JP3551704B2 - Image forming method, image forming apparatus and color filter manufacturing method - Google Patents

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an image forming method, an image forming apparatus, and a color filter manufacturing method using an aqueous solution in which two or more dyes coexist.
[0002]
[Prior art]
Among methods of recording an image on a recording medium such as paper based on an electric signal or an optical signal, methods currently used in printers and the like include a dot impact method, a thermal transfer method, a thermal sublimation method, an inkjet method, and an electronic method. Photographic methods. These methods are roughly classified into three types.
[0003]
The first method is a method in which a sheet in which dye molecules are dispersed, such as an ink ribbon or a donor film, is brought into direct contact with paper or the like, and the dye is transferred onto the paper by mechanical impact or heat. , Dot impact method, thermal transfer method and thermal sublimation method. However, these methods require consumables other than ink and electric power, and have low energy efficiency, resulting in high running costs. In addition, the quality of products obtained by other methods other than the thermal sublimation method is poor.
[0004]
The second method is a non-contact method, and an example of such a method is an ink jet method in which ink is ejected from a head onto paper. This ink jet method does not require consumables other than ink and electric power. However, it is difficult to completely control the dot size, the flying direction, and the like. In addition, energy efficiency is not high in the ink jet method.
[0005]
The third method is a method of forming an image on paper via an intermediate transfer member. As such a method, toner is attached to a latent image on a photoreceptor formed by a laser spot, and this is transferred to paper. To form an image. In this electrophotography, a relatively delicate image can be formed. However, in the electrophotographic method, a high voltage is required to form a latent image on a photoconductor, adsorb toner on the photoconductor, and transfer the adsorbed toner to paper. For this reason, there is a problem that power consumption is large and ozone and nitrogen oxides are generated.
[0006]
In addition, the first, second, and third methods have a problem that the operation sound during image formation is usually quite loud.
[0007]
On the other hand, although there is no versatility as in the above method, other image forming methods are also known. For example, a "color printing apparatus" (Japanese Patent Application Laid-Open No. 60-23051), a "method of manufacturing a color filter" (Japanese Patent Application Laid-Open No. 4-165306), a "patterning method and an electrodeposition original plate used therefor, a method of manufacturing a color filter, and the like" Manufacturing method of optical recording medium ”(JP-A-7-5320). These form an electrodeposition film using a solution in which a pigment or a dye is dispersed in a polymer having an electrodeposition property. The electrodeposited film formed here has a dye fixed in a polymer film as a support matrix, and the content of the dye in the electrodeposited film is only about 30%. That is, only an image having a low density can be obtained instead of consumed energy, and there are problems in energy efficiency and economy. Further, in order to obtain a color image or a color filter by these techniques, a number of coating baths corresponding to the number of primary colors used in the subtractive color method or the additive color method are required, and the electrodeposition step must be performed once for each color. Is required.
[0008]
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming method which can adjust the density and color of an image, is environmentally friendly and consumes less energy.
[0009]
Another object of the present invention is to provide an image forming method capable of simplifying an electrodeposition operation for obtaining a color image.
[0010]
Another object of the present invention is to provide an image forming apparatus using the image forming method.
[0011]
Another object of the present invention is to provide a method for manufacturing a color filter using the above-described image forming method.
[0012]
[Means for Solving the Problems]
The present inventors have focused on the fact that among the water-soluble dye molecules, there are molecules that can precipitate alone from a state of being dissolved in an aqueous solution by an electrochemical reaction, and have completed the following invention.
[0013]
That is, the first image forming method of the present invention is a method of coexisting, at a specific pH, two or more dye groups of the same polarity containing at least one dye that can be precipitated alone from a state dissolved in an aqueous solution by an electrochemical reaction. A voltage is applied between the first electrode immersed or in contact with the aqueous solution dissolved in and a second electrode provided so as to be capable of causing an electrochemical reaction in cooperation with the first electrode. Forming a mixed color image composed of a group of dyes on the first electrode by applying a voltage.
[0014]
In this method, a dye which can be precipitated alone from a state of being dissolved in an aqueous solution by an electrochemical reaction (hereinafter, referred to as a dye having an electrodeposition film forming ability) takes in another dye and precipitates on the first electrode, thereby causing color mixing. An image is formed.
[0015]
Further, since the pigment is provided as an aqueous solution, the adverse effect on the human body as well as the environment is very small.
[0016]
Further, since no ribbons are used, there are no consumables other than dyes and electric power. Further, since the applied voltage at the time of image formation is only about 0.6 to 3 V, power consumption is extremely low. Therefore, running costs are low.
[0017]
Further, since the dye content of the image is high, it is possible to form an image having high density and high quality.
[0018]
Further, in this method, it is possible to adjust the image density by controlling the voltage applied between both electrodes, the application time, and the like.
[0019]
Further, the second image forming method according to the present invention is characterized in that two or more different-polarity dye groups containing at least one kind of dye that can be solely precipitated from an aqueous solution by an electrochemical reaction coexist at a specific pH. A voltage is applied between the first electrode immersed or in contact with the aqueous solution dissolved in and a second electrode provided so as to be capable of causing an electrochemical reaction in cooperation with the first electrode. Applying, at least on the first electrode, a mixed-color image formed of the dye group, or a mixed-color image formed of the dye group and different from the color of the mixed-color image or a single-color image formed of a single dye Is formed.
[0020]
In the second image forming method, a mixed-color image, or a mixed-color image or a single-color image different from the color of the mixed-color image is formed on at least the first electrode. Although the details of the mechanism by which a mixed-color image is formed are not clear, it is considered that one polarity of dye takes up the other polarity of dye.
