JP3063771B2 - Recording method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Application Field of the Invention] The present invention relates to a method for selectively or selectively and reversibly setting a receding contact angle according to a heating temperature on a surface of a recording medium having a specific property. A recording method for forming the indicated area.

[Conventional technology]

As a typical means for dividing the surface into a liquid-adhesive area and a non-liquid-adhesive area for image formation, there is an offset printing method using a lithographic printing plate without water (fountain solution). Can be However, in this offset printing method, it is difficult to incorporate the plate making process from the original plate and the printing process from the printing plate (printing plate) into one device, and it is difficult to reduce the size of the plate printing device. Has become.

For example, even in a relatively small office offset plate making press, the plate making device and the printing device are usually separate.

In order to eliminate such a defect of the offset printing method, a liquid-adhesive area and a non-liquid-adhesive area corresponding to image information can be formed, and recording that can be used repeatedly (has reversibility). Methods and devices have been proposed. Some of them are as follows.

(1) Aqueous development method After applying a charge to the hydrophobic photoconductor layer from the outside, it is exposed to 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, since a means for applying a heat pulse and then quenching for erasing the recorded information pattern is employed, there is an inconvenience that repetitive image formation cannot mimic the complexity.

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 a liquid or a solid that generates a liquid or a vapor at a temperature at which the receding contact angle of the recording medium (A) starts to decrease. Then, the recording material is brought into contact with the contact material (B) by selectively heating the surface of the recording material to a temperature equal to or higher than the temperature at which the receding contact angle starts to decrease or while the surface of the recording material (A) is selectively heated. By doing so, an area showing a receding contact angle corresponding to the heating temperature (a desired pattern area, hereinafter sometimes referred to as a “latent image” or “latent image area” for convenience) is formed on the surface of the recording medium (A). Then, a recording agent is adhered to the area, and this is covered. It proposed a new recording method of transferring the Utsushitai (Japanese Patent Application No. Hei 2-43599). In the present method, the latent image can be erased by heating the surface of the recording medium (A) on which the latent image has been formed in the absence of the contact material (B), and image formation can be performed reversibly. I can do it.

According to the above method, a liquid-adhesive region having a desired pattern can be selectively or selectively and reversibly formed by an easy means, a recording agent is supplied to the liquid-adhesive region, and the recording agent is transferred to paper or the like. By transferring the image to the recording medium, 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 above-described recording method using a recording medium having a specific surface property, depending on the recording agent, the transferability to the transfer receiving substance is poor, and the background may be easily stained.

Therefore, an object of the present invention is to provide the recording method,
An object of the present invention is to provide a recording method using an image recording agent which is excellent in transferability to a transfer receiving body and does not cause background stain.

Still another object of the present invention is to provide printing quality on a transfer receiving body,
It is to provide a recording method with good image quality.

[Means for solving the problem]

According to the present invention, the surface of a recording medium having a surface in which the receding contact angle is reduced in a heated state and when brought into contact with a liquid; Or by selectively heating the contact surface of the recording medium to a temperature at which the receding contact angle starts to decrease or higher in a state where the recording medium is in contact with a contact material selected from a liquid or a solid that generates vapor, or By selectively heating the surface of the recording medium and contacting the contact material in a state where the heating portion of the surface of the recording medium is maintained at or above the temperature at which the receding contact angle of the recording medium decreases. Forming a region having a receding contact angle corresponding to the heating temperature, and then contacting and adhering a recording agent to the region, and transferring the recording agent to a transfer target body, wherein the recording agent comprises a colorant and a colorant. Dissolve or disperse A developing method, wherein the surface tension of the recording agent is greater than the critical surface tension of the recording medium surface after contact heating with the contact material by 5 dyn / cm or more. Is done.

Further, according to the present invention, the surface of the recording medium 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 temperature at which the receding contact angle in the recording medium starts to decrease or less. In the state of being in contact with a contact material selected from a liquid or a solid that generates a liquid or a vapor, by selectively heating the recording body surface to a temperature at which the receding contact angle starts to decrease or higher, or The surface of the recording medium is selectively heated, and the recording section is brought into contact with the contact material in a state where the heating section on the surface of the recording medium is maintained at a temperature at which the receding contact angle of the recording medium starts decreasing or less. A recording in which a region showing a receding contact angle according to the heating temperature is formed on the body surface, and a recording material that is also used as a recording material is used as the contact material, and the recording material attached to the surface of the recording material is transferred to a transfer-receiving material. One Wherein the recording agent contains a colorant and a developing agent that dissolves or disperses the colorant, and the surface tension of the recording agent is the critical surface tension of the recording material surface after contact heating with the contact material. Thus, a recording method characterized by being 5 dyn / cm or more is provided.

