JPH038534B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel record using a substance capable of absorbing visible light or near infrared rays, a method for reading the record, and a record.

In recent years, there has been an increasing demand for recording and reproducing information such as images and audio at high speed, high density, and easily, and various methods and accompanying recordings have been proposed, and some of them have not yet been put into practical use. has been made into

Among these, so-called optical disks, which use laser light to read recorded signals, can record information at an extremely high density, and can also record desired information recorded from any location on the medium. Since it can be read out, it is expected that it will be widely put into practical use.

A typical recording and reading system for conventional optical discs records information by forming fine pits on the surface of light-transmissive plastic, and then deposits metal or other material on the surface where the fine bits are formed. Therefore, a reflective layer is formed, and a spot beam of laser light is generally applied to this from the opposite surface, and changes in the amount of reflected light due to diffraction at the pit edge are detected using a photodiode or the like. This is a method of converting it into a signal and reading out the record.

However, in this method, extremely fine physical shapes of 1μ or less, that is, bits, are formed by physical methods such as injection molding and pressure molding, so it is complicated and requires a number of molds corresponding to each piece of information. At the same time, in order to perform accurate recording on an industrial scale, there are difficulties in recording accuracy and productivity, and significant technical improvements are desired.

The present invention has been achieved without sacrificing the high density of recording and ease of reading out the recording, which are the characteristics of conventional optical discs, and without sacrificing the above-mentioned information recording method of conventional optical discs. To provide a new record, a record reading method, and a record that avoid productivity at once.

Furthermore, according to the method of the present invention, as described above, one information content can not only be easily reproduced in large numbers;
Unlike the above-mentioned conventional method, which requires large numbers of copies for economic reasons and requires a large molding machine, it can be used, for example, as a disk memory to arbitrarily record and store information that you want to store in your home or office. It is also extremely useful for recording and reading out records.

That is, the present invention has maximum absorption in the visible light or near-infrared wavelength region of 1,600 nm to 1,200 nm, and
By irradiation with radiation, electron beam or ion beam,
Ultraviolet rays, Recording is performed by forming a pattern of the presence or absence or strength of infrared absorption ability, and by applying a laser beam having the wavelength of visible light or near infrared rays to the above pattern, detecting the presence or absence or strength of absorption of the laser light and recording. 2. The above visible light or near infrared rays have maximum absorption in the visible light or near infrared wavelength region of 600 nm to 120 nm, and are Ultraviolet rays and X
This is a recorded material that has been irradiated with a beam, an electron beam, or an ion beam to form a pattern of the presence or absence or strength of absorption of visible light or near infrared rays.

It has maximum absorption in the visible light or near-infrared region of 600 nm to 1200 nm used in the present invention, and loses its ability to absorb the above-mentioned visible light or near-infrared light (hereinafter referred to as readout line) by irradiation with the recording line. As the substance (hereinafter referred to as recording substance), any substance having the above-mentioned functions can be used, but very typical examples include aromatic diamine-based metal complexes, aromatic dithiol-based metal complexes, mercaptophenol-based metal complexes, and mercaptophenol-based metal complexes. Phenylamine metal complexes, aliphatic dithiol metal complexes, arylaluminum salts, and the like are used.

Particularly preferred specific examples for use as a recording material in the present invention include bis(4-chloro-o-phenylenediamine) nickel (maximum absorption wavelength λmax [hereinafter referred to as λmax]) 800 nm as an aromatic diamine metal complex; The molar extinction coefficient ε [hereinafter referred to as ε] 66600), and the aromatic dithiol metal complex is bis(1,2,3,4-tetrachloro-5,6-dithiophenolate)nickel()tetra-n- Butylammonium (λmax885nm, ε15700), as a mercaptophenol metal complex, bis(1-mercaptolate-2-naphthlate)nickel()tetra-n
-Butylammonium (λmax1100nm,
ε12290), as an aliphatic dithiol metal complex, bis[cis-1,2-bis(p-methoxyphenyl)ethylene-1,2-dithiolate]nickel (λmax 920 nm, ε35000), as a mercaptophenylamine metal complex is bis(o-mercaptanilide) nickel (λmax825nm, ε8900), and the arylaminium salt is p-methoxyphenyl-bis(diethylaminophenyl)aminium.
SbF ₆ salts (λmax 630 nm and 1025 nm with ε 26800 and 5200, respectively) are used, while in some cases, e.g. It may be a compound such as a compound capable of forming a polymer.

The recording material of the present invention must be a substance or compound that loses or reduces its ability to absorb the readout line upon irradiation with any of the recording lines.

Among the recording lines, ultraviolet rays are most preferable from the point of view of equipment simplicity, usually below 450 nm, especially from 160 to 400 nm.
Irradiation with ultraviolet rays having the following wavelengths is preferred, and examples of ultraviolet ray generators include mercury lamps, high-pressure mercury lamps,
Xenon arc lamps, mercury-xenon arc lamps, deuterium lamps, etc. are commonly used.

Although generators such as X-rays, electron beams, or ion beams are more expensive and complicated than ultraviolet ray generators, they are useful for forming finer patterns.

