JP3115018B2 - 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,
In detail, the surface of the recording medium having a specific property, selectively or selectively and reversibly, so that a region showing a receding contact angle according to the heating temperature (heating energy amount) is formed. The present invention relates to a recording apparatus that forms a latent image, and then or simultaneously with the formation of the latent image, supplies a recording material containing a color developing material to the latent image, visualizes the latent image, and transfers the latent image to recording paper or the like. .

[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 structural change due to 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 new member, which is different from the conventional recording system, in that the receding contact angle is reduced when the member is heated and is brought into contact with the contact material (B). A desired pattern area is formed on the surface of a member having a surface (recording body (A)) selectively or selectively and reversibly by an easy means, and this is visualized and transferred to plain paper or the like. An apparatus is provided.

Another object of the present invention is to provide a novel recording apparatus capable of detecting a rotation unevenness of the recording medium (A) and suppressing the rotation as much as possible to obtain a large number of high-quality transferred images.

[0009]

The recording apparatus according to the present invention comprises selectively heating the surface of the following recording material (A) in contact with the following contact material (B) or the recording material (A). 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), and a recording agent applying means for visualizing the latent image area,
Means for detecting uneven rotation of the recording medium (A). (A) A recording medium having a surface in which the receding contact angle is reduced when heated and brought into contact with a liquid. (B) A liquid, a vapor, or a solid that 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 is formed in the absence of the contact material (B). 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).

The "surface self-orientation function" referred to in (1) means that when a solid formed by forming a certain compound on a support or a solid formed by a certain compound itself is heated in 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.

Summarizing the results of these studies, it is more preferable that 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 a 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 clear from the above description, the surface self-alignment state is related to the receding contact angle, and also between the receding contact angle and the liquid adhesion. That is, the adhesion of the liquid on the solid surface occurs mainly by tacking of the liquid on the solid surface. This tacking can be considered as a kind of frictional force when a liquid slides on a solid surface. Therefore, the “receding contact angle” θr in the present invention is given by cos θr = γ (γs−γse−πe + γf) / γev (where γ: surface tension of solid in vacuum γse: solid-liquid interface tension γev liquid Πe: Equilibrium surface tension γf: Friction 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 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 relationships,
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 in which 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.

FIG. 1 shows an example in which members or materials which "form a surface where the receding contact angle θr decreases when heated and brought into contact with a liquid" 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 in a side chain of a high molecular polymer, wherein a main chain L and a hydrophobic group R are bonded by a bonding group J. doing.

FIG. 1 (b) shows 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) shows 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 and the molecule are connected by a bonding group J, and a self-aggregating or planar structure having a hydrophobic group R at the 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 high molecular 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 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.

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

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 a different 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.

Therefore, 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 used 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.

Furthermore, the surface of the recording medium (A) has a liquid repellency, which can be described by the surface energy of a solid. According to the study of the present inventors, it is found that the surface energy is 50 dyn / cm or less. 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, a compound forming the surface of the recording medium (A) (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, in particular, 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 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
Or a copolymer of a monomer of the formula (XI) with a polymerizable monomer having a functional group.
Product, followed by a copolymer containing many functional groups.
Cross-linking using a cross-linking reagent
Bridging polymers are also excellent materials.

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 cylindrical support (preferably one having a heat-resistant temperature of 50 to 300 ° C.). After the surface member is formed on the plate-like support, the surface member may be formed into a cylindrical shape. In the apparatus of the present invention, the recording medium
When a mixture of the surface forming material (A) and other members, for example, a hydrophobic polymer or 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 above compound. Examples of the heat-resistant support include resin films such as polyimide and polyester, glass and Ni,
Metals such as Al, Cu, Cr, Pt, and metal oxides are preferred.
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, the contact material (B) is 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 vapor 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 more apparent from the description below, when a recording material containing a color developer such as a liquid ink is used as the contact material (B), the latent image is simultaneously formed with the latent image. Will be performed.

Next, the heating means will be described. As a heating means for forming a latent image, 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 thermal head or the like.

FIG. 2A 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 the 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 air, in a vacuum or in an inert gas atmosphere (FIG. 2 (b)), the surface of the film 2 has a receding contact angle θr.
And the liquid repellency is again observed.

As a phenomenon which is 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). 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 is changed according to the image information.
Heat is applied to the membrane 2 under the contact of (as shown in FIG. 3 (b-1) (b-2),
The same applies to the case where the liquid 2 does not exist and the film 2 is brought into contact with the liquid 3 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. In the examples shown in FIGS. 3B-1 and B-2, the film 2 is directly heated. This is an example.

