JP3066603B2 - Recording device - Google Patents

Description

The present invention relates to a novel recording device, and more specifically, selectively or selectively and reversibly attaches to a surface of a recording medium having a specific surface. The present invention relates to a recording apparatus in which a region having a receding contact angle corresponding to a heating temperature is formed, and a recording material containing a color material is supplied to this region to visualize the image.

[Conventional technology]

A typical example of a means 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 (fountain solution). Can be However, in 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 apparatus, and it is difficult to reduce the size of the plate making apparatus. ing.

For example, even in a relatively small office offset plate making press, the plate making device and the printing device are usually separate.

In order to eliminate such a defect of the offset printing method, a liquid-adhesive area and a non-liquid-adhesive area corresponding to image information can be formed, and recording that can be used repeatedly (has reversibility). Methods and devices have been proposed. Some of them are as follows.

(1) Aqueous development method After applying a charge to the hydrophobic photoconductor layer from the outside, it is exposed to light to form a pattern having a hydrophobic portion and a hydrophilic portion on the surface of the photoconductor layer. Transfer to paper etc. by attaching aqueous developer (Japanese Patent Publication No. 40-18992, Japanese Patent Publication No. 40-1)
Nos. 8993, JP-B-44-9512, and JP-A-63-264392).

(2) Method using photochemical reaction of photochromic material A layer containing a material such as spiropyran or an azo dye is irradiated with ultraviolet rays, and the photochromic compound is hydrophilized by the photochemical reaction [for example, "Polymer Papers" No. 37.
Vol. 4, p. 287 (1980)].

(3) Method using the action of internal biasing force An amorphous state and a crystalline state are formed by a physical change to constitute a liquid ink adhesion / non-adhesion area (Japanese Patent Publication No.
No. 54-41902).

According to the method (1), after the aqueous ink is transferred to paper or the like, the hydrophilic portion is erased by static elimination, and another image information can be recorded. That is, one master (photoconductor)
Can be used repeatedly. However, since this method is based on an electrophotographic process, it requires a long process of charging → exposure → development → transfer → discharge, and has a disadvantage that it is difficult to reduce the size, cost, and maintenance of the device.

According to the method (2), hydrophilicity and hydrophobicity can be freely and reversibly controlled by selectively changing the irradiation of ultraviolet light and visible light, but the reaction time is extremely long due to poor quantum efficiency. However, the recording speed is slow and the stability is lacking, so that it has not yet reached the practical level.

Furthermore, according to the method (3), the information recording member used there is stable after recording, but may have a physical structure change due to temperature change before recording. Problems remain in storage stability. In addition to this, a means of applying a heat pulse to the erasing of the recorded information pattern and then quenching is adopted,
Repetitive image formation has the disadvantage that complexity cannot be imitated.

[Problems to be solved by the invention]

An object of the present invention is to selectively or selectively apply a simple means to a surface of a member (recording body (A)) having a surface in which a receding contact angle is reduced when the member is heated and brought into contact with a liquid. It is an object of the present invention to provide a device capable of reversibly forming a desired pattern area.

Another object of the present invention is to provide a good visible image from the beginning by supplying a recording agent (for example, liquid ink) containing a color developing material to the pattern area, and transferring this visible image to plain paper or the like and fixing it. Thus, an apparatus capable of obtaining a clear image with gradation is provided.

Still another object of the present invention is to form a desired pattern region.
A novel recording apparatus capable of performing the above-described steps reversibly a plurality of times by using a recording medium (A) having excellent storage stability and stability in all steps such as erasing, visualizing, and transferring. Is what you do.

Still another object of the present invention is to provide an apparatus in which a good quality recorded matter can be obtained even on a large number of copies by maintaining the surface of the recorded material (A) always in a good state. is there.

[Means for solving the problem]

The apparatus of the present invention selectively heats the surface of the recording body (A) below in contact with the contact material (B) below or contacts the surface of the recording body (A) while heating the surface selectively. Means for supplying a contact material (B) to the surface of the recording medium (A), which forms a latent image area having a receding contact angle corresponding to the heating temperature on the surface of the recording medium (A) by being brought into contact with the material (B); Means for heating the surface of the recording medium (A) for forming a latent image, recording medium applying means for applying a recording medium containing a color developer to the latent image area to visualize the image, and recording medium (A) Means for transferring the recording agent attached to the surface to recording paper, and cleaning means for cleaning the surface of the recording medium (A), and liquid or vapor or heating after transfer to the recording paper. The latent image is formed by heating in the absence of liquid solids. Characterized in that a means for removed by.

(A) A recording medium having a surface in which the receding contact angle is reduced when heated and brought into contact with a liquid.

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

The recording apparatus can form images reversibly.

The present inventors have solved many defects as described in the prior art, and have conducted many studies and studies on a new recording method. As a result, a member having a function of reducing the receding contact angle after cooling by being heated in contact with the liquid and cooling, and increasing the receding contact angle by heating in the absence of the liquid is useful as a recording medium. Was found. The recording medium (A) having such a function is a member whose surface includes (1) an organic compound having a surface self-orientation function of a hydrophobic group,
Or (2) it was also confirmed that the member was an organic compound having a hydrophobic group and the hydrophobic group was 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 a certain compound itself is heated in air, the hydrophobic group on the surface is shifted to the air side (free surface side). It means that it has the property of being oriented toward. This can be similarly applied to (2). Generally, in an organic compound, a hydrophobic group tends to be directed toward a hydrophobic atmosphere. This is a phenomenon that occurs because the surface energy of the solid-gas interface decreases. This phenomenon is more likely to occur as the molecular length of the hydrophobic group becomes longer, because the longer the molecular length, the higher the mobility of the molecules during heating.

More specifically, if the molecule has a hydrophobic group at the end (that is, lowers the surface energy), the surface is easily oriented toward the air side (free surface side). Similarly, in a linear molecule containing CH ₂ , the CH ₂ CH ₂ portion has a planar structure, and the molecular chains are easily oriented. Also, Molecules containing Has a planar structure, and the molecular chains are easily oriented. In particular, a linear molecule containing an element having a high electronegativity such as fluorine has a high self-aggregation property, and the molecular chains are easily oriented.

Summarizing the results of these studies, it is more preferable to include a molecule having a high self-aggregating property or a molecule having a planar structure, and a linear molecule having a hydrophobic group at a terminal, or
Compounds containing such linear molecules can be said to be compounds having a high surface self-orientation function.

As is clear from the above description, there is a relationship between the surface self-alignment state and the receding contact angle, and also between the receding contact angle and the liquid adhesion. That is, the adhesion of the liquid on the solid surface occurs mainly by tacking of the liquid on the solid surface. This tacking can be considered as a kind of frictional force when a liquid slides on a solid surface. Therefore,
The “receding contact angle” θr referred to in the present invention is the friction force γ _f
Then (However, γ: Surface tension of solid in vacuum γs _l : Solid-liquid interfacial tension γ _lV : Surface tension when liquid is in contact with its saturated vapor πe: Equilibrium surface tension γ _f : Friction tension γs: Adsorption layer (It is the surface tension of solids without solids) (Saito, Kitazaki et al., "Journal of the Adhesion Society of Japan" Vo
l.22, No.12, 1986).

