JP3041638B2 - Recorded body - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a recording layer having a surface having specific properties,
The present invention relates to a recording medium used for a recording method for selectively or selectively and reversibly forming a region exhibiting a receding contact angle according to a heating temperature.

[Conventional technology]

As a typical means for dividing the surface into a liquid-adhesive area and a non-liquid-adhesive area for image formation, an offset printing method using a lithographic printing plate without water (fountain solution) is known. No.

Research on forming non-image areas with an ink repellent material and eliminating the supply of water (fountain solution) from the lithographic printing method has been started from an early stage (USP 3,632,375; USP 3,677,178; No. 23042).

Since the late 1960's, ink repellency-imparting components have been broadly classified into silicone-based and fluorine-based components. Silicone rubber-based components were first commercialized by 3M in the United States [Masao Iwamoto: Separate volume polymer processing, 6, (198
Four)〕.

Further, as a waterless planographic printing plate currently commercially available, a waterless printing plate manufactured by Toray Industries, Inc. can be mentioned. This master has a structure in which a photosensitive layer and a silicon layer are provided on an aluminum substrate serving as a base. In plate making printing, an image is formed with the help of the photosensitive layer.

In the case of the positive type, there are complicated steps of raw plate (original plate) → exposed image → development → printing plate → printing. Particularly, in the developing process, a special developing machine and chemicals are required. Since this offset printing method requires such a process, it is difficult to incorporate the plate making process from the original plate to the printing plate (printing plate) and the printing process from the printing plate into one apparatus. Miniaturization of printing apparatuses has become difficult.

For example, even in a relatively small office offset plate making press, the plate making device and the printing device are usually separated from each other due to the complexity of the plate making process.

In order to eliminate such a defect of the offset printing method, a liquid adherent area and a non-liquid adherent area corresponding to image information can be formed, and a reusable (reversible) recording medium can be formed. A recording method or apparatus utilizing the method has been proposed. Some of them are as follows.

(1) Aqueous development method After applying a charge to the hydrophobic photoconductor layer from the outside, it is exposed to light to form a pattern having a hydrophobic portion and a hydrophilic portion on the surface of the photoconductor layer. Transfer to paper etc. by attaching aqueous developer (Japanese Patent Publication No. 40-18992, Japanese Patent Publication No. 40-1)
Nos. 8993, JP-B-44-9512, and JP-A-63-264392).

(2) Method using photochemical reaction of photochromic material A layer containing a material such as spiropyran or an azo dye is irradiated with ultraviolet rays, and the photochromic compound is hydrophilized by the photochemical reaction [for example, "Polymer Papers" No. 37.
Vol. 4, p. 287 (1980)].

(3) Method using the action of internal biasing force An amorphous state and a crystalline state are formed by a physical change to constitute a liquid ink adhesion / non-adhesion area (Japanese Patent Publication No.
No. 54-41902).

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

According to the above method (2), hydrophilicity and hydrophobicity can be freely and reversibly controlled by selectively changing the irradiation of ultraviolet light and visible light, but the reaction time is extremely low due to poor quantum efficiency. It has a disadvantage that it is long, has a low recording speed, and lacks stability, and has not yet reached a practical level.

Furthermore, according to the method (3), the information recording member used there is stable after recording, but may have a physical structure change due to temperature change before recording. Problems remain in storage stability. In addition to this, a means of applying a heat pulse to the erasing of the recorded information pattern and then quenching is adopted,
Repetitive image formation has a disadvantage that complexity cannot be avoided.

Therefore, as one means for solving the drawbacks of the above-mentioned conventional system, one of the present inventors has proposed a recording medium (A) having a surface in which the receding contact angle is reduced when it is first brought into contact with a liquid in a heated state. A state in which the surface of is contacted with a liquid, a vapor, and a contact material (B) selected from liquids or solids that generate a liquid or a vapor below the temperature at which the receding contact angle of the recording medium (A) starts to decrease. Then, the recording material surface is brought into contact with the contact material (B) by selectively heating the recording material surface to a temperature equal to or higher than the temperature at which the receding contact angle starts to decrease or while the recording material (A) surface is selectively heated. Thereby, an area (a desired pattern area, hereinafter referred to as a “latent image” or “latent image area” for convenience) which shows a receding contact angle corresponding to the heating temperature is formed on the surface of the recording medium (A). Proposed a new recording method (Japanese Patent Application No. 2-43599).

According to the above method, a liquid-adhesive region having a desired pattern can be formed selectively or selectively and reversibly by an easy means, and a good image can be obtained by supplying a recording agent to the liquid-adhesive region. After the recording material is supplied, the recording material is transferred to a transfer medium such as paper, so that a clear image with gradation can be obtained. In addition, by using a material having excellent storage stability and stability regardless of before and after recording, it is possible to further form a reversible liquid-adhesive region.

[Problems to be solved by the invention]

However, in the recording method for forming a region showing a receding contact angle according to the heating temperature on the surface of the recording medium as described above,
The recording layer of the recording medium is made of a synthetic resin, particularly a fluororesin having a high triboelectric property (surface specific resistance value: about 1 × 10 ¹³ Ω to 1 × 10 ¹⁸ Ω). The recording medium is charged with static electricity, sucking dust in the atmosphere,
There is a possibility that background contamination or deterioration of the recording medium may occur.

Therefore, an object of the present invention is to provide the recording method,
It is an object of the present invention to provide a recording medium in which background contamination does not occur even when the recording medium is repeatedly used and deterioration of the recording medium is prevented.

[Means for solving the problem]

According to the present invention, the surface of the recording layer having a surface in which the receding contact angle decreases in a heated state and when brought into contact with a liquid, the liquid, the vapor and the liquid at a temperature not more than the temperature at which the receding contact angle in the recording layer starts to decrease. Or by selectively heating in contact with a contact material selected from liquids or solids that generate vapor, or by contacting the contact material with the surface of the recording layer selectively heated A recording medium used in a recording method for forming a region showing a receding contact angle according to a heating temperature on the surface of the recording layer, the recording medium comprising a substrate and the recording layer laminated thereon. Or a recording medium comprising only a recording layer, wherein the recording medium contains a conductive material and / or an antistatic agent, and has a surface specific resistance of 1 × 10 ¹² Ω or less. You.

