JPS60239717A - Display medium - Google Patents

Abstract

PURPOSE:To obtain a high-density display medium for which a chemical change or physical change is utilized by forming the monomolecular film or built-up monomolecular layer film of the clathrate complex which consists of the host molecule having a hydrophilic section, hydrophobic section and inclusion section within the molecule and the guest molecule included in the host molecule and of which the complex forming ratio is not substantially an equal molar ratio on a carrier. CONSTITUTION:The molecules which have the hydrophilic section, hydrophobic section and at least one inclusion complex with the other kind molecules in the suitable positions within the molecule and can form the inclusion complex having a molar ratio substantially unequal to the molar ratio of the other kind molecules are widely usable as the host molecule. The constituting elements which can form the hydrophilic section and hydrophobic section within the molecule are representatively exemplified by various hydrophilic groups, hydrophobic groups, etc. which are generally and widely known. The section which can form the inclusion complex with the other kind molecules is formed by introduction of a hydroxyl group, carbonyl group, carboxyl group, ester group, amino group, nitrile group, thioalcohol group, imino group, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Technical Field The present invention relates to a display medium that performs display using chemical or physical changes in a monomolecular film or a cumulative monomolecular layer of an inclusion complex.

(2) Background Art Conventionally, display media using organic compounds as display layers include those using organic compounds that develop color through redox reactions (electrochromic materials), fluorescent organic compounds, etc. There is.

Several types of display media using electrochromic materials have been proposed (for example, Japanese Patent Application Laid-Open No. 1986-7
No. 1380, No. 50-32858, No. 50-
63950 and 50-136000). All of these conventional methods use a viologen derivative as an electrochromic material, dissolve it in an appropriate electrolytic solution to form a color display layer, and develop a color by applying a voltage. ) relates to display elements. The coloring pattern at this time follows the shape of the electrodes forming the organic EC element. However, in the above-mentioned organic EC device, the electrochromic material has a large degree of freedom because it is dissolved in the electrolyte, has poor responsiveness (time required for color development or decolorization after voltage application), and has a high density. This could not be used as a color display element. In addition, the colored substances deposited on the electrodes begin to dissolve into the solvent (electrolyte) again,
The memory time was short, and the reversibility (color development → color erasure process) was poor. In order to eliminate such drawbacks of the conventional examples, it is necessary that the electrochromic material described above be deposited with a high degree of order on the patterned electrodes constituting the display element.

Also, as a light emitting display element using fluorescent organic compounds,
Several types have been proposed (for example, Japanese Patent Application Laid-open No. 5
2-35587 and 58-172891). All of these conventional devices relate to so-called EL (electroluminescent) light emitting display elements, which use a compound exhibiting electroluminescence as a light emitting display layer and emit light upon application of a voltage. Especially JP-A-52-
In the device disclosed in Japanese Patent No. 35587, a monomolecular film or a cumulative film thereof of a derivative of anthracene, pyrene, or perylene into which hydrophilic groups and hydrophobic groups are introduced at appropriate positions is formed on an electrode plate, and then a second film is formed on the electrode plate. electrodes are deposited on such a thin film. At this time, in order to obtain a high-resolution display element, it is desirable that the molecular distribution of the luminescent molecules in the film maintains a high degree of order, but with derivatives such as the above-mentioned anthracene, a monomolecular film or a cumulative film thereof is highly ordered. It has the disadvantage that careful and complicated operations are required to produce it with good quality. In addition, considerably complicated operations are required to synthesize derivatives such as anthracene, which are constituent molecules of the monolayer or its cumulative film (T
h1n 5olid Film Volume 99 Page 71-7
8 pages 1983).

We have solved the drawbacks of such conventional examples by providing 1) a method for producing various functional films relatively easily, and 2) a method that eliminates the loss or loss of various functions possessed by functional molecules even when the film is made thin. 3) A method for forming a film in such a way that the film can be expressed without being degraded; As a result of various studies on methods for orientation with an ordered structure, the present invention was accomplished. Moreover, by using such a film forming method, it has become possible to easily provide a high-sensitivity, high-resolution display medium with high quality.

