JPH04219271A - Recording apparatus - Google Patents

Abstract

PURPOSE:To certainly erase a latent image and to stably perform the processes from the formation of the latent image to the transfer of an image and the erasure of the latent image two or more times in a recording apparatus utilizing a recording body having a surface whose sweepback contact angle lowers upon the contact with a contact material such as water in a heated state. CONSTITUTION:A latent image S is formed to the surface of a recording body 7 by heating the recording body 7 in the presence of an ink liquid 3a by a thermal head 42 and the ink liquid is bonded to the latent image and transferred to recording paper P to obtain a recording image. The latent image S is erased after transfer but, as an erasing means, a heating roller 8 is used. The heating roller 8 is brought into contact with the recording body 7 in the absence of the ink liquid 3a and the bonded ink liquid 3a' at each time when the recording body 7 makes one revolution to heat the recording body to erase the latent image S.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a novel recording device.
Specifically, a latent image is formed on the surface of a recording medium whose surface has specific properties by selectively or selectively and reversibly forming a region exhibiting a receding contact angle depending on the heating temperature. The present invention relates to a recording apparatus capable of repeating the process of supplying a recording agent containing a color developer to a latent image to make it visible, and then, or simultaneously with the formation of the latent image, transferring the latent image onto recording paper.

0002

2. Description of the Related Art A typical example of means for dividing a surface into a liquid-adhesive region and a non-liquid-adhesive region for image formation is an offset printing method using a lithographic printing plate. 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.

[0003] In order to eliminate such defects in the offset printing method, we have developed a method that can form liquid-adhesive areas and non-liquid-adhesive areas according to image information, and can be used repeatedly (reversible). Increasingly, recording methods and devices 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 having a hydrophobic part and a hydrophilic part on the surface of the photoconductor layer, with only the hydrophilic part being exposed. Apply aqueous developer and transfer to paper etc.
No. 18992, Special Publication No. 18993, Special Publication No. 18993, Special Publication No. 18993
-9512, Japanese Unexamined Patent Publication No. 63-264392, etc.). (2) A method that utilizes photochemical reactions of photochromic materials A layer containing materials such as spiropyran and azo dyes is irradiated with ultraviolet rays, and these photochromic compounds are made hydrophilic through photochemical reactions [for example, "Kobunshi Proceedings" No. 37] Vol. 4, p. 287 (1980)]. (3) A method using the action of internal biasing force Forms an amorphous state and a crystalline state through physical changes, and forms adhesion/non-adhesion areas for liquid ink (Japanese Patent Publication No. 54-41902
Publication No.).

According to the method (1) above, after the water-based ink is transferred to paper or the like, the hydrophilic portion is erased by static electricity removal.
It becomes possible to record other image information. That is, one original version (
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.

According to the method (2) above, hydrophilicity and hydrophobicity can be freely and reversibly controlled by selectively changing the irradiation with ultraviolet rays and visible light, but the reaction time is slow due to poor quantum efficiency. In fact, it has disadvantages such as being extremely long, slow in recording speed, and lacking in stability, so 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. Because of this, there remain problems with storage stability. In addition, since a means of applying a heat pulse and then rapidly cooling is employed to erase the recorded information pattern, there is a disadvantage that repeated image formation becomes complicated.

[0007]

[Problems to be Solved by the Invention] An object of the present invention is to improve the surface of a member (recording body (A)) that has a surface that has a low receding contact angle when brought into contact with a contact material (B) in a heated state. Another object of the present invention is to provide an apparatus that selectively or selectively and reversibly forms a desired pattern area using easy means, visualizes it, and transfers it onto plain paper or the like.

Another object of the present invention is that the recording medium (A) having excellent storage stability and stability is used in all processes such as forming/erasing a desired pattern area, visualization, and transfer. The present invention provides a novel recording device that can reversibly perform the steps described above multiple times.

Still another object of the present invention is to provide a recording apparatus that can reliably erase unnecessary latent images and produce new transferred images of high quality.

0010

[Means for Solving the Problems] The recording device of the present invention can be produced by selectively heating the surface of the following recording body (A) in a state in which it is in contact with the following contact material (B) or
A contact material (B) that forms a latent image area showing a receding contact angle in accordance with the heating temperature on the surface of the recording medium (A) by bringing the surface of the recording medium (A) into contact with the contact material (B) in a selectively heated state.
B) onto the surface of the recording medium (A);
), a recording agent applying means for visualizing the latent image area, a means for transferring the recording agent adhered to the surface of the recording body (A) to recording paper, and a recording medium (A); It is characterized in that it is provided with means for contact heating the surface with a heated rotatable roller in the absence of the contact material (B) and the recording agent to erase the latent image. (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 starts to decrease in the recording medium (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 latent image can be erased reversibly. It is possible to form an image.