Thus, gamma _f value when the value of θr decreases increases. That is, the liquid is less likely to slide on the solid surface, and as a result, the liquid adheres to the solid surface.

As can be guessed from these mutual relations, the liquid adhesion depends on the receding contact angle θr, and the receding contact angle θr is determined by a member having a surface self-orienting function on the surface. Therefore, in the method of the present invention, the recording medium (A) is inevitably required to form a desired pattern area on its surface and / or visualize with a recording agent.
A member having a surface self-orienting function on the surface must be selected.

As described above, the recording medium (A) used in the method of the present invention has a “surface where the receding contact angle θr decreases when it is in a heated state and is in contact with a liquid”.

The shape of the recording medium (A) is arbitrary as long as the surface has the above properties. Therefore, the recording medium (A) may be in the form of a film, or may be provided with another coating film having the above-mentioned properties on a suitable support or molded body. The molded body itself may be used, but its surface must have the above properties.

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

Here, FIG. 1 shows an example in which members or materials that form a surface that forms a surface where the receding contact angle θr decreases when it is brought into contact with a liquid in a heated state are classified into several members. Fig. 1 (a)
Is an example of a compound having a self-orienting function, which is a compound having a hydrophobic group in a side chain of a high molecular polymer, and has a main chain L and a hydrophobic group R
And are bonded by a bonding group J.

FIG. 1 (b) is an example of an organic compound having a hydrophobic group in which the hydrophobic group is oriented on the surface. The organic compound having the hydrophobic group is physically or chemically bonded to the surface of an organic or inorganic material M. This is a member on which compound O is formed.

FIG. 1 (c) is an example of a member made of only 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 present in a side chain of a polymer. The self-aggregating or planar structure having a hydrophobic group R at the terminal, in which the main chain L and the molecule are connected by a bonding group J, is shown. A compound having 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 have a linear shape or a hatched structure. In the example of FIG. 1B, 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 (L)
, Or without the organic / inorganic material (M).

As the hydrophobic group, the terminal of the molecule is preferably -CH
₃ and _{-CF 3, -CF 2 H, -CFH} 2, -C (CF 3) 3, -C (C
H ₃ ) _{3 and the} like, and more preferably those having a long molecular length in terms of high molecular mobility. Among them, as the hydrophobic group, a substituted alkyl group having at least one -F and / or -Cl ( Or an unsubstituted alkyl group having 4 or more carbon atoms. Any of fluorine substitution and chlorine substitution can be used, but fluorine substitution is 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 method is reduced.

Although the principle of this function expression has not yet been completely elucidated, and thus there are many unclear points, the following are presumed.

First, it is considered that the surface of the recording medium (A) formed by 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 motion of the hydrophobic group due to the heating becomes active, and the interaction with the contact material (B) occurs. The orientation (alignment) state of at least a part of the surface of the recording medium (A) is different (that is, another orientation state or a state in which the orientation is disordered).
Instead, it seems to maintain that other state after cooling. It should be noted that heating under the condition that the contact material (B) is in contact with the surface of the recording material (A) depends on whether the surface of the recording material (A) is heated depending on the form of the contact material (B). The liquid comes into contact under the pressure.

Before this heating, the surface energy of the surface of the recording medium (A) is extremely small because the hydrophobic groups are aligned (oriented) on the surface.

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

Further, the surface of the recording medium (A) is heated in another state ("another alignment state" or "a state in which the alignment is disturbed" different from the original alignment state) in the absence of the contact material (B). When,
Since no interaction occurs with the contact material (B), it is considered that the state returns to the original alignment (orientation) state.

Therefore, the presence of the contact material (B) is merely a record (A)
This is not for quenching after heating the surface of the recording medium (A), but for causing some interaction with the compound on the surface of the recording medium (A). State or a state where the orientation is disturbed).

As described above, when an alkyl group or a fluorine- or chlorine-substituted alkyl group is used as the hydrophobic group of the member (compound) forming the surface of the recording medium (A), the alkyl group has 4 or more carbon atoms. It is thought that it is desirable that the number is such that the alkyl groups are arranged (orientated) to some extent on the surface of the element or the recording medium (A), and that the molecules move actively during heating. When the contact material (B) is heated together with the surface of the recording medium (A), the molecules of the contact material (B) may be incorporated into the molecules on the surface of the recording medium (A). Furthermore, if there is fluorine or chlorine having a high electronegativity in the alkyl group, the interaction with a liquid, particularly a polar liquid, becomes large, so that a greater change in adhesion than a compound containing an alkyl group containing only hydrogen can be obtained. .
In addition, an alkyl group containing fluorine has a strong self-aggregating property, has a high surface self-orientation function, and has a low surface energy, and thus is excellent in preventing background contamination.

Furthermore, although the surface of the recording medium (A) has liquid repellency, if this is described in terms of the surface energy of a solid, according to the study of the present inventors, it is desirable that the recording medium be 50 dyn / cm or less. all right. If the value is higher than this, the surface of the recording medium (A) sometimes gets wet with respect to the recording material, which may cause soiling of the background.

Here, the details of the compound forming the surface of the recording medium (A) will be described. First, compounds having an alkyl group (including those substituted with fluorine and / or chlorine) on the side chain of the vinyl polymer can be considered for the types shown in FIGS. 1 (a) and 1 (d). Specifically, formulas (I), (II), (III), and (IV)
(V) (VI) and (VII) _{R: -H, -CH 3, -C} 2 H 5, -CF 3 or -C ₂ F ₅ Rf: C ₄ or higher alkyl group or a fluorine or chlorine-substituted alkyl group group containing, or, in the molecular chain CF _2
l , CH _{2 l} or A polymer having a hydrophobic group (l ≧ 4) having an integer n ′: 1 or more as a monomer.

Other polymers include those shown in formulas (VIII), (IX) and (X).

_{R: -H, -CH 3, -C} 2 H 5, -CF 3 or -C ₂ F ₅ Rf: C ₄ or higher alkyl group or a fluorine or a group containing a chlorine-substituted alkyl group, or, in the molecular chain CF _2
l , CH _{2 l} or A hydrophobic group containing (l ≧ 4) n: an integer of 10 or more In these specific examples, Rf from (1) to (20) below can be exemplified in more detail.

_{(1) -CH 2 CF 2 CHFCF} 3 _{(6) -CH 2 (CF 2} ) 10 H (7) CF 2 6 O-CF 2 CF 3 (8) CH 2 4 NH-CF 2 CF 3 (9) CF 2 6 CF 3 (10) CH 2) ₁₀ C ₈ F _{17 (13) -CH 2 NHSO 2 C} 8 F 17 (15) c · s-CH 2 CH 2 - (CF 3) 6 CF (CF 3) 2 (16) -CH 2 CF 2 CF 2 CF 3 (17) -CH 2 CH 2 CH 2 CH 2 F (18 ) among _{-CH 2 (CF 2) 6 CF} 3 (19) -CH 2 (CF 2) 5 CF 3 (20) CH 2) 3 CF 3 these compounds, in particular, the following materials (XI) [However, R ¹ : hydrogen, -C _n H _{2n + 1} or -C _n F _{2n + 1} (n = 1 or an integer of 2 or more) R ² : CH _{2 p} (an integer of p ≧ 1) or CH _{2 q} N
(R ³ ) SO ₂ — (R ³ is —CH ₃ or —C ₂ H ₅ , q is an integer of 1 or more) m: an integer of 6 or more. Therefore, the most preferred specific compound of the member on the surface of the recording medium (A) in the present invention is And the like.