That is, since the recording material of the present invention has a configuration in which a conductive material and / or an antistatic agent is added and the surface specific resistance is 1 × 10 ¹² Ω or less, antistatic properties are imparted,
Even when used repeatedly, no soiling occurs and deterioration of the recording medium is prevented.

First, the operation of the recording medium surface in the recording method using the recording medium of the present invention will be described.

The present recording method is to selectively heat the surface of the recording medium (A) described below and the contact material (B) in contact with each other, or to selectively heat the surface of the recording medium (A). The recording material (A) is brought into contact with the contact material (B) with
Is characterized by forming a region (desired pattern region, sometimes referred to as “latent image” or “latent image region” hereinafter for convenience) which shows a receding contact angle corresponding to the heating temperature.

(A) A recording medium having a surface in which the receding contact angle is reduced when heated and brought into contact with a liquid.

(B) Liquid, vapor, or solid that becomes liquid or generates liquid or vapor below the temperature at which the receding contact angle on the surface of the recording medium (A) starts to decrease.

In the present method, the latent image area can be visualized by supplying a recording material containing a color developing material, or a liquid recording material containing a color developing material as a contact material (B). In the case of using, it is possible to visualize the latent image simultaneously with the formation of the latent image.

Further, in the present method, 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 image formation can be performed reversibly. It can be done.

When the recording medium of the present invention is heated in contact with a liquid,
The surface has a function of decreasing the receding contact angle after cooling and increasing the receding contact angle when heated in the absence of liquid. More specifically, the recording material (A) has a surface (i) a member containing an organic compound having a surface self-orientation function of a hydrophobic group, or (ii) an organic compound having a hydrophobic group and having a hydrophobic group on the surface. Composed of a member oriented in

The "surface self-orientation function" referred to in (i) means that when a solid formed by forming a certain compound on a support or a solid formed by a certain compound itself is heated in air, the hydrophobic group on the surface is shifted to the air side (free surface side). It means that it has the property of being oriented toward. This can be similarly applied to (ii). Generally, in an organic compound, a hydrophobic group tends to be directed toward a hydrophobic atmosphere. This occurs because the surface energy of the solid-gas interface is reduced. This tendency is recognized as the molecular length of the hydrophobic group becomes longer, because the longer the molecular length, the higher the mobility of the molecule upon heating.

More specifically, if the molecule has a hydrophobic group at the end (that is, lowers the surface energy), the surface is easily oriented toward the air side (free surface side). Similarly, CH _{2 n}
In a linear molecule containing, the CH ₂ CH ₂ portion has a planar structure, and the molecular chains are easily oriented. Also, Molecules containing Has a planar structure, and the molecular chains are easily oriented. In particular, a linear molecule containing an element having a high electronegativity such as fluorine has a high self-aggregation property, and the molecular chains are easily oriented.

There is a relationship between the state of the orientation and the receding contact angle, and also between the receding contact angle and the liquid adhesion. That is, the adhesion of the liquid on the solid surface occurs mainly by tacking of the liquid on the solid surface. This tacking can be considered as a kind of frictional force when a liquid slides on a solid surface. Therefore, the “receding contact angle” θr referred to in the present invention
Is given by γ _f , (However, γ: Surface tension of solid in vacuum γs _l : Solid-liquid interfacial tension γ _lV : Surface tension when liquid is in contact with its saturated vapor πe: Equilibrium surface tension γ _f : Friction tension γs: Adsorption layer Is the surface tension of a solid without a solid) [Saito, Kitazaki et al., "Journal of the Adhesion Society of Japan", 22 , 12, (1986)].

Thus, gamma _f value when the value of θr decreases increases. That is, the liquid is less likely to slide on the solid surface, and as a result, the liquid adheres to the solid surface.

As can be inferred from these relationships, the liquid adhesion depends on the receding contact angle θr, and the receding contact angle θr is determined by any member having a surface self-orienting function on the surface. Therefore, in this method,
In the recording medium (A), a member having a surface self-orientation function on the surface is inevitably selected because it is necessary to form a desired pattern area on the surface and / or visualize the recording medium with a recording agent.

The recording medium (A) used in the present method is, as described above,
"The receding contact angle θ when heated and in contact with liquid
r has a reduced surface. " Recorded body (A)
The shape is arbitrary as long as the surface has the above properties.

In this recording medium (A), depending on the type of the contact material (B), the liquid adhering portion in the latent image area becomes either lipophilic or hydrophilic. Any of the inks can be used as needed.

Here, FIG. 1 shows an example in which members or materials that form a surface that forms a surface where the receding contact angle θr decreases when it is brought into contact with a liquid in a heated state are classified into several members. Fig. 1 (a)
Is an example of a compound having a self-orienting function, which is a compound having a hydrophobic group in a side chain of a high molecular polymer, and has a main chain L and a hydrophobic group R
And are bonded by a bonding group J.

FIG. 1 (b) is an example of an organic compound having a hydrophobic group in which the hydrophobic group is oriented on the surface. The organic compound having the hydrophobic group is physically or chemically bonded to the surface of an organic or inorganic material M. This is a member on which compound O is formed. FIG. 1 (c) is an example of a member consisting only of the organic compound O having a hydrophobic group as shown in FIG. 1 (b).

FIG. 1 (d) shows an example in which a linear molecule is present in a side chain of a polymer. The self-aggregating or planar structure having a hydrophobic group R at the terminal, in which the main chain L and the molecule are connected by a bonding group J, is shown. A compound having a molecular chain N in the middle.

In the examples shown in FIGS. 1 (a) and 1 (d), the main chain L of the polymer compound may have a linear shape or a hatched structure. In the example of FIG. 1B, a hydrophobic group-containing compound O may be further laminated on the hydrophobic group-containing compound O like a cumulative LB film. In the example of FIG. 1 (c), the main chain (L)
, Or without the organic / inorganic material (M).

