JPS61255982A - image forming device - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an image forming device that can be used in display devices, recording devices, etc. The present invention relates to a forming device.

[Conventional technology]

The color changes depending on the light with wavelength λ1, in the dark, with heat or with wavelength λ2.
Functional molecules that return to their original state when exposed to light are called photochromic molecules and have been known for a long time (for example, Fiber and Polymer Materials Research Institute Research Report No. 141 1984-3)
.

However, despite being a functional molecule that reversibly changes color, it has not been used in optical elements such as display elements, recording elements, and memory elements, except in a very limited range. This is because photoresponsiveness does not occur or is insufficient in the solid state.

[Problem that the invention seeks to solve]

Therefore, an object of the present invention is to solve problems that could not be solved by the conventional techniques in this technical field.

In other words, one object of the present invention is to provide an image forming apparatus that has high contrast and is used in a simple (color) display device, a recording device, a storage device, and the like.

[Means for solving problems]

The above object is achieved by the present invention as follows.

That is, the present invention provides an image forming element basically consisting of phase-transition organic compound molecules and functional molecules, a light irradiation means for irradiating the element with light, a thermal signal input means for inputting a signal according to information, and An image forming apparatus is characterized in that it is equipped with a thermal signal scanning means for scanning.

(effect) The image forming element used in the image forming apparatus of the present invention is as follows.

It has an image forming layer consisting of phase changeable organic compound molecules and functional molecules.

Phase transition as used in the present invention refers to when a substance changes from an immobile solid state to a dynamic state due to heat. Therefore, from a solid state to a fluid or flexible state, from a static state to a dynamic state. A change in state, from a crystalline phase to a liquid crystalline phase, from a solid to a liquid, from one kind of liquid crystalline phase to another, etc. are all phase transitions.

Functional molecules refer to image-forming functions (display functions, recording functions, memory functions) and information conversion functions other than image conversion (arithmetic functions), and also include substance or energy transport functions, as well as light and electrical energy transport functions. It is not limited to cases in which functions are expressed by the application of heat, magnetism, pressure, substances, etc., but also includes functions expressed by the application of heat, magnetism, pressure, substances, etc.

Next, the basic driving principle of the element used in the present invention will be explained.

When energy is applied to certain functional molecules, chemical changes occur rapidly in liquids or fluids, but chemical changes do not occur or the changes occur extremely slowly in solid solids.

The organic compound molecules that undergo a phase transition and the functional molecules constituting the mixed film are the molecules described above, that is, molecules that do not undergo chemical change in a solid state, or do not exhibit their functions because they do not undergo chemical changes or are difficult to do so. Since it is easy to undergo chemical changes in a flexible state, materials that can perform functions are selected.

The organic compound is maintained in a highly flexible state by heating the thus configured mixed film to a temperature higher than the phase transition temperature using the heating element. Since the functional molecules existing in such a state are in a state where they are easily chemically changed, they respond rapidly to the application of input energy (4
1! The object of the present invention is achieved by the configuration described above.

In short, the present invention.

1. Liquid media have limited uses and are unstable, so solid media are desired.

2. However, the function cannot be fully expressed in a solid medium.

These two points were solved by mixing a phase-transitionable organic compound.

Further, an example of an image forming element used in the present invention will be explained with reference to the drawings.

FIG. 3 is a cross-sectional view of an image forming element used in the present invention, and FIG. 3(A) is a transmission type image forming element, and FIG. 3(B)
1 and 2 respectively indicate reflective image forming elements. 1 is a substrate, 2 is a heat generating layer, 3 is an image forming layer composed of a mixed film of thermal phase changeable organic compound molecules and functional molecules that exhibit functions by light, and 4 is a protective substrate. The image forming principle of the transmission type image forming element shown in FIG. 3(A) is as follows.

For image formation, the heat generating layer 2 is heated as a bias, and a phase transition change is caused in the phase transition organic compound molecules, which are the constituent components of the image forming layer 3, on the heated heat generating layer 2. As a result, light 6 (infrared, infrared,
The image forming layer 3 is irradiated with visible light, ultraviolet rays, or
It causes the photochemical changes described below in the functional molecules that are the constituent components of. In this way, this photochemically changed pattern or information (photochemically changed area 5) is directly or indirectly captured and displayed or read while illuminating the illumination light 7 from the back side of the element.

