JPH06312523A - Color material transferring and recording method through voltage impression - Google Patents

Abstract

PURPOSE:To provide a color material transferring and recording method wherein a high quality color recorded image can be formed easily and at ease by a simple device. CONSTITUTION:A latent image consisting of different regions having respectively TCH of the phase transition temperature Tc and TCL of the phase transition temperature Tc is formed on an image carrier by application of an image response voltage to the image carrier consisting of a high polymer gel layer 2 with phase transition performance wherein the gel layer can be oxidized or can be reduced electrochemically between two phase transition temperatures of TCH and TCL (TCH>TCL) of the phase transition temperature Tc, the image carrier is set to a temperature between TCH and TCL, and the latent image is converted into an image consisting of a phase transition region and non-phase transition region. An actualized image by the color material is formed by feeding a color material solution having different absorption function of the color material against the phase transition region and non-phase transition region to the converted latent image, a lowering of the color material absorption function in a region herein the color material is absorbed is executed, a transfer paper 22 is made to abut on the image carrier and the actualized image by the color material is transferred onto the transfer paper 22. These processes are executed in order.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color material transfer recording method for transferring a color material image formed according to the application of an electric potential to a transfer material, and more specifically, the wettability change of the color material by applying the electric potential. And a color material transfer electrification recording method using a novel transfer medium in which the transition temperature of adsorption / desorption behavior changes.

[0002]

2. Description of the Related Art Currently, the main qualities required for recording devices are resolution, density, sharpness, gradation expression, color purity, color superimposition and the like. The performance of the recording device is high recording speed, quiet sound, low running cost, small size and light weight, plain paper and recycled paper, maintenance free, etc. Is required. In particular, recently, the basic characteristics of a recording device, such as resolution, density, and recording speed, have risen to a certain level. In addition to these, color expression is possible, and recording paper can be freely selected. Small size and light weight are especially emphasized.

Although various recording methods have been proposed so far, a color plain paper recording apparatus which generally satisfies the above-mentioned requirements has not been realized yet. For example, the electrophotographic method has a problem in gradation expression, and since the mechanism is complicated, it is inevitable that the apparatus becomes large. The thermal fusion transfer method has difficulty in gradation expression, high running cost, and poor printing quality on rough paper. The inkjet method has a problem in gradation expression and has a demerit that the sharpness is lowered due to ink bleeding.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a color material transfer recording method capable of easily and inexpensively forming a high quality color recorded image with a simple apparatus.

[0005]

According to the present invention, the phase transition temperature can be reversibly changed between two phase transition temperatures TCH and TCL (where TCH> TCL), and the electrochemical An electric potential corresponding to image information is applied to an image carrier having a temperature-sensitive phase-transition polymer gel layer that changes between TCH and TCL by redox, and the phase transition temperature Tc is applied to the image carrier. Forming a latent image consisting of different regions, respectively TCH and TCL,
Setting the temperature of the image carrier at a temperature between the TCH and the TCL to convert the latent image into a latent image including a phase transition region and a non-phase transition region; and the conversion of the latent image to the phase transition. Supplying a coloring material solution having a different coloring material adsorption ability to the area and the non-phase transition area to form a visible image with the coloring material corresponding to the image information; An image is recorded by sequentially performing a step of lowering the material adsorption ability and a step of bringing a transfer paper into contact with the image carrier to transfer a visible image of the color material onto the transfer paper. A transfer energization recording method is provided.

In the present invention, the image carrier (also referred to as a transfer medium) is a temperature-sensitive polymer gel that causes a phase transition, and the phase transition temperature Tc changes between TCH and TCL by applying an electric potential. Possible polymer gel layers are used.

This temperature-sensitive polymer gel layer is a polymer having a functional group which is easily redox-reduced in a part thereof, and has a phase transition temperature between TCH and TCL due to oxidation-reduction of the functional group due to application of a potential. Changes reversibly.