As the hydrophobic group, the terminal of the molecule is preferably -CH
₃ and _{-CF 3, -CF 2 H, -CFH} 2, -C (CF 3) 3, -C (C
H ₃ ) _{3 and the} like, and more preferably those having a long molecular length in terms of high molecular mobility. Among them, as the hydrophobic group, a substituted alkyl group having at least one of -F and / or -Cl Alternatively, an unsubstituted alkyl group having 4 or more carbon atoms is desirable. Either fluorine-substitution or chlorine-substitution can be used, but fluorine-substitution is more effective. In these materials, in terms of the relationship between the number of carbon atoms in the alkyl group and the function, if the number of carbon atoms is 3 or less, the function suitable for the recording method is reduced.

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

First, it is considered that the surface of the recording medium (A) formed by 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 motion of the hydrophobic group due to the heating becomes active, and the interaction with the contact material (B) occurs. The orientation (alignment) state of at least a part of the surface of the recording medium (A) changes to another state (that is, another orientation state or a state in which the orientation is disordered), and the other state is maintained after cooling. Seem. The contact material (B) is applied to the surface of the recording body (A).
Heating in a state where is in contact with the contact material (B)
In this case, the liquid is brought into contact with the recording medium (A) while the surface of the recording medium (A) is heated.

Before this heating, the surface energy of the surface of the recording medium (A) is extremely small because the hydrophobic groups are aligned (oriented) on the surface.

However, the heating in the state where the contact material (B) is in contact with the contact material disturbs the orientation state and increases the surface energy. The receding contact angle θr is determined by the balance between the surface energies of the solid and the liquid, regardless of the type of the liquid.
Therefore, if the surface energy of the solid increases, the receding contact angle θr decreases regardless of the type of the liquid. Therefore,
Adhesion to liquids will increase.

Further, the surface of the recording medium (A) is heated in another state ("another alignment state" or "a state in which the alignment is disturbed" different from the original alignment state) in the absence of the contact material (B). When,
Since no interaction occurs with the contact material (B), it is considered that the state returns to the original alignment (orientation) state.

Therefore, the presence of the contact material (B) is simply determined by the recording material (A)
The surface of the recording medium (A) is not intended to be rapidly cooled after heating, but causes some interaction with the compound on the surface of the recording medium (A). (A state in which the orientation is disturbed).

As described above, when an alkyl group or an alkyl group substituted with fluorine or chlorine is used as the hydrophobic group of the member (compound) forming the surface of the recording medium (A), the alkyl group has 4 or more carbon atoms. It is desirable that the alkyl group be aligned (orientated) to some extent on the surface of the recording medium (A),
Moreover, it seems that this is the number necessary for active molecular motion during heating. Further, when the contact material (B) is heated together with the surface of the recording medium (A), it is conceivable that molecules of the contact material (B) are incorporated into molecules on the surface of the recording medium (A). Further, when fluorine or chlorine having a high electronegativity is present in the alkyl group, the interaction with a liquid, particularly a polar liquid, becomes large, so that a greater change in adhesion can be obtained than with a compound containing an alkyl group containing only hydrogen. . In addition, the fluorine-containing alkyl group has a high self-cohesive property, has a high surface self-orientation function, and has a low surface energy, and thus is excellent in preventing background contamination.

Furthermore, the surface of the recording medium (A) has liquid repellency, which can be described by the surface energy of a solid as 50 dyn /
cm or less is desirable as a recording method. At a higher value than this, the surface of the recording medium (A) is
Occasionally, it may become wet and cause soiling of the background.

The recording medium of the present invention has the above-mentioned surface function, but as described above, further comprises a substrate and a recording layer laminated thereon, or comprises only a recording layer, and has a conductive property. Containing a conductive material and / or an antistatic agent,
It is characterized in that the surface specific resistance value is 1 × 10 ¹² Ω or less. That is, referring to the drawings, in FIG. 2, the recording body of the present invention has a configuration in which a recording layer 2 containing a conductive material and / or an antistatic agent 2 'is laminated on a substrate 1. In FIG. 2, the conductive material and / or the antistatic agent 2 'are mixed in the recording layer 2, but they may be mixed in any one of the recording layer 2 and the substrate 1. And it may be mixed in both layers. However, from the viewpoint of producing a recording medium, it is most advantageous to include it in the recording layer 2.

In the recording medium of the present invention, it is also effective to provide a conductive intermediate layer between the substrate and the recording layer.

As the substrate in the recording medium of the present invention, Ni, Cu, Cr, Pt
Metals or alloys, such as ethylene tetrafluoride, silicone, polyimide, polycarbonate, epoxy, melamine, phenol, polyester, polyacetal, urea, polyethylene terephthalate, and other metal oxides. When it is incorporated into a substrate, it is desirable that it be flexible enough to withstand transfer and to withstand the load applied during transfer.
Further, examples of the transfer target body for direct recording include a paper made of cellulose-based natural fiber and a transparent film for OHP or the like as a substrate.

In the present invention, as a material for forming the recording layer, a compound having liquid repellency as described above is used. First, a compound of the type shown in FIGS. 1 (a) and 1 (d) will be described. This type of compound has an alkyl group (including a fluorine- and / or chlorine-substituted one) in a vinyl polymer side chain. Compounds and the like are conceivable. In particular,
Formulas (I) (II) (III) (IV) (V) (VI) and (VII)
And a polymer from the monomer represented by

_{[R: -H, -CH 3, -C} 2 H 5, -CF 3 or -C ₂ F ₅ Rf: C ₄ or higher alkyl groups or fluorine or chlorine-substituted alkyl group group containing, or in the molecular chain CF _{2 l} , CH _2
l or N ': an integer of 1 or more] Other polymers include those represented by formulas (VIII), (IX) and (X).

_{[R: -H, -CH 3, -C} 2 H 5, -CF 3 or -C ₂ F ₅ Rf: C ₄ or higher alkyl groups or fluorine or chlorine-substituted alkyl group group containing, or in the molecular chain CF _{2 l} , CH _2
l or And a hydrophobic group (l ≧ 4) n: an integer of 10 or more] If Rf is described in more detail in these specific examples, the following (1) to (20) can be exemplified.

Among these compounds, a polymer using the following monomer (XI) as a raw material is more preferable.

