DE4010275A1 - Recording process using thermal imaging - with recording material whose contact angle is reduced by heating and liq. ink which adheres to selectively heated areas - Google Patents

Abstract

Recording process comprising (a) and (b) in either order: (a) contacting a contact material (I) with the surface of a recording material (II) having surface characteristics such that the retrogressive contact angle is small when the (II) is contacted with a liq. and is in the heated state, the (I) being chosen from a liq. or vapour or a solid which under temp. conditions below the temp/ at hwich the angle of the (II) begins to become smaller, forms a vapour or a liq. or changes into one of these,a nd (b) selectively heating the surface of the recording material (II) corresponding to image information so latent image is formed on the surface of the (II) where the prevailing retrogressive contact angle corresponds to the temp. of the (II) obtd. by the selective imagewise heating. USE/ADVANTAGE - Simple imaging method which uses imaging materials in which a latentt image can be induced by using property the the retrogressive contact angle of the surface is smaller when the surface is contacted with a hot fluid. A recording medium contg. a colourant may be applied to the surface carrying the latent image to develop the latent image. The developed image may be fixed on the surface of the recording material, or the developed image may be transferred to another substrate and fixed there. After the contact material has been removed from the surface of the recording material, the material may be heated overall to erase the image. The imaging method is simpler w.r.t. appts. than previous imaging systems and allows the construction of compact appts.

Description

The invention relates to a new recording method and in detail a procedure in which an area of a return temperature corresponding to a heating temperature indicating contact angle, selectively and selectively reversible on a surface of a recording medium gers is formed, for what the surface certain Has properties; beyond that it refers to a recording method in which this area equipped with a recording medium, the Colorant for image appearance includes.

Description of the Prior Art

The offset printing process using printing plates without water (water for humidification) as typical Recording material is divided into areas to which a liquid adheres, and areas where the not the case. In this offset printing method is However, it is difficult to complete all processes including Process for the production of the original plates and the printing processes from the plates (printing plates) into one to install the only device. That makes it difficult, a compact To get pressure plate device. That's how it is For example, even in the case of a relatively compact Offset printing device required that the compact Off set pressure device and the pressure device are separated.

To eliminate this disadvantage of the offset printing process, a recording method and apparatus is provided beat, where the areas for liquid separation  and areas without liquid separation on an up formed drawing material according to the image information and repeated use of this recording material is possible (i.e., the Procedure is reversible. Below are some examples For:

1. Water-soluble development process

After a charge externally on a hydrophobic photo electrical layer has been applied, the Exposed material, and on the surface of the photo electric layer, a pattern is formed, the both a hydrophobic and a hydrophilic Part has. A water-soluble developer solution adheres only on the hydrophilic area and gets on Transfer paper or something similar. This Ver drive and devices are in the Japanese Patentver Publication No. 40-18992, Japanese Patent Publication No. 40-18993, Japanese Pat Tent. Publication 44-9512 and Japanese Laid-Open Publication No. 63-264392 and so on.

2. Method using photochemical reac tion of a photosensitive material

In this method, ultraviolet light is generated blasted a layer containing a material such. B. contains a spiropyran or an azo dye, so that a photochemical reaction occurs to the photosensitive substances hydrophilic or similar close. These methods and apparatus are in the Japanese Journal of Polymer Science and Technology (Japanese Journal of Polymer Science and technology), Vol. 37, No. 4, page 287 (1980) wrote.  

3. Procedure using the internal voltage personnel

This is a process in which the parts to which a liquid ink adheres or does not adhere, through the physical transformation of an amorphous Substance and a crystalline substance on the up be formed. (An example is disclosed in Japanese Laid-Open Patent Publication No. 54-41902 described.)

According to the method (1) described above the hydrophilic part after transfer of the water-soluble Printing ink on paper or something similar by removing the charge is removed, so that it is possible to have one record other image information. That means that the an original plate (the photoelectric body) like allows repeated pressure. This method serves but an electron transfer process as a reason situation and therefore requires a long process from charge → exposure → development → over Transmission → discharge, so that there are accompanying problems to make the device compact, its cost to lower and wait.

With the method (2) described above it is possible the reversibility of the hydrophilic and hydrophobic properties by selective irradiation with ultraviolet and visible light at will. Because the Quantum yield, however, is very small, is the Reak tion time extremely long and the recording speed correspondingly low. There is also the Disadvantage of image instability. This procedure has that Level of practical application not yet reached.

In addition, the Ver drive (3) used information recording component  (the recording material), although stable after the Recording is done, but there are cases where at the image recording component by temperature ver Changes before recording a structural Conversion occurs. That is, to remove the recorded information a device is required Apply a heat pulse followed by rapid cooling so that it is difficult to do the picture image frequently to repeat.

Summary of the invention

Accordingly, it is the general task of the inventor tion, a neutral and useful recording method to show, in which the disadvantages described above of the prior art have been eliminated.

Another and more specific object of this invention is to show a method in which by means of a simple process selective or selective and reversible a predetermined pattern area on a record material with a surface for which the returning Contact angle becomes smaller when a heated liquid is brought into contact with it, is formed.

Another object of the invention is a method according to which a recording medium (liquid Printing ink, etc.) including a coloring agent predetermined pattern area on a recording medium can be supplied rial, so that one positive develops developed image. This visible image can be up the surface of the recording material to be fixed. The visible image can also be on a transmission material such as plain paper u. Ä. Transfer and open whose surface is fixed. Likewise, an up A drawing method indicated in which a clear  Image obtained with gradations.

In addition to the tasks described above It is another object of this invention, a new show similar recording method, the all processes for training and deletion of one particular pattern area, in the development of la tenten image as well as the transmission u. Ä. These processes by using a recording material with drawn resistance and stability several times reversible.

The recording method according to the invention includes steps for selectively heating a recording material (A) described below and a contact material (B) when both are in contact so that in the state where the recording material (A ) is selectively heated, at Kon contact with the contact material (B) is formed a region having a returning contact angle corresponding to a heating temperature on the surface of the recording material on (A) (and which is a vorbe certain pattern area, the unit's simplicity below is referred to as either "latent image" or "latent image area").

• (a) A recording material having a surface at the returning contact angle becomes smaller, when it is in a heated state and with a liquid in contact.
• (b) A liquid, vapor or solid which generates a liquid or vapor at a temperature lower than that at which the returning contact angle of the recording material (A) begins to decrease, or into a liquid or converting a steam.

The method according to this invention supplies to the latent image area a recording medium containing a coloring agent and develops a latent image. In addition, the recording agent having the colorant may be used instead of the contact material (B) to form a latent image and to develop it at the same time.

In the state where the contact material (B) has been removed, by the method according to this invention, the deletion of the latent image is performed by heating the surface of the recording material on which the latent image has been formed.

The inventors of this invention have made considerable research and investigations into a novel recording method from which the disadvantages described for the conventional technologies have been eliminated. As a result, the inventors have discovered that a component is effective as a recording material when it has a surface having a function in which the returning contact angle becomes smaller after heating and cooling in the state where it is in contact with a liquid, and wherein the returning contact angle becomes larger by heating in a state where the liquid has been removed. Then, the surface of the recording material (A) having this function is (1) a component including an organic compound having a surface self-alignment function with a hydrophobic moiety, and / or (2) a component comprising an organic compound having a surface self-centering function with a hydrophobic moiety and having a surface oriented hydrophobic moiety.

The (1) "surface self-orientation function" refers focus on an orientation where the hydrophobic residue attaches the surface is oriented to the side of the air (i.e., the free surface side), if one Solid body, one trained on a support body Compound or a solid, by itself a compound has been formed, is heated in air. The same applies to (2). In general wise organic substances the phenomenon that a hydro phober rest slightly to the side of a hydrophobic Atmosphere oriented. This is a phenomenon that occurs when the orientation goes to the side where through the interfacial energy of the boundary solid-gas decreases. In addition, this phenomenon is remarkable for the longer molecular chains of the hydrophobic residue. The reason for this is that when the molecules heat up those with longer molecular chains are more mobile.

More specifically, the orientation is in the case of Molecule with a hydrophobic residue at the end (i.e. Molecule in which the surface energy is low) lighter in the direction of the air side (ie the side with the free surface. Similarly, in the case of Chain molecules with

flat and therefore oriented easily. Additionally have Molecules with

a flat structure for the

and orient themselves easily. Especially the Chain molecules with a chemical element in which the Electronegativity is great, such as. As fluorine, have about a big self-aggregation. At the Kettenmole molecules are mutually orientated on molecular chains simplest.

To summarize the results of this study: It is more desirable to have a chain molecule that a molecule with a flat structure or self-aggregate  and that also includes a chain molecule a hydrophobic residue at its ends, or one Compound that includes such chain molecules as it These are connections that are high Have self-orientation function.

