JPH047193A - recording device - Google Patents

Abstract

PURPOSE:To obtain a recording medium excellent in preservability and stability in a process forming and erasing a desired pattern region, a developing process, a transfer process or the like by forming a region showing the sweepback contact angle corresponding to heating temp. to the surface of a recording material and developing the latent image thereof. CONSTITUTION:A recording medium A is selectively heated in such a state that the surface thereof is brought into contact with a contact material B or the recording medium A is brought into contact with the contact material B in such a state that the surface thereof is selectively heated to form a region showing the sweepback contact angle corresponding to heating temp. to the surface of the recording medium A and, thereafter, the latent image thereof is developed. When the surface of the recording medium A having the latent image formed thereto is heated in the absence of the contact material B, the latent image can be erased and an image can be reversibly formed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel recording device, and more specifically, the present invention relates to a novel recording device, and more specifically, the present invention relates to a novel recording device, and more particularly, to the surface of a recording medium whose surface exhibits specific properties, selectively or selectively and reversibly, Relating to a recording device that forms a latent image by forming a region exhibiting a receding contact angle according to heating temperature, and supplies a recording agent containing a color developer to this latent image to make it visible. .

[Conventional technology]

A typical method for dividing the surface into a liquid-adhesive area and a non-liquid-adhesive area for image formation is an offset printing method using a lithographic printing plate without water (dampening water). It will be done. However, with this offset printing method, it is difficult to incorporate the plate-making process from the original plate and the printing process from the printing plate (printing plate) into one device, making it difficult to miniaturize plate-making printing devices. ing.

For example, even in relatively compact office offset plate making and printing machines, the plate making device and the printing device are usually separate.

In order to eliminate such defects of the offset printing method, liquid adhesive areas and non-liquid adhesive areas can be formed according to image information.

Recording methods and devices that can be used repeatedly (reversible) have been proposed. Some of them are as follows.

(1) Aqueous development method After applying an electric charge to the hydrophobic photoconductor layer from the outside, it is exposed to light to form a pattern on the surface of the photoconductor layer that has a hydrophobic part and a hydrophilic part. An aqueous developer is applied and the image is transferred to paper or the like (Japanese Patent Publications No. 40-18992, Japanese Patent Publication No. 18993-1973, Japanese Patent Publication No. 9512-1982, Japanese Patent Application Laid-Open No. 63-264392, etc.).

(2) Method using photochemical reactions of photochromic materials A layer containing materials such as spiropyran and azo dyes is irradiated with ultraviolet rays, and a photochemical reaction takes place. These photochromic compounds are made hydrophilic [for example, "Kobunshi Papers" Vol. 3]
Vol. 7, No. 4, p. 287 (1980)).

(3) Method using the effect of internal biasing force Forms an amorphous state and a crystalline state through physical changes to form areas to which liquid ink adheres and to which it does not adhere (Japanese Patent Publication No. 41902/1982).

According to the method (1) above, after the aqueous ink is transferred to paper or the like, the hydrophilic portion is erased by static electricity removal, making it possible to record other image information. That is, one original plate (photoconductor) can be used repeatedly. However, since this method is based on an electrophotographic process, it requires a long process of charging, exposing, developing, transferring, and removing static electricity, and has drawbacks such as making it difficult to miniaturize the device, reduce costs, and make it maintenance-free.

Although the method (2) above allows free and reversible control of hydrophilicity and hydrophobicity by selectively changing the irradiation with ultraviolet rays and visible light, the reaction time is extremely slow due to low quantum efficiency. However, it has drawbacks such as long length, slow recording speed, and lack of stability, and the reality is that it has not yet reached a practical level.

Furthermore, according to the method (3) above, the information recording member used therein is stable after recording, but before recording there is a risk that physical structural changes may occur due to temperature changes. There are still problems with storage stability. In addition, since the recorded information pattern is erased by means of applying a heat pulse and then rapidly cooling it, there is a disadvantage that repeated image formation becomes complicated.

[Problem to be solved by the invention]

An object of the present invention is to provide a member (recording body (A
)) A desired pattern area is selectively or selectively and reversibly formed on the surface of the object by easy means, and an apparatus is provided for visualizing the desired pattern area.

Another object of the present invention is to fix the visible image as it is on the surface of the recording medium, or to transfer and fix the visible image onto plain paper or the like without fixing it, so as to produce a clear image with gradation. The present invention provides a device that can obtain the following.

Still another object of the present invention is to use a recording medium (A) with excellent storage stability and stability in all processes such as forming/erasing a desired pattern area, visualization, and transfer, so that reversible The object of the present invention is to provide a new recording device that can perform the above steps multiple times.

[Means to solve the problem]

The device of the present invention has the following surface of the recording medium (A) and the contact material (
The contact material (B) is selectively heated while in contact with the contact material (B), or the contact material (B) is selectively heated while the surface of the recording medium (A) is selectively heated.
) to form an area (a desired pattern area, hereinafter referred to as a "latent image" or "latent image area" for convenience) showing a receding contact angle depending on the heating temperature on the surface of the recording medium (A). The feature is that this latent image is visualized after the image is exposed.

(A) A recording material having a surface whose receding contact angle decreases when brought into contact with a liquid in a heated state.

(B) A liquid, a vapor, or a solid that becomes a liquid or generates a liquid or vapor at a temperature below the temperature at which the receding contact angle begins to decrease in the recording material (A).

In the apparatus of the present invention, the latent image can be erased by heating the surface of the recording medium (A) on which the latent image is formed in the absence of the contact material (B), and the image can be reversibly formed. This is something that can be done.