In the reflective image forming element shown in FIG. 3(B), the illumination light 7 is incident from the protective substrate 4 side, contrary to the transmission type, and the reflective film 9 is provided on the substrate l side from the mixing [13]. The phase-transition organic compound constituting the image forming layer 3 of the display/forming element by capturing the strength, etc. of the reflected light 8 reflected in the photochemical change area 5 and areas other than the photochemical change area is as follows: Examples include (1) Higher fatty acids CH3 (CH2) 12COOH CH3 (CH2) 14COOH CH3 (CH2) tscOOH CH3 (CH2) 18COOH CH3 (CH2) tocOOH CH2=CH (CH2) 8COOH CH2=CH (CH2) 1 5cOOHCH2 =CH(
CH2) 20COOHCH3= (C)12) 17
CCOOHCH2 CH3(CH2) 8C=C-C=C(CH2) 8C
OOHCH3(CI(2)3CH=CHCH=CHCH
=CH(CH2)7COOHCH3(CH2) 7CH
=CH(CH2) 7COOHCH3(CH2) 7C
H=CHCOOHCH3=CH(CH2) 5poon CH3(CH2) 9c==c-C=C(CH2) 8
COOHCH3(CH2)ttc=c-c=c (CH
2) 8COOHCH3(CH2) 13c=cc=c
(CH2) 8COOH (2) Long chain dialkyl salt/Long chain dialkyl ammonium salt (m is a regular button of lO to 30/Long chain dialkyl sulfonic acid mound Φ Long chain dialkyl phosphate (3) Cyanine dye Specification of cyanine dye An example is illustrated below.

(4) Azo dye (R2 is an alkyl group of CIO to 3o) (5) Phospholipid lecithin cephalin sphingomyelin plasmalogen Next, as photo-responsive functional molecules, compounds that change color depending on light , that is, photochromic compounds. Examples of such things include the following:

(6) Spiropyran and analogues (ion elucidation) wavelength λ1
The ions are dissociated by light, changing to the structure on the right, which returns to the structure on the left either thermally in the dark or by light at another wavelength of 2.

(7) Cis-trans isomerization Example of thioindigo azobenzene and its derivatives based on isomerization of unsaturated double bonds such as C=C, C=N, N=N (8) Tautomerization accompanied by hydrogen transfer・Keto-enol isomerization ・act-nitro isomerization 0'''c'Ph (9) Photoclastic reaction ・Cis-stilbene fulgide (lO) valence isomerization reaction containing a heterocycle ・Nitrone-
Oxacillin series (11) 1-phenoxyanthraquinones (12)
Photodimerization reaction (13) Photodimerization reaction to aromatic polycyclic compound (14) Photoredox reaction, thiazine dye system, viologen A method of creating a mixed film by mixing the above-mentioned phase-transition organic compound molecules and the above-mentioned functional molecules as.

Spinner rotation coating method, roller coating method, pull-up coating method, sputtering method, plasma polymerization method.

Bilayer membrane production method, Langmuir-Prodgett method (L
Method B) etc. The object of the present invention can be achieved using any of them.

According to the LB method, it not only has excellent quality and efficiency in image formation, but also has the advantage of obtaining high resolution or ultra-high resolution. It also has features such as significantly expanding the range of material selection.

The case of forming a film using the LB method will be described below.

In the LB method, when a molecule has a parent wood group and a hydrophobic group in its molecule, and the balance between the two (amphiphilic balance) is maintained appropriately, the molecule is placed on the water surface with the parent wood group facing down. This method creates a monomolecular film or a cumulative film of monomolecular layers. When the monomolecular layer on the water surface has the characteristics of a two-dimensional system and zero molecules are sparsely dispersed, the two-dimensional ideal gas equation, nA=kT, is established between the area A per molecule and the surface area n. where k is Boltzmann's constant and T is the absolute temperature.If A is made sufficiently small, the intermolecular interaction becomes strong and a two-dimensional solid becomes a "condensed film (or solid film)". Become.

When the heating resistance layer 3 is formed on the surface of a substrate such as glass, the condensed film can be transferred layer by layer to the surface of the substrate such as glass when the surface reflective film 9 is formed thereon. Using this method, a monomolecular film or a monomolecular layer stack is produced, for example, as follows.

