JPH04152183A - Recording device - Google Patents

Abstract

PURPOSE:To obtain a desired image by a simple operation and reversibly by a method wherein a desired pattern area (latent image) is formed on the surface of a member having a surface of which the sweepback contact angle becomes lower when is brought into contact with a contact material under a heated condition, and this pattern area is developed into an image. CONSTITUTION:On a base 1, a film 2 of a compound to constitute the surface of a recording body is formed, and on this film surface, a contact material, e.g., a liquid 3 exists. When the film 2 is heated, the sweepback contact angle is lowered, and the surface of the film 2 shows remarkable wetting. For example, the liquid 3 is brought into contact with the surface of the recording body 7, and heating is performed from the base 1 side or the liquid 3 side, and a latent image S is formed on the surface of the recording body. After latent image forming and developing, e.g. by providing a means by which a recording agent 3a on the recording body directly comes into contact with a recording paper 61, etc., the image state recording agent 3a is transferred to the recording paper 61 by capillarity of the recording paper, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel recording device, and more specifically, the present invention relates to a novel recording device, and more specifically, the present invention relates to a novel recording device, and more particularly, to the surface of a recording medium whose surface exhibits specific properties, selectively or selectively and reversibly, A region exhibiting a receding contact angle depending on the heating temperature (heating energy amount) is formed, and this region (
The present invention relates to an apparatus useful for a recording method in which a recording agent containing a color developer is supplied to a latent image (latent image) to make it visible, and this is then transferred onto plain paper or the like.

[Conventional technology]

A typical method for dividing the surface into a liquid-adhesive area and a non-liquid-adhesive area for image formation is an offset printing method using a lithographic printing plate without water (dampening water). It will be done. 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 relatively compact office offset plate making and printing machines, the plate making device and the printing device are usually separate.

In order to eliminate such defects of the offset printing method, liquid adhesive areas and non-liquid adhesive areas can be formed according to image information.

Recording methods and devices that can be used repeatedly (reversible) 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 having hydrophobic areas and hydrophilic areas on the surface of the photoconductor layer. An aqueous developer is attached to the image and the image is transferred to paper or the like (Japanese Patent Publications No. 18992-1972, 18993-1973, 9512-1972, 264392-1980, etc.).

(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 photochemical reactions [e.g., R Polymer Papers, Vol. 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 the recorded information pattern is erased by means of applying a heat pulse and then rapidly cooling it, there is a disadvantage that repeated image formation becomes complicated.

[Problem to be solved by the invention]

An object of the present invention is to provide a member (
Recording in which a desired pattern area (latent image) is selectively or selectively and reversibly formed on the surface of a recording medium (A)), and this is visualized and transferred to plain paper, etc. It provides equipment.

Another object of the present invention is to form, erase, and erase a desired pattern area.
By using a recording medium (A) with excellent preservability and stability in all the steps such as visualization and transfer, a recording device is provided that can reversibly perform the above steps multiple times. .

Still another object of the present invention is to provide a novel recording device that is compact, low-cost, and maintenance-free, and that can produce a large number of clear images in a short period of time.

[Means to solve the problem]

The recording device of the present invention can be produced by selectively heating the following recording body (A) while in contact with the following contact material (B), or by contacting the recording body (A) with the surface of the recording body (A) selectively heated. means for supplying a contact material (B) to the surface of the recording medium (A), which forms a latent image area showing a receding contact angle in accordance with the heating temperature on the surface of the recording medium (A) by contacting with the material (B); , a means for heating the surface of the recording medium (A), a recording agent applying means for visualizing the latent image area, a means for transferring a visible image onto recording paper, etc., and a means for preventing charging of the recording medium (A). It is characterized by having a 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 vapor at a temperature below the temperature at which the receding contact angle begins to decrease in the recording material (A).

In such an apparatus of the present invention, if a recording agent such as liquid ink is used, the supply means for the contact material (B) can be omitted, and the contact material (B)
If liquid ink or the like is used as the latent image, the latent image is formed and visualized at the same time, so the recording agent applying means can be omitted.

In addition, in these devices 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 the image can be reversibly erased. Formation is possible.

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, the recording material has a member whose surface has the function of having a low receding contact angle when heated in contact with liquid, even after cooling, and a high receding contact angle when heated in the absence of liquid. I found it useful as a. Then, a recording medium (A
) is also a member whose surface is (1) a member containing an organic compound with a surface self-orientation function of hydrophobic groups, or (2) a member which is an organic compound having a hydrophobic group and has the hydrophobic groups oriented on the surface. It was confirmed (Japanese Patent Application No. 2-43599).

