JPS61201243A - Light recording method - Google Patents

Abstract

PURPOSE:To enable recording high in reliability and density by using a light recording element composed of a triphenylmethane deriv. film, and utilizing an information erasion stage of color lightened or faded by irradiation of light of wavelength lambda1 and an information recording stage of color developed by irradiation of light of wavelength lambda2. CONSTITUTION:The substance for constituting the light recording layer is composed of a molecule having one hydrophilic site, one hydrophobic site, and one site responding to light in one molecule, and the light recording layer is formed by forming its monomolecular film or their built-up molecular films on a base plate 6. The light recording layer 5 composed of the built-up molecular films made of a colorless triphenylmethane deriv. is formed on a reflective layer 7 formed on the base plate 6, and when it is irradiated with UV rays 9 of wavelength lambda1 through a protective layer 8, color developing reaction is caused at the irradiated part, the deriv. is converted into the colored type, thus information is recorded. then, it is irradiated with a monitoring light, and the record is read in accordance with the intensity of the reflected light. After the reading, when it is irradiated with a light of wavelength lambda2, if needed, color fading reaction is caused, the deriv. is converted into the colorless type, and the information is erased.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to an optical recording method using an optical recording element comprising a monomolecular film of a triphenylmethane derivative or a cumulative film thereof. An optical recording method for erasing information by making the monomolecular film or its cumulative film colorless or light-colored, and coloring the irradiated portion of the monomolecular film or its cumulative film by irradiating light with a wavelength of 2, thereby recording information. It is something.

[Prior Art] It has been known for a long time that functional molecules that change color when exposed to light with a wavelength of λ2 and return to their original state when exposed to heat or light with a wavelength of λ2 in the dark are called photochromic molecules (for example, Fiber and Polymer Materials Research Institute Research Report No. 1411”984
-3).

However, although the photochromic molecules have the ability to reversibly change color upon irradiation with light, they are actually used in the form of internegatives in the plate-making process in the form of kneading with a binder etc. and applying it to the film surface. It's just that.

[Problems to be Solved by the Invention] However, although conventional photochromic molecules are functional molecules that reversibly change color, they have not been able to be displayed except in a very limited range. The reason why it has not been used in optical elements such as optical elements, recording elements, and memory elements is because photoresponsiveness does not occur or is insufficient in the solid state.

Therefore, the purpose of the present invention is to provide a method for recording information using a reversible reaction caused by light using an optical recording element formed with a monomolecular film or a cumulative film of a photochromic molecule, particularly a trifluormethane derivative, in this technical field. By erasing the data, the problem that could not be solved by the prior art is solved.

That is, an object of the present invention is to provide an optical recording method using an optical recording element capable of highly reliable and high density recording.

[Means for Solving the Problem] and [Operation] That is, the present invention provides an optical recording device consisting of a monomolecular film or a cumulative film of a triphenylmethane derivative having both a parent group and a hydrophobic group in the molecule. In an optical recording method using an element.

1) An information erasing step in which the monomolecular film or its cumulative film is made colorless or light-colored by irradiation with light of wavelength λ1 2) Coloring of the irradiated portion of the monomolecular film or its cumulative film by irradiation of light with wavelength λ2 This is an optical recording method characterized by comprising an information recording process.

The present invention will be explained in detail below.

The material constituting the optical recording layer of Wood's invention consists of molecules each having at least one wood-philic site, one hydrophobic site, and one photoresponsive site within the molecule. The optical recording element used in the present invention is formed by forming a monomolecular film or a monomolecular cumulative film of such molecules on a carrier. Examples of the constituent elements that can form a woody site or a hydrophobic site include various types of woody groups, hydrophobic groups, etc. that are generally widely known. Examples of the photoresponsive moiety include amino-substituted triphenylmethane hydroxide. The photoresponsive sites are represented by general formulas 1-4 in Table 1.

Note that the substituents of the phenyl group are not limited to the substitution sites shown in the formula.

However, R1 represents a methyl group, ethyl group or other short chain alkyl group, and R2 represents a long chain alkyl group.

Table ■ 11H+ R2 R2 In other words, having a lignophilic site and a hydrophobic site in the molecule means, for example, in the above formula, the hydrophobic site is an alkyl chain, and the hydrophilic site is amino-substituted triphenylmethane hydroxide, etc. When introducing a hydrophobic moiety, which indicates a moiety other than a hydrophobic moiety, a carbon atom number of 5 to 30 is particularly used.
Long chain alkyl groups are preferred.

