JP3132860B2 - Recording method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel recording method,
Specifically, on the surface of the recording medium whose surface shows specific properties,
A recording agent that selectively or selectively and reversibly forms a latent image so as to form a region exhibiting a receding contact angle according to a heating temperature, and then or simultaneously with the formation of the latent image, a recording agent that is fused to the latent image. The present invention relates to a recording method in which (solid ink) is supplied to visualize the image, and if necessary, is transferred to a recording sheet.

[0002]

2. Description of the Related Art An offset printing method using a lithographic printing plate is a typical example of a means for dividing a surface into a liquid-adhesive area and a non-liquid-adhesive area for image formation. 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 apparatus, and it is difficult to reduce the size of the plate making apparatus. ing. 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 can be used repeatedly (reversible). Recording methods or apparatuses have been proposed. Some of them are as follows. (1) Aqueous development method After a charge is applied to the hydrophobic photoconductor layer from the outside, exposure is performed to form a pattern having a hydrophobic portion and a hydrophilic portion on the surface of the photoconductor layer, and only the hydrophilic portion is formed. An aqueous developer is adhered and transferred onto paper or the like (Japanese Patent Publication No. 40-18992, Japanese Patent Publication No. 40-18993, Japanese Patent Publication No. 44-9512, Japanese Patent Application Laid-Open No. 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 these photochromic compounds are hydrophilized by the photochemical reaction [for example, “Polymer Papers” No. 37.
Vol. 4, p. 287 (1980)]. (3) A method using the action of an internal bias force An amorphous state and a crystalline state are formed by physical change,
Constructing the area where liquid ink adheres / non-adheres
-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,
Recording of other image information becomes possible. That is, it is possible to repeatedly use one master (photoconductor). However, since this method is based on the electrophotographic process, it requires a long process of charging → exposure → development → transfer → static elimination,
It has the drawback that it is difficult to reduce the size and cost of the device and to make it maintenance-free.

According to the 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 low due to poor quantum efficiency. It has the drawbacks of being extremely long, slow in recording speed, and lacking stability, and has not yet reached a practical level.

Further, according to the method (3), the information recording member used therein has stability after recording, but may have a physical structural change due to temperature change before recording. However, there is still a problem in storage stability. In addition, since a means for applying a heat pulse and then quenching to erase the recorded information pattern is employed, there is an inconvenience that repetitive image formation cannot mimic the complexity.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a recording medium (A) having a surface having a reduced receding contact angle when heated and brought into contact with a contact material (B). Another object of the present invention is to provide a recording method in which a desired pattern region is selectively or reversibly formed by an easy means, and the desired pattern region is visualized and, if necessary, transferred to plain paper or the like. . Another object of the present invention is to reversibly use a recording medium (A) having excellent storage stability and stability in all steps such as formation / erasing, visualization, and transfer of a desired pattern area. An object of the present invention is to provide a novel recording method in which the above-mentioned steps can be performed a plurality of times. Still another object of the present invention is to provide a recording method capable of obtaining a high-quality transferred image over a long period of time or due to environmental changes.

[0008]

According to the recording method of the present invention, the recording medium (A) is selectively heated by bringing the surface of the following recording medium (A) into contact with the following contact material (B).
The surface of the recording medium (A) is heated at a high heating temperature by contacting the surface of the recording medium (B) with the contact material (B) while the surface of the recording medium is selectively heated.
Forming a latent image with a reduced receding contact angle according to the condition , visualizing the latent image with solid ink, and, if necessary, transferring the ink attached to the surface of the recording medium (A) to recording paper. It is characterized by. (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 method of the present invention, the latent image can be erased by heating the surface of the recording medium (A) on which the latent image is formed in the absence of the contact material (B), and the reversible image can be obtained. The image can be formed in the first place.

[0010] The present inventors have solved many defects as described in the prior art, and have conducted many studies and studies on a new recording method. As a result, a member having a function of being heated in contact with a liquid and having a function of reducing the receding contact angle even after cooling and increasing the receding contact angle by heating in the absence of liquid is useful as a recording medium. It was found that. The recording medium (A) having such a function has a surface (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. It was also confirmed that the member was oriented on the surface.

The “surface self-orientation function” referred to in (i) is:
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, it means that the hydrophobic group is oriented on the surface toward the air side (free surface side). This can be similarly applied to (ii).