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 it has the property of being oriented toward the free surface side. This also applies to (2). In general, organic compounds have a phenomenon in which 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, if the molecule has a hydrophobic group at the end (i.e., lowers the surface energy), it is likely to be surface oriented facing the air side (free surface side), and similarly contains →CH, +-0. In a linear molecule, the -4:CH,CH,( part has a planar structure, and the molecular chains tend to align with each other.
Molecules containing -+o+- also have a planar structure at the 1+o+- portion, and the molecular chains tend 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-orientation state and the receding contact angle, and there is also a relationship between the receding contact angle and the identity of the liquid. That is, the adhesion of a liquid on a solid surface is mainly caused by tacking 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" θr in the present invention has the following formula: (γ: surface tension of solid in vacuum γsa: solid -
A relational expression holds true: liquid interfacial tension πe: equilibrium surface tension γ; frictional tension γS: surface tension of a solid without an adsorbed layer) (Saito, Kitabata, et al., ``Journal of the Japan Adhesion Society JVoL
22, Th12.1986).

Therefore, when the value of θr decreases, the value of γ increases.

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, the liquid adhesion depends on the receding contact angle θr, and the receding contact angle or is determined by the addition of a member having a surface self-alignment function to 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. It must be selected.

As described above, the recording medium (A) used in the apparatus of the present invention has "a surface whose receding contact angle θr decreases when it is heated and comes into contact with a liquid."

The recording medium (A) may have any shape as long as its surface has the properties described above. Therefore, recording body (A)
Even if it is belt-shaped (including endless belt-shaped),
It does not matter if a suitable cylindrical support or molded body is provided with another coating film having the above-mentioned surface properties, or even if the molded body itself has the above-mentioned surface properties. It is necessary to have the following properties.

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. Both ink and electrophotographic liquid developer can be used as needed.

Here, Fig. 1 shows an example of classification of members or materials that form a surface whose receding contact angle θr decreases when brought into contact with a liquid in a heated state. Fig. 1 (a) is an example of a compound having a self-orientation function, which is a compound having a hydrophobic group in the side chain of a high molecular weight polymer, and the main chain and the hydrophobic group R are bonded through a bonding group J.

FIG. 1(b) is an example of a member in which the hydrophobic group is oriented on the surface of an organic compound having a hydrophobic group. This is a member formed with compound O. Figure 1 (C
) 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 O, 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.
, Ya-CF3. -CF2H1-CFH2, -C(CF-
)a, -C(CH,)1, etc., and those with a long molecular length are more preferable in terms of high molecular mobility. Among them, the hydrophobic group is -F and/or -
Substituted alkyl group with one or more CQ (-CF, CF2
CFCF, CF2 (CQ) or an unsubstituted alkyl group, preferably one with 4 or more carbon atoms, can be used either with fluorine or chlorine substitution, but fluorine substitution is better. Effective. In these materials, in terms of the relationship between the number of carbon atoms in the alkyl group and the function, if the number of carbon atoms is 3 or less, the function suitable for the recording device of the present invention becomes 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 surface 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 depends on the type of liquid and is determined by the balance of surface energy between the solid and the liquid. Therefore, as the surface energy of the solid increases, the receding contact angle θr decreases 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 may be aligned (orientated) to a certain extent on the surface of the material (orientation), which may be due to the number required for active molecular movement during heating.

Further, when the contact material (B) is heated together with the surface of the recording medium (A), the contact material (
It is also possible that the molecules of B) are incorporated.

Furthermore, when highly electronegative fluorine or chlorine is present in the alkyl group, the interaction with liquids, particularly polar liquids, increases, resulting in a greater change in adhesion than with compounds containing only hydrogen 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 the surface energy of a solid, the present inventors have found that it is 5 Qdyn/cm or less when recording with the apparatus of the present invention. It has also been confirmed that this is desirable. If the value is higher than this, the recording medium (A)
The surface of the product may sometimes become wet, which may cause the skin to become dirty.

Here, details of the compound forming the surface of the recording medium (A) will be described. First, for the types shown in FIGS. 1(a) and 1(d), compounds having an alkyl group (including fluorine and/or chlorine) in the vinyl polymer side chain are considered.

Specifically, formula (1) (II) (m) (IV) (V) (
VI) and (■) R knee H, -CH,, -C,H,, -CF□ or -C,
F.