FIG. 4 shows an example of the change in the contact angle of the aqueous solution before and after the heating of the film 2 under the contact with the aqueous solution, and the change 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 for forming a latent image on the surface of the recording medium (A) in contact with the contact material (B) is preferably in the range of 50 ° C. to 250 ° C., more preferably 80 ° C. to 150 ° C. The heating time is about 0.1 msec to 1 sec, preferably 0.5 msec to 2 msec. As for the heating timing, after the surface of the recording medium (A) is heated, it is brought into contact with the contact material (B) before cooling, and the recording material (A) is brought into contact with the contact material (B) on the surface thereof. Or heating the surface of the recording medium (A).

On the other hand, the heating means for erasing the latent image is such that the surface of the recording medium (A) is heated to 50 to 300 ° C., preferably 100 to 180 ° C. by a heater, an infrared lamp or the like in the absence of the contact material (B). (Contact heating, non-contact heating). The heating time is about 1 to 10 seconds, preferably 10 to 1 second.

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 selectively heated to form a liquid adhering area on the surface of the recording medium (A) (latent image formation). Apply the recording agent
(Development), followed by transferring the recording agent on the surface of the recording medium (A) onto recording paper or the like (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, after transferring the recording agent to a recording paper or the like, by heating the surface of the recording medium (A) on which the latent image is formed in the absence of liquid or vapor to erase the latent image, the recording medium (A) is a reproducible recording method. Fig. 5 (a),
(b) shows typical processes of an indirect recording method (printing method) and a reversible recording method of a recording medium (repeated recording method).

Next, the configuration 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
Any material may be used as long as it has a film (described as “film 2” or “recording body (A) surface” as before) 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 an organic thin film 12 is deposited on a good heat conductor such as metal as a support (metal substrate 11), 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 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 conductor portion is provided on the support 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.

FIG. 7 schematically shows a typical example of the apparatus of the present invention. In the figure, 3a is a colored ink (recording agent), 3
a 'is the attached ink, 3a''is the recorded image, 42 is the thermal head, 43 is the infrared lamp for erasing the latent image (for removing the image), 43' is the fixing lamp, 7 is the recording medium (A), and 8 is the ink. A tank, 9 is a transfer roller, P is a recording paper, and 3a is a recording material storage container. In this example, the latent image (s) is erased by heating the surface of the recording medium 7 in the absence of the attached ink 3a 'by the infrared lamp 43 each time the recording medium 7 rotates once. Therefore, it is possible to obtain a new transfer image for each rotation of the recording medium 7.

By the way, the recording body 7 sometimes has uneven rotation. When this rotation unevenness occurs, the latent image (s)
Are partially overlapped (Fig. 9). In FIG. 9, s'
The mark indicates where the latent images overlap. According to the observations of the present inventors, the interval between latent images (s) and the latent image
A correlation with the ink liquid adhesion amount to (s) is observed. In other words, the smaller the distance, the smaller the amount of ink liquid attached tends to be. This is thought to be due to the mutual interference between the free surfaces on the ink liquid surface when the ink liquid adheres to the latent image portion, and if the distance between the latent images becomes uneven, the ink liquid adhesion amount also becomes uneven. It is. Of course, even if the latent images overlap, when the development is performed, the attached ink is separated into the two dots, but the amount of the attached ink is smaller than in the case where the latent images do not overlap. Therefore, when the latent images overlap, the diameter of the dots printed on the recording paper or the like at the time of transfer also becomes smaller.

In order to prevent such inconveniences, the apparatus of the present invention is provided with, for example, "means for detecting (detecting) the rotation unevenness of the recording medium 7" as shown in FIG. 8, 101 is a motor, 102, 102 'and 102''are fixed walls, 103
And 103 'are gears, 104 is a coupling, and 105 is a rotary encoder.

Referring to FIG. 8, the gear 103 is rotated by the motor 101, and the gear 103 is rotated to rotate the gear 103 'and the recording medium 7 connected thereto. The state of rotation of the recording body 7 is detected by the rotary encoder 105 via the coupling 104. Record 7
In order to detect the rotation unevenness, it may be considered that a non-contact type laser Doppler system is used instead of the rotary encoder. Rotor encoder 10
By controlling the rotation speed of the motor 101 on the basis of the rotation unevenness detected by 5, the rotation unevenness of the recording body 7 can be reduced.