That is, the present inventors have studied a recording agent capable of forming an image satisfactorily in the above-mentioned new recording method. As a result, the surface tension of the recording agent becomes higher after contact heating with the contact material on the surface of the recording medium. 5dyn / c than the critical surface tension of
m or more, preferably 10 dyn / cm or more, more preferably 15 dyn
It has been found that when the size is larger than / cm, the transferability to the transfer object is excellent and the background is not stained. The critical surface tension of the surface of the recording medium can be determined from the catalyst angle measured for the n-alkane-based reference material by a known Zismann plot.

In the present invention, as long as the recording agent satisfies the above conditions, it can be used regardless of whether it is aqueous or oily. Specific examples of the recording agent used in the present invention include, for example, water as a water-based ink, a water-soluble ink composed of water as a developing agent, a wetting agent and a dye, water as a developing agent, a wetting agent, a pigment and a pigment for dispersion. An aqueous pigment-dispersed ink composed of a molecular compound, an emulsion ink in which a pigment or dye is dispersed in water as a developing agent using a surfactant, and the like are used. Examples of the wetting agent used in the aqueous ink include the following water-soluble organic liquid compounds.

Monohydric alcohols such as ethanol, methanol and propanol; 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..

These solvents are used alone or in combination with water.

As the water-soluble dye used as a coloring material, a dye classified into an acid dye, a direct dye, a basic dye, a reactive dye, and an edible dye in a color index, which is excellent in 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 1,8,13,14,18,26,27,35,37,42,5
2,82,87,89,92,97,106,111,114,115,134,186,249,254,2
89 CI Acid Blue 9,29,45,92,249 CI Acid Black 1,2,7,24,26,94 CI Food Yellow 3,4 CI Food Red 7,9,14 CI Food Black 2 CI Direct・ Yellow 1,12,24,26,33,44,50,142,14
4,865 CI Direct Red 1,4,9,13,17,20,28,31,39,80,8
1,83,89,225,227 CI Direct Orange 26,29,62,102 CI Direct Blue 1,2,6,15,22,25,71,76,79,86,8
7,90,98,163,165,199,202 CI Direct Black 19,22,32,38,51,56,71,74,7
5,77,154,168 CI Basic Yellow 1,2,11,13,14,15,19,21,23,2
4,25,28,29,32,36,40,41,45,49,51,53,63,65,67,70,73,
77,87,91 CI Basic Red 2,12,13,14,15,18,22,23,24,2
7,29,35,36,38,39,46,49,51,52,54,59,68,69,70,73,78,
82,102,104,109,112 CI Basic Blue 1,3,5,7,9,21,22,26,35,41,45,
47,54,62,65,66,67,69,75,77,78,89,92,93,105,117,12
0,122,124,129,137,141,147,155 Basic Black 2,8 etc.

As pigments, organic pigments such as azo, phthalocyanine, anthraquinone, quinacridone, dioxazine, indigo, thioindigo, perinone, perylene, isoindolenone, aniline black, azomethine, carbon black And inorganic pigments such as iron oxide, titanium oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, dark 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. Resin, polyvinylpyrrolidone, polyvinyl alcohol, alkali metal salt of β-naphthalenesulfonic acid formalin condensate, polymer compound having a salt of a cationic functional group such as quaternary ammonium or amino group in the side chain, polyethylene oxide, gelatin,
Proteins such as casein; natural gums such as gum arabic and gum tragacanth; glucosides such as saponin; cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose and methylcellulose; ligninsulfonic acid and salts thereof; natural polymer compounds such as shellac; Is mentioned.

In addition, a surfactant may be added for the purpose of adjusting the surface tension. As surfactants, cationic,
Anionic, nonionic or amphoteric surfactants are used. These may be used alone or in combination of two or more. Specific examples of surfactants include, for example, alkylbenzenesulfonic acid and the like as anionic surfactants, polyoxyethylene derivatives and higher fatty acid esters of sugars as nonionic surfactants, and sulfobetaine as an amphoteric surfactant. System, amino acid system and the like.