Rf: C, a group containing an alkyl group or a fluorine- or chlorine-substituted alkyl group, or -g in the molecular face
Hydrophobic group with 2+a, H, +n or -〇- (Q≧4
) n': A polymer containing an integer of 1 or more as a monomer.

Other polymers include formulas (■) (■) and (X)
Examples include the ones shown below.

Rnee H, -CH,, -C,H,, -CF, or -C,
F.

Rf: a C4 or higher alkyl group, a group containing a fluorine- or chlorine-substituted alkyl group, or a group containing two (c
F. can be exemplified.

(1) -CH, CF, CHFCF3 (6) -CH, (CF, ),. H (7) −+CFl)ro-CFICFI(8)−+C
HJ7NH-CF, CF3(9) −+CF, Masu CF.

(10) (CH,),. C, F□.

(13) -CM, NH30, C, F□7 (14) -
4cF2+p (15) C-8-CH2CH,-(CF,), CF(
CF, )2(16) -CH,CF2CF2CF3(1
7) -CH2CH,CH2CH,F (1g) -CH
, (CF), CF□ (19) -CH2 (CF2),
C.F.

(20) (CH2), CF3 Among these compounds, it is particularly desirable to use the following material (X[).

[However, R1: hydrogen, -CnH2n+1 or -cnFz
n+, (n = 1 or an integer of 2 or more) R” Knee + CH2+- (an integer of p≧1) or -(CH
2+-N (R') So□-q (R3 is =CH (□ or -C, H is an integer of q≧1) m:
It is an integer greater than or equal to 6. ] Therefore, the most preferable specific compounds for the member on the surface of the recording medium (A) in the present invention include the following.

Furthermore, these formulas (1) (II) (III) (rV)
(V) (Vl) (■) and (XI) (copolymers of two or more monomers), other monomers such as ethylene, vinyl chloride, styrene, butadiene,
Isoprene, chloroprene, vinyl alkyl ether.

Copolymers with vinyl acetate, vinyl alcohol, etc. are also suitable as the above compounds.

Furthermore, a monomer of Formula 1 (XI) and a polymerizable monomer having a functional group, such as CH2=C(CH3)Coo (CH2), 0HCH
,=C(CH,)COOCH,CH(OH)C)l.

CH2=CHC00CH, CH(OH)C, F engineering.

Either a copolymer is made with one or more of the following and a large number of functional groups are introduced into the polymer, or a copolymer is made with a monomer of formula (X[) 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. As a crosslinking reagent, formaldehyde,
dialdehyde, N-methylol compound, dicarboxylic acid,
Examples include dicarboxylic acid chlorides, bishalogen compounds, bisepoxides, bisaziridines, and diisocyanates. An example of the crosslinked polymer thus obtained is shown below.

In the above formula, the A block is an alkyl group that brings about the change in thermal properties, while the B block is a site that crosslinks chain polymers (crosslinked using diisocyanate as a crosslinking reagent). be.

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-mentioned seven polymers, 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.

Here, formulas (XI), (xm) and (XIVH: Indicating material R, -〇〇〇H-(XII) R, -OH... (xm) Rt-+CHz h SiX...
(X ■) (Rf: a group containing an alkyl group having 4 or more carbon atoms or a fluorine- or chlorine-substituted alkyl group, or 1
Hydrophobic groups containing +CF, +- 處, -+CH2)II or -〇- in the molecular chain (A≧4)) n: an integer of 1 or more X: chlorine, methoxy group or ethoxy group Materials that are physically adsorbed or chemically bonded to the surface of inorganic materials such as steel or organic materials such as polyimide, polyester, and polyethylene terephthalate (with a surface energy of about 50 dyn)
/cm or less).

Specific examples of formula (XI) (Xffl) and (xrv) are CF, Yun CF, and soup C0OH.

CF, (CF, +rCOOH.

CF, (CF, soup (CH, soup○H2 H (CF2 after C0OH.

H(CF, then CH, OH.

F (CF, Homare CH, CH, -5i (CH3) ICI21
CF, Cl2(CF,)CF(CF2), COOH.

Examples include CF, (CF, ), (CH,), and SiCchi.

The compounds shown in FIG. 1(c) include formula (X II ),
Examples include structures made only of materials of formula (xm) and formula (x■).

Next, a recording medium (A) using the above compound will be described.