[R ¹ : hydrogen, -C _n H _{2n + 1} or -C _n F _{2n + 1} (n = 1 or an integer of 2 or more) R ² : CH _{2 p} (an integer of p ≧ 1) or CH _{2 qN} ( R ³ ) SO ₂ — (R ³ is —CH ₃ or —C ₂ H ₅ , q is an integer of 1 or more) m: an integer of 6 or more] Therefore, preferred specific examples of the compound forming the recording layer in the present invention include: And polymers from the following monomers, and (co) polymers containing a fluorine atom in the side chain are particularly preferable.

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

Further, a monomer of the formula (XI) and a polymerizable monomer having a functional group, for example, CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂ OH CH ₂ ＣC (CH ₃ ) COOCH ₂ CH (OH) CH ₃ CH ₂ = CHCOOCH ₂ CH (OH) C ₈ F ₁₇ and other copolymers are made to introduce a large number of functional groups into the polymer, or a monomer of the formula (XI) and a polymerizable monomer having a functional group A crosslinkable polymer produced by forming a copolymer with the above and then crosslinking the copolymers containing a large number of functional groups with a crosslinking reagent is also an excellent material of the present invention. Examples of the crosslinking reagent include formaldehyde, dialdehyde, N-methylol compound, dicarboxylic acid, dicarboxylic acid chloride, bishalogen compound, bisepoxide, bisaziridine, diisocyanate and the like. An example of the crosslinked polymer thus obtained is shown below.

In the above formula, the A block is an alkyl group which brings about the change in the thermal properties described above, while the B block is a site where the chain polymers are cross-linked (cross-linked using diisocyanate as a cross-linking reagent). is there.

To obtain a crosslinked film, a solution obtained by mixing the copolymer and the crosslinking reagent is applied as a coating solution on a substrate,
The crosslinked polymer film may be obtained by heating, electron beam irradiation, or light irradiation.

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

Next, the compound shown in FIG. 1 (b) will be described.
Here, the materials represented by the formulas (XII), (XIII) and (XIV) R _f -COOH ... (XII) R _f -OH ... (XIII) R _f CH _{2 n} SiX ... (XIV) [R _f : carbon number A group containing four or more alkyl groups or a fluorine- or chlorine-substituted alkyl group, or CF _{2 in the} molecular chain.
_l , CH _{2 l} or A hydrophobic group (l≥4) n: an integer of 1 or more X: chlorine, methoxy group or ethoxy group] and the like, on the surface of an inorganic material such as glass, gold and copper, or an organic material such as polyimide, polyester and polyethylene terephthalate. It is desirable that the material be an adsorbed or chemically bonded material (preferably having a surface energy of about 50 dyn / cm or less).

As specific examples of the formulas (XII), (XIII) and (XIV), CF ₃ CF _{2 5} COOH CF ₃ CF _{2 7} COOH CF ₃ CF _{2 7} (CH _{2 2} OH HCF _{2 10} COOH HCF _{2 10} CH ₂ OH FCF _{2 6 CH 2 CH 2 -Si (} CH 3) 2 Cl CF 2 Cl (CF 3) CF (CF 2) such as _{5 COOH CF 3 (CF 2)} 7 (CH 2) 2 SiCl 3 and the like.

The compounds shown in FIG. 1 (c) include the compounds represented by the formulas (XII) and (X)
III) and a structure composed of only the material of the formula (XIV).

In the recording medium of the present invention, a conductive material and / or an antistatic agent is added to at least one of the recording layer and the substrate made of the material. In this case, the conductive material has an antistatic effect on the surface. And a material having properties such that heat resistance and friction resistance can be imparted. Specific examples of the conductive substance used include, for example, various carbon blacks such as acetylene black, oil black, gas black, fornes black, channel black, and thermal black, as well as carbon fibers and graphite. Further, a metal such as gold, silver, copper, aluminum and titanium, or a metal oxide such as antimony oxide and tin oxide can also be used. Further, a white conductive material or the like in which the surface of fibrous potassium titanate or titanium oxide particles is coated with tin oxide and antimony oxide can be used.

Examples of the antistatic agent include a nonionic polymer and an ionic polymer.
It is important that it be less than × 10 ¹² Ω. The volume resistance of the antistatic agent itself is preferably 10 ⁷ Ωcm or less.

Also, the conductive material is advantageously added as a filler. This is because the process is simple because of the conductive powder dispersion type as compared with the vapor deposition type or the like, and can be applied to a heterogeneous type by applying a paint. The charged voltage and the conductivity can also be adjusted by kneading the conductive powder with plastic, rubber, fiber, or the like and suppressing the volume resistance.

The range of the surface specific resistance value of the recording medium is 1 × 10 ¹² Ω or less, and is preferably such that the surface of the resin layer does not exhibit chargeability, that is, 1 × 10 ⁶ to 1 × 10 ¹² Ω. is important. Therefore, the conductive material and the antistatic agent are added in arbitrary amounts within a range that gives a surface resistivity of about 1 × 10 ⁶ to 1 × 10 ¹² Ω to the recording medium.

The thickness of the recording layer is determined by the combination of the recording layer and the substrate, and by the combination of the three when an intermediate layer is provided between the recording layer and the substrate. It is preferable that the film thickness is as follows.

The recording medium of the present invention is generally obtained by mixing and dispersing the above-mentioned conductive material and the like in a recording layer material, and applying the mixture on a substrate. In this case, a ball mill, a paint shaker, an ultrasonic homogenizer, a sand mill, or the like can be applied as a method for dispersing the conductive material or the like in the recording layer material. The application of the recording layer material in which the conductive material or the like is dispersed to the substrate can be performed by an applicator, a spray coater, a bar coater, a dip coater, a doctor blade, or the like. In addition, since the surface condition of a substrate such as paper is generally not good just by coating, it is also effective to improve the smoothness of the coated surface by performing a surface treatment with a calender or the like.

In the case of obtaining a recording medium in which a conductive material is mixed in a resin substrate, a conductive material or the like is mixed and dispersed in a polymerizable solution or a polymer solution in the same manner as described above to prepare a substrate. A recording layer material (in which a conductive material or the like is mixed and dispersed in some cases) can be obtained by applying the same method as described above. It is also effective to use a commonly used antistatic film.

