JP3063772B2 - Recording device - Google Patents

Description

The present invention relates to a novel recording device, and more specifically, selectively or selectively and reversibly attaches to a surface of a recording medium having a specific surface. A region having a receding contact angle corresponding to the heating temperature (heating energy amount) is formed, and a recording agent containing a color developing material is supplied to this region (latent image) to be visualized. The present invention relates to an apparatus useful for a recording system designed to transfer data to paper or the like.

[Conventional technology]

A typical example of a means for dividing the surface into a liquid-adhesive area and a non-liquid-adhesive area for image formation is an offset printing method using a lithographic printing plate without water (fountain solution). Can be However, in this offset printing method, it is difficult to incorporate the plate making process from the original plate and the printing process from the printing plate (printing plate) into one apparatus, and it is difficult to reduce the size of the plate making apparatus. ing.

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

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

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

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

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

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

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

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

[Problems to be solved by the invention]

An object of the present invention is to selectively and easily apply a simple means to the surface of a member (recording body (A)) having a surface having a reduced receding contact angle when heated and in contact with the contact material (B). Another object of the present invention is to provide a recording apparatus that selectively and reversibly forms a desired pattern region (latent image), visualizes the desired pattern region, and transfers the latent image 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 of forming, erasing, visualizing, transferring, and the like 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 novel recording apparatus which can be reduced in size, cost, and maintenance-free, and can obtain a large number of clear images in a short time.

[Means for solving the problem]

The recording apparatus of the present invention selectively contacts the following recording body (A) with the following contact material (B) in a state where the recording body is in contact with the contacting material (B) or in a state where the surface of the recording body (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), means for applying a recording agent for visualizing the latent image area, means for transferring a visible image to recording paper or the like, and prevention of electrification of the recording medium (A) Means are provided.

(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, if a recording agent such as a liquid ink is used, the contact material (B)
If a material such as liquid ink is used as the contact material (B), the image is visualized at the same time as the formation of the latent image, so that the recording material applying means can be omitted. .

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). It can be formed.

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, when the recording medium is heated while being in contact with the liquid, the receding contact angle is reduced even after cooling, and the receding contact angle is increased by heating in the absence of the liquid. Was found to be useful. The recording medium (A) having such a function has a surface of (1) a member containing an organic compound having a surface self-orientation function of a hydrophobic group, or (2) an organic compound having a hydrophobic group and having a hydrophobic group. (Japanese Patent Application No. 2-43599).

The "surface self-orientation function" referred to in (1) means that when a solid formed from a certain compound on a support or a solid formed by a certain compound itself is heated in the air, hydrophobic groups on the surface are changed to the air side (free surface side). It means that it has the property of orienting toward. This can be similarly applied to (2). Generally, in an organic compound, a hydrophobic group tends to be directed toward a hydrophobic atmosphere. This is a phenomenon that occurs because the surface energy of the solid-gas interface decreases. This phenomenon is more likely to occur as the molecular length of the hydrophobic group becomes longer, because the longer the molecular length, the higher the mobility of the molecules during heating.

More specifically, if the molecule has a hydrophobic group at the end (that is, lowers the surface energy), the surface is easily oriented toward the air side (free surface side). Similarly, in a linear molecule containing CH _{2 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 in the present invention includes: (However, γ: surface tension of solid in vacuum γs _l : solid-liquid interfacial tension γ _lV : surface tension when liquid is in contact with its saturated vapor πe: equilibrium surface tension γ _f : friction tension γs: adsorption layer (It is the surface tension of solids without solids) (Saito, Kitazaki, et al., "Journal of the Adhesion Society of Japan," Vol. 22, No. 12, 1986).

Thus, gamma _f increases when the value of θr decreases.
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, even if the recording material (A) is in a belt shape (including an endless belt shape), another coating film having the above-mentioned properties is provided on a suitable cylindrical support or molded body. It does not matter. The molded body itself may be used, but its surface must have the above properties.

Depending on the type of the contact material (B), the recording material (A) has a liquid-adhesive portion in the latent image area which is either lipophilic or hydrophilic. , And a liquid developer for electrophotography are 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 addition, in the examples of FIGS. 1 (a) and 1 (d), the main chain L of the polymer compound may be a straight chain or a shaded structure. In the example of FIG. 1B, the hydrophobic group-containing compound O may be further laminated on the hydrophobic group-containing compound O like a cumulative LB film. In the example of FIG. 1 (c), the main chain (L)
, Or without the organic / inorganic material (M).