[0021]
In the second image forming method, a two-color image can be formed with one type of solution, and the color image forming process can be reduced and the forming operation can be simplified.
[0022]
Further, in this method, the density and color of an image can be adjusted by controlling the voltage applied between the two electrodes, the application time, and the like.
[0023]
The image forming apparatus of the present invention is a bath for containing an aqueous solution in which two or more dye groups containing at least one kind of dye that can be solely precipitated from an aqueous solution dissolved by an electrochemical reaction are co-dissolved at a specific pH. A first electrode immersed in or in contact with the aqueous solution, a second electrode provided to be capable of causing an electrochemical reaction in cooperation with the first electrode, and the first electrode and Voltage applying means for applying a voltage between the second electrodes.
[0024]
This image forming apparatus can provide the above advantages.
According to the method of forming a color filter of the present invention, a color filter in which an electrodeposited film as a single-color image or a mixed-color image is formed on a transparent electrode as a first electrode by the above-described image forming method.
[0025]
In this method, a color filter can be formed with the above advantages.
[0026]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in more detail.
[0027]
The present invention uses an aqueous solution in which two or more dye groups of the same polarity containing at least one kind of dye that can be solely precipitated from an aqueous solution dissolved by an electrochemical reaction are coexistent at a specific pH. Such a dye is generally an acid dye or a basic dye.
[0028]
For example, fluorescein dyes such as rose bengal and eosin are soluble in water at pH 4 or higher, but are oxidized and insoluble in water below pH 4 to precipitate. Similarly, diazo-based Pro Jet Fast Yellow 2 (manufactured by Zeneca) is soluble in water at pH 6 or higher, but precipitates at lower pH. For reference, FIG. 1 shows an absorption spectrum of a Pro Jet Fast Yellow 2 aqueous solution having a concentration of 20 μM.
[0029]
When a current is applied to a solution in which these dyes are dissolved in pure water (pH 6 to 8), the dyes are oxidized and become insoluble in water, and an electrodeposition film made of dye molecules is formed on the anode electrode. . Further, by applying a voltage between the electrodes so that the electrode on which the electrodeposited film is formed becomes a cathode, or by immersing the electrode in an aqueous solution having a pH of 10 to 12, the dye in the electrodeposited film is reduced and Re-eluted. For reference, FIG. 2 shows an absorption spectrum of the Pro Jet Fast Yellow 2 electrodeposited film formed on the transparent electrode ITO.
[0030]
In addition, oxazine-based basic dye Cathilon Pure Blue 5GH (CI Basic Blue 3) [manufactured by Hodogaya Chemical] and thiazine-based basic dye methylene blue (CI Basic Blue 9), which are one of quinone imine dyes, are used. When the pH is 10 or less, it is dissolved in water, but when the pH exceeds 10, it is reduced and becomes insoluble in water and precipitates. Catilon Pure Blue 5GH easily dissolves in pure water and exists as a cation in an aqueous solution, but becomes insoluble in water and precipitates when the pH becomes 11 or more. For reference, FIG. 3 shows an absorption spectrum of a Catilon Pure Blue 5GH aqueous solution having a concentration of 20 μM.
[0031]
When these dyes are dissolved in pure water and energized, the dyes are reduced and an electrodeposited film made of dye molecules is formed on the cathode-side electrode. Further, by applying a voltage between the electrodes so that the electrode on which the electrodeposited film is formed becomes an anode, or by immersing the electrode in an aqueous solution having a pH of 8 or less, the dye in the electrodeposited film is oxidized and becomes an aqueous solution. Re-elute. For reference, Cathilon Pure Blue formed on a transparent electrode ITO
FIG. 4 shows the absorption spectrum of the 5GH electrodeposited film.
[0032]
In the present invention, the pH of the aqueous solution is adjusted so that two or more types of dyes can coexist without forming a complex or the like or precipitating.
[0033]
When the dyes contained in the aqueous solution are dyes of the same polarity (that is, anionic dyes or cationic dyes), this coexistence can be easily achieved.
[0034]
On the other hand, generally, an aqueous solution of an anionic or cationic dye (eg, an aqueous solution of rose bengal) is mixed with an aqueous solution of a dye having a polarity different from the polarity of the aqueous solution and containing a polymer compound (eg, polyethyleneimine). Then, a precipitate is generated by neutralization, but in the present invention, since an image is formed using a dye having an electrodeposition film forming ability, a polymer compound is not an essential requirement, and a polymer having a different polarity in an aqueous solution is used. Dye coexistence is easily achieved.
[0035]
As the dye having the ability to form an electrodeposition film that can be used in the present invention, a color former having a coloring structure by an external stimulus such as an acid or an alkali can be used. Examples thereof include triphenylmethanephthalide, phenosadine, phenothiazine, fluoran, indolylphthalide, spiropyran, azaphthalide, diphenylmethane, chromenopyrazole, leuco auramine, azomethine, rhodamine. Lactam-based, naphtholactam-based, and triazene-based, and more specifically, Rose Bengal, Pro Jet Fast Yellow 2, Cathilon Pure Blue 5GH, and the like. Further, as the dye having no electrodeposition film forming ability that can be shared with these dyes having the electrodeposition film forming ability, it is possible to select any ionic dye, for example, acridine System, azaphthalide system, azine system, azurenium system, azo system, azomethine system, aniline system, amidinium system, alizarin system, anthraquinone system, isoindolinone system, indigo system, indigoid system, indoaniline system, indolyl phthalide system, Oxazine, carotenoid, xanthine, quinacridone, quinazoline, quinophthalone, quinoline, quinone, guanidine, chrome chelate, chlorophyll, ketone imine, diazo, cyanine, dioxazine, disazo, diphenylmethane System, diphenylamine system, square , Spiropyran, thiazine, thioindigo, thiopyrylium, thiofluorane, triallylmethane, trisazotriphenylmethane, triphenylmethane, triphenylmethanephthalide, naphthalocyanine, naphthoquinone, naphthol System, nitroso system, bisazooxadiazole system, bisazo system, bisazostilbene system, bisazohydroxyperinone system, bisazofluorenone system, bisphenol system, bislactone system, villarozone system, phenoxazine system, phenothiazine system, phthalocyanine system , Fluoran, fluorene, fulgide, perinone, perylene, benzimidazolone, benzopyran, polymethine, porphyrin, methine, merocyanine, monoazo, leuco auramine, b Koki agar, synthetic dyes such as rhodamine, and turmeric, gardenia, piperica, red koji, lac, grape, beet, perilla, berry, corn, cabbage, cacao, etc. Is brilliant blue and the like.