An electric potential image corresponding to the recorded image is applied to the polymer gel layer having this functional group to form regions having different phase transition temperatures. Then, the polymer gel layer is heated to an appropriate intermediate temperature between TCH and TCL to form a phase transition region corresponding to the recorded image, and the surface wettability and the adsorptivity of the phase transition region and the non-phase transition region are formed. By making use of the difference between the two, the color material image pattern is formed on the gel layer by once contacting the color material liquid and then separating. After that, the polymer gel layer is changed to a phase with low surface wettability and adsorption of the coloring material, and the coloring material formed on the gel surface is brought into a weakly adhered state and brought into close contact with the transfer material such as paper to transfer the coloring material. To do. A potential having a polarity opposite to the recording potential is applied to the polymer gel layer to initialize it, and the steps are sequentially repeated.

[0009]

Embodiments of the present invention will be described below with reference to the drawings. The same parts are denoted by the same reference numerals throughout the drawings. Examples 1 and 2 are examples in which an aqueous gel is used as the polymer gel that is the transfer material, and an oil-based coloring material is used as the coloring material. In Examples 3 and 4, the same aqueous gel is used as the polymeric gel, This is an example in which an aqueous coloring material is used as the coloring material. Example 1 FIG. 2 shows a transfer medium (image carrier) 11 of the present invention. As shown in FIG. 2 (b), this transfer medium has a polymer gel layer 2 formed on a sheet-shaped base material (support) 1 as shown in FIG. 2 (a). The polymer gel layer 2 may be formed on the base material (support) 1'on the drum. The polymer gel layer 2 is a temperature-sensitive polymer gel that causes a phase transition, and is composed of a polymer and a solvent having a lower critical solution temperature (LCST) type dissolution characteristic phase diagram. Then, a functional group that is easily electrochemically redox-reduced is introduced into the polymer, so that the phase transition temperature of the polymer can be reversibly controlled by applying a potential. Examples of the polymer that constitutes such a polymer gel include polyethylene oxide, polymethyl vinyl ether, polyvinyl ether having an oxyethylene unit in its side chain, poly (N-isopropylacrylamide), polyacryloylpyrrolidine, and polyacryloylpiperidine. Temperature-sensitive polymer and, for example, ferrocene, viologen, phenothiazine,
A copolymer with a compound having a side chain of a substance that is electrically redox-oxidized such as perylene or thiophene can be used. The solvent for polymer gel is L for polymer.
An organic solvent such as water or alcohol can be used as long as it shows a CST type dissolution characteristic phase diagram.

Further, in order to impart electric conductivity to the polymer gel layer, for example, CaCl ₂ , NaCl, KCl, H
₃ PO ₄ , K ₂ SO ₄ , HNO ₃ , K ₃ Fe (CN)
₆ , NaOH, KOH, Na ₂ SO ₄ , CH ₃ COON
Add any electrolyte such as a. The ratio of electrolyte is
About 0.1 to 7.0 N is preferable.

An example of producing a transfer medium having such a polymer gel layer will be shown below. <Preparation example> The polymer produced here is a copolymer of N-isopropylacrylamide, acryloylpyrrolidine, and vinylferrocene, which is a derivative of ferrocene that is electrochemically redox-reduced.

The N-isopropylacrylamide polymer and the acryloylpyrrolidine polymer undergo LCST type phase separation in water at 31 ° C. and 51 ° C., respectively. Therefore, by adjusting the molar ratio of both monomers, the phase separation temperature of the resulting copolymer can be controlled from 31 ° C to 51 ° C.
It can be set between ° C. The proportion of vinylferrocene for reversibly controlling the phase transition temperature of this copolymer by applying an electric potential is about 1 to 10 mol%. In addition, NaOH was used as the electrolyte and the concentration was adjusted to 4.5N.

Benzophenone was added as a photopolymerization initiator to ethanol containing these monomers in a concentration of about 4 molar to perform photopolymerization to obtain a copolymer solution. To this solution, 0.04 mol of methylenebisacrylamide was added as a cross-linking agent, cast on a surface-hydrophilized polymer film, and then photopolymerized again to obtain a polymer gel. This polymer gel was thoroughly washed in ion-exchanged water to obtain an aqueous gel, and the transfer medium 11 of the present invention was obtained.

