JP3030655B2 - Recording device - Google Patents

Description

Description: TECHNICAL FIELD 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 property. A latent image is formed by forming a region having a receding contact angle corresponding to the heating temperature, and then or simultaneously with the formation of the latent image, a recording material containing a color material is supplied to the latent image to form a latent image. The present invention relates to a recording apparatus that transfers the recording paper to recording paper after the conversion.

[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 can be used repeatedly (reversible). Recording methods or 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 these photochromic compounds are 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 a disadvantage that complexity cannot be avoided.

[Problems to be solved by the invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide a recording apparatus which uses a novel recording medium, makes plate making extremely simple and takes no time, and can easily obtain a clear and toned transfer image.

Another object of the present invention is to use a recording medium which is extremely easy to repeat formation and erasure of a liquid-attached area and has excellent storage stability and stability before and after recording. Another object of the present invention is to provide a recording apparatus which can be reduced in cost and maintenance-free.

Still another object of the present invention is to provide a recording apparatus in which the density of a recording material attached to the same image input signal can be kept constant and the image quality is improved.

[Means for solving the problem]

The recording apparatus of the present invention selectively heats the surface of the recording medium (A) below in contact with the contact material (B) below, or selectively heats the surface of the recording medium (A). The contact material (B) is supplied to the surface of the recording medium (A) to form a latent image area having a receding contact angle corresponding to the heating temperature on the surface of the recording medium (A) by contact with the contact material (B). Means, a means for heating the surface of the recording medium (A) for forming a latent image, a recording agent applying means for visualizing the latent image area, and a recording agent attached to the surface of the recording medium (A). Means for transferring to recording paper, and recording medium (A) for erasing latent images
Means for heating the surface, and means for detecting the concentration of the recording agent attached to the surface of the recording medium (A).

(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 at a temperature equal to or lower than the temperature at which the receding contact angle of the recording medium (A) starts decreasing, or generates a liquid or a vapor.

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 the above (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 the air, the hydrophobic group on the surface is changed to the air side (free surface side). It means that it has the property of orienting toward. This can be similarly applied to the above (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 terminal (that is, the surface energy is lowered), 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,
The molecular chains are easily aligned. 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 in the present invention is: (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 γ _s : adsorption (The surface tension of a solid without a 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 the addition of a 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 0 is formed.

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

As the hydrophobic group of the, end of the molecule is preferably -CH ₃
Or _{-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 It is advantageous. Among them, the hydrophobic group includes 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. Heating in a state where the contact material (B) is in contact with the surface of the recording material (A) means that 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 condition.

Before this heating, the surface energy 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 (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 FCH 2 (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 use of the following materials (XI) It is 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 f -COOH ... (} XII) R f -OH ... (XIII) R f CH 2 n SiX ... (XIV) (R f: the number of carbon atoms A group containing four or more alkyl groups or a fluorine- or chlorine-substituted alkyl group, or
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.

In the apparatus of the present invention, when a mixture of the surface forming material of the recording medium (A) and another member, for example, a hydrophobic polymer or a hydrophobic inorganic material, is formed on the support, the surface of the recording medium (A) is excellent in preventing background smearing. I have. 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, 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.

 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.

Next, a heating unit (a heating unit for forming a latent image or an image) 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. In addition, even when electron beam irradiation and light (UV light) irradiation are performed, the object 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 repulsion occurs 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 contact with the contact material (B) is desirably in the range of 50 ° C to 250 ° C, and more desirably in the range of 80 ° C to 150 ° C. Heating time is 0.1m
The time is about 1 second to 1 second, and preferably 0.5 ms to 2 ms. The timing of heating is such that after the surface of the recording medium (A) is heated, the recording material (B) is brought into contact with the contact material (B) before cooling, and the surface of the recording material (A) is brought into contact with the contact material (B). Or heating 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 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.

The recording paper (transfer object) used in the present invention includes:
A transparent resin film, plain paper, inkjet paper, type paper, etc. are suitable.