[0036]
In the present invention, the polymer compound can be used only when no precipitate is generated. In addition, when using dyes having different polarities, whether a single color image is formed or a mixed color image in which both are formed depends on the properties of the dye, so that a desired color image is formed. It is important to combine the most suitable dyes to do so.
[0037]
In the present invention, an image is formed by applying a current to an aqueous solution in which two or more dyes coexist as described above.
[0038]
When current is passed through a mixed solution in which two types of dyes having the same polarity are mixed, an electrodeposition film having the same color as the color of the mixed solution is formed on an electrode having a polarity opposite to the polarity of the dye. For example, when an electric current is applied to a mixed solution of rose bengal (red), which is an anion dye capable of forming an electrodeposition film, and brilliant blue (blue), which is an anion dye having no ability to form an electrodeposition film, a mixed solution is formed on the anode. A purple electrodeposited film having the same color as that of the above is formed. This is because rose bengal is oxidized while taking in brilliant blue ions and is deposited on the anode. As described above, when a dye having the same polarity is mixed, an image of a mixed color is generally obtained. Further, as can be seen from this example, when two types of dyes having the same polarity are mixed, it is sufficient that one type of dye has an electrodeposition film forming ability.
[0039]
On the other hand, when applying a current to a mixed solution in which two kinds of dyes having different polarities are mixed, different images are formed depending on the polarity of the voltage applied to the electrodes.
For example, the color of an aqueous solution obtained by mixing Pro Jet Fast Yellow 2 (yellow), which is an anion dye capable of forming an electrodeposited film, and Cathilon Pure Blue 5GH (blue), which is a cationic dye capable of forming an electrodeposited film, is a mixture of these colors. Is green. When this solution is energized, as shown in FIG. 5 (A), the anionic dye A (here, Pro Jet Fast Yellow 2) is oxidized while taking in the cationic dye C (here, Cathilon Pure Blue 5GH). An electrodeposited film F1 is deposited on the anode E1 and has the same color as the color of the mixed solution. On the other hand, as shown in FIG. 5 (B), the electrodeposition of a blue color substantially the same as the color of Cathilon Pure Blue 5GH alone (a pale yellow color of Cathilon Pure Blue 5GH during film formation) on the cathode E2 as shown in FIG. The film F2 is formed. As can be seen from this, in the case of a mixed solution in which two types of dyes having different polarities each having an electrodeposition film forming ability are mixed, the electrodeposition film forming ability of each dye is not lost. Electrodeposited films of different colors can be formed on the electrodes. In this example, at least one of the dyes of each polarity has the ability to form an electrodeposition film, but it is sufficient that one of the dyes of either polarity has the ability to form an electrodeposition film.
[0040]
Since the amount of dye adhering to the electrode follows Faraday's law, the thickness of the electrodeposited film controls at least one of the applied voltage, applied charge, applied current, and their application time during electrodeposition film formation. By doing so, it can be changed continuously. In other words, the density of the electrodeposited film (image) can be changed by controlling the applied voltage and the like.
[0041]
Further, in the present invention, the color of the electrodeposited film (image) can be changed by controlling the applied voltage and the like. FIG. 6 is a graph showing the relationship between the value and polarity of the voltage applied to the electrode, and the ratio between Ypeak and Cpeak, by applying the present invention to a 1: 1 mixed solution of Catilon Pure Blue 5GH and Pro Jet Fast Yellow 2. is there. Here, as shown in FIG. 7, Ypeak and Cpeak are the height of the absorption maximum point of Pro Jet Fast Yellow 2 and the height of the absorption maximum point of Cathilon Pure Blue 5GH when the absorption spectrum of the electrodeposited film is taken. Respectively. FIG. 6 shows that changing the value and polarity of the voltage applied to the electrode changes the ratio between Ypeak and Cpeak, in other words, changes the color of the electrodeposited film.
[0042]
In the present invention, the concentration (total) of the dye in the solution is usually 0.1 mM to 1M, and the ratio of each dye can be arbitrarily set. When a dye having no electrodeposition film-forming ability is contained, the ratio of the dye having the electrodeposition film-forming ability to the dye having no electrodeposition film-forming ability can be, for example, 99: 1 to 1:10.
[0043]
8 and 9 show a schematic configuration of an apparatus for forming an image on an electrode by the method of the present invention.