In the case of printing at 300 DPI, the center-to-center distance of the dots is about 85 μm, and it is necessary to minimize the rotation unevenness so that the latent images of the dots do not overlap. A method of detecting unevenness and applying feedback to the rotation speed of the motor 101 is considered to be very effective. As for the method of rotating the recording medium 7 from the motor 101, a timing belt or the like may be used in addition to the gears, or it may be considered that the motor shaft and the recording medium (A) are directly connected and rotated. May be.

Further, by the rotary encoder 105,
It may be naturally considered that the signal from the thermal head 42 is controlled by the detected rotation of the recording medium 7 to keep the dot interval constant. For example, when the rotation of the recording medium 7 suddenly increases, the signal interval may be shortened, and when the rotation of the recording medium 7 decreases, the signal interval may be increased. Furthermore, it is conceivable to combine both the feedback of the rotation speed of the motor 101 and the feedback of the interval between signals from the thermal head 42. If the detected uneven rotation is too large, consideration may be given to turning on a lamp or sounding a buzzer to stop the rotation of the motor 101 and notify the abnormality.

The erasure of the latent image is as described above. However, in consideration of the fact that the latent image is formed again on the recording medium (A), the surface of the recording medium (A) heated by the latent image erasing operation is removed. It is necessary to provide a latent image erasing means (non-contact or direct heating) at a position where it is substantially cooled while being moved to a position where it is heated to form a latent image. The heating temperature required for erasing the latent image varies depending on the material of the film 2,
It is desirable that the temperature be equal to or higher than the starting temperature at which the receding contact angle decreases and equal to or lower than the decomposition point.

Examples of the recording paper (transfer object) include a transparent or opaque resin film, plain paper, ink jet recording paper,
Type paper is 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,
As a recording agent, select and use a recording agent that is compatible with the above-described process from among recording agents used in conventional print recording methods such as writing ink, ink jet recording ink, printing ink, and electrophotographic toner. Can be.

More specifically, for example, the aqueous ink may be a water-soluble ink mainly composed of water, a wetting agent and a dye or an aqueous pigment mainly composed of water, a pigment, a polymer compound for dispersion and 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.

Examples of the pigment include azo, phthalocyanine, anthraquinone, quinacridone, and organic pigments.
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, as in the case of the aqueous ink, 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. 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 oil 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.

[0085]

According to the apparatus of the present invention, the means for detecting uneven rotation of the recording medium (A) is provided, so that the uneven rotation of the recording medium (A) can be detected by the rotation or latent rotation of the recording medium (A). By feeding back to the image formation signal, etc., the overlapping of the latent images of the dots can be prevented, and the recording material due to the overlapping of the latent images of the dots can be prevented.
The decrease in the amount of (ink liquid) adhered no longer occurs, and the amount of recording agent (ink liquid) adhering to the latent image becomes constant.
(The diameter of the dots when the ink adhered to the surface of the recording medium (A) is transferred becomes uniform, and a constant image quality can be obtained.

[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 illustrating that latent images overlap due to uneven rotation of a recording medium (A).

[Explanation of symbols]

 1 ... substrate 2 ... film 3 ... liquid (3a ... colored ink) 4 ... heater 5 ... lens 6 ... shutter 7 ... recording medium (A) 8 ... ink tank 9 ... transfer roller 41, 43, 43 '... infrared lamp 42 ... Thermal head 101… Motor 103,103 '… Gear 104… Coupling 105… Rotary encoder

──────────────────────────────────────────────────続 き Continued on the front page (72) Akira Oyamaguchi, Inventor 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company, Ltd. (72) Yoshio Watanabe 1-3-6 Nakamagome, Ota-ku, Tokyo (56) References JP-A-3-178478 (JP, A) JP-A-1-290498 (JP, A) JP-A-62-297186 (JP, A) JP-A-2-4259 (JP, A) German Patent Application 4010275 (DE, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/00 B41C 1/055

Claims (22)