As mentioned above, the structure of the recording medium (A) includes: (1) one formed from the above-mentioned surface member itself, and (2) one in which the above-mentioned surface member is formed on a support (preferably a heat-resistant support). It is broadly divided into In embodiment (2), the above compound (surface member) itself is formed into a film, plate, or columnar shape. In the case of a film, the thickness of the film is preferably 1-5 mm, and in the case of a 1.degree. square embodiment, the above-mentioned compound may penetrate to some extent into the support. The film thickness of the recording body (A) itself is preferably 30 to 1-1. However, in terms of thermal conductivity, it is 100 to 10 ps, and in terms of wear resistance, it is 10° to ll.
l11 is excellent. The heat resistant temperature of the support is 5
The temperature is preferably 0°C to 300°C.

The shape of the support may be belt-shaped (including endless belt-shaped), plate-shaped, or drum-shaped, and is selected depending on the intended use of the apparatus. In particular, a drum-shaped one is excellent in that it can provide dimensional accuracy in the device. An endless belt type is advantageous for downsizing the device. The plate-shaped one is
The size may be determined depending on the recording paper size.

Furthermore, when a mixture of the above compound (surface forming material of recording medium (A)) and other members such as hydrophobic polymers and hydrophobic inorganic materials is formed on the support, it is excellent in preventing background staining during printing. There is. Also.

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. Heat-resistant supports include resin films such as polyimide and polyester, glass, Ni,
Metals and metal oxides such as AQ, Cu, Cr, and Pt are preferred, and these supports may be smooth, rough, or porous.

Next, 6 contact materials (B) will be explained about contact materials (B).
) is as described above, but to put it simply, it is a liquid or vapor from the beginning, or the recording medium (A)
It is a solid that eventually forms a liquid below the temperature at which the receding contact angle θr begins to decrease. The steam here is the recording medium (
It is sufficient that at least a part of the liquid does not condense to produce a liquid on or near the surface of the recording medium (A), and that the liquid can wet the surface of the recording medium (A). On the other hand, the solid here becomes a liquid, generates a liquid, or generates a vapor below the temperature at which the receding contact angle 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. Examples include polar liquids such as, linear hydrocarbons such as n-nonane and n-octane, cyclic hydrocarbons such as cyclohexane, and nonpolar liquids such as aromatic hydrocarbons such as xylene and benzene. . Further, mixtures thereof, various dispersions, and liquid inks may also be used. More preferably, a polar liquid is better.

In addition to water vapor, any liquid vapor of the contact material (B) can be used as the vapor, which is another one of the contact materials (B). In particular, vapors of organic compounds such as ethanol vapor and 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 the other solid contact material (B) include higher fatty acids, low molecular weight polyethylene, polymer gels (polyacrylamide gel, polyvinyl alcohol gel), silica gel, and compounds containing crystal water.

As will become clearer from what will be described later, when a recording material "containing a color developer" such as the liquid ink described above is used as the contact material (B), the latent image is formed and developed at the same time. This is extremely advantageous in practice.

Next, the heating means will be explained.

Heating means for forming a latent image include contact heating using a heater thermal head or the like, as well as non-contact heating using electromagnetic waves (light beams from a light emitting source such as a laser light source or an infrared lamp are focused with a lens).

In FIG. 2(, ), a film 2 of the compound constituting the surface of the recording medium (A) is formed on the substrate 1, and a contact material (
In B), for example, a state in which liquid 3 is present is shown. In this state, when the film 2 is heated, the receding contact angle θr of the surface of the film 2 decreases, exhibits significant wetting, and is observed to have 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 θr increases on the surface of the film 2, and the liquid repels again. It is acceptable to show gender.

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
In the method described in Japanese Patent No. 902, reversibility cannot be obtained with a simple operation.

As shown in Fig. 3(a), heat is applied to WA2 in contact with liquid 3 according to the image information (Fig. 3(b-1) and (b-
2), the same effect can be obtained by applying heat to the film 2 according to the image information and contacting it with a liquid in the absence of liquid), and when the surface of the film 2 in the heated part is in liquid state. In the figure, 4 represents a heater, 31 a liquid supply port, 41 an infrared lamp, 5 a lens, and 6 a shutter.

3(a) is an example in which the heating of the film 2 is performed through the substrate l, but in the examples shown in FIG. 3(b-1) and (b-2), the heating is performed directly on the film 2. 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, Q represents the advancing contact angle and Δ represents the receding contact angle.

In general, if the receding contact angle is high, such as 90" or above, the surface is liquid repellent; if the receding contact angle is low, below 90", 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 seconds to 1 second, preferably 0.5 seconds to 2 seconds.