As the oil-based recording agent, as in the case of the aqueous ink, an oil-soluble material dye dissolved in an organic solvent as a developing agent, a pigment dispersed in an organic solvent as a developing agent, a pigment or dye as a developing agent What is emulsified in an oily base, and the like are used.

The following are specific examples of the oil-based dye.

CI Solvent Yellow 1,2,3,4,5,6,7,8,9,10,11,1
2,14,16,17,26,27,29,30,39,40,46,49,50,51,56,61,80,
86,87,89,96 CI Solvent Orange 12,23,31,43,51,61 CI Solvent Red 1,2,3,16,17,18,19,20,22,24,2
5,26,40,52,59,60,63,67,68,121 CI Solvent Violet 7,16,17 CI Solvent Blue 2,6,11,15,20,30,31,32,35,36,
55,58 CI Solvent Brown 2,10,15,21,22 CI Solvent Black 3,10,11,12,27 etc.

Further, as a developing agent for dissolving a dye or dispersing a pigment, hydrocarbons such as n-octane, n-decane, mineralane spirit, ligroin, naphtha, benzene, toluene, xylene; dibutyl ether, dihexyl Ethers such as ether, anisole, phenetol and dibenzyl ether; alcohols such as methanol, ethanol, isopropyl alcohol, benzyl alcohol, ethylene glycol, diethylene glycol and glycerin; polyhydric alcohol ethers such as diethylene glycol monobutyl ether; ethylene glycol monomethyl ace Polyhydric alcohol acetates such as tart, ethylene glycol monoethyl acetate and ethylene glycol monobutyl acetate; oleic acid;

Among them, glycerin, ethylene glycol and the like are particularly preferable because of their high surface tension. These solvents can be used alone or as a mixture of two or more as a developing agent.

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.

As described above, the recording medium used in the present invention has a surface having a function of increasing the receding contact angle when heated in contact with a liquid, and then, when cooled in a state where the receding contact angle is decreased when heated in the absence of a liquid. Having. More specifically, the surface of the recording medium is (i) a member including 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 oriented on the surface. Consists of 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 compounded. 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. Also,
This tendency is recognized as the molecular length of the hydrophobic group increases, because the longer the molecular length, the higher the mobility of the molecule in 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 , And the relational expression holds [Saito, Kitazaki et al., "Journal of the Japan Adhesion Association"
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 mutual relations, 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 the method of the present invention, a member having a surface self-orienting function on the surface is inevitably selected from the need for forming a desired pattern area on the surface of the recording medium and visualizing the recording medium with a recording agent.

The recording medium used in the method of the present invention, as described above,
"The receding contact angle θ when heated and in contact with liquid
r has a reduced surface. "

The shape of the recording medium is arbitrary as long as the surface has the above properties. Therefore, the recording medium may be in the form of a film, or may be provided on a suitable support or molded body with another coating film having the above-mentioned properties on the surface. The molded body itself may be used, but its surface must have the above properties.

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 0 is formed. FIG. 1 (c) is an example of a member made of only the organic compound 0 having a hydrophobic group 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, the hydrophobic group-containing compound 0 may be further laminated on the hydrophobic group-containing compound 0 like a cumulative LB film. In the example of FIG. 1 (c), the structure is made of only the hydrophobic group-containing compound 0 without having the main chain (L) or binding to 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 -F and / or -Cl ( Or an unsubstituted alkyl group having 4 or more carbon atoms. 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, the surface of the recording medium formed by the above compound,
It is conceivable that the hydrophobic group has a considerably oriented surface. Therefore, this surface has liquid repellency (because hydrophobic groups have low surface energy). In this state, when the surface of the recording medium is heated by contact with the contact material, the molecular motion of the hydrophobic group due to the heating becomes active, and the interaction with the contact material causes at least a part of the surface of the recording medium to be heated. It is likely that the orientation (alignment) state changes to another state (that is, another orientation state or a state in which the orientation is disordered), and that the other state is maintained after cooling. It should be noted that heating under the state where the contact material is in contact with the surface of the recording medium means that the liquid is brought into contact with the surface of the recording medium while the surface is heated, depending on the form of the contact material.

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

However, the heating in the state where the contact material 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, the adhesion to the liquid will increase.