As is apparent from the above discussion, there is a relationship between the surface self-alignment status and the returning contact angle. In addition, there is also a relationship between the returning contact angle and the liquid adhesion. That is, the adhesion of the liquid to the surface of the solid is mainly due to sticking of the liquid on the surface of the solid. This sticking can be considered as a kind of friction in which the liquid slides along the surface of the solid. Accordingly, in this invention, when the friction force γ f , the "returning contact angle" R r can be determined as follows:

wherein
γ the roughness factor,
γ s is the surface tension of a solid in vacuo,
γ s _{l is} the interfacial tension at the solid-liquid interface,
γ lV the surface tension of the liquid in equilibrium with its saturated vapor,
π e is the equilibrium surface tension,
γ f is the friction stress.

(Saito, Hokuzaki et al .: "Japan Contact Adhesive Associa tion Magazine "(Journal of the Federal Japan), Vol. 22, No. 12, 1986).  

As the value of R r decreases, the value γ f increases accordingly. That is, the liquid is less likely to slide over the surface of the solid.

As can be assumed from this reciprocal relationship, the adhesion of the liquid depends on the retrograde contact angle R r . The returning contact angle R r is determined by the material having a surface with a surface self-aligning function.

In the method of this invention requires recording material (A) the development of a latent image on the surface by forming a vorbe voted pattern region and / or a recording means, and therefore, the recording material (A) must be a material for the tierungsfunktion the Oberflächenselbstorien is selective.

Other objects and further features of the invention go from the following detailed description, when combined with the accompanying drawings read.

Brief description of the drawings

Figs. 1A to 1D are views showing a model of the structure of a material having a surface self-aligning function.

Figs. 2A, 2B, 3A, 3B and 3C are views for describing the basic aspects of the image recording method of this invention.

Fig. 4 is a view showing the changes in the advancing contact angle and the returning contact angle on the surface of the recording material.

Figs. 5A, 5B and 5C show the steps of the image recording method of this invention.

Figures 6A through 14B are views describing the shape of a device forming images according to the image recording method of this invention.

Figs. 15 and 16 show the changes in the front contact angle and the returning contact angle on the surface of the recording material.

Fig. 17 is a view describing another form of apparatus which forms images according to the image recording method of this invention.

Fig. 18 shows the changes in the advancing Kon contact angle and the returning contact angle on the surface of the recording material.

Fig. 19 describes another form of apparatus which forms images according to the image recording method of this invention.

More detailed description of the preferred embodiments

A recording material (A) used in the recording method of this invention is as described above, one having a surface in which the retrograde contact angle R r becomes smaller as the recording material is heated and comes in contact with a liquid.

This recording material (A) may be of any shape as long as its surface has the properties described above. Accordingly, the recording material (A) may be in the form of a film. The recording material (A) may also have a structure where a coating film or the like having the above-described characteristics is provided on the surface of a supporting body or a molded body. The recording material (A) may also be the molding itself. In any case, it is neces sary that the surface of the shaped body image has the properties described above.

Whether the liquid adhesion portion in the latent image portion of the recording material (A) is lipophilic or hydrophilic depends on the kind of the contact material (B) . Accordingly, the use of oil-soluble ink or water-soluble ink is decided as necessary when the object to which the image is to be transferred is present.

Fig. 1A to 1D show here a classification of Ma terialtypen or material portions "having a surface, wherein the returning contact angle R is less than r, if the material is heated and brought into contact with a liquid". Fig. 1A shows the example of a compound having a self-orientation function. This compound has a hydrophobic residue on the side chains of the macromolecule polymer. The main chain L and the hydrophobic radical R are joined by the coupling moiety J.

Fig. 1B shows the example of a material in which the hydrophobic residues in an organic compound are oriented to the surface. The compound O with the hydrophobic group described above is formed by the physical or chemical coupling to the surface of an organic or inorganic surface M. Fig. 1C shows an example of a material consisting only of the organic compound O having the hydrophobic group shown in Fig. 1B.

Fig. 1D shows an example where the chain molecules are located in a side chain of a macromolecule. The chain molecules and the main chain L are connected to each other through the coupling chain J. This is a compound with hydrophobic functional groups at the ends and a molecular chain N that has a flat structure or self-aggregation in the middle.

In the examples shown in Figs. 1A and 1D, the backbone L of the macromolecule compound may have either a linear form or a network structure.

In the example shown in Fig. 1B, as in the case of an applied Langmuir-Blodgett film, it is also possible to use a compound O containing a hydrophobic moiety and then to apply a compound O including a hydrophobic moiety to the substrate. In the example shown in Fig. 1C, there is only one compound having a hydrophobic residue, without a backbone L or coupling to an organic or inorganic material (M) or the like.

The hydrophobic residue described above should be present preferably end molecules such as -CH₃ and -CF₃, -CF₂H, -CFH₂, -C (CF₃) ₃, -C (CH₃) ₃ or the like. Even better, it is from Advantage if this hydrophobic residue is long molecules with has high molecular mobility. Of these can the hydrophobic group described above is a substituent tuted alkyl (such as one with  

o. Ä.), Which has more than one -F and / or -Cl or one unsubstituted alkyl group with a carbon number of 4 or more. One can either fluorine or Use chlorine substitution, but fluorine substitution is more effective. Considering the relationship between the carbon number of the alkyl group and the Functions is the feature in these materials relating to the suitability for a recording method lower if the carbon number is three or less is.

The working principle is not yet fully known, but It is assumed that it runs as described below.

First of all, it is considered that the surface of a recording material (A) formed by the above-described compound and in which the surface has the hydrophobic moiety also described is considerably oriented. Accordingly, this surface has a liquid-repellent property (because the surface energy of hydrophobes is lower). In this state, when the surface of the recording material (A) and the surface of the contact material (B) are brought into contact and heated, the heating increases the molecular motion of the hydrophobic residue. In addition, by the interaction with the contact material (B) , the surface of the recording material (A) changes , so that the orientation state of at least a part thereof changes. (That is, there is either one in their orientation state or that the state by which the orientation takes place is disturbed.) After cooling, it is assumed that the state is retained. Even if the contact material (B) is either steam or a solid before heating, this contact material (B) becomes liquid upon contact with the recording material (A) in the state where the recording material (A) is heated.

Before heating, the surface energy of the recording material (A) is extremely low because the hydrophobic moiety is oriented toward its surface.

However, by heating the recording material (A) to the state in which the contact material (B) is in contact therewith, the orientation state is disturbed and the surface energy is increased. The returning Kon contact angle R r is determined by the balance between the surface energy of the solid and the surface energy of the liquid. If the surface energy of the solid is high, then the returning contact angle R r becomes smaller, regardless of what type of liquid it is. Accordingly, this results in an increase in the adhesion with respect to the liquid.

Moreover, when the surface of the recording material (A) is in another state (either a state having an orientation different from the former orientation state or a state where the orientation has been disturbed), and if so Also, there is the state where there is no contact material (B) and the recording material (A) is heated, no interaction with the contact material (B) occurs, and therefore it is considered that the material returns to the former orientation state.

Accordingly, the contact material (B) is not one which simply performs the cooling after the surface of the recording material has been heated, but one in which there is some interaction with the compound of the surface of the recording material (A) for the expected state change ( either a state in which there is an orientation different from the former orientation state, or a state in which the orientation has been disturbed).

As described above, when the hydrophobic moiety of the component (compound) constituting the surface of the recording material (A) is an alkyl, fluorine or chlorine substitution of the alkyl group, the carbon number of the alkyl must be 4 or more , This carbon number of 4 or more is presumably the number necessary for the active molecular motion upon heating and for a certain degree of orientation of the alkyl on the surface of the recording material (A) . In addition, when the contact material (B) together with the surface of the recording material (A), it is heated, it is believed that the molecules of the contact material (B) in the molecules of the surface of the recording material (A) to be installed. Moreover, when an alkyl including fluorine or chlorine having high electronegativity is used, a significant interaction with liquid occurs, especially when it is a polarity liquid, and therefore, the change in the adhesiveness is larger than in the case of a compound having a polarity contains unsubstituted alkyl. In addition, alkyl-functional groups that also contain fluorine have a strong self-aggregation, and therefore the surface self-orientation function is also high. In addition, alykl functional groups including fluorine have a low surface energy and therefore an excellent effect when it comes to preventing the contamination of the surface of the recording material.

In addition, the surface of the recording material has a liquid-repellent effect. This can be described by the terms of the surface energy of a solid. In the course of the investigations made by the inventors, it is found that this surface energy - at least when used as a recording material - should preferably be 50 dynes / cm or less. Higher values make the surface of the recording material (A) hot and dirty by the recording medium.