The present inventor has solved the defects described in the prior art,
A lot of research and consideration was conducted on new recording methods and devices. As a result, a member whose surface has the function of being heated in contact with a liquid and having a low receding contact angle after cooling, and increasing the receding contact angle when heated in the absence of liquid is useful as a recording medium. I found it. The recording medium (A) having such a function has a surface (
It was also confirmed that the material was 1) a member containing an organic compound with a surface self-orientation function of hydrophobic groups, or (2) a member containing an organic compound having a hydrophobic group with the hydrophobic groups oriented on the surface.

The "surface self-orientation function" referred to in (1) means that when a solid formed by forming a certain compound on a support or a solid formed by the compound itself is heated in air, the hydrophobic groups on the surface move toward the air side (
This means that there is a property of blending toward the free surface side). This also applies to (2). Generally, in organic compounds, hydrophobic groups tend to face toward a hydrophobic atmosphere. This is a phenomenon that occurs because the interfacial energy of the solid-air interface tends to become lower. Furthermore, this phenomenon tends to occur as the molecular length of the hydrophobic group increases, and this is because the longer the molecular length, the higher the mobility of the molecule during heating.

More specifically, molecules having a hydrophobic group at the end (that is, lowering the surface energy) tend to be surface oriented facing the air side (free surface side). Similarly, one + CH2e-1
In a linear molecule containing , the (CH2CH2)- portion has a planar structure, and the molecular chains tend to align with each other. Also,
→A molecule containing 0+-o also has a planar structure at the -+0+- portion, and the molecular chains tend to align with each other. In particular, linear molecules containing highly electronegative elements such as fluorine have high self-aggregation properties, and the molecular chains tend to align with each other.

Summarizing these study results, it is more preferable to use linear molecules that contain molecules with high self-aggregation or molecules that have a planar structure and have a hydrophobic group at the end, or such linear molecules. It can be said that the compound containing this compound has a high surface self-alignment function.

As is clear from the above description, there is a relationship between the surface self-alignment state and the receding contact angle, and there is also a relationship between the receding contact angle and liquid adhesion. That is, the adhesion of a liquid on a solid surface is mainly caused by tacking of the liquid on the solid surface. This tacking can be thought of as a type of frictional force when a liquid slides on a solid surface. Therefore, the "receding contact angle" θr in the present invention is defined as γ, where γ is the surface tension of the solid in vacuum, γSQ is the solid-liquid interfacial tension, πe is the equilibrium surface tension γ, Frictional tension γS: surface tension of a solid without an adsorption layer) holds true (Saito, Kitazaki, et al. "Journal of the Japan Adhesive Association" Vol. 12.2)
2.Na 12. Na 1986).

Therefore, when the value of or becomes low, the value of γ becomes large.

That is, the liquid becomes difficult to slide on the solid surface, and as a result, the liquid adheres to the solid surface.

As can be inferred from these mutual relationships, liquid adhesion depends on the extent of the receding contact angle or, and the receding contact angle or is determined by whether or not the member has a surface self-alignment function on its surface. Therefore, in the apparatus of the present invention, the recording medium (A) necessarily includes a member having a surface self-alignment function on its surface in order to form a desired pattern area on its surface and/or to visualize it with a recording agent. It must be selected.

As described above, the recording medium (A) used in the apparatus of the present invention has "a surface whose receding contact angle or decreases when it is heated and comes into contact with a liquid."

The recording medium (A) may have any shape as long as its surface has the properties described above. Therefore, recording body (A)
It may be in the form of a film, or another coating film having the above-mentioned surface properties may be provided on a suitable support or molded body.

The molded body itself may be used, but its surface must have the properties described above.

Depending on the type of contact material (B), the liquid-adhesive portion in the latent image area of this recording medium (A) is either lipophilic or hydrophilic. Any of the inks can be used as needed.

Here, FIG. 1 shows an example of classification of members or materials that "form a surface whose receding contact angle or decreases when brought into contact with a liquid in a heated state" into several categories. Figure 1 (a) is an example of a compound that has a self-orientation function, and is a compound that has a hydrophobic group in the side chain of a polymer, and the main chain R and the hydrophobic group R are bonded by a bonding group J. There is.

FIG. 1(b) is an example of a member in which the hydrophobic group is oriented on the surface of an organic compound having a hydrophobic group. This is a member formed with compound O. Figure 1 (C
) is an example of a member made only of the organic compound O having a hydrophobic group shown in FIG. 1(b).

Figure 1(d) shows an example in which a linear molecule is on the side chain of a polymer, and the main chain is connected to the molecule by a bonding group J to create a self-aggregating or planar structure with a hydrophobic group R at the end. molecular chain N
is an intermediate compound.

In the examples shown in FIGS. 1(a) and 1(d), the main chain of the polymer compound may be linear or have a mesh structure.

In the example of FIG. 1(b), the hydrophobic group-containing compound 0 may be further laminated on the hydrophobic group-containing compound 0, like a cumulative LB film. In the example shown in FIG. 1(c), the structure is made up of only the hydrophobic group-containing compound 0 without using the main chain (L) or bonding to an organic/inorganic material (M).

The above-mentioned hydrophobic group is preferably -CH at the terminal of the molecule.
, and -CF3, -CF2H1-CFH2, -C(CF3
)3, -C(CH,)3, etc., and those with a long molecular length are more preferable in terms of high molecular mobility. Among them, the hydrophobic group is -F and/or -
Substituted alkyl group with one or more CQ (-CF2CF2C
FCF2CF2 (7) or CQ) or an unsubstituted alkyl group having 4 or more carbon atoms is desirable. Both fluorine-substituted and chlorine-substituted ones can be used, but fluorine-substituted ones are more effective. In these materials, in terms of the relationship between the number of carbon atoms in the alkyl group and the function, if the number of carbon atoms is 3 or less, the function suitable for a recording device will be low.