Generally, in an organic compound, a hydrophobic group tends to be directed toward a hydrophobic atmosphere. This is fixed
This is caused because the surface energy of the air interface is reduced. This tendency is recognized as the molecular length of the hydrophobic group becomes longer. This is 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 terminal (that is, lowers the surface energy), the surface is easily oriented toward the air side (free surface side). Similarly (-CH ₂ -) in the linear molecule containing n (-CH ₂ CH ₂
The portion-) has a planar structure, and the molecular chains are easily oriented. Further, a molecule containing (-Ph-) n is also -Ph-
Has a planar structure, and the molecular chains are easily oriented. Note that -Ph- is a p-phenylene group (the same applies hereinafter). 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 orientation state and the receding contact angle, and also between the receding contact angle and the liquid adhesion. That is, the adhesion of the liquid on the solid surface occurs mainly by 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 includes: cos θr = γ (γs−γse−πe + γf) / γev (where γ: surface tension of solid in vacuum γse: solid-liquid interfacial tension γev (E: equilibrium surface tension, γf: frictional tension, γs: surface tension of a solid without an adsorbed layer) (Saito, Kitazaki et al., “Journal of the Japan Adhesion Association” Vol. .22, No. 12, 1986).

Therefore, when the value of θr decreases, the value of γf increases. That is, the liquid is less likely to slide on the solid surface,
As a result, the liquid will adhere 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 apparatus of the present invention, the recording body (A) needs to form a desired pattern area on its surface and / or visualize with a recording agent,
Inevitably, a member having a surface self-orienting function on the surface must be selected.

The recording medium (A) used in the apparatus of the present invention comprises:
As described above, it has a “surface where the receding contact angle θr decreases when it is in a heated state and is in contact with a liquid”. The shape of the recording medium (A) is arbitrary as long as the surface has the above properties. Therefore, the recording medium (A) may be in the form of a film, or may be configured such that another coating film having the above-mentioned properties is provided on a suitable support or molded body. I don't care. The molded body itself may be used, but its surface must have the above properties.

In the recording medium (A), depending on the type of the contact material (B), the liquid adhering portion in the latent image becomes either lipophilic or hydrophilic, and therefore, when a copy is obtained, an oil-based ink is used. , Water-based ink, etc., are used as needed.

Here, FIG. 1 shows an example in which members or materials which 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) shows 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 a main chain L and a hydrophobic group R are bonded by a bonding group J. are doing.

FIG. 1 (b) shows an example of a member having an organic compound having a hydrophobic group in which the hydrophobic group is oriented on the surface, and the surface of an organic or inorganic material M is physically or chemically bonded to the hydrophobic group. Is a member formed with a compound O having the following formula:

FIG. 1C shows an example of a member made of only the organic compound O having a hydrophobic group shown in FIG. 1B.

FIG. 1 (d) shows an example in which a linear molecule is present in the side chain of a polymer. The main chain L and the molecule are connected by a bonding group J, and a self-aggregating or planar structure having a hydrophobic group R at the terminal. It is a compound in which the molecular chain N having a structure is 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 mesh structure. In the example of FIG. 1B, the hydrophobic group-containing compound O may be further laminated on the hydrophobic group-containing compound O like a cumulative LB film. In the example of FIG. 1 (c), the structure is made of only the hydrophobic group-containing compound O without having the main chain (L) or bonding to the organic / inorganic material (M) or the like.

Examples of the hydrophobic group of the, the end of the molecule is preferably -CH ₃ or _{-CF 3, -CF 2 H, -CFH} 2, -C
(CF ₃ ) ₃ , —C (CH ₃ ) _3, etc., 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 one or more —F and / or —Cl (—CF ₂ CF ₂
C (Cl) FCF ₂ CF ₃ ) or an unsubstituted alkyl group having 4 or more carbon atoms is preferable. Either fluorine-substitution or chlorine-substitution can be used, but fluorine-substitution is more effective. In these materials, the relationship between the number of carbon atoms in the alkyl group and the function is as follows:
If the number of carbon atoms is 3 or less, the function suitable for the recording apparatus used in the method of the present invention will be reduced.

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

First, it is conceivable 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) is changed 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. I think that the. In addition, heating under the state where the contact material (B) is in contact with the surface of the recording body (A) means that the surface of the recording body (A) is heated depending on the form of the contact material (B). The liquid comes into contact under the pressure. 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, the adhesion to the liquid will increase.

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

Therefore, the presence of the contact material (B) is not merely for quenching the surface of the recording medium (A) after heating, but causes some interaction with the compound on the surface of the recording medium (A). It is considered that a change to another state (a different alignment state or a state in which the alignment is disordered) occurs only after this interaction.

As described above, when an alkyl group or a fluorine-substituted or chlorine-substituted alkyl group is employed as the hydrophobic group of the member (compound) forming the surface of the recording medium (A), the carbon number of the alkyl group is It is considered that the reason why the number is preferably 4 or more is based on the number necessary for the alkyl groups to be arranged (orientated) to some extent on the surface of the recording medium (A) and to perform active molecular motion during heating. Also, contact material (B)
When 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 of the surface of the recording medium (A). Furthermore, if 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, an alkyl group containing fluorine has a strong self-aggregating property, has a high surface self-orientation function, and has a low surface energy, and thus is excellent in preventing background contamination.