FIG. 1 shows an example of a recording apparatus for carrying out the recording method of the present invention using a sheet-shaped transfer medium 11. This recording device is provided with a pair of rolls 18a and 18b that are arranged to face each other at a distance.
The transfer medium 11 in the form of a sheet is hung over. Above the one roll 18b, an electrification recording means 12 for recording a potential image on the polymer gel layer 2 of the transfer medium 11 is arranged. The current-carrying recording means 12 can be composed of, for example, a multi-stylus electrode. The other electrode 17
Is a common electrode, which can form a potential image by the electrification recording means 12 and erase image information recorded in the polymer gel layer 2 of the image.

Behind the roll 18b, the transfer medium 11 is heated to a predetermined temperature as will be described later, and the polymer gel layer 2 is heated.
The heating means 13 for changing the adhesion of the coloring material is provided.

Below the roll 18b, a coloring material supplying means 14 for supplying the coloring material solution to the polymer gel layer 2 of the transfer medium 11 is installed. Color material supply means 14 shown in FIG.
Consists of a porous roll 14b partially immersed in a container 14a containing a coloring material solution.
Are arranged so as to contact the transfer medium 11. However, in order to supply the coloring material solution to the polymer gel layer, the transfer medium may be dipped and passed through the tank of the coloring material solution.

The color material solution has a relatively low affinity for polymer gels below the LCST type phase separation temperature,
It has a relatively high affinity for a polymer in a phase-separated state. For example, an arbitrary dye, dye or the like is dissolved in a solvent that has high repellency with respect to a polymer gel having an LCST type phase separation temperature or lower and high wettability with respect to a polymer in an LCST type phase separation state. It is a thing. Alternatively,
A desired color can also be obtained by dissolving a coloring material having a low adsorptivity for a polymer gel having an LCST type phase separation temperature or lower and a high adsorptivity for an LCST type phase separated polymer in a solvent. A material solution can be prepared. More specifically, when the aqueous gel as shown in the above-mentioned preparation example is used as the polymer gel layer, an oily coloring material can be used.

Between the rolls 18a and 18b, means 15 for changing the color material to a weakly adhered state is arranged. The means 15 is a cooling means for cooling the transfer medium 11 to a predetermined temperature or lower. If there is sufficient time for cooling from the supply of the coloring material solution to the polymer gel to the transfer means described below, the cooling means 15 need not be specially provided (natural cooling).

Below the roll 18a, there is provided a transfer means 16 for closely feeding the transfer medium 11 in which the coloring material solution is supplied to the polymer gel layer 2 and sequentially feeding the transfer material (transfer paper) 22. There is. The transfer means 16 in FIG. 1 is composed of a rotating roll.

Next, the recording method according to the first embodiment of the present invention will be described in more detail. <Initialization / latent image formation> First, by the electrification recording means 12,
A potential image corresponding to a recorded image (a negative potential is applied to a character portion or the like to be colored; a reverse image) is applied to the polymer gel layer 2 of the transfer medium 11. At this time, since the positive potential is applied by the common electrode 17, the ferrocene derivative on the upstream side of the transfer medium 11 (in the vicinity of the common electrode 17) is oxidized, and the phase transition temperature of the polymer gel layer rises from TCL to TCH. . On the other hand, the ferrocene derivative near the energization recording means 12 is reduced, only the phase transition temperature of the image area (energized area) of the image is decreased from TCH to TCL, and the non-energized area remains in the oxidized state (TCH). Remain. That is, the latent image is formed by the regions having different phase transition temperatures. <Temperature control> Then, TCH and TCL by the heating means 13
The temperature of the entire transfer medium 11 is raised to an appropriate temperature during the period.
Then, a phase transition occurs in the reduction region (TCL region) having a low phase transition temperature. That is, the phase transition area corresponding to the image area of the recorded image is formed. <Color Material Supply> The color material solution is supplied from the color material supply means 14 while the temperature of the transfer medium 11 does not decrease. Since the repellency / wettability of the color material solution is different between the phase transition area and the non-phase transition area of the polymer gel, the color material solution is retained only in the phase transition area which is the image area of the image. The coloring material solution is not held in the non-phase transition region which is the non-image area of the image. Alternatively, since the phase transition region and the non-phase transition region have different adsorptivity of the color material in the color material solution, the color material solution is retained only in the phase transition area which is the image area of the image. The state at this time is shown in FIG. Figure 3
FIG. 3B shows a case where the wettability of the coloring materials is different from that in FIG.
Indicates the case due to the difference in the adsorptivity of the coloring material. <Color Material Release> After that, the temperature of the transfer medium 11 is lowered to TCL or lower by natural cooling until the next step is performed. As a result, the polymer gel in the image area of the image returns to the same state as the wettability of the coloring material and the adsorptivity of the dye to the non-image area of the image, so that the coloring material formed on the surface of the polymer gel is Change to a weak adhesion state. Note that this cooling may be performed by the cooling means 15. <Transfer> Next, the transfer medium 16 is transferred by the transfer means 16.
The color material is transferred to the transfer-target material 22 that is in close contact with the recording material, and image recording is achieved. At this time, since the coloring material formed on the surface of the polymer gel is in a weakly adhered state as described above, the transfer can be efficiently performed.