The following is a detailed description of a compound which forms the surface of the recording material (A) . The first group contemplated herein relates to a compound having an alkyl group (including fluoro, chloro) in the side chains of a vinyl type macromolecule. More specifically, the monomers given in (I), (II), (III), (IV), (V), (VI) and (VII) are preferred.

R: hydrogen, CH₃, C₂H₅, CF₃ or C₂F₅
Rf: alkyl with C₄ or more, or a functional group including a fluorine- or chlorine-substituted alkyl radical or a hydrophobic radical with

(where n is 4)
n : an integer of 1 or more.

Other polymers are those listed in (VIII), (IX) and (X) surrounded.  

R: -H, CH₃, C₂H₅, CF₃ or C₂F₅
Rf: alkyl radical with C₄ or more, or a functional group including a fluorine- or chlorine-substituted alkyl radical or a hydrophobic radical with

(where n is 4)
n : an integer of 10 or more.

In these specific examples, Rf can be as follows from (1) to (20) indicate:

Even from these compounds, the following Material (XI) selected for special consideration become.

[Wherein:
R¹: hydrogen, -C _n H _{2 n +1} or C _n F _{2 n +1} (with n = 1 or an integer, n 2) R²: (where p = an integer, p 1) or N (R₃ ) SO₂ - (with R³ = -CH₃ or -C₂H₅, where q = an integer, q 1)
m : an integer, m 6].

Accordingly, this is the most suitable compound for use as a component of the surface of the recording material (A) of this invention.

In addition to the monomer pairs (copolymers of two or more monomers) in these formulas (I), (II), (III), (IV), (V), (VI), (VII) and (XI), there is also the mono mers of formulas (I) to (VII) and (XI) and other mo nomere such as Ethylene, vinyl chloride, styrene, butadiene, Isoprene, chloroprene, vinyl alkyl ethers, vinyl acetate, Vinyl alcohol and other copolymers, also known as the can be used above described compound.

In addition, a copolymer of one represented by the formula (XI) represented monomer and at least one of following monomers are prepared, each of which has a functional group has:

CH₂ = C (CH₃) COO (CH₂) ₂OH
CH₂ = C (CH₃) COOCH₂CH (OH) CH₃
CH₂ = CHCOOCH₂CH (OH) C₈F₁₇

As a result, many functional groups in the Copolymer formed. In this way, the herge has Substance exhibited excellent properties as Ver networking polymer type. As a crosslinking agent can ent neither formaldehyde, dialdehyde, N-methylene compounds, di carboxylic acid, dicarboxylic acid chloride, bis-halogeno compounds bis, epoxide, bis-aziridine diisocyanate u. Ä. used become. The following is an example of a networking Polymer obtained in this way indicated:

In the above formula, block A is an alkyl radical which effects the already described change in the thermal state. Block B is the agent that crosslinks pairs of chain polymers (using diisocyanate as the crosslinking agent).

If you want to get a movie through networking, must to coat a substrate with a liquid, which is a mixture of the one already described Copolymer and a cross-linking agent is, and then it either heat or with electrons or light irradiate to obtain a crosslinked film.

For obtaining a polymer from a monomer on the As described above, a method is used which is suitable for the material and either Lö sungspolymerisation, electrolysis, Emul gierungspolymerisation, photopolymerization, radiation polymerization, plasma polymerization, graft polymerisa tion, or by plasma-induced polymerization, poly merization by vapor deposition u. Ä. Can be.

In the following, the connection shown in Fig. 1B will be described. Here, the materials given in formulas (XII), (XIII) and (XIV) are as follows:

Rf: alkyl radical with C₄ or more, or a functional Group including a fluorine or chlorine substituent tuierten alkyl residues or a hydrophobic residue with

(where l 4)
n : an integer greater than 1
X: chlorine, methoxy or ethoxy

It is desirable that this is a material which deals either physically or chemically an inorganic surface such as glass, metal, copper or another inorganic material or resin, Polyimide, polyester, polyethylene, terephthalate or the like is connected (and preferably to a material with a surface energy of about 50 dynes / cm or fewer).

Below are specific examples of the materials in the Formulas (XII), (XIII) and (XIV).

The compound shown in Fig. 1C may have a structure where only the material of the formulas (XII), (XIII) or (XVI) is present.

The following is a description of a recording material (A) using the compounds described above.

The configuration of the recording material (A) is such that it (1) is formed by the above-described surface component itself or (2) by the already described surface component on a support component (preferably, a heat-resistant support component). Those of the above-described compounds (surface components) relating to (1) have either a plate or a film form or may be formed as a cylinder. In this case, it is desirable that the film molds have a film thickness between 1 μm and 5 μm.

In the case of the compounds relating to (2), the above-described compound is allowed to penetrate a certain distance into the supporting body. It is desirable that the film thickness of the recording material (A) itself be between 30 Å and 1 mm. However, in terms of heat conduction, a film thickness between 100 Å and 10 μm is better, and in terms of frictional resistance, a film thickness between 10 μm and 1 mm is more favorable. It is desirable that the heat resistance temperature of the support body is between 50 ° C and 300 ° C.

The support body can be band, plate or cylindrical his. The shape of the support body can be adjusted according to the Select the intended use of the apparatus. Especially Zy Linder forms have the advantage of being dimensional Ge accuracy. In the case of plate forms becomes the size according to the order to be used drawing paper.

When the compounds described above (formed on the surface of the recording material (A) material) also with other components such. B. hydrophobic monomers and hydrophobic inorganic Ma terials mixed and out forms on a support component, it has the advantage that contamination of the base is prevented during printing.

In order to increase the thermal conductivity, may additionally Metal dust or the like with the compound described above be mixed. In addition, the liability between the support component and those described above Improve connections between the support layer and the compound a primer layer  be inserted. The heat-resistant protective layer can a polyamide, a polyester or another type of Resin film, glass, a metal such as Ni, Al, Cu, Cr. Pt. ä. or a metallic oxide. These support bodies can smooth, rough or porous.

The following is a description of the contact material (B) .

The contact material (B) is, as already described above, in its original state either a liquid or a vapor or a solid, which is finally at a temperature below the transition temperature from the beginning to reduce the return Kon contact angle R r in the recording material (A ) , becomes liquid. This vapor liquefies when at least a portion thereof condenses near the surface or on the surface of the recording material (A) . Then, this liquid is enough to wet the surface of the recording material (A) . On the other hand, the solid is either a substance which liquefies upon lowering of the initial temperature of the above-described returning contact angle R r , or generates a liquid or a vapor. The vapor generated by the solid condenses in the vicinity of the surface or on the surface of the recording material (A) and forms a liquid as described for the preceding example.

The following is a more detailed description of the contact material (B) :

The liquids constituting one of the contact materials (B) are water-soluble liquids in addition to water, which include electrolytes, ethanol, n-butanol and other alcohols, glycerine, ethylene glycol and other polyhydric alcohols, liquids of polarity such as e.g. As methyl ethyl ketones and other ketones, n-nonanes, n-octane and liquids without polarity such. As other chain hydrocarbons, cyclohexanes and other ring-shaped hydrocarbons, meta-xylene, benzene or other ring-shaped hydrocarbons include. Also, a substance which is a mixture of these substances is suitable. Also, various types of dispersed liquids and liquid inks may be used. However, liquids with polarity are more suitable.

In addition to water vapor, which may be one of the vapors constituting the contact material (B) , it is also possible to use a vaporized liquid as the contact material (B) . In particular, ethanol vapor and meta-xylene vapor, as well as other organic compound vapors (including those in mist form) can be used. The temperature of these organic vapors must be less than the softening point or lower than the melting point of the compound forming the surface of the recording material (A) .

Some of the solids from which the contact material (B) can be made are high-grade fatty acids, low molecular weight polyethylene, macromolecule gel (polyacrylamide gel, polyvinyl alcohol gel), silica gel and hydrogenated compounds.

Although it will be explained in more detail later, it is already stated here that the formation of the latent image and the development of the image takes place simultaneously when the contact material (B) is "a recording medium containing a colorant".

Below is a description of the heater.  

The heater can be a heater, a thermal head or be another contact heater, but also one Heating device without contact, the electromagnetic radiation used (such as laser light, infrared lamps or some of the light types are derived from a light source radiates and be bundled by a lens). In addition one can also by irradiation with a Electron beam or ultraviolet light to the Ver drive this invention when effective Erwär present.