As the hydrophobic group, the terminal of the molecule is preferably -CH
₃ and _{-CF 3, -CF 2 H, -CFH} 2, -C (CF 3) 3, -C (C
H ₃ ) _{3 and the} like, and more preferably those having a long molecular length in terms of high molecular mobility. Among them, as the hydrophobic group, a substituted alkyl group having at least one -F and / or -Cl ( Or an unsubstituted alkyl group having 4 or more carbon atoms. Both fluorine substitution and chlorine substitution are used, but fluorine substitution is more effective. In these materials, when the number of carbon atoms is 3 or less,
The function suitable for the recording apparatus of the present invention is reduced.

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

First, it is considered that the surface of the recording medium (A) formed by the above compound is a surface in which the hydrophobic groups are considerably oriented. Therefore, this surface has liquid repellency (because hydrophobic groups have low surface energy). In this state, when the surface of the recording medium (A) comes into contact with the contact material (B) and is heated, the molecular motion of the hydrophobic group due to the heating becomes active, and the interaction with the contact material (B) occurs. The orientation (alignment) state of at least a part of the surface of the recording medium (A) is different (that is, another orientation state or a state in which the orientation is disordered).
Instead, it seems to maintain that other state after cooling. In addition, heating under the state where the contact material (B) is in contact with the surface of the recording body (A) means that the surface of the recording body (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 different from that of the recording medium (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 group be aligned (orientated) to some extent on the surface of the recording medium (A),
In addition, it is thought to be due to the number necessary for active molecular motion during heating. When the contact material (B) is heated together with the surface of the recording medium (A), the molecules of the contact material (B) may be incorporated into the molecules on the surface of the recording medium (A). Furthermore, if 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, this can be described by the surface energy of a solid. We have confirmed that it is desirable. 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 of fluorine and / or chlorine) in the vinyl polymer side chain are considered. Specifically, formulas (I), (II), (III), (IV), and (V)
(VI) and (VII) _{R: -H, -CH 3, -C} 2 H 5, -CF 3 or -C ₂ F ₅ Rf: C ₄ or higher alkyl group or a fluorine or chlorine-substituted alkyl group group containing, or, in the molecular chain CF _2
l , CH _{2 l} or A polymer having a hydrophobic group (l ≧ 4) having an integer n ′: 1 or more as a monomer.

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

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

_{(1) -CH 2 CF 2 CHFCF} 3 _{(6) -CH 2 (CF 2} ) 10 H (7) CF 2 6 O-CF 2 CF 3 (8) CH 2 4 NH-CF 2 CF 3 (9) CF 2 6 CF 3 (10) CH 2 10 C ₈ F _{17 (13) -CH 2 NHSO 2 C} 8 F 17 (15) c · s-CH 2 CH 2 - (CF 3) 6 CF (CF 3) 2 (16) -CH 2 CF 2 CF 2 CF 3 (17) -CH 2 CH 2 CH 2 CH 2 F (18 ) among _{-CH 2 (CF 2) 6 CF} 3 (19) -CH 2 (CF 2) 5 CF 3 (20) CH 2 3 CF 3 these compounds, in particular, the use of the following materials (XI) desirable.

[However, R ¹ : hydrogen, -C _n H _{2n + 1} or -C _n F _{2n + 1} (n = 1 or an integer of 2 or more) R ² : CH _{2 p} (an integer of p ≧ 1) or CH _{2 q} N (R ³ ) SO ₂ − (R ³ is —CH ₃ or —C ₂ H ₅ , q is an integer of 1) m: an integer of 6 or more. Therefore, the most preferred specific compound of the member on the surface of the recording medium (A) in the present invention is And the like.

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

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

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

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

In order to obtain a polymer from the above monomers, an appropriate method is selected depending on the material, such as solution polymerization, electrolytic polymerization, emulsion polymerization, photopolymerization, radiation polymerization, plasma polymerization, graft polymerization, plasma-initiated polymerization, or vapor deposition polymerization. .

Next, the compound shown in FIG. 1 (b) will be described.
Here, the formula (XII), (XIII) and 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 can give.

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.

As the configuration of the recording body (A), as mentioned above,
It is broadly classified into those formed by the surface member itself and those 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 a belt shape (including an endless belt shape), a plate shape, or a drum shape, and is selected according to the intended use of the device. In particular, the drum-shaped one is excellent in that the dimensional accuracy in the device can be obtained. An endless belt is advantageous for miniaturization of the apparatus. The size of the plate may be determined according to the size of the recording paper.