 Next, the recording agent will be described.

In order to obtain a visible image on the surface of the recording medium (A) in the recording apparatus of the present invention, it is used in a conventional printing recording method such as a writing ink, an inkjet ink, a printing ink, and an electrophotographic toner as a recording agent. From the recording agents that came
Those that fit the process 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 dispersible polymer compound, 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 and reactive dyes in a color index are used. Examples of typical dyes include CI Acid Yellow 17,23,42,44,79,142 CI Acid Red 1,8,13,14,18,26,27,35,37,42,5
2,82,87,89,92,97,106,111,114,115,134,186,249,254,2
89 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 1,12,24,26,33,44,50,142,14
4,865 CI Direct Red 1,4,9,13,17,20,28,31,39,80,8
1,83,89,225,227 CI Direct Orange 26,29,62,102 CI Direct Blue 1,2,6,15,22,25,71,76,79,86,8
7,90,98,163,165,202 CI Direct Black 19,22,32,38,51,56,71,74,7
5,77,154,168 CI Basic Yellow 1,2,11,13,14,15,19,21,23,2
4,25,28,29,32,36,40,41,45,49,51,53,63,65,67,70,73,
77,87,91 CI Basic Red 2,12,13,14,15,18,22,23,24,2
7,29,35,36,38,39,46,49,51,52,54,59,68,69,70,73,78,
82,102,104,109,112 CI Basic Blue 1,3,5,7,9,21,22,26,35,41,45,
47,54,62,65,66,67,69,75,77,78,89,92,93,105,117,12
0,122,124,129,137,141,147,155 Basic Black 2,8 and the like.

As pigments, azo-based, furocyanine-based, anthraquinone-based, quinacridone-based, dioxazine-based, indigo-based, thioindigo-based, perinone-based, perylene-based, isoindolenone-based, aniline black, azomethine azo-based, carbon black as organic pigments 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 1,2,3,4,5,6,7,8,9,10,11,1
2,14,16,17,26,27,29,30,39,40,46,49,50,51,56,61,80,
86,87,89,96 CI Solvent Orange 12,23,31,43,51,61 CI Solvent Red 1,2,3,16,17,18,19,20,22,24,2
5,26,40,52,59,60,63,67,68,121 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 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 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 a support body. 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 method of forming the film 2 on a substrate or a method of producing the recording body using a molded body itself is preferable. In particular,
Since the molded body generally has low mechanical strength, a method of forming a film on a substrate is desirable. 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 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 described above, the heating source is preferably a contact heating source such as a heater or a thermal head, or a non-contact heating source such as a laser or an infrared tamper using electromagnetic waves. As a specific example, 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). It is desirable to employ means (FIGS. 7 (c) and (d)) for heating the recording medium (A) from the surface side and immediately bringing the liquid 3 into contact with the recording medium heating section (the recording medium (A) 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).

Means for adhering a recording agent (ink) to the liquid adhering area selectively applied according to the image signal by the above means,
That is, the simplest configuration of the recording material applying means is to arrange a tray filled with the recording material 3a in the traveling direction of the recording medium (A) with respect to the position of the latent image forming means and to 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 formation of the latent image and development (visualization), for example, a recording agent on the recording medium (A)
The recording agent 3a is provided on the recording paper 3a by means of a capillary action of the recording paper by providing a means for directly contacting the recording paper (transfer means (A). Although any position may be used, a position where transfer is performed immediately after development is desirable.

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 body (A) 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 contact erasing means is provided at a position where the surface of the recording medium (A) is substantially cooled during a period of time from when heating for erasing is performed to when a latent image is formed again.
The heating temperature required for erasing depends on the material on the surface of the recording medium (A), but is preferably a temperature not lower than the starting temperature at which the receding contact angle of the material on the recording medium (A) becomes lower and lower than the decomposition temperature.
That is, heating may be performed at 50 to 300 ° C, preferably 100 to 180 ° C. The heating time in each case is 1 ms to 10 ms, preferably 1 ms to 1 second.