In Fig. 2A, a film 2 of the above-described compound is formed to form a surface of a recording material (A) on a substrate l . This film surface is held in contact with a liquid 3 which is one of the constituents of the contact material (B) . When the film 2 is heated in this state, the returning contact angle R r of the surface of the film decreases. There is considerable wetting, and it recognizes the liability of the liquid speed. In addition, this film 2 is reheated with the liquid adhesion, either in the atmosphere, in a vacuum, or in an inert gas atmosphere ( FIG. 2B). When this is done, the returning contact angle R r is increased, and it can be seen that water is repelled.

It has already been mentioned that a method showing this phenomenon and similar phenomena has been described in Japanese Patent Laid-Open No. 54-41902. However, this described method differs from the method of this invention in that the recording material is effectively disordered and the mechanism obtains a layer of amorphous memory substance. That is, in the present invention, it is not possible to cause a state change of the surface of the recording material (A) without the presence of the contact material (B) . In addition, with the method described in Japanese Patent Publication No. 54-41902, it is not possible to reverse the method by a simple operation.

As shown in Fig. 3A, the liquid and 3 in contact with the film 2 corresponding to the picture-in formation, the heating takes place (Figure 3B as shown in Fig.) Is in the state where no liquid is present, the film 2 exposed according to the image information of a heat treatment. This is the same as if liquid 3 had been brought into contact with the film 2 when it was in a heated state.

The surface of the heated part film 2 becomes the area where the liquid adheres. In Figs. 3A and 3B, a heater turns on or off according to the image information. The liquid 3 , which comes from a liquid supply port 31 , is guided to the film 2 . Thermal radiation from an infrared heater 41 is radiated to the film 2 through a lens 5 and a shutter 6 .

The shutter 6 turns on and off according to the Bildin formation. Fig. 3A shows an example, where the heating of the film 2 by a carrier material l he follows. In the example shown in FIG. 3C, the heating takes place through the liquid 3 .

Fig. 4 then shows an example of changes in the contact angle for a water-soluble liquid on the film 2 for the state where a water-soluble liquid is brought into contact with the film 2 .

Further, the changes in the contact angle before and after the heating are shown, as well as in the case where this substance is further heated in air. In Fig. 4, O represents the advancing contact angle and Δ represents the returning contact angle.

If the returning contact angle is a high value of 90 ° or more, the surface is in general liquid repellent. Is the returning contact angle 90 ° or smaller, shows up on the surface Liquid adhesion.

In the state of contact with the contact material (B) , the heating temperature for the surface of the recording material (A) should be in the range between 50 ° C and 250 ° C. Preferably, this heating temperature is in the range of 80 ° C to 150 ° C. The heating time should be in the range of 0.1 m to 1 sec, but most preferably in the range of 0.5 m-sec to 2 m-sec. The heating time is determined as follows:

• 1) After heating the surface of the recording material (A) , the contact material (B) is brought into contact before the surface of the recording material (A) is allowed to cool again.
• 2) In the state where the contact material (B) is in contact with the surface of the recording material (A) , the surface of the recording material (A) is heated.

You can do either (1) or (2). When the latent image is to be erased, the surface of the recording material (A) in the state where the contact material (B) is not in contact becomes 50 ° C to 300 ° C, or more preferably 100 ° C to 180 ° C heated. In both cases, the heating time is between 1 m-sec and 10 sec or better, 10 m-sec and 1 sec.

The following is a description of the procedure for actually recording the image information on the surface of the recording material (A) .

As shown in Fig. 5A, the surface of the recording material (A) is heat-treated in accordance with the image signals in a liquid or vapor atmosphere, and on the surface of the recording material (A) to liquid adhesion regions are formed (a latent image, step 100 training). Thereafter, the process is continued such that a recording medium is brought into contact with this latent image area to cause the recording agent to adhere to the latent image area (development, step 102 ). The method of fixing (fixing, step 104 ) on the surface of the recording material (A ) is called a direct recording method. As shown in Fig. 5B, the surface of the recording material (A) is heated in accordance with the image signals in a liquid or vapor atmosphere, and on the surface of the recording material (A) Flüssigkeitsshaf are areas formed (formation of a latent image, step 100 ). Thereafter, processing is continued such that a recording medium is brought into contact with this latent image area to cause the recording agent to adhere to the latent image area (development, step 102 ). Subsequently, the recording medium on the surface of the recording material (A) is transferred to the recording paper by the so-called indirect recording method. Moreover, as shown in Fig. 5B, after the transfer of the recording medium, when it is again transferred to the latent image area, the recording material (A) is used as a printing plate in a printing process.

In addition, in the manner described above, and as shown in Fig. 5C, after transfer of the recording means (step 106 ), the surface of the recording material (A) on which the latent image is formed is subsequently heated in neither the liquid nor the vapor state the latent image is removed (erasure of the latent image, step 108 ), so that the recording material is suitable for reuse (ie, a repeated recording method).

Hereinafter, the structure of the recording mate rials (A) and the structure of a device is described, which performs the formation of images according to the recording method.

When the recording material (A) is a substance having a surface in which the returning contact angle becomes smaller when heated and brought into contact with a liquid [this will be hereinafter referred to as "film 2 " or "the surface of the film Recording material (A) "denotes], then the shape may be arbitrary. Accordingly, the recording material (A) may be either of a rigid cylindrical shape or a flexible film shape. A recording material having a rigid cylindrical shape (ie, a rigid cylinder around which a film 2 has been wound) allows easy control of the position and the like. Ä. By Be movement of the cylinder. Accordingly, it is desirable that a rigid cylinder is used as the recording material. Such a recording material can be produced by forming a film 2 on a support material. The formed body may even be the recording material itself. Specifically, the above-described recording material has technical weaknesses of a general nature, and it is therefore desirable that it is formed on a substrate. Even in cases where the molded body forms the recording material (A) , the film 2 must be formed on the surface thereof.

When a resin is used as a support material for the recording material, it is unlikely to have good thermal conductivity, and it will take some time for the surface of the recording material (A) to reach a temperature at which liquid adheres when heated , Therefore, a good heat conductor is used for the carrier material either completely or partially.

In Fig. 6A, a good conductor such. B. metal used as a carrier material (metal carrier material 11 ). An organic film 12 is vapor-deposited on this metal carrier material 11 and coated with a film 2 . By this construction, the speed of the heat conduction in the vertical direction can be increased. The organic film used is a polyimide, a polyester, a phthalocyanine, or the like. It is believed that the structure is sufficient even in cases where it is dealing with a relatively large printhead. However, it is not suitable for high-precision printing because the heat dispersion in both directions causes the areas where liquid adheres to increase. The structure shown in Fig. 6B has a good heat conduction area on a substrate 1 , which is separated by a partition wall, so that heat dispersion in both directions is prevented. This reduces the size of the area 2 a with the property of the liquid adhesion. In Fig. 6B, the divided by a partition wall and limited metal film 11 a is provided on a heater 4 .

The following is a description of the training mechanism of the latent image by heating. As already described, the heat source may be a heater, a thermal head or other type of contact heating, Laser beam, an infrared lamp or another type from heating without contact, the electromagnetic Radiation used.

The following is a description of the conceptual structure of the mechanism for heating the surface of the recording material (A) in the state where it is in contact with a liquid.

Also described is an example in which a recording material 7 of the type where the film 2 is formed on a substrate 1 is described.

As shown in Figs. 7A and 7B, the liquid 3 is always in a contact state with the lower surface of a recording medium 7 having a cylindrical shape. In this state, the recording material 7 , as it rotates, is selectively heated in accordance with the image information, from the side of the substrate 1 or the side of the liquid 3 . As indicated in FIG. 7C, the surface (film 2 ) of the recording material 7 is selectively heated in accordance with the image information and immediately thereafter brought into contact with the liquid 3 . As shown in Fig. 7D, one can use the laser beam from a laser light source 42 to selectively heat the surface of the recording medium 7 .

FIGS. 7A and 7B show a filled with the liquid 3 tub 35, which is mounted at the bottom of Aufzeichnungsma terials. 7 The lower surface of the recording material 7 is always in contact with the liquid 3 in the tub 35 . Then, a heat source (a thermal head 43 ) of the simplest structure is set up in the middle or near the tub 35 . Instead of the trough 35 , a sponge-like porous substance 34 filled with the liquid 3 may also be provided to make contact with the surface of the recording material 7 . In addition, it is also possible to heat the upper surface of the recording material 7 by an electron beam.

The surface of the recording material 7 is heated as described above and the liquid 3 is brought into contact therewith so that the areas where liquid adheres have a small returning contact angle R r and form the latent image.

A recording medium (ink) is applied to the liquid adhesion area selectively applied to the surface of the recording material 7 in accordance with the information signals and by the above-described mechanism. As shown in Fig. 8, a column filled with the recording means 3 a tray 36 is brought simple configuration in the direction of movement of the recording material 7 and with respect to the position of the latent image formation, so that the recording means 3 a constantly with contact the surface of the recording material 7 is.