Furthermore, in the process using the recording medium of the present invention, the heating at the time of forming the latent image can be performed not only from the recording layer material side but also from the substrate side (the liquid is placed on the recording layer side and the heating is performed from the substrate side). Heating) (see section on heating means). In this case, since the recording material is often heated directly to the substrate material, deterioration of the recording material due to heat is assumed. However, in order to deal with these problems, a heat-resistant back layer is provided on the substrate side. It is effective to provide. A thermosetting resin or a heat-resistant resin having a high softening point is employed for the back layer. It is also effective to include a highly lubricious inorganic pigment in these back layers. The inorganic pigment referred to here refers to fine powder such as talc, mica powder, fine silica powder, molybdenum disulfide, and as a resin material, silicone resin, fluorine resin, epoxy resin, melamine resin, phenol resin, polyimide resin, Resins such as nitrocellulose are effective.

 Next, the contact material will be described.

The contact material is as described above, but in short, it is a liquid or a vapor from the beginning, or a solid that results in a liquid at or below the temperature at which the receding contact angle θr in the recording layer begins to decrease. is there. At least a part of the vapor at or near the surface of the recording layer is condensed to generate a liquid, and it is sufficient that the liquid can wet the surface of the recording layer. On the other hand, the solid here becomes a liquid, generates a liquid, or generates a vapor below the temperature at which the receding contact angle θr starts decreasing. The vapor generated from the solid is condensed on or near the surface of the recording layer to generate a liquid as in the case described above.

More specifically, these contact materials are as follows. That is, as a liquid that is one of the contact materials,
In addition to water, aqueous solutions containing electrolytes, ethanol, alcohols such as n-butanol, polyhydric alcohols such as glycerin and ethylene glycol, and polar liquids such as ketones such as methyl ethyl ketone, and n-nonane and n-octane. Non-polar liquids such as linear hydrocarbons, cyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as m-xylene and benzene. Further, a mixture of these may be used, and various dispersion liquids and liquid inks may be used. More desirably, polar liquids are better.

As the vapor which is another contact material, any vapor of a liquid of the contact material other than water vapor can be used. In particular, vapor of an organic compound such as ethanol vapor or m-xylene vapor (in the form of a spray) is used. Including). The temperature of the organic compound vapor must be lower than the melting point or softening point of the compound forming the surface of the recording layer. Examples of the solid that is another contact material include higher fatty acids, low molecular weight polyethylene, polymer gels (polyacrylamide gels, polyvinyl alcohol gels), silica gel, and compounds containing water of crystallization.

As will be clear from the later description, when a “recording agent containing a color developer” such as the liquid ink is used as the contact material, the visualization is performed simultaneously with the formation of the latent image. become.

 Subsequently, the heating means will be described.

As the heating means, there is non-contact heating using electromagnetic waves (light from a light source such as a laser light source or an infrared lamp is condensed by a lens) in addition to contact heating using a heater or a thermal head.

Subsequently, the properties of the recording medium of the present invention, the formation of a latent image and the formation of a visible image using the recording medium of the present invention will be described with reference to the accompanying drawings.

FIG. 3 (a) shows a state in which a recording layer 2 is formed on a substrate 1 and a contact material (for example, a liquid 3) is present on the layer surface. In this state, as shown in FIG. 4 (a), when the layer 2 is heated, it is recognized that the receding contact angle θr of the surface of the layer 2 is reduced, and the layer 2 shows remarkable wetting and has liquid adhesion. Can be Further, when the layer 2 having the liquid adhesion property is heated again in the air, in a vacuum or in an inert gas atmosphere (FIG. 3 (b)), the receding contact angle θr of the surface of the layer 2 increases, It is again observed to exhibit liquid repellency.

As a method showing a phenomenon somewhat similar to such a phenomenon, there is a method described in Japanese Patent Publication No. 54-41902 mentioned above. However, the method disclosed herein is mechanically different in that it provides a substantially disordered and generally amorphous layer of memory material in the recording material. . That is, in the method using the recording medium of the present invention, no state change can occur on the recording layer surface without the presence of the contact material. In addition, Tokiko Sho 54
In the method described in JP-A-41902, reversibility cannot be obtained by a simple operation.

As shown in FIG. 4 (a), heat is applied to the layer 2 under the contact of the liquid 3 according to the image information [as shown in FIG. 4 (b-1),
The same applies to the case where the layer 2 is brought into contact with a liquid in a state where heat is applied to the layer 2 in the absence of the liquid in accordance with the image information.] . In the figure, 4 is a heater, 31 is a liquid supply port, 41 is an infrared lamp, 5 is a lens, and 6 is a shutter.

FIG. 4 (a) shows an example in which the layer 2 is heated through the substrate 1, while the example shown in FIG. 4 (b-2) is an example in which the heating is performed through the liquid 3.

FIG. 5 shows an example of the change in the contact angle of the aqueous solution before and after the heating of the layer 2 under the contact with the aqueous solution, and the change in the contact angle of the aqueous solution when the layer 2 is further heated in the air. In FIG. 5, ○ indicates a forward contact angle, and △ indicates a receding contact angle.

In general, when the receding contact angle is a high value of 90 ° or more, the surface shows liquid repellency, and when the receding contact angle is a low value of 90 ° or less, the surface shows liquid adhesion.

The heating temperature of the recording layer surface in contact with the contact material is preferably in the range of 50 ° C to 250 ° C, more preferably 8 ° C.
0 ° C to 150 ° C. The heating time is about 0.1 millisecond to 1 second, preferably 0.5 millisecond to 2 milliseconds. As the timing of heating, if a latent image is formed, after the recording layer surface is heated, it is brought into contact with a contact material before being cooled,
The recording layer surface may be heated while the contact material is in contact with the recording layer surface. On the other hand, when erasing a latent image, the surface of the recording layer is
C., preferably 100 to 180.degree. The heating time in each case is about 1 millisecond to 10 seconds, preferably 10 milliseconds.
Milliseconds to 1 second.

Next, means for actually recording image information on the surface of the recording layer will be described in more detail.