Further, when the surface of the recording medium is heated in another state (another orientation state different from the original orientation state or in a state in which the orientation is disturbed) in the absence of the contact material, the contact with the contact material is caused. Since no interaction occurs, it is likely to return to the original alignment (orientation) state.

Therefore, the presence of the contact material is not merely for quenching the surface of the recording medium after heating it, but for causing some interaction with the compound on the surface of the recording medium. (A different alignment state or a state in which the alignment is disturbed).

As described 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, the alkyl group preferably has 4 or more carbon atoms. It is considered that the number is desirably the number necessary for the alkyl groups to be aligned (orientated) to some extent on the surface of the recording medium, and for active molecular motion during heating. It is also conceivable that when the contact material is heated together with the surface of the recording medium, molecules of the contact material are incorporated into molecules on the surface of the recording medium. 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. . Also,
Alkyl groups containing fluorine have strong self-aggregating properties,
Since the surface self-orientation function is high and the surface energy is low, it is excellent in preventing soiling of the background.

Furthermore, the surface of the recording medium has a liquid repellency. If this is described in terms of the surface energy of a solid, it is desirable that the recording energy be 50 dyn / cm or less as a recording method. If the value is higher than this, the surface of the recording medium may sometimes get wet with the recording agent, and the background may be stained.

Here, the details of the compound forming the surface of the recording medium will be described. First, for the types shown in FIGS. 1A and 1D, compounds having an alkyl group (including those substituted with fluorine and / or chlorine) on the side chain of the vinyl polymer can be considered. Specifically, formulas (I), (II), (III), (IV), and (V)
Polymers from the monomers represented by (VI) and (VII) are mentioned.

_{[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} , C
H _{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} , C
H _{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.

_{(1) -CH 2 CF 2 CHFCF} 3 _{(6) -CH 2 (CF 2} ) 10 H (7) CF 2 6 O-CF 2 CF 3 (8) CH 2 4 NH-CF 2 CF 3 (9) CF 2 6 CF 3 (10) CH 2 10 C ₈ F _{17 (13) -CH 2 NHSO 2 C} 8 F 17 (15) c · s-CH 2 CH 2 - (CF 3) 6 CF (CF 3) 2 (16) -CH 2 CF 2 CF 2 CF 3 (17) -CH 2 CH 2 CH 2 CH 2 F (18 ) among _{-CH 2 (CF 2) 6 CF} 3 (19) -CH 2 (CF 2) 5 CF 3 (20) CH 2) 3 CF 3 these compounds, in particular, the raw material monomer of the following (XI) Is more desirable.

[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] Accordingly, preferred specific examples of the member on the surface of the recording medium in the present invention include: Examples include polymers from the following monomers.

Further, these formulas (I) (II) (III) (IV) (V) (V
I) In addition to copolymers of monomers of (VII) and (XI) (two or more monomers), these monomers and other monomers such as ethylene, vinyl chloride, styrene, butadiene, isoprene, chloroprene, and vinylalkyl Copolymers with ether, vinyl acetate 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 excellent as the above material. Formaldehyde,
Dialdehyde, N-methylol compound, dicarboxylic acid,
Examples thereof include 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 above monomers, an appropriate method is selected depending on the material such as solution polymerization, electrolytic polymerization, emulsion polymerization, photopolymerization, irradiation polymerization, plasma polymerization, graft polymerization, plasma initiation polymerization, and vapor deposition polymerization. You.

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 columns 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).

 Subsequently, a recording medium using the above compound will be described.

The configuration of the recording medium is broadly classified into those formed by the surface member itself and those formed by forming the surface member on a support (preferably a heat-resistant support).
In the embodiment, the above compound (surface member) itself is formed into a film, a plate, or a column. At this time, in the case of a film, the length of the film is 1 μm to 5 m.
m is desirable.

In the embodiment, the compound may penetrate into the support to some extent. The thickness of the recording body itself is 30
Å ~ 1mm is desirable. However, in terms of thermal conductivity, 100 to 10
μm and 10 μm to 1 mm in terms of wear resistance are excellent.
The heat-resistant temperature of the support is desirably 50 ° C to 300 ° C.

The shape of the support may be any of a belt shape, a plate shape, and a drum shape, and is selected according to the intended use of the device. In particular, the drum shape is excellent in that dimensional accuracy in the device can be obtained. The size of the plate may be determined according to the size of the recording paper.

