JP3058472B2 - Recording device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel recording device,
More specifically, a latent image is formed by selectively or selectively and reversibly forming a region having a receding contact angle corresponding to a heating temperature on the surface of a recording medium having a specific property. The present invention relates to a recording apparatus in which a process of supplying a recording material containing a color developing material to a latent image, developing the latent image, and transferring the latent image to a recording sheet can be repeatedly performed.

[0002]

2. Description of the Related Art An offset printing method using a lithographic printing plate is a typical example of a means for dividing a surface into a liquid-adhesive area and a non-liquid-adhesive area for image formation. However, with this offset printing method, it is difficult to incorporate the plate making process from the original plate and the printing process from the printing plate (printing plate) into one device, and it is difficult to reduce the size of the plate making and printing device. 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 and apparatuses have been proposed. Some of them are as follows. (1) Aqueous development method After applying a charge from the outside to the hydrophobic photoconductor layer, exposure is performed to form a pattern having a hydrophobic part and a hydrophilic part on the surface of the photoconductor layer, and only the hydrophilic part is formed. Transfer to a paper etc. by attaching aqueous developer (Japanese Patent Publication No. 40-18992)
No., JP-B-40-18993, JP-B-44-9512, JP-A-63-26
Publications such as 4392). (2) A method utilizing photochemical reaction of photochromic material A layer containing materials such as spiropyran and azo dye is irradiated with ultraviolet rays, and these photochromic compounds are hydrophilized by the photochemical reaction (for example, “Polymer Papers” No. 37). Volume 4
Issue, p. 287 (1980)]. (3) An amorphous state and a crystalline state utilizing the action of an internal bias force are formed by a physical change to form a liquid ink adhesion / non-adhesion region (Japanese Patent Publication No. 54-41902).

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

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 low due to poor quantum efficiency. It has the drawbacks of being extremely long, slow in recording speed, and lacking stability, and has not yet reached a practical level.

Further, according to the method (3), the information recording member used therein has stability after recording, but may have a physical structure change due to a temperature change before recording. However, there is still a problem in storage stability. In addition, since a means for applying a heat pulse and then quenching to erase the recorded information pattern is employed, there is an inconvenience that repetitive image formation cannot mimic the complexity.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a recording medium (A) having a surface having a reduced receding contact angle when heated and brought into contact with a contact material (B). Another object of the present invention is to provide an apparatus for selectively or selectively and reversibly forming a desired pattern area by an easy means, visualizing the desired pattern area, and transferring it to plain paper or the like.

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

It is still another object of the present invention to provide a recording apparatus capable of reliably removing unnecessary latent images and obtaining a new high-quality transferred image.

[0010]

The recording apparatus of the present invention comprises a recording medium (A) which is selectively heated by bringing the surface of the following recording medium (A) into contact with the following contact material (B). The contact material (B), which forms a latent image area showing a receding contact angle according to the heating temperature on the surface of the recording medium (A) by contacting the contact material (B) while the surface of the Recorded body (A)
Means for supplying to the surface, means for heating the surface of the recording medium (A), recording agent applying means for visualizing the latent image area, and recording paper adhering to the recording medium (A) And a means for erasing the latent image by contact heating the surface of the recording medium (A) with a rotatable roller heated in the absence of the contact material (B) and the recording agent. It is characterized by. (A) A recording medium having a surface in which the receding contact angle is reduced when heated and brought into contact with a liquid. (B) A liquid, a vapor, or a solid that generates liquid or vapor at or below the temperature at which the receding contact angle of the recording medium (A) begins to decrease.

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 has been formed in the absence of the contact material (B), so that the reversible image can be obtained. The image can be formed in the first place.

The present inventors have solved many defects as described in the above-mentioned prior art, and have conducted 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 (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. It was also confirmed that the material was oriented on the surface (Japanese Patent Application No. 2-43599).

[0013] The "surface self-orientation function" referred to in (1) means that when a solid formed by a certain compound on a support or a solid by a certain compound itself is heated in the air, the hydrophobic group on the surface is changed to the air side (freely). (Surface side). This can be similarly applied to (2). Generally, in an organic compound, a hydrophobic group has a property of easily moving toward a hydrophobic atmosphere. This is a phenomenon that occurs because the surface energy of the solid-gas interface decreases. This phenomenon is more likely to occur as the molecular length of the hydrophobic group becomes longer, because the longer the molecular length, the higher the mobility of the molecules during heating.