One is to heat the recording layer surface in response to an image signal in a liquid or vapor atmosphere to form a liquid adhering area on the surface of the recording layer (formation of a latent image), and then contact the recording material with the latent image portion. This is a method in which a recording agent is adhered to the latent image portion by means (developing), and then this recording agent is fixed on the surface of the recording layer as it is (direct recording method). The other is to heat the surface of the recording layer in response to an image signal in a liquid or vapor atmosphere to form a liquid adhering area on the surface of the recording layer (latent image formation)
Thereafter, the recording agent is attached to the latent image portion by means of bringing the recording agent into contact with the latent image portion (development), and thereafter, the recording agent on the recording layer surface is transferred to recording paper (indirect recording). Method). Further, in the above method, after transferring the recording agent,
If a means for bringing the recording agent into contact with the latent image portion is performed again, a printing method using the recording layer as a printing plate is obtained. Further, in the above method, after transferring the recording agent, by heating the surface of the recording layer having formed a latent image in the absence of liquid or vapor to erase the latent image, a recording method in which the recording layer can be reproduced Become. 6 (a), (b) and (c) show typical processes of a direct recording method, an indirect recording method (printing method), and a reversible recording method of a recording medium (repeated recording method).

Next, an apparatus configuration in a recording medium and a recording method will be described.

If the recording layer has a surface in which the receding contact angle is reduced in a heated state and when brought into contact with a liquid (for convenience, it may be referred to as “layer 2” or “recording layer surface”),
It is not restricted to its form. Therefore, the recording body may be a rigid cylindrical shape, a belt shape, or a plate shape. However, since the rigid cylindrical recording body (the one in which the layer 2 is formed on the surface of the cylindrical rigid body) is less likely to be displaced when the recording body is operated and has excellent controllability,
Desirably, a rigid cylindrical recording medium is used.

When a resin is used for the recording substrate, it is hard to say that it is a good conductor of heat, and it takes some time until the surface of the recording layer is heated to have liquid adhesion. Therefore, it may be conceivable to use a good heat conductor for the entire substrate or for a portion on the substrate 1.

FIG. 7 (a) shows a case where a good heat conductor such as a metal is used as a substrate (metal substrate 11), and an organic thin film 12 is deposited thereon.
Further, the layer 2 is formed thereon, and in this case, the heat conduction speed in the vertical direction is improved. Examples of the organic thin film 12 include polyimide, polyester, phthalocyanine, and the like. This configuration is sufficient when the print dots can be relatively large, but is not suitable for the purpose of further high-density printing because the portion having liquid adhesion is expanded by heat diffusion in both directions. . FIG. 7 (b) shows a structure in which a good heat conductor portion is provided on the substrate 1 so as to prevent heat diffusion in the plane direction and to miniaturize the portion 2a having liquid adhesion. Seventh
In FIG. 2B, reference numeral 11a denotes a miniaturized metal film.

Subsequently, a latent image forming means by heating will be described. As described above, the heating source is preferably a contact heating source such as a heater or a thermal head, or a non-contact heating source using electromagnetic waves such as a laser or an infrared lamp.

As a specific example of these, the recording layer 2 is in contact with a liquid.
The means for heating the surface will be described. First, the liquid 3 is brought into contact with the surface of the recording layer 2 in advance, and the base 1
Means (FIGS. 8A and 8B) for heating from the liquid side or the liquid 3 side, or heating first from the recording layer 2 surface side and immediately applying the liquid 3 to the recording medium heating section (recording layer 2 surface). It is desirable to employ means (FIGS. 8 (c) and 8 (d)) for making contact with the surface.

As a means for supplying the liquid 3, a dish is provided below the recording body 7 and filled with the liquid, the recording layer 2 is always in contact with the liquid 3 in the dish, and a heating source is arranged near or in the dish. This is the simplest configuration. Instead of a dish, a sponge-like porous body filled with a liquid may be used. The latent image forming means using electromagnetic waves is also basically the same as the above-described configuration.

In FIG. 8, reference numeral 42 denotes a laser light source, and 43 denotes a thermal head. Thus, a latent image is formed on the surface of the recording layer 2.

As means for adhering the recording agent (ink) to the liquid adhering area selectively applied in accordance with the image signal by the above-mentioned means, a plate filled with the recording agent 3a may be a recording medium with respect to the latent image forming means arrangement position. (FIGS. 9 and 10). As shown in FIG. 10, when the liquid used for forming the latent image is also used as the recording agent, the apparatus can be constituted by one dish, and the latent image formation and the visualization can be integrated, so that the apparatus can be downsized.

In the case of direct recording, a flexible film or a rigid film is used as a recording body substrate, and a recording layer 2 is formed on the substrate 1 to form a recording body. The recording layer 2 is subjected to latent image formation and visualization by the above-described means. After that, air-drying or heat-drying is performed, and the recording agent adhered on the recording layer 2
Fix 3b. FIG. 11 shows an example of an apparatus desirable for implementing the direct recording method. In the example of FIG. 11, the recording body is moved while the latent image forming means and the visualizing means are fixed.

Further, when the recording medium substrate on which the recording agent is fixed after direct recording is a transparent film, the recording medium can be used as an original plate of an apparatus such as a slide projector by irradiating transmitted light (FIG. 12).
It can also be used as an information storage medium by irradiating reflected or transmitted light in the form of a beam and detecting a change in light intensity due to the presence or absence of a recording agent (FIG. 13). In FIGS. 12 and 13, 52
Is a screen, 53 is a light source, 54 is a detector, and 55 is a motor.

In the case of indirect recording, as described above, for example, a rigid cylindrical tube is advantageously used as the recording substrate. After the formation and development (visualization) of the latent image, for example, the adhering recording agent 3b on the recording medium
Is transferred to the recording paper 61 by a capillary action of the recording paper by providing a means for directly contacting the recording paper 61 (transfer means). The transfer position may be any position on the recording medium after development, but is preferably a position where transfer is performed immediately after development. After the transfer, if the development is repeated without erasing the latent image, the apparatus becomes a printing apparatus. FIG. 14 shows an example of the printing apparatus. When printing of one piece of image information is completed, recording and printing of another piece of image information becomes possible by replacing the recording medium or by erasing the latent image.

