording.

When the surface of this recorded information recording medium was observed under a microscope, clear opaque states (pits) were observed. Furthermore, when a low-output semiconductor laser beam was incident on this information recording medium and the reflected light was detected, a waveform with a sufficient S/N ratio was obtained.

Furthermore, when the recorded information recording medium was irradiated with a semiconductor laser beam focused at low speed rotation and observed under a microscope, the opaque state (pits) was erased and a uniform transparent state was observed.
u'i was confirmed, and it was found that the pit was erased.

Example 9 Compound No. of Example 8, (29) was replaced with the above compound No.
In the same manner as in Example 8, instead of using the compound (3),
An information recording medium was prepared by applying the mixture onto a 0 cm disk-shaped aluminum vapor-deposited glass plate to have a dry film thickness of 2,500 mm.

When information was recorded on this information recording medium in the same manner as in Example 8 and then reproduced, a waveform with a sufficient S/N ratio was observed. Further, after writing the information, observation under a microscope revealed that clear opaque states (pits) had been formed. Furthermore, after being irradiated with a semiconductor laser beam focused at low speed rotation, microscopic observation revealed that it was opaque (pits).
It was confirmed that the pits were erased and a uniform transparent state was confirmed, indicating that the pits were erased.

Example 10 Compound No. of Example 8, (29) was replaced with the above compound No.
An information recording medium was prepared by applying the same method as in Example 8 to a disk-shaped aluminum vapor-deposited glass plate with a diameter of 20 cm in place of the compound (15) to give a dry film thickness of 2,500 mm.

When information was recorded on this information recording medium in the same manner as in Example 8 and then reproduced, a waveform with a sufficient S/N ratio was observed. Further, after writing the information, observation under a microscope revealed that clear opaque states (pits) had been formed. Furthermore, after being irradiated with a semiconductor laser beam focused at low speed rotation, microscopic observation revealed that it was opaque (pits).
It was confirmed that the pits were erased and a uniform transparent state was confirmed, indicating that the pits were erased.

Example 11 Compound No. of Example 8, (29) was replaced with the above compound No.
An information recording medium was prepared by applying the same method as in Example 8 to a disk-shaped aluminum vapor-deposited glass plate with a diameter of 20 cm, except for using the compound (25), so that the dry film thickness was 2,500 mm.

When information was recorded on this information recording medium in the same manner as in Example 8 and then reproduced, a waveform with a sufficient S/N ratio was observed. Further, after writing the information, observation under a microscope revealed that clear opaque states (pits) had been formed. After further irradiation with a semiconductor laser beam focused at low speed rotation, microscopic observation revealed opaque 8 (pits).
It was confirmed that the pits were erased and a uniform transparent state was confirmed, indicating that the pits were erased.

Example 12 Compound No. of Example 8, (29) was replaced with the above compound No.
Instead of using the compound (32), it was applied onto a disc-shaped aluminum vapor-deposited glass plate with a diameter of 20 cm in the same manner as in Example 8 to prepare an information recording medium with a dry 11Q thickness of 2,500 mm.

When information was recorded on this information recording medium in the same manner as in Example 8 and then reproduced, a waveform with a sufficient S/N ratio was observed. Further, after writing the information, observation under a microscope revealed that clear opaque states (pits) had been formed. Furthermore, after being irradiated with a semiconductor laser beam focused at low speed rotation, microscopic observation revealed that it was opaque (pits).
It was confirmed that the pits were erased and a uniform transparent state was confirmed, indicating that the pits were erased.

Example 13 Compound No. of Example 8, (29) was replaced with the above compound No.
An information recording medium was prepared by applying the same method as in Example 8 to a disc-shaped aluminum vapor-deposited glass plate with a diameter of 20 cm in place of the compound (35) so that the dry film thickness was 2,500 mm.

When information was recorded on this information recording medium in the same manner as in Example 8 and then reproduced, a waveform with a sufficient S/N ratio was observed. Further, after writing the information, observation under a microscope revealed that clear opaque states (pits) had been formed. Furthermore, after being irradiated with a semiconductor laser beam focused at low speed rotation, microscopic observation revealed that it was opaque (pits).
It was confirmed that the pits were erased and a uniform transparent state was confirmed, indicating that the pits were erased.

Example 14 Compound No. of Example 8, (29) was replaced with the above compound No.
An information recording medium was prepared by applying the same method as in Example 8 to a disk-shaped aluminum vapor-deposited glass plate with a diameter of 20 cm, except for using the compound (40), so that the dry film thickness was 2,500 mm.