More specifically, it has a hydrophobic group at a terminal.
Molecules (that lower surface energy)
(Free surface side) and easy surface orientation. Similarly, (−CH ₂
-) The linear molecule containing n (-CH ₂ CH ₂ - has a partial planar structures), each other molecular chain is easily oriented. In addition, the molecule containing (-Ph-) n also has a planar structure in the -Ph- portion, and the molecular chains are easily oriented. Note that -Ph-
Represents a p-phenylene group (the same applies hereinafter). 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.

The results of these studies are summarized as follows. More preferably, a linear molecule containing a molecule having a high self-aggregating property or a molecule having a planar structure and having a hydrophobic group at the terminal, or such a linear molecule A compound containing a dendritic molecule can be said to be a compound having a high surface self-orientation function.

As is apparent 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 cos
θr = γ (γs-γse-πe + γf) / γev (where γ: surface tension of solid in vacuum γse: solid-liquid interfacial tension γev surface tension when liquid is in contact with its saturated vapor πe: equilibrium Surface tension γf: frictional tension γs: surface tension of a solid without an adsorbed layer) (Saito, Kitazaki et al., "Journal of the Adhesion Society of Japan" Vol. 22, No. 12, 1986).

Accordingly, the value of γf increases as 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 its surface. Therefore, in the apparatus of the present invention, since the recording medium (A) needs to form a desired pattern area on its surface and / or visualize with a recording agent, a member having a surface self-orientation function on the surface is inevitable. You have to 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 comes into contact with a liquid". The shape of the recording medium (A) is arbitrary as long as the surface has the above-mentioned properties. Therefore, even if the recording medium (A) is in the form of a belt (including an endless belt), 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 is required to have the above-described properties except for the whole or a part thereof.

In the 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, and therefore, when a copy is obtained, Any of ink, water-based ink, and the like 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) shows an example of a compound having a self-orienting function, which is a compound having a hydrophobic group on a side chain of a high molecular polymer, and a main chain L and a hydrophobic group R are bonded by a bonding group J. doing.

FIG. 1 (b) is an example of a member in which the hydrophobic group is oriented on the surface of an organic compound having a hydrophobic group. The member is attached to the surface of the organic or inorganic material M by physical or chemical bonding.
A member on which the compound O having a hydrophobic group 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 the side chain of a polymer. The main chain L is connected to the molecule by a bonding group J, and has a hydrophobic group R at its end. It is a compound having a molecular chain N having a structure 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 mesh 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), without having a main chain (L) or binding to an organic / inorganic material (M), etc.
This is a structure using only the hydrophobic group-containing compound O.

As the above-mentioned hydrophobic group, the terminal of the molecule is preferably -CH ₃ , -CF ₃ , -CF ₂ H, -CFH ₂ , -C (CF ₃ ) ₃ , -C (CH ₃ ) ₃
It is more preferable that the molecular length is long in terms of high molecular mobility. Among them, as the hydrophobic group, -F and / or -Cl is (may be as _{-CF 2 CF 2 C (Cl)} FCF 2 CF 2) 1 or more is a substituted alkyl group or unsubstituted alkyl group And those having 4 or more carbon atoms are desirable. Either fluorine-substitution or chlorine-substitution can be used, but fluorine-substitution is more effective. In these materials, in terms of the relationship between the number of carbon atoms in the alkyl group and the function, if the number of carbon atoms is 3 or less, the function suitable for the recording apparatus of the present invention will be reduced.

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

First, a recording medium formed by the above compound
It is considered that the surface of (A) 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. , Recording body
It is likely that at least part of the orientation (alignment) state of the surface of (A) changes to another state (i.e., another orientation state or a state in which the orientation is disordered), and to maintain that other state even after cooling. .
In addition, heating under the condition that the contact material (B) is in contact with the surface of the recording material (A) depends on the form of the contact material (B), 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,
Regardless of the type of liquid, the receding contact angle θr decreases.
Therefore, the adhesion to the liquid will increase.

Further, when the surface of the recording medium (A) is in another state ("another alignment state" or "a state in which the alignment is disturbed" different from the original alignment state), the surface of the recording material (A) is removed in the absence of the contact material (B). When heated, there is no interaction with the contact material (B), so the original alignment (orientation)
It seems to return to the state.