By the way, when the processes such as latent image formation, development, transfer, and image removal are repeated many times, the same image input signal is applied to the recording paper due to a change in the temperature of the recording material (ink) and the recording medium (A). May not be the same. The reason for this is that the materials constituting the recording medium (A) and the recording agent are deteriorated, or the temperature dependence of these characteristics. Thus, the present inventors have conducted researches to solve such a problem, and as a result, provided a means for detecting the concentration of the recording material adhering to the surface of the recording medium (A), and provided a thermal density detector according to the output signal. Controlling the power supplied to the heating means for forming a latent image such as a head, controlling the temperature of the recording material, or transmitting a signal of the recording medium (A) or the timing of replacing the recording material to the user of the apparatus. By doing so, it has been found that it is always possible to obtain the same recorded image for the same input image signal.

Hereinafter, an example of the configuration of a recording apparatus using a unit for detecting the concentration of the recording agent attached to the surface of the recording medium (A) will be described with reference to FIG.

In FIG. 10, reference numeral 71 denotes a recording body, 72 denotes an endless belt-shaped support made of a film made of an organic material, 73 denotes a thermal head for forming a latent image, 74 denotes an ink liquid, 75 denotes a transfer roller, and 76 denotes a transfer roller. Recording paper, 77 is a cleaning brush, 78 is a heating infrared lamp for erasing a latent image, 79 is an ink liquid heating heater, and 80 is a recording medium for detecting the concentration of ink attached to the surface of the recording medium 71. 71 A light source for irradiating light to the surface, 81 is a light receiving element for receiving the reflected light when the surface of the recording medium 71 is irradiated from the light source 80, 82 is a drive unit for the thermal head 73, and 83 is a heater for heating the ink liquid.
79 drive unit, 84 is a message display board, 85 receives a signal from the light receiving element 81, controls the thermal head drive unit 82 or the heating heater drive unit 13,
Further, a control device for sending a message display signal to the message display plate 84, 86 is a latent image formed on the surface of the recording body 71, and 87 is ink attached on the latent image 86.

When the recording body 71 made of the material described above is heated by the thermal head 73 in the presence of the contact material (B) and the ink liquid 74 which also serves as a recording agent, a liquid-adherent latent image is formed on the surface of the recording body 71. 86 is formed and ink adheres to the latent image portion to form a visible image. By transferring this to the recording paper 76, a recorded image can be transferred. After the transfer, the surface of the recording medium 71 is cleaned by a cleaning brush 77, and the surface of the recording medium 71 is further heated by an infrared lamp 78, whereby the latent image 86 is erased, and the process proceeds to the next recording cycle.

Here, in the present configuration example, the following control is performed in order to stabilize the transferred image on the recording paper 76.

First, a standard image is formed as a latent image 86 on the surface of the recording body 71, and then an ink liquid 74 is adhered to the latent image to form an image 87 on the surface of the recording body 71. The image 87 is illuminated by the light source 80, and the reflected light is detected by the light receiving element 81. The control device 85 receives the output from the light receiving element 81 and outputs an image on the recording medium 71 with respect to the standard input image.
When it is determined that the density of 87 is lower than the preset density, a control signal is sent to the drive unit 82 of the thermal head 73 so as to increase the heating temperature of the thermal head 73, or the control of the heater 79 for heating the ink liquid is performed. Drive unit
A control signal is sent to 83 to increase the temperature of the ink liquid. If the image density does not increase even if these controls are performed, it is considered that the recording medium 71 or the ink liquid 74 has deteriorated, and a message such as replacement of these is displayed on the message display panel 84. In this configuration example, a solid black image or a line image is used as the standard image, but the present invention is not limited to this. Further, the ink 87 attached to the control 86 may be provided with a non-recording part in a part of the recording paper 76 and absorbed by the recording paper 76, or may be removed by the cleaning brush 77. According to this configuration example, by performing these controls, the stability of the transferred image can be greatly improved, and the replacement time of the recording body 71 or the ink liquid 74 is also appropriately indicated, so that the recorded image Product quality can be improved.

