JP3030653B2 - Recording device - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a novel recording apparatus, and more particularly, to a surface of an endless recording medium having a specific property selectively or selectively and reversibly. A recording device that forms a latent image by forming a region having a receding contact angle corresponding to a heating temperature, and supplies a recording material containing a color developing material to the latent image to visualize the latent image. About.

[Prior Art] A lithographic printing plate without water (fountain solution) is used as a typical means for dividing a surface into a liquid-adhesive area and a non-liquid-adhesive area and providing an image. An offset printing method can be used. 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 provide an endless belt-shaped member (recording body (A)) having a surface having a reduced receding contact angle when heated and in contact with a contact material (B), unlike the conventional recording method. It is an object of the present invention to provide a novel recording apparatus in which a desired pattern area is selectively or selectively and reversibly formed on the surface by an easy means, and is visualized and transferred to plain paper or the like.

Another object of the present invention is to reversibly use a recording medium (A) having excellent storage stability and stability in all steps such as formation / erasing, visualization, and transfer of a desired pattern area. An object of the present invention is to provide a recording apparatus capable of performing the above steps a plurality of times.

Still another object of the present invention is to provide a recording apparatus which can perform high-speed recording and drive with low energy, can reduce the size of the apparatus, and is excellent in durability.

[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 in the state where the surface of the recording body (A) is selectively heated. Recording body (A) by contact with contact material (B)
Means for supplying a contact material (B) for forming a latent image area having a receding contact angle corresponding to the heating temperature on the surface of the recording medium (A), and a surface of the recording medium (A) for forming a latent image , A recording agent applying unit for visualizing the latent image area, and a unit for transferring the recording agent formed on the surface of the recording medium (A) to recording paper. .

(A) An endless belt-shaped recording material having a surface in which the receding contact angle decreases when it is 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 a vapor below the temperature at which the receding contact angle of the recording medium (A) starts to decrease.

According to the present invention, a seamless recording medium is preferably used as the endless belt recording medium. This is very advantageous in terms of downsizing, high-speed recording, low-energy driving, and high durability.

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

The present inventors have solved a defect as described in the above-mentioned conventional technique, and have carried out many studies and studies on a new recording method. As a result, a member having a function of reducing the receding contact angle even after cooling when heated in contact with the liquid, and having a function of increasing the receding contact angle by heating in the absence of liquid as a recording medium. I found it useful. The recording medium (A) having such a function
It is also confirmed that the surface is (1) a member containing an organic compound having a surface self-orienting function of a hydrophobic group, or (2) a member having an organic compound having a hydrophobic group and having a hydrophobic group oriented on the surface. I did.

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 has a property of easily moving 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 n} , 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 as referred to in the present invention is the friction force γ _f
Then (However, γ: surface tension of a solid in vacuum γ _sl : solid-liquid interfacial tension γ _lV : surface tension when a liquid is in contact with its saturated vapor π _e : equilibrium surface tension γ _f : frictional tension γ _s : (The surface tension of a solid without an adsorbent layer) holds (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 inferred from these mutual relations, the liquid adhesion depends on the receding contact angle θr, and the receding contact angle θr is determined by any member having a surface self-orienting function on the surface. Therefore, in the apparatus 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 apparatus 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 ink recording agents 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 (b), 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, and the like -C (CH _{3) 3,} and more preferably, the longest molecular length in terms of high molecular mobility Is advantageous. 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 of the alkyl group and the function, if the number of carbon atoms is 3 or less, the function suitable for the recording apparatus will be 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 desirable that the alkyl groups be arranged (orientated) to some extent on the surface of the recording medium (A).
It is thought that the number is derived from the number necessary for active molecular motion during heating. Also, contact material (B)
When is heated together with the surface of the recording medium (A), it is conceivable that molecules of the contact material (B) are incorporated into molecules of the surface of the recording medium (A). Furthermore, if fluorine or chlorine having a high electronegativity is present in the alkyl group, the interaction with a liquid, particularly a polar liquid, becomes large, so that a greater change in adhesion can be obtained than with a compound containing an alkyl group containing only hydrogen. 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, for the types shown in FIGS. 1 (a) and 1 (d), compounds having an alkyl group (including those substituted with fluorine and / or chlorine) on the side chain of the vinyl polymer can be considered. 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 _{(16) -CH 2 CF 2 CF} 2 CF 3 (17) -CH 2 CH 2 CH 2 CH 2 F (18) -CH 2 (CF 2) 6 CF 3 (19) -CH 2 (CF 2) 5 CF ₃ (20) CH ₂ ) ₃ CF ₃ Among these compounds, the use of the following material (XI) is particularly effective.