The principle of this functional expression has not yet been completely clarified, and therefore there are many unknown points, but the following is assumed.

First, it is considered that the surface of the recording medium (A) formed from the above compound is a surface in which the hydrophobic groups are considerably oriented. Therefore, this surface has liquid repellency (because hydrophobic groups have low surface energy). In this state, when the surface of the recording medium (A) comes into contact with the contact material (B) and is heated, the molecular movement of the hydrophobic groups becomes active due to the heating.
And upon interaction with the contact material (B), the recording body (
This seems to be because the orientation (alignment) state of at least a portion of the surface of A) changes to another state (that is, another orientation state or a disordered orientation state) and maintains that other state even after cooling.

Note that heating the recording medium (A) with the surface of the recording medium (A) in contact with the contact material (B) may mean that the surface of the recording medium (A) is heated, depending on the form of the contact material (B). The liquid will come into contact with the

Before this heating, the hydrophobic groups are aligned (orientated) on the surface, so the surface energy of the surface of the recording medium (A) is extremely low.

However, heating the material in contact with the contact material (B) disturbs the orientation state and increases the surface energy. The receding contact angle θr depends on the type of liquid and is determined by the balance of surface energy between the solid and the liquid. Therefore, as the surface energy of the solid increases, the receding contact angle θr decreases regardless of the type of liquid. Therefore, the adhesion to liquids will increase.

Furthermore, the surface of the recording medium (A) is in a different state (a different orientation state different from the original orientation state or a "disturbed orientation state").
When heated in the absence of the contact material (B), no interaction with the contact material (B) occurs, so it is thought that the original alignment (orientation) state is returned.

Therefore, the presence of the contact material (B) is not simply for rapidly cooling the surface of the recording medium (A) after heating, but it is for causing some kind of interaction with the compound on the surface of the recording medium (A). It is thought that this interaction causes a change to another state (another orientation state or a state in which the orientation is disordered).

As mentioned above, when an alkyl group or a fluorine- or chlorine-substituted alkyl group is employed as the hydrophobic group of the member (compound) forming the surface of the recording medium (A), the number of carbon atoms in the alkyl group is 4 or more. What is desirable is that the alkyl groups are aligned (orientated) to a certain extent on the surface of the element and the recording medium (A), and that the number is necessary for active molecular movement when heated.

Further, when the contact material (B) is heated together with the surface of the recording medium (A), the contact material (
It is also possible that the molecules of B) are incorporated.

In addition, the presence of highly electronegative fluorine or chlorine in the alkyl group increases the interaction with liquids, especially polar liquids, resulting in larger changes in adhesion than with compounds containing hydrogen-only alkyl groups. .

In addition, a fluorine-containing alkyl group has a strong self-aggregation property, so it has a high one-surface self-alignment function, and furthermore, since it has a low surface energy, it is excellent in preventing soiling of the background.

Furthermore, the surface of the recording medium (A) has liquid repellency, but when this is described in terms of the surface energy of a solid, the inventor's studies have shown that it is desirable for the recording method to be 50 dyn/Cm or less. Ta. If the value is higher than this, the surface of the recording medium (A) may sometimes become wet with the recording agent, which may cause the background to become smeared.

Here, details of the compound forming the surface of the recording medium (A) will be described. First, for the types shown in FIGS. 1(a) and 1(d), compounds having an alkyl group (including fluorine and/or chlorine) in the vinyl polymer side chain are considered.

Specifically, formula (I) (n) (III) (IV) (V
) (VI) and (■) Rf: A group containing an alkyl group of 04 or more or a fluorine- or chlorine-substituted alkyl group, or a group containing (C
F2←a, -((1, H2←a or -■- hydrophobic group (Q≧4)) A polymer in which an integer of n'=1 or more is used as a monomer can be mentioned.

Other polymers include formulas (■) (■) and (X)
Examples include the ones shown below.

Rnee H5-CH, -C2HS, -CF3 or -C2
F.

to O=C-a Rnee H1-CH3, -C2H5, -CF3 or -C2
F.

Rf: a C4 or higher alkyl group, or a group containing a fluorine- or chlorine-substituted alkyl group, or.

(CF2)- in the molecular chain. , -+CH2) -+2 or -
Hydrophobic group containing 〇- (Q≧4) n: an integer of 10 or more In these specific examples, Rf can be exemplified by the following (1) to (20).

(1) -CH2CF, CHFCF3 (6) cH2(cpz)t. H (7) -CF2CF to -+CF2.

(8) (CH2 sho NH-CF2CF3 (9) → CF,
CH2 CF2) (CH2),oC,F,7 (13)-CH2NH5○2CIIF17(14) (
CF2<ΣF (15) e-5-CH2CH2-(CF,)6CF(
CF3)2(16)-CH2CF2CF2CF.

(17)-CH2CH2CH2CH2F(18)-C
H2(CF2)6CF.

(19) -CH, (CF2), CF.

(21+GHz)3cF3 Among these compounds, the following material (XI) [however, R1: hydrogen, -cn)lzn+x or -CnF
z ne□ (n: 1 or an integer of 2 or more) R2 knee + CH2+ - (an integer of ρ≧1) or any CH2+
-N (R')502-(R' is -CH3 or -C2
H5-Q≧1 (an integer) m86 or more. ] Therefore, the most preferable specific compound for the member on the surface of the recording medium (A) in the present invention is C2H.

Examples include.