The heating timing is as follows: (1) After the surface of the recording medium (A) is heated, it is brought into contact with the contact material (B) before it cools down.

(2) The surface of the recording body (A) is heated while the contact material (B) is in contact with the surface of the recording body (A).

Either one is fine.

On the other hand, in the case of latent image erasing, the surface of the recording medium (A) is heated at 50 to 300°C, preferably at 10°C in the absence of the contact material (B).
Just heat it to 0~180℃, heating time is 1 second~
It is about 10 seconds, preferably 10 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 the recording agent is attached to the latent image area by means of bringing the recording agent into contact with the image area (development), and then the recording agent on the surface of the recording medium (A) is transferred to recording paper or the like (indirect recording method). Furthermore, in the above method, if a means is performed to bring the recording agent 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. The other method is to heat the surface of the recording medium (A) on which the latent image has been formed in the absence of liquid or vapor after transferring the recording material to erase the latent image. (A) is a reproducible recording method. Figures 5 (a) and (b) show the indirect recording method (printing method),
A typical process of a reversible recording method (repetitive recording method) for a recording medium is shown.

Next, the configuration of the recording apparatus including the recording medium will be described.

As mentioned 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 (same as above, for convenience, it is referred to as "film 2" or "recording body (A) surface"). ), it cannot be taken into that form. Therefore, the supporting substrate of the recording body (A) may be a rigid cylindrical shape or a flexible film shape. A recording body (A) having a rigid cylindrical shape is preferable because it has excellent controllability because it is difficult to cause positional deviation when the recording body (^) is operated. ) is preferably produced by forming the film 2 on the substrate or by using the molded body itself. In particular, since the molded body (A) generally has low mechanical strength, it is desirable to form the film 2 on the substrate. It goes without saying that even when the recording medium (A) is made from the molded body itself, the film 2 must be formed on its surface.

If a resin is used as the support substrate for the recording medium (A), it cannot be said to be a good conductor of heat, and if heating is applied from the substrate side, the surface of the recording medium (A) will be heated and the liquid will It takes a certain amount of time to develop adhesion. Therefore, it may be considered to use a good thermal conductor over the entire substrate or a portion on the substrate 1.

Figure 6(a) shows a substrate (
An organic thin film 12 is deposited thereon as a metal substrate 11),
Furthermore, if the film 2 is formed on top of that, the heat conduction speed in the vertical direction 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 goal is higher density printing because the area with liquid adhesion expands due to heat diffusion in the surface direction. , FIG. 6(b) shows, for this reason, a portion 2a having liquid adhesion property prevents heat diffusion in the surface direction by separately providing a good thermal conductor portion on the substrate 1.
This is aimed at miniaturization. In FIG. 6(b),
lla represents a minute metal film.

Next, a latent image forming means by heating will be described. As mentioned 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
) Describe the means for heating the surface. For convenience, the base 1
The description will proceed by taking as an example the type of recording medium (A) on which numerals 1112 are formed.

First, the liquid 3 is brought into contact with the surface of the recording body 7 in advance,
A means for heating from the substrate 1 side or liquid 3 side while in contact with the substrate (Fig. 7(,) and (b)),
) Immediately heat the liquid 3 from the surface side to the recording medium heating section (
It is desirable to employ means (FIGS. 7(C) and (d)) for bringing the recording material into contact with the surface of the recording medium (A).

As a means for supplying the liquid 3, a dish is provided below the recording body (A) and filled with liquid so that the recording body 7 is always in contact with the liquid 3 in the dish, and a heating source is placed near the dish or inside the dish. A sponge-like porous body 34 impregnated with a liquid may be used instead of the simplest one dish. The means for forming a latent image 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 (S) is formed on the surface of the recording medium (A).

As a means for adhering a recording agent (for example, ink liquid) to the liquid adhesive area selectively applied according to an image signal by the above means, a plate filled with the recording agent 3a is placed at a position where the latent image forming means is arranged. The simplest configuration is to arrange it in the traveling direction of the recording medium (A) and keep it in constant contact with the surface of the recording medium (A) (
Figures 8 and 9). As shown in FIG. 9, if the liquid used to form the latent image is also used as the recording material 3a, one dish can be used, and the formation of the latent image and its visualization can be integrated, so that the apparatus can be miniaturized.