Image recording can be continuously performed by repeating the above steps. That is, the transfer medium 11 can be used repeatedly. Second Embodiment In the first embodiment, the example in which the energized recording portion is the image line portion of the image has been described, but the energized recording portion may be the non-image line portion of the image (normal image). As the device, the one shown in FIG. 1 can be used (however, the potentials of the common electrode 17 and the electrification recording means 12 are opposite to those in the first embodiment). <Initialization / latent image formation> First, by the electrification recording means 12,
A potential image corresponding to a recorded image (a positive potential is applied to an uncolored character portion; a regular image) is applied to the polymer gel layer 2 of the transfer medium 11. At this time, since a negative potential is applied by the common electrode 17, the upstream side of the transfer medium 11 (common electrode 1
The ferrocene derivative (near 7) is reduced, and the phase transition temperature of the polymer gel layer decreases from TCH to TCL. On the other hand, the ferrocene derivative near the energization recording means 12 is oxidized, and only the phase transition temperature of the non-image area (current energization area) of the image is TCL.
To TCH, and the non-energized part remains in the reduced state (TCL). That is, the latent image is formed by the regions having different phase transition temperatures. <Temperature control> Then, TCH and TCL by the heating means 13
The temperature of the entire transfer medium 11 is raised to an appropriate temperature during the period.
Then, a phase transition occurs in the reduction region (TCL region) having a low phase transition temperature. That is, the phase transition area corresponding to the image area of the recorded image is formed. <Color Material Supply> The color material solution is supplied from the color material supply means 14 while the temperature of the transfer medium 11 does not decrease. Since the repellency / wettability of the color material solution is different between the phase transition area and the non-phase transition area of the polymer gel, the color material solution is retained only in the phase transition area which is the image area of the image. The coloring material solution is not held in the non-phase transition region which is the non-image area of the image. Alternatively, since the phase transition region and the non-phase transition region have different adsorptivity of the color material in the color material solution, the color material solution is retained only in the phase transition area which is the image area of the image. <Color Material Release> After that, the temperature of the transfer medium 11 is lowered to TCL or lower by natural cooling until the next step is performed. As a result, the polymer gel in the image area of the image returns to the same state as the wettability of the coloring material and the adsorptivity of the dye to the non-image area of the image, so that the coloring material formed on the surface of the polymer gel is Change to a weak adhesion state. Note that this cooling may be performed by the cooling means 15. <Transfer> Next, the transfer medium 16 is transferred by the transfer means 16.
The color material is transferred to the transfer-target material 22 that is in close contact with the recording material, and image recording is achieved. At this time, since the coloring material formed on the surface of the polymer gel is in a weakly adhered state as described above, the transfer can be efficiently performed.