When the recording material 7 rotates, the liquid is a recording medium 3 as to the liquid adhesion area described above (latent image) E is introduced. This recording means 3 a , which adheres to the surface of the recording material 7 forms a visible image. In Fig. 9, the liquid is drawing on a medium 3 in the tub 36 is filled and is in the state where the surface of the clot material is Aufzeich still in contact therewith. Then heated, the thermal head 43, the surface of the recording mate rials 7 selectively from the side of the recording medium 3 a. In the configuration shown in Fig. 9, the signal recording means 3 a enables the formation of a latent image and therefore makes it possible for the apparatus to be manufactured in a compact form.

Fig. 10 shows an example for the direct formation of a visible image on the surface of the material 7 Aufzeich voltage.

A film which may be flexible or rigid is used as the substrate 1 of the recording material. This substrate 1 and the film 2 formed thereon constitute the recording material 7 . The recording material 7 is applied at a constant speed by the rollers 37 and 38 . A porous roller 34 to which the recording medium 3 a has been applied is in contact with the surface of the recording material 7 (ie, the film 2 ). The side with the recording means 3 a opposite side of the recording material 7 is selectively heated according to image information by a thermal head. In the state in which the recording means 3 a is in contact with the recording material 7 , its heating triggers the image followed by the development of the latent image on the surface of the recording material 7 . Then, the force applied to the surface of the recording material 7 is recording means 3 (the latent image) is heated by an infrared heater 41 a, and dried. By this heating and drying, the recording medium adhering to the surface of the recording material is fixed. The drying of the recording medium 3 a can also take place naturally.

As described above, the recording material 7, a transparent film on which a recording medium 3 a was applied, as shown in FIG. 11, be used as a transparency film for the projection may be. That is, when light is emitted from a light source 53 mounted behind the surface of the recording material, the image on the recording material 7 is projected onto a canvas 52 . As shown in Fig. 12, it is also possible to use the recording material as the information storage medium. That is, in the state in which the disc-shaped recording mate rial 7 is rotated at a uniform speed by a motor 55 , a light beam from a laser light source 42 is directed thereto. By determining the light intensity, which is reflected in accordance with the presence or Nichtvorhan densein of the recording medium 3 a on the surface of the recording material 7, one can read the information.

Figs. 13 and 14 show an apparatus having a mechanism (an indirect recording mechanism) for transferring a visible image formed on a recording material to recording paper.

In the indirect recording for transmitting a visible image on recording paper, it is advantageous to use a rigid cylindrical tube as the carrier material 1 for the recording material.

Fig. 13 shows a printing apparatus. In Fig. 13, the recording medium 3 a is filled in the tub 36 . In the state where a lower surface of Aufzeichnungsma is terials 7 in contact with the recording means 3 a, the recording material 7 is rotated at a uniform Ge. A thermal head 43 heats the befin is in contact with the recording medium 3 a lethal surface of the recording material 7 in accordance with the image information. As already explained, adheres to the heated areas of the surface of the recording material 7, the recording means 3 a . Then, the recording medium 3 a adhering to the surface of the recording material is transferred thereto by the capillary action of the recording paper 61 passed between the recording material 7 and the transfer cylinder 62 . The position at which this transfer takes place can be either after development or any other desired position along the recording material 7 . However, it is preferable to carry out the transfer immediately after the development.

In the embodiment shown in Fig. 13, the device remains on recording medium 3 a itself after transfer on the surface of the recording material 7 in the adhesion area E. When this recording means 3 a is brought into contact in this region E , it adheres correspondingly again to this region E and is transferred again to the recording paper 61 . That is, the latent image is not erased from the surface of the recording material 7 , with the result that development and transfer can be performed several times, thereby enabling printing.

When the printing of image information is completed, the exchange of the recording material 7 or the erasure of the latent image makes it possible to print another image information.

Fig. 14A shows a recording apparatus for which different images can be formed one after the other.

The apparatus shown in Fig. 14A has the same mechanisms for forming, developing and transmitting a latent image as that of Fig. 13.

After the transfer, in the state where the liquid or the steam is absent, an infrared heater 41 is provided to heat the surface of the recording material 7 . By deleting the latent image from the surface of the recording material 7 , it becomes possible to reuse it.

In the state where the liquid or the vapor is absent, that is, in air, in a vacuum or in an atmosphere of an inert gas, the latent image is also erased by heating the latent image area from the surface of the recording material 7 . The heater may be a heater, a thermal head or other type of contact heater, but also a non-contact heater that uses electromagnetic radiation. The heating can be carried out on the entire surface or only in the region of the latent image. However, one can also take a simpler mechanism in which the entire surface is heated. In addition, when the latent image erasing mechanism for this purpose carries out the heating, the surface of the recording medium 7 is effectively cooled to a normal temperature until the next image is formed. The warming temperature required for erasure varies depending on the material of the upper surface of the recording material 7 . This heating temperature should be most favorable below the decomposition point and above the starting temperature for the reduction of the returning contact angle R r of the material of the surface of the recording material 7 .

The recording paper (transfer material) can be transparent resin film, plain paper, inkjet paper, typewriter paper or similar.  

Fig. 14B shows a recording apparatus which can form successively different latent images in the same manner as shown in Fig. 14A. In the apparatus shown here, the processes for the formation and the development of the latent image are not performed simultaneously, as is the case with the apparatus shown in Figs. 13 and 14.

In Fig. 14B is a soaked with fluid 3 porous sponge roller 34 is mounted in a position that a filled tray is with respect to the rotational direction of the drawing on the medium 3 forward. In addition, a thermal head 43 is mounted in a position near the front side with respect to the rotational direction of the porous sponge roller 34 . The liquid 3 in the porous sponge roller 34 is always in contact with the surface of the recording material 7 , which is selectively heated by the thermal head according to the image information and has liquid adhesion through contact with the liquid 3 . This area E becomes the latent image. The thus formed image is developed by the recording means 3 a. Then, the visible image obtained by the development of the latent image is transferred to the recording paper 61 . The processes after the transmission are the same as in the apparatus shown in Fig. 14A.

In the apparatus shown in Fig. 14B, the thermal head 43 (the heat source) is not mounted within the recording by means of 3 a , thereby preventing its deterioration by heat. Under remains a damage of the thermal head 43 by the information contained in the recording medium 3 a chemical substances.

The description of the recording medium follows.

In the recording method according to the present invention, the visible image on the surface of the recording material 7 can be obtained by selectively using either ink for writing, ink jet printing ink, printing ink, electrostatic transfer toner or certain other recording mediums. as used in conventional printing processes.

In the case of the particular example of water-soluble inks, it is therefore possible, water-soluble inks, the water and humectants as the Main components include water-based pigmented dispersion inks, the water, pigments, macromolecular compounds for the dispersion and Humectants are included as the main components, or emulsion pressure to use inks in which pigments or dyes the surface acti fourth agents dispersed in water. The in inks on Water-based humectants may be agents from the group of the following water-soluble organic compounds:

Ethanol, methanol, propanol and other monohydric alcohols; Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycerol and other polyhydric alcohols, ethylene glycol monomethyl ester, diethylene glycol monomethyl ester, triethylene glycol monomethyl ester, tetraethylene glycol monomethyl ester, propylene glycol monoethyl ester, ethylene glycol ester, diethylene glycol monomethyl ester, triethylene glycol monomethyl ester, tetraethylene glycol monomethyl ester, propylene ethylene glycol monomethyl ester and other esters of monohydric alcohols; N-methyl-2-pyrrolidone, 1,3-dimethylimidazolirricone, ε- caprolactam and other heterocyclic compounds, monoethanolamine, diethanolamine, triethanolamine, Mo noethylamin, diethylamine, triethylamine and other amines.

The water-soluble pigment can be a pigment that is colored by the color index (color index) into the group of acid pigments, direct pigments, chlorine radical pig pigments, reaction pigments and food pigments is divided.