Accordingly, the presence of the contact material (B) is not merely for quenching the surface of the recording medium (A) after heating, but causes some interaction with the compound on the surface of the recording medium (A). It is considered that a change to another state (a different alignment state or a state where the alignment is disordered) occurs only after this interaction.

As described above, when an alkyl group or a fluorine-substituted or chlorine-substituted alkyl group is employed as the hydrophobic group of the member (compound) forming the surface of the recording medium (A), the carbon number of the alkyl group is It is considered that the reason why the number is preferably 4 or more is based on the number necessary for the alkyl groups to be aligned (orientated) to some extent on the surface of the recording medium (A) and to perform 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.

Further, the surface of the recording medium (A) has a liquid repellency, which can be described by the surface energy of a solid. It has been confirmed that it is desirable as a recording method based on the above. At higher values, the recording medium
The surface of (A) sometimes gets wet and may cause soiling of the background.

Here, the compound forming the surface of the recording medium (A) (the contact material is selectively heated while the surface of the recording medium (A) is selectively heated).
The details of the compound that forms a latent image area having a receding contact angle according to the heating temperature on the surface of the recording medium (A) when contacted with (B) will be described. First, for the types shown in FIGS. 1A and 1D, 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, the formula (I) ( R: -H, -CH ₃ , -C ₂ H ₅ , -CF ₃ or -C ₂ F ₅ Rf: a group containing a C ₄ or more alkyl group or a fluorine-substituted or chlorine-substituted alkyl group, or in the molecular chain And a polymer having a hydrophobic group (P ≧ 4) m having an integer of 1 or more having (—CF ₂ —) p, (—CH ₂ —) p or —Ph—.

Other polymers include compounds of the formulas (VIII) and (IX)
And (X). R: —H, —CH ₃ , —C ₂ H ₅ , —CF _3, or —C ₂ F ₅ Rf: a group containing a C ₄ or more alkyl group or a fluorine-substituted or chlorine-substituted alkyl group, or in the molecular chain (-CF _2- ) p, (-CH _2- ) p
Or a hydrophobic group containing -Ph- (P ≧ 4) n: an integer of 10 or more

Rf in these specific examples is described in more detail below.
Examples of (1) to (20) can be given.

Among these compounds, the following (X
It is desirable to use the material of I). (However, R ¹ : hydrogen, -CxHy or -CxFy (n = 1 or an integer of 2 or more, y = 2x + 1.) R ² : (-CH _2- ) p (p ≧ 1 integer) or ( -CH
_2- ) qN (R ³ ) SO _2- (R ³ is -CH ₃ or -C ₂ H ₅ , q is an integer of 1 or more) m: an integer of 6 or more. ]

Therefore, the most preferred specific compound of the member on the surface of the recording medium (A) in the present invention is CH ₂ ＣC (C
_{H 3) | COO- (CH 2} ) 4 -HCH 2 = C (CH 3) | COO
_{- (CH 2) 5 -HCH 2} = CH | COO- (CH 2) 2 - (CF
_{2) 6 -ClCH 2 = CH |} COO- (CH 2) 2 - (CF 2) 8 -
FCH ₂ = CH | COO- (CH ₂ ) _2- (CF ₂ ) ₆ -FCH _{2
= C (CH 3) | COO-} (CH 2) 2 - (CF 2) 8 -FCH 2 =
_{C (CH 3) | COO- (} CH 2) 2 - (CF 2) 6 -FCH 2 = C
_{H | COO- (CH 2) 2} -N-SO 2 - (CF 2) 8 -F | C 2
_{H 5 CH 2 = CH | COO-} (CH 2) 2 - (CF 2) 9 -
_{FCH 2 = C (CH 3)} | COO- (CH 2) 2 - (CF 2) 10 -
_{FCH 2 = CH | COO-CH} 2 CF 2 CHFCF 3
_{CH 2 = C (CH 3)} | COO- (CH 2) 2 - (CF 2) 9 -F And the like.

Further, these formulas (I) (II) (III (IV) (V) (V
(I) In addition to the monomers of (VII) and (XI) (copolymer of two or more monomers), other monomers such as ethylene, vinyl chloride, styrene, butadiene, isoprene, chloroprene, vinyl alkyl ether, and vinyl acetate And a copolymer with vinyl alcohol and the like are also suitable as the above compound.

Further, it has a monomer of the formula (XI) and a functional group.
Polymerizable monomers such as CH_Two= C (CH_Three) COO (CH_Two)_TwoOH CH_Two= C (CH_Three) COOCH_TwoCH (OH) CH_Three  CH_Two= CHCOOCH_TwoCH (OH) C₈F₁₇  To form a copolymer with at least one of
Having a monomer and a functional group of the formula (XI
A copolymer with a polymerizable monomer is made, followed by a functional group.
Crosslinking of Copolymers Containing a Large Number of Using a Crosslinking Reagent
The cross-linkable polymer produced by
Have been.

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 in the following chemical formula 1.

Embedded image

In the crosslinked polymer represented by the chemical formula 1, A
The block is an alkyl group which causes the above-mentioned change in thermal properties, while the B block is a site which cross-links linear polymers (cross-linked using diisocyanate as a cross-linking reagent). To obtain a crosslinked membrane,
What is necessary is just to apply a solution obtained by mixing the above-mentioned copolymer and the crosslinking reagent on a substrate as a coating solution, and to obtain a crosslinked polymer film by heating or irradiation with electron beam or light.

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

Next, the compound shown in FIG. 1 (b) will be described. Here, the formula (XII), (XII) and the material Rf-COOH · · · shown in (XIV) (XII) Rf- OH ··· (XIII) Rf- (CH 2) n-SiX ··· (XIV (Rf: a group containing an alkyl group having 4 or more carbon atoms or a fluorine-substituted or chlorine-substituted alkyl group, or in the molecular chain
(-CF _2- ) p, (-CH _2- ) p or a hydrophobic group containing -Ph- (P ≧ 4)) n: 1
Integer X: chlorine, methoxy group or ethoxy group) glass, gold, a material obtained by physically adsorbing or chemically bonding to the surface of an inorganic material such as copper, polyimide, polyester, or an organic material such as polyethylene terephthalate (surface energy is about 50 d
yn / cm or less is preferable).

Specific examples of the formulas (XII), (XIII) and (XIV) include CF_Three− (CF_Two)_Five-COOH, CF_Three− (CF_Two)₇-COOH, CF_Three− (CF_Two)₇− (CH_Two)_TwoOH, H- (CF_Two)_Ten-COOH, H- (CF_Two)_Ten-CH_TwoOH, F- (CF_Two)₆-CH_TwoCH_Two-Si (CH_Three)_TwoCl, CF_TwoCl (CF_Three) CF (CF_Two)_FiveCOOH, CF_Three(CF_Two)₇(CH_Two)_TwoSiCl_Three  And so on.

The compound shown in FIG. 1 (c) is represented by the formula (XII),
Examples of the structure include only the material of the formula (XIII) or the formula (XIV).

Next, the recording medium (A) using the above compound will be described. The configuration of the recording medium (A) is such that the above-mentioned surface member is formed on a support (preferably one having a heat-resistant temperature of 50 to 300 ° C.). Therefore, the shape of the recording medium (A) may be a cylindrical shape or an endless belt shape. In the apparatus of the present invention, when a mixture of the surface forming material of the recording medium (A) and other members, for example, a hydrophobic polymer and a hydrophobic inorganic material, is formed on a support, it is excellent in preventing background smearing in printing. 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 a liquid or a 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. The vapor here is at least partially condensed on or near the surface of the recording medium (A) to generate a liquid, and the liquid 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 a recording medium
Condensation at or near the surface of (A) to produce a liquid is the same as in the above case.

More specifically, these contact materials (B) are as follows. That is, as the liquid that 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. And nonpolar liquids such as linear hydrocarbons such as n-nonane and n-octane, cyclic hydrocarbons such as cyclohexane, and 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. In particular, organic vapors such as ethanol vapor and m-xylene vapor can be used. Compound vapors (including those in the nebulized state) are mentioned. 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).

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

As will be clear from the later description, when a "recording agent containing a color developer" such as the above-mentioned liquid ink is used as the contact material (B), the developer is simultaneously developed with the latent image. Imaging will be performed.

Next, the heating means for forming a visible image will be described. As a heating means in response to an image signal, 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.

FIG. 2 (a) shows that a film 2 of the above-mentioned 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 this film surface. It shows the state that it is doing. 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 liquid adhesion is heated again in the air, in a vacuum or in an inert gas atmosphere (FIG. 2B), the surface of the film 2 has a receding contact angle θ.
It can be seen that r increases and shows liquid repellency again.

The method described in Japanese Patent Publication No. 54-41902 mentioned above shows a phenomenon somewhat similar to such a phenomenon. 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). Further, according to the method described in Japanese Patent Publication No. 54-41902, reversibility cannot be obtained by a simple operation.

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

FIG. 3A shows an example in which the film 2 is heated through the support 1, while the example shown in FIG. 3B-1 shows an example in which the film 2 is directly heated. is there.

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 of the contact angle of the aqueous solution when the film 2 is further heated in the air. In FIG. 4, ○ 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 on the surface of the recording medium (A) in contact with the contact material (B) for forming the latent image is 5
The temperature range is preferably from 0 ° C to 250 ° C, more preferably from 80 ° C to
150 ° C. The heating time is about 0.1 ms to 1 second, desirably 0.5 ms to 2 ms. As the timing of heating,
After the surface of the recording medium (A) is heated, the recording medium (A) is brought into contact with the contact material (B) before cooling, and the recording medium (A) is in a state where the contact material (B) is in contact with the surface of the recording medium (A). Heat the surface,
Either may be used.

Next, the means for actually recording image information on the surface of the recording medium (A) will be described in more detail. One is a recording medium in response to an image signal in a liquid or vapor atmosphere.
The surface of (A) is heated to form a liquid adhering area on the surface of the recording medium (A) (latent image formation), and thereafter, the recording agent is applied to the latent image portion by means of contacting the recording agent with the latent image portion. In this method, the recording material on the surface of the recording medium (A) is transferred onto 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 material (A) as a printing plate is obtained. Further, in the above method, a recording material on which a latent image is formed in the absence of liquid or vapor after transferring the recording agent to recording paper
By heating the surface of (A) and erasing the latent image,
(A) is a reproducible recording method. FIGS. 5A and 5B show typical processes of an indirect recording method (printing method) and a reversible recording method of a recording medium (repeated recording method).

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

Next, the structure of the apparatus of the present invention including the recording medium (A) will be described. The surface of the recording medium (A) whose receding contact angle decreases when it is in a heated state and is in contact with a liquid
(Hereinafter, also referred to as “film 2” or “recording body (A) surface” for convenience) may be any as long as it has on the support.

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

FIG. 6 (a) shows an example in which a good heat conductor such as a metal is used as a support (metal substrate 11), an organic thin film 12 is deposited thereon, and a film 2 is further 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 section on the support 1, heat diffusion in the plane direction is prevented, and the portion 2a having liquid adhesion is miniaturized. In FIG. 6B, reference numeral 11a denotes a miniaturized metal film.

Subsequently, a latent image forming means by heating, and further,
The recording agent applying means (visualizing means) 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 the recording agent, those described below are used.

FIGS. 7 and 8 show two typical examples of the apparatus of the present invention. / In the figure, 7 is a recording medium
(A), 8 is a heating roller, 81 is an infrared lamp housed inside the heating roller, 3a is a colored ink (recording agent), 3a 'is an attached ink, 42 is a thermal head, S represents a latent image, and , 9 denotes a sponge roller, 10 denotes a rotating roller, 11 denotes a transfer roller, and P denotes a recording sheet. Note that, in these examples, the heating roller 8 causes the recording material 3a to rotate every time the recording body 7 makes one rotation.
If the recording medium 7 is brought into contact with the recording medium 7 in the absence of the attached ink 3a 'and the surface thereof is heated, the latent image (S) is surely erased. A transfer image can be obtained.

However, electromagnetic waves may be used as heating for image elimination.
Non-contact heating for irradiating (laser light, infrared light) or heating with a thermal head is inevitable. However, according to these methods, sometimes the heating temperature of the surface of the recording medium (A) tends to be higher than necessary, and the thermal head has a small contact area with the recording medium (A). It cannot be denied that the recording medium (A) is worn due to an increase in the surface pressure and some problems remain in the durability.