Further, when a mixture of the above compound (a material for forming a surface of a recording medium) and another member, for example, a hydrophobic polymer or a hydrophobic inorganic material, is formed on a support, it is excellent in preventing background smearing in printing. Further, in order to increase the thermal conductivity, it is preferable to mix a metal powder with the above compound. Further, a primer layer may be provided between the support and the compound in order to improve the adhesion between the support and the compound. As the heat-resistant support, a resin film such as polyimide or polyester, glass, a metal such as Ni, Al, Cu, Cr, or Pt, or a metal oxide is preferable. These supports may be smooth, rough or porous.

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

More specifically, these contact materials are as follows. That is, as a liquid which is one of the contact materials, in addition to water, an aqueous solution containing an electrolyte, an alcohol such as ethanol and n-butanol, a polyhydric alcohol such as glycerin and ethylene glycol, and a ketone such as methyl ethyl ketone are available. Polar liquids, n-nonane, linear hydrocarbons such as n-octane, cyclic hydrocarbons such as cyclohexane,
Non-polar liquids such as aromatic hydrocarbons such as m-xylene and benzene are exemplified. 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 medium.

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.

When a recording material such as the liquid ink is used as the contact material, the visualization is performed simultaneously with the formation of the latent image.

 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.

FIG. 2A shows a state in which a film 2 of the compound constituting the surface of the recording medium is formed on a substrate 1 and a liquid 3 of the contact material exists on the film surface. In this state, when the film 2 is heated as shown in FIG. 3 (a), it is recognized that the receding contact angle θr of the film 2 decreases and the film 2 shows remarkable wetting and has liquid adhesion. . Further, when the film 2 having liquid adherence is heated again in air, in a vacuum, or in an inert gas atmosphere (FIG. 2 (b)), the receding contact angle θr increases on the surface of the film 2 and the liquid 2 is returned again. It shows resilience.

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 present invention, a state change cannot occur on the surface of the recording medium without the presence of the contact material. Further, according to the method described in JP-B-54-41902, reversibility cannot be obtained by a simple operation.

As shown in FIG. 3 (a), heat is applied to the film 2 under contact of the liquid 3 according to the image information [as shown in FIG. 3 (b-1),
The same applies to the case where the film 2 in which no liquid is present is brought into contact with a liquid in a state where heat is applied to the film 2 in accordance with image information]. In the figure, 4 is a heater, 31 is a liquid supply port, 41 is an infrared lamp, 5 is a lens, and 6 is a shutter.

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

FIG. 4 shows an example of the change in the contact angle of the aqueous solution before and after the heating of the film 2 under the contact with the aqueous solution, and the change in the contact angle of the aqueous solution when the film 2 is further heated in the air. 4th
In the figure, ○ 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 surface of the recording medium 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 for the timing of heating, if a latent image is formed, after the surface of the recording medium is heated, it is brought into contact with the contact material before cooling.
The recording medium surface may be heated while the contact material is in contact with the recording medium surface. On the other hand, if the latent image is to be erased, the surface of the recording medium is 50 to 300 in the absence of the contact material.
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 a recording medium will be described in more detail.

In the present invention, the surface of the recording medium is heated in a liquid or vapor atmosphere in accordance with an image signal to form a liquid adhering area on the surface of the recording medium (latent image formation). Is a method in which a recording agent is adhered to a latent image portion by means of contacting (development), and thereafter, the recording agent on the surface of the recording medium is transferred to recording paper (indirect recording method). Further, in the method, when a material that also functions as a recording agent is used as a contact material, latent image formation and development are performed simultaneously. Further, in these methods, if a means for bringing the recording material into contact with the latent image portion again after the transfer of the recording material is performed, a printing method using the recording medium as a printing plate is obtained. Also, in these methods,
After transferring the recording agent, by heating the surface of the recording medium on which the latent image was formed in the absence of liquid or vapor to erase the latent image,
This is a recording method in which the recording medium can be reproduced. 5 (a) and 5 (b) show typical processes of an indirect recording method (printing method) and a reversible indirect recording method (repeated recording method) of a recording medium.