(3) Disclosure of the Invention An object of the present invention is to provide a high-density display medium that utilizes chemical or physical changes in molecular units caused by external factors such as light, heat, electricity, and magnetism.

Another object of the present invention is to provide a medium that is superior to conventional examples in terms of molecular orientation within the plane of the medium, which is an important factor when performing high-density display on a molecular basis. Furthermore,
In manufacturing the above-mentioned display medium, it is an object of the present invention to provide a medium having various properties through relatively simple operational changes.

The above objects of the present invention are achieved by the present invention as follows.

A molecule (host molecule) that has a hydrophilic site, a hydrophobic site, and a site that can be included with other molecules (inclusion site) within the molecule, and a different type of molecule that is included in the host molecule (guest molecule) comprising a display layer formed by forming a monomolecular film or a monomolecular layer cumulative film of an inclusion complex on a carrier, wherein the complex formation ratio of the host molecule and the guest molecule of the inclusion complex is substantially equimolar. A display medium characterized by:

The substance constituting the display layer of the present invention is a molecule that has at least one hydrophilic site, one hydrophobic site, and at least one site that can be included with other molecules (this is called a host molecule). It consists of two types of molecules: a different type of molecule (called a guest molecule) that is included in a host molecule. The display medium of the present invention is formed by forming a monomolecular film or a monomolecular layer cumulative film of an inclusion complex consisting of such a host molecule and a guest molecule on a carrier. However, the complex formation ratio between the host molecule and the guest molecule of the inclusion complex is not substantially equimolar, and one or both of the above two types of molecules are
It is necessary to cause a chemical or physical change by an external cause such as light, heat, electricity, or magnetism. That is, the display medium in the present invention is.

Optical display, thermal display, electrical display, magnetic display, etc. are performed by utilizing the aforementioned chemical and physical changes.

As the host molecules used in the present invention, as mentioned above,
It has a hydrophilic site, a hydrophobic site wave, and at least one site capable of forming an inclusion complex with other species molecules at appropriate positions within the molecule, and has a substantially equimolar ratio with the other species molecules. It can be widely used as long as the molecules form inclusion complexes that are not 0.
Typical constituent elements capable of forming a lignophilic site or a hydrophobic site within a molecule include various widely known lignophilic groups and hydrophobic groups. A site capable of forming an inclusion complex with other species of molecules is formed by introducing a hydroxyl group, a carbonyl group, a carboxyl group, an ester group, an amine group, a nitrile group, a thioalcohol group, an imino group, or the like. Such host molecules are represented by general formulas (Ia) to (Ib)
A specific explanation will be given below using a host molecule having a hydroxyl group represented by as an example.

x 1 R1-C-C=C-C; c-c-R2(Ia)1 0HOH H (Kokote, X=H or C6H5.) That is,
Having a hydrophilic site and a hydrophobic site in the molecule means, for example, in the above formula, a hydrophilic site exists in either the R□ part or the R2 part, and a hydrophobic part exists in the other part, or R1
This means that the R2 portion and the R2 portion both exhibit hydrophilicity or hydrophobicity in relation to the remaining portions other than the front portion. Regarding the structure of the R1 part and the R2 part, when introducing a hydrophobic part, a long chain alkyl group having 5 to 30 carbon atoms is used, and when introducing a hydrophilic part, a long chain alkyl group having 1 to 30 carbon atoms is used. fatty acids are desirable.

More specifically, the host molecule in the present invention is a diacetylene diol derivative (No, 1-r
b, 8. No, lO~No, 15) and hydroquinone derivatives (No, 7~NQ, !1.11k11.18~N
o, 18) etc. can be used. still,
In the following example, m and n are 4 positive integers, and Z is -C
In H3 or -COOH, ph indicates -C, R5.