Furthermore, these formulas (Iin(U)(III)(R')(
V) (VI) (■) and (X[) monomers 2
In addition to copolymers with other monomers such as ethylene, vinyl chloride, styrene, butadiene, isoprene, chloroprene, vinyl alkyl ether, vinyl acetate, vinyl alcohol, etc. suitable as

In addition, a polymerizable monomer having a monomer of formula (XI) and a functional group, such as CH2=C(CH,)Coo (C1(2)20HCH
2=C(CH3)COOCH2CH(OH)CH.

CH2=CHC00CH2CH((IH)CIIF17
Either a copolymer is made with one or more of the following, and a large number of functional groups are introduced into the polymer, or a copolymer is made with a monomer of formula (XI) and a polymerizable monomer having a functional group, and then a copolymer with a functional group is prepared. Materials into which groups have been introduced are excellent as materials for crosslinkable polymers.6 Examples of crosslinking reagents include formaldehyde, dialdehyde, N-methylol compounds, dicarboxylic acids, dicarboxylic acid chlorides, bishalogen compounds, bisepoxides, bisaziridine, and diisocyanates. etc. An example of the crosslinked polymer thus obtained is shown below.

In the above formula, the A block is an alkyl group that brings about the change in thermal properties, while the B block is a site that crosslinks chain polymers (crosslinked using diisocyanate as a crosslinking reagent). be.

In order to obtain a crosslinked film, a solution containing the above-mentioned copolymer and a crosslinking reagent is applied as a coating liquid onto a substrate, and a crosslinked polymer film is obtained by heating, electron beam irradiation, or light irradiation. good.

In addition, in order to obtain a polymer from the above monomer, solution polymerization,
Electrolytic polymerization, emulsion polymerization, photopolymerization, radiation polymerization, plasma polymerization, graft polymerization, plasma initiated polymerization, vapor deposition polymerization, etc.
An appropriate method is selected depending on the material.

Next, the compound shown in FIG. 1(b) will be described.

Here, the materials Rf-COOH...(XII) Rf-OH...(X I[I) Rf(CH2SiX...( XIV)
(Rf: a group containing an alkyl group having 4 or more carbon atoms or a fluorine- or chlorine-substituted alkyl group, or 1+CFz+-a, →Cl2 in the molecular chain). or a hydrophobic group containing -〇- (Q≧4)) n: an integer of 1 or more Materials physically adsorbed or chemically bonded to the surface of organic materials (surface energy of approximately 50 dyn)
/am or less).

A specific example of formula (X[1) (XII[) and (XIV) is CF3 (CF2 juice C0OH).

CF, (CF2 sho C0OH.

CF3 → CF2 juice (CH2 soup ○H.

H→CF2 punishment C○○H.

H→CF2 punishment CH20H.

FiCF21cH2CH2-Si(CH3)2CΩ.

CF2CQ, (CF,)CF(CF2), C○○H.

Examples include CF3(CF2)7(CH2)2S 1CQ3.

The compounds shown in FIG. 1(c) include formula (xn), formula (X
m) and a structure made only of the material of formula (XIV).

Next, the recording medium (A) using the above compound will be described.

The structure of the recording medium (A) is roughly divided into two types: (1) one formed of the above-mentioned surface member itself, and (2) one in which the above-mentioned surface member is formed on a support (preferably a heat-resistant support). In embodiment (2), the above compound (surface member) itself is formed into a film, plate, or columnar shape. At this time, in the case of a film, the thickness of the film is preferably IIJm to 5 mm.

In embodiment 2I, the above compound may penetrate into the support to some extent. The film thickness of the recording body (A) itself is preferably 30 mm to 1 mm. However, in terms of thermal conductivity, 100 people ~ 10 tons, and in terms of wear resistance, 10 μm ~
1mm is excellent. The heat resistant temperature of the support is 5
0°C to 300°C is desirable.

The shape of the support may be belt-shaped, plate-shaped, or drum-shaped, and is selected depending on the intended use of the apparatus.

In particular, the drum shape is excellent in providing dimensional accuracy in the device. The size of the plate-shaped one may be determined depending on the recording paper size.

Furthermore, when a mixture of the above compound (surface forming material of recording medium (A)) and other members such as hydrophobic polymers and hydrophobic inorganic materials is formed on the support, it is excellent in preventing background staining during printing. There is. Further, in order to increase thermal conductivity, metal powder may be mixed into the above compound. Furthermore,
In order to improve the adhesion between the support and the compound, a primer layer may be provided between the support and the compound. Heat-resistant supports include resin films such as polyimide and polyester, glass, Ni, AQ, Cu, Cr,
Metals such as Pt, metal oxides, etc. are preferable. These supports may be smooth, rough or porous.

Next, the contact material (B) will be explained.

The contact material (B) is as described above, but to put it simply, it is a liquid or vapor from the beginning, or
It is a solid that eventually forms a liquid below the temperature at which the receding contact angle Or begins to decrease in the recording medium (A). At least a part of the vapor here condenses to produce a liquid on or near the surface of the recording medium (A), and the liquid is formed on the recording medium (A).
Any material that can wet the surface of A) is sufficient. On the other hand, the solid here becomes a liquid, generates a liquid, or generates a vapor below the temperature at which the receding contact angle or begins to decrease. As in the above case, the vapor generated from the solid condenses on or near the surface of the recording medium (A) to form a liquid.

More specifically, these contact materials (B) are as follows.

That is, in addition to water, liquids that are one of the contact materials (B) include aqueous solutions containing electrolytes, alcohols such as ethanol and n-butanol, polyhydric alcohols such as glycerin and ethylene glycol, and ketones such as methyl ethyl ketone. polar liquids such as, linear hydrocarbons such as n-nonane and n-octane, cyclic hydrocarbons such as cyclohexane,
- non-polar liquids such as aromatic hydrocarbons such as xylene and benzene; Moreover, a mixture of these may be used, or even a polar liquid may be used.

