JP2000275429A - Manufacture of filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a filter having a filter portion with high resolution and translucency and a black matrix portion being excellent in uniformity and light blocking property, etc., and having a good film quality with reflection of little unwanted light. SOLUTION: This manufacturing method includes the process of forming a filter portion by positioning a light-transmitting substrate comprising a light-transmitting base with a light-transmitting conductive film and a light-transmitting semiconductor thin film formed on predetermined portions thereof, in such a manner that the light- transmitting substrate makes contact with an aqueous electrodeposition solution containing a photoelectrodeposition material containing a coloring material which can be electrochemically deposited as an electrodeposition film, then causing a predetermined area of the light-transmitting substrate to conduct current, and depositing an electrodeposition film electrochemically by use of the photoelectrodeposition material containing the coloring material, and the process of forming a black matrix portion by supplying a current to the light-transmitting substrate and causing a black electrodeposition film containing 75 wt.% or more carbon black pigment having a functional group such as a carboxy group on its surface to be deposited on each electrode portion formed in the part of the light-transmitting iubstrate on which the electrodeposition film is not formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a filter such as a color filter used for various display devices such as a CCD camera and a liquid crystal display device and a color sensor. More specifically, the present invention relates to a method for manufacturing a filter capable of easily forming a good black matrix at a high resolution without using a photolithography process.

[0002]

2. Description of the Related Art At present, a method of manufacturing a filter includes:
(1) dyeing method, (2) pigment dispersion method, (3) printing method,
(4) Ink jet method, (5) electrodeposition method and the like are known. Of these, (1) the dyeing method and (2) the pigment dispersion method are both highly technically complete, and color solid-state imaging devices
Although it is often used for (CCD), it needs to be patterned through a photolithography process, and has a problem that the number of processes is large and the cost is high.

On the other hand, (3) the printing method and (4) the ink-jet method do not require a photolithography step, but (3) the printing method involves printing a thermosetting resin in which a pigment is dispersed. Curing method, which is inferior in resolution and uniformity of film thickness. (4) The ink jet method is a method of forming a specific ink receiving layer, performing a hydrophilic / hydrophobic treatment, and then spraying ink on the hydrophilic portion to obtain a color filter layer. Furthermore, there is a high probability that color mixing will occur in the adjacent filter layers, and there is also a problem in terms of positional accuracy.

(5) In the electrodeposition method, a high voltage of about 70 V is applied to a transparent electrode which has been patterned in advance in an electrolytic solution in which a pigment is dispersed in a water-soluble polymer to form an electrodeposition film. Electrodeposition is performed, and this is repeated three times to obtain an RGB color filter layer. In this method, it is necessary to pattern a transparent electrode in advance by photolithography, and since this is used as an electrode for electrodeposition, the shape of the pattern is limited and the method cannot be used for TFT liquid crystal.

In general, a color filter cannot be used only with a color filter layer, and it is necessary to cover each color filter pixel with a black matrix. Normally, photolithography is used to form a black matrix, which is one of the major factors for cost increase.
Therefore, considering the RGB layer and the black matrix, there is currently no known color filter manufacturing method with high resolution, high controllability, no need for photolithography, and a small number of steps. Yes,
In the production of color filters, the yield is not increased, which is a cause of high cost. Furthermore, this black matrix greatly contributes to the characteristics of the filter,
It is desired to form a uniform black matrix capable of blocking light transmission.

A document of a color image is stored in a CPU.
With the development of the image quality, the spread of the image quality and the spread to the society are expanding, and the demand for the high resolution reproduction technology and the high reliability of the printing process are increasing. Therefore, there is a strong demand for a technique for simplifying a pattern forming process by image input using light.

In contrast to the above prior art, the present inventors have proposed an organic or inorganic organic or inorganic image forming method which does not require a transparent conductive film which has been patterned in advance and which can form an arbitrary image pattern without a photolithography step. A method of using a semiconductor as a substrate, irradiating pattern light and depositing dye molecules in an aqueous solution in the form of a dye electrodeposition film on a semiconductor substrate to form an image and applying it to the production of a color filter. I found it, first, Japanese Patent Application No. Hei 9-135410.
Nos. 10-11176 and 10-335330. According to the method described here, there is no need for a photolithography step conventionally required in a method of forming a color filter by an electrodeposition method. Even a fine and complicated pixel arrangement can be handled, a black matrix can be easily formed, and a color filter can be manufactured at low cost. Also,
Similarly, a method of forming a color filter by a similar electrochemical method using a pixel electrode of a liquid crystal display circuit using a transistor or the like is disclosed in Japanese Patent Application No. 11-84190.
No. filed.

When a black matrix electrodeposition film is formed by the photoelectrodeposition method or the driving of the pixel electrode proposed by the present inventors, a black pigment such as carbon black which absorbs light in an electrodeposition solution and a polymer material for an electrodeposition material Is included,
Since the electrodeposition solution is aqueous, it is difficult to contain a large amount of pigment in the electrodeposition film due to the problem of affinity between carbon black and the electrodeposition material. It is necessary to make the layer thicker, and there has been a problem from the demand for thinner color filters.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a filter section having high resolution, high controllability and high light transmission without using photolithography, and excellent uniformity and light shielding properties, and unnecessary light reflection. An object of the present invention is to provide a low-cost, low-cost filter manufacturing technique capable of manufacturing an excellent filter having a good black matrix portion having a small film quality and a small number of steps.

[0010]

In order to achieve the above object, the present inventors reviewed the electrodeposition technique and the principle of the photoelectric effect, and also examined carbon black, which is a black pigment suitable for forming a black matrix. As a result of examining the interaction with the water-soluble polymer which is an electrodeposition material, by using carbon black having a specific surface property,
The present inventors have found that a black matrix which can be stably dispersed in an aqueous electrodeposition solution, has excellent light blocking properties, and has little unnecessary light reflection can be formed, and the present invention has been completed.

That is, the method for producing a filter of the present invention comprises:
A light-transmitting substrate formed by forming a light-transmitting conductive film and a light-transmitting semiconductor thin film on predetermined portions on a light-transmitting substrate, and a photo-deposition material containing a colorant capable of electrochemically depositing an electrodeposition film. Is disposed so as to be in contact with an aqueous electrodeposition solution containing, and an electric current is generated in a predetermined area of the light-transmitting substrate, and an electrodeposition film is electrochemically deposited using a photoelectrode material containing the coloring material. Forming a filter portion by applying a current to the light-transmitting substrate, and then applying a carbon black pigment having a functional group on the surface as a coloring material to an electrode portion formed on an unformed portion of the electrodeposition film. And forming a black matrix portion by depositing a black electrodeposition film containing at least 75% by weight of

According to a second aspect of the present invention, there is provided a filter manufacturing method, wherein a light-transmitting conductive film and a semiconductor thin film having a photovoltaic function are formed on a light-transmitting substrate (hereinafter referred to as an optical semiconductor thin film as appropriate). Arranging a light-transmissive substrate formed successively in contact with an aqueous electrodeposition solution containing a photo-deposition material containing a colorant capable of electrochemically depositing an electrodeposition film; and The substrate is imagewise exposed to generate an electric current in the aqueous electrodeposition liquid only in the light-irradiated portion, and the electrodeposited film is selectively deposited on the light-irradiated portion by using a photo-deposition material containing the coloring material. A step of forming a filter portion, and thereafter, a current is supplied to the light-transmitting substrate, and a carbon black pigment having a functional group on the surface as a coloring material is applied to the electrode portion formed on the unformed portion of the electrodeposition film. Black electrodeposition film containing more than 5% by weight Forming, characterized by having a. Here, the light transmittance refers to a property that shows little absorption at a predetermined wavelength of light to be exposed, and hereinafter, a property that shows the same property when described as “transparent” in the present specification. I do.