Further, these formulas (I), (II), (III), (IV) and (V)
(VI) In addition to the monomers (VII) and (XI) (copolymers of two or more monomers), other monomers such as ethylene, vinyl chloride, styrene, butadiene, isoprene, chloroprene, vinyl alkyl ether, acetic acid Copolymers with vinyl, vinyl alcohol, and the like are also suitable as the above compounds.

Further, a monomer of the formula (XI) and a polymerizable monomer having a functional group, for example, CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂ OH CH ₂ ＣC (CH ₃ ) COOCH ₂ CH (OH) CH ₃ CH ₂ = CHCOOCH ₂ CH (OH) C ₈ F ₁₇ and other copolymers are made to introduce a large number of functional groups into the polymer, or a monomer of formula (XI) and a polymerizable monomer having a functional group A cross-linkable polymer produced by preparing a copolymer of the formula (1) and then cross-linking the copolymers containing a large number of functional groups with a cross-linking reagent is also an excellent material. Examples of the crosslinking reagent include formaldehyde, dialdehyde, N-methylol compound, dicarboxylic acid, dicarboxylic acid chloride, bishalogen compound, bisepoxide, bisaziridine, diisocyanate and the like. An example of the crosslinked polymer thus obtained is shown below.

In the above formula, the A block is an alkyl group that causes the change in the thermal properties described above, while the B block is a site where the linear polymers are cross-linked (cross-linked using diisocyanate as a cross-linking reagent). is there.

To obtain a crosslinked film, a solution obtained by mixing the copolymer and the crosslinking reagent is applied as a coating solution on a substrate,
The crosslinked polymer film may be obtained by heating, electron beam irradiation, or light irradiation.

In order to obtain a polymer from the above monomers, an appropriate method is selected 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. .

Next, the compound shown in FIG. 1 (b) will be described.
Here, the formula (XII), (XIII) and material R-COOH shown in (XIV) ... (XII) R -OH ... (XIII) RCH 2 n SiX ... (XIV) (R: Number 4 or more alkyl group having a carbon Or a group containing a fluorine or base-substituted alkyl group, or in the molecular chain
CF _{2 l,} CH _{2 l} or (N = 1 or more integer X: chlorine, methoxy group or ethoxy group) etc. on the surface of an inorganic material such as glass, gold, copper or the like, or an organic material such as polyimide, polyester or polyethylene terephthalate. It is desirable that the material be a physically adsorbed or chemically bonded material (preferably having a surface energy of about 50 dyn / cm or less).

Formula (XII) (XIII) and CF ₃ CF _{2 5} COOH Specific examples of _{(XIV), CF 3 CF 2} 7 COOH, CF 3 CF 2 7 (CH 2 2 OH, HCF 2 10 COOH, HCF 2 10 CH 2 _{OH, FCF 2 6 CH 2 CH} 2 -Si (CH 3) 2 Cl, CF 2 Cl (CF 3) CF (CF 2) 5 COOH, CF 3 (CF 2) 7 (CH 2) such as ₂ SiCl ₃ is mentioned Can be

The compounds shown in FIG. 1 (c) include the compounds represented by the formulas (XII) and (X)
III) and a structure composed of only the material of the formula (XIV).

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

The structure of the recording medium (A) is roughly classified into a structure formed by the surface member itself and a structure formed by forming the surface member on a support (preferably a heat-resistant support). In the embodiment, the compound (surface member) itself is formed into a film, a plate, or a column. At this time, in the case of a film, the thickness of the film is desirably 1 μm to 5 mm.

In the embodiment, the compound may penetrate into the support to some extent. The thickness of the recording body (A) itself is preferably 30 mm to 1 mm. However, in terms of thermal conductivity, 1
00Å to 10 μm, and 10 μm to 1 mm in terms of wear resistance. The heat-resistant temperature of the support is desirably 50 ° C to 300 ° C.

The shape of the support may be any of a belt shape, a plate shape, and a drum shape, and is selected according to the intended use of the device. In particular, the drum shape is excellent in that dimensional accuracy in the device can be obtained. The size of the plate may be determined according to the size of the recording paper.

Further, the above compound (material for forming the surface of the recording body (A))
When a mixture of the above and other members, for example, a hydrophobic polymer and a hydrophobic inorganic material, is formed on a support, it is excellent in preventing background smearing in printing. Further, in order to increase the thermal conductivity, it is preferable to mix a metal powder with the above compound. Further, a primer layer can 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, a resin film such as polyimide or polyester, glass, a metal such as Ni, Al, Cu, Cr, or Pt, or a metal oxide is preferable. These supports may be smooth, rough or porous.

The thickness of the coating film formed from the above compound (the material for forming the surface of the recording medium (A)) is 0.01 to 100 μm, preferably 1 to 10 μm.

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

The contact material (B) is as described above, but in short, it is liquid or vapor from the beginning, or the result is below the temperature at which the receding contact angle θr of the recording medium (A) starts to decrease. It is a solid that gives rise to a liquid. At least a part of the vapor condenses on or near the surface of the recording medium (A) to generate a liquid, and the vapor can wet the surface of the recording medium (A). Is enough. 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 decreasing. The vapor generated from the solid is condensed on or near the surface of the recording medium (A) to generate a liquid, as in the case described above.

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

That is, as the liquid which is one of the contact materials (B), in addition to water, an aqueous solution containing an electrolyte, an alcohol such as ethanol and n-butanol, a polyhydric alcohol such as glycerin and ethylene glycol, and a ketone such as methyl ethyl ketone. Polar liquids such as n-nonane, linear hydrocarbons such as n-octane, cyclic hydrocarbons such as cyclohexane,
Non-polar liquids such as aromatic hydrocarbons such as m-xylene and benzene. Further, a mixture of these may be used, and various dispersion liquids and liquid inks may be used. More desirably, polar liquids are better.

As the vapor which is another one of the contact material (B), in addition to water vapor, any vapor of a liquid of the contact material (B) can be used. Particularly, vapor of an organic compound such as ethanol vapor or m-xylene vapor can be used. (Including those in the spray state). The temperature of the organic compound vapor must be lower than the melting point or softening point of the compound forming the surface of the recording medium (A).

As another solid which is another contact material (B),
Examples include higher fatty acids, low molecular weight polyethylene, polymer gels (polyacrylamide gel, polyvinyl alcohol gel), silica gel, compounds containing water of crystallization, and the like.

As will be clear from the description below, when a “recording agent containing a color developer” such as the liquid ink is used as the contact material (B), the visualization is performed simultaneously with the formation of the latent image. Will be done.

Subsequently, the heating unit (latent image forming unit) will be described.

As the heating means, there is non-contact heating using electromagnetic waves (light from a light source such as a laser light source or an infrared lamp is condensed by a lens) in addition to contact heating using a heater or a thermal head. Also, in the case of electron beam irradiation and light (UV light) irradiation, the intended purpose can be achieved if the heating is performed substantially.