[0012] The inventors of the present invention have conducted extensive research and study on new recording methods to eliminate the deficiencies described in the prior art. As a result, the recording material has a member whose surface has the function of having a low receding contact angle when heated in contact with liquid, even after cooling, and a high receding contact angle when heated in the absence of liquid. I found it useful as a. A recording medium (A) having such a function has a surface that is (1) a member containing an organic compound having a surface self-alignment function of hydrophobic groups, or (2) a member containing an organic compound having a hydrophobic group and having a surface self-alignment function. It was also confirmed that it was a member with oriented on the surface (Patent Application No. 2-43599)
.

[0013] The "surface self-orientation function" referred to in (1) is
This means that when a solid formed of a certain compound on a support or a solid formed by the certain compound itself is heated in air, the hydrophobic groups on the surface are oriented toward the air side (free surface side). This also applies to (2). Generally, in organic compounds, hydrophobic groups tend to face toward a hydrophobic atmosphere. this is,
This phenomenon occurs because the interfacial energy of the solid-gas 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, it has a hydrophobic group at the end (
In other words, molecules with low surface energy tend to be surface oriented facing the air side (free surface side). Similarly (−
In a linear molecule containing (-CH2-)n, (-CH2CH2-
) has a planar structure, making it easy for the molecular chains to align with each other. Further, molecules containing (-Ph-)n also have a planar structure in the -Ph- portion, and the molecular chains tend to align with each other. In addition, -Ph- is a p-phenylene group (the same applies hereinafter). 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.

[0015] To summarize the results of these studies, 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. Compounds containing such molecules can be said to have a high surface self-alignment function.

As is clear from the above description, there is a relationship between the surface self-orientation 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 includes co
sθr=γ(γs-γse-πe+γf)/γev (where, γ: Surface tension of solid in vacuum γse: Solid-liquid interfacial tension γev Surface tension when liquid is in contact with its saturated vapor πe: Equilibrium surface tension γf: Frictional tension γs: Surface tension of a solid without an adsorption layer).
l. 22, No. 12, 1986).

Therefore, when the value of θr decreases, the γf value increases. In other words, it becomes difficult for liquids to slide on solid surfaces,
As a result, the liquid becomes attached to the solid surface.

As can be inferred from these mutual relationships,
The liquid adhesion depends on the receding contact angle θr, and the receding contact angle θr is determined by whether the member has a surface self-alignment function. Therefore, in the apparatus of the present invention, since it is necessary to form a desired pattern area on the surface of the recording medium (A) and/or to visualize it with a recording agent,
Naturally, a member must be selected that has a surface self-aligning feature on its surface.

The recording medium (A) used in the apparatus of the present invention is:
As mentioned above, it has "a surface whose receding contact angle θr decreases when it comes into contact with a liquid in a heated state." The recording medium (A) may have any shape as long as its surface has the properties described above. Therefore, recording body (A)
Even if it is belt-shaped (including endless belt-shaped),
Another coating film having the above-mentioned surface properties may be provided on a suitable cylindrical support or molded body. It may be the molded body itself, but its surface is
It is necessary that the whole or a part thereof has the above-mentioned properties.

In this recording medium (A), depending on the type of contact material (B), the liquid-adhesive portion in the latent image area is either oleophilic or hydrophilic. Both ink and water-based ink can be used as needed.

FIG. 1 shows an example in which members or materials that "form a surface whose receding contact angle θr decreases when heated and brought into contact with a liquid" are classified into several categories.

FIG. 1(a) shows an example of a compound having a self-orientation function, which is a compound having a hydrophobic group in the side chain of a polymer, and the main chain L and the hydrophobic group R are bonded through a bonding group J. are doing.

FIG. 1(b) shows an example of a member in which the hydrophobic groups are oriented on the surface of an organic compound having a hydrophobic group. This is a member formed of a compound O having the following.

FIG. 1(c) is an example of a member made only of the organic compound O having a hydrophobic group shown in FIG. 1(b).

FIG. 1(d) shows an example in which a linear molecule is on the side chain of a polymer, and the main chain L and the molecule are connected by a bonding group J, and a self-aggregating or planar molecule with a hydrophobic group R at the end is used. This is a compound with a molecular chain N in the middle.

In the examples shown in FIGS. 1(a) and 1(d), the main chain L of the polymer compound may be linear or have a mesh structure. In the example of FIG. 1(b), the hydrophobic group-containing compound O may be further laminated on the hydrophobic group-containing compound O, like a cumulative LB film. In the example of FIG. 1(c), the main chain (
It has a structure consisting only of a hydrophobic group-containing compound O without having L) or bonding to an organic/inorganic material (M).

The above-mentioned hydrophobic group is preferably at the terminal end of the molecule, such as -CH3, -CF3, -CF2H, -CFH2,
-C(CF3)3, -C(CH3)3, etc., and more preferably, those having a long molecular length are advantageous in terms of high molecular mobility. Among them, the hydrophobic group is -F
and/or a substituted alkyl group having one or more -Cl (-C
F2CF2C(Cl)FCF2CF2) 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 the recording device of the present invention becomes low.