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

If the recording medium has a surface in which the receding contact angle decreases in a heated state and when brought into contact with a liquid (for convenience, it may be referred to as “film 2” or “recording medium surface”),
It is not bound by its form. Therefore, the recording medium may be in the form of a rigid cylinder or a flexible film. However, since the rigid cylindrical recording body (the one having the film 2 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, the rigid cylindrical recording body Is preferred. For the production of such a recording body, a method of forming the film 2 on the substrate or a method of producing the recording body itself is adopted. Particularly, a method of forming a film on a substrate is desirable because the molded body generally has low mechanical strength.
It is needless to say that the film 2 must be formed on the surface even when the recording body is formed from the molded body itself.

When a resin is used for the recording medium 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 medium 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. 6 (a) shows that 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 film 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. 6 (b) shows a structure in which a good heat conducting portion is provided on the substrate 1 so as to prevent heat diffusion in the plane direction and to miniaturize the liquid adhering portion 2a. . In FIG. 6B, reference numeral 11a denotes a miniaturized metal film.

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

As a specific example of these, means for heating the surface of a recording medium in contact with a liquid will be described. For the sake of convenience, the description will be given by taking a recording medium of the type in which the film 2 is formed on the base 1 as an example. First, means for preliminarily bringing the liquid 3 into contact with the surface of the recording medium and heating from the substrate 1 side or the liquid 3 side in the state of the contact [FIGS. 7 (a) and 7 (b)]
Alternatively, heating is first performed from the surface of the recording medium, and
To contact the recording medium heating section (recording medium surface) [No.
(C) and (d)].

As the supply means of the liquid 3, the simplest configuration is to provide a plate below the recording medium, fill the liquid so that the recording medium always contacts the liquid 3 in the pan, and arrange a heating source near or in the pan. 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. 7, reference numeral 42 denotes a laser light source, and reference numeral 43 denotes a thermal head. Thus, a latent image is formed on the surface of the recording medium.

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. (FIG. 8 and FIG. 9). As shown in FIGS. 8 and 9, 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 formation of the latent image and the visualization can be integrated. it can.

In indirect recording, as described above, for example, a rigid cylindrical tube is advantageously used as a recording substrate. After formation of the latent image and development (visualization), for example, the recording material 3a on the recording medium
The recording agent 3a 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. Tenth
FIG. 1 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, if the latent image is erased by heating near the latent image portion in the absence of liquid or vapor, that is, in the air, in a vacuum, or in an inert gas, after the transfer means, the recording medium is obtained. The recording device can be used repeatedly (FIG. 11). 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. The heating may be performed on the entire surface of the recording medium, or may be performed 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 medium 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 medium surface, but is desirably a temperature equal to or higher than the temperature at which the receding contact angle of the material of the recording medium lowers, 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.

〔Example〕

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

Example 1 Preparation of Ink A mixture having the following composition was stirred and dissolved at 50 ° C., and an insoluble material was filtered off with a 10 μm Teflon filter to prepare Ink 1.

(Ink 1) CI Direct Black 193% Glycerin 20% Sodium hydroxide (pH adjuster) 0.1% Pure water Remaining Measurement of critical surface tension of recording material functional member Fluorine-containing film material (recording material surface material) Acrylic material Daikin Industries water and oil repellent "TG-702"
Using Freon TF (Mitsui Fluorochemicals)
After diluting twice and coating the slide glass,
After drying for a time, a film having a thickness of about 1 μm was formed. Next, as shown in FIG. 3 (a), this was heated from the glass substrate side while keeping pure water in contact with the surface of the film 2 (heating temperature 130 ° C., 5 ° C.).
Seconds). Using this, as an n-alkane standard liquid, n
The contact angle was measured using -hexane, n-octane, n-nonane, and n-decane, and the critical surface tension was found to be 16 dyn / cm.

Measurement of Ink Surface Tension When the surface tension of Ink 1 was measured with a lifting plate type surface tensiometer (manufactured by Kyowa Kagaku), it was 68 dyn / cm. Therefore, the critical surface tension of the recording member is 52 dyn / cm.
high.

Print evaluation Freon T using TG-702 as the film material as above
It was diluted twice with F, coated on a polyimide film 1 (Kapton 2000V, manufactured by Toray Dubon Co., Ltd.), dried at 90 ° C. for 2 hours to form a film having a thickness of about 1 μm.