First, organic compound molecules (including mixed systems) are dissolved in a solvent,
This is spread on the water surface, and the organic matter is deposited in a film form.Next, to prevent this precipitate from freely diffusing on the water surface and spreading too much, a partition plate (or float) is installed to reduce the development area. The aggregation state of the membrane material is controlled by limiting, and a surface pressure n proportional to the aggregation state is obtained. By moving this partition plate, the developed area is reduced to control the gathering state of the membrane material, and the surface pressure is gradually reduced.
The surface pressure n can be increased to set a surface pressure n suitable for producing a cumulative film. By gently vertically moving a clean substrate up and down while maintaining this surface pressure, a monomolecular film or a mixed monomolecular film of two or more types of molecules is transferred onto the substrate. A monomolecular film is manufactured using the above steps, but a monomolecular layer cumulative film is manufactured using the following steps.
By repeating the above operations, a monomolecular layer stack with a desired degree of stacking is formed.

The film-forming molecule may be one of the organic compound molecules mentioned above or C mole.
More than one species is selected.

,゛-・5, single molecule 1M51 neat, the thickness of the monolayer cumulative film is 3
0 person size 1' = 30 "0, pm' is suitable, especially 300
0λ to 301Lm is suitable.

To transfer the monomolecular layer onto the substrate, use the above-mentioned vertical dipping method, horizontal deposition method, rotating cylinder method, or other methods. The one-rotation cylinder transfer method is a method in which a cylinder is rotated above the water surface to transfer a monomolecular layer onto the substrate surface. In the above-mentioned vertical immersion method, when the substrate is raised in a direction across the water surface, a monomolecular layer is formed on the substrate with the parent wood groups facing the substrate in the first layer. As mentioned above, when the substrate is moved up and down, the monomolecular layers are overlapped one by one in each process.The direction of the film-forming molecules is reversed in the pulling process and the dipping process, so according to this method, each layer is A Y-shaped film is formed in which wood bases and parent wood bases, and hydrophobic groups face each other.

On the other hand, the horizontal deposition method is a method in which the substrate is brought into horizontal contact with the water surface and transferred, and a monomolecular layer with hydrophobic groups facing the substrate is formed on the substrate.

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 in all layers. A side-facing cumulative film is called an X-type film.

The rotating cylinder method is a method in which a cylindrical substrate is rotated above the water surface to transfer a monomolecular layer onto the surface of the substrate. The method of transferring the monomolecular layer onto the substrate is not limited to these methods, and when using a large-area substrate, a method of extruding the substrate from a substrate roll into a water bath may also be used. Furthermore, the orientation of the aforementioned parent wood group and hydrophobic group toward the substrate is in principle, and can be changed depending on the surface heat treatment of the substrate.

When introducing a hydrophobic moiety into a functional molecule in the present invention, a long-chain alkyl group having 5 to 30 carbon atoms is particularly preferred.

Examples of materials that can be used as the substrate 1 include glass, metals such as aluminum, plastics, ceramics, and paper.

In the case of the transmission type shown in FIG. 3(A), it is preferable to use pressure-resistant and transparent glass or plastic, especially colorless or light-colored ones.

As the protective substrate 4, pressure-resistant, translucent glass or plastic is suitable as much as possible, and colorless or light-colored ones are particularly preferable.Providing the protective substrate 4 increases the durability and stability of the mixed film. Although it is preferable in order to improve the properties, the protective substrate may or may not be provided depending on the selection of the film-forming molecules.

As the reflective film 9, a metal film, dielectric mirror, etc., using a metal material or a metal compound material with a high melting point, is provided on the substrate 1 side by a sputtering method, a vapor deposition method, or the like. If it is something like that, it can also be used.

Examples of the heat generating layer 2 include those that utilize heating by infrared irradiation and those that utilize Joule heat such as resistance heating. Examples of the former include various inorganic or organic materials, such as alloys such as Gd/TbΦFe, inorganic pigments such as carbon black, and examples of organic materials include organic dyes such as nigrosine.