[0028] The principle of expression of this function has not yet been completely clarified, and therefore there are many points that are unclear, but the following is assumed.

First, it is considered that the surface of the recording medium (A) formed from the above-mentioned compound is a surface in which the above-mentioned 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 the surface of the recording medium (A) becomes active due to the interaction with the contact material (B). , the orientation (alignment) state of at least a portion of the surface of the recording medium (A) changes to another state (i.e., another orientation state or a disordered orientation state) and maintains the other state even after cooling. I think that the. 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 is determined by the balance of surface energy between the solid and the liquid, regardless of the type of 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, when the surface of the recording medium (A) is in a different state (an "other orientation state" different from the original orientation state or a "disturbed orientation state") in the absence of the contact material (B), When heated, it is believed that the original alignment (orientation) state is restored since no interaction with the contact material (B) occurs.

Therefore, the presence of the contact material (B) is not merely for rapidly cooling the surface of the recording medium (A) after heating, but also 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-substituted 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 The reason why it is desirable that 4 or more is considered to be due to the number necessary for the alkyl groups to be aligned (orientated) to a certain extent on the surface of the recording medium (A) and to cause active molecular movement during heating. In addition, contact material (B)
It is also conceivable that when the contact material (B) is heated together with the surface of the recording medium (A), the molecules of the contact material (B) are incorporated into molecules on the surface of the recording medium (A). Furthermore, when highly electronegative fluorine or chlorine is present in the alkyl group, the interaction with liquids, particularly polar liquids, increases, resulting in a greater change in adhesion than with compounds containing only hydrogen alkyl groups. In addition, fluorine-containing alkyl groups have a strong self-aggregation property, so they have a high surface self-orientation function, and furthermore, because they have a low surface energy, they are excellent in preventing soiling of the skin.

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 present inventors have found that it is 50 dyn/cm or less. It has also been confirmed that this is a desirable recording method. 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 smudged.

Here, the compound forming the surface of the recording medium (A) (when the surface of the recording medium (A) is brought into contact with the contact material (B) in a selectively heated state, the surface of the recording medium (A) The details of the compound (which forms a latent image area exhibiting a receding contact angle depending on the heating temperature) will be described below. First, Figures 1(a) and (d)
Conceivable types include compounds having an alkyl group (including fluorine-substituted and/or chlorine-substituted ones) in the vinyl polymer side chain. Specifically, formula (I) (R: -H, -CH3, -C2H5, -CF3 or -C2
F5Rf: A group containing a C4 or higher alkyl group, a fluorine-substituted or chlorine-substituted alkyl group, or (-CF2-)p, (-CH2-)p or -Ph- in the molecular chain.
Examples include polymers in which the monomer is a hydrophobic group (P≧4) m: an integer of 1 or more.

Other polymers include formula (VIII
) (IX) and (X). R: -H, -CH3, -C2H5, -CF3 or -C2
F5Rf: A group containing a C4 or higher alkyl group, a fluorine-substituted or chlorine-substituted alkyl group, or (-CF2-)p, (-CH2-)p or -Ph- in the molecular chain.
hydrophobic group containing (P≧4) n: an integer of 10 or more

0037
] In more detail, Rf in these specific examples can be exemplified by the following (1) to (20).

Among these compounds, the following (
The use of materials XI) is preferred. [However, R1: hydrogen, -CxHy or -CxFy (
n=1 or an integer greater than or equal to 2, and y=2x+1. )R2
: (-CH2-)p (p≧1 integer) or (-CH2-)
q-N(R3)SO2-(R3 is -CH3 or -C2H
5, an integer of q≧1) m: an integer of 6 or more. ]

Therefore, the most preferable specific compound for the surface member of the recording medium (A) in the present invention is CH2=C
(CH3) | COO-(CH2)4-HCH2=C(C
H3) |COO-(CH2)5-HCH2=CH|CO
O-(CH2)2-(CF2)6-ClCH2=CH|
COO-(CH2)2-(CF2)8-FCH2=CH
|COO-(CH2)2-(CF2)6-FCH2=C
(CH3)｜COO-(CH2)2-(CF2)8-F
CH2=C(CH3) | COO-(CH2)2-(CF
2) 6-FCH2=CH|COO-(CH2)2-N-
SO2-(CF2)8-F｜C2H5 CH
2=CH｜COO-(CH2)2-(CF2)9-FC
H2=C(CH3) | COO-(CH2)2-(CF2
)10-FCH2=CH｜COO-CH2CF2CHF
CF3 CH2=C(CH3) | COO-(
Examples include CH2)2-(CF2)9-F.

Furthermore, these formulas (I) (II) (III
In addition to (IV) (V) (VI) (VII) and (XI) monomers (copolymers of two or more monomers),
Other monomers such as ethylene, vinyl chloride, styrene,
Copolymers with butadiene, isoprene, chloroprene, vinyl alkyl ethers, vinyl acetate, vinyl alcohol, etc. are also suitable as the above compounds.

Furthermore, a polymerizable monomer having a monomer of formula (XI) and a functional group, such as CH2=C(CH3)COO(CH2)2OHCH2=
C(CH3)COOCH2CH(OH)CH3
CH2=CHCOOCH2CH(OH)C8F17
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 of a monomer of formula Cross-linkable polymers produced by cross-linking copolymers containing a large number of 1 and 2 with a cross-linking reagent are also excellent materials.

Examples of crosslinking reagents include formaldehyde, dialdehyde, N-methylol compounds, dicarboxylic acids, dicarboxylic acid chlorides, bishalogen compounds, bisepoxides, bisaziridine, and diisocyanates.

An example of the crosslinked polymer thus obtained is shown in the following chemical formula 1.

[Chemical formula 1]

In the crosslinked polymer represented by formula 1, A
The 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). To obtain a crosslinked membrane,
A solution containing the above copolymer and a crosslinking reagent may be applied as a coating liquid onto a substrate, and a crosslinked polymer film may be obtained by heating, electron beam irradiation, or light irradiation.

[0045] In order to obtain a polymer from the above monomer, an appropriate method may be used depending on the material, such as solution polymerization, electrolytic polymerization, emulsion polymerization, photopolymerization, radiation polymerization, plasma polymerization, graft polymerization, plasma initiated polymerization, or vapor deposition polymerization. selected.

Next, the compound shown in FIG. 1(b) will be described. Here, formulas (XII), (XII) and (X
IV) Material Rf-COOH
...(XII) Rf-OH
...(XII
I) Rf-(CH2)n-SiX
... (XIV) (Rf: a group containing an alkyl group having 4 or more carbon atoms or a fluorine-substituted or chlorine-substituted alkyl group,
Or, (-CF2-)p, (-CH2-
) A hydrophobic group containing p or -Ph- (P≧4) n: an integer of 1 or more Materials that are physically adsorbed or chemically bonded to the surface of organic materials such as (with a surface energy of about 50
(preferably less than dyn/cm).

Formula (XII) (XIII) and (XIV)
Specific examples include CF3-(CF2)5-COOH, CF3-(CF2)7-COOH, CF3-(CF2)7-(CH2)2OH, H-(CF
2) 10-COOH, H-(CF2)10-CH2OH, F-(CF2)6-CH2CH2-Si(CH3)2C
l, CF2Cl(CF3)CF(CF2)5COOH,
Examples include CF3(CF2)7(CH2)2SiCl3.

The compound shown in FIG. 1(c) has the formula (XI
I), a structure made only of the material of formula (XIII) or formula (XIV).

[0049] Next, a recording medium (A) using the above compound
Let's talk about. The recording medium (A) has a structure in which the above-mentioned surface member is formed on a support (preferably one having a heat-resistant temperature of 50 to 300° C.). Therefore, the recording body (A
) may be cylindrical or endless belt-like. In the apparatus of the present invention, the recording medium (A)
Forming a mixture of the surface-forming material and other members such as a hydrophobic polymer or a hydrophobic inorganic material on a support is excellent in preventing background smearing during printing. Further, in order to increase thermal conductivity, metal powder may be mixed into the above compound. Furthermore, a primer layer may be provided between the support and the compound in order to improve the adhesion between the support and the compound. As the heat-resistant support, resin films such as polyimide and polyester, glass, Ni, Al,
Metals such as Cu, Cr, and Pt, metal oxides, and the like 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 θr 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 θr starts 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, the liquid that is one of the contact materials (B) includes aqueous solutions containing electrolytes, alcohols such as ethanol and n-butanol, glycerin,
Polar liquids such as polyhydric alcohols such as ethylene glycol, ketones such as methyl ethyl ketone, linear hydrocarbons such as n-nonane and n-octane, cyclic hydrocarbons such as cyclohexane, m-xylene, benzene, etc. Examples include nonpolar liquids such as aromatic hydrocarbons. Moreover, a mixture of these may be used, or even a polar liquid may be used.

In addition to water vapor, any liquid vapor of the contact material (B) can be used as another type of vapor for the contact material (B). In particular, organic vapors such as ethanol vapor and m-xylene vapor can be used. Examples include vapors of the compound (including those in atomized form). The temperature of this organic compound vapor is recorded on the recording medium (A).
The temperature must be below the melting point or softening point of the compound forming the surface.

[0053] Other solids as the contact material (B) include higher fatty acids, low molecular weight polyethylene, polymer gels (polyacrylamide gel, polyvinyl alcohol gel), silica gel, and compounds containing crystal water. can give.

As will become clearer from what will be described later, when a "recording agent containing a color developer" such as the liquid ink described above is used as the contact material (B), the latent image is formed and developed at the same time. Imaging will take place.

Next, the heating means for forming a visible image will be explained. In addition to contact heating using heaters, thermal heads, etc., there are non-contact heating methods using electromagnetic waves (light beams from a light emitting source such as a laser light source or an infrared lamp are focused by a lens) as heating means in response to an image signal.

In FIG. 2(a), a film 2 of the compound constituting the surface of the recording medium (A) is formed on the support 1, and a liquid 3 of the contact material (B), for example, is present on this film surface. It shows the state in which In this state, when the film 2 is heated, the receding contact angle θr of the surface of the film 2 decreases, exhibits significant wetting, and is observed to have liquid adhesion. Furthermore, when the film 2 with liquid adhesion is heated again in air, vacuum, or an inert gas atmosphere (FIG. 2(b)), the film 2
It is observed that the receding contact angle θr increases and the surface again exhibits liquid repellency.

There is a method described in Japanese Patent Publication No. 41902/1984 mentioned above that exhibits a phenomenon somewhat similar to this phenomenon. However, the method disclosed herein differs mechanically in that it provides a recording material with a layer of memory material that is substantially sequential 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). Furthermore, with the method described in Japanese Patent Publication No. 54-41902, reversibility cannot be obtained with a simple operation.

As shown in FIG. 3(a), heat is applied to the membrane 2 in contact with the liquid 3 according to the image information (FIG. 3(b-1)(b)
-2), the same effect can be obtained when the surface of the heated part of the membrane 2 is brought into contact with the liquid in the state in which heat is applied to the membrane 2 according to the image information in the absence of liquid. 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.

While FIG. 3(a) shows an example in which the membrane 2 is heated through the support 1, the example shown in FIG. 3(b-1) is an example in which the membrane 2 is heated directly. be.

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 film is further heated in air. In FIG. 4, ◯ represents the advancing contact angle, and △ represents the receding contact angle.

Generally, when the receding contact angle is a high value of 90° or more, the surface exhibits liquid repellency, and when the receding contact angle is low, such as 90° or less, the surface exhibits liquid adhesion.

The heating temperature on the surface of the recording medium (A) in contact with the contact material (B) for latent image formation is preferably in the range of 50°C to 250°C, more preferably 80°C to 150°C. It is ℃. The heating time is about 0.1 msec to 1 second, preferably 0.5 msec to 2 msec. The heating timing is as follows: After heating the surface of the recording medium (A), bring it into contact with the contact material (B) before it cools down;
(2) The surface of the recording body (A) may be heated while the contact material (B) is in contact with the surface of the recording body (A).

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 medium (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 medium (A), and then to remove this latent image. The recording agent is attached to the latent image area by means of bringing the recording agent into contact with the image area (
development), and then transfer the recording agent on the surface of the recording body (A) to recording paper (indirect recording method). Furthermore, in this method, if the recording agent is brought 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. In the above method, after the recording material is transferred to the recording paper, the surface of the recording material (A) on which the latent image has been formed is heated in the absence of liquid or vapor to erase the latent image, thereby forming a recording material ( A) is a reproducible recording method. FIGS. 5A and 5B show typical processes of an indirect recording method (printing method) and a reversible recording method of a recording medium (repetitive recording method).

To erase the latent image, move the heating roller to the recording medium (A) such that the surface temperature of the recording medium (A) is 50 to 300°C, preferably 100 to 180°C in the absence of the contact member (B).
) in contact with the front or back surface of the The heating time is about 1 msec to 10 seconds, preferably 10 msec to 1 second. That is, in the method of the present invention, a means of contact heating of the recording medium (A) is employed for heating for image removal.

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 whose receding contact angle decreases when brought into contact with a liquid in a heated state (hereinafter also referred to as "film 2" or "recording body (A)" for convenience).
) surface) on the support.

When resin is used as the support for the recording medium (A), it cannot be said that it is a good conductor of heat;
It takes some time for the surface to heat up and become liquid adhesive. Therefore, it may be considered to use a good thermal conductor over the entire support body or on a portion on the support body 1.

In FIG. 6(a), a good thermal conductor such as metal is used as a support (metal substrate 11), and an organic thin film 1 is placed on it.
By vapor depositing 2 and then forming film 2 on top of that, the heat conduction rate 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 print dots are relatively large, but it is not suitable when the objective is higher density printing because the portion with liquid adhesion expands due to heat diffusion in both directions. For this reason, FIG. 6(b) shows an attempt to miniaturize the portion 2a having liquid adhesion by dividing and providing a good thermal conductor portion on the support 1 to prevent heat diffusion in the surface direction. Figure 6(b)
In the figure, 11a represents a minute metal film.

[0068] Subsequently, a latent image forming means by heating, and further,
The 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.