After latent image formation and development (visualization) 1 For example, by providing a means for directly contacting the recording material 3a on the recording medium (A) with the recording paper etc. 61, the image is transferred to the recording paper etc. 61 by the capillary action of the recording paper etc. The shaped recording material 3a is transferred (transfer means).

The transfer position may be any position on the recording medium (A) as long as it is after development, but it is preferable that the transfer is performed immediately after development.After transfer, development is repeated without erasing the latent image. In other words, this device becomes a printing device. FIG. 10 shows an example of the above-mentioned printing device, and 62 is a transfer roller. Once printing of one image information is completed, it becomes possible to record/print another image information by replacing the recording medium (A) or by erasing the latent image.

Further, after the transfer means, in the absence of liquid or vapor,
That is, the recording medium (A) in air, vacuum or inert gas.
If the latent image (S) is erased by heating the surface, the recording medium (A) becomes a recording device that can be used repeatedly (No. 11)
figure). Note that 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 41' is preferable.Heating may be applied only to the latent image part. However, the recording body (
A) It is possible to heat the entire surface; in fact, it is more preferable to heat the entire surface because it simplifies the device configuration.The latent image erasing means performs heating for erasing and then repeats the formation of the latent image. The recording medium (A) is placed at a position where the surface thereof is substantially cooled during the period of time until the recording medium (A) is cooled down. The heating temperature required for erasing the latent image is as described above, but although it varies depending on the material on the surface of the recording medium (A), it decomposes at or above the starting temperature at which the receding contact angle of the material on the surface of the recording medium (A) becomes low. Temperatures below the point are desirable.

Recording paper, etc. (subject to be transferred) includes transparent or opaque resin film, plain paper, and inkjet recording paper.

Type paper is suitable.

Next, the recording medium will be described.

In order to obtain a visible image on the surface of the recording medium (A) in the apparatus of the present invention, recording agents used in conventional print recording methods such as writing ink, inkjet recording ink, printing ink, and electrophotographic toner are used. Among the recording materials, one that is compatible with the apparatus of the present invention can be selected and used.

To give a more specific example, 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 monobutyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol 7-methyl ether, propylene glycol monomethyl ether, ethylene glycol, diethylene glycol Ethers of polyhydric alcohols such as monoethyl 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 ε-caprolactam; amines such as monoethanolamine, jetanolamine, triethanolamine, monoethylamine, diethylamine, and triethylamine;

As water-soluble dyes, dyes classified as acid dyes, direct dyes, basic dyes, reactive dyes, and food dyes in the color index are used.

Examples of typical dyes include C,1, Acid Yellow 17,23,42,44,
79,142C,1, Acid Red 1,8,13,
14.1g, 26,27,35°37.42,52,8
2,87,89,92,97゜106.111,114
,115,134,186°249.254,289 C,1, Acid Blue 9.29,45,92,24
9,890C, 1, Acid Black 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゜142.144,865 C, 1, Direct Red 1, 4, 9, 13, 17,
20,28,31゜39.80,81,83,89,2
25°C, 1, Direct Orange 26, 29, 62
, 102C, 1, Direct Blue 1, 2, 6, 15
,22,25,71,76°79.86,87,90,
98,163°165.202 C, 1, Direct Black 19, 22, 32, 38
,51,56°71.74,75,77.154,16
8C, 1, Basic Yellow 1, 2, 11, 13,
14,15,19゜21.23,24,25,28,2
9゜32.36, 40, 41, 45, 49゜51.53
, 63, 65, 67.70° 73.77.87, 91 C, 1, Basic Red 2, 12, 13, 14, 1
5.1g, 22゜23.24,27,29,35,36
, 38° 39.46, 49, 51, 52, 54, 59° 68.69, 70, 73, 78, 82, 102° 104
．． 109,112 C, 1, Basic Blue 1, 3, 5, 7, 9, 21
,22,26,35°41.45,47,54,62,
65,66°67.69,75,77.78,89,9
2゜93.105,117,120,122゜124.
Examples include 129, 137, 141, 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 acid resin, water-soluble vinylnaphthalene-acrylic resin, and water-soluble vinylnaphthalene-maleic resin. , polyvinylpyrrolidone, polyvinyl alcohol, alkali metal salts of β-naphthalenesulfonic acid formalin condensates, 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.

Like water-based inks, oil-based recording materials include those in which oil-soluble dyes are dissolved in organic liquid compounds, pigments dispersed in organic liquid compounds, pigments or dyes emulsified in oil-based bases, etc. is used.