Example 3 As the apparatus, the apparatus shown in FIG. 4 is used. The apparatus shown in FIG. 4 is the same as the apparatus shown in FIG. 1 except that the heating means 23 is used instead of the cooling means 15. <Initialization / latent image formation> First, by the electrification recording means 12,
A potential image (a negative potential is applied to a non-colored character portion or the like; a regular image) corresponding to a recorded image is applied to the polymer gel layer 2 of the transfer medium 11. At this time, since the positive potential is applied by the common electrode 17, the upstream side of the transfer medium 11 (the common electrode 1
The ferrocene derivative (near 7) is oxidized, and the phase transition temperature of the polymer gel layer rises from TCL to TCH. On the other hand, the ferrocene derivative in the vicinity of the electrification recording means 12 is reduced and only the phase transition temperature of the non-image area (energization portion) of the image is TCH.
To TCL, and the non-conducting portion remains in the oxidized state (TCH). That is, the latent image is formed by the regions having different phase transition temperatures. <Temperature control> Then, TCH and TCL by the heating means 13
The temperature of the entire transfer medium 11 is raised to an appropriate temperature during the period.
Then, a phase transition occurs in the reduction region (TCL region) having a low phase transition temperature. That is, the phase transition area corresponding to the non-image area of the recorded image is formed. <Color Material Supply> While the temperature of the transfer medium 11 does not decrease, the aqueous color material solution is supplied from the color material supply means 14. Since the repellency / wettability of the aqueous color material solution is different between the phase transition area and the non-phase transition area of the polymer gel, the aqueous color material solution is retained only in the non-phase transition area which is the image area of the image. The aqueous color material solution is not held in the phase transition region which is the non-image area of the image. Alternatively, since the phase transition region and the non-phase transition region have different adsorptivity of the color material in the aqueous color material solution, the aqueous color material solution is retained only in the non-phase transition region which is the image area of the image. <Color Material Release> After that, the transfer medium 11 is heated by the heating means 23.
Is heated to a temperature above TCH. As a result, the polymer gel in the image area of the image returns to the same state as the wettability of the aqueous coloring material and the adsorption of the dye to the non-image area of the image. , Changes to a weak adsorption state. <Transfer> Next, the transfer medium 16 is transferred by the transfer means 16.
Image recording is achieved by transferring the color material to the material to be transferred that is in close contact with. At this time, since the coloring material formed on the surface of the polymer gel is in a weakly adhered state as described above, the transfer can be efficiently performed.

Image recording can be continuously performed by repeating the above steps. That is, the transfer medium 11 can be used repeatedly. The transfer means 16 is
It is preferable to incorporate heating means so that the transfer medium 11, the material to be transferred 22, and the temperature above the TCH can be heated.

Fourth Embodiment In the third embodiment, an example is shown in which the energized portion is the non-image area of the image, but the energized portion may be the image area of the image (reverse image). As the device, the device shown in FIG. 4 is used (however, the common electrode 17 and the electrification recording means 12 are used.
Potential is opposite to that in Example 3). <Initialization / latent image formation> First, by the electrification recording means 12,
A potential image corresponding to a recorded image (a positive potential is applied to a character portion to be colored; a reverse image) is applied to the polymer gel layer 2 of the transfer medium 11. At this time, since a negative potential is applied by the common electrode 17, the ferrocene derivative on the upstream side of the transfer medium 11 (in the vicinity of the common electrode 17) is reduced, and the phase transition temperature of the polymer gel layer decreases from TCH to TCL. . On the other hand, the ferrocene derivative near the energization recording unit 12 is oxidized, only the phase transition temperature of the image area (energized section) of the image rises from TCL to TCH, and the non-energized section remains in the reduced state (TCL). Remain. That is, the latent image is formed by the regions having different phase transition temperatures. <Temperature control> Then, TCH and TCL by the heating means 13
The temperature of the entire transfer medium 11 is raised to an appropriate temperature during the period.
Then, a phase transition occurs in the reduction region (TCL region) having a low phase transition temperature. That is, the phase transition area corresponding to the image area of the recorded image is formed. <Color Material Supply> While the temperature of the transfer medium 11 does not decrease, the aqueous color material solution is supplied from the color material supply means 14. Since the repellency / wettability of the aqueous color material solution is different between the phase transition area and the non-phase transition area of the polymer gel, the aqueous color material solution is retained only in the non-phase transition area which is the image area of the image. The aqueous color material solution is not held in the phase transition region which is the non-image area of the image. Alternatively, since the phase transition region and the non-phase transition region have different adsorptivity of the color material in the aqueous color material solution, the aqueous color material solution is retained only in the non-phase transition region which is the image area of the image. <Color Material Release> After that, the transfer medium 11 is heated by the heating means 23.
Is heated to a temperature above TCH. As a result, the polymer gel in the image area of the image returns to the same state as the wettability of the aqueous coloring material and the adsorption of the dye to the non-image area of the image. , Changes to a weak adsorption state. <Transfer> Next, the transfer medium 16 is transferred by the transfer means 16.
Image recording is achieved by transferring the color material to the material to be transferred that is in close contact with. At this time, since the coloring material formed on the surface of the polymer gel is in a weakly adhered state as described above, the transfer can be efficiently performed.