7 and 8 schematically show two typical examples of the apparatus of the present invention. /In the figure, 7 is a recording body (A), 8 is a heating roller, 81 is an infrared lamp housed inside the heating roller, and 3a is a colored ink (recording agent)
, 3a' is attached ink, 42 is a thermal head, S is a latent image, 9 is a sponge roller, 10 is a rotating roller, 11 is a transfer roller, and P is a recording paper. In these examples, if the heating roller 8 is brought into contact with the recording medium 7 in the absence of the recording agent 3a and the attached ink 3a' each time the recording medium 7 rotates once, and the surface thereof is heated, The latent image (S) is reliably erased, and therefore a new transferred image can be obtained each time the recording body 7 rotates.

However, non-contact heating by irradiating electromagnetic waves (laser light, infrared light) or heating with a thermal head is conceivable as heating for image removal. However, with these methods, the heating temperature of the surface of the recording medium (A) tends to be higher than necessary, and also because the contact area of the thermal head with the recording medium (A) is small. It is undeniable that the surface pressure increases and the recording medium (A) wears out, leaving some problems in durability.

The apparatus shown in FIGS. 7 and 8 also has a recording medium (A
) is used in the form of an endless belt, but as mentioned above, it is not limited to this.

In the apparatus shown in FIG. 7, the heating roller 8 is attached to the recording medium (A
) The surface is directly heated, and in the apparatus shown in FIG. 8, the heating roller 8 heats the surface (film 2) through the support of the recording medium (A). If the heating roller 8 is made of a material that transmits infrared rays, such as glass or hard transparent resin, the recording medium 7 can be efficiently heated by the heating caused by the contact of the heating roller 8 and the radiant heat transfer of the infrared rays.

FIG. 9 shows a heating roller that is somewhat different from the above, in which an infrared lamp 81 is surrounded by a substance (non-metallic substance) 82 having a high absorption rate in the infrared light region, and a black substance such as carbon black. Furthermore, if the roller surface is formed of a material 83 with high thermal conductivity (Cu, Ag, Au, Al, etc.), the heat of the heating roller can be efficiently conducted to the recording medium 7.

FIG. 10 shows that the temperature of the surface of the heating roller 8 for image removal (erasing the latent image (S)) is detected by a thermometer 84.
This is an embodiment in which feedback is provided to the power source 85 of the infrared lamp 81. When the temperature of the surface of heating roller 8 is too high,
Turn off the power source 85 of the infrared lamp 81, or
By lowering the voltage, the temperature of the heating roller 8 can be lowered. When the temperature of the surface of the heating roller 8 becomes low, the temperature of the heating roller 8 can be raised by turning on the infrared lamp 81 if it is off, or by increasing the voltage. In this way, the temperature of the surface of the heating roller 8 can always be maintained at a temperature suitable for image removal of the recording medium 7, and image removal can be performed reliably, and at the same time, the recording medium 7 can be prevented from being excessively heated. It can also be prevented. Note that the surface temperature of the heating roller 8 is determined by measuring the temperature of the recording medium 7 and adjusting the above-mentioned OFF and ON settings based on the temperature of the recording medium 7.
etc. may be done.

FIG. 11 shows an example in which reflective plates 86 are arranged around these heating rollers 8. By providing the reflective plate 86, wasteful radiation of heat from the heating roller 8 can be prevented, thermal efficiency can be increased, and the temperature inside the recording apparatus can be reduced.

In addition to these heating means for image removal, as shown in FIGS. 12(a) and 12(b), in addition to the roller 8', an infrared lamp 81, a roller type heater 87, etc. may be used. A source can also be provided. These have the advantage of simple structure.

The larger the diameter of the heating roller 8 (the same applies to the roller 8'), the larger the contact area with the recording medium 7;
Further, even if the tangential force acting on the contact surface between the heating roller 8 and the recording medium 7 is the same when the radius is small and large, the moment for rotating the heating roller 8 increases by the radius, which is advantageous. Therefore, it is desirable that the diameter of the heating roller 8 is large.

Furthermore, by reducing the force with which the heating roller 8 presses against the recording medium 7 as much as possible and increasing their contact area, the contact pressure per unit area can be reduced, thereby reducing wear on the recording medium 7. I can do it. Furthermore, the wear of the recording medium 7 can be reduced if the surface roughness of the heating roller 8 is as small as possible.

If there is a difference in circumferential speed between the heating roller 8 and the recording medium 7, it is conceivable that surface slippage will occur due to contact and the recording medium 7 will be worn out. For this reason, as shown in FIG. 13(a), if the end surface of the heating roller 8 is made of metal 8a and the portion of the recording medium 7 in contact with the metal surface is made of, for example, rubber 7a, both Since the degree of friction between the heating roller 8 and the recording medium 7 is large, there is no or very little slippage between the heating roller 8 and the recording medium 7. In FIG. 13(a), 88 is a bearing. FIG. 13(b) shows an example in which the circumferential speeds of the heating roller 8 and the recording medium 7 are matched by a belt 89. FIG. 13(c) shows the belt 8 shown in FIG. 13(b).
This is an example in which 9 is replaced with a gear 89'.

