JPS61201238A - Information memorizing device - Google Patents

Abstract

PURPOSE:To obtain an information memorizing device using light recording element high in reliability and capable of high density recording by forming an information recording element composed of a film made of a triphenylmethane deriv. having both of a hydrophilic group and a hydrophobic group and installing means for writing, reading, and erasing information on and from said element. CONSTITUTION:At the time of writing, a recording control circuit 27-2 is connected to a light modulator 26-2, a recording light 24-2 emitted from a recording light source 29-2 is modulated and controlled in accordance with input information, and this light signal is formed into an image displayed on the recording layer of the light recording element 18, and color is developed with a color developing mechanism, and recorded. At the time of reading, a reading light 24-1 emitted from a reading light source 29-1, different in wavelength from the recording light 24-2, is used for reading. The reflected light is converted into an electric signal by casting the light on the light receiving face of a photodiode 25 through a light pickup optical system to execute reproduction and reading of the light. A light 24-3 different in wavelength emitted from an erasing light source 29-3 is used for erasing. the element 18 utilizes the photoreaction of the triphenylmethane deriv. and is composed of colorless or colored layer of a monomolecular film or its built-up molecular films.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an information recording device, and in particular to an information recording device using an optical recording element capable of highly reliable and high-density recording using a highly molecularly oriented organic thin film. This relates to a recording device.

[Background Art] Recently, optical disks have been attracting attention as a central player in office automation (OA). The reason for this is that a single optical disc can record (or memorize) personal documents, literature, etc. Therefore, introducing an information recording device that uses this optical disc will revolutionize the organization and management of documents and literature in offices. It is something that brings. or,
The recording element for the optical disk is inexpensive, easy to manufacture,
Elements made of organic materials that have features such as high-density recording are attracting attention.

Among the conventional techniques using such organic recording materials, a two-component optical recording element that utilizes a color reaction caused by contact between a color former and an auxiliary has been reported (Nikkei Sangyo Shimbun, 1972).
Year 10. 18th of the month).

An example of a recording process by an information recording apparatus using the conventional optical recording element will be explained based on the drawing.The optical recording element has a coloring agent layer 7 and an auxiliary coloring agent layer 5 as shown in FIG. 2(a). and are stacked on the substrate 1, separated by a light absorption layer 6.

The coloring agent (leuco compound) and auxiliary colorant are colorless or light-colored when each exists alone.

When recording on the optical recording element, a laser beam 8 is irradiated onto a desired position of the light absorption layer 6 as shown in FIG. 2(b), and the portion of the light absorption layer irradiated with the laser beam is It absorbs light, melts, and tears, leaving small holes.

As a result, as shown in FIG. 2(c), the coloring agent and the coloring agent separated by the light absorption layer 6 mix through the small holes and develop a color. Information is recorded or stored in the form of coloring points 9, and reading is performed by scanning the recording element with another light source and detecting changes in reflectance, transmittance, etc. due to the coloring points.

[Problem to be Solved by the Invention 1] In the information storage device described in 1- above, in order to achieve high recording density, the optical recording element has a light absorbing layer 6 as thin and flat as possible;
It is also desirable that the film thickness be uniform. however,
In conventional optical recording elements, the light absorption layer is coated on the substrate by, for example, vacuum evaporation or spin coating, so if you try to reduce the thickness to less than 200 to 500A, pinholes tend to occur frequently. However, since the two components, the color former and the auxiliary color agent, come into contact with each other at the pinhole, the color is developed, resulting in a lack of reliability. Second, because the molecular distribution and orientation within the base layer film formed by the above-mentioned conventional coating method is random, light scattering occurs within the film with light irradiation, and when viewed microscopically, each light The degree of chemical reaction that occurs with each irradiation differs. Furthermore, the above-described coating method has drawbacks such as unevenness in film thickness and uneven recording quality when increasing the area of the substrate of an optical disk.

Therefore, as an optical recording element, it is desirable that the molecular distribution and orientation within the film be uniform, that there are no pinholes, and that the film thickness is uniform, and that the film thickness be as thin as possible to achieve high recording density and high reliability. It is requested for the purpose of

The present invention has been made in view of such needs, and an object of the present invention is to provide an information storage device using an optical recording element that is capable of highly reliable and high density recording. Another object of the present invention is to provide an information recording device using an optical recording element that is easy to manufacture and inexpensive. Still another object of the present invention is to provide an information recording device using a large-area optical recording element.