In the present invention, specific examples of triphenylmethane derivatives include compounds 5 to 8.

Table H (0H2}17CH 0 do:, 4CH =ZH・ The compounds listed below are known compounds in themselves, except that a hydrophobic moiety was introduced into the amino group triphenylmethaneh-C-looxy 1, and For example, long-chain aluminum is ■.

Langmuir Langmu developed by et al. a -Blodgett method (LB method) Use.

J method uses monolayer or! This is a method for creating a cumulative film of 11 molecular layers. A monolayer on the water surface has the characteristics of a two-dimensional system. When the molecules are sparsely dispersed, the equation for a two-dimensional onion gas is between the area per molecule A and the surface pressure ■.

nA=kT holds true, resulting in a gas film.Here, is Portsumano's constant and T is the absolute temperature.If A is made sufficiently small, the intermolecular interaction becomes strong, resulting in a condensed film of a two-dimensional solid. (or solid 11)°”. The condensed film can be transferred layer by layer onto the surface of carriers having various materials and shapes, such as glass substrates. A specific method for producing a monomolecular film of the triphenylmethane derivative molecules of the present invention or a cumulative film of triphenylmethane derivative molecular layers using this method includes, for example, the method shown below in 4f.

First, the vertical immersion method will be explained using a film forming apparatus.

As shown in FIGS. 2(a) and 2(b), a frame 12 made of, for example, polypropylene is hung horizontally inside a shallow and wide rectangular water tank 11 containing pure water. I am in charge of 20. A float 13 made of, for example, polypropylene is floated inside the frame 12. The float 13 is a rectangular parallelepiped whose width is slightly shorter than the inner width of the frame 2, and is capable of two-dimensional piston movement in the horizontal direction. A weight 14 for pulling the float 13 to the right in the figure is tied to the float 13 via a pulley 5. In addition, a magnet 1ε fixed to the soil of the float 13 and a pair of magnets 17 which are movable left and right in X above the float 3 and which repel each other when approaching the magnet 16 are provided. Therefore, the float 13 can be moved from side to side in the figure and can be stopped. Instead of such a weight 14 and a set of magnets If, 17, there is also a system in which a rotary motor or a pulley is used to directly move the float 13.

On both sides of the frame 12 are suction nozzles 18 connected to a suction pump (not shown) via a suction pipe 18.
are lined up. This suction nozzle 19 quickly removes the unnecessary monomolecular film, etc. from the diarrhea process on the liquid surface 20 in order to prevent human substances from entering the monomolecular film or monomolecular cumulative film. It is used to remove Furthermore, 2
Reference numeral 1 denotes a carrier that is attached to upper and lower carrier arms 22 and is vertically moved up and down.

Using the above-mentioned film forming apparatus, (1) the target trifelmethane derivative is dissolved in a solvent. This solution is developed in the aqueous phase-L to precipitate the triphenylmethane derivative in the form of a film.

Next, to prevent the precipitates from freely diffusing and spreading over the aqueous phase, a partition plate (or float) is provided to limit the spread area and control the state of aggregation of the membrane material.

Obtain a surface pressure (■) proportional to the aggregate state. By moving this partition plate, the developed area can be reduced to control the state of aggregation of the film material, and the surface pressure can be gradually increased to set the surface pressure (2) suitable for producing a cumulative film. By gently lowering the clean carrier vertically to -L while maintaining this surface pressure, the triphenylmethane derivative film is transferred onto the carrier -L.

A triphenylmethane derivative film is produced as described above, and a triphenylmethane derivative layer cumulative film having a desired degree of accumulation can be formed by repeating the above operations.

To transfer the trinonylmethane derivative layer onto the carrier, -L
In addition to the vertical immersion method described above, methods such as a horizontal attachment method and a rotating cylinder method can be used. The horizontal deposition method is a method in which the phase is transferred by bringing it into horizontal contact with the water surface, and the rotating cylinder method is a method in which a cylindrical carrier is rotated above the water surface to transfer the triphenylmethane derivative layer onto the surface of the phase. . In the vertical immersion method described above, when a carrier with a wood-philic surface is lifted out of water in a direction across the water surface, a triphenylmethane derivative layer is formed on the carrier with the parent wood groups of the triphenylmethane derivative oriented toward the carrier. Ru. When the carrier is moved up and down as described above, 1
Triphenylmethane derivative layers are piled up one by one. Since the direction of the film-forming molecules is reversed between the pulling process and the dipping process, according to this method, between each layer, the parent wood groups of the triphenylmethane derivative are opposite to each other, and the hydrophobic groups of the triphenylmethane derivative are opposite to each other. A mold film is formed. On the other hand, the horizontal deposition method is a method in which the carrier is brought into horizontal contact with the water surface and transferred, and a triphenylmethane derivative layer with the hydrophobic groups of the triphenylmethane derivative oriented toward the carrier is formed on the phase. In this method, there is no change in the direction of the film-forming molecules even when the films are accumulated, and an X-type film is formed in which the hydrophobic groups are oriented toward the carrier in all layers. On the other hand, a cumulative film in which parent wood groups in all layers are oriented toward the carrier is called a Z-type film.