Further, the surface of the recording medium (A) has a liquid repellency, which can be described by the surface energy of a solid. According to the study of the present inventors, the surface of the recording medium (A) is found to be 50 dyn / cm or less. It has been confirmed that it is desirable as a recording method based on the above. If the value is higher than this, the surface of the recording medium (A) sometimes gets wet with respect to the recording material, which may cause soiling of the background.

Here, the formation of the surface of the recording medium (A) is described.
Compound (contact while heating the surface of the recording medium (A) selectively)
Heats the surface of the recording body (A) when it comes into contact with the material (B)
Form latent image area showing receding contact angle according to temperature
Compound) will be described in detail. First, FIGS. 1A and 1D
For the type (1), an alkyl group (F
Including those substituted with nitrogen and / or chlorine)
Compounds can be considered. Specifically, formulas (I) and (II)
(III) (IV) (V) (VI) and (VII)R: -H, -CH_Three, -C_TwoH_Five, -CF_ThreeOr -C_TwoF_Five  Rf: C_FourThe above alkyl group or fluorine substitution or salt
Group containing an alkyl-substituted alkyl group or in the molecular chain
(-CF_Two−) P, (−CH_Two-) Having p or -Ph-
Hydrophobic group (p ≧ 4) m: a polymer having an integer of 1 or more as a monomer
You.

Other polymers include those represented by the formula (VII)
I) those shown in (IX) and (X)
You.R: -H, -CH_Three, -C_TwoH_Five, -CF_ThreeOr -C_TwoF_Five  Rf: C_FourThe above alkyl group or fluorine substitution or salt
Group containing an alkyl-substituted alkyl group or in the molecular chain
(-CF_Two−) P, (−CH_Two-) Including p or -Ph-
Hydrophobic group (p ≧ 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, the use of the following material (XI) is particularly desirable. [However, R ^{1 is} hydrogen, -CxHy or -CxFy (x
= 1 or an integer of 2 or more, y = 2x + 1. ) R ² : (—CH ₂ —) p (p ≧ 1 integer) or (—CH
_{2 -) q-N (R} 3) SO 2 - (R 3 is -CH ₃ or -C
₂ H ₅ , q ≧ 1) m: Integer of 6 or more. ]

Accordingly, the most preferred specific compound of the member on the surface of the recording medium (A) in the present invention is And the like.

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

Further, it has a monomer of the formula (XI) and a functional group.
Polymerizing monomer such as CH_Two= C (CH_Three) COO (CH_Two)_TwoOH CH_Two= C (CH_Three) COOCH_TwoCH (OH) CH_Three  CH_Two= CHCOOCH_TwoCH (OH) C₈F₁₇ To form a copolymer with at least one of
Or a monomer having the formula (XI) and a functional group
To produce a copolymer with a polymerizable monomer
Copolymers Containing Many Functional Groups Using Crosslinking Reagents
Crosslinkable polymer produced by crosslinking is also used as a material
It is excellent.

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 in the following chemical formula 1.

Embedded image

In the crosslinked polymer represented by the chemical formula 1, A
The block is an alkyl group which causes the above-mentioned change in thermal properties, while the B block is a site where the linear polymers are cross-linked (cross-linked using diisocyanate as a cross-linking reagent).

To obtain a crosslinked film, a solution in which the above-mentioned copolymer and a crosslinking reagent are mixed is applied as a coating solution on a substrate, and a crosslinked polymer film is obtained by heating or irradiating an electron beam or light. What should I do?

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

Next, the compound shown in FIG. 1B will be described. Here, the formulas (XII), (XII) and (X
Material shown in IV) Rf-COOH ··· (XII ) Rf-OH ··· (XIII) Rf- (CH 2) n-SiX ··· (XIV) (Rf: Number 4 or more alkyl groups or fluorine atoms A group containing a substituted or chlorine-substituted alkyl group, or a hydrophobic group containing (—CF ₂ —) p, (—CH ₂ —) p or —Ph— in the molecular chain (p ≧ 4) n: 1 or more X: chlorine, methoxy group or ethoxy group) etc. Physically adsorbed or chemically bonded to the surface of an inorganic material such as glass, gold, copper or the like, or an organic material such as polyimide, polyester, polyethylene terephthalate (surface energy is about 50 dyn / cm or less is preferable).