In the present invention, as a coloring material of the electrodeposition material forming the black matrix portion, a functional group,
Preferably, since a carbon black pigment having a functional group exhibiting the same behavior as that of an electrodepositable polymer such as a carboxyl group is used, the affinity with the resin constituting the photoelectric deposition material is good, and Easily and uniformly dispersed in the aqueous electrodeposition solution, a large amount of pigment can be stably retained in the electrodeposition solution, and when energized, it behaves similarly to the electrodeposition material and coagulates simultaneously with the electrodeposition material. , Can be deposited in a large amount in the electrodeposition film, and can form a uniform, defect-free black matrix part having high light-shielding properties.

Here, in the step of forming the black matrix portion, a black electrodeposition film containing an acidic carbon black pigment is formed in an unformed portion of the electrodeposition film by applying a bias voltage to the entire surface of the light transmitting substrate. The step of forming a black matrix portion by precipitation is preferred.
The bias voltage is preferably a voltage exceeding the Schottky barrier of the semiconductor in order to form an electrode portion on a portion where the electrodeposition film is not formed.

The carbon black pigment having a functional group used herein has an average particle diameter of 5.0 nm to 0.7 μm.
It is a preferred embodiment that the functional group of the carbon black pigment having a functional group on the surface contains a carboxyl group. The thickness of the black matrix portion to be formed is preferably in the range of 0.2 μm to 3 μm.

The semiconductor thin film having a photovoltaic function used in the present invention is at least one selected from the group consisting of titanium oxide, silicon carbide, lead oxide, zinc oxide, nickel oxide, tin oxide and molybdenum oxide. Or a compound optical semiconductor containing at least one material selected from the group consisting of metal phthalocyanine pigments, perylene pigments, azo pigments, and polyvinyl carbazole is preferred. .

In the method for producing a filter according to the present invention, after the black matrix portion is formed by the step of forming the black matrix portion, a metal thin film can be further laminated on the black matrix portion by a metal plating method. . Metal plating materials for forming this metal thin film include Ni, Cr, Cu, Au, Ag,
It is preferable to select from a metal selected from Mo, Sn, Zn, and Co and a mixture or alloy thereof.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Here, a description will be given of a photoelectrodeposition method applied to the formation of a filter portion or a black matrix portion in the filter of the present invention.

The electrodeposition material of which the present inventors are interested is composed of a water-soluble polymer as a constituent element.
A substance whose solubility in water greatly changes due to a change in an oxidation state, a neutral state, a reduction state, or the like is used. The change between the state of deposition and dissolution of the electrodeposited film can be achieved by electrochemically directly redoxing the polymer or by changing the pH of the aqueous solution in which the polymer is dissolved.

For example, some water-soluble acrylic resins have a pH of 7
Above, the ions dissociate and dissolve in water, but below pH
The resin component precipitates because the ion dissociation cannot be performed at the value.
In general, a polymer material having a carboxyl hydrophilic group has a hydrogen ion concentration (p
The solubility differs greatly depending on H). For example, some anionic aqueous polymer dispersants dissolve in water at pH 8 or higher, but precipitate at pH 5 or lower. When these materials are dissolved in weakly alkaline water, and the electrodes are immersed in the solution and a voltage is applied, an electrodeposited film made of these polymer materials is formed on the electrodes on the anode side. When a coloring material, for example, a pigment is dispersed in the polymer, and the electrode is immersed in the solution and a voltage is applied, the pigment and the polymer precipitate on the electrode on the anode side, and the pigment and the polymer are mixed. A deposited film is formed. By applying a reverse voltage or immersing the electrodeposited film in an aqueous solution of pH 10 to 12, these electrodeposited films cause ion dissociation again and elute again in the electrolyte.
A decrease in membrane is indicated. By utilizing such an action, light is emitted to a desired region using an optical semiconductor to generate an electromotive force, thereby forming an electrodeposition film.

As described above, the electrodeposition film may be re-eluted depending on the conditions, so that a strong film is formed.
The present inventors have made various improvements and filed a patent application as described above. For example, if the pH value of the electrodeposited film tends to elute due to the electrodeposition liquid or the like remaining on the electrodeposited film, the strength of the film itself may be reduced. In order to make the electrodeposited film stronger, In order to obtain the robustness of the film itself by setting the pH value in a region where the entire contents of the film becomes a sufficiently hard film, a method of adjusting the pH value of the electrodeposited film body after electrodeposition, etc. It is a proposal.

Further, the formation of the electrodeposited film requires a threshold voltage at which an electrodeposition phenomenon occurs at a certain level or more, and if a current flows, the electrodeposited film is not necessarily formed. Therefore,
In the electrodeposition phenomenon using photoelectromotive force, if the electromotive voltage does not exceed the threshold value of the electrodeposition potential, it may be left as it is, but if the photovoltaic voltage does not exceed the threshold value of the electrodeposition potential, the bias voltage is applied. If the photovoltaic power is generated and a potential higher than the threshold value is applied, the electrodeposition phenomenon corresponding to the light irradiation portion does not occur. Here, the voltage level of the bias voltage input from the outside is a small value that does not exceed the Schottky barrier voltage of the photovoltaic material (that is, the semiconductor thin film used here), and an image is formed by applying only the bias voltage. It is necessary to adjust the potential to a level that cannot be performed. Thus, if a semiconductor thin film having a photovoltaic function is used for the substrate to be electrodeposited and light is used for this input signal, photovoltaic power is generated only in the light-irradiated portion by the optical signal, and only the area is charged. The voltage required for deposition is obtained, and an arbitrary electrodeposition film can be formed at a desired position. Hereinafter, the electrodeposited film formed in this manner is appropriately referred to as a photoelectrodeposited film.

Conventionally known electrodeposition techniques require a voltage required for forming an electrodeposition film as high as about 50 V or more. When such a high voltage is applied, the Schottky barrier between the semiconductor and the electrolyte is broken and the entire surface is damaged. As a result, it is impossible to form an image only in a desired area using an electrodeposition phenomenon of only a portion using photovoltaic power as in the present invention. Further, practically, there is no photovoltaic optical semiconductor capable of forming a color filter. For this reason, film formation using photoelectromotive force cannot be performed, and it has been essential to use a photolithography method for patterning a transparent electrode in a method of manufacturing a color filter using a conventional electrodeposition coating technique.