Further, after the transfer means, in the absence of liquid or vapor, that is, in air, in a vacuum, or in an inert gas,
If the latent image is erased by heating the vicinity of the latent image portion, the recording medium becomes a recording device that can be used repeatedly (FIG. 15). As a heating source for erasing a 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 is desirable. Heating may be performed on the entire recording layer or only on the latent image portion. However, heating over the entire surface is more preferable because the device configuration can be simplified. The latent image erasing means is provided at a position where the surface of the recording layer is substantially cooled during a period from the time of heating for erasing to the time of forming a latent image again. The heating temperature required for erasing depends on the material of the recording layer surface, but it is desirable that the temperature of the recording layer surface material be equal to or higher than the temperature at which the receding contact angle starts decreasing and equal to or lower than the decomposition point.

Suitable recording paper (transfer medium) is a transparent resin film, plain paper, inkjet paper, type paper, or the like.

 Next, the recording agent will be described.

In the recording method using the recording medium of the present invention, to obtain a visible image on the recording layer surface, a writing ink as a recording agent,
From the recording agents used in the conventional printing and recording methods, such as ink jet inks, printing inks, and electrophotographic toners, those suitable for the present process can be selected and used.

More specifically, for example, as the aqueous ink, water, a water-soluble ink composed of a wetting agent and a dye, water, an aqueous pigment-dispersed ink composed of a wetting agent, a pigment and a polymer compound for dispersion or a pigment or a dye. An emulsion ink or the like dispersed in water using a surfactant is used. Examples of the wetting agent used in the aqueous ink include the following water-soluble organic liquid compounds.

Monohydric alcohols such as ethanol, methanol and propanol; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol,
Polyhydric alcohols such as dipropylene glycol, glycerin, low molecular weight polyethylene glycol and hexylene glycol; ethylene glycol monobutyl ether;
Polyvalent such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monoethyl ether, etc. Alcohol alkyl ethers; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether; N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactone, etc. Nitrogen-containing heterocyclic compounds such as formamide, N-methylformamide, N, N-dimethylformamide, etc. Earth; monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, amines such as triethylamine; dimethyl sulfoxide, sulfur-containing compounds such as sulfolane; propylene carbonate, ethylene carbonate, etc..

As the water-soluble dye, a dye classified into an acid dye, a direct dye, a basic dye, a reactive dye and an edible dye in a color index and having excellent water resistance and light resistance is used. Specific examples of these dyes include the following.

CI Acid Yellow 17,23,42,44,79,142 CI Acid Red 1,8,13,14,18,26,27,35,37,42,
52,82,87,89,92,97,106,111,114,115,134,186,249,254,
289 CI Acid Blue 9,29,45,92,249,890 CI Acid Black 1,2,7,24,26,94 CI Food Yellow 3,4 CI Food Red 7,9,14 CI Food Black 2 CI Direct・ Yellow 1,12,24,26,33,44,50,142,
144,865 CI Direct Red 1,4,9,13,17,20,28,31,39,8
0,81,83,89,225,227 CI Direct Orange 26,29,62,102 CI Direct Blue 1,2,6,15,22,25,71,76,79,8
6,87,90,98,163,165,202 CI Direct Black 19,22,32,38,51,56,71,74,
75,77,154,168 CI Basic Yellow 1,2,11,13,14,15,19,21,2
3,24,25,28,29,32,36,40,41,45,49,51,53,63,65,67,70,
73,77,87,91 CI Basic Red 2,12,13,14,15,18,22,23,24,
27,29,35,36,38,39,46,49,51,52,54,59,68,69,70,73,7
8,82,102,104,109,112 CI Basic Blue 1,3,5,7,9,21,22,26,35,41,4
5,47,54,62,65,66,67,69,75,77,78,89,92,93,105,117,1
20,122,124,129,137,141,147,155 Basic Black 2,8 etc.

As pigments, organic pigments such as azo, phthalocyanine, anthraquinone, quinacridone, dioxazine, indigo, thioindigo, perinone, perylene, isoindolenone, aniline black,
Azomethine-based, carbon black and the like can be mentioned, and inorganic pigments include iron oxide, titanium oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, navy blue, cadmium red, chrome yellow, and metal powder.

Examples of the pigment dispersing compound include polyacrylamide, polyacrylic acid and alkali metal salts thereof, acrylic resins such as water-soluble styrene acrylic resin, water-soluble styrene maleic acid resin, water-soluble vinyl naphthalene acrylic resin, and water-soluble vinyl naphthalene maleic acid. Resins, polyvinylpyrrolidone, polyvinyl alcohol, alkali metal salts of β-naphthalenesulfonic acid formalin condensate, high molecular compounds containing salts of cationic functional groups such as quaternary ammonium and amino groups, proteins such as polyethylene oxide, gelatin, casein , Gums such as gum arabic, tragacanth, gums such as saponin, cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, ligninsulfonic acid and salts thereof, shellac Natural polymer compounds, and the like.

Examples of the oil-based recording agent include, as in the case of the aqueous ink, 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, and the like. Is used.

Representative examples of oil-based dyes include, for example, the following.

CI Solvent Yellow 1,2,3,4,5,6,7,8,9,10,11,
12,14,16,17,26,27,29,30,39,40,46,49,50,51,56,61,8
0,86,87,89,96 CI Solvent Orange 12,23,31,43,51,61 CI Solvent Red 1,2,3,16,17,18,19,20,22,2
4,25,26,40,52,59,60,63,67,68,121 CI Solvent Violet 7,16,17 CI Solvent Blue 2,6,11,15,20,30,31,32,35, Three
6,55,58,71,72 CI Solvent Brown 2,10,15,21,22 CI Solvent Black 3,10,11,12,13 etc.

Oil bases for dissolving dyes or dispersing pigments include hydrocarbons such as n-octane, n-decane, minerala spirit, ligroin, naphtha, benzene, toluene, xylene; dibutyl ether, dihexyl Ethers such as ether, anisole, phenetole, and dibenzyl ether; methanol, ethanol,
Alcohols such as isopropyl alcohol, benzyl alcohol, ethylene glycol, diethylene glycol, and glycerin; polyhydric alcohol ethers such as diethylene glycol monobutyl ether; and alcohols such as ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, and ethylene glycol monobutyl acetate. Polyhydric alcohol acetates; oleic acid and the like.

