JPH0615947A - Recording apparatus - Google Patents

Abstract

PURPOSE:To provide a recording apparatus wherein a latent image is formed selectively or selectively and reversibly on a recording body (A) having a film exhibiting a property lowering a retreating contact angle when it is brought into contact with a contact material (B) such as water under heated condition on the surface and after it is made into a developed image, it is transferred on a plain paper without contact. CONSTITUTION:After a latent image is formed and it is made into a developed image by heating the surface is heated by means of a thermal head 43 while it is brought into contact with an aqueous ink 3a, the aqueous ink adhered on the surface of the recording body (A) is transferred on a recording paper and then, paper powder, etc., retained in the container of the aqueous ink 3a is removed e.g. by means of a mechanical filter 52a. As the result, a number of clear images with good quality can be obtd. in continuous recording.

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, on the surface of the recording body whose surface shows specific properties,
A region having a receding contact angle depending on the heating temperature is formed selectively or selectively and reversibly, and this region is formed.
The present invention relates to an apparatus useful for a recording system in which a recording material containing a color developing material is supplied to (latent image) to make it visible, and this is transferred in good condition to plain paper or the like.

[0002]

2. Description of the Related Art An offset printing method using a lithographic printing plate is a typical means for dividing a surface into a liquid adhesive area and a non-liquid adhesive area for use in 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 printing device. ing. For example, even in a relatively small office offset plate making printing machine, the plate making apparatus and the printing apparatus 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 can be formed according to image information, and can be repeatedly used (reversible Recording methods and devices have been proposed. Some of them are as follows. (1) Aqueous development method After applying a charge to the hydrophobic photoconductor layer from the outside, it is exposed to form a pattern having a hydrophobic portion and a hydrophilic portion on the surface of the photoconductor layer, and only the hydrophilic portion is formed. Aqueous developer is attached and transferred to paper (Japanese Patent Publication No. 40-18992, Japanese Patent Publication No. 40-18993)
(Japanese Patent Publication No. 44-9512, JP-A No. 63-264392, etc.). (2) Method utilizing photochemical reaction of photochromic material The layer containing materials such as spiropyran and azo dye is irradiated with ultraviolet rays, and these photochromic compounds are hydrophilized by photochemical reaction [for example, "Polymer Papers", No. 37 Volume 4
No., 287 (1980)]. (3) Method utilizing the action of internal biasing force The amorphous state and the crystalline state are formed by physical change,
Forming areas where liquid ink is attached / not attached (Japanese Patent Publication No. 54-41)
No. 902).

According to the method (1), after the water-based ink is transferred onto paper or the like, the hydrophilic portion is erased by the charge removal, and another image information can be recorded. That is, one original plate (photoconductor) can be repeatedly used. However, since this method is based on the electrophotographic process, charging → exposure →
It requires a long process of development → transfer → static elimination, and has the drawbacks that it is difficult to downsize the device, reduce the cost, and make it maintenance-free. According to the method (2), the hydrophilicity and the hydrophobicity can be freely and reversibly controlled by selectively changing the irradiation of ultraviolet rays and visible light, but the reaction time is very long because of poor quantum efficiency. However, it has drawbacks such as slow recording speed and lack of stability, and it is a fact that it has not yet reached a practical level. Further, according to the method of (3), the information recording member used there is stable after recording,
Before recording, there is a possibility that the physical structure may change due to the temperature change, so that there is a problem in storage stability.
In addition to this, since a means for applying a heat pulse and then quenching is adopted for erasing the recorded information pattern, there is a disadvantage that repeated image formation cannot imitate complexity.

[0005]

The object of the present invention is to provide a surface of a member (recording body (A)) having a surface with a receding contact angle which is low when heated and in contact with the contact material (B). In addition, the present invention provides a recording apparatus which selectively or reversibly and selectively forms a desired pattern area (latent image) by an easy means, visualizes it, and transfers it to plain paper or the like.
Another object of the present invention is to provide a novel recording apparatus capable of obtaining a large number of good quality transferred images even in continuous recording by always maintaining the contact material (B) and the recording material in a good state. .

[0006]

The recording device of the present invention is a recording medium (A) or by selectively heating the surface of the recording medium (A) in contact with the following contact material (B). A contact material (B) that forms a latent image area showing a receding contact angle according to the heating temperature on the surface of the recording material (A) by contacting the surface of the recording material (B) with the surface selectively heated. Recording body (A)
A means for supplying to the surface, a means for heating the surface of the recording material (A), a recording agent applying means for visualizing the latent image area, and a recording paper for recording material attached to the surface of the recording material (A). And a means for cleaning the contact material (B) and / or the recording agent are provided. (A) A recording material having a surface which has a reduced receding contact angle when heated and brought into contact with a liquid. (B) A liquid, a vapor, or a solid that becomes a liquid or generates a liquid or a vapor at a temperature at which the receding contact angle of the recording medium (A) starts to decrease. In addition, the recording apparatus of the present invention selectively heats the surface of the recording material (A) or the surface of the recording material (A) by selectively heating the surface of the recording material (A) in contact with the following contact material (B). Supplying the contact material (B) to the surface of the recording material (A) that forms a latent image area showing a receding contact angle according to the heating temperature on the surface of the recording material (A) by contacting with the contact material (B) Means, a means for heating the surface of the recording material (A), a recording agent applying means for visualizing the latent image area, and a recording agent adhered to the surface of the recording material (A) is transferred to a recording paper. And a means for heating the latent image area formed on the surface of the recording material (A) to erase the latent image area, and a means for cleaning the contact material (B) and / or the recording agent. Is characterized by. (A) A recording material having a surface which has a reduced receding contact angle when heated and brought into contact with a liquid. (B) A liquid, a vapor, or a solid that becomes a liquid or generates a liquid or a vapor at a temperature at which the receding contact angle of the recording medium (A) starts to decrease.