Formulas (XII), (XIII) and (XIV)
As a specific example of CF_Three− (CF_Two)_Five-COOH, CF_Three− (CF_Two)₇-COOH, CF_Three− (CF_Two)₇− (CH_Two)_TwoOH, H- (CF_Two)_Ten-COOH, H- (CF_Two)_Ten-CH_TwoOH, F- (CF_Two)₆-CH_TwoCH_Two-Si (CH_Three)_TwoCl, CF_TwoCl (CF_Three) CF (CF_Two)_FiveCOOH, CF_Three(CF_Two)₇(CH_Two)_TwoSiCl_Three  And so on.

The compound shown in FIG. 1 (c) has the formula (XI)
I), a structure composed of only the material of the formula (XIII) or the formula (XIV).

Subsequently, a recording material (A) using the above compound
Is described. The structure of the recording medium (A) is roughly classified into a structure formed by the surface member itself and a structure 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 thickness of the film is desirably 1 μm to 5 mm.

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

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 apparatus.
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-mentioned compound (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. I have. Further, in order to increase the thermal conductivity, it is preferable to mix a metal powder with the above compound.
Further, in order to improve the adhesion between the support and the compound, a primer layer may be provided between the support and the compound. Examples of the heat-resistant support include resins such as tetrafluoroethylene, silicone, polyimide, polycarbonate, epoxy, melamine, phenol, polyester, polyacetal, urea, and polyethylene terephthalate; and metals such as Ni, Al, Cu, Cr, and Pt. Metal oxides and the like are preferred. These supports may be smooth, rough or porous.

Next, the contact material (B) will be described.
The contact material (B) is a liquid, a vapor, or a solid that becomes liquid at a temperature equal to or lower than the temperature at which the receding contact angle on the surface of the recording medium (A) starts to decrease, or generates a liquid or vapor. In short, it is a liquid or a vapor from the beginning, or a solid that eventually generates a liquid at a temperature equal to or lower than the temperature at which the receding contact angle θr on the surface of the recording medium (A) starts to decrease. At least a part of the vapor condenses on or near the surface of the recording medium (A) to generate a liquid, and the vapor can wet the surface of the recording medium (A). Is enough. On the other hand, the solid here is the receding contact angle θr
Liquid, generate liquid, or generate steam at a temperature equal to or lower than the temperature at which the temperature decreases. 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 (B) 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 liquid, n-nonane,
Non-polar liquids such as linear hydrocarbons such as n-octane, 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 one of the contact material (B), any liquid vapor of the contact material (B) can be used in addition to water vapor, and particularly, organic vapor such as ethanol vapor and m-xylene vapor can be used. Compound vapors (including those in a nebulized state) are mentioned. 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 (A).

Examples of the solid which is another contact material (B) include higher fatty acids, low molecular weight polyethylene, polymer gel (polyacrylamide gel, polyvinyl alcohol gel), silica gel, and compounds containing water of crystallization. No.

As will be apparent from the description below, it is assumed that a solid ink melted at a temperature equal to or lower than the temperature at which the receding contact angle of the recording medium (A) starts to decrease is used as the contact material (B). Is very effective because the visualization is performed simultaneously with the formation of the latent image.

Next, 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 that a film 2 of the above-mentioned compound constituting the surface of the recording medium (A) is formed on a support 1, and a liquid 3 of the contact material (B) is present on this film surface. It shows the state that it is doing. In this state, when the film 2 is heated as shown in FIG. 3A, it is recognized that the receding contact angle θr of the surface of the film 2 is reduced and the film 2 shows remarkable wetting, so that the film 2 has liquid adhesion. Further, when the film 2 having the liquid adhesion property is heated again in the air, in a vacuum, or in an inert gas atmosphere (FIG. 2B), the receding contact angle θr increases on the surface of the film 2, and the liquid rebounds again. Is observed.

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, in the method disclosed herein, the recording material differs mechanistically in that it provides a layer of substantially disordered and generally amorphous memory material. . That is, in the present invention, without the presence of the contact material (B),
No state change can occur on the surface of the recording medium (A). Also,
In the method described in Japanese Patent Publication No. 54-41902,
Reversibility cannot be obtained with a simple operation.

As shown in FIG. 3A, heat is applied to the film 2 in contact with the liquid 3 in accordance with image information [as shown in FIG. The same applies to contact with liquid under the condition where heat is applied according to information.)
Then, the surface of the film 2 of the heating portion is made to adhere to the liquid. 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. 3A shows an example in which the film 2 is heated through the support 1, while the example shown in FIG. 3B-2 shows an example in which the film 2 is directly heated. is there.

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. In FIG. 4, ○ indicates a forward contact angle, and △ indicates a receding contact angle.