The recording material of the present invention is usually kneaded into a medium base material such as transparent plastic to form a film or sheet, or the recording material is dissolved in a solvent such as an organic solvent, or a resin or the like having film-forming ability is used. It is generally used in the form of a layer distributed uniformly and continuously along a flat or curved surface, such as by coating the mixture on a base material called a support and drying and removing the organic solvent. The content of the recording material or recording material portion is preferably 5 times or more the extinction coefficient of the medium base material at its maximum absorption wavelength, preferably 10
From the viewpoint of recording/reproducing accuracy, it is preferable to use the number of times the number of times or more.

The object containing the above-mentioned recording material used in the present invention generally has a planar shape such as a film or a sheet, but for example, a curved object such as a cylinder or a sphere, or a tape-like object, etc. It may be of elongated shape.

To form a pattern by applying a recording line to a desired position of an object having a recording material-containing layer formed as described above, a mask material having a part that transmits the recording line and a part that does not transmit the recording line is applied to a corresponding part of the object. Either the recording line is focused into a spot beam, and the layer is scanned by the movement of the beam and/or object in a pulsed manner according to the signal of the recorded content, so that the exposed area is Information is recorded by reducing or eliminating the readout line absorption ability of the readout line and forming a digital pattern based on the presence or absence or strength of the readout line absorption.

It is also possible to record information by automatically adjusting the irradiation amount or irradiation time of the recording line and forming an analog pattern in which the absorption capacity of the readout line is continuously changed.

In forming the above digital pattern,
In order to reduce the influence of noise as much as possible, the absorption capacity of the exposure readout line should be one-half or less, preferably one-fifth or less, and more preferably one-tenth or less of the absorption capacity of the unexposed area. It is common to adjust the intensity, exposure time and/or exposure rate of the light or radiation source.

600nm on the pattern obtained as above.
Laser light is irradiated as a reading line with a wavelength of ~120 nm through a lens, and is irradiated as a spot beam with a diameter of usually less than 1 μm. Differences in transmittance or reflectance of the laser light are detected from the presence or absence of absorption or strength of the laser light. and read the information recorded. The above-mentioned change in the amount of light due to transmission or reflection of the laser beam is converted into an electrical signal by a conventional method such as using a phototube or photodiode, and is connected to reproduction of audio and images or input to a computer.

Examples of laser light generators used include helium neon lasers, argon ion lasers, carbon dioxide lasers, various solid-state lasers, and various semiconductor lasers. Regardless of the laser generation method, as long as the laser has a wavelength of 600 nm to 1200 nm, Although any one can be used, it is preferable to use a laser having a wavelength close to the maximum absorption value of the above-mentioned recording material for reading.

In addition, when reading based on the difference in reflectance of laser light, a smooth reflective layer is formed on the opposite side of the surface irradiated with the laser light by a method such as metal vapor deposition, and the layer containing the recording material is transmitted through the layer. It is better to reflect the laser light.

The recording and recording reading method of the present invention as described above is particularly useful when a large amount of single information is to be reproduced, such as when recording and playing back images such as videos, recording and playing back audio, etc. It is also possible to read multiplexed information digitally recorded in the reading process in a time-division manner, and it can be widely used for recording and reading information on computer memory disks, etc. is much superior to conventional methods in that it allows the user to easily write information.

The present invention will be specifically explained below with reference to Examples, but these are only extremely representative examples for facilitating understanding of the present invention, and the present invention is not limited to these.

Note that parts, percentages, and ratios below are based on weight unless otherwise specified.

Example 1 10 parts of bis(1-mercaptolate-2-naphtholate)nickel()tetra-n-butylammonium (λmax 1100 nm) and 100 parts of polymethyl methacrylate resin were dissolved in a mixed solvent of 500 parts of dichloromethane and 500 parts of methyl ethyl ketone,
Dry coating thickness on a 3mm thick methacrylic resin plate
It was applied to a thickness of 10 μm and dried in a hot air drying oven at 80°C for 30 minutes to form a recording substance-containing layer, and then
Cover with a photo mask with a 1 μ wide slit,
Under a high pressure mercury lamp with an output of 120W/cm
Ultraviolet irradiation was performed for 10 seconds. Then on this sheet
A spot beam (diameter 1μ) of Nd ³⁺ -YAG laser light (wavelength 1060nm) is applied to the material, and the amount of laser light transmitted through the exposed and unexposed parts of the ultraviolet rays is detected by a photodiode and an electrical signal is generated by sliding the material. As a result, a bright signal was obtained when the spot beam passed through the exposure section. Note that the absorption coefficient of the sample exposed to the above-mentioned laser beam under the above-mentioned ultraviolet irradiation conditions without using a mask was 1/8 of the absorption coefficient of the unexposed sample.