FIG. 2 (a) shows that a film 2 of the compound constituting the surface of the recording medium (A) is formed on a substrate 1, and a liquid 3 of the contact material (B) is present on the film surface. The state is shown. In this state, when the film 2 is heated, it is recognized that the receding contact angle θr of the surface of the film 2 is reduced and the film 2 shows remarkable wetting, so that the film 2 has liquid adhesion. Further, when the film 2 having the liquid adhesion property is heated again in the air, in a vacuum, or in an inert gas atmosphere (FIG. 2B), the receding contact angle θr increases on the surface of the film 2, and the liquid rebounds again. Is observed.

As a method showing a phenomenon somewhat similar to such a phenomenon, there is a method described in Japanese Patent Publication No. 54-41902 mentioned above. However, the methods disclosed herein differ mechanistically in that the recording material is provided with a substantially disordered and generally amorphous layer of memory material. That is, in the present invention, a state change cannot occur on the surface of the recording medium (A) without the presence of the contact material (B). Also, Japanese Patent Publication No. 54-41902
According to the method described in Japanese Patent Application Laid-Open Publication No. H06-115, reversibility cannot be obtained by a simple operation.

As shown in FIG. 3 (a), heat is applied to the film 2 in contact with the liquid 3 according to the image information (as shown in FIG. 3 (b-1),
The same applies to the case where the film 2 in which no liquid is present is brought into contact with a liquid in a state where heat is applied to the film 2 in accordance with image information). In the figure, 4 is a heater, 31 is a liquid supply port, 41 is an infrared lamp, 5 is a lens, and 6 is a shutter.

FIG. 3 (a) shows an example in which the film 2 is heated through the substrate 1, while the example shown in FIG. 3 (b-2) shows an example in which the liquid 3 is heated through.

FIG. 4 shows an example of the change in the contact angle of the aqueous solution before and after the heating of the film 2 under the contact with the aqueous solution, and the change in the contact angle of the aqueous solution when the film 2 is further heated in the air. 4th
In the figure, ○ indicates a forward contact angle, and △ indicates a receding contact angle.

In general, when the receding contact angle is a high value of 90 ° or more, the surface shows liquid repellency, and when the receding contact angle is a low value of 90 ° or less, the surface shows liquid adhesion.

The heating temperature of the surface of the recording medium (A) in a state of being in contact with the contact material (B) is preferably in a range of 50C to 250C, more preferably 80C to 150C. Heating time is 0.1m
The time is in the order of seconds to 1 second, preferably 0.5 ms to 2 ms. As for the timing of heating, if a latent image is to be formed, the surface of the recording medium (A) is heated and then brought into contact with the contact material (B) before cooling. Either heating the surface of the recording medium (A) in a state where the contact material (B) is in contact with the surface of the recording medium (A).

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

One is to heat the surface of the recording medium (A) in response to an image signal in a liquid or vapor atmosphere to form a liquid adhering area on the surface of the recording medium (A) (formation of a latent image). In this method, the recording agent is attached to the latent image portion by means of bringing the recording agent into contact with the image portion (development), and thereafter, the recording agent on the surface of the recording medium (A) is transferred to recording paper (indirect recording method). Further, in the above method, if a means for bringing the recording material into contact with the latent image portion again after transferring the recording material is performed, a printing method using the recording body (A) as a printing plate is obtained. Further, in the above method, after transferring the recording material, the surface of the recording medium (A) on which the latent image is formed in the absence of liquid or vapor is heated to erase the latent image, whereby the recording medium (A) is formed. It becomes a reproducible recording method (repeated recording method). 5 (a) and 5 (b) show typical processes of an indirect recording method (printing method) and a reversible recording method of a recording medium (repeated recording method).

 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, a recording agent is used in a conventional print recording method such as a writing ink, an ink jet ink, a printing ink, and an electrophotographic toner. From the recording agents that have been used, those that are compatible with the process applied to the apparatus of the present invention can be selected and used.

To give more specific examples, for example, as the aqueous ink, water, a wetting agent, a water-soluble ink mainly comprising a dye or water, a pigment, a polymer compound for dispersion, an aqueous pigment-dispersed ink mainly comprising a wetting agent, Emulsion ink or the like in which a pigment or dye is dispersed in water using a surfactant is used. Examples of the wetting agent used in the aqueous ink include the following water-soluble organic liquid compounds.

Monohydric alcohols such as ethanol, methanol and propanol; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol,
Polyhydric alcohols such as 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 mono Ethers of polyhydric alcohols such as ethyl ether, tetraethylene glycol monoethyl ether and propylene glycol monoethyl ether; heterocyclic compounds such as N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam Monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, Amines such as triethylamine;

As the water-soluble dye, dyes classified into acid dyes, direct dyes, basic dyes, reactive dyes, and food dyes in a color index are used. Examples of typical dyes include CI Acid Yellow 17,23,42,44,79,142 CI Acid Red 1,8,13,14,18,26,27,35,37,42,
52,82,87,89,92,97,106,111,114,115,134,186,249,254,
289 CI Acid Blue 9,29,45,92,249,890 CI Acid Black 1,2,7,24,26,94 CI Food Yellow 3,4 CI Food Red 7,9,14 CI Food Black 2 CI Direct・ Yellow 1,12,24,26,33,44,50,142,
144,865 CI Direct Red 1,4,9,13,17,20,28,31,39,8
0,81,83,89,225,227 CI Direct Orange 26,29,62,102 CI Direct Blue 1,2,6,15,22,25,71,76,79,8
6,87,90,98,163,165,202 CI Direct Black 19,22,32,38,51,56,71,74,
75,77,154,168 CI Basic Yellow 1,2,11,13,14,15,19,21,2
3,24,25,28,29,32,36,40,41,45,49,51,53,63,65,67,70,
73,77,87,91 CI Basic Red 2,12,13,14,15,18,22,23,24,
27,29,35,36,38,39,46,49,51,52,54,59,68,69,70,73,7
8,82,102,104,109,112 CI Basic Blue 1,3,5,7,9,21,22,26,35,41,4
5,47,54,62,65,66,67,69,75,77,78,89,92,93,105,117,1
20,122,124,129,137,141,147,155 Basic Black 2,8 and the like.

As pigments, azo, phthalocyanine, anthraquinone, quinacridone, dioxazine, indigo, thioindigo, perinone, perylene, isoindolenone, aniline black, azomethine azo, carbon black And the like, as inorganic pigments iron oxide, titanium oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow,
Navy blue, cadmium red, chrome yellow, and metal powder are exemplified.

Pigment dispersing compounds include polyacrylamide, polyacrylic acid and alkali metal salts thereof, acrylic resins such as water-soluble styrene acrylic resin, water-soluble styrene maleic acid resin, water-soluble vinyl naphthalene acrylic resin, and water-soluble vinyl naphthalene maleic resin Polyvinylpyrrolidone, polyvinyl alcohol, β-naphthalenesulfonic acid formalin condensate, an alkali metal salt, a polymer compound containing a salt of a cationic functional group such as a quaternary ammonium or an amino group, polyethylene oxide, gelatin, proteins such as casein, Gum arabic, natural gums such as tragacanth gum, glucoxides such as saponin, cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, ligninsulfonic acid and salts thereof, ceramics Natural polymer compounds, and the like.

Examples of the oil-based recording agent include, as in the case of the aqueous ink, 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, those in which a pigment or dye is emulsified in an oil-based base, and the like. Is used.

Representative examples of oil-based dyes include CI Solvent Yellow 1,2,3,4,5,6,7,8,9,10,11,
12,14,16,17,26,27,29,30,39,40,46,49,50,51,56,61,8
0,86,87,89,96 CI Solvent Orange 12,23,31,43,51,61 CI Solvent Red 1,2,3,16,17,18,19,20,22,2
4,25,26,40,52,59,60,63,67,68,121 CI Solvent Violet 7,16,17 CI Solvent Blue 2,6,11,15,20,30,31,32,35, Three
6,55,58,71,72 CI Solvent Brown 2,10,15,21,22 CI Solvent Black 3,10,11,12,13 and the like.

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

The pigments exemplified above can be used for the oil-based ink. Examples of oil-based pigment dispersants include polymethacrylates, polyacrylates, methacrylate-acrylate copolymers, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polyvinylpyrrolidone, polyvinyl butyral, and the like. Examples include vinyl copolymers, cellulose resins such as ethyl cellulose and methyl cellulose, polycondensation resins such as polyester, polyamide and phenol resin, and natural resins such as rosin, ceramic, gelatin, casein and the like.

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

The recording medium (A) has a surface (the “film 2” or “the surface of the recording medium (A)” may be described for convenience) whose receding contact angle decreases when the recording medium (A) is brought into contact with a liquid in a heated state. Is not limited to that form. Therefore, the recording medium (A) may have a rigid cylindrical shape or a flexible film shape. A rigid cylindrical recording body (a cylindrical rigid body having the film 2 formed on its surface) is excellent in controllability since the recording body is less likely to be displaced when the recording body is operated. Good body. For the production of such a recording body (A), a method in which the film 2 is formed on a substrate or a method in which the recording body (A) is produced using a molded body itself is preferable.
Particularly, a method of forming a film on a substrate is desirable because the molded body generally has low mechanical strength. It is needless to say that the film 2 must be formed on the surface of the recording body (A) even when the recording body (A) is formed from the molded body itself.

When a resin is used for the recording medium substrate, it is not a good heat conductor, and it takes a certain amount of time before the surface of the recording medium (A) is heated to have liquid adhesion. Therefore, it may be conceivable to use a good heat conductor for the entire substrate or for a portion on the substrate 1.

FIG. 6 (a) shows a case where a good heat conductor such as a metal is used as a substrate (metal substrate 11), an organic thin film 12 is deposited thereon, and a film 2 is further formed thereon. The heat conduction speed of the material is improved. Examples of the organic thin film 12 include polyimide, polyester, phthalocyanine, and the like. This configuration is sufficient when the print dots need to be relatively large, but is not suitable for further high-density printing because the portion having liquid adhesion is expanded by heat diffusion in both directions. FIG. 6 (b) shows a structure in which a good heat conducting portion is provided on the substrate 1 so as to prevent heat diffusion in the plane direction and to miniaturize the liquid adhering portion 2a. In FIG. 6B, reference numeral 11a denotes a miniaturized metal film.

Subsequently, a latent image forming means by heating will be described. As described above, as the heating source, 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 desirable.

As a specific example of these, means for heating the surface of the recording medium (A) in contact with the liquid will be described. For the sake of convenience, the description will be given taking a recording body (A) of a type in which a film 2 is formed on a substrate 1 as an example. First, the liquid 3 is brought into contact with the surface of the recording medium (A) in advance, and heating is performed from the substrate 1 side or the liquid 3 side in the contact state (FIGS. 7A and 7B). The liquid 3 is heated from the surface side of the recording medium (A), and the liquid 3 is immediately supplied to the recording medium heating section (recording medium (A)).
It is desirable to employ means (FIGS. 7 (c) and (d)) for making contact with the surface.

As a means for supplying the liquid 3, a dish is provided below the recording body (A) so that the recording medium is filled with the liquid so that the recording body (A) is always in contact with the liquid 3 in the dish, and the heating source is arranged near or in the dish. This is the simplest configuration. Instead of a dish, a sponge-like porous body filled with a liquid may be used. The latent image forming means using light or an electron beam is basically the same as the above configuration.

In FIG. 7, reference numeral 42 denotes a laser light source, and reference numeral 43 denotes a thermal head. Thus, a latent image is formed on the surface of the recording medium (A).

As means for adhering the recording agent (ink) to the liquid adhering area selectively applied in accordance with the image signal by the above-mentioned means, a plate filled with the recording agent 3a may be a recording medium with respect to the latent image forming means arrangement position. The simplest configuration is to arrange in the traveling direction of (A) and always contact the recording medium (A) (FIGS. 8 and 9). As shown in FIGS. 8 and 9, when the liquid used for forming the latent image is also used as the recording agent, the apparatus can be constituted by one dish, and the formation of the latent image and the visualization can be integrated. it can.

In the case of indirect recording, as described above, for example, a rigid cylindrical tube is advantageously used as the recording substrate. After the latent image is formed and developed (developed), for example, the recording material on the recording medium is transferred to the recording paper by means of the capillary action of the recording paper by providing means for directly contacting the recording paper (transfer means). . The transfer position may be any position on the recording medium after development, but is preferably a position where transfer is performed immediately after development. If the development and the transfer are repeated without erasing the latent image after the transfer, this apparatus becomes a printing apparatus. When printing of one image information is completed, the latent image is erased, so that recording and printing of another image information can be performed.

Further, after the transfer by the transfer means, if the latent image is erased in the absence of liquid or vapor, that is, by heating the vicinity of the latent image portion in air, in a vacuum, or in an inert gas, The recording medium is a recording device that can be used repeatedly. As a heating source for erasing a 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 desirable. Heating may be performed on the entire surface of the recording medium, or may be performed only on the latent image portion. However, heating over the entire surface is more preferable because the device configuration can be simplified. The latent image erasing means is provided at a position where the surface of the recording medium is substantially cooled during the time from when the heating for erasing is performed to when the latent image is formed again. The heating temperature required for erasing depends on the material on the surface of the recording medium, but it is desirable that the temperature be equal to or higher than the starting temperature at which the receding contact angle of the material on the recording medium decreases and lower than the decomposition point. The heating temperature required for erasing depends on the material of the surface of the recording medium (A).
It is desirable that the temperature be equal to or higher than the starting temperature at which the receding contact angle of the material on the surface of the recording medium (A) becomes lower and lower than the decomposition point. That is, 50-
It may be heated to 300 ° C, preferably 100 to 180 ° C. The heating time is 1 msec to 10 sec at any temperature, preferably 10 m
Seconds to 1 second.

Suitable recording paper (transfer medium) is a transparent resin film, plain paper, inkjet paper, type paper, or the like.