Examples of such light-absorbing dyes include metal phthalocyanines such as copper phthalocyanine and vanadium phthalocyanine;
Examples include metal-containing azo dyes, acidic azo dyes, and xanthine dyes such as fluorescein. However, it itself does not melt under a certain amount of heat. For the latter, metal compounds such as hafnium boride and tantalum nitride, and alloys such as nichrome are suitable.0 The film thickness of the heat generating element 2 affects energy transfer efficiency and resolution.From these points of view, the heat generating element 2 The preferred film thickness is 100 to 2000. When the image forming element is a transmissive type, the heat generating element 2 is required to be transparent to visible light (for example, an Si02 film in the former case, and an indium tin oxide Itl in the latter case). However, even if the heating element 2 is not specially provided, the substrate 1 can also serve as a heating element by selecting a substrate material having the above characteristics.

The temperature at which the phase transition occurs, ie, the phase transition temperature (Tc), is unique depending on the substance. For example, Tc is preferably 40 to lOO°C.

Tc of palmitic acid is 60 to 63°C, and Tc of dialkylammonium salt is 20 to 60°C. Generally Tc
increases with alkyl chain length.

Mixing ratio of the mixed film, i.e. phase transition organic compound molecules (A)
The ratio of the functional molecule (B) to the functional molecule (B) is preferably 1/10-10/l.

Next, an example of an image forming apparatus according to the present invention will be explained with reference to the drawings.

FIGS. 2A and 2B are partial schematic diagrams of an image forming apparatus according to the present invention. 10 is an image forming element, which includes the previously described image forming layer 3;
and a radiation absorbing layer 2.

A thermal signal input means 11 is a means for applying a thermal input signal 12 (for example, infrared rays, etc.) to a predetermined position on the image forming element IO (especially the radiation absorption layer 2).

The heat signal input means 11 mainly uses a light source (for example, infrared S
> and a light modulator (both not shown), etc. In this case, the light emitted from the light source can be absorbed by the radiation absorption layer 2 and converted into heat, but it cannot photochemically change the functional molecules. Therefore, they mainly belong to infrared and near-infrared wavelengths. Note that if the light source itself has a switching function, an optical modulator is not necessary. (For example, semiconductor devices, etc.).

Reference numeral 13 denotes a light irradiation means, which irradiates light 14 that causes a photochemical reaction to a predetermined position on the image forming element 10, especially the image forming layer 3, and applies a light bias. As mentioned above, when the optically biased region is irradiated with the thermal input signal 12, a corresponding image is obtained.

2nd rI! J(B) shows another embodiment of the image forming apparatus of the present invention.

This is a case where a heat generating resistor layer 1 is used as the heat generating element 2 instead of the radiation absorbing layer, and the heat signal input means 15 is composed of a drive system, a power supply, etc. for heating a predetermined position of the heat generating resistor M2 by Joule. use In this case, in order to apply a heat signal to a predetermined position on the image forming element 10, a segment-shaped or dot-shaped heating element (both not shown) is used as the heating element.

FIG. 1 is a block diagram of an image forming apparatus according to the present invention. 2
2 is an image generation circuit, 23 is a control circuit, and 24 is an image amplification circuit.

Reference numeral 30 denotes thermal signal scanning means, which in the case of radiation heating is comprised of, for example, a horizontal ψ/vertical drive circuit 25 and a horizontal-vertical scanner 28 .

In the case of Joule heating using a dot matrix resistive heating element, it is comprised of a line sequential scanning circuit and a selection circuit (both not shown).

31 is a thermal signal input means, in the former case from the light source 26 and the optical modulator 27, and in the latter case from the power supply and drive circuit (
(both not shown).

29 is a light irradiation means for photochemical reaction.

Image creation is performed in the following steps.

The image signal output from the image generation circuit 22 is sent to the control circuit 23.
The image is amplified by the image amplifying circuit 24 via the image amplifying circuit 24.

For example, the optical modulator 27 is driven by the input of the increased image signal, and modulates the radiation heating light beam emitted from the light source 26.

On the other hand, a horizontal synchronization signal and a vertical synchronization signal are outputted from the control circuit 23, for example, via the horizontal-vertical drive circuit 25.
Drive the horizontal/vertical scanner 28.

During this time, an optical bias is applied to a predetermined region of the image forming layer 3 of the image forming element 10 by the operation of the heating means 29.