Next, as shown in FIG.
And a thermal head 43 was disposed directly below the film in contact with the film. The ink supply unit is filled with the ink 1 and the thermal head 43 is driven in accordance with the image information, and the film is moved in the direction of the arrow.
The ink 3b adhered to the upper part according to the image information, and was transferred to a recording paper. The transferred image was clear without background contamination. Even after the transfer, the ink adhesion of the film 2 was maintained, and the same pattern could be repeatedly printed. Further, when the film 2 was heated in the air, the ink adhesion was removed.

Example 2 Preparation of Ink A mixture having the following composition was stirred and dissolved at 50 ° C., and an insoluble substance was filtered off with a 10 μm tephrofilter to prepare Ink 2.

(Ink 2) CI Direct Black 154 4% Ethylene glycol 30% Formamide 10% Tetramethylammonium hydroxide (15%
Aqueous solution) 0.5% pure water remaining amount Using the above-mentioned ink 2, the surface tension was measured and the printing evaluation was performed in the same manner as in Example 1.
At 50 dyn / cm, the difference from the critical surface tension of the recording member is 34 dyn / cm
Met. The image was clear and had no background stain.

Example 3 Preparation of Ink A mixture having the following composition was stirred and dissolved at 50 ° C., and an insoluble material was filtered off with a 10 μm Teflon filter to prepare Ink 3.

(Ink 3) CI Food Black 24% Glycerin 35% Diethylene glycol monobutyl ether 5% Sodium hydroxide 0.2% Pure water Remaining Using the above ink 3, the surface tension was measured and the printing evaluation was performed in the same manner as in Example 1. , The ink surface tension is
35dyn / cm, the difference from the critical surface tension of the recording member is 19dyn / cm
Met. The image was clear and had no background stain.

Example 4 Preparation of Ink A mixture having the following composition was stirred and dissolved at 50 ° C., and an insoluble material was filtered off with a 10 μm Teflon filter to prepare Ink 4.

(Ink 4) CI Solvent Black 27 4% Ethylene glycol 40% Diethylene glycol monobutyl ether 56% Using the above ink 4, the surface tension was measured and the printing evaluation was performed in the same manner as in Example 1.
At 30 dyn / cm, the difference from the critical surface tension of the recording member is 14 dyn / cm
Met. The image was clear and had no background stain.

Example 5 Preparation of Ink A mixture having the following composition was stirred and dissolved at 50 ° C., and an insoluble material was filtered off with a 10 μm Teflon filter to prepare Ink 5.

(Ink 5) CI Direct Blue 199 3% Glycerin 35% Diethylene glycol monobutyl ether 5% Silicon surfactant (K607; manufactured by Shin-Etsu Chemical Co., Ltd.) 0.01% Sodium hydroxide 0.2% Pure water Remaining amount When surface tension measurement and printing evaluation were performed in the same manner as in Example 1, the ink surface tension was
At 32 dyn / cm, the difference from the critical surface tension of the recording member is 16 dyn / cm
Met. The image was clear and had no background stain.

Example 6 Preparation of Ink A mixture having the following composition was stirred and dissolved at 50 ° C., and an insoluble material was filtered off with a 10 μm Teflon filter to prepare Ink 6.

(Ink 6) CI Direct Red 94 4% Ethylene glycol 25% Diethylene glycol monophenyl ether 5% Sodium hydroxide 0.2% Pure water Remaining Using Ink 6, the surface tension was measured and the printing evaluation was performed in the same manner as in Example 1. The ink surface tension is
34dyn / cm, the difference from the critical surface tension of the recording member is 18dyn / cm
Met. The image was clear and had no background stain.

Comparative Example 1 Preparation of Ink A mixture having the following composition was stirred and dissolved at 50 ° C., and an insoluble material was filtered off with a 10 μm Teflon filter to prepare Ink 7.

(Ink 7) CI Direct Black 154 4% Glycerin 40% Fluorosurfactant (Fluorard F129; manufactured by Sumitomo 3M Limited) 0.5% Pure water Remaining amount Using Ink 7, the surface tension of the ink was measured in the same manner as in Example 1. When the ink surface tension was 18 dyn / cm and the difference from the critical surface tension of the recording member was 2 d
yn / cm. Further, the image was blurred and the background dirt was terrible.

Comparative Example 2 Preparation of Ink A mixture having the following composition was stirred and dissolved at 80 ° C., and an insoluble material was filtered off with a 10 μm Teflon filter to prepare Ink 8.