Image recording can be continuously performed by repeating the above steps. That is, the transfer medium 11 can be used repeatedly. The transfer means 16 is
It is preferable to incorporate heating means so that the transfer medium 11, the material to be transferred 22, and the temperature above the TCH can be heated.

In the first to fourth embodiments of the present invention described above, as shown in FIG. 1, the current-carrying recording means 12 and the common electrode 17 are arranged on the gel surface along the moving direction of the image carrier, Along with forming a latent image, the image information recorded on the polymer gel layer 2 was erased. In the above method, the gel sheet support 1 is assumed to be an insulator, but a conductive material may be used as the gel sheet support 1. In this case, using the device shown in FIG.
The recording medium 11 is sandwiched between the common electrode 17 and the common electrode 17, and the gel surface is changed to a predetermined phase state by applying a predetermined potential. After that, temperature control, color material supply, color material discharge, and transfer are performed by the same steps as those in the above-described embodiment. The image information recorded on the transfer medium 11 after the transfer is erased by applying a potential having a polarity opposite to the recording potential by the initialization unit 24 separately provided on the downstream side of the transfer unit 16. .

[0027]

According to the present invention, there is provided a color material transfer electrification recording method capable of easily and inexpensively forming a high quality color recorded image with a simple apparatus. More specifically, a color recorded image can be easily formed by appropriately replacing the color material, and a good recorded image can be obtained by using any paper as the transfer target material. Further, since the coloring material is required only in the image area, the running cost is low and the resource is saved. Also, a multi-color recording device having a plurality of devices for implementing such a recording method can be easily obtained.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of an apparatus for carrying out a color material transfer electrification recording method of the present invention.

2A and 2B are diagrams showing a transfer medium of the present invention, in which FIG. 2A is a sheet-like one and FIG. 2B is a drum-like one.

3A and 3B are graphs for explaining the adhesion between the transfer medium of the present invention and a coloring material, in which FIG. 3A is a diagram showing wettability and FIG. 3B is a diagram showing adsorption.

FIG. 4 is a diagram showing another example of an apparatus for carrying out the color material transfer electrification recording method of the present invention.

FIG. 5 is a diagram showing still another example of an apparatus for carrying out the color material transfer electrification recording method of the present invention.

[Explanation of symbols]

1, 1 '... Support, 2 ... Polymer gel layer, 11 ... Transfer medium, 12 ... Electrical recording means 13 ... Heating device, 14 ... Color material supplying means, 15 ... Cooling means, 16 ... Transfer means 17 ... Common electrode , 18 ... rotating roll, 22 ... material to be transferred,
23 ... Heating means 24 ... Initialization means

Claims (1)

[Claims] 1. The phase transition temperature can be reversibly changed between two phase transition temperatures TCH and TCL (where TCH> TCL), and is changed between the TCH and the TCL by electrochemical redox. By applying a potential corresponding to image information to an image carrier having a temperature-sensitive phase transition polymer gel layer, different regions where the phase transition temperatures Tc are TCH and TCL are applied to the image carrier. Forming a latent image consisting of: a step of setting the image carrier at a temperature between TCH and TCL to convert the latent image into a latent image consisting of a phase transition region and a non-phase transition region; Supplying to the converted latent image a coloring material solution having different coloring material adsorption capacities for the phase transition area and the non-phase transition area to form a visible image of the coloring material corresponding to the image information; , The coloring material adsorption capacity of the area where the coloring material is adsorbed is low. Process and, colorant transfer current recording method and recording an image by sequentially performing the step of transferring the visible image by the coloring material is brought into contact with the transfer paper onto the transfer sheet to the image bearing member to be.