FIG. 11 shows an example in which an electrometer 88 is used as a means for detecting the attached ink concentration in place of the optical detecting means shown in FIG.
In this example, attention is paid to the fact that the dielectric constant of the ink is different from the dielectric constant of the air, and the dielectric constant of the attached ink 87 is measured by the electrometer 88 to detect the density. Electrometer
Each control based on the output of 88 is the same as that of FIG.

In the above two examples, the standard image is input and the
Although the density of the ink 87 adhering to the recording device is detected, the control can be performed using the image itself input when the recording apparatus is actually used. FIG. 12 shows the device configuration in that case, and the same elements as those in FIG. 10 are denoted by the same reference numerals,
Reference numeral 89 denotes an image input device. With this image input device 89,
The input image signal is applied to the thermal head 73 and sent to the control device 85. By keeping the linear velocity of the recording body 71 constant in advance or monitoring it during driving, it is possible to know when the signal applied to the thermal head 73 passes near the detecting means such as the light receiving element 81.
The ink adhesion density at the time of the passage is detected, and the detected density is compared with a preset density to grasp the ink adhesion characteristic at the present time, and various controls can be performed similarly to the above-described example. This method is different from loading a standard image,
There is an advantage that it is not necessary to create a non-printable area on the recording paper 76, and it is not necessary to clean the attached ink. Furthermore, since the ink adhesion characteristics can be controlled based on the currently input image, there is an advantage that the characteristics of the input image can be more easily reflected.

〔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. If desired, printing of only one sheet or printing of many sheets can be easily performed. In addition, a clear and toned transfer image can be easily obtained, and a means for detecting the density of the recording material attached to the recording medium surface is provided. Can be controlled to be kept constant, so that the image quality can be further improved.

[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 θr observed on the surface of the recording medium (A) when the surface of the recording medium (A) is heated while the liquid is in contact with the surface of the recording medium (A) used in the embodiment of the present invention. FIG. FIG. 5 shows two embodiments when the apparatus of the present invention is used. FIGS. 6, 7, 8 and 9 are views showing an embodiment of the device of the present invention. FIG. 10 is a diagram schematically showing an example of a main part of an apparatus according to the present invention having a means for optically detecting the attached ink concentration. FIG. 11 is a diagram showing an example of detecting the attached ink concentration using an electrometer. FIG. 12 is a diagram showing an example in which the contact of the attached ink density is performed using the input image itself when the apparatus is used. DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Film (recording body) 3 ... Liquid 71 ... Recording body 72 ... Support 73 ... Thermal head 74 ... Ink liquid 75 ... Transfer roller 76 ... Recording paper 79 ... Heater for ink liquid heating 80 ... Light source 81 ... Light receiving Element 82: Driving unit for thermal head 83 ... Driving unit for heater for ink liquid heating 84 ... Message display board 85 ... Control device 86 ... Latent image 87 ... Adhered ink 88 ... Electrometer

Continuing from the front page (72) Inventor Yasuyuki Okada 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Akira Oyamaguchi 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Company (56) References JP-A-60-255482 (JP, A) JP-A-3-55283 (JP, A) JP-B-54-41902 (JP, B2) JP-B-43-23712 (JP, A) B1) (58) Field surveyed (Int. Cl. ⁷ , DB name) B41M 5/00 B41M 5/26 B41C 1/10

Claims (2)

(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, recording agent applying means for visualizing the latent image area, and recording paper adhered to the surface of the recording medium (A). And a means for heating the surface of the recording medium (A) for erasing the latent image, and a means for detecting the concentration of the recording agent attached to the surface of the recording medium (A). A recording device, comprising: (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 (B) supply means and recording agent applying means are combined into one.