JPS62132689A - 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 cyanine methine compound of a specified formula. CONSTITUTION:A cyanine methine compound of formula I, II or III is laminated, or incorporated in mixture, as a light-absorbing coloring matter to produce an information-recording medium capable of recording and erasing information. In the formulas, each of Z1 and Z2 is an atomic group necessary for completing a substd. or unsubstd. nitrogen-containing heterocyclic ring; each of Z3 and Z4 is a bivalent hydrocarbon group for forming a substd. or unsubstd. 5- or 6-membered ring; each of R1 and R2 is hydrogen or a substd. or unsubstd. alkyl; each of R3 and R4 is hydrogen, a halogen, hydroxyl, carboxyl, alkyl, substd. or unsubstd. aryl or acyloxyl; each of R5 and R6 is hydrogen or a halogen; X<-> is an acid anion; each of m and n is 0 or 1; and l is 0, 1 or 2. This information-recording medium is capable of displaying information by heating a specified region thereof to a specified temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Industrial field of use The present invention allows information to be reversibly recorded and erased by heating.
Regarding information recording and erasable information recording media using optical means for heating, more specifically, high-temperature recording materials such as 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, photochromic substances include organic compounds such as spiropyran and inorganic compounds such as silver halide dispersed in a glass-like matrix, 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 glasses, 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. 57-1
17140) 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. 4. Information can be displayed by heating to a specific temperature. This is a sign of shi.

Further, in the present invention, a cyanine methine compound is used as the material that absorbs the wavelength light of the light source.

The information recording medium according to the present invention is a heat-sensitive material that becomes uniformly transparent (g11) or opaque when heated and cooled to a specific temperature, and has absorption characteristics in the visible and near-infrared wavelength regions, and absorbs light. Made of a mixture or laminated layer of light-absorbing materials that effectively absorb and convert into thermal energy, this information recording medium can record and erase high-speed, high-density information by heating a specific area to a specific temperature. has.

[Means for solving the problem] and [action] Typical cyanine methine compounds have the following general formula [I]
[IL] can be represented by [ml or [IV].