Generally, 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 (A) in the state of being in contact with the contact material (B) is preferably in the range of 50 ° C. to 250 ° C., more preferably 80 ° C. to 150 ° C. 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 to be formed, the surface of the recording material (A) is heated and then brought into contact with the contact material (B) before cooling, and the contact material (B) is applied to the surface of the recording material (A). The surface of the recording medium (A) may be heated under the state of contact. On the other hand, if the latent image is to be erased, the surface of the recording medium (A) is heated to 50 to 300 ° C., preferably 100 to 18 in the absence of the contact material (B).
What is necessary is just to heat to 0 degreeC. In each case, the heating time is about 1 millisecond to 10 seconds, preferably 10 milliseconds to 1 second.

Next, means for actually recording image information on the surface of the recording medium (A) will be described in more detail.
One is to heat the surface of the recording medium (A) in response to an image signal in a liquid or vapor atmosphere to form a liquid adhering area on the surface of the recording medium (A) (latent image formation). A recording agent (melted solid ink) is brought into contact with the latent image portion by means of contact (development), and thereafter the recording agent is fixed on the surface of the recording medium (A) as it is ( Direct recording method). The other is to heat the surface of the recording medium (A) in response to an image signal in a liquid or vapor atmosphere to form a liquid adhering area on the surface of the recording medium (A) (latent image formation).
Then, ink is attached to the latent image portion by means of bringing the molten solid ink into contact with the latent image portion (development), and subsequently, the ink on the surface of the recording medium (A) is transferred to recording paper. (Indirect recording method). Further, in this method, if the means for attaching the molten solid ink to the latent image portion again after transferring the ink is performed, a printing method using the recording medium (A) as a printing plate is obtained. Further, in the above method, after transferring the ink to the recording paper, the surface of the recording medium (A) on which the latent image is formed in the absence of liquid or vapor is heated to erase the latent image, thereby obtaining the recording medium (A). ) Is a reproducible recording method. FIGS. 5A, 5B and 5C show typical processes of a direct recording method, an indirect recording method (printing method), and a reversible recording method (repeated recording method) of the recording medium (A).

In these processes, the melting point of the “melted solid ink” is such that the receding contact angle (indicated by the solid line) with respect to the heating temperature of the recording medium (A) in the liquid, as shown in FIG. Must be lower than the temperature at which the temperature begins to change (shown at point T). If a solid ink having a melting point higher than the point T is used, it is impossible to maintain the flow state of the ink and not to change the receding contact angle of the surface of the recording medium (A).

Next, the structure of the method of the present invention including the recording medium (A) will be described. The recording medium (A) has a surface in which the receding contact angle is reduced when the recording medium is brought into contact with a liquid in a heated state (for convenience, sometimes referred to as “film 2” or “recording medium (A) surface”). Is not limited to that form. Therefore, the recording medium (A) may have a rigid cylindrical shape or a flexible film shape. However, the rigid cylindrical recording body (the one in which the film 2 is formed on the surface of the cylindrical rigid body) has excellent controllability since the recording body (A) is hardly displaced when the recording body (A) is operated. (A) is preferable. For the production of such a recording body (A), a method of forming the film 2 on a substrate or a method of producing the molded body itself is adopted. In particular, since the molded body generally has low mechanical strength, a method of forming a film on a support is desirable. It is needless to say that the film 2 must be formed on the surface of the recording body (A) even when the recording body (A) is formed from the molded body itself.

When a resin is used for the support of the recording medium (A), it is hard to say that it is a good conductor of heat, and it takes some time before the surface of the recording medium (A) is heated to have liquid adhesion. Cost. Thus, it may be conceivable to use a good heat conductor for the entire support or for a portion on the support 1.

FIG. 7 (a) shows a case where a good heat conductor such as a metal is used as a support (metal substrate 11), an organic thin film 12 is deposited thereon, and a film 2 is further formed thereon. However, this increases the rate of heat conduction in the vertical direction. Examples of the organic thin film 12 include polyimide, polyester, and phthalocyanine. 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. 7B shows a configuration in which a good heat conducting portion is provided on the support 1 so as to prevent heat diffusion in the surface direction and to miniaturize the portion 2a having liquid adhesion. . In FIG. 7B, reference numeral 11a denotes a miniaturized metal film.

Subsequently, a latent image forming means by heating, and further,
The recording agent (ink) applying means (visualizing means) 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 infrared lamp. Further, a solid ink is used as the recording agent in the method of the present invention.