[0044]
In the apparatus shown in FIG. 8, a platinum electrode 1 as a first electrode and a platinum electrode 2 as a second electrode immersed in an aqueous solution 3 in which two kinds of dyes are dissolved are connected to a power supply (not shown). A saturated calomel electrode 5 as a reference electrode is immersed in a saturated KCl aqueous solution 4 electrically connected to the aqueous solution 3 via a salt bridge 6, and the saturated calomel electrode 5 is connected to the power supply via a potentiometer (not shown). Have been. In this apparatus, for example, when the aqueous solution 3 is a mixture of rose bengal (red) and brilliant blue (blue), a voltage is applied between the platinum electrodes 1 and 2 so that the platinum electrode 1 becomes an anode. Then, a purple electrodeposited film is formed on the platinum electrode 1. When the aqueous solution 3 is a mixture of Pro Jet Fast Yellow 2 (yellow) and Cathilon Pure Blue 5GH (blue), a green electrodeposition film is formed on the platinum electrode serving as the anode, and the cathode is used as the cathode. A blue electrodeposition film is formed on the platinum electrode.
[0045]
On the other hand, in the apparatus shown in FIG. 9, only the platinum electrode 1 as the first electrode is immersed in the aqueous solution 3, and the saturated electrode 8 is electrically connected to the aqueous solution 3 through the salt bridge 7. A certain platinum electrode 2 is immersed, and the platinum electrodes 1 and 2 are connected to a power source (not shown). A saturated calomel electrode 5 as a reference electrode is immersed in a saturated KCl aqueous solution 4 electrically connected to a saturated KCl aqueous solution 8 via a salt bridge 6, and the saturated calomel electrode 5 is connected to the power supply via a potentiometer (not shown). It is connected to the. In this apparatus, for example, when the aqueous solution 3 is a mixture of rose bengal (red) and brilliant blue (blue), a voltage is applied between the platinum electrodes 1 and 2 so that the platinum electrode 1 becomes an anode. Then, a purple electrodeposited film is formed on the platinum electrode 1. When the aqueous solution 3 is a mixture of Pro Jet Fast Yellow 2 (yellow) and Cathilon Pure Blue 5GH (blue), a voltage is applied between the platinum electrodes 1 and 2 so that the platinum electrode 1 becomes an anode. Then, a green electrodeposition film is formed on the platinum electrode 1, and when a voltage is applied between the platinum electrodes 1 and 2 so that the platinum electrode 1 becomes a cathode, a blue electrodeposition film is formed on the platinum electrode 1. Is done. As described above, a dye film of two colors can be obtained from one kind of mixed solution only by changing the polarity of the voltage applied to the electrode.
[0046]
8 and 9, the voltage applied between the platinum electrodes 1 and 2 is usually 0.6 to 3V.
[0047]
In order to form a two-color image on the same substrate, it is necessary to previously separate a region for applying a positive voltage and a region for applying a negative voltage on the substrate, as in a substrate 80 shown in FIG. There is. The electrode substrate 80 includes a support 82 formed of an insulating material such as glass. On the support 82, electrodes (for example, platinum electrodes) 84 are formed in a matrix. It is preferable that each electrode 84 is wired so that a desired positive or negative voltage is applied independently.
[0048]
Using this substrate 80, as shown in FIG. 11, two electrodes or two regions on the substrate 80 are connected via a DC power supply 81, and the substrate 80 is an aqueous solution in which two or more dyes having different polarities are dissolved. By immersing in 86 and applying a voltage between the electrodes or regions, a two-color image, that is, a single-color image composed of a single dye and a mixed-color image composed of two or more dyes are formed simultaneously. Is done. FIG. 11 shows the substrate 80 on which a single-color image is formed on the area P and a mixed-color image is formed on the area N. This method utilizes the same principle as that used in the apparatus of FIG. 8, and the substrate 80 has a first electrode and a second electrode.
[0049]
On the other hand, as shown in FIG. 12, a counter electrode 92, two DC power supplies 94 and 95 and a switch 93 are prepared, and the switch 93 is connected to the counter electrode 92 and the cathode side of the DC power supply 94 or the anode side of the DC power supply 95. To the counter electrode 92 and the DC power supplies 94 and 95 as described above. The anode side of the DC power supply 94 and the cathode side of the DC power supply 95 are connected to an arbitrary electrode or region on the substrate 80, and the substrate 80 is immersed in an aqueous solution in which two or more dyes having different polarities are dissolved. Is turned to the DC power supply 94 side, a single color image or a mixed color image is formed on an arbitrary electrode or region on the substrate 80. When the switch 93 is turned to the DC power supply 95 side, a mixed-color image or a single-color image is formed on an arbitrary electrode or region on the substrate 80. According to this method, a single color image and a mixed color image can be sequentially formed. At this time, the counter electrode 92 may be immersed in the aqueous solution together with the substrate 80, or may be immersed in an aqueous solution different from the aqueous solution in which the substrate 80 is immersed using a salt bridge. In this method, the plurality of electrodes on the substrate 80 are all first electrodes, and the counter electrode 92 corresponds to a second electrode.
[0050]
In the present invention, when a transparent substrate is used as an electrode in these devices, a color filter in which a monochromatic or mixed color electrodeposition film is formed on the transparent substrate can be produced.
[0051]
Further, in the present invention, the image formed on the electrode may be transferred to a transfer medium such as paper. There are two methods for transferring an image formed on an electrode onto a transfer-receiving medium. One is a method of transferring an image from the electrode to the transfer medium by applying pressure by bringing the electrode on which the image is formed and the transfer medium into close contact with each other. In another method, as shown in FIG. 13, a substrate 80 on which an image is formed and a counter electrode 92 are arranged so as to face each other, and a transfer medium 96 is arranged between the substrate 80 and the counter electrode 92. In this method, a voltage is applied between the electrode 84 and the counter electrode 92 so that the polarity of the electrode 84 on the substrate 80 is opposite to the polarity at the time of film formation. As a result, the dye attached on the electrode 84 moves toward the counter electrode 92 and is transferred onto the transfer medium 96 disposed between the electrode 84 and the counter electrode 92. When the density of the image on the electrode is different, a transfer image corresponding to this image can be formed. The density of the transferred image may be adjusted by adjusting the density of the image on the electrode by controlling the applied voltage and the like during film formation as described above. Adjustments may be made by controlling at least one of the currents and their application time.