In addition to water vapor, the vapor that is another contact material (B) can be used as long as it is the liquid vapor of the contact material (8), but in particular organic compound vapor such as ethanol vapor or m-xylene vapor can be used. (including those in a spray state).

The temperature of this organic compound vapor must be below the melting point or softening point of the compound forming the surface of the recording medium (A).

Other examples of the solid contact material (B) include higher fatty acids, low molecular weight polyethylene, polymer gels (polyacrylamide gel, polyvinyl alcohol gel), silica gel, and compounds containing water of crystallization. .

Next, the heating means will be explained.

In addition to contact heating using heaters, thermal heads, etc., heating means include non-contact heating using electromagnetic waves (light from a light source such as a laser light source or an infrared lamp is focused with a lens). Further, the present invention can also be achieved by electron beam irradiation and light (Uv light) irradiation as long as heating is substantially performed.

In FIG. 2(a), a film 2 of the compound constituting the surface of the recording medium (A) is formed on the substrate 1, and a contact material (
In B), for example, a state in which liquid 3 is present is shown. In this state, when the film 2 is heated, the receding contact angle er decreases on the surface of the film 2, resulting in significant wetting and liquid adhesion. Furthermore, when this liquid-adhesive film 2 is heated again in air, vacuum, or an inert gas atmosphere (Fig. 2(b)), the receding contact angle or the surface of the film 2 increases and the liquid repels again. It is acceptable to show gender.

As a phenomenon somewhat similar to this one,
There is a method described in the above-mentioned Japanese Patent Publication No. 54-41902. However, the method disclosed herein differs mechanically in that it provides a layer of memory material in the recording material that is substantially disordered and generally amorphous. That is, in the present invention, no change in state can occur on the surface of the recording medium (A) without the presence of the contact material (B). In addition, special public service
In the method described in Japanese Patent No. 902, reversibility cannot be obtained with a simple operation.

As shown in Figure 3 (a), heat is applied to the membrane 2 in contact with the liquid 3 according to the image information (as shown in Figure 3 (b-1), the image information is applied to the membrane 2 in the absence of liquid. (The same is true when the membrane 2 is brought into contact with a liquid while being heated depending on the temperature), the surface of the heated portion of the membrane 2 becomes liquid-adhesive. In the figure, 4 represents a heater, 31 a liquid supply port, 41 an infrared lamp, 5 a lens, and 6 a shutter.

3(a) shows an example in which the heating of the film 2 is performed through the substrate 1, but in the example shown in FIG. 3(b-2), the heating of the film 2 is performed through the liquid 3.
This is an example in which heating is performed through the

FIG. 4 shows an example of the variation in the contact angle of the aqueous solution before and after heating the film 2 in contact with the aqueous solution, and the variation in the contact angle of the aqueous solution when this membrane 2 is further heated in air. In FIG. 4, O represents the advancing contact angle and Δ represents the receding contact angle.

Generally, if the receding contact angle is high, such as 90° or more, the surface is liquid repellent; if the receding contact angle is low, such as 90" or less, the surface is liquid repellent.
Its surface exhibits liquid adhesion.

The heating temperature of the surface of the recording medium (A) in contact with the contact material (B) is preferably in the range of 50°C to 250°C,
More preferably, the temperature is 80°C to 150°C. The heating time is about 0.1 seconds to 1 second, preferably 0.5 msec to 2 seconds.
ffi seconds. The timing of heating is to form a latent image: 1. After heating the surface of the recording medium (A), bring it into contact with the contact material (B) before it cools down; 2. ) is in contact with the recording medium (
Either A) heating the surface may be used.

On the other hand, if the latent image is to be erased, the surface of the recording medium (A) is heated at 50 to 300°C, preferably 100 to 300°C in the absence of the contact material CB).
Just heat it to 180°C. In either case, the heating time is about 1 msec to 10 seconds, preferably 10 msec to 1 second.

Next, the means for actually recording image information on the surface of the recording medium (A) will be explained in more detail.

One is to heat the surface of the recording layer (A) in accordance with an image signal in a liquid or vapor atmosphere to form a liquid adhering area (latent image formation) on the surface of the recording layer (A), and then to remove this latent image area. This is a method in which a recording agent is attached to the latent image area (development) by means of bringing the recording agent into contact with the surface of the recording medium (A), and then this recording is fixed as it is on the surface of the recording medium (A) (direct recording method). The other is a recording medium (
The surface of A) is heated to form a liquid adhesion area on the surface of the recording medium (A) (latent image formation), and then the recording agent is attached to the latent image area by means of bringing the recording agent into contact with this latent image area. This is a method of developing (developing) and then transferring the recording material on the surface of the recording medium (A) to recording paper (indirect recording method). Furthermore, in the above method, if a means is performed to bring the recording agent into contact with the latent image area again after the recording agent is transferred, a printing method using the recording medium (A) as a printing plate can be obtained. Furthermore, in the above method, after the recording agent is transferred, the surface of the recording medium (A) on which the latent image has been formed is heated in the absence of liquid or vapor to erase the latent image. This is a playable recording method. Figure 5 (
Representative processes of a direct recording method, an indirect recording method (printing method), and a reversible recording method (repetitive recording method) of a recording medium are shown in a), (b), and (C).

Next, the configuration of the apparatus of the present invention including the recording medium (A) will be described.

