JPH11133224A - Production of color filter, color filter and apparatus therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing color filters having high controllability with high resolution with a smaller number of stages without using photolithography. SOLUTION: A substrate 18 successively formed with a transparent conductive film 14 and a semiconductor thin film 16 on a transparent substrate 12 is prepd. An aq. liquid 22 contg. color materials and an electrodeposition material which is chemically dissolved, deposited or settled by a change in pH is prepd. in a vessel 20 capable of holding the liquid. The substrate 18 connected with means 24 capable of supplying electric currents or electric fields according to image patterns is so fixed that the semiconductor thin film 16 is immersed into the aq. liquid 22. A counter electrode 26 which is the other of the electrode pair is arranged in the vessel 20. Prescribed mask patterns 28 are arranged on the transparent substrate 12 of the substrate 18 and are subjected to photoirradiation. Electrodeposited films 30 contg. the electrodeposition material are selectively deposited on the parts where electromotive force by the photoirradiation is generated, by which the color filters of a single color are formed. The color filters of multiple colors may be formed by repeating the stages of forming the plural color filter by changing the color tones of the color materials.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter used for various display devices such as a CCD camera and a liquid crystal display device and a color sensor and a technique for forming the same, and more particularly, to a method for producing a colored layer and a black matrix. Specifically, a method for manufacturing a novel color filter capable of easily forming a colored layer or a black matrix at a high resolution without using a photolithography process, a manufacturing apparatus used for the method, and a transparent filter in the filter obtained by the method. The present invention relates to a highly smooth color filter having a semiconductor film.

[0002]

2. Description of the Related Art At present, as a method for producing a color filter, (1) a dyeing method, (2) a pigment dispersion method, (3) a printing method, (4) an ink jet method, and (5) an electrodeposition method are known. I have. (1) The dyeing method is to form a water-soluble polymer to be dyed on a glass substrate, pattern this into a desired shape through a photolithography process, and then immerse the dye in a dye solution to form a colored pattern. And this was repeated three times. G. FIG. B. This is a method for obtaining a color filter layer.
The obtained filter has high transmittance, rich hue, and high technology perfection.
D) was frequently used. However, since a dye was used, the light resistance was poor and the number of manufacturing steps was large.
For CD), the pigment dispersion method has recently been replaced. (2) The pigment dispersion method is the most mainstream color filter manufacturing method in recent years. First, a resin layer in which a pigment is dispersed is formed on a glass substrate, and this is patterned through a photolithography process. This was repeated three times. G. FIG.
B. To obtain a color filter layer. This manufacturing method is disadvantageous in that the technology is highly complete, but the number of steps is large and the cost is high. (3) In the printing method, a pigment is dispersed in a thermosetting resin, and printing is repeated three times. G. FIG. B. And then applying heat to cure the resin to obtain a color filter layer. This method is described in R. G. FIG. B. In forming the layer, photolithography is not required, but there is a problem in resolution and uniformity of film thickness. (4) In the ink-jet method, a water-soluble polymer ink-receiving layer is formed on a substrate, and a hydrophilic / hydrophobic treatment is performed on the ink-receiving layer. G. FIG. B. This is a method of obtaining a color filter layer by applying different layers. This method is also described in R. G. FIG. B. The formation of the layer does not require photolithography,
Poor in resolution. In addition, there is a high probability that small droplets of ink will scatter and mix colors when sprayed on the adjacent filter layer, and the position accuracy is also poor. (5) In the electrodeposition method, a high voltage of about 70 V is applied to a pre-patterned transparent electrode in an electrolytic solution in which a pigment is dispersed in a water-soluble polymer to form an electrodeposition film by electrodeposition coating. And this is repeated three times. G. FIG. B. To obtain a color filter layer. This method has a drawback in that it is necessary to pattern a transparent electrode in advance by photolithography and use this as an electrode for electrodeposition, and since the shape of the pattern is limited, it cannot be used for TFT liquid crystal.

[0003] The present inventors have studied the electrodeposition technique itself from a fundamental point of view, and found that some of water-soluble dye molecules contain water in an oxidized state, a neutral state, and a reduced state. We focused on the fact that there are molecules whose solubility changes significantly. As an example of a compound having such properties, for example, rose bengal and eosin, which are fluorescein dyes, take a reduced state at pH 4 or higher and dissolve in water, but are oxidized to a neutral state at a pH lower than 4 And precipitates and precipitates. In addition, it is generally known that the solubility of a dye material having a carboxyl group greatly changes depending on the hydrogen ion concentration (pH) of a solution without causing a structural change. The dye is soluble in water above pH 6 but precipitates below it. When these dyes are dissolved in pure water and the electrodes are immersed in the solution and a voltage is applied, an electrodeposited film composed of these dye molecules is formed on the anode-side electrode. Also, a water-soluble acrylic resin, which is a kind of polymer having a carboxyl group, is p-type.
If H is 6 or more, it is soluble in water, but if it is less than H, it precipitates.
When the pigment is dispersed in the polymer, the electrode is immersed in the solution, and a voltage is applied, the pigment and the polymer are deposited on the electrode on the anode side to form an electrodeposition film in which the pigment and the polymer are mixed. You. These electrodeposited films are applied with a reverse voltage or pH
By immersing it in the aqueous solution of No. 12, it can be re-eluted into the aqueous solution. In addition, an oxazine-based basic dye Cathilon Pure B, which is one of quinone imine dyes, is used.
lu5GH (CI BasicBlue 3) and thiazine-based basic dye methylene blue (CIBa)
sicBlue 9) takes on an oxidized state at a pH of 10 or less and develops a color, but at a higher pH, it is reduced to insolubilize and precipitate. When these dyes are dissolved in pure water, and the electrodes are immersed in the solution and a voltage is applied, an electrodeposited film composed of these dye molecules is formed on the cathode-side electrode. By applying a reverse voltage or immersing the dye electrodeposition film in an aqueous solution having a pH of 8 or less, these dye electrodeposited films return to the original state and are eluted again in the aqueous solution.

In the conventional electrodeposition technique, the voltage required for forming an electrodeposition film is as high as about 70 V. When such a high voltage is applied, the Schottky barrier between the semiconductor and the electrolyte is broken, and image formation is not possible. Can not. In addition, there was no semiconductor that was transparent and practically usable for forming a color filter.
For this reason, in the above-described conventional method for manufacturing a color filter using electrodeposition coating, patterning of the transparent electrode is required, which is a factor that limits the shape of the pattern of the color filter. I have.

A method of forming an image with light using a dye for doping and undoping of a conductive polymer has also been proposed. However, it is necessary to form an electrodeposition film using only a dye without a conductive polymer. Is possible. However, the voltage required to form an electrodeposited film with the dye itself is higher than when a conductive polymer is present. On the other hand, the photovoltaic power is
Is about 0.6 V, and photovoltaic power alone is not sufficient for image formation. Therefore, a method such as raising a bias by applying a bias voltage is conceivable. However, when the voltage exceeds a certain voltage (a voltage depending on the band gap of the semiconductor to be used), the semiconductor and the solution necessary for forming the photovoltaic power are increased. There is a problem that the Schottky barrier is broken during this period, and there is a limit to the bias voltage that can be applied. For this reason, image formation in an aqueous solution using photovoltaic power has been limited to those using a photopolymerization reaction of a conductive polymer such as polypyrrole that is redox-reduced at 1.0 V or less. Further, in Japanese Patent Application Laid-Open No. 5-119209 (“Color filter manufacturing method and electrodeposited substrate for manufacturing color filter”) and Japanese Patent Application Laid-Open No. 5-157905 (“Color filter manufacturing method”), which are well known in this field, The electrodeposition voltage is increased from 20 V to 80 V, and utilizes a redox reaction of a polymer as an electrodeposition material. As described above, a polymer generally well known as an electrodeposition coating has a voltage required for electrodeposition of 10 V or more. Therefore, photoconductive properties such as ZnO ₂ for electrophotography have been used for image formation, but no practical material that can be used in an aqueous liquid that is easy to handle has been found.

In addition, a color filter is rarely used only in a color filter layer, and a color filter in which each color filter pixel is covered with a black matrix is generally used. Normally, photolithography is used to form a black matrix, which is one of the major factors for cost increase. Therefore, R. G. FIG. B.
Considering the layers and the black matrix, at present, there is no color filter manufacturing method which has high resolution, high controllability, does not require a photolithography step, and has a small number of steps. For example, it is well known that color filters occupy a large part of the cost in liquid crystal color display devices and the like,
This is also a major factor in the production of color filters because the yield is not increased and the cost is high.