C.I. Acid Yellow: | 17, 23, 42, 79, 142; C. I. Acid Red: 1, 8, 13, 14, 18, 26, 27, 35, 37, 42, 52, 82, 87, 89, 92, 97, 106, 111, 114, 115, 134, 186, 249, 254, 289; C. I. Acid Blue: 9, 29, 45, 92, 249, 890; C. I. Acid Black: 1, 2, 7, 24, 26, 94; C.I. Food Yellow: 3, 4; C. I. Food red: 7, 9, 14; C. I. Food Black: 2; C.I. Direct Yellow: 1, 12, 24, 26, 33, 44, 50, 142, 144, 865; C. I. Direct Red: 1, 4, 9, 13, 17, 20, 28, 31, 39, 80, 81, 83, 89, 225, 227; C.I. Direct Orange: 26, 29, 62, 102; C. I. Direct Blue: 1, 2, 6, 15, 22, 25, 71, 76, 79, 86, 87, 90, 98, 163, 165, 202; C. I Direct Black: 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168; C.I. Base Yellow: 1, 2, 11, 14, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 40, 41, 45, 49, 51, 53, 63, 65, 67, 70, 73, 77, 87, 91; C.I. Base Red: 2, 12, 13, 14, 15, 18, 22, 23, 24, 27, 29, 35, 36, 38, 39, 46, 49, 51, 52, 54, 59, 68, 69, 70, 73, 78, 82, 102, 104, 109, 112; C.I. Base 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, 120, 122, 124, 129, 137, 141, 147, 155; C.I. Base Black: 2, 8 and the same.

The pigment can be an organic pigment. In question, for example azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone Pigments, dioxazine pigments, indigo pigments, dioindigo pigments, Perynon pigments, perylene pigments, iso-indolenone pigments, aniline black, Azomethine azo pigments, carbon black and others. The inorganic pigments can iron oxide, titanium oxide, calcium carbonate, barium sulfate, ammonium hydroxide, Barium yellow, Prussian blue, cadmium red, chrome yellow and metal powder.

The dispersed pigment compounds may be the following: poly acrylamide, polyacrylate and their alkali metal salts, soluble styrene-acrylic resins and resins of their acrylic family, soluble vinyl-naphthalene acid resins, Polyvinylpyrrolidone, polyvinyl alcohol and its alkali metal salts, makromo lecular compounds containing salts with cationic functional groups such as For example, include ammonium and amino radicals, etc., Polyethy lenoxides, gelatin, casein and other proteins, gum arabic, rubber and other natural gums, saponin and other glycoxides, carboxyms cellulose, hydroxyethylcellulose, methylcellulose and other cellulose in fertilizers, lignosulfonic acids and their salts, ceramics and other natural products macromolecular compounds and the like.

The oil-based recording agents may be opened as in the case of the inks Water-based, those in which a lipophilic pigment in an organic Compound is dissolved, or those in which a pigment in an orga nischer compound is dispersed, or be those in which a pigment or a coloring agent is emulsified in an oily base, and the like. Representative examples of oil-based pigments are the following:

CI Solvent Yellow: | 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 16, 17, 26, 27, 29, 30, 39, 40, 46, 49, 50, 51, 56, 61, 80, 86, 87, 89, 96; C. I. Solvent Orange: 12, 23, 31, 43, 51, 61; C. I. Solvent Red: 1, 2, 3, 16, 17, 18, 19, 20, 22, 24, 25, 26, 40, 52, 59, 60, 63, 67, 68, 121; C. I. Solvent Violet: 7, 16, 17; C. I. Solvent Blue: 2, 6, 11, 15, 20, 30, 31, 32, 36, 55, 58, 71, 72; C.I. Solvent Brown: 2, 10, 15, 21, 22; C. I. Solvent Black: 3, 10, 11, 12, 13.

In addition, oil-like raw materials in which a pigment is dissolved close or in which a pigment is dispersed, the following compounds: n- Octane, n-decane, Milanese spirit (milanese spirit), ligroin, naphtha, benzene, Toluene, xylene and other hydrocarbons; Dibutyl ether, dihexyl ether, Anisole, phenetole, dibenzyl ether and other elastomers; Methanol, ethanol, isopro pyl alcohol, benzyl alcohol, ethylene glycol, diethylene glycol, glycerin and others Alcohols.

It is also possible to use the pigments described above just as for printing inks to use oil-based. Examples of Pigment Dispersants on Oil Ba The following compounds include: polymethacrylate ester, poly acrylate esters, copolymers of methacrylate esters and acrylate esters, ester cel cellulose, methylcellulose and other cellulose resins, polyester, polyamide, phe nolharze and other polymer resins, pine rosin, ceramics, gelatin, Casein and other natural resins and the like.

Examples Example 1

The film material (the material of the surface of the recording material (A) ) is a water and oil repellent "TG-702" or "TG-602" as sold by Daikin Manufacturing Co., Ltd. will be produced. This is an acrylate material that includes fluorine. This liquid starting material was diluted to double volume with Freon TF (manufactured by Mitsui Fluoro Chemical Co., Ltd.). Thereafter, it was coated on a polyimide film (manufactured by Toray-Dupont Co., Ltd., 200V), and then dried at 90 ° C for 2 hours to form a film of approximately 1 μm in thickness. Thereafter, the material was as shown 3 A in Fig., In the state in which the surface of the film 2 in contact with a liquid 3 (pure water) was heated from the side of the polyimide film 1 by using a ceramic heater 4 (heating temperature 120 ° C, time: approximately 1 second). Before and after this heating, a noticeable decrease in the return contact angle of the surface of the film 2 was observed due to the presence of pure water for the material (surface energy: approximately 10 dynes / cm). This means that the upper surface of the film 2 had deposited the water. In addition, when the film 2 was left in this state, the liquid adhesion remained.

In addition, the same effect was observed when instead of pure water, n-nonane, m-xylene or other non-polar liquid or n-butanol or other polar liquid was used. Moreover, in cases where n-butanol or m-xylene was used, the contact angle was measured as shown in FIGS. 15 and 16.

example 2

The film material (the material of the surface of the recording material (A) ) is a water and oil repellent "FURORAD FC-720" manufactured by Sumitomo-3M. This is an acrylate material that includes fluorine. This water and oil repellent agent was coated on a polyimide film (manufactured by Toray-Dupont Co., Ltd., 500 H) and then dried at 90 ° C for 2 hours to form a film of approximately 3 μm in thickness. Thereafter, as shown in Fig. 13, this film was roll-formed and wound around an aluminum cylinder having a diameter of 100 mm and a length of 100 mm to prepare a recording material A. The heating zone of a thermal head for a thermal transfer printer was arranged to be in contact with the film. In addition, this thermal head was also so arranged with respect to the ink receptacle container (ink receptacle vat) that it was in contact with the recording dye. The material used as the liquid ink was a phthalocyanine type cyan ink (having a dye concentration of 1% by weight, the solvent being a concentrated aqueous solution containing 0.05 mole of NaOH).

The moment the appropriate electrical signals of the image information were fed to the thermal head to cause it to heat up, the ink only adhered to the parts that had been heated. Further, when recording paper 61 (manufactured by Mitsubishi Paper Manufacturing Co., Ltd., NM-coated paper) was brought to be in contact with the cylindrical recording material, the ink was transferred onto the paper, as shown in FIG. 13 is indicated. After this step, the part of the recording material A to which the ink had been transferred showed adhesion of the ink when left in the state. This recording device thus functioned as a printing device.

example 3

The preparation of the film 2 on a polyimide substrate was carried out under the same conditions as in Example 1. Further, in the same manner as in Example 1, heating was performed at the moment when the liquid was in the state of contact and the surface of the film 2 showed liquid adhesion. As shown in Fig. 14, this liquid-adhesion-exhibiting film and the surface of the recording material (A) were heated in air with an infrared lamp to a temperature of approximately 130 ° C for a period of approximately 1 second. As shown in Fig. 4, it was observed that the returning contact angle due to the heating of the recording material (A) in the state of contact with the liq fluid was smaller and then to an angle before heating in the state of contact with the liquid by heating the recording material in the air returned. This means that the liquid repellency has been reversed. It was confirmed that the image information could be picked up and deleted from the results of this series of operations.

example 4

After the operations described in Example 2, durchge had been used, a ceramic heater was used to make a uniform Heat-up in air to clear the pattern, for which the ink had adhered. In this way it was possible Information of different nature on a recording paper from Format A4 to print.

example 5

A polycarbonate film (2 cm × 2 cm × 100 cm) was used as a substrate. The material used for the film 2 was "Dyefree MS-443" or "Dyefree MS-743" manufactured by Diakin Manufacturing Co., Ltd.