When information was recorded on this information recording medium in the same manner as in Example 8 and then reproduced, a waveform with a sufficient S/N ratio was observed. Further, after writing the information, observation under a microscope revealed that clear opaque states (pits) had been formed. Furthermore, after being irradiated with a semiconductor laser beam focused at low speed rotation, microscopic observation revealed that it was opaque (pits).
It was confirmed that the pits were erased and a uniform transparent state was confirmed, indicating that the pits were erased.

Example 15 The above compound No.
A solution prepared by dissolving the compound (37) in dichloroethane was applied to a dry film thickness of 500 g, and then 50 parts by weight of a copolymer resin of vinylidene fluoride and hexafluoroacetone and 50 parts by weight of a polymethyl methacrylate resin were applied. An information recording medium was prepared by dissolving a part by weight in ethyl acetate and applying the solution to a dry film thickness of 5K.

When information was recorded on this information recording medium in the same manner as in Example 8 and then reproduced, a waveform with a sufficient S/N ratio was observed. Further, after writing the information, observation under a microscope revealed that clear opaque states (pits) had been formed. Furthermore, after being irradiated with a semiconductor laser beam focused at low speed rotation, microscopic observation revealed that it was opaque (pits).
was erased and a uniform transparent state was confirmed, indicating that the bits were erased.

Example 16 A disk-shaped glass plate with a diameter of 20 cm was prepared by dissolving 50 parts by weight of a copolymer resin of vinylidene fluoride and hexafluoroacetone and 50 parts by weight of a polymethyl methacrylate resin in methyl ethyl ketone until the dry film thickness was 800 cm. The compound No. (32) is applied on top of the compound No.
A solution prepared by dissolving the compound in dichloroethane has a dry film thickness of 1
000 people, and an information record was created.

When information was recorded on this information recording body in the same manner as in Example 8 except that semiconductor laser light was irradiated from the disc-shaped glass plate surface and then reproduced, a waveform with a sufficient S/N ratio was observed. Ta. After writing the information, observation under a microscope revealed that clear opaque states (pits) had been formed. Further, after irradiation with semiconductor laser light focused at low speed rotation, wJWk mirror observation was performed, and the opaque state (bit) was erased, and a uniform transparent state was confirmed, indicating that the bit had been erased.

[Brief explanation of drawings]

FIG. 1 and FIG. 2 are curve diagrams each showing the spectral absorption characteristics of a compound that absorbs recording light used in the present invention. FIG. 3 is a cross-sectional view of one embodiment of the information recording medium constituting the present invention. FIG. 4 is a schematic longitudinal sectional side view of an example of the information recording, reproducing and displaying device of the present invention. 1-111 information record body. 2-111 base material. 3-111 Heat-sensitive materials. 4-111 Recording light source absorbing material.

Claims (4)

[Claims] (1) An information recording medium and an information recording, erasing, and recording apparatus that records information on the information recording medium using optical means, in which the information recording medium is heated to a specific temperature and cooled to a uniform transparent state or An information recording medium that is laminated or contains a mixture of a heat-sensitive material that becomes cloudy and a light-absorbing material consisting of at least one croconic metine compound, and can display or read information by heating a specific range to a specific temperature. A record of information, an erasable information record body characterized by: (2) Recording of information according to claim 1, wherein the at least one croconic metine compound is a compound represented by the following general formula [I], [II] or [III];
Erasable information recorder. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R_1 and R_2 are substituted or unsubstituted alkyl groups, cyclic alkyl groups, allyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group. Z_1 and Z_2 represent a group of nonmetallic atoms necessary to complete a substituted or unsubstituted heterocycle. m and n are 0 or 1. M^■ represents a cation, and X^■ represents an anion. ) General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. and R_6 is a hydrogen atom,
Indicates a halogen atom, an alkyl group, an alkoxy group, or a hydroxy group. Furthermore, R_3 and R_4 may be combined to form a benzene ring, and R_3 and R_4 may be combined with R_5.
and R_6 may be bonded to each other to form a benzene ring. ) (3) An information recording medium capable of recording and erasing information according to claim 1, wherein the optical means comprises a semiconductor laser. (4) The information recording medium capable of recording and erasing information according to claim 3, wherein the at least one croconic metine compound is a compound particle having substantially no absorption in the visible range.