General formula [1] General formula [H general formula [ml zl and z2 are substituted or unsubstituted nitrogen-containing heterocycles,
For example, thiazole series nuclei (e.g. 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-bromo Benzothiazole, 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.
naphtho(2,1-d)thiazole, naphtho(1,2-
cl) Thiazole, 5-methoxynaphtho(1,2-d)
Thiazole, 5-ethoxynaphtho(1,2-d)thiazole, 8-methoxynaphtho(2,1-d)thiazole,
7-methoxynaphtho(2,1-d)thiazole, etc.),
Nuclei of the thionaphthene (7,6-d)thiazole series (e.g., 7-medoxythionaphthene[7°6-d]thiazole), nuclei of the oxazole series (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 1,5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 5 C2,1-d) oxazole,
naphtho(1,2-d)oxazole, etc.), selenazole series nuclei (e.g., 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazole series nuclei (e.g., benzoselenazole, 5-chlorobenzo selenazole, 5-methylbenzoselenazole, 5.6-
Dimethylbenzoselenazole, 5-methoxybenzoselenazole, 5-methyl-6-methoxybenzoselenazole, 5,6-cyoxymethylenebenzoselenazole, 5
-hydroxybenzoselenazole, 4,5,6,7-titrahydrobenzoselenazole, etc.), naphthoselenazole series nuclei (e.g. naph) (2,1-d) selenazole, nut (:1.2-d) ) selenazole), thiazoline series nuclei (e.g., thiazoline, 4-methylthiazoline, 4-hydroxymethyl-4-methylthiazoline, 4,4-bis-hydroxymethylthiazoline, etc.),
Oxazoline series nuclei (e.g. oxazoline), selenazoline series nuclei (e.g. selenazoline), 2-quinoline series nuclei (e.g. quinoline, 6-methylquinoline, 6
-chloroquinoline, 6-medoxyquinoline, 6-nitoxyquinoline, 6-hydroxyquinoline), 4-quinoline series nuclei (e.g. quinoline, 6-medoxyquinoline,
7-methylquinoline, 8-methylquinoline), 1-isoquinoline series nuclei (e.g. inquinoline, 3,4-dihydroisoquinoline), 3-isoquinoline series nuclei (e.g. inquinoline), 3,3-dialkylindo Nuclei of the renin series (e.g. 3,3-dimethylindolenine,
3.3-dimethyl-5-chloroindolenine, 3.3.
5-)dimethylindolenine, 3゜3,7-1-dimethylindolenine), pyridine series nuclei (e.g. pyridine, 5-methylpyridine), benzimidazole series nuclei (e.g. 1-ethyl-5,6- Cyclopenzimidazole, l-hydroxyethyl-5,6-dichlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1-ethyl-5,6-dibromobenzimidazole, 1-ethyl-5-phenyl Benzimidazole, ■=ethyl-5-fluorobenzimidazole, 1-ethyl-5-cyanobenzimidazole, 1-(β-acetoxyethyl)-5-cyanobenzimidazole, l-
ethyl-5-chloro-6-cyanobenzimidazole,
-Ethyl-5-fluoro-6-diatubenzimidazole, 1-ethyl-5-acetylbenzimidazole,
1-ethyl-5-carboxybenzimidazole, l-
ethyl-5-ethoxycarbonylbenzimidazole,
l-ethyl-5-sulfamylbenzimidazole, 1
-Ethyl-5-N-ethylsulfamylbenzimidazole, 1-ethyl-5,6-difluorobenzimidazole, l-ethyl-5,6-dicyazbenzimitazole, 1-ethyl-5-ethylsulfonylbenzo imidazole, ■-ethyl-5-methylsulfonylbenzimidazole, ■-ethyl-5-trifluoromethylbenzimidazole, 1-ethyl-5-trifluoromethylsulfonylbenzimidazole, l-ethyl-5-trifluoromethylsulfinylbenzimidazole, etc.) Represents a group of nonmetallic atoms necessary to complete the process.

Z3 and Z4 are substituted or unsubstituted divalent hydrocarbon groups forming a 5- or 6-membered ring (-CH2-CH2-1
-C) (2-CH2-CH2OCH3 H-, etc.), and these 5- or 6-membered rings may be fused with a benzene ring, a naphthalene ring, etc.

R1 and R2 are hydrogen atoms or alkyl groups (for example,
Methyl group, ethyl group, n-propyl group, 1so-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.)
and further other alkyl groups, such as substituted alkyl groups (e.g., 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 2-acetoxyethyl group), (, carboxymethyl group, 2-carboxy Ethyl group, 3-carboxypropyl group, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3
-sulfatepropyl group, 4-sulfatebutyl group, N-(methylsulfonyl)-rubamylmethyl group, 3
-(acetylsulfamyl)propyl group, 4-(acetylsulfamyl)butyl group, etc.), cyclic alkyl group (e.g. cyclohexyl group, etc.), allyl group (CH2=C
H-CH2-), aralkyl group ((e.g., benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group), substituted aralkyl group (sidelight, carboxybenzyl group, sulfobenzyl group, hydroxyl group), benzyl group, etc.).

R3 and H4 are hydrogen atoms, halogen atoms (chlorine atoms, bromine atoms, iodine atoms, etc.), hydroxy groups, carboxyl groups, alkyl groups (methyl groups, ethyl groups, propyl groups, butyl groups, etc.), substituted or unsubstituted Aryl group (
phenyl group, α-naphthyl group, β-naphthyl group, carboxyphenyl group, hydroxyphenyl group, tolyl group, xylyl group, etc.) or acyloxy group (acetyloxy group, propionyloxy group, benzoyloxy group, etc.).

R5 and R6 represent a hydrogen atom or a halogen atom (chlorine atom, bromine atom, iodine atom).

X is chloride ion, bromide ion, iodide ion, perchlorate ion, benzenesulfonate ion, P
-toluenesulfonate ion, methylsulfate ion,
represents an anion such as ethyl sulfate ion, propyl sulfate ion, etc., and X represents an anion group such as -3O3,03O3, -Coo
, SO2NH-1-3O2-. m and n represent O or l, and erect represents 0.1 or 2.

General formula [IV Koba Zl and Z2 are substituted or unsubstituted nitrogen-containing heterocycles,
For example, thiazole series nuclei (e.g. thiazole, 4-
Methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4-
(2-chenyl)-thiazole, etc.), benzthiazole series nuclei (e.g. benzothiazole, 5-chlorobenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5-bromo Benzothiazole, 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. natu[2,1-d]thiazole, nand[1,2- d
]thiazole, 5-methoxynaphtho[1,2-d]thiazole, 5-ethoxynaphtho[1,2-d]thiazole, 8-methoxynaphtho[2,1-d']thiazole, 7-medoxynaf) [2, 1-dl thiazole, etc.)
, thionaphthene[7,6-d]thiazole series nuclei (e.g. 7-medoxythionaphthene[7,6-d]thiazole), oxazole series nuclei (e.g. 4-methyloxazole, 5-methyloxazole, 4-phenyl Oxazole, 4.5-diphenyloxazole, 4-ethyloxazole, 4.5-dimethyloxazole, 5-phenyloxazole) 1-benzoxazole series nucleus (
For example, benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5
．． 6-dimethylbenzoxazole, 5-methoxybenzoxazole, 6-medoxybenzoxazole,
5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.), naphthoxazole series nuclei (e.g. naphtho[2,1-d]oxazole, naphtho
[l,2-d]oxisazole, etc.), selenazole series nuclei (e.g. 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazole series nuclei (e.g. benzoselenazole, 5-chlorobenzoselenazole, 5-methylbenzoselenazole, 5,6-dimethylbenzoselenazole, 5-methoxybenzoselenazole,
5-Methyl-6-methoxybenzoselenazole, 5.6
-cyoxymethylenebenzoselenazole, 5-hydroxybenzoselenazole, 4°5.6.7-titrahydrobenzoselenazole, etc.), naphthoxole series nuclei (e.g., natto[2,1-d]selenazole, natto[1 , 2-d] selenazole), thiazoline series nuclei (
For example, thiazoline, 4-methylthiazoline, 4-hydroxymethyl-4-methylthiazoline), 4,4-bis-
hydroxymethylthiazoline), oxazoline series nuclei (e.g. oxazoline), selenazoline series nuclei (e.g.
(e.g. selenazoline), 2-quinoline series nuclei (e.g. quinoline, 6-methylquinoline, 6-chloroquinoline,
6-medoxyginoline, 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
- nuclei of the inquinoline series (e.g. isoquinoline); 3.
Nuclei of the 3-dialkylindolenine series (e.g. 3,3-
Dimethylindolenine, 3,3-dimethyl-5-chloroindolenine, 3,3.5-)dimethylindolenine,
3,3,7-1-dimethylindolenine), hyridine series nuclei (e.g. pyridine, 5-methylpyridine), benzimidazole series nuclei (e.g. l-ethyl-5,6-
Dichlorobenzimidazole, 1-hydroxyethyl-
5,6-dichlorobenzimidazole, l-ethyl-5
-chlorobenzimidazole, 1-ethyl-5,6-dibromobenzimidazole, l-ethyl-5-phenylbenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-ethyl-5-cyanobenzimidazole, ■-( β-acetoxyethyl)-5-cyanobenzimidazole, 1-ethyl-5-chloro-6-cyanobenzimidazole, 1-ethyl-5-fluoro-6-
Cyanobenzimidazole, l-ethyl-5-acetylbenzimitazole, 1-ethyl-5-carboxybenzimidazole, ethyl-5-ethoxycarbonylbenzimidazole, 1-ethyl-5-sulfamylbenzimidazole, ■-ethyl-benzimidazole 5-N-ethylsulfamylbenzimidazole, l-ethyl-5,6-difluorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-ethyl-5-ethylsulfonylbenzimidazole, 1-ethyl- 5-methylsulfonylbenzimidazole, ■-ethyl-5-trifluoromethylbenzimidazole, ■-ethyl-5-trifluoromethylsulfonylbenzimidazole, 1-
ethyl-5-trifluoromethylsulfinylbenzimidazole, etc.).