(Ink 8) CI Solvent Black 27 4% Ethylene glycol 60% Ethylene glycol monobutyl ether 35% 1H, 1H, 9H-Hexadecafluoro-1-nonanol 1% Using the above Ink 8, the same as in Example 1 When the surface tension measurement and printing evaluation were performed, the ink surface tension was 17 dyn / cm, and the difference from the critical surface tension of the recording member was 1 d.
yn / cm. Further, the image was blurred and the background dirt was terrible.

From the above results, it can be seen that according to the recording method of the present invention, a clear image without background stain can be obtained.

〔The invention's effect〕

According to the recording method of the present invention, the recording material is selected so that the surface tension of the recording material is at least 5 dyn / cm higher than the critical surface tension of the recording material after contact heating with the contact material. With this configuration, according to the recording method, it is possible to obtain an image that is clear, has no background contamination, and has high resolution and high gradation.

Further, since the recording method of claim (2) uses a material that also serves as the recording material as the contact material, the formation of the latent image and the visualization can be unified. The effect that the recording device can be miniaturized 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. 2 and 3 are diagrams for basically explaining the method of the present invention. FIG. 4 is a diagram showing a change in the receding contact angle θr observed on the surface of a recording medium when the surface of the recording medium is heated while the liquid is in contact with the surface of the recording medium used in the embodiment of the present invention. FIG. 5 shows two embodiments of the method of the present invention. FIG. 6, FIG. 7, FIG. 8, FIG. 9, FIG. 10, FIG. 11, and FIG. DESCRIPTION OF SYMBOLS 1 ... board | substrate, 2 ... recording layer, 2a ... micronized recording layer, 3 ... liquid, 3a ... recording agent, 3b ... adhering recording agent, 4 ... heater, 5 ... lens, 6 shutter, 7 recording body, 11 metal substrate, 11a miniaturized metal film, 12 organic thin film, 31 liquid supply port, 34
... sponge-like porous material, 35 ... ink supply unit, 41 ... infrared lamp, 42 ... laser light source, 43 ... thermal head, 61 ... recording paper, 62 ... transfer roller.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-60-255482 (JP, A) JP-A-3-55283 (JP, A) JP-B-54-410902 (JP, B2) (58) Field (Int.Cl. ⁷ , DB name) B41M 5/00 B41C 1/10 B41M 5/26

Claims (2)

(57) [Claims] 1. A surface of a recording medium having a surface in which a receding contact angle is reduced when heated and catalyzed with a liquid, and a liquid, a vapor, and a liquid at a temperature equal to or lower than a temperature at which the receding contact angle in said recording medium starts decreasing. Or in a state of contact with a contact material selected from a liquid or a solid that generates a vapor, by selectively heating the recording body surface to a temperature at which the receding contact angle starts to decrease or higher, or By selectively heating the surface, the heating unit of the surface of the recording body is brought into contact with the contact material in a state of being maintained at or above the temperature at which the receding contact angle of the recording body decreases, thereby causing the surface of the recording medium to be heated. After forming an area showing a receding contact angle according to the heating temperature, a recording agent is brought into contact with and adhered to the area, and the recording agent is transferred to an object to be transferred. Dissolution or dispersion Containing the agent, moreover recording method the surface tension of the recording agent is the critical surface tension after contact heating and the contact material of the recording surface, and wherein the 5 dyn / cm or more greater. 2. A surface of a recording medium having a surface in which a receding contact angle is reduced when heated and in contact with a liquid; Or in a state of contact with a contact material selected from a liquid or a solid that generates a vapor, by selectively heating the recording body surface to a temperature at which the receding contact angle starts to decrease or higher, or By selectively heating the surface and contacting the contact material in a state where the heating portion of the surface of the recording medium is maintained at or above the temperature at which the receding contact angle of the recording body decreases, the surface of the recording medium is contacted. To form a region showing a receding contact angle according to the heating temperature,
In addition, a recording method in which a recording material that also functions as a recording material is used as the contact material, and the recording material attached to the surface of the recording medium is transferred to a transfer-receiving body, wherein the recording agent dissolves or disperses the colorant and the colorant A recording method, comprising a developing agent, wherein the surface tension of the recording agent is at least 5 dyn / cm higher than the critical surface tension of the surface of the recording medium after contact heating with the contact material.