[However, R ^1: hydrogen, -C _n H _{2n + 1} or _{-C n F 2n + 1 (n} = 1 or 2 or more _{^{integer) R 2: CH 2 p (}} p ≧ 1 integer) 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) 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 may be used to form a copolymer and introduce a large number of functional groups into the polymer, or a monomer of the 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 materials shown in (XIV) R -COOH ... (XII ) R -OH ... (XIII) R CH 2 n SiX ... (XIV) (R f: Number 4 or more carbon An alkyl group or a group containing a fluorine- or chlorine-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 such that the above-mentioned surface member is formed on an endless belt-like support (preferably one having a heat-resistant temperature of 50 to 300 ° C.). Of course, it is conceivable to use a drum-shaped support. However, when such a drum-shaped recording medium is used, even if the latent image forming unit, the developing unit (developing unit), and the transfer unit are made smaller, Must be arranged in the circumferential direction of the drum, so that the size of the entire apparatus can be expected to be somewhat reduced, and cannot be obtained as a thinner apparatus.

In the apparatus of the present invention, the recording body (A) is in the form of an endless belt. Therefore, the space of the recording body (A) can be reduced by considering the position and number of the rollers. It is possible to reduce the size and thickness. Furthermore, if the latent image forming, developing (developing) and transfer portions are made thinner, the whole apparatus can be further reduced in size, thickness or ultra-thinness.

In the apparatus of the present invention, a seamless type endless belt-shaped recording medium (A) is particularly preferably used. Use of this type of recording medium (A) has the following advantages.

In general, in an apparatus using a belt-shaped recording material having a joint, if the joint comes to a latent image forming unit (for example, a thermal head), the thermal head may be sometimes damaged. The life of the head is shortened. At the joint, the latent image,
Development may not be performed properly. To avoid the seam, extra driving energy and time for transporting the recording medium are required. Further, when the recording medium is shortened in order to further reduce the size of the apparatus, these become more remarkable. However, these problems have been solved all at once by adopting a seamless type as the endless belt-shaped recording medium (A), and the recording apparatus is more excellent in miniaturization, high-speed recording, low-energy driving, and durability. Can be provided.

Seamless type endless belt recording material (A)
As the support, a seamless belt formed by blow molding a resin or glass such as polyimide or polyester, or a seamless belt formed by metal electroplating is used. And
As the recording medium (A), the above-mentioned material is provided on a support in such a manner that no seams occur.

In the apparatus of the present invention, the support and the recording medium (A)
May be provided with a mechanical buffer layer. This buffer layer
This is particularly effective when a metal is used as the support material. That is, as described above, a resin film such as polyimide or polyester, glass, metal, or the like is used as the support. Among these, the metal is more difficult to heat by a latent image forming means (such as a thermal head) than other materials. On the other hand, there is an advantage that thermal expansion is small and deformation is difficult. However, since the metal is hard, the thermal head is easily damaged. Therefore, when the buffer layer is provided, the damage of the metal support to the thermal head is reduced, and the advantage of the metal support that the thermal expansion is small due to heating by the thermal head and that the metal support is hard to deform can be used. Thus, the life of the recording medium can be extended, and the durability of the apparatus can be improved. As the material used for the buffer layer, for the above purpose, silicone rubber, urethane rubber, rubber having high elasticity such as a foamed urethane home is preferably used, but any other material having high elasticity can be used. It goes without saying that it can be used.