FIGS. 8 to 12 show the outline of five typical examples of the method of the present invention. In the figure, 3 is a liquid,
3a is a molten solid ink (recording agent) 3a '
Is a solid head, 42 is a thermal head, 43 is a heater, 8 is a holding member, 81 is a pumping roller, 82 is an ink adhering roller, 91 is a transfer roller, 92 is a transport roller, 9
Reference numeral 9 denotes a heat dissipation member, S denotes a latent image, and I denotes an image. In these examples, if the surface of the recording body 7a or 7b is heated by the infrared lamp 41 'each time the recording body 7a or 7b makes one rotation in the absence of the liquid 3, the latent image (S ) Is erased, so that the recording body 7a or 7
A new transfer image can be obtained for each rotation of b. Prior to erasing the latent image, a means for cleaning the surface of the recording body 7a or 7b may be employed.

FIG. 8 shows that the recording head (A) is heated by the thermal head 42 in the presence of, for example, water 3 in the presence of water 3 to form a latent image (S). 3a to contact the latent image (S) with the ink 3
After adhering a, the desired image I is obtained by transferring it to a recording paper P. The solid ink (3a ') is heated by a suitable means such as a heater 43.

The solid ink 3a used here is 5
Although it has a melting point in the range of 0 to 200 ° C., it is needless to say that it must have a melting point lower than the T point explained in FIG. The solid ink 3a contains a dye / pigment and a binder as main components, and typical examples thereof are as follows.

As the water-soluble dye, dyes classified into acid dyes, direct dyes, basic dyes, reactive dyes and food dyes in the color index and having excellent water resistance and light resistance are used. As specific examples of these dyes,
For example, the following are mentioned.

[0075] etc.

Examples of the pigment include azo, phthalocyanine, anthraquinone, quinacridone, and organic pigments.
Dioxazine-based, indigo-based, thioindigo-based, perinone-based, perylene-based, isoindolenone-based, aniline black, azomethine-based, carbon black, and the like.Examples of inorganic pigments include iron oxide, titanium oxide, calcium carbonate, and barium sulfate. Examples include 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 resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl Naphthalene maleic acid resin, polyvinylpyrrolidone, polyvinyl alcohol, alkali metal salt of β-naphthalenesulfonic acid formalin condensate, a 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, gum arabic, natural gums such as tragacanth gum, glucoxides such as saponin, carboxymethyl cellulose, hydroxyethyl cellulose, cellulose derivatives such as methyl cellulose,
Natural polymer compounds such as ligninsulfonic acid and salts thereof, shellac and the like.

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

Examples of the binder include natural waxes such as polyacrysate, polyethylene oxide, ethylene vinyl acetate copolymer, carnauba wax, candelilla wax, whale wax, beeswax, wood wax, jojoba wax, tetracosanol, Examples include higher alcohols such as hexacosanol and their esters, higher fatty acids and their esters. These melting points are all in the range of 30 to 200 ° C.

The temperature of the solid ink 3a is changed by heating means such as a heater 43 to control the viscosity of the ink. That is, when the recording apparatus is in use, the heater 43 is turned on to maintain the ink at a flowable viscosity (melt state 3a), and when not in use, the heater 43 is in the OFF state and the ink is a solid state 3 '.

FIG. 9 (a) shows the molten solid ink 3
a ′ is held by the holding member 8 and the recording member 7b having the latent image (S), the recording member 7b and the holding member 8 are moved, and solid ink is applied to the latent image (S) portion of the recording member 7b. 3a is adhered and transferred to the recording paper P to obtain an image I.

In the image formation in this case, the molten ink 3
a is held at least between the recording member 7b and the holding member 8 at the position of the point B in FIG. 9 (FIG. 9B). Where B
If the heat radiating member 99 is desirably provided between the point C and the point C, the ink is extremely sufficiently cooled and solidified. Therefore, when the holding member 8 is separated from the recording body 7b, The ink remains in the region where the receding contact angle is small, but the ink does not adhere to the region where the receding contact angle is large and the ink adheres to the holding member 8 so that development is performed (FIG. 9C). ). At this time, the area of the ink 3a and the holding member 8, the area of the ink 3a and the recording body 7b where the receding contact angle is large, and the area of the ink 3a and the recording body 7b where the receding contact angle is small (the area having the latent image (S)). The magnitude relationship between the three adhesive forces is <<.

As the heat dissipating member 99, a material having a high heat conductivity such as a metal having a heat conductivity of 0.01 to 1 (cal / cm · sec · ° C.) such as Al and Ni is used. Further, a cooling means such as a Peltier element may be used. The position may be provided on the substrate side of the recording medium.

The place where the heat radiating member 99 is installed is shown in FIG.
In other words, it is between the point B and the point C, and preferably between the latent image forming section (laser beam irradiation section) and the point C.