Further, among the color filters manufactured by the methods (1) to (5), those obtained by the methods (1), (2) and (5) by a photolithography step are formed by lithography. Irregularities are formed on the surface of the substrate and the formed color filter layer, and those obtained by the methods (3) and (4) using printing technology have uneven portions on the surface of the ink layer. In any case, there is a problem in the surface smoothness. For this reason, even if a simple protective layer is formed on the upper portion, the unevenness cannot be sufficiently reduced by the thickness of the protective layer. At present, it is not possible to achieve a typical smoothness.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing a color filter having high resolution and high controllability, without using photolithography, with a small number of steps. Another object of the present invention is to provide a simple color filter manufacturing method and a manufacturing apparatus used therefor that can cope with a fine and complicated pixel arrangement, easily form a black matrix, and can be mass-produced. Still another object of the present invention is to provide a highly applicable color filter which can cope with a fine and complicated pixel arrangement, has excellent surface smoothness, and has a transparent semiconductor film in the filter. .

[0009]

In order to achieve the above object, the present inventors have reviewed the electrodeposition technique itself from a fundamental point of view. The physical properties and the like of the above-mentioned molecules whose solubility in water greatly changed were examined in detail. Dissolution or precipitation due to changes in the solubility of this molecule,
The phase change of the precipitate can be achieved by directly redoxing the molecule electrochemically or by changing the pH of the aqueous solution in which the molecule is dissolved. These electrochemically phase-change materials are hereinafter appropriately referred to as electrodeposition materials. The method for manufacturing a color filter of the present invention forms a transparent conductive film on a transparent substrate, prepares a substrate on which an organic semiconductor film or an inorganic semiconductor film is formed, and a color material in a container capable of holding a liquid. An aqueous liquid containing an electrodeposition material that is chemically dissolved or precipitated / precipitated due to a change in pH is prepared, and the substrate having a means for supplying an electric current or an electric field connected to the transparent conductive film is immersed in the semiconductor thin film in the aqueous liquid. A device having a counter electrode, which is the other of the pair of electrodes, is placed in the container, and the substrate is irradiated with light on a transparent substrate. A monochromatic color filter by depositing an electrodeposited film containing an electrodeposited material.

According to this method, the electrodeposited material is dissolved and dispersed in an aqueous liquid, and the electrode is immersed in the aqueous liquid to apply a voltage. A film is formed. When the electrodeposition material is a colorless or light-colored polymer material, a coloring material such as a pigment is dispersed in the polymer, and the electrode is immersed in a solution and a voltage is applied. The polymer is precipitated in a state where the pigment is contained, and a colored electrodeposition film in which the pigment and the polymer are mixed is formed. When the electrodeposition material itself is a colored substance, a colored electrodeposition film is formed as it is. In this case, it is not necessary to add a coloring material. The term “electrodeposited material that is chemically dissolved or precipitated / precipitated by the method” also includes an electrodeposited material composed of a dye which itself becomes a coloring material. These electrodeposited films may be applied with a reverse voltage or at a pH of high solubility (for anionic electrodeposited materials,
By immersion in an aqueous solution having a pH of 10 to 13 or a pH of 1 to 4 for a cationic electrodeposition material, it can be re-eluted into the aqueous solution. In the present invention, "aqueous liquid" is a general term for an aqueous solution or an aqueous dispersion in which all or a part of an electrodeposition material (dye, pigment, polymer compound, etc.) is dissolved or dispersed in an aqueous medium.

The formation of the electrodeposited film requires a certain threshold voltage or more, and if a current flows, the electrodeposited film is not necessarily formed. Therefore, if a bias voltage is applied, an image can be formed even if the voltage level inputted from the outside is small. Therefore, if a transparent semiconductor layer is formed on the substrate to be electrodeposited and light is used for the input signal, an arbitrary electrodeposition film can be formed at a desired position.
Hereinafter, the electrodeposited film thus formed is referred to as a photoelectrically deposited film. Here, the electrodeposition material may form an electrodeposition film by the sum of the electromotive force caused by light irradiation on the semiconductor layer and the bias voltage applied to the transparent electrode, and the application of the bias voltage depends on the photoelectromotive force. The bias voltage applied to the transparent electrode can be omitted if the photovoltaic power of the semiconductor is sufficient to form an electrodeposition film.

The color filter manufacturing technique using the photo-deposited film proposed by the present inventors is based on the above findings, and the outline of the image forming method is based on the use of an organic or inorganic transparent semiconductor as a substrate. By irradiating light, an electrodeposition material containing (or serving as) a coloring material in an aqueous solution is deposited on a semiconductor substrate in the form of a dye electrodeposition film to form an image. A transparent conductive film that has been patterned in advance, which is necessary in the method of forming a filter, is not required, and an arbitrary image pattern can be formed without a photolithography step.

In the multicolor filter layer according to the present invention, a transparent semiconductor thin film is formed on a transparent electrode, and a bias voltage is applied to the transparent electrode in an electrodeposition solution containing a color filter forming material. By irradiating light to generate a photoelectromotive force, the pH in the vicinity of the substrate is changed, and an electrodeposited film utilizing the difference in solubility of the polymer or dye molecule due to the pH is selectively formed on the light-irradiated portion. It can be formed by forming and repeating this step a plurality of times. For example, by repeating the color material three times with red (R), green (G), and blue (B), a full-color color filter is achieved.

According to the method of manufacturing a color filter of the present invention, a high-resolution photoelectric film is obtained by utilizing a Schottky junction between a transparent semiconductor thin film and an electrodeposition solution or a pn junction or a pin junction of the transparent semiconductor thin film itself. A deposition film can be formed.

Further, if the method for manufacturing a color filter of the present invention is applied, after forming a color filter layer,
By applying a voltage in the electrodeposition solution containing the black matrix forming material (with or without light at this time), the electric resistance of the already formed color filter layer is high. By the adjustment, the black matrix containing the electrodeposition material is selectively formed only on the portion where the color filter layer is not formed, and the black matrix can be easily formed. The black matrix is not limited to the method of forming by electrodeposition, but may be formed by using an ultraviolet curable resin.

The color filter of the present invention comprises a transparent conductive layer, a transparent organic semiconductor layer or an inorganic semiconductor layer, a coloring component and a polymer which is chemically dissolved or precipitated / sedimented by a change in pH on a transparent substrate. It is characterized in that a colored electrodeposition film layer formed by the contained electrodeposition material is sequentially laminated. By providing a plurality of colored electrodeposition film layers with different colors, a multicolor color filter may be provided, and a black matrix may be provided in addition to the color filter layer. This color filter is made of
Since the color filter is preferably provided by using photovoltaic power, the surface of the obtained color filter is extremely smooth and has excellent surface characteristics. Further, the substrate may have a semiconductor layer, and an electronic device can be formed directly on the surface of the color filter.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail. First, a molecule (electrodeposition material) that changes its solubility due to a change in pH such as alkalinity or acidity or an electrochemical change, and dissolves, or precipitates or precipitates, is required. The electrodeposition material is a dye itself, or has a property that a transparent polymer precipitates in an alkaline or acidic state, and a coloring material may be used by dispersing it with the polymer. When a colorant is dispersed in a polymer and used, not only a dye but also a pigment can be used. In the case of a color filter used for a part where high light resistance is required, it is desirable to use a color filter in which a pigment is dispersed in an aqueous polymer.

As a compound having a property of causing a phase change of dissolution, precipitation, or precipitation due to such a change in electrochemical conditions, for example, as a dye material, it takes a reduced state at pH 4 or more and dissolves in water. In the region below pH 4, fluorescein dyes such as rose bengal and eosin, which are oxidized to a neutral state to precipitate and precipitate,
Hydrogen ion concentration (pH) of solution without structural change
And a dye material having a carboxyl group whose solubility changes greatly (specifically, an ink jet dye having improved water resistance, which dissolves in water at a pH of 6 or more but precipitates at a pH below 6). Examples of the polymer material include a specific water-soluble acrylic resin which is a kind of a polymer having a carboxyl group which dissolves in water at a pH of 6 or more but precipitates at a pH below 6. In addition, an oxazine-based basic dye Cathilon Pure Blue, which is one of quinone imine dyes, is also used.
5GH (CI Basic Blue 3) and thiazine-based basic dye methylene blue (CI Basic)
Blue 9) takes on an oxidized state and develops color when the pH is 10 or less, but is reduced and insolubilized and precipitated when the pH is 10 or more. When these dyes are dissolved in pure water, and the electrodes are immersed in the solution and a voltage is applied, an electrodeposited film composed of these dye molecules is formed on the cathode-side electrode. By applying a reverse voltage or immersing the dye electrodeposition film in an aqueous solution having a pH of 8 or less, these dye electrodeposited films return to the original state and are eluted again in the aqueous solution.