The photoelectric deposition film proposed by the present inventors and the related technology are based on the above findings, and the outline of the image forming method is to irradiate light using an organic or inorganic semiconductor as a substrate. In order to form an image by depositing an electrodepositable material in an aqueous solution in the form of a film on a semiconductor substrate by using a conventional method of forming a color filter by an electrodeposition method,
The necessary patterning transparent conductive film is unnecessary,
An arbitrary image pattern can be formed only by image light irradiation without a photolithography process. In addition, this technology can be applied to a method for manufacturing a transistor-integrated color filter in which a color filter is formed for each pixel electrode using the same material and a pixel electrode provided in a transistor circuit as an electromotive force. Hereinafter, the photoelectric deposition film is simply referred to as an electrodeposition film.

An object of the present invention is to provide a method of manufacturing a filter, comprising: forming an optical semiconductor thin film on a photoselective transparent electrode; and an electrodeposition solution containing a polymer photoelectrode material as a filter forming material and a predetermined colorant. By applying a bias voltage to the transparent electrode and irradiating it with light to generate a photoelectromotive force, or by activating a predetermined pixel electrode of the transistor circuit, the pH of the electrodeposition liquid near the substrate is increased. Is used to selectively form an electrodeposition film on the light irradiation section or the electrode operation section by utilizing the difference in solubility of the polymer material due to the pH. A washing treatment is performed with an aqueous solution adjusted to a pH value at which precipitation is easy (that is, a pH value at which re-elution is difficult), and unnecessary adhered electrodeposition liquid is removed to form a filter portion. Once for a single color filter,
In the case of a color filter, this is repeated three times for each color of RGB to form a filter portion.

Thereafter, a black matrix layer is formed thereon to complete the manufacture of the filter. Conversely, the filter layer can be formed after the black matrix layer is first provided. The completed electrodeposition film (the filter and the black matrix) can be transferred to another filter substrate to form a filter on a desired substrate. By providing the transfer step, a highly transparent and highly accurate color filter without an optical semiconductor thin film that absorbs light on the substrate can be realized.

The formation of a high-resolution photo-electrodeposition film is performed by using a Schottky junction between the photoconductor thin film to be used and the electrodeposition solution, or a pn junction or a pin junction of the photo-semiconductor thin film itself to obtain a light necessary for electrodeposition. An electromotive force is obtained. And, when transferring the filter layer or the black matrix layer as described above, a photo-deposited substrate having the photoconductor thin film,
It can be used repeatedly. In this case, the formed electrodeposition film is transferred onto another desired filter substrate by using heat or pressure, whereby a highly accurate color filter can be realized in a simplified process.

Here, the black matrix layer which is a main part of the present invention will be described in detail. The function of the black matrix layer is required to have both light-shielding properties and light-reflecting properties. If the thickness is not thin, it becomes difficult to form a fine pattern of the black matrix layer. That is, a thin layer is formed that is a thin layer, and the matrix material itself of the layer has a high light transmittance, and as a whole the layer has both functions of being able to shield incident light by absorption rather than reflection. Indicates more excellent characteristics.

For the black matrix layer of the present invention, carbon black particles having a high degree of blackness and a stable particle diameter are used, and the particles impart electrodeposition properties by introducing a functional group to the surface. By bonding or adsorbing a molecule having a carboxyl group on the surface of carbon black, or adsorbing a small amount of electrodepositable material, a functional group is introduced into these carbon black particles to increase the affinity with the electrodeposited material. And preferably imparts electrodeposition ability to the pigment itself, and forms a thin film on the electrode layer surface by electrodeposition by electrodeposition.

The carbon black pigment having a functional group introduced therein, as used in the present invention, has a good affinity for an electrodeposition solution in which an electrodeposition material is dispersed, so that the blackness and conductivity of the formed film can be maintained. In the present invention, the carbon black pigment in the formed black electrodeposition film (the dried carbon black layer) has a weight component ratio of 75%. % Is in the range of 100%. More preferably, the range is 85% to 95%. If it is less than 75%, the light-shielding property tends to decrease, which is not preferable. Thus, by being able to increase the content of the carbon black pigment, the reflectivity and light transmittance are low, the number of preparation steps is small, and further, a thin black matrix layer having excellent conductivity is formed. it can.
Since the black matrix layer has excellent conductivity, a laminated layer structure in which plating and electrodeposition processes are performed next becomes possible, and a metal thin film is laminated on the carbon black layer by a metal plating method. This can be easily performed, and when such a metal thin film is formed, the light shielding property is further improved.

The functional group binding to the surface of the carbon black pigment includes, for example, a carboxylic acid group, a sulfonic acid group,
Examples thereof include an amino group, a phenol group, a quinone group, a hydroxyl group, an ammonia group and a derivative group thereof, and these may be used alone or in combination of two or more. The carbon black having such a functional group can be produced, for example, according to a reaction formula shown in the following schematic diagram.

[0032]

Embedded image

In the formula, RX is a functional group to be introduced,
Represents a linking group which is optionally introduced. This reaction is described in detail in Akihiro Oshima (Cabot Specialty Chemicals, Inc.) et al., “Surface Modification of Black Pigment: A New Approach to the Development of Highly Functional Carbon Black”. Although an example in which a group, a carboxylic acid group, and a quaternary amine are introduced is shown, other functional groups can be introduced in the same manner. Carbon black having a carboxylic acid group on the surface is, for example, CAB-O-JE
It is also available as a commercial product such as T300 (manufactured by Cabot). The average particle diameter of the carbon black particles in these black matrix layers is from 5.0 nm to 0.5 nm.
A material having a range of 7 μm is preferable, and a range of 10 nm to 300 nm is more preferable. If the average particle diameter is less than 5.0 nm, excessive cost and a huge apparatus are required to obtain carbon black particles having a uniform particle shape. If the average particle diameter exceeds 0.7 μm, optical scattering occurs and light transmission is obtained. All of which are not preferred.

According to the present invention, a simple and light-absorbing material
The formation of a uniform black matrix having a high light-shielding property is achieved by forming a filter layer and then dispersing and dissolving a carbon black pigment having a functional group on the surface and an electrodeposition material as a black matrix forming material in an electrodeposition solution. By applying a voltage (with or without light at this time), the electrodeposition material height in which the carbon black pigment having the specific functional group is dispersed only in the portion where the color filter layer is not formed is formed. Form a black thin film by precipitating molecules,
The electrodeposition film is used as a black matrix layer.

The black matrix layer obtained by using a carbon black pigment having a functional group which satisfies these conditions has a high light-shielding property even if it is a single layer, and has a high light-shielding property.
Even with a thickness of μm or less, it has sufficient light-shielding properties as a black matrix, so that the thickness of the black matrix layer can be reduced to 1/3 or less as compared with the conventionally used electrodeposition film type in which carbon black is dispersed in a resin. Therefore, it is possible to reduce the level difference on the filter surface, and to form a film having a high density of black particles, the black matrix layer is a layer having a function of absorbing external light in a portion where external light enters. This not only enhances the reliability of the formation of the filter layer, but also reduces the leakage light of the filter and enables the production of a high-resolution color filter having a black matrix layer pattern having a pattern width of 10 μm or less. Also, in the manufacturing process, since the electrodeposition method and the like proposed by the present inventors can be applied as they are, film formation is easy, the reliability of the obtained black electrodeposition film is high, and the black matrix layer is thin. Therefore, high-resolution color filters can be manufactured.