Note that if the circumferential speed of the heating roller 8 is faster than the circumferential speed of the recording medium 7, tensile stress will be generated in the recording medium 7, and as described above, the recording medium 7 will be easily worn out. Therefore, it is desirable that the circumferential speed of the heating roller 8 be equal to or slightly less than the circumferential speed of the recording medium.

The erasing of the latent image is as described above, but considering that the latent image is formed on the recording medium (A) again, the recording medium (A) heated by the latent image erasing operation
It is necessary to provide the latent image erasing means at a location where the latent image erasing means is substantially cooled while being moved to the point where it is heated to form the latent image. In addition, the heating temperature required for erasing is
Although it varies depending on the material, a temperature above the starting temperature at which the receding contact angle of the film 2 becomes low and below the decomposition point is desirable.

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

Next, the recording material 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, a recording agent used in a conventional print recording method such as writing ink, inkjet ink, printing ink, or electrophotographic toner is used. Among the recording materials that have been available, one that is compatible with the above process can be selected and used.

To give a more specific example, the water-based ink may be a water-soluble ink containing mainly water, a wetting agent, and a dye, or an aqueous pigment containing mainly water, a pigment, a dispersing polymer compound, and a wetting agent. Dispersion inks, emulsion inks in which pigments or dyes are dispersed in water using a surfactant, 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, and propanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, and 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 monoethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monoethyl ether, etc. ethers of polyhydric alcohols; N-methyl-2-
Pyrrolidone, 1,3-dimethylimidazolidinone, ε-
Heterocyclic compounds such as caprolactam; amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine, etc.

As water-soluble dyes, dyes classified as acid dyes, direct dyes, basic dyes, and reactive dyes in the color index are used. Examples of typical dyes include C. I. acid yellow 17, 23, 42, 44,
79,142C. I. 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, 289C
．． I. acid blue 9, 29, 45, 92, 249
, 890C. I. acid black 1, 2, 7, 24
, 26, 94C. I. Food Yellow 3,4 C. I. Food Red 7, 9, 14 C. I. Hood Black 2 C. I. Direct Yellow 1, 12, 24, 26,
33,44,50,142,144,865 C. I. Direct Red 1, 4, 9, 13, 17,
20, 28, 31, 39, 80, 81, 83, 89, 2
25,227 C. I. Direct Orange 26, 29, 62, 10
2C. I. Direct Blue 1, 2, 6, 15, 22
,25,71,76,79,86,87,90,98,
163, 165, 202C. I. Direct black 19, 22, 32, 38, 51, 56, 71, 74, 7
5,77,154,168C. I. Basic yellow 1, 2, 11, 13, 1
4, 15, 19, 21, 23, 24, 25, 28, 29
,32,36,40,41,45,49,51,53,
63, 65, 67, 70, 73, 77, 87, 91 C. I. 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. I. 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,
129, 137, 141, 147, 155 basic
Black 2, 8, etc. can be mentioned.

Pigments include organic pigments such as azo-based, phthalocyanine-based, anthraquinone-based, quinacridone-based,
Dioxazine type, indigo type, thioindigo type, perinone type, perylene type, isoindorenone type, aniline black, azomethine azo type, carbon black, etc., and inorganic pigments include iron oxide, titanium oxide, calcium carbonate, barium sulfate, Aluminum hydroxide, barium yellow, dark 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. Maleic acid resin, polyvinylpyrrolidone, polyvinyl alcohol, alkali metal salts of β-naphthalenesulfonic acid formalin condensates, high molecular compounds containing salts of cationic functional groups such as quaternary ammonium and amino groups, polyethylene oxide, gelatin,
Proteins such as 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, natural polymer compounds such as ceramics,
etc.

Similar to water-based inks, oil-based recording agents include those in which an oil-soluble dye is dissolved in an organic liquid compound, those in which a pigment is dispersed in an organic liquid compound, and those in which a pigment or dye is emulsified in an oil-based base. Things, etc. are used.

Typical examples of oil-based dyes include C.I. I.
Solvent Yellow 1, 2, 3, 4, 5, 6, 7, 8
,9,10,11,12,14,16,17,26,2
7, 29, 30, 39, 40, 46, 49, 50, 51
, 56, 61, 80, 86, 87, 89, 96 C. I. Solvent Orange 12, 23, 31, 43
, 51, 61C. I. Solvent Red 1, 2, 3,
16, 17, 18, 19, 20, 22, 24, 25, 2
6, 40, 52, 59, 60, 63, 67, 68, 12
1C. I. Solvent violet 7, 16, 17C
．． I. Solvent Blue 2, 6, 11, 15, 20,
30, 31, 32, 35, 36, 55, 58, 71, 7
2 C. I. Solvent Brown 2, 10, 15, 21,
22C. I. Solvent Black 3, 10, 11, 1
2, 13, etc. are mentioned.