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

 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, and various dispersion liquids and liquid inks may be used. More desirably, polar liquids are better.

As the vapor which is another one of the contact material (B), in addition to water vapor, any 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 description below, when a recording agent containing a developer such as the above-mentioned liquid ink is used as the contact material (B), the visualization is performed simultaneously with the formation of the latent image. This is very practically advantageous.

 Subsequently, the heating means will be described.

As a heating means for forming a latent image, in addition to contact heating using a heater, a thermal head, or the like, 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).

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

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

As shown in FIG. 3 (a), heat is applied to the film 2 in contact with the liquid 3 according to the image information (FIGS. 3 (b-1) and (b-)).
The same applies to the case where the surface of the heated portion of the film 2 is in contact with the liquid 2 in a state where heat is applied to the film 2 according to image information as in 2)). Be adhered. In the figure, 4 is a heater, 31 is a liquid supply port, 41 is an infrared lamp, 5 is a lens, and 6 is a shutter.

FIG. 3 (a) shows an example in which the film 2 is heated through the substrate 1, whereas the examples shown in FIGS. 3 (b-1) and (b-2) show that 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. 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).

On the other hand, in the case of erasing a latent image, the surface of the recording medium (A) is heated to 50 to 300 ° C., preferably 100 to 18 ° C. in the absence of the contact material (B).
What is necessary is just to heat to 0 degreeC. The heating time is about 1 to 10 seconds, preferably 10 to 1 second.

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). This is a method in which the recording agent is adhered to the latent image portion by means of bringing the recording agent into contact with the image portion (development), and thereafter, the recording agent on the surface of the recording medium (A) is transferred to recording paper or the like (indirect recording method). . further,
In the above method, if the recording material is transferred and the latent image portion is again brought into contact with the recording material, a printing method using the recording material (A) as a printing plate is obtained. The other method is to heat the surface of the recording medium (A) on which a latent image has been formed in the absence of liquid or vapor to erase the latent image in the above-described method. (A) is a reproducible recording method. FIGS. 5 (a) and 5 (b) show an indirect recording method (printing method) and a reversible recording method of a recording medium (repeated recording method).
The following shows a typical process.

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

As described above, the recording body (A) has a surface where the receding contact angle is reduced when it is brought into contact with a liquid in a heated state (as described above, the “film 2” or the “recording body (A) surface” for convenience). Is not limited to that form. Therefore, the support substrate of the recording body (A) may be a rigid cylindrical shape or a flexible film shape. The rigid cylindrical recording body (the one having the film 2 formed on the surface of the cylindrical rigid body) is excellent in controllability since the recording body (A) is less likely to be displaced when the recording body (A) is operated. The recording body (A) having a shape is good. For the production of such a recording body (A), a method in which the film 2 is formed on a substrate or a method in which the recording body (A) is produced using a molded body itself is preferable. In particular,
Since the molded article (A) 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 substrate of the recording body (A), it is not a good conductor of heat, and in a type in which heating is performed from the substrate side, the surface of the recording body (A) is heated and the liquid is heated. It takes a certain amount of time to have adhesion.
Therefore, it may be conceivable to use a good heat conductor for the entire substrate or a portion on the substrate 1.

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

Subsequently, a latent image forming means by heating will be described. As described above, as the heating source, a contact heating source such as a heater or a thermal head, or a non-contact heating source using electromagnetic waves such as a laser or an infrared lamp is desirable.

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

As a means for supplying the liquid 3, a plate is provided below the recording medium (A) so that the recording medium 7 is filled with the liquid so that the recording medium 7 is always in contact with the liquid 3 in the pan, and the heating source is arranged near or in the pan. Is the simplest configuration. Instead of the dish, a sponge-like porous body 34 containing 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 (S) is formed on the surface of the recording medium (A).

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

After the latent image formation and development (visualization), for example, the recording material (A)
By providing means for directly contacting the recording material 3a with the recording paper 61 or the like, the image-form recording material 3a is transferred to the recording paper or the like 61 by a capillary action of the recording paper or the like (transfer means). The transfer position may be any position on the recording medium (A) as long as it is after development, but is preferably a position where transfer is performed immediately after development. After the transfer, if the development is repeated without erasing the latent image, the apparatus becomes a printing apparatus. FIG. 10 shows an example of the above printing apparatus, and 62 is a transfer roller. When printing of one piece of image information is completed, recording and printing of another piece of image information becomes possible by replacing the recording medium (A) or by erasing the latent image.