By the way, the surface of the recording medium (A) according to the present invention becomes fatigued in proportion to the frequency of use thereof, the change between the liquid adhesion and the repulsion becomes small, and finally a recorded image cannot be formed, When the recording agent is transferred to the recording paper, background contamination may occur. This phenomenon is considered to be due to the fact that the surface of the recording medium (A) is made to adhere to the liquid or to be repelled by the liquid, or is changed regularly or irregularly. When the recording material on the recording medium (A) is transferred to the recording paper, the recording material is completely transferred to the recording paper depending on the type of the recording medium (A), the recording material or the recording paper, or a combination thereof. And may remain on the recording medium (A). In such a case, when the recording medium (A) is heated to remove the latent image of the recording medium (A), the liquid component in the recording agent evaporates, but the coloring material adheres to the surface of the recording medium (A). Resulting in. In the recording material area where the color material is fixed, the latent image formation, development, and transfer after the next cycle are not performed well, resulting in background smearing and deterioration in print quality. Alternatively, the recording medium (A) is deteriorated, and the number of durable repeated use is reduced. Further, as described above, the recording material is supplied to the recording medium (A) by a plate or a roller. Regardless of whether the recording medium (A) is of a belt type or a drum type, the recording material is supplied as shown in FIG. 7 or the printing width as shown in FIG. However, when the recording material 3a is supplied up to the width of the edge of the recording material 7 as shown in FIG. 10, the recording material 3a easily adheres to the side surface of the recording material 7. By repeated use, the recording agent 3a 'attached to this side surface accumulates and protrudes onto the surface of the recording medium 7 to easily cause background contamination. Further, when the recording material 3a is supplied by the printing width as shown in FIG.
Since the surface of the recording material 3a is exposed at the edge portion of the contact surface between the recording material 3a and the recording material supply means, the recording material 3a easily adheres to the recording body 7 and also causes the background stain. In Fig. 11, 3b
Is the surface of the recording material edge, 3a ″ is the attached recording material, 43 is the thermal head, 43a is the edge of the thermal head 43, 44
Is a thermal element.

Therefore, in the apparatus of the present invention, these problems are solved by employing the following means.

First, in the example shown in FIG. 12, the blade 52a is brought into contact with the surface of the recording medium 7 after the recording agent 3a is transferred to the recording paper 61, and the recording agent and paper dust remaining on the surface of the recording medium 7 are removed. In this case, a means is used for slightly shaving the surface of the recording body 7. Therefore, the blade 52a needs to be adjusted so as to contact the surface of the recording medium 7 with a constant pressure. Suitable materials for the blade 52a include metals, polymer materials, and ceramics. In the figure, reference numeral 18 denotes the removed remaining recording agent, paper dust, and the scraped recording material 7
Scraps on the surface and the like are shown, and these are discharged from the dirt receptacle 53 to the outside.

Since the blade 52a is in contact with the surface of the recording body 7,
Fine scratches occur on the surface of the recording medium 7. However, this flaw can be repaired by heating the surface of the recording medium 7 to a temperature near its melting temperature, for example, with an infrared lamp 41 or the like.

FIG. 13 shows an example in which the blades 52b are arranged in such a manner that they are held in the direction of travel of the recording medium 7. In such an embodiment, removal of the remaining recording agent and paper dust and polishing of the surface of the recording medium 7 are performed more effectively than in the example of FIG. However, in this example, if the pressure between the surface of the recording medium 7 and the blade 52b is not properly maintained, chatter is generated and the surface of the recording medium 7 is deeply damaged.

In FIG. 14, a brush 52c is used in place of the blades 52a and 52b to remove the remaining recording agent and paper dust. The brush 52c is insufficient in terms of grinding the surface of the recording medium 7 as compared with the blades 52a and 52b, but has the advantage of being easily mounted.

In the examples shown in FIGS. 12, 13, and 14, when recording a large number of sheets, the heating of the surface of the recording body 7 by the infrared lamp 41 or the like is performed after the recording of the large number of sheets. Further, the blades 52a, 52b and the brush 52c may not be always in contact with the surface of the recording medium 7 but may be in intermittent contact.

The above is an example using a polishing means (blade, brush) for polishing the surface of the recording medium (A) as the cleaning means. Next, refer to FIG. 15 for an example using a means for contacting the cleaning liquid as the cleaning means. I will explain while.

In FIG. 15, reference numeral 71 denotes an endless belt-shaped recording medium,
a, 72b, 72c are rollers, 73 is an ink liquid, 73a is attached ink, 73b is residual ink, 74 is a thermal head for forming a latent image, 75 is a transfer roller, 76 is a recording paper, and 77 is a latent image erasing. A heating means such as an infrared heating lamp, 78 is a cleaning liquid, and 79 is a blade. In this example, after the attached ink 73a on the recording medium 71 is transferred to the recording paper 76,
It is characterized in that the surface is brought into contact with the cleaning liquid 78. As a result, the recording medium 71 is not transferred to the recording paper 76.
The ink 73b and the like remaining on the surface can be removed. Therefore, the liquid adhering area (latent image) of the recording body 71
Is changed to liquid repellency by a heating means 77 such as an infrared lamp, and the image is reliably removed. For this reason, the image after the next cycle does not cause background smearing or deterioration in print quality.

Here, the cleaning liquid will be described. No. 16
The figure shows the state of the surface of the recording medium 71 immediately after the transfer to immediately after the image removal. (A) is immediately after transfer, (b) is immediately after cleaning, and (c) is immediately after image removal. P is a liquid adhesive area, Q is a liquid repellent area, and R is residual ink that has not been transferred to recording paper. There are two conditions required for the cleaning liquid used in the present invention. One is that the ink dissolves well, and the other is that the difference in adhesion between P and Q is small. Since the former condition is natural, the second condition will be described in detail. If the liquid that adheres to the recording medium is different, the adhesion to P and Q will be absolutely different. If the liquid has both strong adhesion to P and q or both are weak, that is, if the difference between the adhesion of liquid to P and Q is small, the liquid does not adhere to Q but does not adhere to P . On the other hand, liquid P
If the adhesion to Q is greater than the adhesion to Q,
That is, if the difference between the adhesion of the liquid to P and Q is large, the liquid adheres to P. If the cleaning liquid remains on the surface of the recording medium after dissolving R in itself, it will hinder subsequent image removal. Therefore, a liquid having a small difference in adhesion between P and Q is suitable as a cleaning liquid. Specific examples of such a cleaning liquid include glycerin, formamide, ethylene glycol,
Examples include one or more wetting agents such as diethylene glycol and propylene glycol or water. These are also used as ink wetting agents and solvents.However, since the coloring material mainly contributes to ink adhesion, the liquid used for the ink wetting agent and solvent is used as a cleaning liquid. I can't do anything. Even if the liquid remains on the surface of the recording medium, there is no problem since it is vaporized during image removal. Since the residual ink dissolved in the cleaning liquid diffuses throughout the cleaning liquid, the concentration of the coloring material near the surface of the recording medium is low, and the coloring material hardly adheres to the surface of the recording medium.

FIG. 17 shows a modification of the means for cleaning by bringing the surface of the recording body 71 into contact with the cleaning liquid 78. 78A in the figure
Is a filter and 78B is a pump. This example is characterized in that the cleaning liquid 78 is circulated by a pump 78B, and a filter 78A is provided on the way. According to such a configuration, the cleaning liquid always containing no coloring material
Since 78 can be supplied to the surface of the recording body 71, it is possible to reliably prevent the coloring material from re-adhering to the surface of the recording body 71, and improve the reliability.

FIG. 18 shows another modification of the means for cleaning by bringing the surface of the recording body 71 into contact with the cleaning liquid 78. This example is characterized in that a color material density detecting device 78C for detecting the density of the color material in the cleaning liquid 78 and a replacement time display plate 78D are provided. The color material density detector 78C uses the cleaning liquid 78
When the density of the color material is detected and the density of the color material is equal to or higher than the density that hinders the cleaning effect, a predetermined signal is output, and the replacement time display plate 78D or the like notifies the user of the replacement time.
Therefore, as in the example of FIG. 17, it is possible to reliably prevent the color material from re-adhering to the surface of the recording body 71 and improve the reliability.