Further, in the apparatus of the present invention, when a mixture of the surface forming material of the recording medium (A) and other members, for example, a hydrophobic polymer or a hydrophobic inorganic material, is formed on the support, it is possible to prevent background smearing in printing. It is excellent. 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 above compound. As the heat-resistant support, a resin film such as polyimide or polyester, a metal such as Ni, Al, Cu, Cr, or Pt, or a metal oxide is preferable. These supports may be smooth, rough or porous.

 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, 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, or a polar liquid may be used.

As the vapor which is another one of the contact material (B), in addition to water vapor, any liquid vapor 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 later description, when a “recording agent containing a color developer” such as a liquid ink is used as the contact material (B), the visualization is performed simultaneously with the formation of the latent image. Will be.

 Subsequently, the heating means 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 substantially performed.

FIG. 2 (a) shows that a film 2 of the compound constituting the surface of the recording medium (A) is formed on a support 1 and a liquid 3 of the contact material (B) is present on the film surface. It shows the state where it is. In this state, when the film 2 is heated, the film 2
It is recognized that the surface has a decreased receding contact angle θr, exhibits remarkable wetting, and 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 under the contact of the liquid 3 according to the image information (FIG. 3 (b-1), (b-2)
The same applies to the case where the surface of the film 2 in the heated portion is liquid-adhesive when the film 2 is in contact with a liquid in a state in which heat is applied to the film 2 in accordance with image information. Be transformed into
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. 3A shows an example in which the film 2 is heated through the support 1. In the example shown in FIGS. 3B-1 and B-2, the film 2 is directly heated. This is an example.

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 about 1 second to 1 second, and 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 material (A) is heated and then brought into contact with the contact material (B) before cooling, and the contact material (B) is applied to the surface of the recording material (A). Or heating the surface of the recording medium (A) under the contacted state.

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 then the recording agent on the surface of the recording medium (A) is transferred to recording paper (indirect recording method). Further, in this 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. Also, in the above method,
After transferring the recording agent to the recording paper, 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, so that the recording medium (A) can reproduce the recording. Method. 5 (a) and 5 (b) show the indirect recording method (printing method),
A typical process of a reversible recording method (repeated recording method) of a recording medium will be described.

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

 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, it has been used as a recording agent in a conventional print recording method such as a writing ink, an inkjet ink, a printing ink, and an electrophotographic toner. A recording agent suitable for the above process can be selected and used from the recording agents.

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, 39,80, 81,83,89,225,227 CI Direct Orange 26,29,62,102 CI Direct Blue 1,2,6,15,22,25,71,76,79,86,87,90,98,163,165,202 CI Direct Orange Black 19,22,32,38,51,56, 71,74,75,77,154,168 CI Basic Yellow 1,2,11,13,14,15,19, 21,23,24,25,28,29, 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 , 24,27,29,35,36,38,39,46,49,51,52,54,59,68,69,70,73,78,82,102,104,109,112 CI Basic Blue 1,3,5, 7,9 , 21,22,26,35,41,45,47,54,62,65,66,67,69,75,77,78,89,92,93,105,117,120,122,124,129,137,141,147,155 Basic Black 2,8 etc. Can be mentioned.

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, 30,39,40,46,49,50,51,56,61,80,86,87,89,96 CI Solvent Orange 12,23,31,43,51,61 CI Solvent Red 1,2, 3,16,17,18,19,20,22,24,25,26,40,52,59,60,63,67,68,121 CI Solvent Violet 7,16,17 CI Solvent Blue 2,6, 11,15,20,30,31,32,35,36,55,58,71,72 CI Solvent Brown 2,10,15,21,22 CI Solvent Black 3,10,11,12,13 etc. Is mentioned.

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 surface of the recording medium (A), in which the receding contact angle decreases when the recording medium (A) is heated and brought into contact with a liquid, may be referred to as “film 2” or “recording medium (A) surface” as before. What is necessary is just to have it on an endless belt.

When a resin is used for the support of the recording medium (A), it is not a good heat conductor, and it takes a certain time for the surface of the recording medium (A) to be heated and have liquid adhering properties. Therefore, a good heat conductor is applied to the entire support or to the support 1.
It may be considered for use in the upper part.