Representative examples of oil-based dyes include C,1, Solvent Yellow 1,2,3,4,5,6
,7,8,9゜10.11,12,14,16,17゜26.27,29,30,39,40゜46.49,5
0,51,56,61°80,86,87,89
, 96C, 1, Solvent Orange 12, 23, 3
1, 43, 51, 61C, 1, Solvent Red 1,
2, 3, 16, 17, 18, 19, 20°22.24,
25, 26, 40, 52, 59°60.63, 67.6
8,121 C, 1, Solvent Violet 7.16.17C,
1, Solvent Blue 2.6, 11, 15, 20, 3
0, 31, 32° 35.36, 55.5g, 71.72 C, 1, Solvent Brown 2, 10, 15, 21.
22C, 1, Solvent Black 3, 10, 11, 1
2.13 etc. are mentioned.

Oil bases for dissolving dyes and dispersing pigments include n-octane, n-decane, minerane spirit, ligroin, naphtha, benzene, toluene,
Hydrocarbons such as xylene; Ethers such as dibutyl ether, dibutyl ether, anisole, phenetol, dibenzyl ether; Examples include alcohols such as methanol, ethanol, isopropyl alcohol, benzyl alcohol, ethylene glycol, diethylene glycol, and glycerin. I can do it.

The pigments exemplified above can also be used in oil-based inks. Examples of oil-based pigment dispersants include polymethacrylic esters, polyacrylic esters, methacrylic ester-acrylic ester copolymers, polyvinyl acetate, vinyl chloride copolymers, polyvinylpyrrolidone, polyvinyl butyral, and other vinyl dispersants. cellulose resins such as ethyl cellulose and methyl cellulose, condensation polymer resins such as polyester, polyamide, and phenolic resins,
Natural resins such as rosin, ceramic, gelatin, casein, etc. are available.

By the way, in the device of the present invention, FIGS. 1O and 11
As shown in the figure, the visible image formed on the surface of the recording medium (A) is transferred to recording paper 61 such as plain paper. When this transfer operation is performed, the surface of the recording medium (A) is sometimes charged due to contact with recording paper or the like 61, and the amount of charge may be unevenly distributed. When such charging occurs, due to the electrostatic force, the ink (recording agent) 3a attached to the surface of the recording medium (A) in accordance with the image signal receives an attractive or repulsive force and may move slightly on the surface of the recording medium (A). As a result, the image quality becomes degraded.

In order to prevent such an unexpected situation from occurring, the apparatus of the present invention is provided with means for preventing charging of the recording medium (A). Although it is not unthinkable to charge the recording medium (A) itself, it is actually quite difficult to do so in view of the materials used for the recording medium (A). Therefore, in the apparatus of the present invention, a method is adopted in which the charge generated on the surface of the recording medium (A) is quickly removed to prevent the charge that substantially affects the image quality.

The first method for quickly removing the surface potential is to bring a grounded conductive member into contact with the recording medium (A) to release the charge through the conductive member.

The second method is to make the recording agent in contact with the recording medium (A) conductive and grounded. The third method is to place a grounded conductive member close to the surface of the recording medium (A) in a non-contact manner. The fourth method is the recording body (
A) is a method in which at least a portion of the support substrate is made conductive and this portion is grounded.

As the conductive member used in the first method, it is preferable to use a soft member as much as possible so as not to abrade the surface of the recording medium.

Preferably, the conductive material is metal, conductive rubber, or conductive plastic, and the shape is preferably a thin plate, a brush made of fibers, or a roller. It may be placed at any position on the recording body (A), but it is better to place it immediately before the formation of the latent image.Moreover, it may be placed at a plurality of locations, and the contact portion may be at least a part of the recording body (A). In the second method, in order to make a recording material such as an ink liquid conductive, in the case of an aqueous ink, the simplest method is to add an organic or inorganic salt or the like.

In the case of oil-based ink, there is a method of adding conductive fine particles such as metal.

FIG. 12(a) is an example in which a roller-shaped conductive member 52 is used as the first means. FIG. 12(b) shows an example in which a conductive brush 53 is used as the first means, a plate-shaped conductive member 54 is used as the second means, and these means are combined. FIG. 13 shows an example in which an arcuate plate-shaped conductive member 55 is placed as close as possible to the recording medium 7 (the distance between the two is preferably in the range of about 10 to several layers).

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

Thus, by using the apparatus of the present invention, the charge on the surface of the recording medium (A) is quickly removed, and a high-quality transferred image can be obtained.

