JPS60103329A - Optical image writing element - Google Patents

Abstract

PURPOSE:To obtain an optical image writing element with which a colored pattern having a sharp continuous gradation is obtainable by laminating a high polymer layer of the system having a linear conjugate chain and a photoconductive layer contg. dopant and sandwiching the laminated body thereof with transparent electrodes. CONSTITUTION:An optical image writing element is constituted basically of a high polymer layer of the system having such a linear conjugate chain as polyene, poly-yne, polymethinimine, polyphenylene, polyaryl acetylene and polyacetylene and a photoconductive layer 2 and utilizes the color change which the conjugate polymer makes in the doped and undoped state. The laminated body of the layer 1 and the layer 2 is sandwiched by two sheets of transparent electrodes 3, 3'. A voltage is impressed to the electrodes 3, 3' respectively and writing light (light beam or light image pattern) is irradiated from the electrode 3' side of the layer 2. The image formed on the layer 1 is viewed from the electrode 3 side.

Description

[Detailed description of the invention] Technical field The present invention relates to optical image-containing devices.

Background Art Many display devices using liquid crystals have been proposed and have already been put into practical use in light display devices, displays, memorinas, and the like. However, the viewing angle dependence of the liquid crystal itself and the fact that it is unclear and difficult to see under bright ambient light) remain the same as the drawbacks of the liquid crystal 2-tone LCD. However, the shortcoming is that the memory effect is only about 24 hours.

Instead of such liquid crystal display elements (LCD), EC materials (
Display elements (EOD) using electrochromic
) has been attracting more and more attention recently. This EOD
According to EC, the aforementioned drawbacks such as viewing angle dependence and blurriness
There is an advantage in that it can be resolved with a fee.

The EC material currently considered to be practical is tungsten tungsten, and an optical image writing element using this is shown in FIG. 4, where 12 is 112SO. Now, the WO3 thin film 11ill is made negative, and the opposite '[I
When the L pole 3' side is directly DC/Seias, WO3 thin j1
The transmittance of λ11 changes with time, and when white light is incident on this device and the transmitted light is viewed, it appears blue vcH. ) When the polarity of the ζias sulfur pressure is reversed, the coloring disappears and returns to the initial state. In addition to crystallized tungsten, pyogen salts are also being considered as EC materials. EOD using this biogen salt applies the principle that a colorless pyogen solution causes an electrochemical redox reaction to produce an insoluble colored broken film on the cathode (display electrode).

However, there still remains the problem that sufficient gradation cannot be obtained with these conventional FiODs.

Objective: The present invention provides an original image writing element that does not have the above-mentioned drawbacks and can provide clear continuous tone coloring/e-turn.

B14 The first aspect of the optical image writing element according to the present invention is 1. A polymer layer of a system having linear conjugate transport such as Ie-liene, polyyne, polymethineimine, polyphenylene, polyarylacetylene, and polyacetylene and a photoconductive layer are laminated, and these are sandwiched between electrodes to form a polymer. The electrode on the side that is in contact with the layer is at least transparent, and the polymer layer and/or the photoconductive layer contains a dopant. Another optical image implantation device according to the present invention is characterized in that an image is formed on the polymer layer by irradiating the surface with a light beam or a light image pattern. 1
In this apparatus, a polymer layer and a photoconductive layer are not laminated, but are faced to each other with a dope-containing layer interposed therebetween,
Further, the present invention is characterized in that the polymer layer and/or the photoconductive layer contain a dopant as necessary.

Incidentally, the present inventors particularly selected polymers having linear conjugated chains as EC materials, and among them, 11i1i
Or, a good optical image writing element can be obtained by laminating a layer containing a combination of these polymers (polymer J@) as a colored jd on a photoconductive layer, and sandwiching this laminate between transparent electrodes. The present invention was completed based on these findings.

Book-A4 will be described in more detail below with reference to the accompanying drawings.