Next, still another example of the cleaning means will be described with reference to FIG.

In FIG. 19, 81 is a recording body, 82 is a roller, 83 is ink, 83a is adhesion ink, 83b is residual ink, 84 is a latent image forming thermal head, 85 is a transfer roller, 86 is recording paper,
87 is a roller, 88 is fine particles, 89 is a blade, and 90 is an infrared lamp for image removal. In this example, after transfer, liquid absorbing fine particles 88 are applied to the remaining ink 83b,
After absorbing the 3b into the fine particles 88, the fine particles are removed to remove the residual ink 83b.

As the liquid-absorbing fine particles 88, the hardness is softer than the surface of the recording medium 81 to prevent abrasion of the recording medium 81,
A material that is insoluble in the ink 83 is desirable. Also, the recording body 81
A material that is non-adhesive to the recording medium 81 and that does not contaminate the surface of the recording medium 81 is preferable so that it can be easily removed from the surface. Furthermore, it is better that the surface area is large like a porous material,
About 30~900m ² / g, and preferably suitably in the range of about 100~800m ² / g. The particle size is in the range of 0.1 to 20 μm, preferably 1
Thicknesses in the range of 1010 μm are easy. It is desirable that the liquid absorbing ability can absorb 10 to 500 g of liquid per 1 g of fine particles. Specific materials include porous furnace black, carbon black, carbon such as kaolin,
Organic pigments such as clay or zinc oxide, titanium oxide, and quinacridone can be used. Further, a polymer absorber can also be used.

In this example, the roller 87 is used as a means for applying the fine particles 88 to the recording medium 81, but a porous foaming roller is particularly preferable, and the material thereof is foaming sponge rubber, polyurethane, silicone resin, or the like. . Also, fine particles 88
A mixture of fine particles 88 and carrier particles may be used to improve the transportability of the particles. In this case, the carrier particles include granular silicone and granular Teflon. In this example, the particles 87 are applied to the recording medium by placing a roller 87 in a particle container as shown in FIG.
The roller 87 is applied to the surface of the recording medium 81 while stirring the roller 88. The fine particles 88 that have absorbed the remaining ink 83b
Remove with 9. A brush or the like may be used for the removal.
The removed fine particles 88 may be discarded, or may be reused after drying.

FIG. 20 shows another example of cleaning the surface of the recording medium 81 using the liquid absorbing fine particles 88. Here, the particles 88
The web 91 is used as a means for applying the recording medium 81 to the recording medium 81.
Even with such a configuration, the same effect as that of FIG. 19 can be obtained. Further, a brush or the like can be used as the application means.

Next, still another example of the cleaning unit will be described.

In this example, when the problem described with reference to FIGS. 10 and 11 occurs or does not occur, a means for removing or cleaning the recording material attached to the non-printed portion or the side surface of the recording material is used. It is characterized by having been provided. As such a removing and cleaning means, a roller, a web, a blade, or the like made of a liquid-absorbing member, and a means for directly contacting a recording medium to physically absorb a recording agent and at the same time to scrape the recording medium are suitable. FIGS. 21 (a) and (b) show two examples of means for removing the recording agent attached to the side surface of the drum type recording medium 91. FIG.
(A) is removal by the blade 93, and (b) is removal by the roller 94. FIG. 22 shows an example of the means 95 for removing the recording agent attached to the non-printing portion on the surface of the recording medium 92. FIG. 23 shows the positional relationship between the removing unit 95 and the printing unit on the surface of the recording medium 92 at this time. In this example, a thermal head 97 was used as a heat source, and a recording material 96 was held between the recording medium 92 and the thermal head 97. As shown, the printing portion extends to the end of the row of the heating elements (97a). The end surface 96a of the recording material 96 is near the thermal head edge. The end of the recording material removing means (roller in this figure) 95 attached to the non-printing portion is arranged so as to be located between the recording material surface 96a and the end of the printing portion. As shown in FIG. 24, the removing means 95, 95 disposed at both ends of the recording medium may be integrated. In FIG. 24, a roller is used for the removing means 95, and the rollers are connected by one shaft. Further, the recording material side surface and the recording material removing means on the recording surface may be integrated. No.
Figure 25 shows this example, using rollers 95A and 95B with different diameters,
The surface of the recording medium is cleaned on the peripheral surface of 5A, and the side surface of the recording material is cleaned on the peripheral surface of 95B. Fig. 26 shows another removal means integrated with a blade.
95 'is an example. Also, depending on the size of the recording paper,
The recording material removal area on the 92 surface may be changed. FIG. 27 shows this example. The printing area also changes according to the width of the recording paper. Accordingly, the removal area on the surface of the recording medium 92 is changed by the moving mechanism 98 of the removing means. As the moving mechanism 98, a mechanical means such as a motor and a solenoid coil, a piezoelectric element, and the like are effective.

〔Example〕

Example 1 A water- and oil-repellent "Fluorard FC-720" manufactured by Sumitomo 3M was used as a fluorinated acrylate material, coated on a polyimide film (500H manufactured by Toray DuPont), dried at 90 ° C for 2 hours, and dried to about 100 µm Thick film (surface energy: about 1
0dyn / cm). As shown in FIG. 12, this film was rolled up and wrapped around an aluminum cylinder having a diameter of 100 mm and a length of 100 mm to prepare a recording medium, and a heating portion of a thermal head for a thermal transfer printer was arranged in contact with the film surface. Further, this thermal head was placed in an ink container (dish) so that the liquid ink was in contact therewith. As the liquid ink, a phthalocyanine-based cyan ink (dye concentration 1% by weight, solvent: concentration
0.05M NaOH aqueous solution).

When an appropriate signal is sent to the thermal head and heated,
The ink adhered only to the heating section. Further, as shown in FIG. 12, when the recording paper (NM coated paper manufactured by Mitsubishi Paper Mills) was conveyed in contact with the cylindrical recording body, the ink was transferred to the paper. The ink-attached portion exhibited ink-adhesiveness even when left as it was, and functioned as a printing machine.

After recording about 1,000 sheets, the surface of the recording medium (A) was brought into contact with the surface of the polyurethane rubber blade at a force of 20 gf / cm to remove the residue 8, and the recording was continued again. As a result, a good quality copy was obtained.

Example 2 A film was formed on a polyimide substrate under the same conditions as in Example 1. Further, in the same manner as in Example 1, heating was performed in contact with the recording agent to make the film surface liquid-adhesive and at the same time copying was performed. This film was heated in air at 130 ° C. for about 1 second by an infrared lamp in air as shown in FIG. As a result of the liquid adhesion and the recovery of the liquid repellency at this time, as shown in FIG. 4, the receding contact angle reduced by the heating in the liquid is returned to the original value by the heating in the air. Admitted. That is, it can be seen that the liquid repellency has been restored. From the result of this series of operations, storage and deletion of image information could be confirmed.