Oil bases for dissolving dyes and dispersing pigments include hydrocarbons such as n-octane, n-decane, mineral spirit, ligroin, naphtha, benzene, toluene, and xylene; Butyl ether, dihexyl ether, anisole, phenethole,
Examples include ethers such as dibenzyl ether; alcohols such as methanol, ethanol, isopropyl alcohol, benzyl alcohol, ethylene glycol, diethylene glycol, and glycerin.

The pigments exemplified above can also be used in oil-based inks. Examples of oil-based pigment dispersants include:
polymethacrylic acid ester, polyacrylic acid ester,
methacrylic ester-acrylic ester copolymer,
Vinyl copolymers such as polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinylpyrrolidone, polyvinyl butyral,
Examples include cellulose resins such as ethyl cellulose and methyl cellulose, polycondensation resins such as polyester, polyamide, and phenol resins, and natural resins such as rosin, ceramics, gelatin, and casein.

[0093]

The recording apparatus of the present invention provides the following effects. (1) Image removal (latent image erasure) is performed by bringing a heated rotatable roller into contact with the recording medium (A). )
Image quality is improved because excessive heating is prevented. Furthermore, since the wear of the recording medium (A) is reduced, the durability of the recording medium (A) is improved. (2) By arranging a material with high absorption rate inside the roller for image removal, the roller can efficiently absorb the radiant heat from the infrared lamp, resulting in very high efficiency. (3) By arranging a material with high thermal conductivity on the outer surface of the heating roller, the heat of the heating roller can be efficiently transferred to the recording medium.
(A) It is possible to conduct heat to , resulting in very high efficiency. (4) A means for detecting the temperature of the outer surface of the heating roller for image removal or the temperature of the recording medium, and a means for feeding back the intensity of heating of the heating source inside the roller based on the detected temperature. The surface temperature of the heating roller can be maintained at a temperature suitable for image removal of the recording medium (A),
Image removal can be performed more reliably, and at the same time, the recording medium (A) is not heated excessively, so that the image quality is improved and the durability of the recording medium (A) is also improved.

[Brief explanation of the drawing]

FIG. 1 is a diagram of four typical examples of forms having a surface self-alignment function.

FIG. 2 is a diagram for basically explaining the device of the present invention.

FIG. 3 is a diagram for basically explaining the device of the present invention.

FIG. 4: 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 of the recording medium (A). A diagram showing changes in θr.

FIG. 5 is a diagram showing two embodiments when the device of the present invention is used.

FIG. 6 is a diagram showing how the device of the present invention is implemented.

FIG. 7 is a diagram showing how the device of the present invention is implemented.

FIG. 8 is a diagram showing how the device of the present invention is implemented.

FIG. 9 is a diagram showing how the device of the present invention is implemented.

FIG. 10 is a diagram showing how the device of the present invention is implemented.

FIG. 11 is a diagram showing how the device of the present invention is implemented.

FIG. 12 is a diagram showing how the device of the present invention is implemented.

FIG. 13 is a diagram showing how the device of the present invention is implemented.

[Explanation of symbols]

1...Substrate 2...Membrane 3...Liquid (3a...colored ink) 4...Heater 5...Lens 6...Shutter 7... Recording body (A) 8, 8’…Heating roller 9...Sponge roller 41...Infrared lamp 42...Thermal head

Claims (6)

[Claims] Claim 1: By selectively heating the surface of the recording medium (A) described below while in contact with the contact material (B) described below, or by contacting the surface of the recording medium (A) with the surface of the recording medium (A) selectively heated. means for supplying a contact material (B) to the surface of the recording medium (A), which forms a latent image area exhibiting a receding contact angle in accordance with the heating temperature on the surface of the recording medium (A) by contacting with the material (B); , a means for heating the surface of the recording medium (A) in accordance with an image signal, a recording agent applying means for visualizing the latent image area, and a means for applying the recording agent attached to the surface of the recording medium (A) to the recording paper. It is characterized by being provided with means for transferring, and means for contact heating the surface of the recording medium (A) with a heated rotatable roller in the absence of the contact material (B) and the recording agent to erase the latent image. recording device. (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 starts to decrease in the recording medium (A). 2. The recording apparatus according to claim 1, wherein liquid ink is used as the contact material (B), and the supply means and the recording agent applying means are integrated into one. 3. The recording apparatus according to claim 1, wherein the latent image erasing heating roller has an infrared lamp as a heating source built in a transparent cylindrical body. 4. The latent image erasing heating roller includes an infrared lamp serving as a heating source and a substance having a high absorption rate in the infrared region surrounding the infrared lamp. recording device. 5. The recording apparatus according to claim 1, wherein the latent image erasing heating roller has an outer peripheral surface made of a material with high thermal conductivity. 6. Means for detecting the temperature of the outer surface of the heating roller for latent image erasing or the surface temperature of the recording medium (A), and a heating source inside the heating roller for latent image erasing according to the detected temperature. 3. The recording apparatus according to claim 1, further comprising means for feeding back the intensity of heating.