These electrochemically phase-change materials are hereinafter referred to as electrodeposition materials as appropriate. When the electrodeposited material is dissolved in pure water, the electrode is immersed in the solution, and a voltage is applied, an electrodeposited film made of these electrodeposited materials is formed on the electrode on the anode side. When the electrodeposition material is a colored substance, a colored electrodeposition film is formed as it is. When the electrodeposition material is a colorless or light-colored polymer material, a pigment is dispersed in the polymer, and the electrode is immersed in a solution. When a voltage is applied, the pigment and the polymer precipitate on the electrode on the anode side, and an electrodeposition film in which the pigment and the polymer are mixed is formed. These electrodeposition films apply a reverse voltage or
Highly soluble pH (pH 10 to 10 for anionic electrodeposited materials)
13. The cationic electrodeposition material can be re-eluted into the aqueous solution by immersing it in an aqueous solution having a pH of 1 to 4). The formation of the electrodeposited film requires a certain threshold voltage or more, and if a current flows, the electrodeposited film is not necessarily formed. Therefore, if a bias voltage is applied, an image can be formed even if the voltage level inputted from the outside is small. Therefore, using a semiconductor for the substrate to be electrodeposited,
If light is used for this input signal, an arbitrary electrodeposition film can be formed at a desired position. Hereinafter, the electrodeposited film thus formed is referred to as a photoelectrically deposited film.

As an example of a compound capable of forming such a photo-deposited film, Pro Jet Fast Yel manufactured by Zeneca Co., Ltd., which is an acid dye and has a capability of forming an electrodeposition itself.
A description will be given taking low2 as an example. This dye is pure water (p
H6 to 8), easily dissolved and present as an anion in an aqueous solution, but having a property of being insolubilized and precipitated when the pH is 6 or less. This Pro Jet fast Ye
When immersed energized platinum electrode in an aqueous solution of llow2, OH in the aqueous solution near the anode ^- ions are consumed becomes O _2, pH is lowered by increasing the hydrogen ions. This is because the following reaction occurs in which the hole (p) and the OH ^- ion are connected near the anode. 2OH ⁻ + 2p ⁺ → 1/2 (O ₂ ) + H ₂ O A constant voltage is required for this reaction to take place.
Is reduced. Therefore, when a voltage exceeding a certain level is applied, Pro Jet fars occurs on the anode side of the electrode.
That is, the solubility of t Yellow2 is reduced to make it insoluble and a thin film is formed.

The present invention utilizes the photovoltaic power generated by irradiating a semiconductor with light to obtain the constant threshold voltage. Various attempts have been made so far to utilize photovoltaic power. For example, A. Fujis
Hima, K .; Honda Nature Vol. 2
38, p37, (1972), an n-type semiconductor TiO ₂
Was irradiated with light to electrolyze water. Further, in connection with the study of photoelectrochromism, an example in which an image is formed by doping / undoping by irradiating light onto a Si substrate to electrochemically polymerize pyrrole, is described in H.-J. Yoneya
Ma et al. Electrochem. So
c. , P2414, (1985). The present inventors have also previously filed a patent application for a method of forming an image with light using a dye for doping and undoping of a conductive polymer. On the other hand, it is possible to form an electrodeposited film only with a dye without using a conductive polymer, but the voltage required for forming the electrodeposited film is higher than when a conductive polymer is used. On the other hand, the photovoltaic power is at most 0.6 V in Si, and photovoltaic power alone is not sufficient for image formation. Therefore, a method such as raising a bias by applying a bias voltage is conceivable. However, when the voltage exceeds a certain voltage (a voltage depending on the band gap of the semiconductor to be used), the semiconductor and the solution necessary for forming the photovoltaic power are increased. There is a problem that the Schottky barrier is broken during this period, and there is a limit to the bias voltage that can be applied. For this reason, image formation in an aqueous solution utilizing the redox of a substance using photovoltaic power is limited to those using a photopolymerization reaction of a conductive polymer such as polypyrrole which is redox-reduced at 1.0 V or less. I was However, the present inventors utilize the difference in solubility of the above molecules depending on the pH for image formation, so that a colored polymer layer can be formed at a low voltage, and electrodeposition by photovoltaic using various semiconductors is possible. A colored image can be formed by the film, that is, a colored film of a color filter can be formed.

The transparent polymer electrodeposition material has both hydrophobic and hydrophilic groups in the molecule, and the number of the monomer groups constituting the polymer is 4 times the ratio of the total number of the hydrophilic groups to the hydrophobic groups.
It is in the range of 0% to 80%, and 50% or more of the hydrophilic group portion has the property of being able to reversibly change from a hydrophilic group to a hydrophobic group by a change in pH, and has an acid value of 30 to 600. It is preferable to use the coalescing from the viewpoint of the deposition property and the retention of the formed electrodeposited film, and by using a fine particle coloring material in combination, a colored layer having excellent light resistance can be formed. Further, as described above, a compound having both a unit that precipitates and precipitates by changing the pH in the molecule and a coloring material unit can be used as the electrodeposition material.

Next, the base of the color filter of the present invention will be described. In the present invention, since a photovoltaic force is used for forming a color filter, the substrate needs to be transparent. Therefore, the substrate is preferably a glass substrate which can be suitably used also as a semiconductor substrate. First, a transparent conductive layer is formed on a glass substrate. As the conductive layer, a known conductive layer can be used arbitrarily.
What is necessary is just to form a film.

A transparent organic or inorganic semiconductor layer is formed on the transparent conductive layer. As the semiconductor layer, titanium oxide is particularly preferable. This titanium oxide is transparent, having an absorption of only 400 nm or less, and can be used as it is as a substrate for producing a color filter. In recent years, titanium oxide has been produced by various methods such as a sol-gel method, a sputtering method, and an electron beam evaporation method.
A semiconductor having good characteristics is obtained as a type semiconductor. Here, TiO ₂ which is a suitable transparent semiconductor will be described. Ti
O ₂ is a transparent oxide semiconductor and generates photovoltaic energy when irradiated with ultraviolet light. Therefore, a photo-deposition film can be formed on a transparent substrate by applying ultraviolet rays from the back of the substrate. Ti
Several methods are known for the film formation of O ₂ . For example, a thermal oxide film method, a sputtering method, an electron beam method (EB method), a sol-gel method and the like are well known. We formed TiO ₂ films by the EB method and the sol-gel method. However, the efficiency of the ordinary film forming method is poor, and the photocurrent necessary for electrodeposition does not flow. Therefore, a reduction treatment was performed to increase the conversion efficiency of the photocurrent. The reduction treatment is generally performed by heating at about 550 degrees in hydrogen gas. For example, Y. Hamaki et al. Elect
rochem. Soc. Vol. 141, No
3. In p660 and 1994, heating is performed in hydrogen gas at about 550 degrees for about one hour. However, we have about 360
A sufficient effect was obtained by a low-temperature and short-time treatment of 10 minutes at a temperature. This was achieved by heating with a flow rate of 1 liter per minute using 3% hydrogen mixed nitrogen gas.

As the semiconductor film applicable to the color filter substrate of the present invention, basically, any transparent thin film substrate that generates an electromotive force by light irradiation can be used. Specifically, as a transparent semiconductor, an organic semiconductor is polyvinylcarbazole, polyacetylene, or the like. As an inorganic semiconductor, Ga-N, diamond, C-BN,
SiC, ZnSe, TiO ₂ , ZnO and the like can be mentioned. The semiconductor includes an n-type semiconductor and a p-type semiconductor, and any semiconductor can be used in the present invention. Furthermore, p
When a stacked structure using an n-junction or a pin junction is used, a photocurrent flows well, an electromotive force can be reliably obtained, and the contrast is improved, which is more desirable.

Next, a combination of a semiconductor and a material capable of forming an electrodeposition film is determined by the polarity of the semiconductor used. A photovoltaic voltage is formed by using a Schottky barrier or a pn or pin junction generated at an interface in contact with a semiconductor, as is well known as a solar cell. As an example, an n-type semiconductor will be described with reference to the schematic diagram of FIG. The schematic diagram of FIG. 1A shows the case of the Schottky junction, and the schematic diagram of FIG. 1B shows the case of the PIN junction. n
When there is a Schottky barrier between the mold semiconductor and the solution, the current flows in the forward direction when the semiconductor side is negative, but does not flow when the semiconductor side is positive. However, even in a state where the semiconductor side is positive and no current flows, when light is irradiated, electron-hole pairs are generated, and the holes move to the solution side and the current flows. In this case, since the semiconductor electrode is made positive, the material to be electrodeposited must be negative ions. Accordingly, a combination of an n-type semiconductor and an anionic molecule is formed, and conversely, a cation is electrodeposited in a p-type semiconductor.