The recording body (A) has a surface (sometimes referred to as "film 2" or "recording body (A) surface" for convenience) that reduces the receding contact angle when brought into contact with a liquid in a heated state. If something exists, it cannot take that form. Therefore, the recording body (
A) may have a rigid cylindrical shape or a flexible film shape. Rigid cylindrical recording body (
A rigid cylindrical body (with a film 2 formed on the surface) has excellent controllability because positional deviation is less likely to occur when the recording body (A) is operated.
A) is good.

Such a recording body (A) can be preferably produced by forming the film 2 on a substrate or by using the molded body itself. In particular, since the molded body generally has low mechanical strength, a method of forming a film on a substrate is desirable. Note that the molded body itself is a recording medium (
It goes without saying that even when producing A), the film 2 must be formed on its surface.

When a resin is used for the recording medium substrate, it cannot be said to be a good thermal conductor, and it takes a certain amount of time for the surface of the recording medium (A) to be heated and to have liquid adhesion. Therefore,
It may be conceivable to use a good thermal conductor over the entire substrate or on parts of the substrate 1.

Figure 6(a) shows a substrate (
An organic thin film 12 is deposited thereon as a metal substrate 11),
Furthermore, if the film 2 is formed on top of that, the heat conduction speed in the vertical direction is improved. Examples of the organic thin film 12 here include polyimide, polyester, and phthalocyanine. This configuration is sufficient when the printing dots can be relatively large, but it is not suitable when the objective is higher density printing because the area with liquid adhesion expands due to heat diffusion in both directions. For this reason, FIG. 6(b) shows a structure in which the substrate 1 is provided with sections with good heat conductivity to prevent heat diffusion in the surface direction and to miniaturize the portion 2a having liquid adhesion. In FIG. 6(b).

11a represents a minute metal film.

Next, a latent image forming means by heating and a recording agent applying means (visualizing means) will be described. As mentioned above, the heating source is preferably a contact heating source such as a heater or a thermal head, or a non-contact heating source using electromagnetic waves such as a laser or an infrared lamp. Further, as the recording agent, those listed below are used.

By the way, if a recording agent is used as a contact member for forming a latent image, the latent image and image development can be performed at the same time, thereby simplifying the apparatus configuration. However, depending on the type of recording agent, heating may cause deterioration of the recording medium, and repeated use of the recording medium (A) may cause significant deterioration. When using such a recording material, it is necessary to use a contact member dedicated to forming a latent image and to separate the latent image area and the developing area. Further, by providing a dividing means and integrating the contact member for forming a latent image and the recording material for visualization, the apparatus configuration can be simplified.

Figures 7(a), 7(b) and 7(c) show two typical sides of the device of the present invention.

FIG. 7(a) shows that with the contact material 3 in contact with the surface of the recording medium 7, heating is performed from the contact material 3 side to create a latent image (S), which is visualized by the recording agent 21. It is something. Here, the contact material 3 and the recording agent 21 are housed in one dish, but they are completely separated by an osmosis membrane or a reverse osmosis membrane 9 so that they do not mix. However, if the contact material (8) is solid, it will not mix with the recording agent 21, but if the contact material (B) is a vapor, it will not mix with the recording agent 21, if appropriate. It is necessary to prevent mixing of the two. In the example of FIG. 7(a), when pure water is used as the contact material 3 and water-based ink is used as the recording material 21, the pure water adheres to the latent image area, and then the adhesion is removed in the water-based ink. The purified water will be mixed with the water-based ink. Therefore, the concentration of the water-based ink gradually decreases, but due to the reverse osmosis phenomenon of the reverse osmosis membrane 9,
Since the pure water moves toward the latent image forming means through the reverse osmosis membrane 9, the concentration of the aqueous ink is maintained constant, and no problems occur during repeated recording.

Figures 7(b) and (e) show that when the contact material (B) is a liquid,
The contact material 3 and the recording agent 21 have different specific gravities, and
This shows an embodiment suitable for forming and developing a latent image using those materials with poor compatibility.

In such an example, the contact material 3 is pure water and the recording material 2 is
For example, when 1 is an oil-based ink, the contact material 3 is n-nonane, and the recording agent 21 is a water-based ink.

Incidentally, a latent image forming means using light or an electron beam may be basically the same as the above structure, and for example, a laser light source may be used in place of the thermal head shown in FIG. 7(a).

In the case of direct recording, a flexible film or a rigid film is used as the recording body substrate, and a film 2 is formed on the substrate 1 to form a recording body (A). A latent image is formed and visualized on this recording medium (A) by the above-described means.

After this, air drying or heat drying is performed to form a recording medium (A).
The recording agent 21 attached thereto is fixed. An example of a preferred apparatus for implementing the direct recording method is shown in FIG.

In the example shown in FIG. 8, the latent image forming means and the visualizing means are fixed and the recording medium 7 is moved.

Furthermore, if the recording medium substrate on which the recording agent is fixed after direct recording is a transparent film, it can be used as an original for a device such as a slide projector by irradiating it with transmitted light (FIG. 9).

It can also be used as an information storage medium by irradiating a beam of reflected light or transmitted light and detecting changes in the intensity of the light depending on the presence or absence of a recording agent (FIG. 10). In FIG. 10, 52 is a screen, 53 is a light source, 54 is a detector, and 55 is a motor.

In the case of indirect recording, as mentioned above, it is advantageous for example to use a rigid cylinder as the recording substrate. After latent image formation and development (visualization) 1 For example, by providing a means for direct liquid contact between the recording agent on the recording medium (A) and the recording paper, the recording agent is transferred to the recording paper 61 by the capillary action of the recording paper. (transfer means). Where should the transcription be performed?