FIG. 1 shows a conventional black electrodeposition film using carbon black having no functional group, a black electrodeposition film using carbon black having a functional group (carboxyl group-introduced product) of the present invention, 4 is a graph showing the relationship between the film thickness and the transmission optical density of a black electrodeposition film of the invention in which a nickel plating layer is laminated and a nickel plating layer. In FIG. 1, the black electrodeposited film using the carboxyl group-introduced carbon black of the present invention is shown by a two-dot broken line (a), and the black electrodeposited film of the present invention laminated with a nickel plating layer is represented by a solid line (b). A black electrodeposition film using carbon black having no conventional functional group is indicated by a circle and a dashed line (c), and a nickel plating layer is indicated by a dashed line (d). Since the black electrodeposition film obtained by the method of the present invention has a higher content ratio of the carbon black pigment than the conventional product, it was confirmed that the film thickness could be reduced. Although the metal plating film is thin and has excellent light-shielding properties, the film itself has a metallic luster and is therefore unsuitable for use alone.

FIG. 2A is a schematic cross-sectional view schematically showing a black matrix obtained by the production method of the present invention and a filter layer provided around the black matrix. FIG. 2B shows a conventional carbon black. It is a schematic sectional drawing which shows typically the black matrix contained and the filter layer provided around. Here, a colored film (filter portion) 30 formed on a substrate 18 having a transparent conductive film 14 and a semiconductor thin film 16 formed on a transparent substrate 12 and a black matrix layer 32 according to the present invention are displayed (FIG. 2A). . FIG.
In (B), a conventional black electrodeposition film 34 is displayed on the black matrix layer. By comparing these, it can be seen that the black matrix obtained by the method of the present invention has the same effect as the conventional product even if the layer is made thinner, and is therefore preferable from the viewpoint of the resolution of the filter.

The technique of the present invention will be described in detail below with specific examples of other materials. The electrodeposition liquid for forming a filter requires a substance (photoelectrodeposition material) that is reduced in solubility and dispersibility due to alkalinity or acidity and precipitates. The substance to be deposited is a polymer material, and a substance having a property of being precipitated in an alkaline or acidic state is used. When the polymer material is transparent, a coloring material may be dispersed in the polymer and used. When the polymer material itself is colored, it can be used as it is. When using color materials dispersed in polymers, not only dyes but also color materials
Pigments can also be used. When used as a color filter, high light resistance is required, and therefore, it is desirable to use an aqueous polymer in which a pigment is dispersed as a photo-deposition material.

FIG. 3 is a graph showing the dissolution characteristics of the dye as a function of pH, as a guide for selecting the photo-deposition material. FIG. 3 is a graph showing the relationship between the dissolution characteristics of various materials and the pH of the solution. Graph A (shown by solid line) in some materials
Such as a sudden precipitation at a certain pH value,
Some materials have good solubility irrespective of the pH value, such as the material in graph B (shown by a broken line), and some are insoluble regardless of the pH value, such as the material in graph C (shown by a dashed line). The characteristics also change depending on the relationship between the material, the solvent used, and the dispersion medium.

Further, two types of ions having different polarities, for example, Pro Jet which is anionic and has an electrodeposition film forming ability.
First Yellow 2 (yellow) and Cathilon Pure Bl, which are cationic and capable of forming an electrodeposited film
When the electrode is electrochemically oxidized in a mixed solution containing ue 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. 4, one compound is dissolved in a solvent in a neutral region as shown in a graph A (shown by a solid line); Some low pH
Precipitation occurred sharply in the values, and the other compound
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.

As an example of the photo-deposited polymer material, a water-soluble acrylic resin having a carboxylic acid group can be cited as having a capability of forming electrodeposition. This material is weakly alkaline water
(pH 8 to 9), and has the property of being present as an anion in an aqueous solution, but insolubilizing and precipitating when the pH becomes 7 or less. When a platinum electrode is immersed in this aqueous solution and energized,
In the vicinity of the anode, OH-ions in the aqueous solution are consumed to become O ₂ , and the hydrogen ions increase to lower the pH. This is because the following reaction occurs in which the hole (P) and OH- ions are connected near the anode. ^{2OH - + 2p + → 1/} 2 (O 2) + H 2 O

In order for this reaction to take place, it is necessary to dissociate ions of water by applying a constant voltage, and as the reaction proceeds, the concentration of hydrogen ions in the aqueous solution increases and the pH decreases. Therefore, when a voltage exceeding a certain level is applied, the solubility of the water-soluble acrylic resin on the anode side of the electrode decreases, and the resin becomes insoluble and a thin film is formed on the electrode. The present invention utilizes the photoelectromotive force generated by irradiating a semiconductor with light to obtain a constant threshold voltage of the electrodeposition voltage. Various attempts have been made so far to use photovoltaic power. For example, A. Fujishima, K. Honda Natu
In re Vol.238, p37, (1972), TiO ₂ , an n-type semiconductor, was irradiated with light to electrolyze water. In connection with the research on photoelectrochromism, H. Yoneyama et al. Reported that J. Electrochem.
chem. Soc., p2414, (1985). Also,
In addition, there is a proposal for a method of forming an image with light using a dye for doping and undoping of a conductive polymer.

However, according to the present invention, it is possible to form an electrodeposition film without a conductive polymer. However, the voltage required for forming an electrodeposited film is higher than when a conductive polymer is present. On the other hand, photovoltaic power is
It is 0.6V, and photovoltaic power alone is not enough to form an image. Therefore, a method such as raising the voltage by applying a bias voltage is also conceivable. However, when the voltage exceeds a certain level (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 formed. The Schottky barrier during the breakage was broken, and the electrodeposition phenomenon of the image faithfully reproduced to the optical image did not occur, which became a problem. There is a limit to the bias voltage that can be applied.For this reason, image formation in an aqueous solution using a photovoltaic force uses a photopolymerization reaction of a conductive polymer such as polypyrrole that is redox-reduced at 1.0 V or less. Was limited. For example, in the patent of Dai Nippon Printing `` Color filter production method and electrodeposited substrate for color filter production '' (JP-A-5-119209) and `` Color filter production method '' (JP-A 5-157905), the electrodeposition voltage is 20V to 100V
The electrodeposition material utilizes a redox reaction of a polymer. As described above, the electrodepositable polymer material generally well known as electrodeposition coating requires a voltage of 20 V or more for electrodeposition, and practically mainly 100 V in consideration of efficiency.
To 300V. Therefore, external photoelectric effect characteristics such as ZnO ₂ for electrophotography were used for image formation, but they were not water-based and practical materials.

However, since the material system of the present invention is based on the principle of solubility / dispersibility change depending on pH, it is possible to form a thin film at a low voltage. Can be formed. In particular, it was shown that titanium oxide is transparent in the visible region, enables exposure from the back, has good light irradiation efficiency, and is very effective as a base material for producing color filters. In recent years, titanium oxide with good characteristics has been obtained as an n-type semiconductor by various methods such as a sol-gel method, a sputtering method, and an electron beam evaporation method.