Example 2 Bis(1,2,3,4-tetrachloro-5,6
-dithiophenolate)nickel()tetra-
75 parts of n-butylammonium (λmax 885 nm) was kneaded into 1000 parts of injection molding grade methacrylic resin in a molten state to obtain a recording material-containing sheet having a thickness of 1.2 mm by injection molding. Cover this with the photomask having a 1μ slit used in Example 1,
X-rays targeting aluminum were irradiated for 5 seconds. Next, a spot beam (diameter 1 μ) of AlGaAs laser light (wavelength 850 nm) is applied to this sheet, and the sheet is slid to detect the amount of laser light that passes through the X-ray exposed and unexposed areas using a photodiode. As a result of converting it into an electrical signal, a bright signal was obtained when the spot beam passed through the exposure section. Incidentally, the absorption coefficient of the sample exposed to the above-mentioned laser beam under the above-mentioned ultraviolet irradiation conditions without using a mask was 1/12 of the absorption coefficient of the unexposed sample.

Example 3 p-methoxyphenyl-bis(diethylaminophenyl)aminium SbF ₆ salt (λmax630nm) 12
100 parts of polyethylene phthalate resin,
After kneading in a molten state, the mixture was rolled into a film having a thickness of 100 μm to obtain a film containing a recording substance.

This film was exposed by scanning an electron beam focused to a diameter of 1 μm using an electron beam lithography system for producing high-density integrated circuits.

Next, a spot beam (diameter 1μ) of He-Ne laser light (wavelength 633nm) was applied to the above film.
As a result of detecting the amount of laser light transmitted through the exposed and unexposed areas of the electron beam using a photodiode and converting it into an electrical signal, a bright signal was obtained when the spot beam passed through the exposed area.

In addition, under the above-mentioned ultraviolet irradiation condition, the absorption coefficient of the exposed area to the laser beam was 1/15 of that of the unexposed area.

Example 4 The ultraviolet rays emitted from a 300W mercury lamp were passed through a diaphragm whose light intensity was continuously varied from 0 to 100% on the sheet having the recording substance-containing layer obtained in Example 1, and the ultraviolet rays were then applied to a spot beam with a diameter of 5μ. The sheet was then slid. The UV-exposed area was traced using the laser spot beam used in Example 1, and the amount of laser light transmitted was detected by a phototube and converted into an electrical signal. As a result, it was found that there is a proportional relationship with the change in the aperture during UV irradiation. I got a signal.

Example 5 Bis(1-mercaptolate-2-
bis(4-methyl-o) instead of nickel()tetra-n-butylammonium
A film containing a recording material was obtained in the same manner as in Example 1, except that nickel (λmax 795 nm, ε 55100) was used. A photomast having a 2 μ wide slit was placed on top of this film, and ultraviolet rays were irradiated for 10 seconds under a metal halide lamp with an output of 120 W/cm. Next, this film was irradiated with a moving spot beam (beam diameter 1.7μ) of semiconductor laser (emission wavelength 780nm) light, and the amount of light in the ultraviolet exposed and unexposed areas on the film was detected using a photodiode. , a clear signal was obtained when the spot beam passed through the exposure section. Note that the absorption coefficient of the sample exposed to the above-mentioned laser beam under the above-mentioned ultraviolet irradiation conditions without using a mask was 1/10 of the absorption coefficient of the unexposed sample.

Example 6 Bis(1-mercaptolate-2-
bis[cis-1,2-naphthlate)nickel()tetra-n-butylammonium
Bis(p-methoxyphenyl)ethylene-1,2
-dithiolate]Nickel (λmax920nm,
ε35000, ε28000 at 1060nm)
A film containing a recording material was obtained in the same manner as in Example 1. Next, after ultraviolet irradiation was performed in the same manner as in Example 1, the exposed and unexposed areas were detected. As a result, a clear signal was obtained when the spot beam passed through the exposed area. Note that the absorption coefficient of the sample exposed to the above-mentioned laser beam under the above-mentioned ultraviolet irradiation conditions without using a mask was 1/8 of the absorption coefficient of the unexposed sample.

Example 7 Instead of bis(1,2,3,4-tetrachloro-5,6-dithiophenolate)nickel()tetra-n-butylammonium in Example 2, bis(o-mercaptoanilide)nickel( As a result, a clear signal was obtained when the spot beam passed through the exposure section.
Note that the absorption coefficient of the sample exposed to the above-mentioned laser beam under the above-mentioned ultraviolet irradiation conditions without using a mask was 1/10 of the absorption coefficient of the unexposed sample.

Claims (1)

[Claims] 1. Has maximum absorption in the visible light or near-infrared wavelength region of 600 nm to 1200 nm, and loses or reduces the above-mentioned visible light or near-infrared absorption ability by irradiation with ultraviolet rays, X-rays, electron beams, or ion beams; Aromatic diamine metal complexes, aromatic dithiol metal complexes (excluding benzenedithiol nickel complexes), mercaptophenol metal complexes, mercaptophenol amine metal complexes, aliphatic dithiol metal complexes, arylaminium salts A desired position of an object containing a recording material selected from the group consisting of is irradiated with ultraviolet rays, The present invention is a recording method in which a laser beam having a wavelength in the visible light or near infrared region is applied to the pattern, and the recording can be read by detecting the presence or absence or strength of absorption of the laser beam. How to characterize it.