Example 3 As a recording material, a polymer obtained by solution polymerization (solution: 1-1-1-trichloroethane) using a fluorine-containing acrylate monomer Biscoat 17F (manufactured by Osaka Organic Chemical Co., Ltd.) as a raw material was used. This polymer was diluted with Freon 113 to obtain a cord solution. A recording material layer was formed on a support made of a 30 mm-diameter polyimide seamless film (manufactured by Toray DuPont: Kapton) by spin coating.
For 1 hour. The thickness of the recording material layer is about 1μ
m. The heating surface of the thermal head was placed in contact with the surface of the recording medium, and this thermal head was placed in an ink container so that the aqueous black ink (contact material and recording agent) was in contact therewith. Further, the cleaning means was configured as shown in FIG. The arrangement of other means is the same as in FIG. Here, titanium oxide having an average particle size of 5 μm is adopted as the absorbent fine particles used in the cleaning means, and this is put in a polyethylene container, and stirred with a urethane sponge roller.
The composition was applied to the surface of a recording medium, and fine particles were removed with a silicone resin blade. As a result, the attached ink could be almost completely removed.

Example 4 A recording material was formed by forming a recording material layer on the support in the same manner as in Example 3, except that a silicone resin roller having a diameter of 15 mm was used as the support. The contact material and the heating means for forming the latent image were the same as in Example 3, and the cleaning means was configured as shown in FIG. Here, titanium oxide having an average particle diameter of 5 μm is used as the absorbing fine particles used in the cleaning means, and the titanium oxide is put in a polyethylene container, stirred with a web made of acrylic fiber, applied to the surface of the recording material, and coated with a silicone resin. Fine particles were removed with a blade. As a result, the same effect as in the third embodiment was obtained.

Example 5 A recording apparatus was constructed in the same manner as in Example 3 except that the cleaning means having the structure shown in FIG. 22 was used. This cleaning means uses filter paper as a water absorbing member and winds it around an aluminum roller. With such a configuration, the same effect as described above was obtained.

Example 6 A recording apparatus was constructed in the same manner as in Example 4 except that the cleaning means having the structure shown in FIG. 26 was used. In this cleaning means, filter paper is used as a water absorbing member, which is laminated to form a blade as shown in FIG. When cleaning was performed by bringing this blade into contact with the non-printing area shown in FIG. 22, the same effect as above was obtained.

Example 7 A 50 μm-thick polyimide film (manufactured by Toray DuPont) was used as a recording medium substrate, and a fluorine-containing acrylate material 17F (manufactured by Osaka Organic Chemical Industry) was placed thereon.
A layer of a recording material made of a polymer solution-polymerized in trichloroethane was formed. Using an aqueous black ink as the latent image forming liquid and the ink, and using a borate aqueous solution having a pH of 10 as the cleaning liquid, image recording was performed using the apparatus configuration shown in FIGS. As a result, as in the other examples, the ink remaining on the recording medium could be almost completely removed.

〔The invention's effect〕

According to the apparatus of the present invention, the liquid attachment area and the non-liquid attachment area can be easily formed on the recording medium, and it is easy to return the two divided areas to the original state. Therefore, it is possible to easily print a large number of sheets.
Further, since the cleaning means for the residual ink on the surface of the recording medium is provided, it is possible to provide a high-quality recorded image without background contamination.

[Brief description of the drawings]

FIG. 1 is a diagram of four typical examples of a form having a surface self-orientation function. 2 and 3 are diagrams for basically explaining a method applied to the apparatus of the present invention. FIG. 4 shows the receding contact angle observed on the surface of the recording medium (A) when the surface of the recording medium (A) is heated in the state that the liquid is in contact with the surface of the recording medium (A) used in the embodiment of the present invention. It is a figure showing change of (theta) r. FIG. 5 shows two embodiments of the method applied to the apparatus of the present invention. FIGS. 6, 7, 8 and 9 are views showing an embodiment of the device of the present invention. FIG. 10 and FIG. 11 are views showing a state in which the recording agent adheres and remains on the non-printing area on the surface of the recording medium and the side surface of the recording medium. FIGS. 12, 13, and 14 are views showing a configuration example of a recording apparatus provided with a cleaning unit. FIG. 15 is a view showing a configuration example of a recording apparatus provided with another type of cleaning means. FIG. 16 is a diagram showing the state of the surface of the recording medium from immediately after transfer to immediately after image removal. 17 and 18 are views showing a modification of the cleaning means of the type shown in FIG. FIG. 19 and FIG. 20 are views showing a configuration example of a recording apparatus provided with still another type of cleaning means. FIG. 20, FIG. 21, FIG. 22, FIG. 23, FIG. 24, FIG. 25, FIG.
26 and 27 are explanatory views of still another type of cleaning means. DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Film 3 ... Liquid (3a ... Recording agent) 7,71,81,81 ', 92 ... Recording body 52a, 52b ... Blade 52c ... Brush 78 ... Cleaning liquid 88 …… Particles 93 …… Blades 94,95,95A, 95B …… Rollers

Continued on the front page (72) Inventor Takeshi Takemoto 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Yasuyuki Okada 1-3-6 Nakamagome, Ota-ku, Tokyo Co., Ltd. Ricoh (56) References JP-A-60-255482 (JP, A) JP-A-3-55283 (JP, A) Patent 3030445 (JP, B2) JP-B-54-41902 (JP, B2) (58) Field surveyed (Int. Cl. ⁷ , DB name) B41M 5/00 B41C 1/10 B41M 5/26

Claims (6)

(57) [Claims] 1. The method according to claim 1, wherein the surface of the recording medium (A) is selectively heated while in contact with the following contact material (B), or the surface of the recording medium (A) is selectively heated. Means for supplying a contact material (B) to the surface of the recording medium (A), which forms a latent image area having a receding contact angle corresponding to the heating temperature on the surface of the recording medium (A) by being brought into contact with the material (B); Means for heating the surface of the recording medium (A) for forming a latent image, means for applying a recording agent containing a color developer to the latent image area to visualize the image, and recording medium (A) Means for transferring the recording agent attached to the surface to recording paper, and cleaning means for cleaning the surface of the recording medium (A), and liquid or vapor or heat after transfer to the recording paper. The latent image is erased by heating in the absence of liquid solids. Recording apparatus characterized in that a latent image erasing means for. (A) A recording medium having a surface in which the receding contact angle is reduced when heated and brought into contact with a liquid. (B) A liquid, a vapor, or a solid that becomes a liquid or generates a liquid or a vapor below the temperature at which the receding contact angle of the recording medium (A) starts to decrease. 2. A recording apparatus according to claim 1, wherein said contact material supply means and said recording material applying means are combined into one. 3. The apparatus according to claim 1, wherein said cleaning means is a polishing means for polishing a surface of the recording medium (A).
Or the recording device according to 2. 4. The recording apparatus according to claim 1, wherein said cleaning means is means for bringing the surface of the recording medium (A) into contact with a cleaning liquid. 5. The cleaning means according to claim 1, wherein fine liquid-absorbing fine particles are applied to the surface of the recording medium (A), and the fine particles are removed after absorbing the remaining recording agent. 3. The recording device according to 1 or 2. 6. The cleaning device according to claim 1, wherein the cleaning unit is a unit that removes a non-printing area on the surface of the recording medium (A) and / or a recording agent attached to a side surface of the recording medium (A).
Or the recording device according to 2.