The photovoltaic semiconductor which can be used in the present invention as a non-optical memory (having almost no light hysteresis effect) is basically a semiconductor thin film which generates electromotive force by light irradiation and has no strong light hysteresis effect. All can be used. Specifically, as photovoltaic semiconductor materials, Si, GaN, aC, BN, SiC, ZnSe,
TiO ₂ , GaAs-based compound, CuS, Zn ₃ P ₂ , phthalocyanine pigment-based material, perylene pigment-based material, azo pigment-based material, various organic photoconductive materials, etc. are single layer or multiple layers, but the basic material is Although a high-purity substance or a single-crystal system is required, a mixed substance or the like can be used. In some cases, a protective layer is present on the surface, and the thickness of these semiconductor layers is in the range of 0.05 μm to 3 μm, which is a use range in which good characteristics can be obtained. If the thickness is less than 0.05 μm, the obtained optical power is too weak, which causes a problem in image formation. Also, 3
When the thickness is in the range of μm or more, charges generated by light are trapped in the layer, and the light hysteresis phenomenon becomes too large to cause a problem in image formation. In addition, in order to easily obtain the electric power required for the film deposition by the electrodeposition method in consideration of the power generation efficiency by light, these semiconductor films are formed of a single semiconductor, and made of resin or the like. Mixing or inclusion of insulating materials must be avoided. Mixing or inclusion of an insulating material such as a resin in the semiconductor layer also causes a large light hysteresis phenomenon. The semiconductor includes an n-type semiconductor and a p-type semiconductor, and any semiconductor can be used in the present invention. Furthermore, if a stacked structure using a pn junction or a pin junction is used, more photocurrent flows and an electromotive force can be obtained with certainty, 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. 5A shows the case of the Schottky junction, and the schematic diagram of FIG. 5B 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 when the semiconductor side is positive and no current flows, when the light is irradiated, an electron-hole pair is generated, 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 even with Si having a relatively high potential. However, materials that can be electrodeposited at 0.6V are limited. Therefore, it is necessary to compensate for the insufficient voltage 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 flows also in an area not exposed to light, and an electrodeposition film is formed on the entire area of the semiconductor substrate, so that an image cannot be formed. For example,
If the material is electrodeposited at 2.0V, applying a 1.5V bias voltage and irradiating light will add 0.6V to the photovoltaic power of the semiconductor.
The voltage is 2.1 V, which exceeds the threshold voltage required for electrodeposition, and a photo-deposited film is formed only in the area irradiated with light. The mechanism used here is a photovoltaic mechanism different from the external photocurrent effect mechanism in which the conductivity is simply increased by light and the conduction current is increased by the applied voltage of the bias.

The structure of the electrodeposition material for a filter is constituted by a copolymer having a minimum monomer unit of a molecule having a hydrophilic group capable of dissociating ions and a hydrophobic group promoting insolubilization in water, and is preferably a polymer obtained by random polymerization. Good material.
The number of hydrophobic groups in the monomer units of the polymerized electrodeposition material is such that the ratio of the total number of hydrophilic groups to hydrophobic groups is in the range of 40% to 80%, and more preferably 55% to 70%.
% Is particularly high in electrodeposition deposition efficiency,
The electrodeposition characteristics showed that a film could be formed at a low electrodeposition potential, and the liquid properties of the electrodeposition solution were stable. Electrodeposition of the electrodeposition material containing a hydrophilic group portion of a monomer unit capable of reversibly changing from a hydrophilic group to a hydrophobic group by a change in pH at least 50%, more preferably at least 75%, of the hydrophilic group portion of the monomer unit. It is composed of materials.

If the ratio of the total number of the hydrophilic groups to the hydrophobic groups in the monomer units of the electrodeposited material is less than 40%, the electrodeposition film formed at the time of electrodeposition is insufficient in water resistance and film strength. It became. When the number of hydrophobic groups in the monomer unit of the electrodeposition material is 80% or more of the total number of the hydrophilic groups and the hydrophobic groups, the solubility in the aqueous liquid becomes insufficient, and the electrodeposition liquid becomes cloudy.
The electrodeposition material precipitates and the viscosity of the electrodeposition liquid becomes unstable, which causes problems.

The hydrophobic group in the structure of the electrodeposition material for a filter has a strong affinity for an organic pigment used as a coloring material, has an adsorptive ability, and imparts a good pigment dispersing function. In addition, a printing function for instantaneously depositing an image is imparted to the hydrophilic detachment of the hydrophilic group portion of the electrodeposited material due to the energization phenomenon caused by the application of a voltage. In particular, when the number of hydrophobic groups in the monomer unit of the electrodeposition material is from 40% to 80% of the total number of hydrophilic groups and hydrophobic groups,
%, The effect of reducing the electrodeposition potential for forming a strong film is great, and thus becomes an indispensable condition for completing a low-potential printing process using photoelectromotive force by light input. ing. Good electrodeposition characteristics can be obtained when the acid value of this electrodeposition material of the type which deposits an image on the positive electrode is in the range of 60 to 300. Particularly in the range of 90 to 195, better electrodeposition properties can be obtained. If the acid value of the electrodeposition material is 60 or less, the solubility in the aqueous liquid becomes insufficient, the solid content concentration of the electrodeposition liquid cannot be increased to an appropriate value, or the liquid becomes cloudy or precipitates are generated, Problems arise such as an increase in liquid viscosity. When the acid value of the electrodeposition material is 300 or more, the formed film has low water resistance and the electrodeposition efficiency with respect to the amount of electricity supplied is low.

In particular, those in which the hydrophilic group capable of ion dissociation is a carboxyl group or an amino group show characteristics of forming an electrodeposition film having high image deposition efficiency and high robustness in an electrodeposition phenomenon. These two groups have high efficiency of reversibly changing from a hydrophilic group to a hydrophobic group due to a change in pH, and these characteristics are obtained. Further, the electrodeposition material for a filter has a structure containing a thermoplastic resin component, and must exhibit sufficient solubility in the adjusted aqueous liquid. It is necessary that a change in the pH of the electrodeposition material in which the electrodeposition material is dissolved changes from a solution state / dispersion state of the electrodeposition material to a supernatant, and a liquid property change causing precipitation occurs within the pH range region 2. It is said. To obtain more favorable properties, the pH range is 1
It is required that With the characteristics in this range, it is possible to instantaneously deposit an image even when the pH changes sharply due to energization, and to increase the cohesive force of the deposited image and reduce the rate of re-dissolution in the electrodeposition solution. Making it possible. This makes it possible to obtain a filter layer having high translucency and water resistance of an image. If the pH range of the liquid property change that causes precipitation from the dissolved state with respect to the change in the pH value of the electrodeposition liquid is larger than 2, the printing speed decreases to obtain a sufficient image structure, and the water resistance of the deposited image decreases. Problems such as lack of print characteristics remain.