Further, the shape of the heat radiating member 99 is not particularly limited, but, for example, (1) a plate-like shape (including a curved shape) which is close to the recording medium (A) (FIG. 12)
(B)), (2) A heat dissipating member 99 similar to the above (1) is brought into contact with the inner peripheral surface side of the ink adhering roller 82 (FIG. 12 (c)), and (3) the above (1) and (3). / Or (2)
Having a fin on the surface (FIG. 12)
(D)), (4) the air guide itself (FIG. 12)
(E)), and the like. Two or more of these heat radiating members 99 may be used depending on the installation location. FIG.
The example of FIG. 2B is effective when the heat radiation member 99 is transparent to laser light.

FIG. 10 shows a state in which the surface of the recording body 7a is brought into contact with the molten solid ink 3a and heated in accordance with an image signal to simultaneously carry out latent image formation and visualization. .

FIG. 11 shows a recording medium 7c obtained by coating or impregnating the above-mentioned compound forming the film 2 on paper, cloth or the like.
This is intended to directly obtain an image.

As described above, in the apparatus shown in FIG. 12, both the laser beam irradiation surface and the heat radiating member 99 are at point B-.
The heat radiation member 99 is set so as to be located between the points C, and is located between the laser beam irradiation surface and the point C. The solid ink is melted in the container, and
1 is also molten. On the ink adhering roller 82,
The ink is solidified at least up to the point B. The latent image is formed by irradiating a laser beam,
Is heated and melted. After that, at the point C, the recording medium 7b and the solid ink are separated, but by the point C, the solid ink is completely solidified. As described above, a heat radiating member, a cooling means, and the like may be provided between B and C in order to promote solidification of the solid ink.

FIGS. 8 to 12 show application examples of the method of the present invention, but further modifications thereof may be considered.

[0090]

Next, the method of the present invention will be described more specifically with reference to examples.

Example 1 An image was recorded using the recording apparatus shown in FIG. The thermal head for latent image formation has a thermal element pattern of 200 × 1
The pitch is 00 μm and 8 dots / mm. Pure water was used as the latent image forming liquid. The recording material (A) used was a polymer of a fluorine-containing acrylate material 17F (manufactured by Osaka Organic Chemical Industry Co., Ltd.) coated on a polyimide substrate. The temperature corresponding to the point T in FIG. 6 of the recording body (A) was about 80 ° C. The main component of the solid ink was paraffin wax SP-0110 (manufactured by Nippon Seisaku Co., Ltd.), and a black dye was dissolved therein to obtain a solid ink. Since the melting point of this solid ink is about 44 ° C., the heater is about 5 ° C.
At 0 ° C., the ink was kept fluid. When the image was recorded under the above conditions, a clear image was obtained even after a long period of time.

Example 2 An image was recorded using the recording apparatus shown in FIG. Latent image formation and transfer were performed in the same manner as in Example 1. Thermal element pattern of thermal head for latent image formation is 200 × 100μ
m pitch, 8 dots / mm. Pure water was used as the latent image forming liquid. The recording material (A) used was a polymer of a fluorine-containing acrylate material 17F (manufactured by Osaka Organic Chemical Industry Co., Ltd.) coated on a polyimide substrate. The temperature corresponding to the point T in FIG. 6 of the recording body (A) was about 80 ° C. The solid ink is kept at 50 ° C.
The recording medium (A) is further sandwiched with the recording medium (A), the ink is allowed to cool naturally, and then the holding member 8 is peeled off from the recording medium (A). Although the ink is fluid, it is solid at point C. The heat radiation member 99 is omitted here.

Example 3 An image was recorded by the recording apparatus shown in FIG. Here, the latent image forming liquid is a molten solid ink. The thermal element pattern of the thermal head for forming a latent image is 200 × 1
00 μm, pitch 8 dots / mm. Recorded body (A)
The material used was a polymer of a fluorine-containing acrylate material 17F (manufactured by Osaka Organic Chemical Industry Co., Ltd.) coated on a polyimide substrate. The temperature corresponding to the point T in FIG. 6 of the recording body (A) was about 80 ° C. The main component of the solid ink was paraffin wax SP-0110 (manufactured by Nippon Seisaku Co., Ltd.), in which a black dye was dissolved to obtain a solid ink. When an image was recorded under the above conditions, a clear image was obtained as in Example 1. Further, the size of the apparatus can be reduced since the latent image forming section does not become large.

Example 4 An image was recorded by the recording apparatus shown in FIG. Here, since the recording medium (A) is impregnated in the paper with the components forming the film 2, direct recording is possible. As in the third embodiment, the latent image forming liquid is a molten solid ink. The thermal head for latent image formation has a thermal element pattern of 200 × 100μ
m, pitch 8 dots / mm. The recording body (A) is obtained by impregnating a paper with a polymer of a fluorine-containing acrylate material 17F (manufactured by Osaka Organic Chemical Industry Co., Ltd.). The main component of the solid ink is paraffin wax SP-0110 (manufactured by Nippon Seiro Co., Ltd.), in which a black dye is dissolved. When the image was recorded under the above conditions, a clear image was obtained. Further, since the transfer step is unnecessary, the apparatus can be downsized.