In general, the photovoltaic power of a semiconductor is only 0.6 V at most even with relatively large Si. However,
Materials that can be electrodeposited at 0.6 V are limited. Therefore,
The missing voltage must be compensated by applying a bias voltage. The upper limit of the bias voltage that can be applied is up to the limit at which the Schottky barrier is maintained. When the Schottky barrier is broken, a current also flows in a region not exposed to light, and an electrodeposition film is formed on the entire region of the semiconductor substrate, so that an image cannot be formed. For example, if the material is electrodeposited at 2.0 V, when a bias voltage of 1.5 V is applied and light is applied, the photovoltaic power of the semiconductor is added to 0.6 V to 2.1 V, which is a threshold necessary for electrodeposition. The photoelectric deposition film is formed only in the region where the voltage is exceeded and the light is irradiated.

Substance (electrodeposition material) capable of forming this electrodeposition film
FIG. 2 is a graph showing the dissolution characteristics of the electrodeposited material with a change in pH, as a guideline for selecting. FIG. 2 is a graph showing the relationship between the dissolution characteristics of various materials and the pH of the solution. Some of the materials, such as graph A (shown by a solid line), rapidly precipitate at a certain pH value, and graph B (shown by a broken line)
Good solubility regardless of the pH value, such as the material of
Some materials are insoluble irrespective of the pH value, such as the material in graph C (indicated by a dashed line), and these characteristics vary depending on the relationship between the material and the solvent (dispersion medium) used. In the present invention, as shown in graph A, it is preferable that precipitation occurs sharply at a certain pH value, and as this graph A shows a so-called hysteresis curve,
What does not re-dissolve rapidly and is kept in a precipitated state for a certain period of time is ideal from the viewpoint of the stability of the formed image. Therefore, it is preferable to select a combination of an electrodeposition material and a solvent having such characteristics.

The ionic molecules used in the production of the color filter of the present invention include known anionic and cationic molecules as long as their solubility changes as described above due to a change in pH. Any of the sex molecules can be used. Specifically, triphenylmethanephthalide type, phenosadine type, phenothiazine type, fluoran type, indolylphthalide type, spiropyran type, azaphthalide type, diphenylmethane type, chromenopyrazole type, leuco auramine type, azomethine type, rhodamine Lactal compounds, naphtholactam compounds, triazene compounds, triazole azo compounds, thiazole azo compounds, azo compounds, oxazine compounds, thiazine compounds, benzothiazole azo compounds, quinone imine compounds, and the like are typical examples.

As these electrodeposition materials, not only one kind of compound can be used but also two or more kinds of compounds can be used in combination. For example, (1) a mixture of same polarity molecules such as a mixture of two or more anionic molecules and a mixture of two or more cationic molecules, and (2) a heteropolar mixture such as a mixture of an anion molecule and a cationic molecule. Various mixtures can be used, such as a mixture of molecules, (3) a mixture of dye and pigment, and (4) a mixture of polymer and pigment. If two or more compounds have different hues, a mixed color will be obtained. In the case of a mixture, it is necessary to include at least one kind of substance having a property that the solubility changes due to a change in pH and a thin film is formed by itself. By using in combination with this substance, even if the material alone does not have the ability to form a thin film, a mixed color can be obtained because the electrodeposited film is formed in the state of being incorporated into the material having the ability to form the film at the time of film formation. is there. For example, rose bengal and eosin, which are fluorescein dyes, take a reduced state at pH 4 or higher and dissolve in water.
Below that, it is oxidized to a neutral state and precipitates. Similarly, a diazo-based Pro Jet First Yellow
w2 and certain water-soluble acrylic resins are soluble in water above pH 6, but precipitate below that. When these molecules are dissolved in pure water and the electrodes are immersed in the solution and a voltage is applied, an electrodeposited film composed of these molecules is formed on the electrode on the anode side. These electrodeposited films are applied with reverse voltage or pH.
By immersing in 10 to 12 aqueous solutions, it can be re-eluted into the aqueous solution. As described above, Rose Bengal, Eosin, and Pro Jet First Yellow 2 are materials having a capability of forming an electrodeposition film by themselves, but when mixed with a dye material having no capability of forming an electrodeposition film, a mixed color electrodeposition film can be obtained. At this time, the dye material to be mixed may or may not have ionicity. Further, depending on the characteristics of the substances to be combined, substances having different ion polarities can be used together.

Consider the case where two types of ions are mixed. In general, when a basic solution and an acidic solution are mixed, they are neutralized to form another precipitate such as a complex and precipitate. Therefore, when two types of dyes are mixed to produce a mixed color, it is common to use a non-polar pigment or disperse a material of the same polarity. However, certain dyes take a state in which no complex is formed and ions coexist. In this case,
Even when a basic solution and an acidic solution are mixed, the precipitate can be suppressed, and a combination of ions having different polarities can be used. We have considered the case where two kinds of dye ions are mixed using this property.

First, two kinds of ions having the same polarity, for example, brilliant blue (blue) which is the same anionic but has no electrodeposition film forming ability as Rose Bengal (red) which is anionic and has an electrodeposition film forming ability. Is electrochemically oxidized in a mixed solution in which is mixed, a purple electrodeposited film having the same color as the mixed solution is formed on the electrode. This is because brilliant blue ions are taken into Rose Bengal, which has an electrodeposition film forming ability, to form a film. As described above, when two kinds of ions having the same polarity are mixed, any one of them is used.
It is only necessary that the type of ions have an electrodeposition film forming ability.

Next, two types of ions having different polarities, for example, Pro Jet F which is anionic and has an electrodeposition film forming ability.
Cat Yellow Pure Blue which is cationic and has an electrodeposition film forming ability
e When electrochemically oxidized in a mixed solution containing 5GH (blue), a green electrodeposited film having the same color as the mixed solution is formed on the electrode. Conversely, when electrochemical reduction is performed, a blue electrodeposited film of CatilonPure Blue 5GH alone is formed on the electrode. To explain the characteristics of such an ionic compound, for example, as shown in a graph of FIG. 3, one compound is dissolved in a solvent in a neutral region as shown in a graph A (shown by a solid line); At a certain low pH value, precipitation occurs rapidly, and the other compound is shown in graph B.
In the case of a material having a characteristic that it dissolves in a solvent in a certain neutral region such as a material (shown by a broken line) and rapidly precipitates at a high pH value, it maintains high solubility in a neutral region and has a specific p.
At the H value, a phase change of dissolution and precipitation occurs, so that it can be used in combination. In the case of having such characteristics, when an electrochemical reaction is performed in a mixed solution of an anionic dye solution and a cationic dye solution, only the polarity of the applied voltage is changed, and different dyes are applied on the same electrode. An electrodeposition film can be formed.

When a pigment is used as a coloring material, it may be used in combination with a transparent or light-colored polymer material having an electrodeposition property, such as a water-soluble acrylic resin or a water-soluble styrene resin, and dispersed in an aqueous solution. Similarly, when the electrodeposition material similarly forms an electrodeposition film, a colored electrodeposition film containing a pigment is obtained.

Next, the conductivity and the pH of the solution will be described.
According to our experiments, the conductivity is related to the electrodeposition speed, in other words, the amount of electrodeposition. As the conductivity increases, the film thickness of the electrodeposition film deposited for a certain period of time increases, and
Saturates at mS / cm ² . (See FIG. 4) Accordingly, when the conductivity of the dye ion alone is insufficient, the electrodeposition speed can be increased by adding an acidic or alkaline substance which does not affect the electrodeposition characteristics, for example, Na ⁺ ion or Cl ⁻ ion. Can be controlled, for example, by applying a voltage of 5 V or less, the electrodeposition film can be formed. Further, the pH of the aqueous solution naturally affects the formation of the electrodeposited film. For example, if the electrodeposited film is formed under the condition that the solubility of the dye molecule is saturated before the electrodeposited film is formed, it is difficult to dissolve again after the film is formed. However, when the electrodeposited film is formed at the pH of the solution in an unsaturated state, even if the electrodeposited film is formed, the film starts to be redissolved as soon as the current is stopped. Therefore, it is desirable to form the electrodeposited film at the pH of the solution at which the solubility is saturated.