[Example of diacetylene diol derivative]

Cup 1 0H0H 60≧m10n≧9. n≧0 應2 0H0H 30≧m+n≧9. n≧O 6 0H0H 30≧m10n≧5. n≧1 /l64 0H' 0H 30≧m+n≧5. n≧1 /P65 0H0H 30≧m+n≧5zn≧0 &6 0H0H 30≧m+n≧5. n≧0 [Example of hydroquinone derivative] 7 60≧m +'n≧16. n≧D 8 30≧m10n≧9. n≧1 ya9 60≧m+n≧9. n≧0 - [Example of diacetylene diol crocodile conductor] Situation 10 0H0H 60≧ n≧3 11 0H0H 60≧ n≧3 Flat 12 0H0H 60≧ n≧1 Flat 16 60 ≧ n ≧ 1 /IFA 14 60≧ n ≧ 1 Ya 15 60 ≧ n ≧ 1 Examples of engineered hydroquinone derivatives] 616 H 17 H 30 ≧ n ≧ 1 18 H The above-mentioned compounds have a long-chain alkyl group, a long-chain carboxylic acid, etc. substituted in the host molecule to obtain wood-loving properties. It is a known compound in itself, except for the fact that it has introduced hydrophobicity, and it is also a known compound in that the host molecule, which is not modified with a long-chain alkyl group, forms crystalline inclusion complexes with various guest molecules. Also described in Journal of the Chemical Society of Japan, pp. 2238-242 (1983).

As guest molecules that can form inclusion complexes with these host molecules, molecules that can form strong hydrogen bonds with the host molecules are generally desirable. Therefore, as mentioned above, when the host molecule has a hydroxyl group as an inclusion site, examples of the guest molecule include aldehydes, ketones, amines, sulfoxides, and the like. In addition, various halogen compounds or π-electron compounds such as alkenes, alkynes, and arenes can also be selected as guest molecules. In any case, a molecule is selected in which the inclusion complex formed has a structure that exhibits the desired display function.

Specifically, such a guest molecule is Bio9gen (
No. 1111), tetrathiofulvalene (No. 20
) and other molecules that develop color through redox reactions, 21
Possible examples include polycyclic aromatic hydrocarbons that emit light through redox reactions, as exemplified by No. 0.29.

Nu19 (where R= -cas t or -C, H,,X''''
;Br-eCI-, I- or cxo; ) Magneto2O N[L21 N[L22 IIL23 As a method for creating a monolayer film or a monolayer cumulative film of an inclusion complex consisting of such a host molecule and a guest molecule, , for example 1. The Langmuir-Prodgett method (CLB method) developed by Langmuir et al. The Langmuir-Prodgett method is based on the Langmuir-Prodgett method. For example, when a molecule has a parent tree group and a hydrophobic group in its molecule, and the balance between the two (balance of amphiphilicity) is maintained appropriately, the molecule will react to the parent tree on the water surface. This is a method for creating a monomolecular film or a cumulative film of monomolecular layers by utilizing the fact that the group faces downward to form a zero monomolecular layer. A 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, nA = kT, holds 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 will become stronger, resulting in a two-dimensional solid "condensed film (or solid film)."Condensed films can be made of various materials and shapes, such as glass substrates. By using this method, a monomolecular film (hereinafter referred to as a monocomplex molecular film) of host molecules including the guest molecules of the present invention or a monocomplex film can be transferred layer by layer to the surface of a carrier having As a specific method for manufacturing the molecular layer stack film, for example, the following five methods A to H can be mentioned.

[A] The host molecule and guest molecule of the intended inclusion complex are dissolved in a solvent, and this is spread on an aqueous phase to precipitate the inclusion complex in the form of a film. In this case, the structure of the host molecule is N
o, 1-No., If the molecule has both a lignophilic site (carboxyl group) and a hydrophobic site (alkyl group) at both ends as shown in 9, the inclusion complex that precipitates on the aqueous phase is Regardless of the hydrophilicity or hydrophobicity of the guest molecule, it is developed on the aqueous phase with the hydrophilic site of the host molecule facing the aqueous phase. On the other hand, the host molecules are No, 10- No, 18
In the case of the structure shown in Z=-CH3, where both ends of the molecule are composed of only hydrophobic sites, the inclusion complex precipitated on the aqueous phase is formed by directing the hydrophilic site of the guest molecule toward the aqueous phase. Develop on the water phase in the state shown in Figure 3.