In the apparatus shown in FIGS. 7 and 8, the recording medium (A)
As mentioned above, an endless belt-shaped one is used, but it is not limited to this.

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

FIG. 9 shows a heating roller slightly different from that described above, in which an infrared lamp 81 is made of a material having a high absorptance in the infrared region.
(Non-metallic material) 82 For example, the roller surface is surrounded by a black material such as carbon black, and a material having a high thermal conductivity (C
If it is formed of u, Ag, Au, Al, etc. 83, the heat of the heating roller can be efficiently conducted to the recording medium 7.

FIG. 10 shows an embodiment in which the temperature of the surface of the heating roller 8 for image removal (erasing of the latent image (S)) is detected by the thermometer 84 and fed back to the power supply 85 of the infrared lamp 81. If the surface temperature of the heating roller 8 is too high,
By turning off the power supply 85 or lowering the voltage, the temperature of the heating roller 8 can be lowered. When the temperature of the surface of the heating roller 8 becomes low, the infrared lamp 81
If the power supply is turned off, the temperature of the heating roller 8 can be increased by turning it on or increasing the voltage. In this way, the temperature of the surface of the heating roller 8 can always be kept at a temperature suitable for removing the image of the recording medium 7,
The image can be reliably removed, and at the same time, the recording body 7 can be prevented from being excessively heated. The surface temperature of the heating roller 8 may be determined by measuring the temperature of the recording medium 7 and performing the above-described OFF, ON, or the like based on the measured temperature.

FIG. 11 shows an example in which a reflection plate 86 is provided around these heating rollers 8. By providing the reflection plate 86, it is possible to prevent unnecessary heat radiation from the heating roller 8,
The thermal efficiency can be increased and the temperature inside the recording device can be reduced.

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

The larger the diameter of the heating roller 8 (the same applies to the roller 8 ′), the larger the contact area with the recording body 7, and the smaller the tangential force acting on the contact surface between the heating roller 8 and the recording body 7, the smaller the radius. Even if the time is small and the time is the same, it is advantageous because the moment for rotating the heating roller 8 is increased by the radius. Therefore, it is desirable that the diameter of the heating roller 8 is large.

Further, the contact pressure per unit area can be reduced by minimizing the pressing force of the heating roller 8 against the recording medium 7 and increasing the contact area thereof, so that the wear of the recording medium 7 can be reduced. Can be. Also,
If the surface roughness of the heating roller 8 is as small as possible, the wear of the recording medium 7 can be reduced.

If there is a difference in the peripheral speed between the heating roller 8 and the recording medium 7, it is conceivable that surface slippage occurs due to contact and the recording medium 7 is worn. For this reason, as shown in FIG. 13 (a), if the end surface of the heating roller 8 is made of metal 8a and the portion of the recording body 7 in contact with the metal surface is made of rubber 7a, for example, Since the degree of friction between them is large, there is no or extremely small slippage between the heating roller 8 and the recording medium 7. In FIG. 13A, reference numeral 88 denotes a bearing. Figure 1
FIG. 3B shows an example in which the peripheral speeds of the heating roller 8 and the recording medium 7 are adjusted by the belt 89. FIG. 13 (c) shows an example in which the belt 89 shown in FIG. 13 (b) is replaced by a gear 89 '.

When the peripheral speed of the heating roller 8 is higher than the peripheral speed of the recording body 7, a tensile stress is generated in the recording body 7, and the recording body 7 is easily worn as described above. Therefore, the heating roller 8
It is desirable to make the peripheral speed equal to the peripheral speed of the recording medium or to make it slightly smaller.

The erasing of the latent image is as described above. However, considering that the latent image is to be formed again on the recording medium (A), the recording medium (A) heated by the latent image erasing operation is used. It is necessary to provide the latent image erasing means at a position where the latent image is substantially cooled while being moved to a position where the latent image is heated for image formation. Further, the heating temperature required for erasing depends on the material of the film 2, but it is desirable that the temperature be equal to or higher than the starting temperature at which the receding contact angle of the film 2 becomes lower and lower than the decomposition point.

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

Next, the recording agent will be described. To obtain a visible image on the recording medium (A) surface in the recording apparatus of the present invention,
Writing ink, ink jet ink,
From the recording agents used in the conventional print recording method, such as printing ink and electrophotographic toner, those suitable for the above process can be selected and used.