The method for manufacturing the color filter of the present invention will be described with reference to FIG. First, a transparent conductive film 14 is formed on the transparent substrate 12 as described above (FIG. 5).
(A)), a substrate 1 having a semiconductor thin film 16 formed thereon.
8 (FIG. 5B) is prepared. Next, using a device having a triode arrangement commonly used in electrochemistry as shown in FIG. 6, the material is chemically dissolved or precipitated / sedimented by a change in the colorant and pH in a container 20 capable of holding a liquid. The substrate 18 is filled with an aqueous liquid 22 containing an electrodeposition material and further connected to the transparent conductive film 14 with a means 24 capable of supplying a current or an electric field according to at least an image pattern in the container 20. Is fixed so as to be immersed in the aqueous liquid 22, and the counter electrode 26, which is the other of the electrode pairs, is similarly arranged in the container 20. On the other hand, the saturated calomel electrode 25
Was placed in a container 23 filled with a saturated aqueous solution of potassium chloride as a reference liquid interface, and a salt bridge 27 was provided between the container and the container 22 containing the electrodeposited material. Here, the saturated calomel electrode 2
5, a TiO ₂ electrode 16 is used as a working electrode.

When a predetermined mask pattern 28 is arranged on the transparent substrate 12 of the substrate 18 and light irradiation is performed, a color containing an electrodeposition material and a coloring material selectively in a portion where an electromotive force is generated by the light irradiation. The electrodeposition film 30 is deposited, and this becomes a coloring layer of a monochromatic color filter. The coloring layer 30 is fixed by removing the substrate 18 on which the colored electrodeposition film is formed from the aqueous liquid 22 and removing the solvent. Here, the portion where the electromotive force is generated is determined by arranging the mask pattern 28. However, writing is performed directly by laser light without using the mask pattern 28, so that the electromotive force is generated by irradiation of light on a predetermined portion. It can also be done.

At this time, the color tone of the color material is changed to, for example, red (R), green (G), and blue (B), and this step (the step of forming a monochromatic color filter) is repeated. A multi-color filter can be easily formed only by performing the same process while changing the mask pattern 28 (FIG. 5C). Further, a black matrix layer 32 is formed as described later (FIG. 5).
(D)) If necessary, a protective layer 34 is formed on the substrate 18.
A multicolor filter including the semiconductor film 16 therein is obtained (FIG. 5E).

The saturated calomel electrode potential is 20 ° C., 25 ° C.,
0.2444V, 0.2412 respectively at 30 ° C
V, 0.23878V, which is almost equal to the ground potential = 0V. In forming an image, a container (electrolyte) can be used with a ground connection without using a saturated calomel electrode. However, in order to clarify the potential of the work electrode (deposition side electrode), as described above, Alternatively, the electrolyte may be connected to the saturated calomel electrode to set the potential of the electrolyte surface to the standard potential of the saturated calomel electrode.

Next, an exposure apparatus for producing a photoelectrically deposited film will be described. Since it is necessary to expose through the mask pattern from the back of the color filter, the exposure light source must have a wavelength sensitive to the transparent semiconductor. Then 40
It is necessary to perform exposure with a light source of 0 nm or less, and usually, a mercury lamp, a mercury xenon lamp, a He-Cd laser, an N ₂ laser, an excimer laser, and the like are preferably used.

Next, a method of forming a black matrix will be described. The formation of the black matrix is conventionally known as a common method of forming a color filter layer using photolithography, or a black matrix is formed only in a portion without a color filter layer using an ultraviolet curable resin. Although various methods are available, various measures are required to completely perform the shielding, which is a major factor in increasing the cost of the color filter. However, when a color filter layer is formed using our photo-electrodeposition method, the semiconductor is exposed in a region where the photo-electrodeposition film is not formed, and an electrodeposition film for a black matrix is easily formed in this part. it can. Furthermore, since the formed electrodeposition film is generally an organic thin film and has high insulation properties, it is rather difficult to form a further photoelectrodeposition film on the formed color filter layer. Therefore, if a voltage is applied in an electrolytic solution for a black matrix after forming a color filter layer by using a photoelectrodeposition method (at this time, light may or may not be present, so no particular exposure is required). The black matrix electrodeposition film is formed so as to cleanly fill the unformed region of the color filter layer.
As described above, the use of the photoelectric deposition film makes it possible to easily form the black matrix at low cost. In addition, even if an ultraviolet curable resin is used, an electrodeposited film is formed cleanly in a region where the color filter layer is not formed, so that an ultraviolet curable resin may be used instead of forming the electrodeposited film. However, when a color filter layer is formed using a highly conductive electrodeposition material, it is possible to further laminate an electrodeposition film, and when forming a color filter layer having a different function, it is useful. However, when the black matrix is formed by the method described above,
It is necessary to pay attention to conditions such as applied voltage.

A protective layer can be provided on the color filter layer and the black matrix thus formed for improving smoothness and durability. The protective layer can be formed by a conventional method using a resin material such as an acrylic resin, a polyimide resin, and a polyester resin.

As shown in FIG. 5D, the color filter of the present invention obtained by the above-mentioned manufacturing method is as follows.
On a transparent substrate, a transparent conductive layer, a transparent organic semiconductor layer or an inorganic semiconductor layer, a coloring component and a colored electrodeposition film layer formed of an electrodeposition material that is chemically dissolved or precipitated / sedimented by a change in pH, It is characterized by being laminated, and any pigment or dye can be used as a coloring material, and desired light resistance and color tone can be selected. In addition, by adjusting the conditions for forming the electrodeposited film, a smooth surface can be obtained, so that a color filter having excellent smoothness can be manufactured at a low cost by a simple method, and has an advantage that the application range is wide. .
Further, since the substrate contains a semiconductor film and has good surface smoothness, it can be suitably used for applications in which an electronic device is formed directly on the surface of a color filter.

In the specification of the present application, a description has been given mainly of an example of manufacturing a filter composed of RGB and a black matrix. However, an electrodeposition material containing a cyan, magenta, and yellow colorant is added or changed by increasing or changing the colorant. May be used to create the CMY color filters. In this case, it can be suitably used as a reflection type filter. Further, a combination of three or more colors, for example, a six-color filter can be formed in combination with an RGB filter. Further, the black matrix may be formed last or first. According to the production method of the present invention, a transparent substrate, a transparent conductive film, an inorganic or organic semiconductor film, preferably a transparent electrodeposition colorant layer containing a colorant having an RGB color separation filter and a black matrix are laminated in this order. A color filter can be manufactured. This color filter can be used as it is as a color filter device, or only the transparent electrodeposition colorant layer can be transferred and used.

In the method for producing a color filter of the present invention, a color filter layer is formed on a hard substrate by an electrochemical method. Therefore, even if a defect is found, a predetermined portion of the color filter layer is removed. By using a new mask pattern, a new layer can be formed by depositing only a desired portion, and defect repair can be easily performed. In addition, defective products can be easily removed because the formed filter can be easily removed, and the substrate can be easily reused because the substrate is reusable. This significantly improves the production yield and generates waste. Is also advantageous.

【Example】

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. (Example 1) As shown in FIG. 7, a transparent conductive film 14 of ITO was formed on a glass substrate 12 having a thickness of 1 mm by sputtering.
A 0 nm film is formed, and then a TiO ₂ 16 film of 250 nm is formed. Next, a reduction process is performed to improve the photocurrent characteristics of TiO ₂ 16. The reduction treatment was performed by annealing at 350 ° C. for 10 minutes in pure nitrogen gas mixed with 3% hydrogen gas. This was converted to a styrene-acrylic acid copolymer (molecular weight of 13,00) as an electrodeposition material in a three-electrode arrangement generally used in electrochemical using the apparatus shown in FIG.
0, an aqueous solution 22 containing a pigment obtained by dispersing a hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio of 65%, an acid value of 150) and an azo red ultrafine particle pigment as a coloring material in a solid content ratio of 1: 1. In the inside, the TiO ₂ electrode 16 is used as a working electrode with respect to the saturated calomel electrode 25, and the working electrode is set to 1.7 V and a mercury xenon lamp (Yamashita Denso, wavelength 365) is set from the back side of the substrate.
When light was irradiated at a light intensity of 50 mW / cm ² for 10 seconds through the photomask 28, a red filter pattern was formed on the TiO ₂ 16 surface only in the irradiated region. The filter pattern was dried to reliably perform film formation.