FIG. 1 is a schematic diagram of the first optical image writing element (device) according to the present invention, and FIG. 2 is a schematic diagram of the second device 6. Polymer layer, 2 light guides 7
1t layer, 3.3"kJ set electrode 4 represents a dopant-containing layer. For convenience, we will focus on the device shown in the M1 diagram here. Polymers having linear conjugated chains include polyenes such as polyacetylene, substituted polyacetylene, polythenylene, polypyrrole, polyparaphenylene, polyphenylene sulfide, polythiazyl, polyyne, polymethinimine, or polyphenylene1). Kiru.i fc, Unexamined Japanese Patent Publication No. 5
7-361.06 and Japanese Unexamined Patent Publication No. 57-105403 vcH pi, lit! Clear arylacetylene,
Since +5 remer and the like can be dissolved, polyacetylene which can be used in a mixed system can also be used as the polymer layer of the present invention even when mixed in a dispersed system.

By the way, when the polymer layer (polymer layer 1) of the thread having these linear conjugated chains (hereinafter sometimes simply referred to as "conjugated polymer") is subjected to optical image writing, it becomes colored. Since this is a layered area, it is inappropriate for the color to be dark from the beginning. That is, the conjugated polymer is obtained in the form of a film by the manufacturing method. For example, in the case of IFU Chenin, when it is chemically synthesized from polyhalides, it becomes a black powder, and even if it is made into a film by molding, it does not have a dotted color. Therefore, it cannot be employed as the polymer layer 1 of the present invention. Therefore, in order to make polychenine into a polymer 1d1, it is necessary to employ an electrolytic polymerization method.

Depending on the combination with the dopant, conjugated polymers can be doped to transfer all groups from the insulating band,
Semiconductor → metal transfer occurs, and as a result of the transfer, the 42 Kaede state (
(or in a state similar to that of a metal even in a semiconductor), reflections at the plasma edge are observed.

Furthermore, since the conjugated polymer is a reentrant conjugate system, it is thought that the above-mentioned transition may occur due to doping with conjugated polymers other than the conjugated polymers (such as polyacetylene) mentioned above as a specific example.

Light guiding, multilayer 2 interest, selenium, 8eTe, As2
Se3.

Selenium compounds such as 0d8e, Cd S T PbO
+ Zn O+T 02 + Z n 8 + m root conductor such as amorphous silicon; organic photoconductors such as anthracene or its conductor, polypynyl carno ζ zole or its derivatives, phthalocyanine, quinacridone, triazine, etc. are used. The photoconductor 1-2 can be formed by a physical method such as vacuum evaporation of these photoconductors and stirring them. This is done by employing a chemical method of 1β cloth and drying.

The original image one-image writing element of the present invention is composed of the above-mentioned polymer layer and a photoconductive layer 2, and the conjugated polymer changes color in the doped and undoped states. We are using. Therefore, the compound must be contained in either or both of the polymer layer 1 and the photoconductive layer 2.

Dopants include Li, Na, K, donors such as tetrabutylammonium, C41'21 Br'l+
ASFfflPF'6, 13F3. Fe(]t3
．． -VO2, MoO43, 'ri04, Zr0t4
.

Examples include acceptors such as Ir046 and 803.

A method for incorporating a dopant into the polymer layer 1 or the photoconductive layer 2 (a variety of methods can be considered, but among them, the polymer layer) is formed by an electrolytic polymerization method. It is advantageous to let them do so.

The laminate of these components 11 and photoconductive layer 2 is sandwiched between two electrodes 3.3'. Den 4 3 (or 3') is a support 31 (or t
The conductive film 32 (also 1i3z') is provided on the electrode 31'), and the electrode 3 in contact with the polymer layer 1
-The readout electrodes must be transparent. The written image must be viewed from three directions of the electrodes (to the left in the drawing). Electrode 3' - Electrode on the side of the body -
does not necessarily have to be transparent as long as the writing light (light beam or optical image, R-turn) from the direction of the arrow can reach the photoconductor I@2; Since it has to be absorbed into Calendar 2,
I like that it is already bright. For this reason, 1,1 pole 3
, 3' are preferably made of Nesa glass, transparent glass, or a resin film coated with a transparent vapor deposited film such as InO2 or 5nOJA. A voltage (electric field) can be applied to each of the electrodes 3 and 3'.