More specific examples include, for example, water-based inks such as water-soluble inks mainly composed of water, a wetting agent and a dye, or water-based pigments, high-molecular compounds for dispersion, and aqueous pigments mainly containing a wetting agent. A dispersion ink, an emulsion ink in which a pigment or dye is dispersed in water using a surfactant, and the like are 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; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol and glycerin; ethylene glycol monobutyl ether , Diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monoethyl ether, etc. Polyvalent alcohol Ethers; heterocyclic compounds such as N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam; amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine Kind.

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 1,8,13,14,18,26,27,35,37,42,52,
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 1,12,24,26,33,44,50,142,14
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 19,22,32,38,51,56,71,74,75,
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 2,12,13,14,15,18,22,23,24,27,
29,35,36,38,39,46,49,51,52,54,59,68,69,70,73,78,8
2,102,104,109,112 CI Basic Blue 1,3,5,7,9,21,22,26,35,41,45,4
7,54,62,65,66,67,69,75,77,78,89,92,93,105,117,120,
122, 124, 129, 137, 141, 147, 155 Basic Black 2, 8 and the like.

As the pigment, azo-based, phthalocyanine-based, anthraquinone-based, quinacridone-based, and organic pigments may be used.
Dioxazine-based, indigo-based, thioindigo-based, perinone-based, perylene-based, isoindolenone-based, aniline black, azomethineazo-based, carbon black, and the like.Examples of inorganic pigments include iron oxide, titanium oxide, calcium carbonate, and barium sulfate. Aluminum hydroxide, barium yellow, navy blue, cadmium red, chrome yellow,
Metal powder.

Examples of the pigment dispersing compound 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, water-soluble vinyl naphthalene Maleic acid resin, polyvinylpyrrolidone, polyvinyl alcohol, alkali metal salt of β-naphthalenesulfonic acid formalin condensate, polymer compound containing a salt of a cationic functional group such as quaternary ammonium or amino group, polyethylene oxide, gelatin,
Proteins such as casein, gum arabic, natural gums such as tragacanth gum, glucooxides such as saponin, carboxymethylcellulose, hydroxyethylcellulose, cellulose derivatives such as methylcellulose, ligninsulfonic acid and salts thereof, natural polymer compounds such as ceramics,
And the like.

As the oil-based recording agent, an oil-soluble dye dissolved in an organic liquid compound, a pigment dispersed in an organic liquid compound, and a pigment or dye emulsified in an oil base, as in the case of the aqueous ink. Things, etc. are used.

Representative examples of oily dyes include CI Solvent Yellow 1,2,3,4,5,6,7,8,9,10,11,12,
14,16,17,26,27,29,30,39,40,46,49,50,51,56,61,80,8
6,87,89,96 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, Five
5,58,71,72 CI Solvent Brown 2,10,15,21,22 CI Solvent Black 3,10,11,12,13 and the like.

The oily base for dissolving the dye or dispersing the pigment includes hydrocarbons such as n-octane, n-decane, mineralane spirit, ligroin, naphtha, benzene, toluene and xylene; Butyl ether,
Examples thereof include ethers such as dihexyl ether, anisole, phenetol, and dibenzyl ether; and alcohols such as methanol, ethanol, isopropyl alcohol, benzyl alcohol, ethylene glycol, diethylene glycol, and glycerin.

The pigments exemplified above can also be used in oil-based inks. Examples of oil-based pigment dispersants include:
Polymethacrylate, polyacrylate,
Methacrylic acid ester-acrylic acid ester copolymer,
Polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl pyrrolidone, vinyl copolymers such as polyvinyl butyral,
Cellulose resins such as ethylcellulose and methylcellulose; polycondensation resins such as polyester, polyamide and phenolic resins; and natural resins such as rosin, ceramic, gelatin, casein, and the like.