[Means for Solving the Problems] and [Operation] That is, the present invention provides a photonic film composed of a monomolecular film or a cumulative film of a triphenylmethane derivative having both a colorless or colored hydrophilic group and a hydrophobic group. a recording element, an information writing means for writing and recording information on the optical recording element, an information reading means for reading the information written and recorded on the optical recording element, and an information reading means for reading the information written and recorded on the optical recording element; The information storage device is characterized by comprising information erasing means for erasing and reproducing the information. FIG. 1 is a block diagram showing an example of an information storage device according to the present invention. In FIG. 1, the information storage device of the present invention includes an optical recording element 18 (for example, an optical disk) made of a monomolecular film or a cumulative film of a normally colorless or colored triphenylmethane derivative, and a control circuit 27- 2, an information writing means consisting of an optical pickup optical system (for example, 19-1, etc.), and an information reading means, consisting of an output circuit 28 and an optical pickup optical system (for example, 19-1, etc.).

Writing is performed as follows. The control circuit 27-2 is connected to the optical modulator 26-2, and modulates and controls the recording light beam 24-2 emitted from the recording light source 28-2 according to input information. The optical signal 24-2 passes through the optical pickup optical system shown in FIG. 1, and is focused, for example, on the recording layer 2 of the optical recording element (optical disk) 18 which is rotating synchronously, and is then imaged by the coloring mechanism described later. Recorded in color.

Reading is performed as follows. A light beam having a different wavelength from the recording light beam 24-2 emitted from the reading light source 28-1 is used as the reading light beam 24-1. Note that in some cases, the recording light beam can be used for reading by reducing the output to such a level that color recording is not performed.

The reading light beam forms an image on the substrate surface of the optical recording element (optical disk) 18 and is reflected, but since the reflectance differs between the coloring point and the non-coloring point, this reflected light is passed through the optical pickup optical system to the photodiode 25. By applying the light to the light-receiving surface of the sensor, it is converted into an electrical signal and read out for reproduction.

In order to increase the contrast of such reproduced signals and improve image quality, it is preferable to provide a metal reflective layer such as aluminum on the substrate of the optical recording element.

The thickness of the metal reflective layer is preferably 1,0OOA to 2,0OOA. In addition, a dielectric mirror may be used as necessary.

Deletion is performed as follows.

Light m having a different wavelength from both the recording light beam 24-2 and the reading light beam 24-1 emitted from the erasing light source 28-3.
24-3 is used as the erasing light beam.

The wavelength of the light beam 24-3 must be such that it can restore the recorded color of the triphenylmethane derivative.

Note that an arbitrary area can be erased using the erasing control circuit 27-3 and the optical modulator 26-3 connected thereto.

Furthermore, a protective layer may be provided on the surface of the outermost layer to protect the monomolecular film or the cumulative film of the optical recording element. Suitable materials for such a protective layer include dielectrics such as Si07, plastic resins, and other polymerizable LB films.

The optical recording element used in the present invention utilizes the photoreaction of triphenylmethane derivatives.

Therefore, the optical recording element used in the present invention is usually composed of a monomolecular film of a colorless or colored triphenylmethane derivative or a layer consisting of a cumulative film thereof.

The triphenylmethane derivatives used in the present invention are represented by the general formulas ↓ to ↓.

H RIRI H Note that the substituents of the phenyl group are not limited to the substitution sites shown in the formula. Further, R1 represents a short chain alkyl group such as a methyl group or ethyl group, and R2 represents a long chain alkyl group.

Further, one feature of the present invention is that the optical recording element is composed of a monomolecular film of a triphenylmethane derivative or a cumulative film thereof. Therefore, the triphenylmethane derivatives mentioned above must each have a hydrophilic group, a hydrophobic group, or both groups introduced at appropriate sites within the molecule.

Any commonly used hydrophobic group and hydrophilic group can be used, but particularly preferred hydrophobic groups include long-chain alkyl groups having 5 to 30 carbon atoms, and hydrophilic groups include hydroxyl groups and cyan groups. , or salts thereof are desirable.

Specific examples of triphenylrimethane derivatives in the present invention include the following compounds.

H (CH2)17 CH3 H G(CH2)1 no GH3 In addition, materials used for the substrate in the present invention include:
Semiconductor materials such as silicon, metal materials such as aluminum, preferably tempered glass, more preferably plastic materials such as acrylic (PMMA), polycarbonate (PC), polypropylene, polyvinyl chloride (PVC), polystyrene, and ceramics. Materials are preferred. As mentioned above, one feature of the optical recording element used in the present invention is that it is composed of a monomolecular film of a triphenylmethane derivative or a cumulative film thereof.

As a method for producing a monomolecular film or a cumulative film thereof having such high orderliness and orientation of molecules, for example, 1. L
The Langmuir-Prodgett method (LB method) developed by Angmuir et al. is used. The Langmuir-Blodgett method, for example, calculates the balance between hydrophilic and hydrophobic groups (balance of amphiphilicity) in molecules with a structure that includes both hydrophilic and hydrophobic groups.
This is a method to create a monomolecular film or a cumulative film of monomolecules by utilizing the fact that when the water is maintained at a suitable level, molecules form a monomolecular layer on the water surface with their hydrophilic groups facing downward. The monolayer on the water surface has the characteristics of a two-dimensional system. When the molecules are sparsely dispersed, the two-dimensional ideal gas equation, 11A=kT, holds true between the area per molecule A and the surface pressure ■, resulting in a gas film.Here, k is Boltzmann's constant, T, is the absolute temperature.If A is made sufficiently small, the intermolecular interaction becomes strong, resulting in a two-dimensional solid "condensation film (or solid H layer)".Condensation films can be formed on various types of substrates, such as plastic substrates and glass substrates. can be transferred layer by layer onto the surface of a carrier having the following material and shape.

Next, the method for forming a monomolecular film or a cumulative film thereof of an organic molecule having both a hydrophilic group and a hydrophobic group which are a leuco dye, a phenolic compound, or a light-absorbing substance used in the present invention will be described in detail.

First, the organic molecule is dissolved in a volatile solvent such as n-hexane, benzene, chloroform, etc., and the aqueous phase 1 in the water tank lO of the monomolecular cumulative film forming apparatus shown in FIG.
Expand on 1.

As the solvent evaporates, the organic molecules develop on the water phase 11 with the hydrophilic groups 12 facing the water phase and the hydrophobic groups 13 facing the gas phase.

Next, in order to prevent the precipitates (organic molecules) from freely diffusing on the aqueous phase 11 and spreading too much, a partition plate (or float) 14 is provided to limit the spread area and control the aggregation state of the membrane substance.
Obtain a surface pressure (■) proportional to the aggregate state. This partition plate 1
4, the developed area can be reduced to control the aggregation state of the membrane material, and the surface pressure can be gradually increased to set a surface pressure suitable for producing a cumulative membrane. While maintaining this surface pressure, the monomolecular film 1 can be gently lowered vertically as shown in FIGS. 4(a) to (C).
6 is transferred to the substrate. The monomolecular layer 1B is manufactured as follows, and the monomolecular layer cumulative film 17 is formed by repeating the above-described operations to form a desired cumulative number of monomolecular layer cumulative films.

For example, the substrate 15 whose surface is wood-loving is crossed across the water surface.

When the monomolecular film 16 is lifted out of the water in the direction shown in FIG. When the substrate 15 is moved up and down as described above, the monomolecular films 16 are stacked one by one in each step. Since the orientation of the film-forming molecules is reversed between the pulling process and the dipping process, this method forms a so-called Y-shaped film in which the hydrophilic groups of the organic molecules face each other, and the hydrophobic groups of the organic molecules face each other between the layers. (Figure 4(a)) The Y-type film is strong because the hydrophilic groups and hydrophobic groups of the organic molecules face each other.

In contrast, only when lowering the substrate 15 into the water,
There is also a method of transferring the organic molecules onto the substrate surface.

In this method, there is no change in the direction of the film-forming molecules even if they are accumulated, and an X-shaped film is formed in which the hydrophobic groups face the substrate 15 in all layers (Fig. 4(b)). A cumulative film in which the hydrophilic groups in all layers face the substrate 15 side is called an X-type film (Fig. 4 (C)). obtained by transferring.

The monomolecular film and monomolecular layer stack formed on the substrate by the method described in Section 2 have a high density and a high degree of order and orientation. , a recording element capable of photothermal recording and having a high-density, high-resolution recording function can be obtained. Furthermore, as can be seen from the principles of these film forming methods, they are very simple methods.

A recording element having an excellent recording function as described in -1- can be provided at low cost.

The substrate on which the monomolecular film or monomolecular cumulative film is formed in the present invention as described above is not particularly limited, but if a surfactant is attached to the surface of the substrate, when the monomolecular layer is transferred from the water surface, the monomolecular layer may be removed. Since the molecular film is disturbed and a good monomolecular film or monomolecular layer stack cannot be formed, it is necessary to use a substrate with a clean surface.

The monomolecular film or monomolecular layer stack on the substrate is sufficiently strongly fixed and hardly peels off or peels off from the substrate. An adhesive layer can also be provided between the molecular layer stacks. Furthermore, the adhesion force can be strengthened by selecting the monomolecular layer formation conditions, such as the hydrogen ion concentration of the aqueous phase, the ion species, the water temperature, the rate of raising and lowering the carrier, or the surface pressure.

When forming the reflective layer in the present invention, a conventional method can be used for forming the reflective layer,
Among them, for example, vacuum evaporation method, sputtering method, etc. are preferable.

In addition, the method for forming the protective layer in the present invention can be any conventionally practiced method, including, for example, a plasma GVD method, a photo CVD method, a vacuum evaporation method, a sputtering method, a coating method, etc. preferable.

The optical recording element used in the present invention can be easily manufactured by the forming method described below.

Next, embodiments of the structure of the optical recording element used in the present invention and an optical recording method using light-induced coloring and decoloring reactions of triphenylmethane derivatives according to the present invention will be described.

FIGS. 5(a) to 5(c) are longitudinal sectional views showing one embodiment of an optical recording element according to the present invention. In addition, each figure is a schematic diagram,
It does not specifically indicate the shape of the molecule. Figure 5 (
a) shows one example of an optical recording element according to the present invention, in which a recording layer 3 made of a cumulative film made of a colored triphenylmethane derivative
0 is formed on a substrate 31 via a reflective layer 32.

Next, when visible light 34 with a wavelength of 2 is irradiated through the protective layer 33 according to a certain pattern, the formula (
I) As shown in formula (I), a decoloring reaction occurs and a change to a colorless triphenylmethane derivative occurs, making it possible to obtain an optical recording element on which information is recorded.

Next, the optical recording element is irradiated with monitor light 1, and the recording can be read based on the intensity of the reflected light. Furthermore, after reading the record, when irradiating with an amount of ultraviolet light 35 as shown in FIG. 5(b) if necessary, a coloring reaction occurs as shown in formula (I), and as shown in FIG. 5(C). As shown in the figure, it changes from colorless to colored triphenylmethane derivatives and can erase records. Note that recording and erasing of information can also be performed by irradiating ultraviolet light or visible light, contrary to the above.

Recording is performed by the method described above. Moreover, this coloring and decoloring reaction is a reversible reaction and can be controlled. Therefore, repeated use is possible. Furthermore, since the film has high density and high orderliness, it is an excellent recording material.

As described above, the optical recording element used in the present invention can record information by forming a coloring point or a colorless point at the position by irradiating light of an appropriate wavelength.

[Example] EXAMPLES The present invention will be explained in more detail by showing examples below.

Example 1 - Example of creating an optical recording element After dissolving compound No. 5 as a triphenylmethane derivative molecule in n-hexane at a concentration of 5X10-3M, p.
) 18.4 was developed in the aqueous phase of distilled water. n of solvent
- After removing hexane by evaporation, the surface pressure was reduced to 27.5 dyne/
cm to precipitate the triphenylmethane derivative in the form of a film. After this, while keeping the surface pressure constant, 100OA of aluminum with a sufficiently clean surface and wood-friendly
A vertical speed of 0.4 cm/m is applied to the glass substrate deposited to a thickness of
The triphenylmethane derivative molecular film was transferred onto the substrate by gently moving it up and down in the direction across the water surface, and the 31st layer, B
Imaging media were produced in which images were formed by triphenylmethane derivative cumulative films of 1 layer, 81 layers, and 121 layers. 1 each time the substrate is lifted from the aqueous phase during this cumulative stroke.
The water adhering to the substrate was evaporated off by leaving it for 5 minutes or more. The film forming equipment used is L manufactured by LAUDA, West Germany.
angmuir-Trough was used.

・Example of information recording/reading/erasing An optical recording element used in the present invention manufactured by the method described above and a conventional similar structure as a comparative example (all structures are constructed without using a middle molecular film or its cumulative film) An optical disc is recorded using the information recording device according to the present invention shown in FIG.
Each element uses a Ne ion laser (3
33 layer m) The beam 29-2°24-2 is irradiated according to the input information, and the optical modulator 26-2 switches the laser beam 24-2 according to the command from the recording control circuit 27-2 based on the input information. , a color reaction (green color) was performed and high-density optical recording was performed.

Recording is read using a krypton ion laser (847#Lm) beam 29-1.24 with a spot diameter of 10JJ.
-1 to scan the recording surface, and the intensity of the reflected light is captured by a light receiving element 25 (photodiode) (not shown) and output to an output circuit 28.
It was amplified by

At this time, since the recording spot is green, the reflected light (647
The reflected light is very weak because it is absorbed by the layer (m), but it is strongly reflected on the scanning surface other than the recording spot, so the record can be read by the strength of the reflected light.

Erasing was attempted by irradiating an arbitrary recording spot with a beam 24-3 of an argon laser (488 layers m) 29-3 having a spot diameter of topm. As a result, it was confirmed that the green recording spot irradiated with the 488 nm argon ion laser beam returned to colorless.

Furthermore, as a result of repeatedly performing this recording and erasing,
Sufficient reproducibility was observed.

[Effect of the invention] The effects of the present invention are listed below.

(1) High density using Langmuir-Prodgett method,
Since a highly ordered monomolecular film or monomolecular cumulative film can be easily produced, the signal/noise ratio is high and recording reliability can be improved.

(2) It is possible to increase the area of the optical recording element.

(3) high density using Langmuir-Prodgett method;
High-density recording is possible because monomolecular films or monomolecular cumulative films with high orderliness can be easily produced.

(4) Repeated recording is possible.

[BRIEF DESCRIPTION OF THE DRAWINGS] FIG. 1 is a block diagram showing an example of an information storage device according to the present invention, and FIGS. 2(a) to 2(c) show a recording process of a conventional optical recording element. An explanatory drawing, FIG. 3 is a schematic cross-sectional view of the monomolecular cumulative film forming apparatus, and FIGS. 4(a) to 4(c).
) is a manufacturing process diagram of a monomolecular cumulative film and Figures 5(a) to 5.
Figure (c) is a schematic cross-sectional view showing an embodiment of an optical recording element used in the information storage device of the present invention. 1.15... Substrate, 2... A layer, 3.6... Light absorption layer, 4... B layer, 5... Auxiliary color agent layer, 7... Color forming agent layer, 8 ... Laser light, 9... Colored light, 10...
water tank, 11... water phase, X2... hydrophilic group, 13...
Hydrophobic group, 14... Partition plate, 15... Substrate, 16...
- Monomolecular film, 17... Monomolecular cumulative film, 18... Optical recording element, 19-1.19-2.19-3... Objective lens, 20... Bow 74 wavelength plate, 2+-1 ,21-2,21
-3...Reflector, 22-1.22-2.22-3...
・Beam expander 123... Polarizing beam splitter, 24-1... Reading light beam, 24-2... Recording light beam, 24-3... Erasing light beam, 25... Light receiving element ( photodiode), 2B-1,
26-2, 26-3... Optical modulator 27-1... Reading control circuit, 27-2... Recording control circuit, 27-3... Erasing control circuit, 28... output circuit,
28-1... Reading light source, 29-2... Recording light source, 29-3... Erasing light source, 30... Optical recording layer, 31... Substrate, 32... Reflective layer , 33... Protective layer, 34... Visible light (or ultraviolet light), 35...
Ultraviolet light (or visible light), 36... Colored triphenylmethane derivative, 37... Colorless triphenylmethane derivative, 38... Hydrophilic site, 39... Hydrophobic site.

Claims (1)

[Claims] An optical recording element comprising a monomolecular film of a triphenylmethane derivative having both a hydrophilic group and a hydrophobic group in its molecule or a cumulative film thereof, an information writing means for recording information on the optical recording element, and the optical recording element. An information recording device comprising an information reading means for reading the information recorded on the optical recording element, and an information erasing means for erasing and reproducing the information recorded on the optical recording element.