In addition, Z=-C where both ends of the molecule are composed of only lignophilic sites
In OOH, the inclusion complex formed on the aqueous phase develops on the aqueous phase in a state as shown in FIG. 4, with the hydrophilic site of the host molecule facing the aqueous phase.

Next, to prevent this precipitate from freely diffusing on the aqueous phase and spreading too much, a partition plate (or float) is installed to limit the area of development and control the state of aggregation of the membrane material, and Obtain surface pressure ■. 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 (5) suitable for producing a cumulative film. By gently raising and lowering the clean carrier vertically while maintaining this surface pressure, the single chain molecular film is transferred onto the carrier. A single complex molecular layer film is produced in the above manner, but a single complex molecular layer cumulative film having a desired degree of accumulation is formed by repeating the above operations.

In order to transfer the monocomplex molecular layer onto the carrier, in addition to the above-mentioned vertical dipping method, a method such as a horizontal deposition method or a rotating cylinder method can be used. The horizontal adhesion method is a method in which the carrier 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 on the water surface to transfer a single-chain molecular layer onto the surface of the carrier. In the vertical immersion method described above, when a carrier with a hydrophilic surface is lifted out of water in a direction transverse to the water surface, a monocomplex molecule layer is formed on the carrier with the host molecules of the host molecules facing toward the carrier.

As mentioned above, when the carrier is moved up and down, 1,000 layers of single complexes are stacked up one at a time in each process.The direction of the film-forming molecules is reversed between the pulling process and the dipping process, so this method In this case, a Y-shaped film is formed in which the parent wood groups of the host molecules face each other, and the hydrophobic groups of the host molecules face each other. On the other hand, the horizontal adhesion method is a method in which the carrier is brought into horizontal contact with the water surface and transferred, and a monocomplex molecular layer with the hydrophobic groups of the host molecules facing the carrier is formed on the carrier. in this way,
Even when accumulated, there is no change in the direction of the film-forming molecules, and an X-type film is formed in which the hydrophobic groups face the carrier side in all layers. On the other hand, a cumulative film in which the parent tree groups in all layers face the carrier side is called an X-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 a large-area carrier is used, a method of extruding the carrier from a carrier roll into an aqueous phase may also be used.

Furthermore, the orientation of the aforementioned parent wood group and hydrophobic group toward the carrier is a general rule, and can be changed by surface treatment of the carrier.

In the above film-forming process, the in-plane orientation control of the film material has conventionally been achieved mainly by controlling the surface pressure. Except in the case of straight-chain fatty acids, it has been extremely difficult to obtain high orderliness. However, in the present invention, since an inclusion complex is used as a membrane material, a highly ordered membrane can be obtained relatively easily. That is, when the inclusion complex precipitates in a film form on the aqueous phase, hydrogen bonds, van der Waals forces, etc. cause bonds between host molecules and guest molecules, between host molecules and host molecules, and between guest molecules and guest molecules. The steric configuration between molecules is fixed, and each host molecule and guest molecule are arranged with crystal lattice order. In addition, when only the guest molecule has functionality, chemical modification to this guest molecule, i.e.,
Since no hydrophobic groups or parent wood groups are introduced, there is no reduction in functionality due to film formation.

[B] A water-soluble guest molecule is dissolved in the aqueous phase. Next, host molecules are dissolved in a solvent and spread on the aqueous phase. At the same time, an inclusion complex is formed between the host molecule and the guest molecule, and the mixture is deposited in the form of a film. Regarding the combination of host molecules and guest molecules and the following film-forming operations, refer to [A
] Follow the method shown in .

[C] A water-soluble guest molecule is dissolved in the aqueous phase. Next, the host molecules and guest molecules of the intended inclusion complex are dissolved in a solvent, and this is spread on the aqueous phase to precipitate the inclusion complex in the form of a film. The combination of post molecules and guest molecules and the following film forming operations follow the method shown in [A].

[D] Dissolve the host molecule in a solvent and develop it in the aqueous phase. Thereafter, using a closed system device, the gas phase side, that is, the space inside the device, is made into a guest molecule gas atmosphere. At this time, the guest molecules on the gas phase side are simultaneously included, and an inclusion complex is precipitated in the form of a film. This method is particularly effective when the guest molecule is a compound with a low boiling point and easily vaporized, such as acetone. The combination of post molecules and guest molecules and the following film forming operations follow the method shown in [A].