FIG. 6 (a) shows an example in which an organic thin film 12 is vapor-deposited thereon using a good heat conductor such as a metal as a support (metal substrate 11).
Further, when the film 2 is formed thereon, the heat conduction speed in the vertical direction 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)
By providing a good heat conductor portion on the support 1 so as to prevent heat diffusion in the plane direction, the portion 2a having liquid adhesion is miniaturized. In FIG. 6 (b), 11
a represents a miniaturized metal film.

Next, a latent image forming unit by heating and a recording agent applying unit (visualizing unit) will be described. As mentioned 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 the recording agent, those described later are used.

FIG. 7, FIG. 8, FIG. 9, FIG. 10, and FIG. 11 schematically show four typical examples of the apparatus of the present invention. In the figure,
7 is an endless belt-shaped recording material (A) (preferably a seamless type), 8 is a roller, 42 is a thermal head, 9 is a sponge roller, 3 is a liquid, 3a is a recording agent, 3a 'is an attached ink, S Denotes a latent image, P denotes a recording paper, 81 denotes a transfer roller, and 42 denotes an infrared lamp. In addition,
In these examples, each time the recording medium 7 makes one revolution, the infrared ray lamp 42 causes the recording medium (A)
If the film 2 is heated, the latent image S is erased, so that a new transferred image can be obtained every rotation of the recording medium 7.

The formation of a latent image by these devices will be described with reference to FIG. Here, the recording medium 7 is moved from the back surface of the recording medium 7 (the surface of the support 1 opposite to the film 2) by the thermal head 42.
Is heating. As described above, the heating source may be contact heating of a heater or the like or non-contact heating of electromagnetic waves such as a laser or an infrared lamp in addition to the thermal head 42 as described above.

In FIG. 7, with respect to the latent image and the development, in accordance with an image signal, heating is performed from the back surface of the recording body 7 in a state where the surface of the recording body 7 is in contact with a recording agent (liquid ink) 3a which is a liquid, thereby forming a latent image. And the developing operation are performed simultaneously. Of course, as shown in FIG. 9, first, a latent image (S) is formed, and then,
A form in which this latent image is visualized may be adopted.
To simultaneously form the latent image and visualize the film 2, the film 2 is heated and immediately thereafter brought into contact with the recording material 3a (FIG. 8).
Means such as heating with the film 2 in contact with the recording material 3a (FIG. 10) may be employed. The liquid 3 or the recording material 3a may be supplied to the recording body 7 by the sponge roller 9 or the liquid or the recording material 3a may be directly attached to the recording body 7.

Next, the transfer means will be described. A recording agent 3a adheres to the latent image portion (S) of the recording medium 7 after development, and the adhering ink 3a 'is applied to the recording paper P by the transfer roller 81. Is adhered to the recording paper P, the adhered ink 3a 'is transferred to the recording paper P, and a clear transfer image is obtained on the recording paper P. In the apparatus of the present invention, an endless belt-shaped recording medium 7 is used. Therefore, due to the elasticity and tension of the recording medium 7, when the transfer roller 81 is pressed through the recording paper P, the recording medium 7 moves along the transfer roller 81. As a result, the recording medium 7 is somewhat deformed, the contact area between the recording paper P and the recording medium 7 is increased to some extent, and the adhesion is improved, the image quality is improved, and the contact pressure is kept small and constant. Easy for vibration,
It is less likely to cause noise.

Although the erasure of the latent image is as described above, considering that the latent image is formed again on the recording medium (A),
The latent image erasing means (non-contact or direct) is located at a position where the surface of the recording medium (A) heated by the latent image erasing operation is substantially cooled while being moved to a position where it is heated to form a latent image. Heating). Further, the heating temperature required for erasing depends on the material of the film 2, but it is desirable that the heating temperature be equal to or higher than the starting temperature at which the receding contact angle of the film 2 becomes lower and lower than the decomposition point. That is, heating may be performed at 50 to 300 ° C, preferably 100 to 180 ° C. The heating time is about 1 ms to 10 seconds in each case, preferably 10 ms to 1 second.