The monomer unit containing a hydrophilic group used in the electrodeposition material includes methacrylic acid, acrylic acid, hydroxyethyl methacrylate, acrylamide, maleic anhydride, trimellitic anhydride, phthalic anhydride, hemi-mellitic acid, succinic acid , Adipic acid, propiolic acid, propionic acid, fumaric acid, itaconic acid and the like and derivatives thereof. In particular, methacrylic acid and acrylic acid have a large effect / effect on the electrodeposition phenomenon, and are useful hydrophilic monomer structural units having high electrodeposition efficiency due to pH change and high hydrophilicity efficiency.

The monomer units containing a hydrophobic group used in the electrodeposition material include an alkyl group, a styrene group, an α-methylstyrene group, an α-ethylstyrene group, a methyl methacrylate group, a butyl methacrylate group, an acrylonitrile group,
A vinyl acetate group, an ethyl acrylate group, a butyl acrylate group, a lauryl methacrylate group, and the like, and derivatives thereof are used. In particular, styrene groups and α-methyl-styrene groups have high hydrophobizing efficiencies, so they have high electrodeposition deposition efficiency, and have high controllability during polymerization in production and are useful hydrophobic monomer structural units for electrodeposition materials. ing.

It is a polymer substance obtained by copolymerizing these molecules containing a hydrophilic group and a hydrophobic group in the above-mentioned ratio, and the type of each hydrophilic group and hydrophobic group is not limited to one. And
From the viewpoint of the properties of the electrodeposited film and the adhesive strength of the film, the average molecular weight is 6,
2,000 to 25,000 give a good electrodeposited film. From the viewpoints of more preferable film properties and adhesive strength of the film, those having an average molecular weight of 9,000 to 20,000 can provide a good electrodeposited film. If the average molecular weight is lower than 6,000, the film is uneven and the water resistance is low. Therefore, an electrodeposited film having high robustness cannot be obtained, and the film property is low and the powder is easily formed. If the average molecular weight is higher than 25,000, the solubility in the aqueous liquid becomes insufficient, the solid content concentration of the electrodeposition liquid cannot be increased to an appropriate value, the liquid becomes cloudy or a precipitate is formed, A problem such as an increase in viscosity occurs. The thermal properties of these materials include a glass transition point lower than 100 ° C., a flow start point lower than 180 ° C., and a decomposition point of 150 ° C.
By using a material having higher characteristics, the control margin of the transfer process using heat is widened, and high translucency and good transition characteristics of the electrodeposited film can be obtained. When used in combination with a pigment, a transparent polymer material with an electrodeposition property, such as a water-soluble acrylic resin, can be used by dispersing it in an aqueous solution. .

Next, the conductivity of the electrodeposition solution for a filter was
The pH is described. According to the experiment, the conductivity can be translated into the electrodeposition speed, and the lower the resistivity in relation to the amount of electrodeposition, the thicker the electrodeposition film deposited in a certain period of time,
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
mS / cm ² (see FIG. 6), in other words, the volume resistivity is about 10 Ω · cm, and the electrodeposition amount tends to be saturated. Electrodeposition is performed by controlling the low efficiency of the electrodeposition liquid to a range of 1 Ω · cm to 10 ⁵ Ω · cm, and in this range, a good electrodeposition phenomenon can be performed. In the range of 10 ⁵ Ω · cm or more, a sufficient current cannot be obtained, so that only a small amount of electrodeposition is obtained.
In the range of m or less, the controllability of the amount of electrodeposition deteriorates. Therefore, when the conductivity of the dye ion alone is insufficient, an acidic or alkaline substance that does not affect the electrodeposition properties, such as Na
^The electrodeposition speed can be controlled by adding ⁺ ions, Cl ^- ions, SO ₄ ^- ions, or the like.

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, for unsaturated solutions,
When the electrodeposited film is formed at pH, even if the electrodeposited film is formed, the film starts to be redissolved as soon as the power supply is stopped. Therefore, it is desirable to form the electrodeposited film at a pH of the solution at which the solubility is saturated.

Next, regarding the removal of the unnecessary electrodeposition liquid on the electrodeposited substrate after the electrodeposition, immediately after the electrodeposition, the unnecessary electrodeposition liquid adheres to various places on the electrodeposited substrate. As an effective means for completely removing the unnecessary electrodeposition liquid, there is a liquid cleaning, and in particular, cleaning with a transparent and highly safe inert liquid is effective. However, immediately after the formation of the electrodeposited film, if the electrodeposited film is washed, the electrodeposited film immediately after the deposition has insufficient physical and chemical strength, and there is a possibility that the electrodeposited film may be undesirably lost due to the washing. For this purpose, an effective method is to wash the electrodeposition film with a cleaning liquid having a property of promoting solidification of the film, and to remove unnecessary electrodeposition liquid. An example of a liquid having such an effect is an aqueous liquid having a pH value at which the pH value is more easily precipitated than the starting pH value of the electrodeposition solution (a value that is difficult to redissolve). The solidification is promoted by contact with the liquid, the unnecessary coloring material components of the electrodeposition liquid aggregate and lose their adhesiveness, and can be easily washed off. The cleaning liquid using this phenomenon is a very effective means for the subsequent processing steps. As a result, the pH value inside the electrodeposited film is also lower than at the time of electrodeposition, and the electrodeposited film has a stable pH value.
Because of the H value condition, the robustness is increased and the resolution is high,
High quality image formation is achieved. In order to further enhance the effect of the cleaning of the cleaning solution and the hardening of the film, it is preferable that the pH value is set to a value that is 2 or more than the pH value at the starting point of the deposition of the electrodeposition solution so as to facilitate the deposition.

Next, TiO ₂ which is a transparent semiconductor in the visible region will be described. TiO ₂ is a transparent oxide semiconductor in the visible region, 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. Several methods are known for forming a TiO ₂ film. For example, a thermal oxide film method, a sputtering method, an electron beam method (EB method), and a sol-gel method are well known. When a TiO ₂ film was formed by the EB method and the sol-gel method, the photovoltaic power conversion efficiency was poor with the usual film forming method, and a sufficient photovoltaic power required for electrodeposition could not be obtained. Therefore, a reduction treatment was performed to increase the conversion efficiency of the photocurrent. In the reduction treatment, it is usual to heat at about 550 ° C. in hydrogen gas. For example, Y. Hamasaki et al. J. Electr
In ochem. Soc. Vol. 141, No. 3 p. 660, 1994, heating is performed in hydrogen gas at about 550 ° C for about 1 hour. However, we obtained a sufficient effect at a low temperature and a short time of about 360 ° C for 10 minutes. This is performed at 1 L / min. Using 3% hydrogen mixed nitrogen gas. This was achieved by performing the heat treatment while flowing the above flow rate.

Next, an exposure apparatus for producing a photoelectrically deposited film will be described. In the present invention, since it is necessary to generate an electromotive force in the optical semiconductor by exposing from the back surface of a transparent substrate for forming a filter and an electrodeposition film for a black matrix, light having a wavelength sensitive to transparent light is required. Must be exposed. For this reason, it is necessary to use a light source having a wavelength of 400 nm or less as an exposure light source. Usually, a mercury lamp, a mercury xenon lamp, a He-Cd laser, an N ₂ laser, an excimer laser, and the like are used. In consideration of imagewise exposure of a desired region, laser exposure or the like in which the exposure region can be easily controlled is preferable.