Example 5 Image recording was performed with the apparatus configuration shown in FIG. 12A (however, a thermal head was used instead of laser beam irradiation).
The thermal element pattern of the thermal head for forming a latent image is 200
× 100 μm, pitch 8 dots / mm. The recording material (A) used was a polymer of a fluorine-containing acrylate material 17F (manufactured by Osaka Organic Chemical Industry Co., Ltd.) coated on a polyimide substrate. The temperature corresponding to the point T in FIG. 6 of the recording body (A) was about 80 ° C. The main component of the solid ink was paraffin wax SP-0110 (manufactured by Nippon Seisaku Co., Ltd.), in which a black dye was dissolved to obtain a solid ink. When the image was recorded under the above conditions,
A clear image was obtained as in Example 1. Further, the size of the apparatus can be reduced since the latent image forming section does not become large.

[0096]

According to the method of the present invention, since the solid ink is used, the handling surface is improved, and a change in the physical properties of the ink is prevented, so that a high-quality clear image can be obtained for a long period of time.

[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 diagram for basically explaining the function of a recording medium (A) used in the method of the present invention.

FIG. 3 is a diagram for basically explaining the function of a recording medium (A) used in the method of the present invention.

FIG. 4 shows a case where the surface of the recording medium (A) is heated while a liquid is in contact with the surface of the recording medium (A) used in the method of the present invention.
FIG. 5 is a diagram showing a change in receding contact angle θr observed on the surface of the recording medium (A).

FIG. 5 is a diagram showing two embodiments when the method of the present invention is used.

FIG. 6 is a diagram illustrating a relationship between a temperature indicating a receding contact angle of a recording medium (A) and a melting temperature of a solid ink.

FIG. 7 is a diagram showing an embodiment of the method of the present invention.

FIG. 8 is a diagram showing an embodiment of the method of the present invention.

FIG. 9 is a view showing an embodiment of the method of the present invention.

FIG. 10 is a diagram showing an embodiment of the method of the present invention.

FIG. 11 is a diagram showing an embodiment of the method of the present invention.

FIG. 12 is a view of five examples showing a state of carrying out the method of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Recording layer 3 ... Liquid (3a ... solid ink) 4 ... Heater 3a ... Melted solid ink 3b ... Solid solid ink 5 ... Lens 6 ... Shutter 7a, 7b, 7c ... Recording body (A) 8 ... Holding member 11: Metal substrate 11a ...
Miniaturized metal film 12 ... Organic thin film 41, 4
1 '... infrared lamp 42 ... thermal head 43 ... heater 44 ... laser light source (laser light) 81 ... pumping roller 82 ... ink adhering roller 85 ... fan 86 ... blowing guide 99 ... heat dissipation member

────────────────────────────────────────────────── (5) References JP-A-3-178478 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41L 19/00-19/16 B41C 1 / 00-1/16 B41M 1/00-5/26

Claims (5)

(57) [Claims] 1. A method of selectively heating the surface of a recording medium (A) below in contact with the following contact material (B) or contacting the surface of the recording body (A) selectively heating A latent image having a receding contact angle reduced according to the heating temperature is formed on the surface of the recording medium (A) by contact with the material (B), and the latent image is visualized with solid ink. A recording method comprising, as necessary, transferring ink attached to the surface of the recording medium (A) to recording paper. (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. 2. The solid ink in the visualization,
The recording method according to claim 1, wherein the recording material (A) is melted at a temperature lower than a temperature at which the receding contact angle starts decreasing. 3. The visualization of the latent image is performed by uniformly applying solid ink melted on a recording medium (A) having a latent image at a temperature at which the receding contact angle of the recording medium (A) starts to decrease. After the ink is supplied, the ink layer is sandwiched between the holding member and the recording medium (A), and after the ink is cooled and solidified, the holding member and the solid image other than the latent image are used as the recording medium (A).
2. The recording method according to claim 1, wherein the recording method is performed by peeling off from the recording medium. 4. The latent image formation and the visualization are performed in a single step by using a solid ink melted at a temperature lower than the temperature at which the receding contact angle of the recording medium (A) starts to decrease as the contact material (B). 2. The recording method according to claim 1, wherein: 5. The recording medium (A) is brought into contact with a solid ink layer, and the recording medium (A) and the solid ink are heated only when the latent image is formed, so that the solid ink is melted to form a latent image. The recording method according to claim 2, wherein the solid ink is solidified until the solid ink layer is peeled off from the recording medium (A), and is adhered to the surface of the recording medium (A). .