[0093]

According to the recording apparatus of the present invention, the following effects can be obtained. (1) Image removal (latent image erasure) is performed by bringing the heated rotatable roller into contact with the recording medium (A), so that the image can be reliably removed and the recording medium (A) is removed. ) Is prevented from being excessively heated, so that the image quality is improved. Also,
Since the wear of the recording body (A) is reduced, the durability of the recording body (A) is improved. (2) By arranging a substance having a high absorptance inside the roller for image removal, the roller can efficiently absorb the radiant heat from the infrared lamp, so that the efficiency is extremely improved. (3) By placing a substance with high thermal conductivity on the outer surface of the heating roller, the heat of the heating roller can be efficiently transferred to the recording medium (A).
Heat can be conducted, and the efficiency becomes very good. (4) A means for detecting the temperature of the outer surface of the heating roller or the temperature of the recording medium of the heating roller for image removal, and providing a means for feeding back the intensity of heating of the heating source inside the roller based on the detected temperature. The surface temperature of the heating roller can be maintained at a temperature suitable for the image removal of the recording medium (A), and the image removal can be performed more reliably, without excessively heating the recording medium (A), The image quality is improved, and the durability of the recording body (A) is improved.

[Brief description of the drawings]

FIG. 1 is a diagram of four typical examples of a form having a surface self-orientation function.

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

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

FIG. 4 shows a receding contact angle observed on the surface of the recording medium (A) when the surface of the recording medium (A) is heated while a liquid is in contact with the surface of the recording medium (A) used in the embodiment of the present invention. The figure showing the change of (theta) r.

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

FIG. 6 is a diagram showing an embodiment of the device of the present invention.

FIG. 7 is a diagram showing an embodiment of the device of the present invention.

FIG. 8 is a diagram showing an embodiment of the device of the present invention.

FIG. 9 is a diagram showing an embodiment of the apparatus of the present invention.

FIG. 10 is a diagram showing an embodiment of the device of the present invention.

FIG. 11 is a diagram showing an embodiment of the device of the present invention.

FIG. 12 is a diagram showing an embodiment of the device of the present invention.

FIG. 13 is a diagram showing an embodiment of the device of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Film 3 ... Liquid (3a ... Colored ink) 4 ... Heater 5 ... Lens 6 ... Shutter 7 ... Recording medium (A) 8, 8 '... Heating roller 9 ... Sponge roller 41 ... Infrared lamp 42 ... Thermal head

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masaji Murakami 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Kiyobun Nagai 1-3-3 Nakamagome, Ota-ku, Tokyo No. 6 Inside Ricoh Co., Ltd. (72) Takeshi Takemoto, Inventor 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Yoshio Watanabe 1-3-6, Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (56) References JP-A-3-178478 (JP, A) JP-A-2-128894 (JP, A) German Patent Application Publication 4010275 (DE, A1) (58) Fields investigated (Int.Cl. ⁷ , DB name) B41M 5/00 B41C 1/055

Claims (6)

(57) [Claims] 1. A surface of the following recording material (A) is contacted with the following contact material (B)
The surface of the recording medium (A) is heated to a heating temperature by selectively heating while in contact with the recording medium (A) or by contacting the surface of the recording medium (A) with the contact material (B) while selectively heating the surface. Contact material that forms a latent image area with a corresponding receding contact angle
(B) means for supplying the surface of the recording medium (A), means for heating the surface of the recording medium (A) according to an image signal, recording agent applying means for visualizing the latent image area, and recording Means for transferring the recording agent attached to the surface of the recording medium (A) to recording paper, and contact heating of the surface of the recording medium (A) with a rotatable roller heated in the absence of the contact material (B) and the recording agent And a means for erasing the latent image. (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 generates liquid or vapor at or below the temperature at which the receding contact angle of the recording medium (A) begins to decrease. 2. The recording apparatus according to claim 1, wherein liquid material is used as the contact material (B), and a supply unit and a recording agent applying unit are provided as one unit. 3. The recording apparatus according to claim 1, wherein the latent image erasing heating roller has a built-in infrared lamp as a heating source in a transparent cylindrical body. 4. The heating roller for erasing a latent image according to claim 1, wherein an infrared lamp serving as a heating source and a substance having a high absorptance in an infrared region are built around the infrared lamp. Recording device. 5. The latent image erasing heating roller according to claim 1, wherein the outer peripheral surface is made of a material having a high thermal conductivity.
5. The recording device according to 1, 2, or 4. 6. A means for detecting the temperature of the outer surface of the latent image erasing heating roller or the surface temperature of the recording medium (A), and a heating source inside the latent image erasing heating roller in accordance with the detected temperature. 3. The recording apparatus according to claim 1, further comprising means for feeding back the intensity of the heating.