FIG. 7 is a schematic diagram showing an image recording apparatus of the present invention used in the first embodiment described later. In the image recording apparatus, a transparent substrate 3 provided with a work electrode capable of inputting an image signal from the back surface is placed in an electrodeposition solution bath filled with the electrodeposition solution 1 such that the back surface comes out of the bath. A counter electrode 5 and a control electrode 6 using a salt bridge are also provided in the bath 1. The transparent substrate 3 is made of a laminated structure of a two-layer titanium oxide thin film optical semiconductor layer on a 4 mm-thick plate glass substrate provided with an ITO transparent conductive layer, and the ITO conductive layer is used as a work electrode. The surface of the layer is smooth without any steps.
Each of the electrodes is connected to a potentiostat power supply 4, and an image is input to the optical image input section on the rear surface of the transparent substrate 3 by, for example, an image projection device. Of the electrodeposition liquid to deposit an electrodeposition material in the electrodeposition liquid on the surface of the transparent substrate 3 to form an image. The image recorded here can be transferred and fixed to a transfer target such as plain paper or a plastic film, if desired.

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.
(A)), a substrate 1 having a semiconductor thin film 16 formed thereon.
8 (FIG. 8B) is prepared. Next, using a device having a three-electrode arrangement commonly used in electrochemistry as shown in FIG. 7, the material is chemically dissolved or precipitated / sedimented in a container 20 capable of holding a liquid by a change in colorant and pH. Means 2 capable of filling an electrodeposition liquid 22 containing an electrodeposition material and further providing a current or an electric field in the container 20 according to at least an image pattern.
4 is connected to the transparent conductive film 14, the substrate 18 is fixed so that the semiconductor thin film (electrode) 16 is immersed in the aqueous liquid 22, and the counter electrode 26, which is the other of the electrode pair, is similarly arranged in the container 20. I do. 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 colored material containing an electrodeposition material and a coloring material selectively at 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, whereby the aqueous liquid 22 is formed. The multi-color filter can be easily formed only by performing the same process while changing the mask pattern 28 (FIG. 8C). Further, the black matrix layer 32 is formed as described above (FIG. 8).
(D)). Thereafter, the filter layer and the black matrix layer are transferred to another filter substrate by heating and pressurizing, and the transparent substrate is peeled off. A color filter can be formed thereon.

In the present invention, the black matrix is formed by the same principle as that of the filter layer using the conventionally known general photolithography. After the filter layer is formed, the black matrix is formed as described above. A method in which the entire surface is formed only in the region where the filter layer (forming the insulating resin layer) is not formed, and a method in which the ultraviolet curable resin is used only in the region where the filter layer is not formed using the same whole surface exposure means. and so on. In particular, in the method of the present invention, a color filter layer is formed by using a photoelectric deposition method. In this case, a semiconductor is exposed in a region where the photoelectric deposition film is not formed, and an electrodeposition film for a black matrix is formed in this portion. Can be easily formed. In general, the electrodeposition film has a high insulating property, and it is difficult to form a photoelectrodeposition film by stacking it on the color filter layer. Therefore, after forming a color filter layer using the photoelectrodeposition method, if a voltage is applied or light irradiation or both are performed in a carbon black dispersion liquid for a black matrix, both light and an electric field are not present at this time. Even though there is no color filter layer, a uniform and thin carbon black film fills the area. As described above, when the method for forming a photo-deposited film is used for the black matrix layer, a thin-film, high-performance color filter can be easily formed in one step. The black matrix layer formed here employs an electrodeposition method using an electrodeposition solution in which specific carbon black particles are dispersed, so that a film rich in carbon black particles can be deposited. By using this method, it is possible to deposit a film by controlling a thin film only at a pattern portion where a current is generated, such as a defective portion of a filter deposition structure.

The black matrix containing the acidic carbon black pigment according to the present invention exhibits uniform and high light absorption and light-shielding properties even in one layer. It can be applied to a configuration having a structure. That is, when a metal thin film is laminated, the light-shielding property is further enhanced, and a thin-film structure having sufficient light-shielding property and non-reflection property is possible even with a thickness of 1/3 or less as compared with a conventional type of a film having only a resin dispersed pigment layer. The width of the tapered portion at the film deposition end is kept small, which not only increases the dimensional reliability of the small width structure of the filter, but also reduces the leakage light at the edge of the filter. It also improves performance. When a metal thin film is formed, it is preferable to use a metal plating method. However, as a metal material to be used, it is difficult to use an amphoteric metal material, and it is easy to use a plating metal having high robustness itself. For example, matrix metal materials that are easy to use include Ni, Cr, Cu, Au,
Ag, Mo, Sn, Zn, Co, Ti, Ta, Pb, R
It is also possible to use a metal selected from r, an alloy of multiple metals, or a mixture of multiple metals.

As described above, when a carbon black pigment-dispersed electrodeposition method having a functional group with specific physical properties is used as a method for forming an electrodeposition film on a black matrix layer, a thin, high-performance color filter can be easily formed. it can.

[0067]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 A transparent conductive layer of ITO was formed on a quartz glass substrate having a thickness of 0.8 mm by sputtering to a thickness of 0.23 μm.
m, and 0.4 μm of TiO ₂ was further formed. Next, in order to improve the photocurrent characteristics of TiO ₂ , a reduction treatment was performed in a mixed gas of hydrogen and nitrogen. The treatment was performed by annealing at 440 ° C. for 40 minutes in pure nitrogen gas mixed with 4% hydrogen gas to obtain a transparent substrate.

(Formation of Filter Section) Using this transparent substrate, an image was recorded using an image recording apparatus as shown in FIG. In the image recording apparatus, as shown in FIG. 57, an image holding member 3 provided with a work electrode capable of inputting an image signal from the back side is placed on an electrodeposition solution bath 2 containing the following electrodeposition solution 1, and the back surface is outside the bath. And the control electrode 6 using a salt bridge was placed in the bath. In a general triode configuration in the electrochemical field, an electrodepositable polymer material (styrene-acrylic acid random copolymer-molecular weight 19000), a molar ratio of hydrophobic group / (hydrophilic group + hydrophobic group) 73%, acid Value 90,
Glass transition point 45 ° C, flow start point 90 ° C, decomposition point 247
In a water-based electrodeposition solution containing a pigment at which a precipitation start point pH 5.8) and an azo red ultrafine particle pigment are dispersed at a solid content ratio of 5: 5, a TiO ₂ electrode is used as a work electrode with respect to a saturated calomel electrode. A 1.7 V bias potential was applied to the work electrode, and a mercury xenon lamp (Yamashita Denso,
When the light was irradiated for 2.5 seconds using a photomask of a mask pattern image at a light intensity of 50 mW / cm ^{2 at a} wavelength of 365 nm, the red mask filter pattern was applied only to the area where the transmitted light was irradiated on the TiO ₂ surface. Been formed.