Further, after the transfer means, the latent image (S) is erased by heating the surface of the recording medium (A) in the absence of liquid or vapor, that is, in the air, in a vacuum, or in an inert gas. Then, the recording body (A) becomes a recording device that can be used repeatedly (FIG. 11). 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 41 'is desirable. The heating may be performed only on the latent image portion, or may be performed on the entire surface of the recording medium (A). Rather, heating over the entire surface is more desirable because the device configuration can be simplified. Incidentally, the latent image erasing means, after performing heating for erasing, again,
It is provided at a position where the surface of the recording medium (A) is substantially cooled during the time until the latent image is formed. Although the heating temperature required for erasing the latent image is as described above, it depends on the material on the surface of the recording medium (A). A temperature below the point is desirable.

As the recording paper (transfer object), a transparent or opaque resin film, plain paper, ink jet recording paper, type paper and the like are suitable.

 Next, the recording agent will be described.

In order to obtain a visible image on the surface of the recording body (A) in the apparatus of the present invention, a recording agent has been used in a conventional printing recording system such as a writing ink, an ink jet recording ink, a printing ink, and an electrophotographic toner. Among the recording agents, those that are compatible with the apparatus of the present invention can be selected and used.

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

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

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

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

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

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

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

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

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

In the apparatus of the present invention, as shown in FIGS. 10 and 11, the visible image formed on the surface of the recording medium (A) is transferred to recording paper 61 such as plain paper. ing. When this transfer operation is performed, the surface of the recording medium (A) is sometimes charged by contact with the recording paper 61 or the like, and the amount of charge may be unevenly distributed. When such charging occurs, the ink (recording agent) 3a adhered to the surface of the recording medium (A) according to an image signal due to the electrostatic force may be slightly attracted or repelled and move slightly on the surface of the recording medium (A). Yes, as a result, only the picture quality is produced.

The apparatus of the present invention is provided with an antistatic means for the recording medium (A) in order to prevent such an unexpected situation from occurring. Although it is not impossible to consider that the recording medium (A) itself is difficult to be charged, it is actually difficult in terms of the material used for the recording medium (A). Therefore, in the apparatus of the present invention, a method is employed in which the charge generated on the surface of the recording medium (A) is quickly removed to prevent the charge which substantially affects the image quality.

As a method for quickly removing the surface potential, the first is a method in which a grounded conductive member is brought into contact with the recording medium (A) to release charges through the conductive member. The second method is
This is a method in which the recording material in contact with the recording medium (A) is made conductive and grounded. The third method is a method in which a grounded conductive member is arranged in a non-contact state close to the surface of the recording medium (A). A fourth method is a method in which at least a part of the support substrate of the recording medium (A) is made conductive and this part is grounded. As the conductive member used in the first method, it is desirable to use a member that is as soft as possible so as not to wear the surface of the recording medium.

As the conductive material, metal, conductive rubber, conductive plastic, or the like is desirable, and the shape is preferably a thin plate shape, a brush-like spring with fibers, or a roller-like shape. The position for disposing this member may be any position on the recording medium (A), but is more preferable immediately before the formation of the latent image. Further, a plurality of places may be arranged. Further, the contacting portion may be at least a part of the recording medium (A). In the second method, in order to make a recording agent such as an ink liquid conductive, the method of adding an organic or inorganic salt is the simplest in the case of an aqueous ink. In the case of oil-based ink, there is a method of adding conductive fine particles such as metal.

FIG. 12 (a) shows an example in which a roller-shaped conductive member 52 is used as a first means. FIG. 12 (b) shows an example in which a conductive brush 53 is used as the first means, and a plate-shaped conductive member 54 is used as the second means, and these means are combined. FIG. 13 shows an example in which an arc-shaped plate-like conductive member 55 is brought as close as possible to the recording body 7 (the interval between them is preferably in the range of about 10 μm to several mm).

FIG. 14 shows an example in which the support of the recording substrate (A) is formed by a conductive member. However, in the means shown in FIG. 14, the thickness of the film 2, which is the surface layer, needs to be considerably thin because a tunnel effect is expected.