This base liquid was mixed with carbon black (ASTM name: N 330) in an amount of 0.5% by weight. This mixed liquid was cast into a polycarbonate film to produce a film having a thickness of approximately 10 μm. The surface energy of this film 2 was measured; the reading was approximately 20 to 30 dynes / cm. The source of electromagnetic waves was a semiconductor laser (manufactured by Matsushita Electronic MFG Co., Ltd., LN 9850, 50 MW). The material used as a liquid printing ink was a phthalocyanine-type cyan printing ink (solvent: aqueous solution containing 0.05 mol of NaOH). This ink was coated as a layer on the entire surface of the film 2 , and the irradiation of laser light focused by a lens was made from the side of the polycarbonate film. At the time when the ink was removed, it was confirmed that the ink had adhered only to those parts of the film 2 which had been irradiated with laser light.

example 6

After the procedures of Example 1 were carried out, the ink remaining (recording medium) was removed by washing with water. Thereafter, the surface of the film 2 was dried, and radiation of a laser beam from a semiconductor laser was again directed to these parts in the air. After a few seconds, ink was again applied to the surface of the film 2 , and there was no adhesion of the ink to those parts which had been irradiated. This means that it was confirmed that the image information had been deleted.

example 7

The material used as the surface of the recording material (A) was a monomer called "Viscoat 17 F" manufactured by Osaka Organic Chemical Co., Ltd. was produced. This material was used as the polymer after solution polymerization using 1,1,1-trichloroethane as a liquid was carried out. In addition, a 0.2 mm thick aluminum foil was used as a substrate, and the polyimide layer was spin-coated on this aluminum foil. On top of this polyimide layer, a layer of the solution of the material for the surface of the recording material (A) was applied after being diluted to twice the volume. The film was dried at 90 ° C for 2 hours, and a film of approximately 1 μm in thickness was prepared. The film had a surface energy of approximately 10 dynes / cm. Pure water was placed on top of the film 2 and heated by a thermal printer for heat transfer from the side of the substrate. Measurements of the return contact angle of the surface of the recording material before and after the heating showed that it was possible to achieve a remarkable reduction in the return contact angle for a ten times shorter heating time as compared to Example 2. The surface of the film 2 showed the adhesion of a clear liquid.

example 8

On a surface of a polyimide sample having a thickness of approximately 50 .mu.m and having sides of approximately 50, 75, 100 and 15 .mu.m was an Alumi nium pattern with a height of approximately 50 microns and at a distance of 200 dpi in the direction of Scanning (scan) of the electrical signal formed. Thereafter, the same procedure as described in Example 1 was carried out. There was thus formed a film 2 of a recording material (A) on the surface opposite to the surface having the pattern. Ink ink was applied to this surface, and the surface was brought into contact with a thermal head for a 200 dpi thermal transfer printer having approximately 100 μm × 200 μm thermal pixels and heated. After heating, the state of adhesion of the ink to the film 2 was observed under a microscope, and in the case of a pattern of approximately 150 μm square, it was observed that printing ink had been applied there almost continuously despite the fact that they were not heated areas between the patterns were only approximately 100 microns wide. This can be interpreted in terms of its meaning in such a manner that the heat in the process steps in which the heat is scattered into the surface of the recording material (A) and the polyimide film from the heated aluminum pattern is scattered in the direction of the primary scanning , In the case of a pattern having a size of approximately 75 μm square, the measure of the part of liquid adhesion was the degree of the heating element.

example 9

The recording material (A) used was a film on which the film 2 prepared in accordance with Example 1 was coated. As shown in Fig. 17, on the film 2, an ink supplying portion is provided, and on the immediately adjacent film, a thermal head is placed in contact with the film. The liquid 3 a is a printing ink using n-octane as a liquid printing ink and carbon black as a pigment.

The film is moved in the direction indicated by the arrow while the thermal head is operated together with the image information. The ink 3 b adheres to the film 2 in accordance with the Bildinfor mation and acts as a recording material (A) .

After this adhered ink 3 b was transferred onto the recording paper 61 , the ink adhesion of the film 2 remained. Moreover, when the film 2 was heated in air, the color adhesion disappeared.

A printing ink in which carbon black as a pigment and benzene as a solvent Ver find a use, as well as a printing ink, in the methyl isobutyl ketone as Solvent use leads to the same result as above given.

example 10

An acrylate ester copolymer having a perfluoroalkyl group having numerous hydroxyl functional groups was used; This is from the company Mitsubishi Rayon Co., Ltd. manufactured under the name "AR-989". This initial liquid was diluted to twice the volume with xylene, and 90 mg of toluenediisocyanate was used as a crosslinking agent on 3 g of the diluted liquid; the product was dried. A glass plate was used as a substrate of the recording material (A) . Thereafter, it was heated to 110 ° C for 1 hour. The film 2 thus prepared showed a surface energy value of 30 to 40 dyn / cm when measured.

Thereafter, this film was brought into contact with the liquid at a thickness of approximately 10 μm and heated (at 100 ° C for 1 second). The variations in the contact angle in the case before and after the heating and the variations in the contact angle in the case of heating in pure water over the case when another heating operation in the air (for 1 second at 120 ° C) was performed shown in FIG . As shown in Fig. 18, heating in the liquid and heating in air indicate that the water repellency and the liquid adhesion of the liquid on the surface of the recording material (A) change in such a manner that they are reversed. Thereafter, uncoated paper was used for photocopying at a pressure of 20 gf, and no scratches or scratches were observed when rubbed on the surface of the film 2 .

example 11

A recording material (7) prepared under the same conditions as in Example 10 was used, and printing was performed as shown in FIG . A thermal head 43 was used as a heat source. Water-soluble ink 3 a was dropped on the recording material, and the surface of the film 2 was brought into contact with the recording material. The moment the image signals were transferred to the thermal head 43 and heat was applied to the surface of the recording material (A) via the water-soluble ink 3 a , the ink was caused to adhere to the surface of the film 2 .

example 12

The material for the film 2 was a copolymer prepared from perfluoromethyl methacrylate monomer and methyl methacrylate monomer ("Viscose 17 F", manufactured by Osaka Organic Manufacturing Co., Ltd.) and 06945 00070 552 001000280000000200012000285910683400040 0002004010275 00004 06826d 1,1,1-trichloroethane as a liquid. This was then dissolved in Freon 113, and a coating liquid containing 7% by weight was prepared. This coating liquid was then poured on a polycarbonate plate having a thickness of 1 mm, and this was dried to form the recording material. The surface energy of the film 2 of the recording material was measured; this resulted in a value of approximately 10 dynes / cm. This recording material was then heated by means of a thermal head using the apparatus shown in Fig. 10 in accordance with the image signals, and then dried using an infrared lamp. The ink used was a water-soluble ink using a black acid dye.

example 13

The material for the film 2 was a copolymer prepared from perfluoroalkyl methacrylate monomer and methyl methacrylate monomer ("Viscoat 17 F" manufactured by Osaka Organic Chemical Co., Ltd.) and a methyl methacrylate monomer in a molar ratio of 1: 1. The recording material was precipitated This material, which had a surface energy of approximately 10 to 20 dynes / cm, was prepared in the same manner as in Example 1. This recording material was evaluated as having advantageous functions.

example 14

A copolymer was prepared by solution polymerization using a n- Butylmethacrylatmonomers produced. This material (with a surface energy of approximately 30 to 40 dynes / cm) was in contact with pure water in the same manner as in Example 1 and brought to a temperature heated above 180 ° C. It consequently showed fluid bath häsion.  

example 15

A polished platinum plate was used as a substrate for the recording material. This platinum plate was preheated to 60 ° C, and solid CF₃ (CF₂) ₆COOH (fixed at 25 ° C) was placed thereon. 10 minutes later, the molten CF₃ (CF₂) ₆COOH was removed with a platinum wire and thus formed the above compound in a single molecular layer (film 2 ) on the paltin. After the formation of the film, the returning contact angle of the surface of the recording material (A) for n-octane was approximately 60 °. This recording material (A) was heated to 80 ° C on contact with n-butane. The contact angle became approximately 40 ° and the recording material (A) exhibited adhesion with respect to n-octane.

Further, after the n-octane was removed, the above-described recording material (A) was heated in air at 80 ° C for 1 second. After cooling, the returning contact angle with respect to n-octane is approximately 60 °.

example 16

Poly (perfluorooctylcarbamoyl methacrylate) was used as the compound the surface self-orientation shows. Perfluoroctylcarbamoylmethacrylat was used as the monomer.

This compound was heated in ethyl acetate ester at 80 ° C for 15 hours and agitated to produce the polymer described above. The resulting Substance was purified by monomer resedimentation.

This polymer was dissolved in a mixed liquid of benzotrifluoride: dissolved 1, and this liquid (the film 2 forming liquid) was poured imide film on a poly heated to 100 ° C for 90 minutes to: He xafluorxylol: ethyl acetate in a mixing ratio of 1: 1 to dry them and to form the recording material (A) . This was then brought into contact with pure water and warmed up in the same manner as in Example 1. Water-soluble ink adhered to the heated parts.