In the example shown in FIG. 11, the inside of the support 1 (the roller 8
This shows an apparatus for obtaining a copied image by a recording body 7 having a film 2 formed on the side (side). However, this recording body 7
In FIG. 12, as shown in FIG. 12, the diameter of the roller 8 is increased so that the roller 8 comes into contact with the recording medium 7 only at both ends in the width direction of the recording medium 7, and the recording medium 7 on which the recording medium 7 is disposed is provided. It is preferable to reduce the diameter of the roller 8 so that the roller 8 does not come into contact with the recording body 7 at the center in the width direction. According to such an example, a latent image forming and developing unit, a transfer unit,
Since the latent image erasing section and the like are all housed inside the belt-shaped recording body 7, it is extremely effective for reducing the size and thickness of the apparatus.
The latent image forming means using light or an electron beam may be basically considered in the same manner as the above configuration. For example, a laser light source may be used instead of the thermal head.

In the configuration example described above, a seamless type endless belt-shaped recording material (A) is particularly preferably used (for example, a seamless belt formed by blow molding polyimide). In this case, as described above, damage to the thermal head can be prevented, and since there is no seam, the latent image and development can be performed smoothly, which is advantageous in terms of miniaturization, high-speed recording, low-energy driving, and durability.

〔Example〕

 Next, examples of the present invention will be described.

Example 1 A water- and oil-repellent "Florald FC-720" manufactured by Sumitomo 3M was used as a fluorinated acrylate material, coated on a polyimide film (500H, manufactured by Toray DuPont) having a width of 20 cm and a length of 90 ° C. After drying for 2 hours to form a film having a thickness of about 100 μm (surface energy: about 10 dyn / cm), this was processed into an endless belt to form a recording medium (A). This was mounted at the position shown in FIG. 7, and the heating section of the thermal head for a thermal transfer printer was placed 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 cyanine ink (dye concentration: 1% by weight, solvent: 0.05 mol NaOH aqueous solution) was used.

When an appropriate signal was heated on the thermal head, the ink adhered only to the heated portion. Further, as shown in FIG. 7, when the recording paper (NM coated paper 61) was conveyed in contact with the endless belt-shaped recording body 7, 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.

Example 2 Preparation of the film 2 on a polyimide support was performed under the same conditions as in Example 1. Further, in the same manner as in Example 1, heating was performed in a state of contact with the recording agent to make the surface of the film 2 liquid-adhesive and to perform copying. As shown in FIG. 7, the surface of the recording medium 7 was heated at 130 ° C. for about 1 second by the infrared lamp 42 in the 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 this series of operation results, storage and deletion of image information could be confirmed.

[Effects of the Invention] According to the apparatus of the present invention, a liquid adhesion area and a non-liquid adhesion area can be easily formed on a recording medium, and the two divided areas can be returned to the original state. Not only is it easy, but it is also possible to easily print only one sheet or many sheets as desired. In addition, since an endless belt-shaped recording medium is used, processes such as latent image, development, transfer, and image erasing can be performed reversibly and stably a plurality of times. A reduction in thickness is achieved. Further, by using a seamless type recording medium, in addition to the above-mentioned advantages, it is advantageous in terms of high-speed recording, low-energy driving, and durability.

[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 the device 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 when the apparatus of the present invention is used. FIG. 6, FIG. 7, FIG. 8, FIG. 9, FIG. 10, FIG. 11, and FIG. DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Film 3 ... Liquid (3a ... Recording agent) 4 ... Heater 5 ... Lens 6 ... Shutter 7 ... Recording body (A) 8 ... Roller (81 ... Transfer roller) 9 Sponge roller 42 Thermal head

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yasuo Katano 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Yoshio Watanabe 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (56) References JP-A-60-255482 (JP, A) JP-A-3-55283 (JP, A) JP-B-54-41902 (JP, B2) (58) Int.Cl. ⁷ , DB name) B41M 5/00 B41M 5/26 B41C 1/10

Claims (3)

(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 for visualizing the latent image area, and recording paper formed on the surface of the recording medium (A) Means for transferring the image to a recording device. (A) An endless belt-shaped recording material having a surface in which the receding contact angle decreases when it is 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 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 recording medium (A) is a seamless endless belt-shaped recording medium. 3. A recording apparatus according to claim 1, wherein said contact material supply means and said recording material applying means are integrated into one.