Thus, according to the use of the device of the invention, the recording medium (A)
The charge on the surface is quickly removed, and a high quality transferred image can be obtained.

〔Example〕

Example 1 A film material (surface layer material of the recording medium (A)) was prepared by solution polymerization in 1,1,1-trichloroethane using perfluoromethyl methacrylate (manufactured by Osaka Organic Chemicals, Biscoat 17FM) as a monomer. did. After purifying this material, it was dissolved in Freon 113, and this solution was cast on a polyimide film. Using this as a recording medium (A), φ100 mm
A recording device was formed with the configuration shown in FIG. The thermal head used had a thermal element of 8 dot / mm pitch. Further, as shown in FIG.
A grounded brush-like conductive member comprising m stainless steel fibers was placed in contact with the recording medium (A). When an image was recorded by this apparatus, no dot disturbance was observed on the image, which was observed when there was no conductive member.

Embodiment 2 The recording body (A), the latent image forming unit and the recording agent attaching unit are the same as those in Embodiment 1. An aqueous ink in which a black direct dye was dissolved and the pH was adjusted to 11 with sodium hydroxide was used as the ink liquid. When this ink was grounded as shown in FIG. 12 (b) to perform image recording, the amount of charge on the surface of the recording body (A) was extremely small (−30 V / c) as compared with the case where the ink was not grounded.
m ² ), and a good image was obtained.

Embodiment 3 The recording body (A), the latent image forming means and the recording agent attaching means are the same as in the first embodiment. As the ink liquid, an aqueous ink prepared by dissolving an acidic black dye and adjusting the pH to 11 with sodium hydroxide was used. Grounded circular conductive plate (made of copper)
As shown in FIG. 13, they were arranged at intervals of about 0.5 mm. In the absence of this member, the charge amount on the surface of the recording medium (A) was about -1 KV / cm ² , but this member reduced the charge amount to about -100 V / cm ² and improved the image quality.

Example 4 The film 2 was made of perfluoromethyl methacrylate (Viscoat 17FM, manufactured by Osaka Organic Chemicals Co., Ltd.) as a monomer.
It was prepared by solution polymerization in 1,1-trichloroethane. After purifying this material, it was dissolved in Freon 113, and this solution was cast on a nickel seamless belt.
Using this as a recording body (A), a recording apparatus was created with the configuration shown in FIG. The thermal head used had a thermal element of 8 dot / mm pitch. Further, as shown in FIG. 14, a nickel seamless belt was grounded. When image recording was performed by this apparatus, dot disturbance on the image, which was observed when the substrate was not a conductive member, was reduced.

〔The invention's effect〕

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

[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 method of the present invention. FIG. 4 shows the change in 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) according to the present invention. FIG. FIG. 5 shows two embodiments of the device of the present invention. FIG. 6, FIG. 7, FIG. 8, FIG. 9, FIG. 10, FIG.
FIG. 12, FIG. 13 and FIG. 14 are views showing an embodiment of the device of the present invention. DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Film 3 ... Liquid 4 ... Heater 52, 53, 54, 55 ... Conductive member

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yasuyuki Okada 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (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 B41C 1/10 B41M 5/26

Claims (6)

(57) [Claims] 1. A method of selectively heating the surface of a recording medium (A) below in contact with the following contact material (B) or contacting the surface of the recording medium (A) while heating the surface selectively. Means for supplying a contact material (B) to the surface of the recording medium (A), which forms a latent image area having a receding contact angle corresponding to the heating temperature on the surface of the recording medium (A) by being brought into contact with the material (B); Means for heating the surface of the recording medium (A), means for applying a recording agent for visualizing the latent image area, means for transferring a visible image to recording paper or the like, and prevention of electrification of the recording medium (A) And a recording device. (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. 2. A recording material is used as the contact material, so that the supply means for the contact material (B) and the recording material applying means can be combined with one another.
The recording device according to claim 1. 3. The recording apparatus according to claim 1, wherein the antistatic means is configured to bring a conductive member into contact with the surface of the recording medium (A) and ground the conductive member. 4. The recording apparatus according to claim 1, wherein the antistatic means is configured to bring a conductive member close to the surface of the recording medium (A) and ground the conductive member. 5. The recording apparatus according to claim 1, wherein the antistatic means is configured such that at least a part of a support substrate of the recording medium (A) is made conductive and the conductive part is grounded. 6. A recording apparatus according to claim 1, wherein said antistatic means is configured to ground said recording material.