Next, a styrene-acrylic acid copolymer (molecular weight 13,000, molar ratio of hydrophobic group / (hydrophilic group + hydrophobic group) 65%, acid value 150) and a phthalocyanine green-based ultrafine particle pigment were mixed with a solid content ratio. Using a TiO ₂ electrode as a working electrode with respect to a saturated calomel electrode in an aqueous solution containing a pigment dispersed one-to-one with a 1.7-V working electrode, a mercury-xenon lamp (Yamashita Denso, wavelength: 365
When light was irradiated at a light intensity of 50 mW / cm ² for 10 seconds through a photomask, a green filter pattern was formed on the TiO ₂ surface only in the irradiated region. Similarly, a styrene-acrylic acid copolymer (molecular weight 13,000, hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio 65%, acid value 150) and a phthalocyanine blue-based ultrafine particle pigment in a solid content ratio of 1: 1 Using a TiO ₂ electrode as a working electrode with respect to a saturated calomel electrode in an aqueous solution containing the pigment dispersed in 1, and setting the working electrode to 1.7 V, a mercury xenon lamp (Yamashita Denso, wavelength: 365 nm) was applied from the back side of the substrate.
Light intensity of 50 mW / cm ² ) through a photomask.
When light was irradiated for 0 seconds, a blue filter pattern was formed only on the light-irradiated region on the TiO ₂ surface, and a color filter layer was formed.

After each color filter layer is fixed,
After washing with pure water, a styrene-acrylic acid copolymer (molecular weight: 13,000, hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio: 6)
5%, acid value 150) and carbon black powder (average particle size 80 nm) dispersed in an aqueous solution containing a pigment in a solid content ratio of 1 to 1 using a TiO ₂ electrode as a working electrode with respect to a saturated calomel electrode, When a voltage was applied to the working electrode at 2.0 V, a thin film containing carbon black was formed only in the region without the color filter layer, and a black matrix was formed. After washing, a protective layer was coated on the upper part to obtain a color filter. Observation of the surface of the color filter revealed that the surface was extremely smooth and could be suitably used as a general color filter and also used for forming an electronic device directly on the color filter.

(Embodiment 2) As shown in FIG.
A transparent conductive film of ITO is formed to a thickness of 100 nm on the glass substrate by sputtering, and a TiO ₂ film of 250 nm is further formed. Next, a reduction treatment is performed to improve the photocurrent characteristics of TiO ₂ . The reduction treatment was performed by annealing at 350 ° C. for 10 minutes in pure nitrogen gas mixed with 3% hydrogen gas. This was converted to a styrene-acrylic acid copolymer (molecular weight 13,000, hydrophobic group / (hydrophilic group + hydrophobic group)) in a general three-electrode arrangement in electrochemical manner as in Example 1.
In a water solution containing a pigment having a molar ratio of 65% and an acid value of 150) and an azo red ultrafine particle pigment dispersed at a solid content ratio of 1: 1 using a TiO ₂ electrode as a working electrode with respect to a saturated calomel electrode. The working electrode was set to 1.7 V, and a mercury-xenon lamp (manufactured by Yamashita Denso, light intensity of 365 nm, 50 mW / cm ² ) was applied from the back side of the substrate through a photomask to 10 V
When the light was irradiated for ₂ seconds, a red filter pattern was formed on the TiO ₂ surface only in the area where the light was irradiated.

Next, a styrene-acrylic acid copolymer (molecular weight 13,000, molar ratio of hydrophobic group / (hydrophilic group + hydrophobic group) 65%, acid value 150) and a phthalocyanine green-based ultrafine particle pigment were mixed with a solid content ratio. Using a TiO ₂ electrode as a working electrode with respect to a saturated calomel electrode in an aqueous solution containing a pigment dispersed one-to-one with a 1.7-V working electrode, a mercury-xenon lamp (Yamashita Denso, wavelength: 365
When light was irradiated at a light intensity of 50 mW / cm ² for 10 seconds through a photomask, a green filter pattern was formed on the TiO ₂ surface only in the irradiated region. Similarly, a styrene-acrylic acid copolymer (molecular weight 13,000, hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio 65%, acid value 150) and a phthalocyanine blue-based ultrafine particle pigment in a solid content ratio of 1: 1 Using a TiO ₂ electrode as a working electrode with respect to a saturated calomel electrode in an aqueous solution containing the pigment dispersed in 1, and setting the working electrode to 1.7 V, a mercury xenon lamp (Yamashita Denso, wavelength: 365 nm) was applied from the back side of the substrate.
Light intensity of 50 mW / cm ² ) through a photomask.
When light was irradiated for 0 seconds, a blue filter pattern was formed only on the light-irradiated region on the TiO ₂ surface, and a color filter layer was formed.

Next, after the formed color filter layer was washed with pure water, a styrene-acrylic acid copolymer (molecular weight 13,000, hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio 65%, acid In the aqueous solution containing a pigment in which a carbon black powder (average particle diameter: 80 nm) and carbon black powder (average particle diameter: 80 nm) are dispersed at a solid content ratio of 1: 1, a TiO ₂ electrode is used as a working electrode with respect to a saturated calomel electrode. .6 V and a mercury xenon lamp (Yamashita Denso, wavelength 3
When a light intensity of 65 nm and a light intensity of 50 mW / cm ² ) was applied to the entire surface for 10 seconds, a copolymer thin film containing carbon black was formed only in a region where the color filter layer was not formed,
It became a black matrix. After washing, a protective layer was coated on the upper part to obtain a color filter. In this embodiment, the entire surface of the mercury xenon lamp was used for the formation of the black matrix. However, a good black matrix similar to that of the first embodiment in which a voltage was applied without using light irradiation was formed.

(Embodiment 3) As shown in FIG.
ITO transparent conductive film on glass substrate by sputtering
100nm film is formed and sol-gel method is applied on ITO thin film.
250nm TiO _TwoTo form a film. Film formation on ITO substrate
TiO by spin coating_TwoAlkoxide (Nippon Soda)
Manufactured by Atron NTi-092) at 1500 rotations
Roll, form a film in 20 seconds, then heat at about 500 degrees for 1 hour
TiO_TwoIs formed. Example of reduction processing
As in 1, in pure nitrogen gas mixed with 3% hydrogen gas
Annealing was performed at 350 degrees for 10 minutes. this
Was subjected to the same electrochemistry as in Example 1 as shown in FIG.
In a typical triode arrangement, styrene-acrylic acid
Polymer (molecular weight 13,000, hydrophobic group / (hydrophilic group + hydrophobic
Group) molar ratio 65%, acid value 150) and azo red ultrafine particles
Water containing pigments in which the pigments are dispersed at a solid content ratio of 1: 1
In solution, the TiO is saturated against the calomel electrode._TwoWorking electrode
It is used as an electrode, and the working electrode is set to 1.7 V to the back of the substrate.
Mercury xenon lamp (Yamashita Denso, wavelength 365n)
m light intensity 50 mW / cm^Two) Through the photomask
When light was irradiated for 10 seconds, TiO_TwoLight irradiates the surface
The red filter pattern is formed only in the
Was. Next, a styrene-acrylic acid copolymer (molecular weight 1
3,000, hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio of 65
%, Acid value 150) and ultra fine particles of phthalocyanine green
Aqueous solution containing pigment in which pigment is dispersed at a solid content ratio of 1: 1
TiO to saturated calomel electrode in liquid_TwoElectrode to working electrode
The working electrode is set to 1.7V and the back side of the substrate
From a mercury xenon lamp (Yamashita Denso, wavelength 365nm)
Light intensity 50mW / cm^Two) Through a photomask for 10
When irradiated with light for seconds, TiO_TwoThe surface is illuminated with light
The green filter pattern is formed only in the area
Was. Similarly, a styrene-acrylic acid copolymer (molecular weight 1
3,000, hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio of 65
%, Acid value 150) and phthalocyanine blue-based ultrafine particles
Aqueous solution containing a pigment in which a pigment is dispersed at a solid content ratio of 1: 1
TiO2 for saturated calomel electrode in_TwoElectrode as working electrode
And set the working electrode to 1.7V from the back side of the substrate
Mercury xenon lamp (Yamashita Denso, light with a wavelength of 365 nm)
Strength 50mW / cm^Two) Through a photomask for 10 seconds
Irradiating the light between the TiO_TwoLight shined on the surface
The blue filter pattern is formed only in the area,
A color filter layer was formed. Next, the formed color
-After washing the filter layer with pure water,
Luic acid copolymer (molecular weight 13,000, hydrophobic group / (hydrophilic group)
+ Hydrophobic group) 65%, acid value 150) and carbon
Rack powder (average particle diameter 80 nm) is 1 to 1 in solid content ratio.
Saturated calomel electrode in aqueous solution containing pigment dispersed in 1
Against TiO_TwoUsing the electrode as the working electrode
To 1.6V, from the back side of the substrate, a mercury xenon lamp
(Yamashita Denso, light intensity at a wavelength of 365 nm 50 mW / cm
^Two) Is irradiated on the entire surface for 10 seconds.
Co-load containing carbon black only in the unformed area of the luster layer
A coalesced thin film was formed to form a black matrix.
After cleaning, coat a protective layer on top of
-Filter was obtained. In this embodiment, the sol-gel method is used.
TiO_TwoWas formed by sputtering method.
As in the case, a good color filter was obtained.

(Embodiment 4) As shown in FIG.
ITO transparent conductive film on glass substrate by sputtering
100nm film is formed and sol-gel method is applied on ITO thin film.
250nm TiO _TwoTo form a film. Film formation on ITO substrate
TiO by spin coating_TwoAlkoxide (Nippon Soda)
Manufactured by Atron NTi-092) at 1500 rotations
Roll, form a film in 20 seconds, then heat at about 500 degrees for 1 hour
TiO_TwoIs formed. Example of reduction processing
As in 1, in pure nitrogen gas mixed with 3% hydrogen gas
Annealing was performed at 350 degrees for 10 minutes. this
Is a triode-type arrangement commonly used in electrochemistry as shown in FIG.
Styrene-acrylic acid copolymer (molecular weight 1)
3,000, hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio of 65
%, Acid value 150) and azo red ultrafine particle pigment in solid content ratio
In an aqueous solution containing pigment dispersed 1: 1 at a
TiO to chrome electrode_TwoUse electrode as working electrode
The working electrode was set to 1.7 V and the mercury
Non-lamp (manufactured by Yamashita Denso, light intensity 50 at a wavelength of 365 nm)
mW / cm^Two) Illuminate through a photomask for 10 seconds
When shot, TiO_TwoOnly the area where light was irradiated on the surface
A red filter pattern was formed. Next,
Len-acrylic acid copolymer (molecular weight 13,000, hydrophobic
Group / (hydrophilic group + hydrophobic group) molar ratio 65%, acid value 150)
And phthalocyanine green based ultrafine pigment
Calorie in an aqueous solution containing pigment dispersed one-to-one with
TiO_TwoUsing the electrode as a working electrode,
Electrode for 1.7V and the mercury xenon lane from the back side of the substrate
Pump (Yamashita Denso, light intensity of 365mW, 50mW /
cm^Two) Was irradiated with light through a photomask for 10 seconds.
However, TiO_TwoGrease only in the area where light was irradiated on the surface
A filter pattern was formed. Similarly, stille
Acrylic acid copolymer (molecular weight 13,000, hydrophobic group
/ (Hydrophilic group + hydrophobic group) molar ratio 65%, acid value 150)
1 phthalocyanine blue-based ultrafine pigment at a solid content ratio of 1
Saturated calomel charge in aqueous solution containing pigment dispersed one-to-one
The TiO2 electrode is used as the working electrode for the
1.7V mercury xenon lamp from back side of substrate
(Yamashita Denso, light intensity at a wavelength of 365 nm 50 mW / cm
^Two) Was exposed to light for 10 seconds through a photomask.
TiO_TwoOnly the area of the surface where light was
Filter pattern is formed, and the color filter layer
Been formed.

After the formed color filter layer was washed with pure water, carbon black powder (average particle diameter 80 n
m) was brought into contact with the UV-curable resin solution dispersed therein, and UV light was irradiated from the back side of the substrate. As a result, a carbon resin thin film was formed in a region where no color filter layer had been formed, and a black matrix could be formed. Then, after washing, a protective layer was coated on the upper part to obtain a color filter. In this embodiment, an ultraviolet curable resin solution was used to form the black matrix. However, the same good black matrix as each of the above-mentioned embodiments using the electrodeposition material was formed.

(Embodiment 5) As shown in FIG.
ITO transparent conductive film on glass substrate by sputtering
100nm film is formed and sol-gel method is applied on ITO thin film.
250nm TiO _TwoTo form a film. Film formation on ITO substrate
TiO by spin coating_TwoAlkoxide (Nippon Soda)
Manufactured by Atron NTi-092) at 1500 rotations
Roll, form a film in 20 seconds, then heat at about 500 degrees for 1 hour
TiO_TwoIs formed. Example of reduction processing
As in 1, in pure nitrogen gas mixed with 3% hydrogen gas
Annealing was performed at 350 degrees for 10 minutes. this
Is a triode-type arrangement commonly used in electrochemistry as shown in FIG.
In an aqueous solution containing an azo red dye,
TiO to chrome electrode_TwoUse electrode as working electrode
The working electrode was set to 2.0 V and the mercury
Non-lamp (manufactured by Yamashita Denso, light intensity 50 at a wavelength of 365 nm)
mW / cm^Two) Light through a photomask for 10 seconds
When shot, TiO_TwoOnly the area where light was irradiated on the surface
A red filter pattern was formed. Next,
Len-acrylic acid copolymer (molecular weight 13,000, hydrophobic
Group / (hydrophilic group + hydrophobic group) molar ratio 65%, acid value 150)
And Cathilon Pure Blue5GH
Saturated in aqueous solution containing dyes dispersed 1: 1 in fractional ratio
TiO to calomel electrode_TwoUse electrode as working electrode
The working electrode was set to 2.0 V and the mercury
Non-lamp (manufactured by Yamashita Denso, light intensity 50 at a wavelength of 365 nm)
mW / cm^Two) Light through a photomask for 10 seconds
When shot, TiO_TwoOnly the area where light was irradiated on the surface
A blue filter pattern was formed. Similarly,
0.01M Pro Jet First Yellow
w2 and 0.01M Cathilon Pure Bl
Saturated calomel electrode in aqueous solution mixed with 5GH
Against TiO_TwoUsing the electrode as the working electrode
X 2.0 V from the back side of the substrate
(Yamashita Denso, light intensity at a wavelength of 365 nm 50 mW / cm
^Two) Was irradiated with light through a photomask for 10 seconds.
TiO_TwoGreen area only in the area where light was irradiated on the surface
Filter pattern is formed, color filter layer
Was formed. Next, after washing with pure water, styrene-a
Crylic acid copolymer (molecular weight 13,000, hydrophobic group / (parent
(Water group + hydrophobic group) molar ratio 65%, acid value 150) and carbohydrate
Black powder (average particle diameter 80 nm) in solid content ratio
Saturated calomel in aqueous solution containing pigments dispersed 1: 1
TiO to electrode_TwoUsing the electrode as a working electrode
The electrode is set to 1.6 V and the mercury xenon lan
(Yamashita Denso Co., light intensity of wavelength 365nm 50mW / c
m^Two) Was irradiated on the entire surface for 10 seconds.
The carbon thin film covers only the area where there is no
The matrix can be formed. After washing, on top of it,
A color filter was obtained by coating the protective layer. Book
In the embodiment, an electrodeposition film may be formed as an electrodeposition material.
Red and green filter pattern using dye
Was formed. Also in this case, the polymer electrodeposition material and the coloring material are used together.
Good color filters as in the above examples
was gotten.

(Example 6) Ti under the same conditions as in Example 4
Exposure corresponding to the black matrix pattern was performed on the O ₂ film to first form a black matrix on the substrate. Next, red, green, and blue filter patterns were formed in the region where the black matrix was not formed on the TiO ₂ film under the same conditions as in Example 4 by changing the electrolytic solution and the exposure pattern. After washing, a protective layer was coated on the top to obtain a color filter. In the present embodiment, a black matrix is formed on a substrate first, and then a filter pattern of each color is formed.
The same good color filters as in No. 4 were obtained.

[0057]

According to the method for producing a color filter of the present invention, a color filter having high resolution, high controllability and high smoothness can be formed at low cost without using photolithography, with a small number of steps. Can be. In particular, it is possible to cope with a fine and complicated pixel arrangement, and it is possible to easily form a black matrix and to produce a large quantity. According to the color filter manufacturing apparatus used therein, a color filter corresponding to a complicated pixel arrangement with a simple structure can be easily manufactured. Further, the color filter of the present invention can cope with fine and complicated pixel arrangement, has excellent surface smoothness, and has high applicability having a transparent semiconductor film in the filter.

[Brief description of the drawings]

FIGS. 1A and 1B are schematic diagrams showing energy bands of a semiconductor in the case of a Schottky junction and a PIN junction, respectively.

FIG. 2 is a graph showing dissolution characteristics of an electrodeposition material with a change in pH.

FIG. 3 is a graph showing dissolution characteristics of two electrodepositable materials having different polarities and which can be used together with a change in pH.

FIG. 4 is a graph showing a change in the amount of electrodeposition of the electrodeposition material when the conductivity is changed.

FIGS. 5A to 5E are schematic cross-sectional views illustrating a manufacturing process of a color filter.

FIG. 6 is a schematic configuration diagram of an apparatus used for manufacturing a color filter.

FIG. 7 is a schematic diagram illustrating a structure of a transparent n-type semiconductor serving as a substrate of a color filter.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Motohiko Tsuchiya 430 Nakai-cho Sakai, Kami-gun, Kanagawa Prefecture Green Tech Nakai Inside Fuji Xerox Co., Ltd.

Claims (24)

[Claims] 1. A substrate in which a transparent conductive film is formed on a transparent substrate and an organic semiconductor film or an inorganic semiconductor film is formed on the transparent conductive film is prepared, and a colorant and a pH change are contained in a container capable of holding a liquid. An aqueous liquid containing an electrodeposition material that dissolves or precipitates and precipitates is prepared, and means for supplying a current or an electric field is connected to the transparent conductive film, and the substrate is fixed so that the semiconductor thin film is immersed in the aqueous liquid. At the same time, a device having a counter electrode, which is the other of the pair of electrodes, is disposed in the container, the substrate is irradiated with light on a transparent substrate, and a selective electrodeposition material is applied to a portion where electromotive force is generated by the light irradiation. A monochromatic color filter by depositing an electrodeposited film containing the same. 2. The color filter according to claim 1, wherein a step of forming a plurality of monochromatic color filters by changing the color tone of the color material is repeated to form a multicolor color filter. Production method. 3. The method according to claim 2, wherein the electrodeposition material includes a color material capable of forming a black matrix. Forming a black matrix of the electrodeposited film on the portions where the electrodeposited films of a plurality of colors are not formed. 4. A color material capable of forming a black matrix is contained as the electrodeposition material, and after forming a color filter of a plurality of colors by the method according to claim 2, the entire surface of the substrate is irradiated with light. A method for manufacturing a color filter, comprising: forming a black matrix of an electrodeposited film on a portion of a color filter where an electrodeposited film of a plurality of colors is not formed, by applying a current. 5. A black matrix electrodeposition film is selectively used only in a region where no color filter is formed, using a material having a high insulating property as the electrodeposition material and utilizing the insulating property of the color filter electrodeposition film surface. The method for producing a color filter according to claim 3, wherein the color filter is formed. 6. The semiconductor thin film formed on the substrate has a thickness of n
The method for producing a color filter according to any one of claims 1 to 5, wherein a compound comprising a type semiconductor and having a carboxyl group in a molecule is used as the electrodeposition material. 7. The semiconductor thin film formed on the base,
It is composed of a semiconductor having a pn junction in which an n-type semiconductor and a p-type semiconductor are sequentially stacked, or a pin junction in which an n-type semiconductor, an i-type semiconductor, and a p-type semiconductor are sequentially stacked, and having a carboxyl group in a molecule as the electrodeposition material. The method for producing a color filter according to any one of claims 1 to 5, wherein a compound is used. 8. The semiconductor thin film formed on the base is p
The method for producing a color filter according to any one of claims 1 to 5, wherein a compound comprising a type semiconductor and having an amino group or an imino group in a molecule is used as the electrodeposition material. 9. The semiconductor thin film formed on the base,
a semiconductor having a pn junction in which a p-type semiconductor and an n-type semiconductor are sequentially stacked, or a pin junction in which a p-type semiconductor, an i-type semiconductor, and an n-type semiconductor are sequentially stacked; The method for producing a color filter according to any one of claims 1 to 5, wherein a compound having a group is used. 10. The electrodeposition material according to claim 1, wherein the electrodeposition material comprises a dye having a carboxyl group in a molecule or a mixture thereof, and has a property that solubility changes with a change in pH. 13. The method for producing a color filter according to the above item. 11. The electrodeposition material has both a hydrophobic group and a hydrophilic group in the molecule, and the number of hydrophobic groups in monomer units constituting the polymer is 40% to 80% of the total number of hydrophilic groups and hydrophobic groups.
%, A property that at least 50% of the hydrophilic group portion can be reversibly changed from a hydrophilic group to a hydrophobic group by a change in pH, and a copolymer having an acid value of 30 to 600, and fine particles. The method for producing a color filter according to any one of claims 1 to 9, further comprising a coloring material. 12. The electrodeposition material according to claim 1, wherein the electrodeposition material contains a compound having both a unit that precipitates and precipitates by changing pH in a molecule and a coloring material unit. 2. The method for producing a color filter according to item 1. 13. The semiconductor device according to claim 6, wherein titanium oxide is used as said n-type semiconductor.
13. The method for producing a color filter according to the above item. 14. A method for controlling the pH of an aqueous liquid containing an electrodeposition material by adding an acidic or alkaline substance that does not affect electrodeposition properties to the aqueous liquid containing the electrodeposition material, and applying a voltage of 5 V or less to the electrodeposited film. The method for producing a color filter according to any one of claims 1 to 5, wherein formation is enabled. 15. A substrate in which a transparent conductive film is formed on a transparent substrate, and an organic semiconductor thin film or an inorganic semiconductor thin film is formed thereon is prepared, and a colorant and a change in pH are set in a container capable of holding a liquid. An aqueous liquid containing an electrodeposition material that dissolves or precipitates and precipitates is prepared, and at least a means capable of supplying an electric current or an electric field in accordance with an image pattern is connected to the transparent conductive film. A device having a counter electrode, which is the other of the pair of electrodes, is placed in the container, light is irradiated on the transparent substrate of the substrate, and a portion where an electromotive force is generated by the light irradiation is selected. A method for producing a color filter, comprising forming an electrodeposition film containing an electrodeposition material to form a monochromatic color filter. 16. The potential of the means capable of supplying the current or electric field with respect to the standard electrode potential when a saturated calomel standard electrode is connected to the aqueous liquid via a salt bridge is 5 V or less. 16. The method according to claim 1, wherein:
The method for producing a color filter according to any one of the above. 17. The method according to claim 17, further comprising the step of: containing a color material capable of forming a black matrix as the electrodeposition material, repeating the step of forming a plurality of monochromatic color filters after forming the black matrix. A method for manufacturing a color filter according to claim 1. 18. A substrate in which a transparent conductive film is formed on a transparent substrate, and an organic semiconductor film or an inorganic semiconductor film is formed on the transparent conductive film is prepared. A device that prepares an aqueous liquid containing an electrodeposition material that dissolves or precipitates and precipitates, and fixes the substrate so that the semiconductor film is immersed in the aqueous liquid, and also has a counter electrode that is the other of the electrode pair. Placed in the container, irradiating light on the transparent substrate of the substrate while arbitrarily applying a bias voltage to the transparent conductive film, and selectively applying an electrodeposition material to a portion where an electromotive force is generated by the light irradiation. A method for producing a color filter, comprising: depositing an electrodeposited film containing the same to form a monochromatic color filter. 19. A transparent conductive layer, a transparent organic semiconductor layer or an inorganic semiconductor layer, an electrodeposition material containing a coloring component and a polymer which is chemically dissolved or precipitated / precipitated by a change in pH on a transparent substrate. A color filter, wherein a colored electrodeposition film layer is sequentially laminated. 20. The color filter according to claim 19, wherein the colored electrodeposition film layers have red, green, and blue hues in the same layer. 21. The color filter according to claim 19, further comprising a black matrix. 22. A polymer constituting the colored electrodeposition film,
It has both a hydrophobic group and a hydrophilic group, and the number of the hydrophobic groups of the monomer unit constituting the polymer is 40% of the ratio of the total number of the hydrophilic group and the hydrophobic group.
% To 80%, wherein 50% or more of the hydrophilic group portion has the property of being able to reversibly change from a hydrophilic group to a hydrophobic group by a change in pH, and has an acid value of 30 to 600. The color filter according to any one of claims 19 to 21, wherein 23. A color filter manufactured by the method for manufacturing a color filter according to claim 1. Description: 24. A substrate in which a transparent conductive film is formed on a transparent substrate, and an organic semiconductor thin film or an inorganic semiconductor thin film is formed on the transparent conductive film. A container filled with an aqueous liquid containing the material, a means capable of applying a current or an electric field according to at least an image pattern, and a counter electrode which is the other of the electrode pair,
A light source for irradiating light on the transparent substrate of the substrate, a means capable of supplying the current or the electric field to the transparent conductive film is connected, and the substrate is fixed so that the semiconductor thin film is immersed in the aqueous liquid. An apparatus for manufacturing a color filter.