[E]v, Using a closed group device, the gas phase side, that is, the space inside the device, is made into a guest molecule gas atmosphere, and the host molecules and guest molecules of the zero-order target inclusion complex are dissolved in a solvent, This is developed on an aqueous phase to precipitate the inclusion complex in the form of a film. The combination of host molecules and guest molecules and the following film forming operations follow the method shown in [A].

Specific examples of such display media are shown in FIGS.
The present invention will be explained in more detail with reference to the drawings.

FIG. 1 is an example of a display medium that utilizes color development due to the redox reaction of guest molecules.

For example, using the aforementioned diacetylene dibol derivative as a host molecule, No. 1. In combination with guest molecules such as No. 2, etc., an inclusion complex is formed. A single complex molecular film or a single chain molecular layer cumulative film composed of these molecules is used as an electrode 20.
In this example, a carrier 5 having the following structure is formed on a flat substrate or the like, and is used as a display layer. Instead of forming the electrode 20 on the carrier 5, a carrier that can serve as an electrode may be used.A cell 8 is formed in which the electrolytic solution 6 is injected to cover this film. Furthermore, an electrode (counter electrode) 21 that is electrically insulated from the above-mentioned electrode (display electrode) 20 is provided in a part of the cell 8 to form a display medium. The electrode 21 may be provided on a part of the carrier 5.

Note that it is necessary that both or one of the carrier 5 and the cell 8 be formed of a transparent material (such as glass), and that the electrodes bonded to these transparent parts be transparent electrodes. In the thus formed display medium, a display electrode 20 is used as a cathode, and a counter electrode 2 is used as a cathode.
When a DC voltage is applied using No. 1 as an anode, for example, when the guest molecule is viologen (No. 111), it is reduced according to the formula CH) and develops color.

Colorless oxidation type voltage application Reverse voltage application Violet to blue Therefore, if the display electrode 20 is formed in a pattern, it is possible to develop color in a pattern. To erase the color, apply a reverse DC voltage. The film thickness is particularly preferably from 100 to 500 mm.

FIG. 2 is an example of a display medium that utilizes light emission caused by a redox reaction of guest molecules.

For example, the aforementioned diacetylene diol derivative is used as a host molecule, and this is combined with guest molecules exhibiting electroluminescence such as No. 21 to No. 29 to form an inclusion complex. A single chain molecular film consisting of these molecules,
A cumulative film of monocomplex molecular layers is formed on a carrier 9 that can serve as an electrode, in this example a flat substrate or the like, and used as a display layer. After film formation, the film side is covered with another electrode plate 19. Of these two electrode plates,
Both sides are transparent electrodes. When the recording medium thus formed is energized, the guest molecules are reduced on the cathode side and emit light.

Therefore, if one of the electrodes is formed in a pattern and a voltage is applied, light is emitted in a pattern and display is possible.

In the above display media, the film thickness is particularly between 3000 and 1000.
0A is preferred.

The carrier that forms the single-chain molecular film or monomolecular layer cumulative film in the present invention is not particularly limited, but if a surfactant is attached to the surface of the carrier, the single-chain molecular layer will be transferred from the water surface. When taking the carrier, it is necessary to use a carrier with a clean surface because the single complex molecular film is disturbed and a good single complex molecular film or single complex molecular layer cumulative film cannot be formed. Examples of carriers that can be used include glass, metals such as aluminum, plastics, ceramics, and the like.

A single complex molecule film or a cumulative film of single chain molecular layers on a carrier is sufficiently strongly fixed and hardly peels off or peels off from the carrier. An adhesive layer can also be provided between the membranes or the stack of single complex molecular layers. The adhesion force can also be strengthened by selecting the conditions for forming a monocomplex molecular layer, 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.

Providing a protective film on a monomolecular film or a monomolecular layer stack is preferable in order to improve the chemical stability of the monomolecular film or monolayer stack; Depending on selection, a protective film may or may not be provided. EXAMPLES The present invention will be explained in more detail by showing examples below. In addition, compounds No. 81 to No. 84 in the following examples are shown in Table 1.