〔Example〕

Example 1 The film material (surface layer material of the recording medium (A)) was prepared by solution polymerization in 1,1.1-trichloroethane using perfluoromethyl methacrylate (manufactured by Osaka Organic Chemical Co., Ltd., Viscoat 17FM) as a monomer. did. After this material was purified, it was dissolved in Freon 113 and the solution was cast onto a polyimide film. This was used as a recording medium (A) and wound around a drum having a diameter of 100 mm to produce a recording device having the configuration shown in FIG. 9. Thermal head is 8dot/Peng■
A device with a pitch-sized thermal element was used. Further, as shown in FIG. 12(b), a grounded brush-like conductive member made of a bundle of about 20 stainless steel fibers was placed in contact with the recording medium (A). When an image was recorded using this device, there was no disturbance of dots on the image, which was observed when there was no conductive member.

Example 2 The recording medium (A), latent image forming means, and recording agent adhesion means are the same as in Example 1. The ink liquid used was an aqueous ink in which a black direct dye was dissolved and the pH was adjusted to 11 with sodium hydroxide. An image was recorded by applying this ink to the ground as shown in FIG. 12(b).

Compared to the case where the recording medium (A) was not grounded, the amount of charge on the surface of the recording medium (A) was extremely small (-30 V/cd), and a good image was obtained.

Example 3 The recording medium (A), latent image forming means, and recording agent adhesion means are the same as in Example 1. The ink liquid used was an aqueous ink in which an acidic black dye was dissolved and the pH was adjusted to 11 with sodium hydroxide. Grounded arc-shaped conductive plates (made of steel) were arranged at intervals of about 0.5 V++ as shown in FIG. Without this member, the amount of charge on the surface of the recording medium (A) is -
The charge amount was about IKV/cd, but with this member, the charge amount was reduced to about -100V/(j) and the image quality was improved.

Example 4 The membrane 2 material used perfluoromethyl methacrylate (manufactured by Osaka Organic Chemical Co., Ltd., Viscoat 17FM) as a monomer,
It was prepared by solution polymerization in 1,1.1-trichloroethane. After this material was purified, it was dissolved in Freon 113 and the solution was cast onto a nickel seamless belt. Using this as a recording medium (A), a recording device was created with the configuration shown in FIG. Thermal head is 8 dots/■■
A device with a pitch-sized thermal element was used. Furthermore, as shown in Fig. 14, a nickel seamless belt was grounded.

When an image was recorded using this device, the disturbance of dots on the image, which was observed when the substrate was not a conductive material, was reduced.

〔Effect of the invention〕

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

[Brief explanation of drawings]

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 method of the present invention. Figure 4 shows the change in the receding contact angle θr observed on the surface of the recording medium (A) when the surface of the recording medium (A) according to the present invention is heated with a liquid in contact with the surface. FIG. FIG. 5 shows two embodiments of the device of the present invention. 6, 7, 8, 9, 10, 11, 12, 13, and 14 are diagrams showing how the apparatus of the present invention is implemented. 1... Substrate 2... Membrane 3... Liquid 4... Heater 52. 53, 54, 55... Conductive member patent applicant
Rico Co., Ltd.

Claims (6)

[Claims] (1) By selectively heating the surface of the recording body (A) below while in contact with the contact material (B) below, or by selectively heating the surface of the recording body (A) below, the contact material ( B
), a means for supplying a contact material (B) onto the surface of the recording medium (A) to form a latent image area showing a receding contact angle in accordance with the heating temperature on the surface of the recording medium (A); means for heating the surface of (A), means for applying a recording agent to visualize the latent image area, means for transferring a visible image onto recording paper, etc., and means for preventing static electricity on the recording medium (A). A recording device comprising: (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). (2) The recording apparatus according to claim 1, wherein a recording agent is used as the contact material, so that the contact material (B) supplying means and the recording agent applying means are combined into one. (3) The recording apparatus according to claim 1 or 2, wherein the antistatic means includes a conductive member brought into contact with the surface of the recording medium (A), and the conductive member is grounded. (4) The recording apparatus according to claim 1 or 2, wherein the antistatic means has a chargeable member brought close to the surface of the recording medium (A), and the conductive member is grounded. (5) The recording apparatus according to claim 1 or 2, wherein the antistatic means comprises making at least a part of the support substrate of the recording medium (A) conductive, and grounding the conductive part. (6) The recording apparatus according to claim 1 or 2, wherein the antistatic means grounds the recording agent.