z3 is a divalent hydrocarbon group forming a 5- or 6-membered ring (
For example, -CH2-CH2-, -CH2-CH2-CH
2-, -CH=CH-.

-CH=CH-CH2-), and these 5 or 6 members
The membered ring may be fused with a benzene ring, a naphthalene ring, etc.

R1 and R2 are hydrogen atoms or alkyl groups (for example,
Methyl group, ethyl group, n-propyl group, 1so-propyl group, n-butyl group, 5eC-butyl group, 1so-butyl group, t-butyl group, n-7 mil group, t-7 mil group, n
-hexyl group, n-octyl group, t-octyl group, etc.)
and further includes other alkyl groups, such as substituted alkyl groups (e.g., 2- and droxyethyl groups, 3-hydroxypropyl groups, 4-hydroxybutyl groups, 2-acetoxyethyl groups, carboxymethyl groups, 2-carboxyethyl groups, 3-carboxypropyl group, 2-sulfoethyl group, 3
-Sulfopropyl group, 4-sulfobutyl group, 3-sulfatepropyl group, 4-sulfatebutyl group, N-(
methylsulfonyl)-carbamylmethyl group, 3-(acetylsulfamyl)propyl group, 4-(acetylsulfamyl)butyl group, etc.), cyclic alkyl group (e.g., cyclohexyl group, etc.), allyl group (CH2= CH-CH
2-), aralkyl groups (e.g., benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, etc.), substituted aralkyl groups (e.g., carboxybenzyl group, sulfobenzyl group, hydroxybenzyl group, etc.). do.

A represents an oxygen atom, a sulfur atom, a substituted or unsubstituted imide group (imide, methylimide, ethylimide, propylimide, butylimide, benzylimide, etc.), or a divalent organic residue. Examples of divalent organic residues include OR4. However, R3, R4 and R
5 represents a hydrogen atom or an alkyl group (the same as those listed in the examples of R1 and R2 above). l, m and n are l
and P and q are 0, 1 or 2.

The general formula [Eco, [IT], [III]
Specific examples of the cyanine methine compounds represented by and [IV] are shown below.

The general formula [I], [II], [II
Specific examples of compounds represented by I]
C2r15 Specific examples of compounds represented by the above general formula [IV] The cyanine methine compounds shown by the above general formulas [I], [II] and [m] are, for example, N
Heterocyclic quaternary 11x and triethoxypropene, pentadiocyanyl, iriphorone, etc. are reacted in one or two steps using a condensing agent such as caustic alkali pyridine, piperidine, trialkylamine, acetic anhydride, etc. Can be synthesized.

Further, the cyanine methine compound represented by the general formula [IV] is indan-2-one, cyclohexanone, cyclopentanone, cyclohexen-one, cyclopentadien-one or 1°2.3.4-tetrahydronaphthalene-2 Benzothiazolium salts, which are commonly used in the field of cyanine chemistry, are obtained by dehydration condensation reaction of cyclic ketone compounds such as -one with dicyanomethane, barbylic acid or its derivatives, or logenine or its derivatives; benzoxacillium salt, quinolium salt,
It can be easily obtained by reaction with naphthothiazolium salt.