Further, after the printing ink was removed, the surface of the recording material (A) was heated at 130 ° C for 10 seconds, and the recording material (A) exhibited water repellency.

example 17

Vinyl-n-heptafluorobutyrate,

was used as a monomer. 2 g of this monomer and 0.08 g of acetyl peroxide (25% liquid) were heated together with dimethyl phthalate and agitated at 45 ° C for 15 hours to prepare a polymer. This was stretched in the direction of the molecules to form a film, which itself was used as recording material (A) . As in Example 1, this recording material (A) was then heated in accordance with the image signals through a water-based ink. There was some adhesion of the ink to the heated spots.

Comparative Example 1

A perfluoromethyl methacrylate monomer having a carbon number of 2 ("Viscoat 3 FM"; manufacturer: Osaka Organic Chemical Co. Ltd.) and the procedure was as described in Example 12 carried out. The functions of a recording medium showed this mate rial, however, not.  

Comparative Example 2

Using a methyl methacrylate monomer, a copolymer was prepared, and the process steps described in Example 1 were carried out to prepare the recording material (A) for a second comparison. After the recording material was brought into contact with the liquid heated at 200 ° C and heated, there was still no change in the contact angle before and after the surface of the recording material was warmed up.

Comparative Example 3

Polystyrene and polycarbonate, which are materials having no alkyl functional groups, were used for the same process steps as in Example 1 to prepare a recording material (A) for comparison. These materials were evaluated. There was no change in the returning contact angle for the case before and after the heating in the state of contact with the liquid.

Comparative Example 4

A copolymer of vinyl alcohol and a methyl methacrylate monomer ("Viscoat 17 F" manufactured by Osaka Organic Chemical Co., Ltd.) was formed on a support substrate to prepare the recording material (A) . Film 2 had a surface energy of 55 dynes / cm. This film 2 was brought into contact with a water-soluble ink ( γ = 45 dyn / cm). It showed an adhesion of the ink on the entire surface.

Claims (27)

A recording method comprising, in an arbitrary order, the following steps (a) and (b):

• (a) contacting a contact material (B ; 3 ) with a surface of a recording material (A ; 2 ), the surface having a characteristic in which the returning contact angle becomes small when the recording material (A ; 2 ) is brought into contact with a liquid and in the heated state, wherein the contact material (B ; 3 ) is selected from a liquid or a vapor or a solid tur conditions under tempera below a temperature at which the return Kon contact angle of the recording material (A 2 ) begins to decrease, forms neither a vapor or a liquid or changes to, and
• (b) selectively heating the surface of the recording material (A ; 2 ) in accordance with image information;
• wherein a portion as a latent image on the surface of Aufzeichnungsma terials, is formed of the receding contact angle corresponding to a temperature of the recording material (A 2) (A 2) which is obtained (by selectively heating the surface of the recording medium A, 2 ) in accordance with image information.

2. Recording method according to claim 1, characterized in that Step (a) expires before step (b). 3. Recording method according to claim 1, characterized in that Step (b) expires before step (a).   The recording method according to claim 1, characterized in that the recording method further comprises a step of removing the contact material (B ; 3 ) from the surface of the recording material (A ; 2 ) and heating the surface of the recording material to obtain the latent image Clear. 5. A recording method according to claim 1, characterized in that the recording method further comprises a step (102) of supplying a recording means (3 a), which includes a colorant, comprising the surface of the recording material on which a latent image has been formed, the latent To dye picture with the dye. A recording method according to claim 4, characterized in that the recording method further comprises a step ( 104 ) of fixing a visible image on the surface of the recording material developed on the surface of the recording material (A ; 2 ). A recording method according to claim 5, characterized in that the recording method further comprises a step ( 106 ) of transferring a visible image developed on the surface of the recording material (A ; 2 ) to a medium ( 61 ) for image transfer and fixing of the visible image on a surface of the medium ( 61 ) for image transfer. A recording method according to claim 1, characterized in that the surface of said recording material (A ; 2 ) comprises an organic compound including a hydrophobic radical, said hydrophobic radical being of a nature orienting to a side Air is open when the surface of the recording material is heated in air. 9. Recording method according to claim 8, characterized in that the organic compound has a molecular chain structure with a hydrophobic Radical at the ends of the chains, wherein the chain molecules an Al kylenradikal with a number of carbon atoms of 4 or more and the surface energy of the organic compound is 50 dyne / cm or less. 10. Recording method according to claim 8, characterized in that the organic compound has a molecular chain structure with a hydrophobic Radical at the ends of the chains, wherein the chain molecules an Al in which a fluoride contains at least one hydrogen Has replaced alkylene group and which has a number of carbon atoms of 4 or more, and wherein the surface energy of the organic Ver bond is 50 dyn / cm or less. 11. Recording method according to claim 8, characterized in that the organic compound is an alkyl group having a number of carbon atoms of 4 or more and the surface energy of the organic Compound is 50 dyn / cm or less. 12. Recording method according to claim 8, characterized in that the organic compound includes an alkyl group in which a fluoride is at least has replaced a hydrogen of the alkyl group and a number of Having carbon atoms of 4 or more, and the surface energy of organic compound is 50 dyn / cm or less. 13. Recording method according to claim 8, characterized in that the organic compound includes an alkyl group in which a chlorine atom has replaced at least one hydrogen of the alkyl group and a number of carbon atoms of 4 or more, and the surface energy the organic compound is 50 dyn / cm or less.   14. Recording method according to claim 8, characterized in that the organic compound includes an alkyl group in which a chlorine and a Fluorine atom have replaced at least two hydrogens of the alkyl group and the has a number of carbon atoms of 4 or more, and the upper surface energy of the organic compound is 50 dyn / cm or less. 15. A recording method comprising, in an arbitrary order, the following steps (a) and (b):

• (a) In contacting a recording medium (3 a), which includes a colorant, with a surface of a recording material (A 2), said surface having a characteristic in which a back traveling contact angle is lowered when the recording material ( a; 2) is brought into contact with a liquid and when it is in the heated state.
• (b) selectively heating the recording material in accordance with image information,
• wherein a visible image of the colorant is formed on the surface of the recording material (A ; 2 ) in a region having a returning contact angle corresponding to a temperature of the recording material (A ; 2 ) obtained by selectively heating the surface of the recording material (A ; 2 ) in accordance with image information.

16. Recording method according to claim 15, characterized in that Step (a) expires before step (b). 17. Recording method according to claim 15, characterized in that Step (b) expires before step (a).   18. Recording method according to claim 15, characterized in that the recording method also includes a step of removing the up drawing means from the surface of the recording material and the Er warming the surface of the recording material to cover the area Clear. The recording method according to claim 15, characterized in that the recording method further comprises a step ( 104 ) of fixing the visible image developed on the surface of the recording material (A ; 2 ) on the surface of the recording material (A ; 2 ) summarizes. A recording method according to claim 15, characterized in that the recording method further comprises a step ( 106 ) of transferring a visible image developed on the surface of the recording material (A ; 2 ) to a medium ( 61 ) for image transfer and fixing of the visible image on a surface of the medium ( 61 ) for image transfer. The recording method according to claim 15, characterized in that the surface of said recording material (A ; 2 ) comprises an organic compound including a hydrophobic radical, said hydrophobic radical being of such a nature as to orient to a side is open to air when the surface of the recording material is heated in air. 22. Recording method according to claim 21, characterized in that the organic compound has a molecular chain structure with a hydrophobic Radical at the ends of the chains, wherein the chain molecules an alkylene radical having a number of carbon atoms of 4 or more and the surface energy of the organic compound is 50 dyne / cm or less.   23. Recording method according to claim 21, characterized in that the organic compound has a molecular chain structure with a hydro phobic radical at the ends of the chains, wherein the chain molecules an alkylene group in which a fluoride contains at least one water Substance of the alkylene group has replaced and the surface energy of the organic Compound is 50 dyn / cm or less. 24. Recording method according to claim 21, characterized in that the organic compound includes an alkyl radical having a number of Having carbon atoms of 4 or more, and the surface energy of organic compound is 50 dyn / cm or less. 25. Recording method according to claim 21, characterized in that the organic compound includes an alkyl group in which a fluoride has replaced at least one hydrogen of the alkyl group, and a number of carbon atoms of 4 or more, and the surface energy the organic compound is 50 dyn / cm or less. 26. Recording method according to claim 21, characterized in that the organic compound includes an alkyl group in which a chlorine atom replaced at least one hydrogen of the alkyl group and a number of Having carbon atoms of 4 or more, and the surface energy of organic compound is 50 dyn / cm or less. 27. Recording method according to claim 2, characterized in that the organic compound includes an alkyl group in which a chlorine and a Fluorine atom replace at least 2 hydrogen atoms of the alkyl group and the has a number of carbon atoms of 4 or more, and the upper surface energy of the organic compound is 50 dyn / cm or less.