In the apparatus of the present invention, if a recording material such as a liquid ink is used, the means for supplying the contact material (B) can be omitted, and the liquid ink can be used as the contact material (B). If such a material is used, the latent image is formed and the image is visualized at the same time, so that the recording agent applying means can be omitted. In the device of the present invention, the latent image can be erased by heating the surface of the recording medium (A) on which the latent image is formed in the absence of the contact material (B), and reversible image formation can be performed. Can be done.

The present inventors have made many studies and studies on a novel recording method by eliminating the defects described in the above conventional technique. As a result, a member having a function of reducing the receding contact angle after cooling when it is heated in contact with a liquid and increasing the receding contact angle by heating in the absence of liquid is a recording material. Found to be useful as The recording material (A) having such a function has a surface whose member is (1) a member containing an organic compound having a surface self-alignment function of a hydrophobic group, or (2) an organic compound having a hydrophobic group and having a hydrophobic group. It was also confirmed that it is a member having the surface oriented on the surface (Japanese Patent Application No. 2-43599).

The "surface self-orienting function" referred to in (1) means that when a solid compound formed on a support or a solid formed by the compound itself is heated in air, the hydrophobic group on the surface is free to the air side (free). It means that it has a property of being oriented toward the surface side). This also applies to (2). Generally, in an organic compound, the hydrophobic group has a property of being easily oriented toward the hydrophobic atmosphere. This is a phenomenon that occurs because the interfacial energy of the solid-gas interface becomes lower. Further, this phenomenon is observed as the molecular length of the hydrophobic group becomes longer, and this is because the mobility of the molecule upon heating increases as the molecular length becomes longer.

More specifically, it has a hydrophobic group at the end.
When it is a molecule (that is, it lowers the surface energy), it is on the air side.
It is easy to orient to the surface (free surface side). Similarly (-CH ₂
-) The linear molecule containing n (-CH ₂ CH ₂ - has a partial planar structures), each other molecular chain is easily oriented. Further, in the molecule containing (-Ph-) n, the -Ph- portion has a planar structure, and the molecular chains are easily oriented. Note that −
Ph- is a p-phenylene group (hereinafter the same). In particular, a linear molecule containing an element having a high electronegativity such as fluorine has a high self-aggregating property, and the molecular chains are easily oriented.

Summarizing the results of these examinations, it is more preferable that a straight-chain molecule containing a molecule having a high self-aggregation property or a molecule having a planar structure and having a hydrophobic group at the end, or such a straight-chain molecule. It can be said that the compound containing the linear molecule has a high surface self-orientation function.

As is clear from the above description, there is a relationship between the surface self-alignment state and the receding contact angle, and also between the receding contact angle and the liquid adhesion. That is, the adhesion of the liquid on the solid surface occurs mainly by the tacking of the liquid on the solid surface. This tacking can be regarded 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 liquid Surface tension when is in contact with its saturated vapor πe: Equilibrium surface tension γf: Friction tension γs: Surface tension of solid without adsorption layer) (Saito, Kitazaki et al. Vol. 22, No. 12, 1986).

Therefore, the γf value increases as the value of θr decreases. That is, the liquid does not easily 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 degree of the receding contact angle θr, and the receding contact angle θr is determined by how the member having the surface self-orienting function on the surface. Therefore, in the device of the present invention, the recording medium
In the case of (A), a member having a surface self-orienting function on the surface must be selected inevitably because it is necessary to form a desired pattern region on the surface and / or to visualize it with a recording agent.

As described above, the recording medium (A) used in the apparatus of the present invention has "a surface on which the receding contact angle θr decreases when it is heated and in contact with a liquid". The recording medium (A) may have any shape as long as the surface has the above-mentioned properties. Therefore, even if the recording material (A) has a belt shape (including an endless belt shape), another coating film having the above-mentioned properties on the surface is provided on a suitable cylindrical support or molded body. It doesn't matter even if it is. Although it may be the molded body itself, the surface thereof is required to have the above-described properties except for the whole or a part thereof.

In this recording medium (A), the liquid adhering portion in the latent image area becomes either lipophilic or hydrophilic depending on the type of the contact material (B), and therefore, when obtaining a copy, it is oily. Ink, water-based ink, liquid developer for electrophotography, and the like can be used as needed. However, in the device of the present invention, as described above, it is advantageous to use the water-based ink in which the liquid-adhesive portion is hydrophilic.

FIG. 1 shows an example in which some members or materials "form a surface whose receding contact angle .theta.r decreases when heated and brought into contact with a liquid" are classified into several types.

FIG. 1 (a) is an example of a compound having a self-orienting function, which is a compound having a hydrophobic group on the side chain of a high molecular polymer, in which the main chain L and the hydrophobic group R are bonded by a bonding group J. is doing.

FIG. 1 (b) shows an example of a member in which an organic compound having a hydrophobic group has the hydrophobic group oriented on the surface thereof. The surface of the organic or inorganic material M is physically or chemically bonded to the surface.
It is a member in which the compound O having the hydrophobic group is formed.

FIG. 1 (c) shows an example of a member made of only the organic compound O having a hydrophobic group as 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 linking group J, and a self-aggregating or planar surface having a hydrophobic group R is attached. It is a compound having a molecular chain N having a structure in the middle.

In the examples of FIGS. 1 (a) and 1 (d), the main chain L of the polymer compound may be linear or may have 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, as in the cumulative LB film. In the example of FIG. 1 (c), without having a main chain (L) or binding to an organic / inorganic material (M),
The structure is composed only of the compound O containing the hydrophobic group.

Examples of the hydrophobic group of the, the end of the molecule is preferably -CH ₃ or _{-CF 3, -CF 2 H, -CFH} 2, -C (CF 3) 3, -C (CH 3) 3
Etc., and more preferably, one having a long molecular length is advantageous in terms of high molecular mobility. Among them, the hydrophobic group, -F and / or -Cl is a substituted alkyl group having one or more (may also be such as -CF ₂ CF ₂ C (Cl) FCF ₂ CF ₂ ) or an unsubstituted alkyl group However, those having 4 or more carbon atoms are desirable. Both fluorine substitution and chlorine substitution can be used, but fluorine substitution is more effective. In these materials, the relationship between the number of carbon atoms in the alkyl group and the function is
When the carbon number is 3 or less, the function suitable for the recording apparatus of the present invention is deteriorated.

The principle of this function expression has not been completely clarified yet, and therefore, although there are many unclear points, the following is presumed.

First, a recording body formed of 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 the hydrophobic group has a small surface energy). In this state, when the surface of the recording material (A) is heated by contacting the contact material (B), the molecular motion of the hydrophobic group is activated by the heating and the interaction with the contact material (B) is received. , Recording body
It seems that at least part of the (A) surface's orientation (alignment) state changes to another state (i.e., another orientation state or a state in which the orientation is disturbed), and that other state is maintained even after cooling. .
Heating under the condition that the contact material (B) is in contact with the surface of the recording material (A) means that the surface of the recording material (A) is heated depending on the form of the contact material (B). The liquid comes into contact with the source. Prior to this heating, since the hydrophobic groups are aligned (orientated) on the surface, the surface energy of the surface of the recording material (A) is extremely small.

However, the heating in the state in which the contact material (B) is in contact with the contact material (B) disturbs the orientation state and increases the surface energy. The receding contact angle θr is determined by the balance of the surface energies of the solid and the liquid, regardless of the type of the liquid. Therefore, if the surface energy of the solid increases,
The receding contact angle θr decreases regardless of the type of liquid.
Therefore, the adhesion to the liquid will be increased. Furthermore, the surface of the recording material (A) is in a different state (a different orientation state different from the original orientation state or a state in which the orientation is disturbed)
When it is heated in the absence of (B), the interaction with the contact material (B) does not occur, and it is considered that the original alignment (orientation) state is restored. Therefore, the presence of the contact material (B) is merely a recording medium (A).
It is not for quenching after heating the surface of the recording medium, but for some kind of interaction with the compound on the surface of the recording medium (A).
It is thought that the change to (another orientation state or a state where the orientation is disturbed) occurs.

As described above, when an alkyl group or a fluorine-substituted or chlorine-substituted alkyl group is adopted as the hydrophobic group of the member (compound) forming the surface of the recording material (A), the carbon number of the alkyl group It is thought that the reason why the value of 4 or more is desirable is that the alkyl groups are aligned (orientated) to some extent on the surface of the recording material (A) and that the number is necessary for vigorous molecular movement during heating. Further, when the contact material (B) is heated together with the surface of the recording material (A), the molecules of the contact material (B) may be incorporated into the molecules of the surface of the recording material (A). Further, when 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 larger change in adhesiveness can be obtained as compared with a compound containing an alkyl group containing only hydrogen. Further, the fluorine-containing alkyl group has a strong self-aggregating property and thus has a high surface self-orienting function, and further has a low surface energy, and is therefore excellent in terms of preventing the background stain.

Furthermore, the surface of the recording medium (A) has liquid repulsion property, which is described by the surface energy of solid. According to the study by the present inventors, it is 50 dyn / cm or less. It is also confirmed that it is desirable as a recording method by. If the value is higher than this, the recording material
The surface of (A) sometimes gets wet, which may cause soiling of the background.

Here, a compound forming the surface of the recording material (A) (a contact material in a state where the surface of the recording material (A) is selectively heated)
The details of the compound that forms a latent image area showing a receding contact angle on the surface of the recording material (A) when brought into contact with (B) will be described. First, regarding the types shown in FIGS. 1 (a) and 1 (d), compounds having an alkyl group (including those having fluorine substitution and / or chlorine substitution) in the side chain of a vinyl-based polymer are considered. Specifically, formulas (I) (II) (III) (IV) (V) (VI) and (VI
I) R: -H, -CH ₃ , -C ₂ H ₅ , -CF ₃ or -C ₂ F ₅ Rf: C ₄ or more alkyl group or group containing a fluorine-substituted or chlorine-substituted alkyl group, or in the molecular chain To (-C
A polymer having an integer of 1 or more as a hydrophobic group (P ≧ 4) m: 1 having F ₂ −) p, (—CH ₂ —) p or —Ph— is a polymer.

Other polymers include those of formula (VIII) (IX)
And those shown in (X). _{R: -H, -CH 3, -C} 2 H 5, -CF 3 or -C ₂ F ₅ Rf: C ₄ or higher alkyl group or fluorine-substituted or chlorine-substituted alkyl group group containing or molecular chain in To (-CF
_2- ) p, (-CH _2- ) p or -Ph-containing hydrophobic group (P ≥ 4) n: integer of 10 or more

More specifically, Rf in these specific examples is as follows.
Examples are (1) to (20).  

Among these compounds, the following (X
Use of material I) is preferred. (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 -C
H ₃ or -C ₂ H ₅ , an integer of q ≧ 1) m: An integer of 6 or more. ]

Therefore, the surface of the recording material (A) in the present invention is
The most preferable specific compound of the member is And so on.

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

Further, the monomer of the formula (XI) and a polymerizable monomer having a functional group such as CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₂ OH CH ₂ = C (CH ₃ ) COOCH ₂ CH (OH) CH ₃ CH ₂ = CHCOOCH ₂ CH (OH) C ₈ F _17, etc. to form a copolymer with at least one functional group or to introduce a large number of functional groups into the polymer, or to formula (XI A crosslinkable polymer produced by forming a copolymer with a monomer and then crosslinking the copolymers containing a large number of functional groups with a crosslinking reagent is also excellent as a material.

Examples of the crosslinking reagent include formaldehyde, dialdehyde, N-methylol compound, dicarboxylic acid, dicarboxylic acid chloride, bishalogen compound, bisepoxide, bisaziridine and diisocyanate.

An example of the cross-linked polymer thus obtained is shown below.

[Chemical 1]

In the crosslinked polymer represented by Chemical formula 1, A
The block is an alkyl group that brings about the change in the thermal properties described above, while the B block is a site where the chain polymers are crosslinked (crosslinked using diisocyanate as a crosslinking reagent). In order to obtain a crosslinked membrane,
A solution obtained by mixing the above-mentioned copolymer and a crosslinking reagent may be applied as a coating solution on a substrate to obtain a crosslinked polymer film by heating or electron beam irradiation or light irradiation.

In order to obtain a polymer from the above monomers, solution polymerization, electrolytic polymerization, emulsion polymerization, photopolymerization, radiation polymerization, plasma polymerization, graft polymerization, plasma initiation 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 -Ph-containing hydrophobic group (P≥4)) n: integer of 1 or more X: chlorine, methoxy group or ethoxy group) etc. ,
An inorganic material such as copper or an organic material such as polyimide, polyester, or polyethylene terephthalate, which is physically adsorbed or chemically bonded (the surface energy is preferably about 50 dyn / cm or less) is preferable.

[0040] Formula (XII) (XIII) and Specific examples of _{(XIV) CF 3 - (CF} 2) 5 -COOH, CF 3 - (CF 2) 7 -COOH, CF 3 - (CF 2) 7 - _{(CH 2) 2 OH, H-} (CF 2) 10 -COOH, H- (CF 2) 10 -CH 2 OH, F- (CF 2) 6 -CH 2 CH 2 -Si (CH 3) 2 Cl, such as _{CF 2 Cl (CF 3) CF} (CF 2) 5 COOH, CF 3 (CF 2) 7 (CH 2) 2 SiCl 3 and the like.

The compound shown in FIG. 1 (c) includes formula (XII) and formula
Examples of the structure include only the materials of (XIII) and formula (XIV).

Next, the recording material (A) using the above compound will be described. As the constitution of the recording body (A), as mentioned above, the one formed by the surface member itself,
A support (preferably a heat-resistant support) on which the above-mentioned surface member is formed, and a conductive member which is in contact with the contact material (B) which forms at least a latent image area and which inserts an electric charge into the contact material. It is roughly divided into those that have. In this embodiment, the compound (surface member) itself is formed into a film, a plate, or a column. At this time, in the case of a film, the film thickness is 1 μm to 5 mm.
Is desirable. In the above embodiment, the above compound may penetrate into the support to some extent. Recording body (A)
It is desirable that the film thickness of itself is 30Å ~ 1 mm. However, in terms of thermal conductivity, 100Å to 10 μm, and in terms of wear resistance, 10 μm to 1 mm.
Is excellent. The heat-resistant temperature of the support is 50 ℃ ~ 30
0 ° C is desirable. In the embodiment of the present invention, as will be described in detail later, it has a conductive member that is sufficiently smaller than the size of one latent image region which is considered to be the smallest, and a recording material that has been used for visualization through this conductive member. The device is designed to inject a charge into the agent. In the use of the recording material (A) having the above-mentioned configuration, the tip of only the recording agent provided for visualization is brought into contact with the conductive thin wire 16 to which a voltage is applied, as shown in FIG. 11, for example. The recording medium 3a 'is then injected with electric charges. 11A is a schematic perspective view of the state, and FIG. 11B is a schematic sectional view. The mode will be described in detail later.

The shape of the support may be belt-shaped (including endless belt-shaped), plate-shaped or drum-shaped, and is selected according to the intended use of the apparatus. Particularly, the drum-shaped one is excellent in that the dimensional accuracy in the device can be obtained. The endless belt type is advantageous for downsizing the device. The size of the plate-shaped material may be determined according to the size of the recording paper.

Further, when a mixture of the above compound (the surface forming material for the recording material (A)) and another member, for example, a hydrophobic polymer or a hydrophobic inorganic material is formed on a support, it is possible to prevent the background stain in printing. It's excellent. Further, in order to improve the thermal conductivity, it is advisable to mix a metal powder with the above compound. Furthermore, a primer layer may be provided between the support and the compound to improve the adhesion between the support and the above compound. As a heat resistant support, resin films such as polyimide and polyester, glass, Ni, Al, Cu, Cr, P
Metals such as t and metal oxides are 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 not more than 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 on the surface of the recording material (A) or near the surface thereof, at least a part of which is condensed to form a liquid, and the liquid can wet the surface of the recording material (A). Is enough. On the other hand, the solid here is a liquid, a liquid is generated, or a vapor is generated at a temperature at which the receding contact angle θr is reduced or lower. The vapor generated from the solid is a recording material
The condensation on the surface of (A) or in the vicinity thereof to generate a liquid is similar to the above case.

More specifically, these contact materials (B) are as follows.

That is, as the liquid which is one of the contact materials (B), in addition to water, an aqueous solution containing an electrolyte, ethanol, n-
Alcohols such as butanol, polyhydric alcohols such as glycerin and ethylene glycol, polar liquids such as ketones such as methyl ethyl ketone, straight chain hydrocarbons such as n-nonane and n-octane, and cyclic hydrocarbons such as cyclohexane. , Non-polar liquids such as m-xylene and aromatic hydrocarbons such as benzene. Also, a mixture of these may be used, and various dispersions and liquid inks can also be used. More desirably, polar liquids are better.

As the vapor which is another one of the contact materials (B), in addition to water vapor, any vapor of the liquid of the contact material (B) can be used. In particular, organic vapor such as ethanol vapor and m-xylene vapor can be used. Examples include vapors of compounds (including those in a spray state). The temperature of this organic compound vapor needs to be lower than the melting point or softening point of the compound forming the surface of the recording material (A).

Other solids as the contact material (B) are higher fatty acids, low molecular weight polyethylene, polymer gels (polyacrylamide gel, polyvinyl alcohol gel), silica gel, compounds containing water of crystallization and the like. can give.

As will be more apparent from the description below, when a recording material "containing a color developing agent" such as the liquid ink is used as the contact material (B), it is developed at the same time as the latent image formation. Imaging is performed, which is extremely advantageous in practical use.

Next, the heating means will be described.

As a heating means for forming a latent image, in addition to contact heating with a heater, a thermal head, etc., an electromagnetic wave is used.
There is non-contact heating by (the light from the light source such as a laser light source and an infrared lamp is condensed by a lens).

In FIG. 2 (a), a film 2 of the compound forming the surface of the recording material (A) is formed on a substrate 1, and the liquid 3 of the contact material (B) is present on the film surface. It shows the state. In this state, when the film 2 is heated, the receding contact angle θr of the surface of the film 2 is lowered and the film 2 shows remarkable wetting, and it is recognized that the film 2 has liquid adhesion. Further, when the film 2 having liquid adhesion property is heated again in air, vacuum or inert gas atmosphere (FIG. 2 (b)), the surface of the film 2 recedes at a contact angle θr.
It can be seen that the liquid repelling property is again exhibited as the liquid crystallinity increases.

As a method showing a phenomenon somewhat similar to such a phenomenon, there is the method described in Japanese Patent Publication No. 54-41902 mentioned above. However, the methods disclosed herein are largely mechanically different in that the recording materials provide a layer of substantially discontinuous and generally amorphous memory material. That is, in the present invention, the state change cannot occur on the surface of the recording body (A) without the presence of the contact material (B). Further, with the method described in Japanese Patent Publication No. 54-41902, reversibility cannot be obtained by a simple operation.

As shown in FIG. 3 (a), the liquid 3
Is applied to the film 2 under the contact of (in the state in which the liquid is absent, as shown in (b-1) and (b-2) of FIG. (It is the same even if it is brought into contact with liquid 3 with and)
Then, the surface of the film 2 in the heating portion is made liquid-adhesive. 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. Figure 3
(a) is an example in which the film 2 is heated through the substrate 1, while the example shown in FIGS. 3 (b-1) and (b-2) is an example in which the film 2 is directly heated. .

An example of the variation of the contact angle of the aqueous solution before and after heating the membrane 2 in contact with the aqueous solution and the variation of the contact angle of the aqueous solution when the film 2 is further heated in air is shown in FIG. In FIG. 4, ◯ indicates a forward contact angle and Δ indicates a backward contact angle. Generally, when the receding contact angle is a high value of 90 ° or more, the surface exhibits liquid repulsion, and when the receding contact angle is a low value of 90 ° or less, the surface exhibits liquid adhesion.

The heating temperature of the surface of the recording material (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. Heating time
It is preferably about 0.1 msec to 1 sec and 0.5 msec to 2 msec. As for the timing of heating, after heating the surface of the recording material (A), the material is brought into contact with the contact material (B) before it is cooled, and the surface of the recording material (A) is brought into contact with the contact material (B). Alternatively, the surface of the recording material (A) may be heated.

On the other hand, in the case of erasing the latent image, the contact material (B)
The recording medium (A) surface at 50 to 300 ° C, preferably 10
It may be heated to 0 to 180 ° C. The heating time is about 1 msec to 10 sec, preferably 10 msec to 1 sec.

Next, the means for actually recording image information on the surface of the recording medium (A) will be described in more detail.

One is to heat the surface of the recording body (A) in a liquid or vapor atmosphere in response to an image signal to form a liquid adhesion area (latent image formation) on the surface of the recording body (A), and thereafter. , The recording agent is adhered to the latent image portion by the means of bringing the recording agent into contact with the latent image portion (development), and after the charge is injected into the recording agent, the recording agent on the surface of the recording medium (A) Is a non-contact transfer method (indirect recording method). Further, in the above-mentioned method, after the recording agent is transferred in a non-contact manner, if a means for bringing the recording agent into contact with the latent image portion again and injecting an electric charge into the latent image portion is performed, a printing method using the recording material (A) as a printing plate is obtained. .

In another method, after the recording material is transferred in the above method, the surface of the recording medium (A) on which the latent image is formed is heated in the absence of liquid or vapor to erase the latent image. The recording method is such that the recording medium (A) can be reproduced. 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).

Next, in order to make the structure of the apparatus of the present invention including the recording material (A) easier to understand, (1) charges are injected into the recording material on the surface of the recording material (A) on which a visible image is formed. The description will proceed from the recording apparatus in the state where the means is removed and (2) the means for transferring the visible image onto the recording paper or the like in a non-contact manner is removed.

As described above, the recording medium (A) has a surface on which the receding contact angle decreases when it is heated and brought into contact with a liquid.
As long as it has a "membrane 2" or a "recording body (A) surface" for convenience as described above, it is not limited to the form. Therefore, the support substrate of the recording body (A) may have a rigid cylindrical shape or a flexible film shape. A rigid cylindrical recording medium (a film with a film 2 formed on the surface of a cylindrical rigid medium) is excellent in controllability because it is unlikely to cause misalignment when operating the recording medium (A). Shaped recording material (A) is good. The recording body (A) is preferably manufactured by a method of forming the film 2 on a substrate or a molding body itself. In particular, since the recording body (A) made of the molded body itself generally has low mechanical strength, a method of forming a film on a substrate is preferable. Even when the recording body (A) is made from the molded body itself, the film 2 is
Needless to say, must be formed.

When a resin is used for the support substrate of the recording body (A), it is hard to say that this is a good conductor of heat, and in the case of a type in which heating is performed from the substrate side, the surface of the recording body (A) is It takes some time to be heated and have liquid adhesion. Therefore, a good conductor of heat is applied to the entire substrate or the substrate 1
It may be considered to be used for the upper part.

In FIG. 6 (a), if a good heat conductor such as metal is used as a substrate (metal substrate 11), an organic thin film 12 is vapor-deposited thereon, and a film 2 is further formed thereon. The heat transfer rate in the vertical direction is improved. Examples of the organic thin film 12 here 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 area with liquid adhesion expands due to thermal diffusion in the surface direction. .

For this reason, FIG. 6 (b) shows a structure in which a good heat conductor portion is provided on the substrate 1 in a divided manner to prevent heat diffusion in the surface direction and to miniaturize the portion 2a having liquid adhesion. . In FIG. 6 (b), 11a represents a minute metal film.

Next, the latent image forming means by heating will be described. As described above, the heating source is preferably a contact heating source such as a heater or a thermal head or a non-contact heating source using electromagnetic waves such as a laser or an infrared lamp.
As a specific example of these, a recording medium (A) in a state of being in contact with a liquid
The means for heating the surface will be described. For the sake of convenience, the description will proceed with a recording body (A) of the type in which the film 2 is formed on the substrate 1. First, record beforehand
7 Means for contacting the liquid 3 on the surface and heating the substrate 1 side or the liquid 3 side in the contact state ((a) and (b) of FIG. 7)
Or, first, heat the recording material (A) from the surface side and immediately
To contact the heating unit of the recording medium (the surface of the recording medium (A)) (Fig.
It is desirable to adopt (c) and (d)).

As a means for supplying the liquid 3, a plate is provided below the recording medium (A) so that the liquid 3 is filled and the recording medium 7 is always in contact with the liquid 3 in the plate. The simplest configuration is the one that is placed in. Instead of the dish, a sponge-like porous body 34 containing a liquid may be used. The latent image forming means using light or an electron beam is basically the same as the above configuration. In FIG. 7, 42 is a laser light source and 43 is a thermal head. In this way, a latent image is formed on the surface of the recording medium (A).
(S) is formed.

As a means for adhering the recording agent (for example, ink liquid) to the liquid adhering region selectively applied according to the image signal by the above means, a plate filled with the recording agent 3a is placed at the latent image forming means position. On the other hand, the simplest configuration is one in which the recording medium (A) is arranged in the traveling direction and is always in contact with the surface of the recording medium (A) (FIGS. 8 and 9). As shown in FIG. 9, when the liquid used for latent image formation is also used as the recording agent 3a such as ink liquid, it can be configured with one dish, and the latent image formation and the visualization thereof can be integrated, so that the apparatus can be made compact. Can be converted.

In the case of indirect recording, as described above, for example, a rigid cylindrical tube is advantageously used as the recording substrate. As shown in FIGS. 10 and 11, latent image formation and development
After (visualization), for example, the recording agent 3a on the recording body 7 is provided with a means for directly contacting the recording sheet 61, whereby the recording agent 3a is transferred to the recording sheet 61 by the capillary action of the recording sheet (transfer means). . The position where the transfer is performed may be any position on the recording body as long as it is after the development, but it is desirable that the position where the transfer is performed immediately after the development. After the transfer, if the development and transfer are repeated without erasing the latent image, this device becomes a printing device. When printing of one image information is completed, another image information can be recorded / printed by replacing the recording body 7 or by erasing the latent image.

After the transfer means, the latent image portion (S) is heated near the latent image portion (S) in the absence of liquid or vapor, that is, in the air, vacuum, or inert gas. If is erased, the recording body 7 becomes a reusable recording device.
A heating source for erasing the latent image is preferably a contact heating source such as a heater or a thermal head, or a non-contact heating source using electromagnetic waves such as a laser or an infrared lamp 41.
The entire surface of the recording body 7 may be heated, and the latent image portion (S)
You may go only. However, it is more preferable to heat the entire surface because the device configuration can be simplified. The latent image erasing means is provided at a position where the surface of the recording body 7 is substantially cooled during the time until the latent image is formed again after heating for erasing. The heating temperature required for erasing varies depending on the material of the surface of the recording body 7, but it is desirable that the heating temperature is equal to or higher than the starting temperature at which the receding contact angle of the material of the surface of the recording body 7 becomes lower and lower than the decomposition point.

As the recording paper (transfer target) 61, transparent resin film, plain paper, ink jet paper, type paper, etc. are suitable. Further, as the recording agent, those described below can be used.

By the way, as described above, in the recording apparatus of the present invention, in order to form a latent image on the surface of the recording medium (A),
The use of the contact material (B) (see FIG. 7) and the use of a recording agent to visualize the latent image (see FIGS. 8 and 9) are required. The material (B) and / or the recording agent is a recording material in the latent image forming step or the visualization step.
When it comes into contact with (A), it is contaminated by the paper dust and dust ash attached to the surface of the recording material (A), and the contact material (B) during repeated use.
It is also possible that these paper powders, etc., accumulate in the storage container and / or the recording agent container. Therefore, when the latent image is formed, these paper dust and dust ash impede heating, resulting in variations in the latent image obtained, and further, in the visualization process, a difference in the amount of the recording material attached causes a high difference. It becomes difficult to obtain a quality visible image. In addition, these paper dust and dust ash may mix between the heating source and the recording material (A) during latent image formation or latent image formation during visible image formation, which may damage the surface of the recording material (A). is there.

Therefore, in the recording apparatus of the present invention, means for cleaning the contact material (B) and / or the recording material is employed (FIGS. 10 and 11).

As a means for cleaning the contact material (B) and / or the recording agent, any method can be used as long as it can remove the debris such as paper powder and dust ash contained in these liquids. can do.

Here, a method using a mechanical filter (FIG. 10) and a method using an electrostatic filter (FIG. 11) will be described, but of course, the cleaning means according to the present invention is not limited to these.

FIG. 10 shows a recirculating mechanical filter for removing paper dust and dust ash. In FIG. 10, 52a is a mechanical filter, and 63 is a liquid pump such as a bellows pump or a tube pump. Mechanical filter
The material of 52a is preferably a material which is not corroded by the contact material (B) or the recording agent 3a, and examples of such a material include a synthetic resin porous body of ceramics such as polytetrafluoroethylene or silicone resin, a porous ceramic body, and a sintered body. There are binding metals. There is no special restriction on the pore size of the filter, but 0.1μ
The range of m to 10.0 μm is suitable. It is desirable to replace the filter at a proper time depending on the use mode.

FIG. 11 shows an electrostatic filter that uses an electrophoretic phenomenon to remove paper dust and dust ash. 52b is an electrostatic filter, and 64 is an electrode. According to this device, when an electric field is applied between the electrodes, positively charged dust ash and the like adhere to the negative electrode side and negatively charged dust ash and the like adhere to the positive electrode side.

In this case, if the liquid is agitated by a fan or the like, the cleaning efficiency becomes high. The shape and size of the electrode or the size of the electric field may be appropriately determined according to the capacity thereof.
It is desirable to clean the electrodes in a timely manner according to the amount of dust ash and the like attached.

10 and 11 show the cleaning means as a contact material (B)
As an example, when a "recording agent containing a liquid ink color developer" is used, that is, a mode in which it is attached to a recording apparatus that visualizes at the same time as latent image formation is shown. Of course, it can be similarly applied to a recording device in which formation and visualization are performed by separate liquids.

Next, the recording agent will be described. In order to obtain a visible image on the surface of the recording material (A), a recording agent that has been used in conventional print recording methods such as writing ink, ink jet recording ink, printing ink, electrophotographic toner, etc. as a recording agent. From among these, those suitable for the device of the present invention can be selected and used.

As a more specific and preferable example, for example, the water-based ink is mainly composed of water, a wetting agent, a water-soluble ink mainly containing a dye or water, a pigment, a polymer compound for dispersion, and a wetting agent. An aqueous pigment dispersion ink, an emulsion ink in which a pigment or a dye is dispersed in water using a surfactant, and the like are used. Examples of the wetting agent used for the water-based 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. Multi-valued alco Heterocyclic compounds such as N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone and ε-caprolactam; amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine and triethylamine Kind etc.

As the water-soluble dye, dyes classified in the color index into acid dyes, direct dyes, basic dyes, reactive dyes and the like are used. Examples of representative 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 can be mentioned.

As the pigments, organic pigments such as azo type, phthalocyanine type, anthraquinone type, quinacridone type,
Dioxazine-based, indigo-based, thioindigo-based, perinone-based, perylene-based, isoindrenone-based, aniline black, azomethine azo-based, carbon black and the like, iron oxide, titanium oxide, calcium carbonate, barium sulfate, as inorganic pigments, Aluminum hydroxide, barium yellow, navy blue, cadmium red, chrome yellow,
Examples include metal powder.

As the compound for dispersing pigment, polyacrylamide, polyacrylic acid and its alkali metal salt, acrylic resin such as water-soluble styrene-acrylic resin, water-soluble styrene-maleic acid resin, water-soluble vinylnaphthalene acrylic resin, water-soluble vinylnaphthalene Maleic acid resin, polyvinylpyrrolidone, polyvinyl alcohol, alkali metal salt of β-naphthalenesulfonic acid formalin condensate, polymer compound containing cationic functional group salt such as quaternary ammonium or amino group, polyethylene oxide, gelatin,
Proteins such as casein, natural gums such as gum arabic and tragacanth, glucooxides such as saponin, cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, ligninsulfonic acid and its salts, natural polymer compounds such as ceramics, etc. Can be mentioned.

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

Typical examples of oily dyes are 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.

Further, as an oily base for dissolving the dye or dispersing the pigment, n-octane, n-decane,
Mineranes spirit, ligroin, naphtha, benzene,
Hydrocarbons such as toluene and xylene; dibutyl ether, dihexyl ether, anisole, phenetole,
Examples thereof include ethers such as dibenzyl ether; alcohols such as methanol, ethanol, isopropyl alcohol, benzyl alcohol, ethylene glycol, diethylene glycol and glycerin.

The pigments exemplified above can also be used in the oil-based ink. Examples of oily pigment dispersants include:
Polymethacrylic acid ester, polyacrylic acid ester,
Methacrylic acid ester-acrylic acid ester copolymer,
Polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinylpyrrolidone, polyvinyl butyral and other vinyl copolymers,
Examples include cellulosic resins such as ethyl cellulose and methyl cellulose, polycondensation resins such as polyester, polyamide and phenol resins, and natural resins such as rosin, ceramics, gelatin and casein.

[0091]

EXAMPLES The present invention will be described in more detail below with reference to examples. Example 1 Image recording was performed using the recording apparatus shown in FIG. As the recording material (A), a fluorine-containing acrylate material (trade name: VISCOAT 17F: Osaka Organic Chemical Industry Co., Ltd.) is spin-coated on a polyimide seamless film (trade name: Kapton: manufactured by DuPont Toray) with a diameter of 30 mm and a thickness of 50 μm. What was done was used. Aqueous black ink was used as the contact material (B) and the recording agent, and a thermal head was used as the heating source. A mechanical filter made of sintered stainless steel (pore size: 3 μm) was used as a filter, a bellows pump was used as a circulation pump (pressurized at 1 atm), and a silicone tube was used as a channel. When the image was recorded under the above conditions,
It was found that the dust in the recording material was eliminated and the image quality was improved compared to the conventional case.

[0092]

According to the apparatus of the present invention, a large number of high-quality clear images can be reversibly obtained over a long period of time even in continuous recording, and the deterioration of the recording material (A) is significantly suppressed.

[Brief description of drawings]

FIG. 1 is a diagram showing four schematic examples of a form having a surface self-alignment function.

FIG. 2 is a diagram for basically explaining the operation of the recording medium (A) in the apparatus of the present invention.

FIG. 3 is a diagram for further explaining the operation of the recording medium (A) in the device of the present invention.

FIG. 4 shows a change in receding contact angle θr observed on the surface of the recording material (A) when the surface of the recording material (A) is heated while the liquid is in contact with the surface of the recording material (A) according to the present invention. It is the represented figure.

FIG. 5 shows two embodiments when the device of the present invention is used.

FIG. 6 is a diagram showing two examples of means useful for heating a recording medium (A).

FIG. 7 is a diagram showing four examples of means for forming a latent image on the surface of a recording material (A).

FIG. 8 is a diagram showing a method of visualizing (developing) a latent image.

FIG. 9 is a view showing a means for forming a visible image together with formation of a latent image.

FIG. 10 is a diagram showing how the device of the present invention is implemented.

FIG. 11 is a diagram showing how the device of the present invention is implemented.

[Explanation of symbols]

 1 substrate 2 film 3 liquid (3a ... colored ink) 4 heater 5 lens 6 shutter 7 recording medium (A) 52a mechanical filter 52b electrostatic filter

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Takeshi Takemoto 1-3-3 Nakamagome, Ota-ku, Tokyo Stock company Ricoh Co., Ltd. (72) Yasuyuki Okada 1-3-6 Nakamagome, Ota-ku, Tokyo Shares Inside Ricoh Company (72) Inventor Yoshio Watanabe 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company, Ltd.

Claims (2)

[Claims] 1. The following contact material (B) is applied to the surface of the following recording medium (A).
To the heating temperature on the surface of the recording material (A) by selectively heating the surface of the recording material (A) or by contacting the surface of the recording material (A) with the contact material (B). Contact material that forms a latent image area with a corresponding receding contact angle
Means for supplying (B) to the surface of the recording material (A), means for heating the surface of the recording material (A), means for applying a recording agent for visualizing the latent image area, and surface of the recording material (A) A recording apparatus, comprising: a unit for transferring the recording agent attached to the recording sheet onto a recording sheet; and a unit for cleaning the contact material (B) and / or the recording agent. (A) A recording material having a surface which has a reduced receding contact angle when heated and brought into contact with a liquid. (B) A liquid, a vapor, or a solid that becomes a liquid or generates a liquid or a vapor at a temperature at which the receding contact angle of the recording medium (A) starts to decrease. 2. The following contact material (B) is applied to the surface of the following recording medium (A).
To the heating temperature on the surface of the recording material (A) by selectively heating the surface of the recording material (A) or by contacting the surface of the recording material (A) with the contact material (B). Contact material that forms a latent image area with a corresponding receding contact angle
Means for supplying (B) to the surface of the recording material (A), means for heating the surface of the recording material (A), means for applying a recording agent for visualizing the latent image area, and surface of the recording material (A) Means for transferring the recording agent adhered to the recording paper to the recording paper, means for heating the latent image area formed on the surface of the recording medium (A) to erase the latent image area, and the contact material
A recording apparatus comprising (B) and / or a cleaning agent cleaning means. (A) A recording material having a surface which has a reduced receding contact angle when heated and brought into contact with a liquid. (B) A liquid, a vapor, or a solid that becomes a liquid or generates a liquid or a vapor at a temperature at which the receding contact angle of the recording medium (A) starts to decrease.