By forming an information recording body containing at least a heat-sensitive material and a light-absorbing material in a layered manner or a mixture as described above, 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 above the separation temperature and cooling again. .

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, the 719, which uses a small and low-cost semiconductor laser, enables highly sensitive and high-density recording.

In addition, when displaying recorded information, by using the above-mentioned light-absorbing material that does not absorb in the visible region, it is possible to make the unrecorded part transparent and display 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. 1 is a sectional view of one embodiment of an information recording medium constituting the present invention.

This information recording body (1) is made of a base material 2 such as glass or plastic in the shape of a disk, sheet, or belt, and a layer of a mixture of the above-mentioned heat-sensitive material 3 and a material 4 having an absorption property for a recording light source. It is formed by Film thickness is 0.01 gm-
1000 jLm, preferably 1 lm to 200 pLm 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 appropriate film thickness of the heat-sensitive material 3 is 0.01 to 11000K, preferably Igm to 200pm.

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 record body (2) and (
The film thickness of the heat-sensitive material 3 in 3) is 0.01 to 110007t,
Preferably, 17 zm to 2007 pm is appropriate. 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 preferably about 0.01 μm to 10 μm.

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,
Examples include chlorobutadiene, imbutylene, maleic anhydride, 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. be.

In addition, as polymer blend systems, polyester, polyamide, polyacrylate, polymethacrylate, polystyrene, silicone resin, polyvinyl chloride, vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-7-crylonitrile copolymer, polycaprolactone, ethylene- Examples include vinyl acetate copolymer, polycarbonate chlorinated rubber, polyvinylidene fluoride, polycyanide vinylidene, fluororesin, and the above-mentioned copolymers, and two or more types of polymers may be selectively mixed and used. I can do it. When these combinations of polymers are heated to 100-200℃, 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. .

In particular, in order to apply the polymer, it is better to make the polymer soluble in an organic solvent. For example, JP-A-59-135
Vinylidene fluoride-based copolymers soluble in organic solvents, such as a copolymer of vinylidene fluoride and hexafluoroacetone as shown in No. 257 or a copolymer of vinylidene fluoride and trifluoroethylene, are suitable.

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, an example of the present invention will be explained with reference to the drawings.

FIG. 2 is a schematic diagram of the main parts of a recording, erasing, and display device to which the present invention is applied.

10 is a vertical awn packaging box; 20 is a display image viewing window formed with a large opening on the front surface of the box; generally a transparent plate 3, such as a glass plate, is attached thereto. Further, 40 is the aforementioned information recording body, which is an endless tape stretched between a driving pulley (or roller) 50 and a driven pulley (t or roller) 60, which are installed horizontally in the upper and lower parts of the outer box. It is belt-shaped, and hereinafter this information recording body will be referred to as a belt. This belt 40 is rotationally driven in the direction of the arrow by the rotation of the drive pulley, and the outer surface of the stretched portion of the belt 40 moves and passes through the display image viewing window 20 in the direction of the arrow. 70 and 80 are a pair of tension rollers that are placed vertically in contact with each other with a slight interval on the back side of the center area on the slack side of the belt, and 9o is an erasing section where images formed in a sheet form need to be erased. Accordingly, the data is erased in the erasing section 90. 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 partially erase the image by using an erasing section 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 bag Hioo is a light beam scanning type, which generates a modulation-controlled light beam L corresponding to a time-series electric pixel signal output from an electronic calculator, etc. The belt is swung in the width direction 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-mentioned configuration, when the bell 40 passes through the optical device 100 during its rotation process, 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 operating a button that commands the belt to rotate again, the belt 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 are high-density optically detectable small pits (e.g., approximately 1 µm) formed in a thin information recording layer provided on a substrate in the form of spiral or circular tracks. Information 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 φ energy irradiated onto 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 the opaque portion with a laser beam 1 heating element or the like and slowly cooling it. By forming pits, optically detectable transmittance difference 1 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 50 parts by weight of a vinylidene fluoride copolymer resin consisting of vinylidene fluoride and hexafluoroacetone as a heat-sensitive material and 50 parts by weight of a polymethyl methacrylate resin were dissolved in a methyl ethyl ketone solution, and then a light absorbing material and the above compound were dissolved. 25 parts by weight of No. (18) were added and mixed. This mixed liquid was applied onto a polyethylene terephthalate belt to prepare an information recording medium with a dry film thickness of 701 L.

The information recording body thus prepared was mounted on the display device shown in FIG. 1, and the display device 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 85 Recorded area 12 Further, even when image display was repeated 1000 times or more, good image display could be performed.

Comparative Example 1 Light-absorbing material used in Example 1 Compound N
A comparative information recording body was prepared in exactly the same manner as in Example 1 except that o and (18) were omitted.

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 problem even if light absorbing material compound No. (18) was mixed. .

Examples 2-12 Compound No. of Example 1, No. (18) The aforementioned compound No., (1), (11), (17).

(23), (2B), (37), (44).

Instead of each of the compounds (50), (60), and (67), they were coated on a polyethylene terephthalate substrate in the same manner as in Example 1 so that the dry film thickness was 70 #L to prepare an information recording body. and each compound was prepared in Examples 2 to 12.
And so.

Images of the information recording bodies of Examples 2 to 12 thus prepared were displayed in the same manner as in Example 1, 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 section Recorded section 737 87, 2
3 12 67 87,
28 Example 13 Into a methyl ethyl ketone solution of 50 parts by weight of the vinylidene fluoride copolymer resin made of vinylidene fluoride and hexafluoroacetone and 50 parts by weight of polymethyl methacrylate resin, 10% of the compound No. (30) was added.
Parts by weight were added and mixed. This mixed liquid was heated to a diameter of 20 cm.
Coated on a disc-shaped aluminum vapor-deposited glass plate with a dry film thickness of 2.
An information record was created to reach 500 people.

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 (bits) 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.

In addition, when the recorded information recording medium was irradiated with a focused semiconductor laser beam rotating at a low speed and observed under a microscope, the opaque state (bits) was erased and a uniform transparent state was confirmed, and the pits were erased. I found out that there is.

Example 14 Compound No. of Example 13, (30) was replaced with the above compound No.
, instead of the compound (20), it was applied on a disc-shaped aluminum vapor-deposited glass plate with a diameter of 20 cm in the same manner as in Example 13,
An information recording medium was created to have a dry film thickness of 2,500 people.

When information was recorded on this information recording medium in the same manner as in Example 13 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. Further, after irradiation with semiconductor laser light focused at low speed rotation, microscopic observation revealed that the opaque state (pits) had disappeared and a uniform transparent state was confirmed, indicating that the pits had been eliminated.

Example 15 Compound No. of Example 13, (30) was replaced with the above compound No.
, instead of the compound (24), it was applied on a disc-shaped aluminum vapor-deposited glass plate with a diameter of 20 cm in the same manner as in Example 13,
An information recording medium was created to have a dry film thickness of 2,500 people.

When information was recorded on this information recording medium in the same manner as in Example 13 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 irradiation with semiconductor laser light focused at low speed rotation, microscopic observation revealed that the opaque state (pits) had disappeared and a uniformly transparent state had been confirmed, indicating that the pits had been eliminated.

Example 16 Compound No. of Example 13, (30) was replaced with the above compound No.
, instead of the compound (35), it was applied on a disc-shaped aluminum vapor-deposited glass plate with a diameter of 20 cm in the same manner as in Example 13,
An information recording medium was created to have a dry film thickness of 2,500 people.

When information was recorded on this information recording medium in the same manner as in Example 13 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 irradiation with semiconductor laser light focused at low speed rotation, microscopic observation revealed that the opaque state (pits) had disappeared, and a uniformly transparent state was confirmed, indicating that the pits had been eliminated.

Example 17 Compound No. of Example 13, (30) was replaced with the above compound No.
, , (39) was used in the same manner as in Example 13 to prepare an information recording medium by coating it on a disc-shaped aluminum vapor-deposited glass plate with a diameter of 20 cm 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 13 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 irradiation with semiconductor laser light focused at low speed rotation, microscopic observation revealed that the opaque state (pits) had disappeared, and a uniformly transparent state was confirmed, indicating that the pits had been eliminated.

Example 18 Compound No. of Example 13, (30) was replaced with the above compound No.
, (46') was used in the same manner as in Example 13 to prepare an information recording medium by coating it on a disc-shaped aluminum vapor-deposited glass plate with a diameter of 20 cm 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 13 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 irradiation with semiconductor laser light focused at low speed rotation, microscopic observation revealed that the opaque state (pits) had disappeared, and a uniformly transparent state was confirmed, indicating that the pits had been eliminated.

Example 19 Compound No. of Example 13, (30) was replaced with the above compound No.
, instead of the compound (48), it was applied on a disc-shaped aluminum vapor-deposited glass plate with a diameter of 20 cm in the same manner as in Example 13,
An information recording medium was created to have a dry film thickness of 2,500 people.

When information was recorded on this information recording medium in the same manner as in Example 13 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. Further, after irradiation with a semiconductor laser beam that rotated at a real speed at a low speed, microscopic observation was performed, and it was found that the opaque state (pits) had disappeared and a uniform transparent state had been confirmed, indicating that the pits had been eliminated.

Example 20 Compound No. of Example 13, (30) was replaced with the above compound No.
, (51) was used in the same manner as in Example 13 to prepare an information recording medium by coating a disc-shaped aluminum vapor-deposited glass plate with a diameter of 20 cm to a dry film thickness of 2,500 mm.

When information was recorded on this information recording medium in the same manner as in Example 13 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 irradiating with a semiconductor laser beam that rotated at a real speed at a low speed, microscopic observation was performed, and the opaque state (pits) was erased, and a uniform transparent state was confirmed.
・I found out that it has been deleted.

Example 21 Compound No. of Example 13, (30) was replaced with the above compound No.
, instead of the compound (54), it was applied on a disc-shaped aluminum vapor-deposited glass plate with a diameter of 20 cm in the same manner as in Example 13,
An information recording medium was created to have a dry film thickness of 2,500 people.

When information was recorded on this information recording medium in the same manner as in Example 13 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. Further, after irradiation with a semiconductor laser beam that rotated at a real speed at a low speed, microscopic observation was performed, and it was found that the opaque state (pits) had disappeared and a uniform transparent state had been confirmed, indicating that the pits had been eliminated.

Example 22 Compound No. of Example 13, (30) was replaced with the above compound No.
, instead of the compound (55), it was applied on a disc-shaped aluminum vapor-deposited glass plate with a diameter of 20 cm in the same manner as in Example 13,
An information recording medium was created to have a dry film thickness of 2,500 people.

When information was recorded on this information recording medium in the same manner as in Example 13 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. Further, after irradiation with a semiconductor laser beam that rotated at a low speed and at a real speed, microscopic observation was performed, and it was found that the opaque state (pits) was erased and a uniform transparent IE was confirmed, indicating that the pits were erased.

Example 23 Compound No. of Example 13, (30) was replaced with the above compound No.
, instead of the compound (66), it was applied on a disc-shaped aluminum vapor-deposited glass plate with a diameter of 20 cm in the same manner as in Example 13,
An information recording medium was created to have a dry film thickness of 2,500 people.

When information was recorded on this information recording medium in the same manner as in Example 13 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. Further, after irradiation with a semiconductor laser beam that rotated at a real speed at a low speed, microscopic observation was performed, and it was found that the opaque state (pits) had disappeared and a uniform transparent state had been confirmed, indicating that the pits had been eliminated.