The pigments exemplified above can also be used for the oil-based ink. Examples of oil-based pigment dispersants include polymethacrylate, polyacrylate, methacrylate-acrylate copolymer, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinylpyrrolidone,
Examples include vinyl copolymers such as polyvinyl butyral, cellulosic resins such as ethyl cellulose and methyl cellulose, polycondensation resins such as polyester, polyamide, and phenolic resins, and natural resins such as rosin, shellac, gelatin, and casein.

〔Example〕

Next, the present invention will be described in more detail by way of examples. In addition, all the parts shown below are based on weight.

Synthesis Example Polymerization of (1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate) A thermometer was attached to a three-necked eggplant flask, 100 parts of 1,1,1-trichloroethane, 1H, 1H, 2H, 2H-heptadecafluorodecyl. 100 parts of acrylate [Viscose 17F: manufactured by Osaka Organic Chemical Industry Co., Ltd.], azobisisobutyronitrile (ATB
N) After charging 0.3 part and performing nitrogen substitution while stirring for about 30 minutes, polymerization was performed at 70 ° C. for 5 hours while stirring under a nitrogen stream to obtain a product separated into 1,1,1-trichloroethane. .

This product was purified by dissolving in Freon-113 and precipitating in methanol. In addition, 10
Drying under reduced pressure at 0 to 120 ° C gave 35 parts of the desired product.

Example 1 Using a polyimide film as a substrate, a recording layer material containing a conductive material and the like was coated to prepare a recording body of the present invention, and its evaluation was performed. Materials used, manufacturing conditions, and the like are as follows.

(I) Recording medium substrate: polyimide film (Kapton 300V; manufactured by Toray Dupont) (ii) Conductive substance: Ketjen Black EC (iii) Recording layer coating liquid composition and coating method: 13 parts of CFC-113 obtained by synthesis example 1 part of the obtained polymer 1 part of Ketjen Black EC 0.3 part In the above ratio, the polymer obtained in the synthesis example and Ketjen Black were mixed and mixed with Freon-113, and then immediately cast-coated on a polyimide film, and 130 ° C. For 30 minutes.

(Iv) Evaluation: Using the obtained recording medium, an image was formed by a predetermined method using a thermal head for a thermal transfer printer. The surface resistivity is 2.4 × 10 ⁸
Ω, and the surface chargeability was also suppressed.

Example 2 A recording medium of the present invention was prepared and evaluated in the same manner as in Example 1 except that Chemistat 1005 (manufactured by Sanyo Chemical Industries) was used as an antistatic agent instead of Ketjen Black EC. .

(Iv) Evaluation: Using the obtained recording medium, an image was formed by a predetermined method using a thermal head for a thermal transfer printer. The surface resistivity is 5.0 × 10
^{It was 11} Ω, and the surface chargeability was also suppressed.

Comparative Example A comparative recording medium was prepared and evaluated in the same manner as in Example 1 except that Ketjen Black EC was not used.

(Iv) Evaluation: When an image was formed with a predetermined size using a thermal head for a thermal transfer printer using the obtained recording medium, good running properties were exhibited, but the surface resistivity was 10%.
^A large chargeability of about ¹⁵ Ω was observed.

〔The invention's effect〕

The recording medium according to claim 1 comprises a substrate and a recording layer laminated thereon, further includes a conductive material and / or an antistatic agent, and has a surface specific resistance of 1 × 10 ¹² Ω or less. Thus, antistatic properties are imparted, no contamination occurs even when used repeatedly, and deterioration of the recording medium is prevented.

Further, since the recording material of claim (2) uses a material that also functions as a recording agent as a contact material,
Since the formation of the latent image and the visualization can be integrated, the effect of reducing the size of the recording apparatus is added.

Furthermore, in the recording medium of claim (3), the recording layer is made of a compound containing a fluorine atom in a side chain.
The effect that the formation of the latent image on the recording layer and the erasure of the latent image are further facilitated is added.

[Brief description of the drawings]

FIG. 1 is a diagram of four typical examples of a form having a surface self-orientation function. FIG. 2 is a schematic sectional view showing the structure of the recording medium of the present invention. FIG. 3 and FIG. 4 are diagrams for basically explaining the properties of the recording medium of the present invention. FIG. 5 is a diagram showing a change in the receding contact angle θr observed on the surface of the recording layer of the recording medium of the present invention when the recording layer surface is heated while the liquid is in contact with the surface. FIG. 6 shows three embodiments of the recording method using the recording medium of the present invention. FIG. 7, FIG. 8, FIG. 9, FIG. 10, FIG. 11, FIG. 14, and FIG. FIG. 12 and FIG. 13 show an application example of the recorded matter obtained from the recorded body of the present invention. DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Recording layer, 2a ... Miniaturized recording layer, 2 '... Conductive material, antistatic agent, 3 ... Liquid, 3a
…… Recording agent, 3b …… Adhesive recording agent, 4 …… Heater, 5…
... Lens, 6 ... Shutter, 7 ... Recorded body, 11 ... Metal substrate, 11a ... Miniaturized metal film, 12 ... Organic thin film, 31 ... Liquid supply port, 34 ... Sponge-like porous Body, 41
…… Infrared lamp, 42 …… Laser light source, 43 …… Thermal head, 52 …… Screen, 53 …… Light source, 54 …… Detector, 55 …… Motor, 61 …… Recording paper, 62 …… Pressure roller .

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) B41J 2/325 B41C 1/055 501 B41J 2/32 B41M 5/00 B41N 1/14

Claims (3)

(57) [Claims] A recording layer having a surface in which the receding contact angle decreases when heated and brought into contact with a liquid, and a liquid, a vapor, and a liquid at a temperature equal to or lower than the temperature at which the receding contact angle in the recording layer starts decreasing. Or by selectively heating in contact with a contact material selected from liquids or solids that generate vapor or by bringing the surface of the recording layer into contact with the contact material while being selectively heated A recording medium used in a recording method for forming a region having a receding contact angle corresponding to a heating temperature on the surface of the recording layer, wherein the recording medium contains a conductive material and / or an antistatic agent, A recording medium having a resistance value of 1 × 10 ¹² Ω or less. 2. A recording medium according to claim 1, wherein said contact material is a liquid recording agent containing a color developing material. 3. The recording medium according to claim 1, wherein said recording layer contains a compound containing a fluorine atom in a side chain.