Example 1 The display medium shown in FIG. 1 was created and displayed.

Using any of No. 81 to No. 14 as the host molecule, dissolve this and methyl viologen in chloroform at a ratio of 1:2, and then add water with a cadmium chloride concentration of 4 x 10'4 mol/l at pH 8.5. It was expanded to Aigami. After the solvent chloroform was removed by evaporation, the surface pressure was increased and the
5 dynes/am, and the inclusion complex was deposited in the form of a film. Thereafter, while keeping the surface pressure constant, the glass substrate 5 having the transparent electrode (display electrode) 20 is gently moved up and down in the direction across the water surface (up and down speed 2 cm/win) to form a single-chain molecular film or a single-chain molecular layer. The accumulated film was transferred onto the substrate 5 to form a display layer consisting of a linear film. Thereafter, a counter electrode 21 is made of gold to surround the display electrode 20, and an electrolytic solution (0.3+*ol/I of KBr) is then formed to cover these electrodes.
A cell 8 containing an aqueous solution 6 was formed of a glass plate and used as a display medium.

When a DC voltage of 0.8 V was applied to the display medium using the display electrode 20 as a cathode, only that portion developed a blue color depending on the shape of the display electrode 20. Particularly good color development was observed in display media having a cumulative film of 5 to 21 layers. The color disappeared when a reverse voltage was applied. The display life of this process of coloring → decoloring was at least 5,000 times or more.

When display media similar to the above were created using various electrode patterns, high-density images with high resolution were obtained in all cases.

Example 2 The display medium shown in FIG. 2 was created and displayed.

Using any of No. 81 to No. 64 as a host molecule, dissolve this and anthracene and 22 in chloroform at a ratio of 1:2, and then adjust the concentration of cadmium chloride to 4 x 10'4 mol/I at pH 8.5. was developed on the aqueous phase. After the solvent chloroform was removed by evaporation, the surface pressure was increased to 30 dynes/cm to precipitate the inclusion complex in the form of a film. After that, while keeping the surface pressure constant, the Nesa glass substrate 9, which is a transparent electrode, is gently moved up and down in the direction across the water surface (vertical speed 0.?c+s/win), and the single complex molecular film is transferred onto the substrate 9, and the single chain Molecular membrane and 9, till,
A cumulative film of single complex molecular layers accumulated in 51.101.201.401 layers was prepared and used as a display layer. Aluminum 10, which constitutes the other electrode, was deposited on these films to a thickness of 300 mm to form a display medium.

When 45 V of direct current or alternating current was applied, blue light emission was observed in the display layer only when the current was applied. In particular, strong light emission was observed in display media having a cumulative film of 101 layers or more.

When display media similar to the above were created using various electrode patterns, high-density images with high resolution were obtained in all cases.

As explained above, the present invention makes it possible to provide a display medium with high density and high resolution at low cost.

Table 1

[Brief explanation of the drawing]

Figures 1 to 2 are longitudinal sectional views illustrating examples of the display medium according to the present invention, and Figures 3 to 4 illustrate the state of the inclusion complex according to the present invention on an aqueous phase. FIG. 1-11 host molecule 2-1-guest molecule 3---hydrophilic site 5-m-substrate 4---long-chain alkyl site 9.1!9,20.21--one electrode 7---lead Line 6---Electrolyte 8-m-Cell 10.11--1 Inclusion site 12.13-11 Inclusion site 18-m-Lyophilous site 14-m-Long chain fatty acid site 15-m -Hydrophobic site 16---Aqueous phase patent applicant Canon Corporation! Figure 1 Figure 2 (b) Figure 3 (b) Figure 4

Claims (1)

[Claims] A monomolecular film or a stacked monomolecular layer film of an inclusion complex consisting of a host molecule having a hydrophilic site, a hydrophobic site, and an inclusion site within the molecule and a guest molecule included in the host molecule is placed on a carrier. 1. A display medium comprising a display layer formed by forming an inclusion complex, wherein the complex formation ratio of host molecules and guest molecules of the inclusion complex is not substantially equimolar.