Example 24 The above compound No.
A solution obtained by dissolving the compound (21) in dichloroethane is applied to a dry film thickness of 500 g, and then the vinylidene fluoride copolymer resin consisting of vinylidene fluoride and hexafluoroacetone is applied on top of the solution to give a dry film thickness of 50 g. A solution obtained by dissolving 50 parts by weight of polymethyl methacrylate resin in ethyl acetate was applied to give a dry film thickness of 5 JL to prepare an information recording body.

When information was recorded on this information recording medium in the same manner as in Example 13 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 irradiation with semiconductor laser light focused at low speed rotation, microscopic observation revealed that the opaque state (pits) had disappeared, and a uniformly transparent state was confirmed, indicating that the pits had been eliminated.

Example 25 A solution prepared by dissolving 50 parts by weight of the vinylidene fluoride copolymer resin consisting of vinylidene fluoride and hexafluoroacetone and 50 parts by weight of polymethyl methacrylate resin in methyl ethyl ketone was placed on a disc-shaped glass plate with a diameter of 20 cm. was applied to a dry film thickness of 800 mm, and on top of that, a solution prepared by dissolving the compound No. (16) in dichloroethane was applied to a dry film thickness of 1000 mm, and the information was recorded. Created a body.

When information was recorded and reproduced in the same manner as in Example 13, except that this information recording medium was irradiated with semiconductor laser light from the disk-shaped gaffra plate surface and recorded, sufficient S.
A waveform having a /N ratio was observed. After writing the information, observation under a microscope revealed that clear opaque states (pits) had been formed. Furthermore, after irradiation with semiconductor laser light focused at low speed rotation, microscopic observation revealed that the opaque state (pits) had disappeared and a uniformly transparent state had been confirmed, indicating that the pits had been eliminated.

[Brief explanation of drawings]

FIG. 1 is a sectional view of one embodiment of an information recording medium constituting the present invention. FIG. 2 is a schematic longitudinal sectional side view of an example of the information recording, reproducing and display device of the present invention. ■ -111 information record body. 2-111 base material. 3-111 Heat-sensitive material 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 This information recording medium is made by laminating or mixing a heat-sensitive material that becomes cloudy and a light-absorbing material made of at least one cyanine methine compound, and can display or read information by heating a specific range to a specific temperature. An information recordable and erasable information recording body characterized by: (2) Information can be recorded and erased according to claim 1, wherein the compound having at least one cyanine methine is a compound represented by the following general formula [I], [II], [III] or [IV]. An information record. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Z_1 and Z_2 represents an atomic group necessary to complete a substituted or unsubstituted nitrogen-containing heterocycle. Z_3 and Z_4 are substituted or unsubstituted 5- or 6-membered
Indicates a divalent hydrocarbon group forming a membered ring. R_1 and R_2 represent a hydrogen atom or a substituted or unsubstituted alkyl group. R_3 and R_4 are hydrogen atoms,
Indicates a halogen atom, hydroxy group, carboxyl group, alkyl group, substituted or unsubstituted aryl group, or acyloxy group. R_5 and R_6 represent a hydrogen atom or a halogen atom. X^■ represents an acid anion. m and n are 0 or 1
, l represents 0, 1 or 2. ) General formula [IV] ▲ Numerical formulas, chemical formulas, tables, etc. Represents a divalent hydrocarbon group forming a 6-membered ring. R_1 and R_2 represent a hydrogen atom or a substituted or unsubstituted alkyl group. A represents an oxygen atom, a sulfur atom, a substituted or unsubstituted imide group, or Represents a divalent organic residue. l, m and n represent 0 or 1, p and q represent 0, 1 or 2.) (3) An information recording medium capable of recording and erasing information as set forth in claim 1, wherein the optical means comprises a semiconductor laser. (4) The information recording body capable of recording and erasing information according to claim 3, wherein the at least one cyanine methine compound is a compound having substantially no absorption in the visible range.