The thickness of the conductive film 32, 32' in the electrode is 0.1 to 1.
The thickness of the supports 31 and 31' is approximately several pm to several tens of micrometers, which is appropriate. The thickness of the photoconductive layer 2 is 0.1
Good results can be obtained when the thickness of the polymer layer 1 is 0.1 to several pm, but it is necessary to change the applied voltage depending on the thickness. Generally speaking, the content of donocent is either not possible for males, or it is generally advantageous to have a large amount of donocent.

On the other hand, in contrast to the device shown in FIG. 1, the device shown in FIG.
It is further provided between. The dopant-containing layer 4 may be either a solid layer or a liquid layer, but it is a liquid layer (formed from an electrolytic solution and a dopant) when considering the effective dopant injection and pouring. In FIG. 2, the spacer for the dopant-containing layer is omitted.

The reason for the failure to provide dopant inclusion No. 4 is (a) As mentioned above, is it possible to form the polymer layer 1 using the electrolytic polymerization method and at the same time contain the dopant in 1 crystal molecule 1?
Supplementation of dopant when dope eagle is low, (b) 1st
In the device shown in the figure, either the polymer layer 1 and the photoconductive layer 2 are in the same phase, making it difficult for the dopant to move, or a liquid-phase dopant-containing layer (dopant-containing liquid layer) is provided to facilitate the movement of the dopant. 1 in an undozo state, etc. K) (B) is effective because it can increase the coloring density. Further, since the case (c) is assumed, when the dopant-containing layer 4 is provided, the inclusion of a dopant in the polymer layer 1 or the light guide layer 2 is optional. The appropriate thickness of the dopant-containing layer 4 is 0.1 to several pm.

Next, we will explain the optical image writing method using these devices, but since the image forming means is the same for the four devices shown in FIGS.
The following explanation will focus on the device shown in the figure.

It is preferable to first irradiate the entire surface with light and apply a reverse electric field to transfer the dopant to the photoconductive layer 2. When writing light is irradiated with a voltage applied to the electrode 3 on the bladder skewer side, the resistance of the exposed part of the photoconductive layer 2 decreases, and an electric field is directly applied to the partial molecular layer 1 in the lowered part. As a result, the polymer layer 1 is doped with the dopant. The portions that are not exposed to light are insulated by the optical mz layer 2, so no movement of the dopant occurs. As a result, the observer can observe the modulated light incident from the sharp observer side (reading side) and/or the transmitted light from the writing side as readout light.

Note that, as mentioned above, if the polymer layer 1 contains a dopant (
The polymer layer 1 changes color depending on whether it is doped or not, and readout light of various colors can be obtained by various combinations with conjugated polymer binders. Therefore, the types of conjugated thread polymer and dopant may be selected as appropriate depending on the purpose.

A laser beam such as 1ie-Ne or YAIG, a xenon flash, or a mercury vapor lamp is used as the writing light, and these are appropriately selected in relation to the photosensitivity of the photoconductor M2.

When the circuit is opened, that is, when the voltage application is stopped after the image pattern has been formed, the image pattern is retained and stored in memory.

Subsequently, a voltage with a polarity opposite to that used when forming both holes is applied to the electrode 3, so that the image 1:9 or the deviation is erased.

The optical image writing element according to the present invention has the above-mentioned configuration, but as with the conventional BCD, if necessary,
A viewing body mirror, an antireflection film, a light shielding film, etc. may be provided alone or in combination.

Example 1, J a (t) about Q, 3 pm on a polyester film (support) 31 of about '1 Opm thickness as shown in the figure.
A transparent electrode 3 provided with a thick In01 (conductive layer) 32 is connected to the positive electrode and Af #5 is connected to the negative electrode, and a layer containing BP (dopant) of about 3 μm is formed on the surface of the transparent electrode by electrolytic polymerization. A laminate A was obtained by forming a thick polychenine film (polymer layer) 1 (3rd (2)
(see figure). The electrolytic polymerization conditions are: remission solution: Benjie) IJ
Le, electrolyte: Bu4NBF4 (1 mol), heptamer:
Thiophene (0.1 mol), current density: 2 mh/cd
(t o minutes).