[0052]
FIG. 14 shows a schematic configuration of an apparatus for forming an image on an electrode and transferring the formed image to a medium to be transferred by pressure. The apparatus shown in FIG. 14 includes a roll 115 rotatable in the direction of arrow B. A plurality of finely divided first electrodes are formed on the outer periphery of the roll 115. Below the roll 115, a bath 114 containing a mixed solution 113 of the dye is arranged such that an electrode arranged at the bottom of the roll 115 contacts or is immersed in the mixed solution 113. The second electrode 112 is immersed in the bath 114. A transfer roll 116 is disposed above the roll 115, and the paper 117 is transported between the two rolls. A cleaning blade 118 for removing the dye remaining on the roll 115 is provided downstream of the transfer roll 116 in the rotation direction of the roll 115. Further, the apparatus shown in FIG. 14 includes a controller 119 connected to each of the first electrodes formed on the outer periphery of the roll 115 and the second electrode 112, and the individual electrodes on the roll 115 are independently controlled by the controller 119. A voltage is applied between the electrode on the roll 115 and the second electrode 112 so as to be an anode or a cathode.
[0053]
In this apparatus, the electrodeposited film 111 formed on the electrode on the roll 115, when the electrode on which the electrodeposited film 111 is formed is disposed on the top of the roll 115, is transferred to the The image is transferred onto the paper 117 conveyed between the transfer roller 116 and the roll 116 by pressing the transfer roll 116.
[0054]
FIG. 15 shows a schematic configuration of an apparatus for forming an image on an electrode and transferring the formed image to a transfer medium by applying a voltage. The apparatus shown in FIG. 15 differs from the apparatus shown in FIG. 14 in that a transfer roll 120 whose outer periphery is formed of a conductive material is connected to a controller 119. In this apparatus, the electrodeposition film 111 is By applying a voltage between the electrode and the transfer roll 120 so that the polarity of the formed electrode is opposite to the polarity at the time of image formation, the electrodeposition film 111 is transferred onto the paper 117. In this apparatus, water having a desired pH may be applied to the paper 117 during transfer.
[0055]
By forming a plurality of first electrodes on a roller as in the apparatus shown in FIGS. 14 and 15, it is possible to form images continuously.
[0056]
When printing three or more color images using the present invention, an apparatus in which two apparatuses in FIG. 14 or FIG. 15 are combined, or one roll and two apparatuses each including two or more dyes For example, an apparatus having two baths containing different kinds of mixed liquids and a washing bath containing water for washing can be used.
[0057]
In the present invention, the materials of the first and second electrodes are not particularly limited, and metals, organic or inorganic semiconductors and the like can be used, but noble metals such as platinum and gold, and electrochemical materials such as carbon. A stable material is preferred. As a transparent substrate used for manufacturing a color filter, a transparent substrate in which an electrode such as ITO or a conductive polymer is formed on a transparent support such as glass or a transparent film can be used.
[0058]
【Example】
Hereinafter, the present invention will be described in detail based on examples.
[Example 1]
The apparatus shown in FIG. 9 and an aqueous solution (pH = 7.2) obtained by mixing a 0.02 M aqueous solution of rose bengal (red) and a 0.02 M aqueous brilliant blue solution (blue) were used. When a voltage was applied between the platinum electrodes 1 and 2 for 30 seconds so that the potential difference between the saturated calomel electrode 5 and the platinum electrodes 1 and 2 became +1.0 V, a purple (mixed color) thin film was formed on the platinum electrode 1. Was formed. Next, the platinum electrode 1 is pulled up from the aqueous solution, and paper is sandwiched between the counter electrode 92 and the platinum electrode 1 using the apparatus shown in FIG. Was applied, an image formed of a purple thin film on paper was obtained.
[0059]
From this example, a mixed color electrodeposition film can be formed from a mixed solution containing a dye having an electrodeposition film forming ability and a dye having the same polarity as the dye but having no electrodeposition film forming ability, It can be seen that an image can be transferred to paper by applying a voltage between the first electrode and the counter electrode such that the polarity of the first electrode is opposite to the polarity during film formation.
[Example 2]
9 and an aqueous solution (pH = 0.05M) obtained by mixing a 0.02M Pro Jet Fast Yellow 2 (manufactured by Zeneca) aqueous solution (yellow) and a 0.02M Cathilon PureBlue 5GH (Hodogaya Chemical) aqueous solution (blue). 7.2) was used. When a voltage was applied for 30 seconds between the platinum electrodes 1 and 2 so that the potential difference between the saturated calomel electrode 5 and the platinum electrodes 1 and 2 became +2.0 V, a green (mixed color) thin film was formed on the platinum electrode 1 Was formed. Next, when the platinum electrode 1 was pulled out of the aqueous solution and brought into contact with paper to apply pressure, an image formed of a green thin film on paper was obtained.
[0060]
Next, when a voltage was applied between the platinum electrodes 1 and 2 for 30 seconds so that the potential difference between the saturated calomel electrode 5 and the platinum electrodes 1 and 2 became −2.0 V in the apparatus having the arrangement shown in FIG. A thin yellow thin film was formed on the platinum electrode 1, and after one minute, the color of the thin film changed to blue. Next, when the platinum electrode 1 was pulled out of the aqueous solution and brought into contact with paper to apply pressure, an image formed of a blue thin film on paper was obtained.
[0061]
From this example, it can be seen that a two-color image can be obtained from a mixture of two kinds of dyes having different polarities, and the image can be transferred to paper by further applying pressure.
[Example 3]
The apparatus shown in FIG. 9 and an aqueous solution obtained by mixing a 0.02 M aqueous solution of Pro Jet Fast Yellow 2 (yellow) and a 0.02 M aqueous solution of Cathilon Pure Blue 5GH (blue) were used. When a voltage was applied for 30 seconds between the platinum electrodes 1 and 2 so that the potential difference between the saturated calomel electrode 5 and the platinum electrodes 1 and 2 became +2.0 V, a green (mixed color) thin film was formed on the platinum electrode 1 Was formed. Next, the platinum electrode 1 is pulled up from the aqueous solution, and paper is sandwiched between the counter electrode 92 and the platinum electrode 1 using the apparatus shown in FIG. 13, and a voltage of −2.0 V is applied between the counter electrode 92 and the platinum electrode 1. Was applied for 30 seconds, and an image formed of a green thin film on paper was obtained.
[0062]
Next, in the apparatus having the arrangement shown in FIG. 9, a voltage was applied between the platinum electrodes 1 and 2 for 30 seconds so that the potential difference between the saturated calomel electrode 5 and the platinum electrodes 1 and 2 was -2.0 V. A blue thin film was formed on the platinum electrode 1. Next, the platinum electrode 1 is pulled out of the aqueous solution, and paper is sandwiched between the counter electrode 92 and the platinum electrode 1 using the apparatus shown in FIG. 13, and a voltage of +2.0 V is applied between the counter electrode 92 and the platinum electrode 1. Upon application for 30 seconds, an image formed of a blue thin film on paper was obtained. From this example, an image of two colors was obtained from a mixture of two kinds of dyes having different polarities, and the first electrode and the counter electrode were connected so that the polarity of the first electrode was opposite to the polarity at the time of film formation. It can be seen that an image can be transferred to paper by applying a voltage between them.
[Example 4]
The apparatus shown in FIG. 9 using an ITO electrode formed on a glass substrate as the first electrode, and a 0.02 M aqueous solution of Pro Jet Fast Yellow 2 (yellow) and a 0.02 M aqueous solution of Cathilon Pure Blue 5GH (blue) Was used. When a voltage was applied for 30 seconds between the ITO electrode and the platinum electrode 2 so that the potential difference between the saturated calomel electrode 5 and the ITO electrode and the platinum electrode 2 became +2.0 V, a green (mixed color) was displayed on the ITO electrode. A thin film was formed. FIG. 16 shows the absorption spectrum at this time.
[0063]
Next, when a voltage was applied for 90 seconds between the ITO electrode and the platinum electrode 2 so that the potential difference between the saturated calomel electrode and the ITO electrode and the platinum electrode 2 became -1.0 V, a blue thin film was formed on the ITO electrode. Was formed. FIG. 17 shows the absorption spectrum at this time.
[0064]
This example shows that a dye film usable as a color filter can be formed on a transparent electrode. Further, it was clearly supported that there was a difference in the formed dye film due to the difference in the polarity of the applied voltage based on the absorption spectrum.
[Example 5]
The apparatus shown in FIG. 9 and an aqueous solution obtained by mixing a 0.02 M aqueous solution of Pro Jet Fast Yellow 2 (yellow) and a 0.02 M aqueous solution of Cathilon Pure Blue 5GH (blue) were used. A voltage is applied between the saturated calomel electrode 5 and the platinum electrodes 1 and 2 so that the potential difference between the saturated calomel electrode 5 and the platinum electrodes 1 and 2 changes from 0 V to +3.0 V in +0.5 V steps. After 20 seconds, green (mixed color) thin films having different dye concentrations were formed on the platinum electrode 1 according to the applied voltage. Next, when the platinum electrode 1 was pulled up from the aqueous solution and brought into contact with paper to apply pressure, an image formed on the paper with a green thin film having an image density corresponding to the applied voltage was obtained.
[0065]
Next, in the apparatus shown in FIG. 9, the saturated calomel electrode 5 and the platinum electrode 1 are changed so that the potential difference between the saturated calomel electrode 5 and the platinum electrodes 1 and 2 changes from 0 V to −3.0 V in steps of −0.5 V. When a voltage was applied between the two and the application time was set to 20 seconds, a blue thin film having a different dye concentration was formed on the platinum electrode 1 in accordance with the applied voltage. Next, when the platinum electrode 1 was pulled out of the aqueous solution and brought into contact with paper to apply pressure, an image formed on the paper with a blue thin film having an image density corresponding to the applied voltage was obtained.
[0066]
From this example, two color images were obtained from a mixture of two dyes, and the thickness of the dye film, in other words, the image density was changed by the applied voltage. As a result, transferred images having different image densities were obtained. It is understood that it can be done.
[Example 6]
The apparatus shown in FIG. 9 and an aqueous solution obtained by mixing a 0.02 M aqueous solution of Pro Jet Fast Yellow 2 (yellow) and a 0.02 M aqueous solution of Cathilon Pure Blue 5GH (blue) were used. A voltage is applied between the saturated calomel electrode 5 and the platinum electrodes 1 and 2 so that the potential difference between the saturated calomel electrode 5 and the platinum electrodes 1 and 2 becomes +2.0 V, and the application time is 10 seconds from 0 seconds to 50 seconds. As a result, a green (mixed color) thin film having a different dye concentration was formed on the platinum electrode 1 depending on the applied time. Next, when the platinum electrode 1 was pulled out of the aqueous solution and brought into contact with paper to apply pressure, an image formed on the paper with a green thin film having an image density corresponding to the application time was obtained.
[0067]
Next, in the apparatus shown in FIG. 9, a voltage is applied between the saturated calomel electrode 5 and the platinum electrodes 1 and 2 so that the potential difference between the saturated calomel electrode 5 and the platinum electrodes 1 and 2 becomes −2.0 V. When the application time was changed every 10 seconds from 0 seconds to 50 seconds, a blue thin film having a different dye concentration was formed on the platinum electrode 1 depending on the application time. Next, when the platinum electrode 1 was pulled out of the aqueous solution and brought into contact with paper to apply pressure, an image formed on the paper with a blue thin film having an image density corresponding to the application time was obtained.
From this example, two color images were obtained from a mixture of two types of dyes, and the thickness of the dye film, in other words, the image density, changed depending on the voltage application time. As a result, transferred images having different image densities were obtained. Is obtained.
[Example 7]
The apparatus shown in FIG. 9 and an aqueous solution obtained by mixing a 0.02 M aqueous solution of Pro Jet Fast Yellow 2 (yellow) and a 0.02 M aqueous solution of Cathilon Pure Blue 5GH (blue) were used. The current flowing through the platinum electrode 1 is 0 mA to +10 mA (the surface area of the electrode is 2 cm ² ) Was applied for 10 seconds so as to change in steps of +1 mA, a green (mixed color) thin film having a different dye concentration was formed on the platinum electrode 1 according to the applied current. Next, when the platinum electrode 1 was pulled out of the aqueous solution and brought into contact with paper to apply pressure, images formed on the paper with a green thin film having an image density corresponding to the amount of current were obtained.
[0068]
Next, in the apparatus shown in FIG. 9, when current was applied for 10 seconds so that the current flowing through the platinum electrode 1 changed from 0 mA to -10 mA in steps of -1 mA, the dye was applied on the platinum electrode 1 in accordance with the applied current. A blue thin film having a different concentration was formed. Next, when the platinum electrode 1 was pulled up from the aqueous solution and brought into contact with paper to apply pressure, images formed on the paper with a blue thin film having an image density corresponding to the amount of current were obtained.
[0069]
According to this embodiment, images of two colors are obtained from a mixture of two kinds of dyes, and the thickness of the dye film, in other words, the image density changes depending on the amount of current flowing, and as a result, transferred images having different image densities Is obtained.
Example 8
A substrate 80 shown in FIG. 10 in which platinum electrodes were formed in a matrix on a glass substrate was formed by a sputtering method. The electrodes on the substrate are divided into a region marked with green (first electrode) and a region marked with blue (second electrode), and as shown in FIG. Pro Jet Fast Yellow 2 (Zeneca) aqueous solution (yellow) and 0.02M Cathilon
The sample was immersed in a mixed solution with Pure Blue 5GH (manufactured by Hodogaya Chemical) aqueous solution (blue). Next, when a voltage of 4 V was applied to the electrodes in both areas for 20 seconds so that the electrodes in the area marked in green became the anode, a green (mixed color) thin film was formed on the anode side. On the other hand, a blue thin film was formed on the cathode side. Next, when the substrate 80 was brought into contact with the paper and pressure was applied, two patterns of green and blue were formed at once on the paper as shown in FIG.
[0070]
From this example, it can be seen that a two-color image can be obtained from a mixture of two dyes by one voltage application, and a two-color image can be obtained simultaneously by one transfer.
[0071]
【The invention's effect】
As described above in detail, according to the image forming method of the present invention, the density of an image can be adjusted, the influence on the environment is small, and the image can be formed with a small amount of energy consumption.
[0072]
Further, in the second image forming method of the present invention, it is possible to form a two-color image from one kind of aqueous solution by applying a current to a mixed solution in which dyes having different polarities are mixed.
[0073]
The image forming apparatus of the present invention can also achieve the above advantages.
When a color filter is manufactured using the above-described image forming method, the number of manufacturing steps is greatly reduced.
[Brief description of the drawings]
FIG. 1 shows an absorption spectrum of an aqueous solution of Pro Jet Fast Yellow 2, which is an anionic dye used in the present invention.
FIG. 2 shows an absorption spectrum of a thin film of Pro Jet Fast Yellow 2, which is an anionic dye used in the present invention.
FIG. 3 shows an absorption spectrum of Cathilon Pure Blue 5GH aqueous solution, which is a cationic dye used in the present invention.
FIG. 4 shows an absorption spectrum of a thin film of Cathilon Pure Blue 5GH which is a cationic dye used in the present invention.
FIG. 5 is a diagram illustrating the principle of the present invention, illustrating how different electrodeposited films are formed depending on the polarity of the electrode.
FIG. 6 is a graph showing the relationship between the ratio of Ypeak and Cpeak and the value and polarity of a voltage applied to an electrode.
FIG. 7 is an absorption spectrum of a color mixture film.
FIG. 8 is a schematic configuration diagram of an apparatus used in the present invention.
FIG. 9 is a schematic configuration diagram of an apparatus according to another embodiment used in the present invention.
FIG. 10 shows a substrate used in the present invention, in which electrodes are formed in a matrix on a support.
11 is a schematic configuration diagram of an apparatus for simultaneously forming two color electrodeposition films on the substrate of FIG.
12 is a schematic configuration diagram of an apparatus for sequentially forming two-color electrodeposition films on the substrate of FIG.
13 is a schematic configuration diagram of an apparatus for transferring an electrodeposition film of two colors formed on the substrate of FIG.