Any position on the recording medium is fine as long as it is after development, but
A position where transfer is performed immediately after development is desirable. After the transfer, if development can be repeated without erasing the latent image, this device becomes a printing device. Once printing of one image information is completed, it becomes possible to record/print another image information by replacing the recording medium (A) or by erasing the latent image.

Further, after the transfer means, in the absence of liquid or vapor,
That is, if the latent image is erased by heating the vicinity of the latent image in air, vacuum, or inert gas, the recording medium (A
) becomes a recording device that can be used repeatedly. Note that as a heating source for erasing the latent image, a contact heating source such as a heater or a thermal head, or a non-contact heating source using electromagnetic waves such as a laser or an infrared lamp is preferable. Heating may be applied to the entire surface of the recording medium or only to the latent image area. However, full-surface heating is more desirable because it simplifies the device configuration. It should be noted that the latent image erasing means erases the recording medium (A) during the time from when it is heated for erasing to when the latent image is again produced.
Provided at a location where the surface is substantially cooled. The heating temperature required for erasing varies depending on the material on the surface of the recording medium (A), but it is preferably a temperature above the starting temperature at which the receding contact angle of the material on the surface of the recording medium (A) becomes low and below the decomposition point.

As the recording paper (subject to be transferred), transparent resin film, plain paper, inkjet paper, type paper, etc. are suitable.

Next, the recording agent will be described.

In order to obtain a visible image on the surface of the recording medium (A) in the recording apparatus of the present invention, recording agents used in conventional printing recording methods such as writing ink, inkjet ink, printing ink, and electrophotographic toner are used. It is possible to select and use a recording material suitable for this process from among the recording materials listed above.

To give a more specific example, for example, water-based inks include water-soluble inks containing water, a wetting agent, and dyes, or water;
Water-based pigment dispersion inks containing pigments, dispersing polymer compounds, and wetting agents as main components, emulsion inks in which pigments or dyes are dispersed in water using surfactants, and the like are used. Wetting agents used in water-based inks include the following water-soluble organic liquid compounds.

Monohydric alcohols such as ethanol, methanol, propatool; ethylene glycol, diethylene glycol,
triethylene glycol, tetraethylene glycol,
Polyhydric alcohols such as polyethylene glycol, propylene glycol, dipropylene glycol, glycerin; ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol, diethylene glycol Ethers of polyhydric alcohols such as ethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monoethyl ether; N-methyl-2-pyrrolidone,
Heterocyclic compounds such as 1,3-dimethylimidazolidinone and ε-caprolactam; amines such as monoethanolamine, jetanolamine, triethanolamine, monoethylamine, dinitylamine, and triethylamine;

As water-soluble dyes, dyes classified as acid dyes, direct dyes, basic dyes, reactive dyes, and food dyes in the color index are used.

Examples of typical dyes include C,1, Acid Yellow 17,23,42,44,
79,142C,1, Acid Red 1,8,13,
14, 18, 26, 27, 35° 37.42, 52, 8
2,87,89,92,97゜106.111,114
,115,134,186°249.254,289 C,1, Acid Blue 9.29,45,92,24
9,890C, 1, Acid Black 1, 2, 7, 2
4,26,94C,1, Foot Yellow 3,4 C,1, Hood Red 7.9.14 C,1, Hood Black 2 C,1, Direct Yellow 1,12,24,26,
33,44,50゜142.144,865 C, 1, Direct Red 1, 4, 9, 1.3, 17
,20,28,31゜39.80,81,83,89,
225°C, 1, Direct Orange 26, 29, 6
2,102C,1, Direct Blue 1.2,6,1
5, 22, 25, 71, 76° 79.86, 87, 90
, 98, 163° 165.202 C, 1, Direct Black 19, 22, 32, 38
,51,56°71.74,75,77.154,16
8C, 1, Basic Yellow 1, 2, 11, 13,
14,15,19゜21.23,24,25,28,2
9゜32.36,40,41,45,49゜51,5
3, 63, 65, 67, 70.

73.77.87.91 C, 1, Basic Red 2, 12, 13, 14, 1
5,18,22゜23.24,27,29,35,36
, 38° 39.46, 49, 51, 52, 54, 59° 68.69, 70, 73, 78, 82, 102° 104
．． 109,112 C, 1, Basic Blue 1.3, 5, 7, 9, 21
,22,26,35°41.45,47,54,62,
65,66°67.69,75,77.78,89,9
2゜93.105,117,120,122゜124.
Examples include 129, 137, 141, 147° Basic Black 2,8.

Pigments include organic pigments such as azo, phthalocyanine, anthraquinone, and quinacridone.

Dioxazine-based, indigo-based, thioindigo-based, perinone-based, perylene-based, isoindorenone-based, aniline black, azomethine azo-based, carbon black, etc., and inorganic pigments include iron oxide, titanium oxide, calcium carbonate, and aluminum sulfate. , aluminum hydroxide, barium yellow, navy blue, cadmium red, chrome yellow,
Examples include metal powder.

Pigment dispersing compounds include polyacrylamide, polyacrylic acid and its alkali metal salts, acrylic resins such as water-soluble styrene acrylic resin, water-soluble styrene-maleic acid resin, water-soluble vinylnaphthalene acrylic resin, and water-soluble vinylnaphthalene nonmaleic acid. Resins, polyvinylpyrrolidone, polyvinyl alcohol, alkali metal salts of β-naphthalenesulfonic acid formalin condensates, polymeric compounds containing salts of cationic functional groups such as quaternary ammonium and amino groups, proteins such as polyethylene oxide, gelatin, and casein. , natural rubbers such as gum arabic and gum tragacanth, glucoxides such as saponin, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, and methyl cellulose, lignin sulfonic acid and its salts, and natural polymer compounds such as ceramics.