On the other hand, an 8e thin film (4% light layer) with a thickness of approximately 3 μm was deposited on the surface of the transparent polarized layer 3, which was exactly the same as above, by vacuum evaporation.
2 was formed to obtain a B-layer body (Fig. 3 (3)). These were crimped to form the device shown in Fig. 1.

Next, a voltage of about 15V is applied to the transparent electrode 3, and the YAG
When image writing light (writing light) using a laser was irradiated, an image pattern was obtained in which the reflected light from the reading side changed from anti-color to ^-color. Its switching time is f
J 80 m5ec. When the circuit was opened, the blue image pattern was retained and stored in memory.

Next, when a voltage of 0 to -1 ov was applied to the transparent electrode 3, the evening color of the image area changed to red and the image pattern was erased.

This pattern change from red to blue could be repeated several hundred times or more, and there was almost no change in its operating characteristics.

Fu Agricultural Example 2 Fill the space between the one shown in Figure 3 (2) and the one shown in Figure 3 (3) with acetonate (acetonyl) IJ Ru Bu4NBF4 and install the apparatus shown in Figure 2. The thickness of several dopant-containing layers is approximately 3 μm).

Example 3 Example 1 (J) A polypyrrole BF4 film with a thickness of about 1 μm was formed on the surface of the transparent electrode 3 using the same method as in making the A laminate, and a polyvinyl film with a thickness of about 3 Pm was formed in place of the Se thin film of the BFR layer. The device shown in FIG. 2 was constructed by forming a carbazole layer and intervening an approximately 3 pm thick dopant-containing layer injected with an acetonitrile-BLI4NBF4m solution.

Seven Comparative Examples The LCD shown in FIG. 5 was prepared. In addition, in FIG. 3, 2 is a polyvinyl carbazole layer with a thickness of about 6 pm, 3
, 3' is approximately 0 on a 12 μm thick polyester film.
．． A transparent electrode provided with In and O with a thickness of 3 μm, 6 a reflective film, 7 an 8i02 alignment film, 8 a spacer, and 9 a nematic liquid crystal layer (about 9 pm thick).

Images were written in the same manner as in Example 1 using the devices (optical image writing elements) 8 of Examples 2, 3, and Comparative Examples. The conditions and results are shown in Table 1 together with those of Example 1. The apparatuses of Examples 2 and 3 were so successful that almost no change was observed in their operating characteristics even after the color pattern was changed several hundred times or more.

Table-1 Note) ○ means good, Δ means normal, and X means bad.

Effects As is clear from the above description, the optical image writing device of the present invention has fast response speed, high contrast, wide viewing angle, semi-permanent storage, and easy colorization. Effects such as poor gradation are produced.

[Brief explanation of drawings]

1 and 2 are schematic views of the two sides of the optical image writing element according to the present invention, FIG. Both Figures 5 and 5 are schematic diagrams of devices for comparison. l...Polymer layer 2...Photoconductive layer

Claims (1)

[Claims] 1. A polymer layer having a linear conjugated chain such as holien, polyyne, polymethineimine, polyphenylene, polyarylacetylene 1, or tPU acetylene is laminated with a photoconductive layer, and these are laminated with an electrode. The electrodes 11111, which are sandwiched between them and in contact with the polymer 1e4K, are at least a little transparent, but the polymer 1eft and/or the photoconductive layer contains a dopant, and an electric field is applied to the device. An optical image writing element characterized in that an image is formed on the embryonic molecular layer by irradiating a light beam or a single image pattern of light from the direction of the electrode surface on the photoconductive layer side. 2. A polymer layer having a linear conjugated chain such as polyene, polyyne, polymethineimine, polyphenylene, polyarylacetylene, or polyacetylene and a photoconductive layer are opposed to each other with a dopant-containing layer interposed therebetween, and these are sandwiched between electrodes. , the electrode on the side in contact with the polymer layer is at least transparent, and if necessary, the polymer layer and/or the photoconductive layer contains a dopant,
Applying an electric field and increasing the electric field 44i jI on the photoconductive layer side
1. An optical image writing element characterized in that a painter is formed on a polymer layer by irradiating a light beam or a light image pattern from the + direction.