FIG. 14 is a schematic configuration diagram of an apparatus used in the present invention and capable of image formation and image transfer.
FIG. 15 is a schematic configuration diagram of another embodiment of an apparatus capable of forming an image and transferring an image used in the present invention.
FIG. 16 shows an absorption spectrum of a color filter in which a mixed film of Pro Jet Fast Yellow 2 and Cathilon Pure Blue 5GH is formed on a transparent substrate.
FIG. 17 shows an absorption spectrum of the electrodeposited film of a color filter in which an electrodeposited film of Cathilon Pure Blue 5GH is formed on a transparent substrate.
FIG. 18 shows two-color patterns obtained from the substrate of FIG.
[Explanation of symbols]
1 Platinum electrode (first electrode)
2 Platinum electrode (second electrode)
3 aqueous solution
7 Shiohashi
8 Saturated KCl solution
80 substrate
81 DC power supply
84 electrodes
92 Counter electrode
93 switch
94 DC power supply
95 DC power supply
96 Transfer media
112 2nd electrode
113 aqueous solution
115 roller (first electrode)
116 transfer roller
117 paper
119 Controller
120 Transfer roller (counter electrode)

Claims (18)

A dye immersed in or contacted with an aqueous solution in which two or more dye groups of the same polarity containing at least one kind of dye that can be solely precipitated from a state dissolved in an aqueous solution by an electrochemical reaction are dissolved in a coexisting state at a specific pH. A voltage is applied between one electrode and a second electrode provided so as to be capable of causing an electrochemical reaction in cooperation with the first electrode, so that the dye group is formed on the first electrode. An image forming method comprising the step of forming a mixed-color image constituted by: A dye immersed in or contacted with an aqueous solution in which two or more different-polarity dye groups containing at least one kind of dye that can be solely precipitated from an aqueous solution dissolved by an electrochemical reaction at a specific pH in a coexisting state. A voltage is applied between one electrode and a second electrode provided so as to be capable of causing an electrochemical reaction in cooperation with the first electrode, so that the dye is formed on at least the first electrode. An image forming method comprising the step of forming a mixed-color image formed of groups, a mixed-color image formed of the dye group and different from the color of the mixed-color image, or a single-color image formed of a single dye. The second electrode is immersed or in contact with the aqueous solution, a voltage is applied between the two electrodes to form a mixed-color image composed of the dye group on one electrode, and the other electrode is formed by the dye group. The image forming method according to claim 2, wherein the image forming method is configured to form a mixed-color image different from the color of the mixed-color image or a single-color image formed of a single dye. The first electrode and the second electrode are formed on the same substrate, and a mixed color image formed of the dye group on the substrate and a mixed color image formed of the dye group and different from the color of the mixed color image 3. The image forming method according to claim 2, wherein a single color image composed of a single dye is simultaneously formed. A plurality of the first electrodes are formed on the same substrate, and a mixed-color image formed of the dye group on the substrate and a mixed-color image formed of the dye group and different from the color of the mixed-color image or a single mixed-color image. 3. The image forming method according to claim 2, wherein at least one of the monochromatic images composed of the dyes is sequentially formed. The image forming method according to claim 1, wherein the aqueous solution contains an anionic dye having a carboxyl group and / or a cationic dye having an imino group. The image formation according to any one of claims 1 to 6, wherein when forming an image, the density of the image is controlled by controlling at least one of an applied voltage, an applied charge amount, an applied current, and an application time thereof. Method. 7. The image forming apparatus according to claim 1, wherein when forming an image, at least one of an applied voltage, an applied charge amount, an applied current, and an application time thereof is controlled to control the color of the image. Method. The image forming method according to claim 1, further comprising a step of transferring an image formed on the electrode to a transfer medium. The image forming method according to claim 9, wherein the electrode on which the image is formed is brought into contact with the transfer medium, and the image is transferred to the transfer medium by applying pressure. The electrode on which an image is formed is brought into contact with the medium to be transferred, and the electrode on which an image is formed and the electrode facing the electrode are arranged such that the polarity of the electrode on which an image is formed is opposite to the polarity at the time of image formation. The image forming method according to claim 9, wherein the image is transferred to the transfer-receiving medium by applying a voltage between the electrode and the electrode. 12. The image forming apparatus according to claim 9, wherein when transferring an image, at least one of an applied voltage, an applied charge amount, an applied current, and an application time thereof is controlled to control the image density. Method. A bath containing an aqueous solution in which two or more dye groups including at least one dye that can be precipitated alone from a state dissolved in the aqueous solution by an electrochemical reaction are dissolved in a coexisting state at a specific pH;
A first electrode immersed or in contact with the aqueous solution;
A second electrode provided to enable an electrochemical reaction to occur in cooperation with the first electrode;
Voltage applying means for applying a voltage between the first electrode and the second electrode;
An image forming apparatus comprising: The image forming apparatus according to claim 13, wherein the second electrode is immersed or in contact with the aqueous solution. 14. The image forming apparatus according to claim 13, wherein the first electrode and the second electrode are formed on a same substrate. 14. The image forming apparatus according to claim 13, wherein the plurality of first electrodes are formed on the same substrate. The image forming apparatus according to claim 13, further comprising a transfer unit configured to transfer an image formed on the electrode to a transfer medium. The image forming method according to any one of claims 1 to 8, wherein the color mixture image formed of the dye group or the color mixture image formed of the dye group on the transparent electrode as the first electrode. A color filter manufacturing method for manufacturing a color filter on which an electrodeposition film is formed as a mixed color image different from the above or as a single color image composed of a single dye.

Images