Like water-based inks, oil-based recording materials include those in which oil-soluble dyes are dissolved in organic liquid compounds, pigments dispersed in organic liquid compounds, pigments or dyes emulsified in oil-based bases, etc. is used.

Representative examples of oil-based dyes include C,1, Solvent Yellow 1,2,3,4,5,6
,7,8,9゜10.11,12,14,16,17゜26.27,29,30,39,40゜46.49,5
0,51,56,61°80.86,87,89.96 C,1, Solvent Orange 12,23,31,43
, 51, 61C, 1, Solvent Red 1, 2, 3,
16,17,18,19,20゜22.24,25,2
6,40,52,59゜60.63,67.68,12
1 C, 1, Solvent Violet 7.16.17C,
1, Solvent Blue 2, 6, 11, 15, 20, 3
0, 31, 32° 35.36, 55, 58, 71.72 C, 1, Solvent Brown 2, 10, 15, 21.
22C, 1, Solvent Black 3, 10, 11, 1
2.13 etc. are mentioned.

Oil bases for dissolving dyes and dispersing pigments include n-octane, n-decane, minerane spirit, ligroin, naphtha, benzene, toluene,
Hydrocarbons such as xylene; ethers such as dibutyl ether, dibutyl ether, anisole, phenetol, dibenzyl ether; alcohols such as methanol, ethanol, isopropyl alcohol, benzyl alcohol, ethylene glycol, diethylene glycol, glycerin, etc. I can do it.

The pigments exemplified above can also be used in oil-based inks. Examples of oil-based pigment dispersants include polymethacrylic esters, polyacrylic esters, methacrylic ester-acrylic ester copolymers, polyvinyl acetate, vinyl chloride copolymers, polyvinylpyrrolidone, polyvinyl butyral, and other vinyl dispersants. cellulose resins such as ethyl cellulose and methyl cellulose, condensation polymer resins such as polyester, polyamide, and phenolic resins,
Natural resins such as rosin, ceramic, gelatin, casein, etc. are available.

〔Example〕

Example 1 A homopolymer prepared by solution polymerization in 1,1,1-trichloroethane using perfluoromethyl methacrylate (Viscoat 17FM, manufactured by Osaka Organic Chemical Co., Ltd.) as a monomer was used as a molding material. After purification, it was diluted with Freon 113 (Freon TFJ manufactured by Mitsui Fluorochemical Co., Ltd.) to prepare a coating solution of 7 weight da.This coating solution was cast onto a polyimide film (a recording medium with a thickness of 3 vocal membranes was formed). A device was fabricated by wrapping it around a circular aluminum tube with a diameter of 100+ nm and having the configuration shown in Figure 7(a).Pure water was used as the contact material for the latent image forming means, and was separated from the ink by a reverse osmosis membrane. The latent image was formed using a thermal head with a heating element on the end face of 8 dat/mm.As the ink, a water-based ink in which an acidic black dye was dissolved in NaOH water of PHIO was used. there was.

When latent image formation, development, ink transfer, and latent image erasure were repeated based on various image information, no image deterioration was observed even after 10,000 repetitions.

Example 2 The same recording medium as in Example 1 was used. Pure water was used as a contact material for the latent image forming means. As the ink, an oil-based ink in which carbon black was dispersed using n-octane as a solvent was used. As shown in FIG. 7(b), a combination of a thermal head and an ink container (dish-shaped) was first filled with ink, and then a recording medium was placed in contact with the ink. At this time, the ink was prevented from coming into contact with the end of the thermal head.

Next, a structure as shown in FIG. 7(b) was created by filling the vicinity of the end of the thermal head with pure water. When images were repeatedly recorded using this device, no image deterioration was observed even after 10,000 images were recorded.

Comparative Example In the apparatus of Example 1, when recording was repeatedly performed using ink as the member used for the latent image forming means, 100
Image deterioration occurred after about 0 times.

〔Effect of the invention〕

According to the apparatus of the present invention, a desired image can be obtained reversibly with a simple operation.

[Brief explanation of drawings]

FIG. 1 is a schematic four-sided view of a configuration having a surface self-alignment function. FIGS. 2 and 3 are diagrams for basically explaining the apparatus of the present invention. Figure 4 shows the receding contact angle observed on the surface of the recording medium (A) when the surface of the recording medium (A) used in the practice of the present invention is heated with a liquid in contact with the surface. It is a figure showing the change of or. FIG. 5 shows three embodiments of the system according to the present invention. FIG. 6, FIG. 7, and FIG. 8 are diagrams showing how the apparatus of the present invention is implemented. FIG. 9 and FIG. 10 show an example of application of recorded matter made by the apparatus of the present invention. 1...Substrate 2...Membrane 3...Liquid 4...Heater patent applicant Rico Co., Ltd.

Claims (1)

[Claims] (1) A recording material (A) having a surface whose receding contact angle decreases when brought into contact with a liquid in a heated state, and a liquid, a vapor, and a recording material (A) that has a surface that has a surface whose receding contact angle decreases when brought into contact with a liquid. A contact material (B) selected from a liquid or a solid that generates vapor is selectively heated while the contact material (B) is in contact with the surface of the recording medium (A), or the recording medium (A) is heated while being in contact with the surface of the recording medium (A). a latent image forming means for forming a region on the surface of the recording medium (A) exhibiting a receding contact angle according to the heating temperature by bringing the surface of the recording medium (A) into contact with the contact material (B) in a selectively heated state; A recording device characterized in that a recording agent applying means for visualizing an image is integrated with a dividing means.