(57) [Claims] 1. A liquid to the receding contact angle decreases when heated in the state after cooling in contact, and the receding contact angle is Ri a high Heating the portion becomes lower its receding contact angle in the absence of liquid , yet reversible recording material the change using a member having a surface the function of Ru reversible der. 2. A liquid to the receding contact angle decreases when heated in the state after cooling in contact, and the receding contact angle is Ri a high Heating the portion becomes lower its receding contact angle in the absence of liquid , yet the change is a reversible recording medium using a member having a surface the function of Ru reversible der, reversible, characterized in that it comprises at least a partial area receding contact angle is lower on the surface Sex record. Wherein the receding contact angle is lowered in a cooled and heated in a state of being in contact with the liquid, and when heated portion becomes lower its receding contact angle in the absence of liquid that the receding contact angle is Ri higher , yet the change is a reversible recording medium using a member having a surface the function of Ru reversible der, on at least a portion of the surface, after the receding contact angle is lower, higher receding contact angle again A reversible recording medium, characterized in that the reversible recording medium has an area where the recording medium has been changed. 4. The reversible recording medium according to claim 1, wherein a layer of a polymer compound having a hydrophobic group in a side chain is formed on a support. of
Reversible recording medium. 5. The reversible recording body according to claim 1, wherein the reversible recording body is formed by forming a layer in which an organic compound having a hydrophobic group is oriented on the surface of a support.
Reversible recording medium. 6. The reversible recording body, support and reversible recording material according to claim 4 or 5, wherein further comprising a primer layer between the layer formed of a compound having a hydrophobic group. 7. The method according to claim 4, wherein the hydrophobic group is an alkyl group having at least fluorine or chlorine.
7. The reversible recording material according to any one of 6. 8. The compound containing an alkyl group having fluorine or chlorine is a polymer of at least one compound selected from the compounds represented by the following general formulas (I) to (VII). The reversible recording medium according to the above. [Here, R is hydrogen, group -CH _3, -C ₂ H _5, a -CF ₃ or -C ₂ F _5, Rf is containing a C ₄ or higher alkyl groups or fluorine or chlorine-substituted alkyl group, Alternatively, a hydrophobic group having (—CF ₂ —) _p , (—CH ₂ —) _p or —Ph— in the molecular chain (p ≧ 4), and m represents an integer of 1 or more. ] 9. The copolymer containing at least one compound selected from the compounds represented by formulas (I) to (VII) as a monomer component, wherein the compound containing an alkyl group having fluorine or chlorine is a compound containing as a monomer component. Claim 7.
Reversible recording medium. 10. The reversible reversal according to claim 2 , according to an image signal.
A recording method comprising heating the surface of a recording medium. 11. The reversible reversal according to claim 2 , according to an image signal.
The latent image portion comprising a liquid adherent region in a surface of the reversible recording material is formed by heating the surface of the sex recording medium, then the recording material in contact, and developed by adhering to the latent image portion, Further, thereafter, a recording agent on the surface of the reversible recording medium is transferred to recording paper. 12. The reversible reversing device according to claim 2 , wherein the reversing device responds to an image signal.
The latent image portion comprising a liquid adherent region in a surface of the reversible recording material is formed by heating the surface of the sex recording medium, then the recording material in contact, and developed by adhering to the latent image portion, After that, after the recording agent on the surface of the reversible recording medium is transferred onto the recording paper, the steps of developing and transferring the recording agent are repeated again. 13. After the transfer of the recording material, the surface portion of the reversible recording medium on which a latent image has been formed in the absence of liquid or vapor is heated to erase the latent image, whereby the reversible image is erased.
13. The recording method according to claim 11, wherein the recording medium is set in a reusable state. 14. A recording characterized in that it comprises a reversible <br/> recording material according to any one of claims 1-9, heating means for heating the surface of the reversible recording medium in accordance with image signals apparatus. 15. A liquid supply device for supplying a liquid for forming a latent image portion formed of a liquid-adhesive region when heated by said heating device.
The recording device as described in the above. 16. The recording apparatus according to claim 14, further comprising a recording agent applying unit for applying a recording agent to a latent image portion formed of a liquid-adhesive region formed by heating by said heating unit. apparatus. 17. The recording apparatus according to claim 16, further comprising transfer means for transferring a recording material applied to said latent image portion by said recording material applying means to recording paper. 18. The method according to claim 18, further comprising the step of supplying the recording agent to the latent image portion by the recording agent applying portion after the recording agent is transferred to the recording paper by the transfer portion, and applying the recording agent to the latent image portion by the transferring portion. 18. The recording apparatus according to claim 17, further comprising means for repeatedly transferring the recording material onto recording paper. 19. Furthermore, after the transfer of the recording agent on the recording paper by the transfer unit, the acceptable-in the absence of liquid or vapor
19. The recording apparatus according to claim 17, further comprising a latent image erasing unit that erases the latent image by heating the inverted recording medium. 20. A printing plate comprising the reversible recording medium according to claim 1. Description: 21. A printing method using the printing plate according to claim 20. 22. A printing apparatus using the recording apparatus according to claim 14. Description: