JPH041081A - Recording device - Google Patents

Abstract

PURPOSE:To make it possible to perform large quantity recording by the same image in a short period of time, and at the same time, present a recording device with an excellent durability, for which the deterioration, etc. of a recording element (A) is extremely suppressed even after repeated usages, by a method wherein on the surface of a member with a surface of which recessing contact angle decreases when coming into contact with a specified contact material under a heated condition, a desired pattern area is formed, and this pattern area is made into a latent image and transferred to an ordinary paper, etc. CONSTITUTION:On a support body 1, a film 2 of a compound to constitute the surface of a recording element (A) with a surface of which recessing contact angle Q decreases when coming into contact with a liquid, under a heated condition, is formed. On the surface of this film 2, a liquid 3, among a liquid, vapor or solid (B) which becomes a liquid or generates a vapor at a temperature which is not more than the decrease starting temperature for recessing contact angle mentioned for the recording element (A), exists. While being contact with the liquid 3, the surface of the recording element (A) is heated in response to a image signal, to form a liquid adhering area (latent image area) on the surface of the recording element (A). Then, by a means to bring a recording material into contact with this latent image part, a recording agent is adhered to the latent image part (development), and the recording agent on the surface of the recording element (A) is transferred to a recording paper.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel recording device, and more particularly, the present invention relates to a novel recording device, and more particularly, the surface of a recording medium whose surface has specific properties is selectively or selectively and reversibly brought into contact with a receding surface depending on the heating temperature. A latent image is formed in such a manner that an area indicating a corner is formed, and then or simultaneously with the formation of the latent image, a recording agent containing a color developer is supplied to the latent image to make it visible, and then this is recorded. The present invention relates to a recording device that transfers images onto paper. [Prior Art] A water (dampening water)-less planographic printing plate is used as a typical method for dividing the surface into a liquid-adhesive area and a non-liquid-adhesive area for image formation. An example is an offset printing method. 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, making it difficult to miniaturize plate-making printing devices. ing. For example, even in office-use off-cent plate-making and printing machines that are relatively compact, the plate-making device and the printing device are usually separate. In order to eliminate such defects of the offset printing method, we have developed a method that can form liquid-adhesive areas and non-liquid-adhesive areas according to image information, and can be used repeatedly (
Reversible recording methods and devices have been proposed. Some of them are as follows. (1) Aqueous development method After applying an electric charge to the hydrophobic photoconductor layer from the outside, it is exposed to light to form a pattern on the surface of the photoconductor layer that has a hydrophobic part and a hydrophilic part. Apply an aqueous developer and transfer to paper etc. (Special Publication No. 4018992, Special Publication No. 4
No. 0-18993, Japanese Patent Publication No. 44-9512, Japanese Patent Publication No. 6
Publications such as No. 3-264392). (2) Method using photochemical reactions of photochromic materials A layer containing materials such as spiropyran and azo dyes is irradiated with ultraviolet rays, and these photochromic compounds are made hydrophilic by the photochemical reaction [for example, "Kobunshi Papers" No. 37]
Vol. 4, p. 287 (1980)). (3) Method using the effect of internal biasing force Forms an amorphous state and a crystalline state through physical changes to form areas to which liquid ink adheres and to which it does not adhere (Japanese Patent Publication No. 41902/1982). According to the method (1) above, after the aqueous ink is transferred to paper or the like, the hydrophilic portion is erased by static electricity removal, making it possible to record other image information. That is, one original plate (photoconductor) can be used repeatedly. However, since this method is based on an electrophotographic process, it requires a long process of charging, exposing, developing, transferring, and removing static electricity, and has drawbacks such as making it difficult to miniaturize the device, reduce costs, and make it maintenance-free. According to method (2) above, hydrophilicity and hydrophobicity can be freely and reversibly controlled by selectively changing the irradiation with ultraviolet rays and visible light, but the reaction time is extremely long due to poor quantum efficiency. However, it has disadvantages such as slow recording speed and lack of stability, and the reality is that it has not yet reached a practical level. Furthermore, according to the method (3) above, the information recording member used therein is stable after recording, but before recording there is a risk that physical structural changes may occur due to temperature changes. There are still problems with storage stability. In addition, since a method of applying a heat pulse and then rapidly cooling is employed to erase the recorded information pattern, repeated image formation is unavoidably complicated. [Problems to be Solved by the Invention] The purpose of the present invention is to create a member (recording member) having a surface that has a low receding contact angle when brought into contact with the contact material (B) in a heated state, unlike conventional recording methods. To provide an apparatus for selectively or selectively and reversibly forming a desired pattern area on the surface of a body (A)), visualizing it, and transferring it to plain paper, etc. be. Another object of the present invention is to provide a recording device which is capable of recording a large number of sheets of the same image in a short period of time, and which has excellent durability by significantly suppressing deterioration of the recording medium (A) even after repeated use. . [Means for Solving the Problems] The recording device of the present invention can be produced by selectively heating the surface of the recording body (A) described below while in contact with the contact material (B) described below, or by The surface of the recording medium (A) is brought into contact with the contact material (B) in a selectively heated state.
) for forming a latent image showing a receding contact angle in accordance with the heating temperature on the surface of the recording medium (A) with a contact material (B); a means for forming the latent image, a recording agent applying means for making the latent image visible, a means for transferring the recording agent attached to the surface of the recording medium (A) onto the recording paper, and a releasing mechanism for the latent image forming means. It is characterized by: (A) A recording material having a surface whose receding contact angle decreases when brought into contact with a liquid in a heated state. (B) A liquid, a vapor, or a solid that becomes a liquid or generates a liquid or vapor at a temperature below the temperature at which the receding contact angle begins to decrease in the recording material (A). Further, the recording device of the present invention can be used by selectively heating the surface of the recording body (A) described below while in contact with the contact material (B) described below, or by selectively heating the surface of the recording body (A). A contact material (B) is supplied to the surface of the recording medium (A), which forms a latent image showing a receding contact angle according to the heating temperature on the surface of the recording medium (A) by contacting the contact material (B) in a state of a means for heating the surface of the recording medium (A) to form a latent image; a recording agent applying means for making the latent image visible; and a recording agent attached to the surface of the recording medium (A). A means for transferring the latent image onto the recording paper, a means for heating and erasing the latent image formed on the surface of the recording medium (A), a releasing mechanism for the latent image erasing means, and a releasing mechanism for the latent image forming means. It is characterized by (A) A recording material having a surface whose receding contact angle decreases when brought into contact with a liquid in a heated state. (B) A liquid, a vapor, or a solid that becomes a liquid or generates a liquid or a vapor at a temperature below the temperature at which the receding contact angle starts to decrease in the recording medium (A). The inventors of the present invention have conducted extensive research and study on new recording methods to eliminate the defects described in the prior art. As a result, a member whose surface has the function of having a low receding contact angle even after cooling when heated in contact with a liquid, and a high receding contact angle when heated in the absence of liquid, can be used as a recording medium. I found it useful. A recording medium (A) having such a function has a surface that is (1) a member containing an organic compound having a surface self-alignment function of hydrophobic groups, or (2) a member containing an organic compound having a hydrophobic group and having a surface self-alignment function. It was also confirmed that it was a member with oriented on the surface. The "surface self-orientation function" referred to in (1) means that when a solid formed of a certain compound on a support or a solid made of the compound itself is heated in air, the hydrophobic groups on the surface move toward the air side (
This means that there is a property of blending toward the free surface side). This also applies to (2). Generally, in organic compounds, hydrophobic groups tend to face toward a hydrophobic atmosphere. This is a phenomenon that occurs because the interfacial energy of the solid-air interface tends to become lower. Furthermore, this phenomenon tends to occur as the molecular length of the hydrophobic group increases, and this is because the longer the molecular length, the higher the mobility of the molecule during heating. More specifically, molecules having a hydrophobic group at the end (that is, lowering the surface energy) tend to be surface oriented facing the air side (free surface side). Similarly, in a linear molecule containing (CH2+.), the (CHzCH2+ part has a planar structure, and the molecular chains tend to align with each other. Also, (0+
. Molecules containing -4:0 also have a planar structure, making it easy for the molecular chains to align with each other. In particular, linear molecules containing highly electronegative elements such as fluorine have high self-aggregation properties, and the molecular chains tend to align with each other. Summarizing these study results, it is more preferable to use linear molecules that contain molecules with high self-aggregation or molecules that have a planar structure and have a hydrophobic group at the end, or such linear molecules. It can be said that the compound containing this compound has a high surface self-alignment function. As is clear from the above description, there is a relationship between the surface self-alignment state and the receding contact angle, and there is also a relationship between the receding contact angle and liquid adhesion. That is, the adhesion of a liquid on a solid surface is mainly caused by the cutting of the liquid on the solid surface. This tacking can be thought of as a type of frictional force when a liquid slides on a solid surface. Therefore, the "receding contact angle" or as used in the present invention is (where γ is the surface tension of a solid in vacuum γS:
A relational expression holds true: liquid interfacial tension πe, equilibrium surface tension γ, :Jl frictional tension γS: surface tension of a solid without an adsorption layer) (Saito, Kitabata et al. 1 Journal of Japan Adhesion Society, Vol. 22)
．． 412. Nct No. 1986). Therefore, when the value of or becomes low, the value of γ becomes large. That is, the liquid becomes difficult 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, liquid adhesion depends on the extent of the receding contact angle or, and the receding contact angle or is determined by the number of members that have a surface self-alignment function on the surface. . Therefore, in the apparatus of the present invention, the recording medium (A) necessarily includes a member having a surface self-alignment function on its surface in order to form a desired pattern area on its surface and/or to visualize it with a recording agent. As mentioned above, the recording medium (A) used in the apparatus of the present invention that must be selected has a surface whose receding contact angle or when brought into contact with a liquid in a heated state. The recording medium (A) may have any shape as long as its surface has the properties described above. Therefore, recording body (A)
It may be in the form of a film, or another coating film having the above-mentioned surface properties may be provided on a suitable support or molded body. The molded body itself may be used, but its surface must have the properties described above. Depending on the type of contact material (B), the liquid-adhesive portion in the latent image area of this recording medium (A) is either lipophilic or hydrophilic. Any of the ink recording agents can be used as needed. Here, the receding contact angle θ when heated and in contact with liquid is

Figure 1 shows an example of the classification of components or materials that form a surface where the It is a compound that has a hydrophobic group on the main chain, and the main chain R and the hydrophobic group R are bonded by a bonding group J. Figure 1 (b) shows an organic compound that has a hydrophobic group with the hydrophobic group oriented on the surface. This is an example of a member in which the compound O having the hydrophobic group is formed on the surface of an organic or inorganic material M by physical or chemical bonding.
) is an example of a member made only of the organic compound O having a hydrophobic group shown in FIG. 1(b). Figure 1(d) shows an example in which a linear molecule is on the side chain of a polymer, and the main chain is connected to the molecule by a bonding group J to create a self-aggregating or planar structure with a hydrophobic group R at the end. molecular chain N
is an intermediate compound. In the examples shown in FIGS. 1(a) and 1(d), the main chain of the polymer compound may be linear or have a mesh structure. In the example of FIG. 1(b), the hydrophobic group-containing compound 0 may be further laminated on the hydrophobic group-containing compound 0, like a cumulative LB film. The example shown in FIG. 1(c) has a structure consisting only of the hydrophobic group-containing compound O without having a main chain (L) or bonding to an organic/inorganic material (M). The above-mentioned hydrophobic group is preferably -CH at the terminal of the molecule.
3, -CF3, -CF2H1-CF)+2, -C(CF
3) 3, -C(CH3)3, etc., and more preferably, those with a long molecular length are advantageous in terms of high molecular mobility. Among them, the hydrophobic group is a substituted alkyl group having one or more -F and/or cn (-CF2CF2C
FCF2CF217)Q) or an unsubstituted alkyl group, preferably one having 4 or more carbon atoms. Both fluorine-substituted and chlorine-substituted ones can be used, but fluorine-substituted ones are 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 a recording device will be low. The principle of this functional expression has not yet been completely clarified, and therefore there are many unknown points, but the following is assumed. First, it is considered that the surface of the recording medium (A) formed from the above compound is a surface in which the hydrophobic groups are considerably oriented. Therefore, this surface has liquid repellency (because hydrophobic groups have low surface energy). In this state, when the surface of the recording medium (A) comes into contact with the contact material (B) and is heated, the molecular movement of the hydrophobic groups becomes active due to the heating.
And upon interaction with the contact material (B), the recording body (
This seems to be because the orientation (alignment) state of at least a portion of the surface of A) changes to another state (that is, another orientation state or a disordered orientation state) and maintains that other state even after cooling. Note that heating the recording medium (A) with the surface of the recording medium (A) in contact with the contact material (B) may mean that the surface of the recording medium (A) is heated, depending on the form of the contact material (B). The liquid will come into contact with the Before this heating, the hydrophobic groups are aligned (orientated) on the surface, so the surface energy of the recording medium (A) is extremely low. However, heating the material 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 surface energy between the solid and the liquid, regardless of the type of liquid. Therefore, if the surface energy of the solid increases, the receding contact angle or will decrease regardless of the type of liquid. Therefore, the adhesion to liquids will increase. Furthermore, the surface of the recording medium (A) is in a different state (a "different orientation state" different from the original orientation state or a "disturbed orientation state").
When heated in the absence of the contact material (B), no interaction with the contact material (B) occurs, so it is thought that the original alignment (orientation) state is returned. Therefore, the presence of the contact material (B) is not simply for rapidly cooling the surface of the recording medium (A) after heating, but it is for causing some kind of interaction with the compound on the surface of the recording medium (A). It is thought that this interaction causes a change to another state (another orientation state or a state in which the orientation is disordered). As mentioned above, when an alkyl group or a fluorine- or chlorine-substituted alkyl group is employed as the hydrophobic group of the member (compound) forming the surface of the recording medium (A), the number of carbon atoms in the alkyl group is 4 or more. It is desirable to have a recording medium (A
) The alkyl groups are aligned (orientated) to a certain extent on the surface of the material, and this is thought to be due to the number necessary for active molecular movement during heating. It is also conceivable that when the contact material (B) is heated together with the surface of the recording medium (A), the molecules of the contact material (B) are incorporated into molecules on the surface of the recording medium (A). Furthermore, the presence of highly electronegative fluorine or chlorine in the alkyl group increases the interaction with liquids, especially polar liquids, resulting in a greater change in adhesion than in compounds containing hydrogen-only alkyl groups. . In addition, fluorine-containing alkyl groups have a strong self-aggregation property, so they have a high surface self-orientation function, and furthermore, because they have a low surface energy, they are excellent in preventing soiling of the skin. Furthermore, the surface of the recording medium (A) has liquid repellency, but when this is described in terms of solid surface energy, the present inventors have found that it is desirable for the recording device to have a repellency of 50 dyn/cm or less. Understood. If the value is higher than this, the surface of the recording medium (A) may sometimes become wet with the recording agent, which may cause the background to become smeared. Here, details of the compound forming the surface of the recording medium (A) will be described. First, regarding the types shown in Figures 1(a) and (d), we will start with an alkyl group (fluorine substitution and/or
or chlorine-substituted compounds). Specifically, formula (I)(n)(m)(I
V) (V) (VI) and (■) R knee H1-C■3
t-C2Hs+-CF3 or -C2F5RI: A group containing a C4 or higher alkyl group or a fluorine- or chlorine-substituted alkyl group, or →σ2+-skin, -+ in the molecular chain
A hydrophobic group having CH2+ or -〇- (Q≧4) n': A polymer in which an integer of 1 or more is used as a monomer can be mentioned. Other polymers include formulas (■) (■) and (X)
Examples include those shown below. ■ 0ORf layer 0 = C-Rf R knee H1-C) +3, -C2H6, -CF3 or -C
2F5RI: A group containing a C4 or higher alkyl group or a fluorine- or chlorine-substituted alkyl group, or a hydrophobic group containing *CF2+-, (CH2+- or -O-) in the molecular chain (Q≧4) n: 10 The above integers In these specific examples, R1 can be exemplified by the following (1) to (20): (1) CH2CF2CHFCF3 (8) A CHzhNHCF2CF3 (9) ACF 2), c F3 (10) (CH2)I. CsF+y (II) CHIN 5O2C! 1F172H5 (12) (CH2)IONSO2C8F+tH3 (+3) CH2NH302C8F+7(+5)c
-s CH2CH2(CF3)6CF(CF3)2(
+6) CH2CF2CF2CF3(+7)-CH
2CH2CH2CH2F(18)-CH2(CF2)6
CF3 (6) CH2(CF2) l0H(19)-C
H2(CF2)5CF3 (20) (CH2) 3 CF 3 Among these compounds, especially (7) of the following (XI)
)+CFzhO-CF2CF3 material is effective. [However, R] hydrogen, -Cy, H2n++ or -cJ2n
+l (n=l or an integer of 2 or more) R2: (CHz+- (an integer of p≧1) or iCH2)-N(R3)SO□ (R3 is -CI (3 or an integer of -C2H5, 9≧1) )m
, is an integer of 6 or more. ] Therefore, the most preferable specific compound for the member on the surface of the recording medium (A) in the present invention includes 2H5 COO(CH Tsuji-CF2'hCQ). (IV) (V
) (VI) (■) and (XI) (copolymers of two or more monomers), other monomers such as ethylene, vinyl chloride, styrene, butadiene, imprene, chloroprene, vinylalkyl Copolymers with ethers, vinyl acetate, vinyl alcohol, etc. are also suitable as the above compounds. Furthermore, a polymerizable polymer having a monomer of formula (XI) and a functional group, such as C)+2=c (CI(3) COO(CH2) 20
HC)12=C(C)+3)COOC82CH(OH)
CH3CH2”CHCOOCH2CH(OH)C8F+
7 etc. to introduce a large number of functional groups into the polymer, or create a copolymer of the monomer of formula (XI) and a polymerizable monomer having a functional group, and then,
Crosslinkable polymers produced by crosslinking copolymers containing a large number of functional groups using a crosslinking reagent are also excellent materials. Examples of the crosslinking reagent include formaldehyde, dialdehyde, N-methylol compound, dicarboxylic acid, dicarboxylic acid chloride, bishalogen compound, hisepoxide, bisaziridine, diisocyanate, and the like. An example of the crosslinked polymer thus obtained is shown below. -(H2-CH-CH2-C)+2- ] 1 In the above formula, the A block is an alkyl group that brings about the change in the thermal properties, while the B block crosslinks chain polymers. (crosslinked using diisocyanate as a crosslinking reagent). In order to obtain a crosslinked film, a solution containing the above-mentioned copolymer and a crosslinking reagent is applied as a coating liquid onto a substrate, and a crosslinked polymer film is obtained by heating, electron beam irradiation, or light irradiation. good. In addition, in order to obtain a polymer from the above monomer, solution polymerization,
Electrolytic polymerization, emulsion polymerization, photopolymerization, radiation polymerization, plasma polymerization, graft polymerization, plasma initiated polymerization, vapor deposition polymerization, etc.
An appropriate method is selected depending on the material. Next, the compound shown in FIG. 1(b) will be described. Cocoteha, formulas (X[I), (Xm) and (XIV)i:
Material shown R-COOH・(XIr) R-OH・(Xm) R(CH))H3iX・(XTV)(R
A group containing an alkyl group having 4 or more carbon atoms or a fluorine- or chlorine-substituted alkyl group, or a group containing (CF→
], (CI-1→] or -〇--containing hydrophobic group (Q≧4)
) Integer X of n'1 or more: chlorine, methoxy group, or ethoxy group Energy is about 50 dyn
/cn+ or less) is desirable. A specific example of formula (X[1) (XI[I) and (XIV)] is CF3→CF 2hCOOH. CF3−+CF2hCOOH. CF3+CFzh(CHzhOH.
2CQ(CF3)CF(CF2)5COOH. CF3 (CF2)? Examples include (CH2)23i CQ3. The compounds shown in FIG. 1(c) include formula (XI), formula (X
Examples include structures made only of materials of formula (XIV) and formula (XIV). Next, a recording medium (A) using the above compound will be described. The structure of the recording medium (A) includes a support (heat resistant temperature 50~
300° C.) on which the surface member is formed. Therefore, the recording medium (A) may have a cylindrical shape or an endless belt shape. In the apparatus of the present invention, forming a mixture of the surface forming material of the recording medium (A) and other members such as a hydrophobic polymer and a hydrophobic inorganic material on the support is excellent in preventing background staining during printing. . Further, in order to increase thermal conductivity, metal powder may be mixed into the above compound. Furthermore, a primer layer may be provided between the support and the compound in order to improve the adhesion between the support and the compound. As the heat-resistant support, resin films such as polyimide and polyester, glass, metals such as Ni, AQ, Cu, CI, PT, metal oxides, etc. are preferable. These supports may be smooth, rough or porous. Next, the contact material (B) will be explained. The contact material (B) is as described above, but to put it simply, it is a liquid or vapor from the beginning, or
It is a solid that eventually forms a liquid at a temperature below the temperature at which the receding contact angle or, referred to in the recording medium (A), begins to decrease. At least a part of the vapor condenses at or near the surface of the recording medium (A) to produce a liquid, and the liquid is
Any material that can wet the surface of A) is sufficient. On the other hand, the solid in this case becomes a liquid, generates a liquid, or generates a vapor below the temperature at which the receding contact angle or begins to decrease. As in the above case, the vapor generated from the solid condenses on or near the surface of the recording medium (A) to form a liquid. More specifically, these contact materials (B) are as follows. That is, in addition to water, liquids that are one of the contact materials (B) include aqueous solutions containing electrolytes, alcohols such as ethanol and n-butanol, polyhydric alcohols such as glycerin and ethylene glycol, and ketones such as methyl ethyl ketone. Polar liquids such as linear hydrocarbons such as n-nonane and n-octane, cyclic hydrocarbons such as cyclohexane, m-
Examples include nonpolar liquids such as aromatic hydrocarbons such as xylene and benzene. Also, a mixture of these may be used,
Furthermore, it may be a polar liquid. In addition to water vapor, any liquid vapor of the contact material (B) can be used as the vapor that is one of the other contact materials (B), but in particular organic compound vapors such as ethanol vapor and m-xylene vapor can be used. (including those in a spray state). The temperature of this organic compound vapor must be below the melting point or softening point of the compound forming the surface of the recording medium (A). Examples of solids other than the contact material (B) include higher fatty acids, low molecular weight polyethylene, polymer gels (polyacrylamide gel, polyhinyl alcohol gel), silica gel, and compounds containing crystal water. It will be done. As will become clearer from what will be described later, when a "recording agent containing a color developer" such as liquid ink is used as the contact material (B), development occurs at the same time as latent image formation. It will be. Next, the heating means will be explained. In addition to contact heating using heaters, thermal heads, etc., heating means include non-contact heating using electromagnetic waves (light from a light source such as a laser light source or an infrared lamp is focused with a lens). In FIG. 2(a), a film 2 of the compound constituting the surface of the recording medium (A) is formed on the support l, and a liquid 3 of the contact material (B), for example, is present on this film surface. It shows the state of being. In this state, when the film 2 is heated, the receding contact angle or on the surface of the film 2 decreases, exhibiting significant wetting, and exhibiting liquid adhesion. Furthermore, when this liquid-adhesive film 2 is heated again in air, vacuum, or an inert gas atmosphere (Fig. 2 (b)), the receding contact angle θ [on the surface of the film 2] increases and the liquid becomes liquid again. It is observed that it exhibits repellency. As a phenomenon somewhat similar to this one,
There is a method described in the above-mentioned Japanese Patent Publication No. 54-41902. However, the method disclosed herein differs mechanically in that it provides a layer of memory material in the recording material that is substantially disordered and generally amorphous. That is, in the present invention, no change in state can occur on the surface of the recording medium (A) without the presence of the contact material (B). In addition, special public service 54-41
In the method described in Japanese Patent No. 902, reversibility cannot be obtained with a simple operation. As shown in Figure 3 (a), heat is applied to the membrane 2 in contact with the liquid 3 according to the image information (Figure 3 (b-)) (b-2)
The same effect can be obtained by applying heat to the membrane 2 according to the image information and then bringing it into contact with the liquid (as shown in the figure), and the surface of the membrane 2 in the heated part is liquid-adhesive. be converted into In the figure, 4 represents a heater, 31 a liquid supply port, 41 an infrared lamp, 5 a lens, and 6 a shunter. Figure 3(a) shows an example in which the membrane 2 is heated through the support 1, but in the examples shown in Figures 3(b-1) and (b-2), the membrane 2 is heated directly. This is an example. FIG. 4 shows an example of the variation in the contact angle of the aqueous solution before and after heating the film 2 in contact with the aqueous solution, and the variation in the contact angle of the aqueous solution when this membrane 2 is further heated in air. In Fig. 4, ○ indicates the advancing contact angle. △ represents the receding contact angle. In general, if the receding contact angle is high (90° or more), the surface is liquid repellent; if the receding contact angle is low (90" or less), the surface is liquid repellent.
Its surface exhibits liquid adhesion. The heating temperature of 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, the temperature is 80°C to 150°C. The heating time is about 0.1 msec to 1 second, preferably 0.5 msec to 2 m.
Seconds. As for the timing of heating, in the case of latent image formation, (1) after heating the surface of the recording medium (A), before it cools down, the contact material (
■ Contact material (B) is brought into contact with the surface of the recording medium (A).
) may be heated while the surface of the recording medium (A) is in contact with the recording medium (A). On the other hand, if the latent image is erased,
The surface of the recording medium (A) in the absence of the contact material (B) is
What is necessary is just to heat to 300 degreeC, desirably 100-180 degreeC. In either case, the heating time is about 1 msec to 10 seconds, preferably IO+n seconds to 1 second. Next, the means for actually recording image information on the surface of the recording medium (A) will be explained in more detail. One is to heat the surface of the recording medium (A) in accordance with an image signal in a liquid or vapor atmosphere to form a liquid adhering area (latent image formation) on the surface of the recording medium (A), and then to remove this latent image. This is a method in which a recording agent is attached to a latent image area (development) by means of bringing the recording agent into contact with the image area, and then the recording agent on the surface of the recording body (A) is transferred to recording paper (indirect recording method). Furthermore, in this method, if the recording agent is brought into contact with the latent image area again after the recording agent is transferred, a printing method using the recording medium (A) as a printing plate can be obtained. In the above method, after the recording material is transferred to the recording paper, the surface of the recording material (A) on which the latent image has been formed is heated in the absence of liquid or vapor to erase the latent image, thereby forming a recording material ( A) is a reproducible recording method. FIGS. 5(a) and 5(b) show typical processes of an indirect recording method (printing method) and a reversible recording method (repetitive recording method) of a recording medium. Next, the configuration of the apparatus of the present invention including the recording medium (A) will be described. The recording medium (A) has a surface (as before, the F film 2) whose receding contact angle decreases when brought into contact with a liquid in a heated state.
Alternatively, any support may be used as long as it has a surface on the support, which may be referred to as [recording body (A) surface]. When a resin is used as the support for the recording medium (A), it cannot be said to be a good thermal conductor, and it takes a certain amount of time for the surface of the recording medium (A) to be heated and to have liquid adhesion. Therefore, it may be considered to use a good thermal conductor for the entire support or for a portion on the support j. FIG. 6(a) shows that if a good thermal conductor such as a metal is used as a support (metal substrate I1), an organic thin film 12 is deposited on it, and a film 2 is further formed on it. directional heat conduction speed is improved. Examples of the organic thin film 12 here include polyimide, polyester, and phthalocyanine. This configuration is sufficient when the printing dots can be relatively large, but it is not suitable when the objective is higher density printing because the area with liquid adhesion expands due to heat diffusion in both directions. For this reason, FIG. 6(b) shows a structure in which good heat conductor parts are divided and provided on the support 1 to prevent heat diffusion in the surface direction and to miniaturize the part 2a that has liquid adhesion. In FIG. 6(b), Ila represents a minute metal film. Next, a latent image forming means by heating will be described. As mentioned above, as a heating source, a contact heating source such as a heater or a thermal head, or a non-contact heating source using electromagnetic waves such as a laser or an infrared lamp is preferable. A
) Describe the means for heating the surface. For convenience, the substrate l
The description will proceed by taking as an example a type of recording medium (A) on which a film 2 is formed. First, the liquid 3 is brought into contact with the surface of the recording medium (A) in advance, and a means for heating from the substrate 1 side or the liquid 3 side while in contact with it (see FIGS. 7(a) and (b)) is used. Means for heating the recording body (A) from the surface side and immediately bringing the liquid 3 into contact with the recording body heating part (recording body (A) surface) (Fig. 7 (c)
) and (d)) are preferable. As a means for supplying the liquid 3, a dish is placed below the recording body (A) and filled with liquid so that the recording body (A) is always in contact with the liquid 3 in the dish, and a heating source is placed near the dish or inside the dish. The arrangement is the simplest. A sponge-like porous body 34 filled with liquid may be used instead of the dish. The latent image forming means using light or electron beams is basically the same as the above structure. 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). As a means for adhering the recording agent (ink) to the liquid adhesive area selectively applied according to the image signal by the above means, a plate filled with the recording agent 3a is placed on the recording body at the position where the latent image forming means is arranged. (A) is always placed in the direction of movement of the recording medium (
A) is the simplest configuration (FIGS. 8 and 9). As shown in Figures 8 and 9, if the liquid used to form the latent image is also used as a recording agent, it can be configured in one dish, and the latent image formation and visualization can be integrated, making the apparatus more compact. can. In the case of indirect recording, as mentioned above, it is advantageous for example to use a rigid cylindrical tube as the recording substrate. Figure 10,
As shown in FIGS. 1I, 12, and 13, after forming a latent image and developing (visualizing), for example, the recording agent 3a on the recording medium 7 can be provided with a means for directly contacting the recording paper 61. The recording agent 3a is transferred to the recording paper 61 by the capillary action of the recording paper (transfer means). The transfer position may be any position on the recording medium as long as it is after development, but it is preferable that the transfer be performed immediately after development. After the transfer, if development and transfer can be repeated without erasing the latent image, this device becomes a printing device. Once printing of one piece of image information is completed, the recording medium 7
By replacing the image or erasing the latent image, it becomes possible to record and print different image information. Further, after the transfer means, in the absence of liquid or vapor,
That is, the latent image portion (
S) If the latent image is erased by heating the vicinity, the recording body 7 becomes a recording device that can be used repeatedly. As a heating source for erasing the latent image, a contact heating source such as a heater or a thermal head, or a non-contact heating source using electromagnetic waves such as a laser or an infrared lamp [4] is preferable. Heating may be applied to the entire surface of the recording medium 7, or only to the latent image area (S). However, full-surface heating is more desirable because it simplifies the device configuration. The latent image erasing means is provided at a position where the surface of the recording medium 7 is substantially cooled during the period of time after heating for erasing and before forming a latent image again. The heating temperature required for erasing varies depending on the material on the surface of the recording body 7, but it is preferably a temperature above the starting temperature at which the receding contact angle of the material on the surface of the recording body 7 becomes low and below the decomposition point. As the recording paper (transferred material) 61, a transparent resin film,
Plain paper, inkjet paper, type paper, etc. are suitable. By the way, as described above, the recording apparatus according to the present invention heats the surface of the recording medium (A) in accordance with an image signal in a liquid or vapor atmosphere, forms a latent image, and then injects a recording agent into the latent image area. 3a is attached and developed, and after this recording agent 3a is transferred to the recording paper 61, when the means of bringing the recording agent 3a into contact with the latent image area is carried out again, printing using the recording medium (A) as a printing plate is performed. However, when recording multiple sheets of the same image, if heating means is applied to form a latent image each time, the latent image formation time becomes the rate-determining step, so the recording time for the second and subsequent sheets will also be the same. The recording time is the same as that for the first sheet, making it impossible to shorten the recording time, and the recording medium may also be thermally degraded by a heat source such as a thermal head. In addition, in the above method, a recording medium (A
) to erase the latent image, it becomes a printer device that can reproduce recorded images. However, when recording multiple sheets of the same image using such a recording device, the latent image forming means and the latent image erasing device must be removed each time. If this method is implemented, the latent image forming time and erasing time become rate-determining steps, and the recording time for the second and subsequent sheets will be the same as that for the first sheet. Furthermore, since the thermal head, which is a heat source, is in contact with the recording medium, the recording medium may be worn out and deteriorated when recording a large number of sheets. Furthermore, repeating latent image erasing each time may cause gradual thermal deterioration of the recording medium. Therefore, in the recording apparatus of the present invention, when recording a large number of sheets according to the same image pattern, the latent image forming means and/or the latent image erasing means are used as appropriate in order to shorten the recording time and prevent deterioration of the recording medium. A release mechanism is provided. That is, when the recording apparatus of the present invention is used for printing, when a multi-sheet recording signal is input to the recording apparatus and then an image pattern signal to be recorded is input, the latent operation is performed only when recording the -th sheet of recording paper. A mechanism is provided for activating the image forming means and releasing the latent image forming means from the second and subsequent recordings. Furthermore, when the recording device of the present invention is used as a printer device,
When a multi-sheet recording signal is input to the recording device and then an image pattern signal to be recorded is input, the latent image forming means operates only when recording on the first sheet of recording paper, and from recording on the second and subsequent sheets. The latent image forming means is released. Further, the latent image erasing means is already released from the recording of the -th sheet, and this latent image erasing means is activated when the last recording is completed. By adopting the above-described configuration, the recording device of the present invention can record a large number of sheets of the same image in a short time, and can suppress thermal deterioration of the recording medium (A), etc., so it can be used repeatedly for a long period of time. Provides high-quality recorded images. Hereinafter, the configuration of the latent image forming means and/or latent image erasing means of the present invention will be explained along with the drawings. FIG. 10 shows a printing-only device provided with a mechanism for releasing the latent image forming means. In the figure, 52a is a release mechanism for the latent image forming means attached to the thermal head 43. In FIG. 1O, when a multi-sheet recording signal is input to the recording apparatus, heating is performed by the thermal head 43 in accordance with the image pattern signal to be recorded, and a latent image is formed on the surface of the recording medium (A). Next, the latent image portion is visualized by the recording agent 3a, and is subsequently subjected to a transfer process, and is transferred to the recording paper 6.
1, and recording of the -th sheet is completed. After the transfer, the recording medium (A) is introduced again into the latent image forming section consisting of the thermal head 43 and the liquid 3 while rotating. Here, the release mechanism of the latent image forming means is activated, the thermal head 43 is separated from the surface of the recording medium, and the latent image forming means is released. Therefore, the latent image formed on the surface of the recording medium (A) is directly transferred to the visualization step and the transfer step, and continuous recording of the same image is repeatedly performed. FIG. 11 shows a printing-only recording device provided with a release mechanism for the latent image forming means, similar to FIG. 10, but the difference is that the latent image forming means and the visualization means are operated at the same time. Be looked at. In this device as well, the latent image forming means operates only when recording the first sheet, and the release mechanism 52 operates from recording the second sheet onward.
It stops working due to a. FIG. 12 shows a recording device for a printer equipped with a releasing mechanism for a latent image forming means and a releasing mechanism for a latent image erasing means. In FIG. 12, when a signal for recording multiple sheets is input to the recording apparatus, heating is performed by the thermal head 43 in accordance with the image pattern signal to be recorded, and a latent image is formed on the surface of the recording medium (A). Next, the latent image portion is visualized by the recording agent 3a, and is subsequently subjected to a transfer process, and is transferred to the recording paper 6.
1, and recording of the -th sheet is completed. After the transfer, the recording medium is rotated and introduced into a latent image erasing section comprising an infrared lamp 41 and the like. Here, since the latent image erasing means has been released from the time of recording the -th sheet, the latent image formed on the surface of the recording medium is not erased and is returned to the latent image forming section consisting of the thermal head 43 and the liquid 3. will be introduced in Here, the release mechanism of the latent image forming means is activated, the thermal head 43 is separated from the surface of the recording medium, and the latent image forming means is released. For this reason, the recording medium (A
) The latent image formed on the surface is directly transferred to a visualization step and a transfer step, and continuous recording of the same image is repeatedly performed. FIG. 13 shows a recording device for a printer equipped with a mechanism for releasing the latent image forming means, similar to FIG. 12, but the difference is that the latent image forming means and the visualization means are operated at the same time. Be looked at. In this device as well, the latent image forming means operates only when recording the first sheet, and the release mechanism 52 operates from recording the second sheet onward.
The latent image forming means has been released since the recording of the first sheet. As the releasing mechanism for the latent image forming means according to the present invention, any mechanism can be employed as long as it is capable of releasing the heating means used for latent image formation. In this case, if a means for bringing a heating source such as a heater or a thermal head into contact with the recording medium (A) (contact heating source) is used as a heating means for forming a latent image, it is possible to not only stop the operation of the heating source but also to , recording body (A
It is important to remove the heating source from the surface of the recording medium ().
This is preferable for improving the wear resistance of A). Specific examples of the releasing mechanism for the latent image forming means include a mechanical releasing mechanism 54 using a motor as shown in FIG. 14, and a mechanism using a piezoelectric element 55 as shown in FIG. 15. However, it is not limited to these. Note that when separating the latent image forming means from the recording medium,
The distance may be any distance as long as it does not undergo mechanical contact, but it is better to keep it as short as possible to avoid increasing the size of the device.Specifically, 10. -100. Therefore, it is appropriate. Furthermore, the easiest way to release the latent image erasing means is to stop the operation of the heating source, such as an infrared lamp, used to erase the latent image, but if the heating source requires warm-up time, As shown in FIG. 16, it is desirable to provide a heat shielding plate 56 such as silicone resin between the recording medium and the heat source. Next, the recording medium will be described. In order to obtain a visible image on the surface of the recording medium (A) in the recording apparatus of the present invention, a recording agent used in a conventional print recording method such as a writing ink, an inkjet ink, a printing ink, or an electrophotographic toner is used. Among the recording materials that have been available, one that is compatible with the above process can be selected and used. More specific examples include 1. For example, water-based inks include water-soluble inks containing water, a wetting agent, and dyes, or water;
Water-based pigment dispersion inks containing pigments, dispersing polymer compounds, and wetting agents as main components, emulsion inks in which pigments or dyes are dispersed in water using surfactants, and the like are used. Wetting agents used in water-based inks include the following water-soluble organic liquid compounds. Monohydric alcohols such as ethanol, methanol, propatool: ethylene glycol, diethylene glycol,
triethylene glycol, tetraethylene glycol,
Polyhydric alcohols such as polyethylene glycol, propylene glycol, dipropylene glycol, glycerin, ethylene glycol motubutyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol, diethylene glycol monomethyl ether Ethers of polyhydric alcohols such as ethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monoethyl ether; N-methyl-2-pyrrolidone,
Heterocyclic compounds such as 1,3-dimethylimidazolidinone and E-caprolactam; amines such as monoethanolamine, jetanolamine, triethanolamine, monoethylamine, diethylamine, and triethylamine; As water-soluble dyes, dyes classified as acid dyes, direct dyes, basic dyes, and reactive dyes in the color index are used. Examples of typical dyes include C91, acid yellow +7.23, 42, 44,
79.1420.1. Acid Red], 8.13
．． 14. Ill, 26.27.35°37.42,
52,82,117,89,92,97°106, Il
l, 114,115,134.1g6249.254,
289 C11, Acid Blue 9.29, 45, 92, 24
9,890C, 1, acid blank 1, 2, 7, 2
4, 26.94C, 1, Hood Yellow 3, 4 C, 1, Hood Red 7.9.14 C, 1, Hood Black 2 C, 1, Direct Yellow 1, 12, 24, 26,
33,44,50゜142.1441165 C11, Direct Let 1, 4, 9.13.17,
20.2g, 3] 39.80.8+, 83,89,22
5°C, 1, Direct Orange 26, 29, 62.
102C, 1, Direct Blue 1.2, 6. +5.
22, 25, 7], 76° 79.86, 87, 90, 9
8,163°165.202 C01, Direct Black +9.22, 32, 31
1,5], 56°7+, 74,75,77, 154.1
68C, 1, Basic Yellow 1.2.11.13
．． 14. +5.19゜21.23.24, 25.28
,29°32.36,40,41,45,49°51.
53,63,65,67.70゜73.77.87.9
1 C11, Basic Red 2. +2.13.14.
15. +8.22°23.24,27,29,35,
36,3839.46,49.5+,52,54,59
゜6g, 69,70,73.7g, 82.102゜10
4.109,112 c, 1. Basic Blue 1.3, 5, 7, 9, 21
,22,26,35°41.45,47,54,62,
65,66°67.69,75,77.78,119,
92°93.105,117,120,122°124
．． Examples include 129, 137, 141, and 147° Basic Black 2.8. Pigments include organic pigments such as azo, phthalocyanine, anthraquinone, quinacridone, dioxazine, indigo, thioindigo, perinone, perylene, isoindorenone, aniline black, azomethine azo, and carbon black. Inorganic pigments include iron oxide, titanium oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, dark blue, cadmium red, chrome yellow, and metal powder. Pigment dispersing compounds include polyacrylamide, polyacrylic acid and its alkali metal salts, acrylic resins such as water-soluble styrene-acrylic resin, water-soluble styrene-maleic resin, water-soluble vinylnaphthalene-acrylic resin, and water-soluble vinylnaphthalene-maleic resin. , polyvinylpyrrolidone, polyvinyl alcohol, alkali metal salts of formalin condensates of β-naphthalenesulfonic acid, polymeric compounds containing salts of cationic functional groups such as quaternary ammonium and amino groups, proteins such as polyethylene oxide, gelatin, and casein; Examples include natural rubbers such as gum arabic and gum tragacanth, glucoxides such as saponin, cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, and methylcellulose, ligninsulfonic acid and its salts, and natural polymer compounds such as ceramics. As with water-based inks, oil-based recording materials include those in which an oil-soluble dye is dissolved in an organic liquid compound, those in which a pigment is dispersed in an organic liquid compound, those in which a pigment or dye is emulsified in an oil-based base, etc. is used. Representative examples of oil-based dyes include C11, Solvent Yellow 1, 2, 3, 4, 5, 6.
,7,8,9゜10,11.12.14.16. +7
゜26.27, 29, 30, 39, 40゜46.49,
50.5+, 56.6+. 80, 86.8? , 89.96 C01, Solgecito Orange +2.23.3+, 43
．． 51.6IC11, Solvent Red 1, 2, 3,
16,17.18.19.20゜22.24,25,2
6,40,52.59゜60.63,67.68.12
1 C, 1, Solvent Violet 7, 16.17C6
1, Solvent Blue 2.6. II, +5.20,3
0.3+, 32° 35.36, 55, 58.71.72 C, 1, Solvent Brown 2. +0.15.21
．． 22C, 1, Solvent Black 3.10. II
, 12.13, etc. Oil bases for dissolving dyes and dispersing pigments include n-octane, n-decane, minerane spirit, ligroin, naphtha, benzene, toluene,
Examples include hydrocarbons such as xylene, ethers such as dibutyl ether, dibutyl ether, anisole, phenetol, dibenzyl ether; alcohols such as methanol, ethanol, isopropyl alcohol, benzyl alcohol, ethylene glycol, diethylene glycol, glycerin, etc. I can do it. The pigments exemplified above can also be used in oil-based inks. Examples of oil-based pigment dispersants include polymethacrylic ester, polyacrylic ester, methacrylic ester-acrylic ester copolymer, polyvinyl acetate, hydrochloric acid and copolymer, polyvinylpyrrolidone, polyvinyl butyral, etc. Vinyl copolymers, cellulose resins such as ethyl cellulose and methyl cellulose, polycondensation resins such as polyester, polyamide, and phenolic resins,
Natural resins such as rosin, ceramic, gelatin, casein, etc. are available. [Effects of the Invention] The recording apparatus of the present invention can record a large number of sheets of the same image in a short time, and even when used repeatedly, deterioration of the recording medium (A) is suppressed, and it has excellent durability.

[Brief explanation of the drawing]

FIG. 1 is a schematic four-sided view of a configuration having a surface self-alignment function. FIGS. 2 and 3 are diagrams for basically explaining the apparatus of the present invention. Figure 4 shows the delayed contact observed on the surface of the recording medium (A) when the surface of the recording medium (A) used in the practice of the present invention is heated with a liquid in contact with the surface of the recording medium (A). It is a figure showing the change of angle or. FIG. 5 shows two embodiments in which the apparatus of the present invention is used. Figures 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, and 16
The figure is a diagram showing how the apparatus of the present invention is implemented. 1.Substrate 2..Membrane 3..Liquid (3a, colored ink) 4.Heater 5.Lens 6..Shutter 7..Recording body (A) Patent applicant Rico Co., Ltd.

Claims (4)

[Claims] (1) By selectively heating the surface of the recording medium (A) below while in contact with the contact material (B) below, or by heating the surface of the recording medium (A) selectively while contacting the contact material (
B) means for supplying a contact material (B) onto the surface of the recording medium (A) to form a latent image on the surface of the recording medium (A) showing a receding contact angle according to the heating temperature; A means for heating the surface of the recording medium (A) to form a latent image, a recording agent applying means for making the latent image visible, and a means for transferring the recording agent attached to the surface of the recording body (A) onto recording paper. and a release mechanism for latent image forming means. (A) A recording material having a surface whose receding contact angle decreases when brought into contact with a liquid in a heated state. (B) A liquid, a vapor, or a solid that becomes a liquid or generates a liquid or a vapor at a temperature below the temperature at which the receding contact angle starts to decrease in the recording medium (A). (2) By selectively heating the surface of the recording material (A) below while in contact with the contact material (B) below, or by selectively heating the surface of the recording material (A) below, the contact material (
B) means for supplying a contact material (B) onto the surface of the recording medium (A) to form a latent image on the surface of the recording medium (A) showing a receding contact angle according to the heating temperature; A means for heating the surface of the recording medium (A) to form a latent image, a recording agent applying means for making the latent image visible, and a means for transferring the recording agent attached to the surface of the recording body (A) onto recording paper. A recording device comprising: a means for heating and erasing the latent image formed on the surface of the recording medium (A); a releasing mechanism for the latent image erasing means and a releasing mechanism for the latent image forming means. . (A) A recording material having a surface whose receding contact angle decreases when brought into contact with a liquid in a heated state. (B) A liquid, a vapor, or a solid that becomes a liquid or generates a liquid or a vapor at a temperature below the temperature at which the receding contact angle starts to decrease in the recording medium (A). (3) A claim characterized in that the latent image forming means is a heating means using a contact heating source, and the releasing mechanism of the latent image forming means is provided with a mechanism for separating the contact heating source from the recording medium (A). The recording device according to item (1) or (2). (4) A claim characterized in that the latent image erasing means is a heating means using a non-contact heating source, and the release mechanism of the latent image erasing means consists of a heat shield plate provided between the non-contact heating source and the recording medium. The recording device according to item (2).