The rotating cylinder method is a method in which a cylindrical carrier is rotated on the water surface to transfer a monomolecular layer onto the carrier surface.

The method of transferring the monomolecular layer onto the carrier is not limited to these methods, and when using a large-area receptor, a method of extruding the carrier from a carrier roll into water may also be used.

Furthermore, the directions of the hydrophilic groups and hydrophobic groups described above toward the carrier are in principle, and can be changed by surface treatment of the carrier.

The triphenylmethane derivative film and the triphenylmethane derivative layer cumulative film formed on the carrier by the above-mentioned method have high density and a high degree of order, and by constructing the recording layer with these films, Depending on the function of the triphenylmethane derivative, it is possible to obtain an optical recording element having high-density and high-resolution recording performance capable of optical recording, thermal recording, electrical recording, magnetic recording, etc.

Next, an optical recording method using light-induced coloring and decoloring reactions of triphenylmethane derivatives according to the present invention will be explained.

FIGS. 1(b) to 1(d) are longitudinal sectional views showing one embodiment of an optical recording element according to the present invention. Note that each figure is a schematic diagram and does not specifically show the shape of the molecules. FIG. 1(b) shows an example of an optical recording element according to the present invention, in which an optical recording layer 5 made of a cumulative film made of a colorless triphenylmethane derivative is formed on a substrate 6 via a reflective layer 7. It is something.

Next, as shown in FIG. 1 (C), when ultraviolet light 9 with a wavelength λ1 is irradiated through the protective layer 8 according to a certain pattern, the formula (I) formula (I) 0 { Gb}u[113 Colorless 0(Glb)ucH3 A coloring reaction occurs as shown in green, and a change to a colored triphenylmethane derivative occurs, making it possible to obtain an optical recording element that records information. 'Next, the optical recording element is irradiated with monitor light, and the recording can be read based on the intensity of the reflected light. Furthermore, after reading the record, if necessary, irradiation with visible light causes a decoloring reaction as shown in formula (I), and as shown in Figure 1(d), the colored to colorless triphenyl It turns into a methane derivative and can erase records.

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.

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

Example 1 A compound of N0.5 as a triphenylmethane derivative molecule was dissolved in n-hexane at a concentration of 5 x 10-3M, and then developed on an aqueous phase of a potassium hydroxide solution at pH 12.-2. . After the solvent n-hexane was removed by evaporation, the surface pressure was increased to 20 dyne/c+s to precipitate the triphenylmethane derivative in the form of a film. After this, while keeping the surface pressure constant, aluminum was deposited on the surface to make it sufficiently clean, and the glass substrate was gently moved up and down in one direction across the water surface at a vertical speed of 0.4 cm/win to coat the triphenylmethane derivative molecular film on the substrate. Optical recording elements were manufactured by transferring triphenylmethane derivative cumulative films to 30 layers, 60 layers, 90 layers, and 120 layers. During this cumulative process, each time the substrate was lifted from hydration, it was allowed to stand for 15 minutes or more to evaporate and remove moisture adhering to the substrate. The film forming equipment used is West German L.
Lanzmuir-Trough manufactured by AUDA was used. The produced optical recording element was colorless.

This device uses a Me ion laser (333
A color reaction (green) was performed by irradiating the sample with a (nm) beam according to the input information, and high-density optical recording was performed. The recording was read by scanning the recorded surface with a Krybton ion laser (B47n layer) beam with a spot diameter of 10 gm, and the intensity of the reflected light was captured by a light receiving element (not shown) and amplified by an output circuit. At this time, since the recording spot is green, it absorbs the reflected light (847 nm), so the reflected light is very weak, but it is strongly reflected on the scanning surface other than the recording spot, so it is difficult to read the record depending on the strength of the reflected light. It can be done.

Erasing is done using an argon laser (488n) with a spot diameter of 10 mm.
An attempt was made by irradiating an arbitrary recording spot with the beam of (2). 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 repeating this recording and erasing many times, sufficient reproducibility was observed.

Example 2 A compound of N0.8 as a triphenylmethane derivative molecule was dissolved in n-hexane at a concentration of 5 x 10-3M, and then developed on an aqueous phase of potassium hydroxide solution of pO2.2. After removing the solvent 1-hexane by evaporation, the surface pressure was reduced to 20,0
The triphenylmethane derivative was precipitated in the form of a film by increasing the concentration to dyne/cm. Thereafter, an optical recording element consisting of 120 accumulated triphenylmethane derivative films was manufactured while keeping the surface pressure constant. The moisture adhering to the substrate was removed by evaporation by leaving it for more than this cumulative process. The film forming equipment used is Langmuir-Trou, g manufactured by LAUDA, West Germany.
h was used. The produced optical recording element was colorless. The following will be recorded, read, and recorded using the same method and conditions as in Example 1.
I deleted it. As a result, the same results as in Example 1 were obtained, and as a result of repeated recording and erasing many times, sufficient reproducibility was observed.

Example 3 A compound of N0.7 as a triphenylmethane derivative molecule was dissolved in n-hexane at a concentration of 5.times.10@-3 M, and then developed in an aqueous potassium hydroxide solution having a p of 2.2. After removing the solvent n-hexane by evaporation, the surface pressure was reduced to 20-
The triphenylmethane derivative was precipitated in the form of a film by increasing the concentration to Odyne/cm-. After this, while keeping the surface pressure constant, the glass substrate coated with clear aluminum was gently raised and lowered in the direction across the water surface at a speed of -L lowering of 0-4c/win to obtain the triphenylmethane derivative. Transfer the molecular film onto the substrate and form 30 layers, 60 layers, and 90 layers.

An optical recording element consisting of a triphenylmethane derivative cumulative film having 120 layers was manufactured. During this cumulative process, the substrate was raised from the aqueous phase and allowed to stand for 15 minutes or more to evaporate and remove moisture adhering to the substrate. The film-forming equipment used is Lang uir-Tro manufactured by TaunA in West Germany.
I used ugh. The produced optical recording element was colorless. Recording, reading, and erasing were performed in the same manner and under the same conditions as in Example 1. As a result, the same results as in Example 1 were obtained, and as a result of repeated recording and erasing many times, sufficient reproducibility was observed.

[Effects of the invention 1 The effects of the present invention are listed below.

Since a monomolecular film or a monomolecular cumulative film having high density and high orderliness can be easily produced using the L-Langmuir-Prodgett method, high-density recording is possible.

2. Since a monomolecular film or a monomolecular cumulative film having high density and high orderliness can be easily produced using the Langmuir-Brosiet method, coloring and decoloring reactions occur efficiently.

[Brief explanation of drawings]

FIG. 1(a) is an explanatory diagram of a single molecule according to the present invention. 1(b) to 1(d) are vertical cross-sectional views showing one embodiment of an optical recording element according to the present invention, in which FIG. 1(b) shows an information recording process, and FIG. 1(C) shows an information recording process. Erasing process, Fig. 1(d) shows the state of the element after information erasure, Fig. 2(a), (b)
) is an explanatory diagram showing an example of a conventional film forming apparatus. l...Colorless trinonylmethane derivative 2--Colored triphenylmethane derivative 3...Hydrophobic site 4
... Tree-loving part 5 ... Optical recording layer 7 ... Reflection layer 9 ... Ultraviolet light 11 ... Water tank 13 ... - Float 15 ... Pulley 17 ... Counter-magnet ls ...・Suction nozzle 21...Carrier 6...Substrate 8...Protective layer lO-...Visible light 12...Frame 14...Weight 16...Magnet 18...Suction pipe 20... Liquid level 22... upper and lower arms of carrier

Claims (1)

[Claims] In an optical recording method using an optical recording element consisting of a monomolecular film of a triphenylmethane derivative having both a parent group and a hydrophobic group in the molecule or a cumulative film thereof, 1) the monomolecular film is or 2) an information erasing step of making the accumulated film colorless or light-colored; 2) an information recording step of making the irradiated portion of the monomolecular film or its accumulated film colored by irradiation with light of wavelength λ_2; Method.