In this way, a two-dimensional image corresponding to the image signal is formed on the image forming layer 3 of the image forming element 10.

Examples are given below to explain the present invention in more detail.

Manufacturing Example 1 of Image Forming Element 1 part of spiropyran represented by (m) and 1 part of myristic acid represented by (rV) were dissolved and mixed in 20 wB of chloroform to form a 50 mm square glass e Me ■ (m) CH3 (CH2 ) 12COOH (■) It was coated onto the surface of the substrate using a spin coater to obtain a colorless image forming layer 2 with a film thickness of 5 pm. Furthermore, a glass substrate was placed as a protective substrate 3 on the image forming layer 2 to produce an image forming element.

Manufacturing Example 2 of Image Forming Element A Gd-TbφFe layer having a thickness of 1500 was deposited on the surface of a 50 mm square glass substrate by sputtering to form an infrared absorbing layer 2.

In order to prevent this oxidation of G da T-b * Fe.

In order to prevent this Gd·Tb5Fe from oxidizing, a 5io2 protective film was coated thereon.

Next, 1 part of the cis-trans photoisomerizable compound represented by (m) and 1 part of the diazo compound represented by Cr) (m) (IV) were dissolved in chloroform to a concentration of 2.5X 10-3 mol/l. Image forming elements B each having a monomolecular film having a calendar number of 51 were manufactured by the same method and conditions as in Example 1 except that the solution was used.

EXAMPLE The image forming apparatus shown in FIG. 1 was manufactured using an IOOW mercury lamp as a light irradiation means, a 200 W infrared lamp as a thermal signal input means, and A, B; e as image forming elements.

Next, when light was irradiated and signals corresponding to image information were scanned and applied, the respective signals responded.

Clear two-dimensional blue and red images were obtained.

〔effect〕

The main effects of the present invention are summarized as follows.

(1) It is possible to arrange one of the irradiation parts or heating parts of a minute monomolecular film or a monomolecular layer cumulative film in a high density arrangement as an image element unit.

Capable of forming high-resolution images.

(2) Still images or moving images including slow motion can be easily displayed by adjusting or selecting functional molecules.

(3) Color 7 display can be easily implemented by adjusting and selecting functional molecules.

(4) Since the structure of the element is relatively simple, its productivity is excellent, and the element has high durability and reliability.

(5) Applicable to a wide range of drive systems.

(6) Since a monomolecular film or a monomolecular layer accumulation film can be created using the Langmuir-Prodgett method, it is extremely easy to increase the area.

(7) Since no liquid such as liquid crystal is used, manufacturing is easy and safe.

(8) Since the phase transition temperature is not so high, less power is required for the image forming element, etc., and the power supply section, i.e.,
The image forming device can be downsized.

(9) Two-dimensional image formation can be quickly obtained.

(10) Image erasure/reproduction is also possible.

(11) Since it approximates the function of biological lipids, it is compatible with molecular devices, bioelectronics, etc.

[Brief explanation of drawings]

FIG. 1 is a block diagram showing an image forming apparatus of the present invention, and FIG.
Figures (A) and CB) are partial schematic diagrams of the image forming layer device of the present invention, and Figures 3 (A) and (B) are sectional views of the image forming element used in the image forming apparatus of the present invention. 1 Substrate 2 Heat generating element 3 Image forming layer 4 Protective plate 5 Photochemical change section 6 Light 7.8 Illumination light 9 Reflective layer 10 Image forming element 11.15 Thermal signal input means 12 Thermal input signal 13 Light irradiation means 14 Light beam 22 Image generation Circuit 23 Control circuit 24 Image amplification circuit 25 Horizontal/vertical drive circuit 26 Light source 27 Light modulator 28 Horizontal/vertical scanner 29 Light irradiation means 30 Thermal signal scanning means 31 Thermal signal input means 20th (A > 2nd area B) l 3rd U≧] and A) ;d;3L) go and l gora

Claims (1)

[Claims] An image forming element that basically consists of phase-transition organic compound molecules and functional molecules, a light irradiation means that irradiates the element with light, a thermal signal input means that inputs a signal according to information, and a thermal signal that scans the signal. An image forming apparatus comprising a scanning means.