Next, in the same manner, the polymer material
Tylene-acrylic acid copolymer and phthalocyanine green
Pigments in which an ultrafine pigment is dispersed at a solid content ratio of 5: 5
TiO for saturated calomel electrode in electrodeposition solution containing_TwoMake electrodes
The working electrode is set to 1.8 V and the back of the substrate
Mercury xenon lamp (Yamashita Denso, 365nm wavelength)
Light intensity 50mW / cm^Two) Through a photomask for 4 seconds
Irradiated with TiO _TwoOnly the area where light was irradiated on the surface
A green mask filter pattern was formed. So
After washing cascade thoroughly with pH adjusted liquid with pH value of 4.2
Purified. Similarly, the polymer material styrene-a
Crylic acid copolymer and phthalocyanine blue-based ultrafine particles
Aqueous solution containing pigment in which the pigment is dispersed at a solid content ratio of 5: 5
TiO for saturated calomel electrode in_TwoElectrode as working electrode
Utilize and set the working electrode to 1.9V.
And TiO_TwoOnly the area of the surface where the transmitted light is
Screen filter pattern is formed, color filter
A layer was formed.

(Formation of Black Matrix Part) Carbon black particles having a styrene-acrylic acid copolymer (0.8% by weight) and a carboxyl group on the surface (CAB-O- JET
300, average particle diameter: 13 nm) 8% by weight, and the remainder is immersed in a dispersion liquid obtained by ultrasonic dispersion in a mixed liquid composed of pure water, and the entire substrate on which the filter is formed is immersed in the dispersion liquid. A negative bias voltage of 5.0
V was applied for 2 seconds, thereby depositing a black electrodeposition film on the conductive portion other than the colored filter film,
A black matrix was formed with a thick carbon black particle-containing electrodeposition material thin film. The optical transmission density of the obtained black matrix film was 2.9. Next, a protective layer was coated thereon to form a color filter. When the optical characteristics of the boundary between the filter portion and the black matrix portion of the prepared color filter were evaluated, the deviation of the edge portion of the boundary could be realized with high accuracy within 4.6 μm.

(Comparative Example 1) The carbon black pigment having a functional group used in the formation of the black matrix was replaced with ordinary carbon black (pH value: 8.5, average particle diameter: 41 nm, oil absorption (DPB): 60 cc). / 100 g) was prepared in the same manner as in Example 1 except that the pigment was changed to the ultrafine pigment. When the surface of the black matrix portion of the prepared color filter was observed with an optical microscope, cracks considered to have occurred during drying of the electrodeposited film were partially observed. Further, when the optical characteristics of the boundary between the filter portion and the black matrix portion were evaluated in the same manner as in Example 1, the deviation of the boundary edge portion was 12 μm, and a color filter with a level of accuracy that was not problematic in practice could be realized. The accuracy was slightly lower than that of Example 1.

Example 2 A transparent conductive film of ITO having a thickness of 0.3 μm was formed on a non-alkali glass substrate (7095) having a thickness of 7 mm by a sputtering method, and 0.4 μm was further formed thereon.
A film of TiO ₂ having a thickness was formed by a sputtering method. Next,
In order to improve the photocurrent characteristics of TiO ₂ , annealing was performed at 450 ° C. for 25 minutes in pure nitrogen gas mixed with 5% hydrogen gas as a reduction treatment.

(Formation of Black Matrix Section) Thereafter, in a three-electrode type arrangement generally used in electrochemistry as shown in FIG. 7, cascade cleaning was sufficiently performed with a pH adjusting liquid having a pH value of 4.5. Next, a dispersion liquid of carbon black black pigment particles having an acryl group adsorbed with an average particle diameter of 23 nm is mixed and dispersed stepwise little by little in a plating solution at a ratio of 12% by weight, and the mixture is added to the plating solution while forcibly stirring. While immersing the entire electrodeposited substrate and irradiating a negative-positive reverse image pattern with light, a reverse voltage of 2.6 V is applied to the entire back surface of the substrate, and a black matrix pattern is applied to a portion not exposed to light. A film was formed. The energization / exposure time at that time was 3.5 seconds. The plating film thickness formed at that time was a carbon black pigment particle film having a thickness of 0.61 μm. Thereby, a black matrix layer having a black thin layer and a uniform pattern could be formed. At that time, the optical transmission density of the black matrix film was 3.3.

(Formation of Filter Section) Next, in a tripolar arrangement generally used in electrochemistry, a styrene-acrylic acid copolymer (molecular weight 14,000, hydrophobic group / (hydrophilic group + hydrophobic group)) was used. Molar ratio 73%, acid value 96, glass transition point 47 ° C,
Flow start point 92 ° C, decomposition point 248 ° C, precipitation start point pH
5.9) and azo red ultrafine particle pigment in a solid content ratio of 6: 4
In the aqueous solution containing the pigment dispersed in, the TiO ₂ electrode is used as the working electrode with respect to the saturated calomel electrode, and the working electrode is set to 1.
A 7 V mercury xenon lamp (Yamashita Denso, light intensity of 365 nm, 50 mW / cm ² ) was irradiated from the back side of the substrate through a red photomask for 6 seconds, and the TiO ₂ surface was irradiated with light. A red mask filter pattern was formed only in the region where the masking was performed. Thereafter, the substrate was washed with a pH adjusting liquid having a pH value of 4.3.

Then, a saturated calomel electrode and a TiO ₂ electrode were placed in an aqueous solution containing the same electrodepositable polymer material and phthalocyanine green-based ultrafine particle pigment as described above in a solid content ratio of 6: 4. Is used as a working electrode, the working electrode is set to 1.7 V and the mercury xenon lamp is
(Yamashita Denso, light intensity of 365 nm wavelength, 50 mW / cm ² ) was irradiated for 9 seconds through a green photomask.
A green mask filter pattern is formed only in the region where the light is irradiated on the surface of the iO ₂ , and thereafter, a pH value of 4.
Washed with pH adjusted liquid of 3. Similarly, in an aqueous solution containing a pigment in which the same electrodepositable polymer material and phthalocyanine blue-based ultrafine particle pigment are dispersed at a solid content ratio of 6: 4, a saturated calomel electrode and a TiO ₂ electrode are used as working electrodes. Using a working electrode of 1.8 V, a mercury xenon lamp (manufactured by Yamashita Denso, light intensity of 365 nm, light intensity 50 mW / cm ² ) was irradiated from the back side of the substrate for 9 seconds through a blue photomask. However, a blue mask filter pattern was formed only in the region where light was irradiated on the TiO2 surface, and a color filter layer was formed. Next, it was washed with a pH adjusting liquid having a pH value of 4.6. A color filter was formed by coating a protective layer thereon. The optical transmission density of the obtained black matrix film was 3.1. When the optical characteristics of the boundary between the filter portion and the black matrix portion of the prepared color filter were evaluated, no leakage light was observed at the boundary, and the deviation of the edge portion could be realized with high accuracy within 4 μm.

Example 3 A transparent conductive film of ITO was formed to a thickness of 0.3 μm on a 1.2 mm thick Pyrex glass substrate by sputtering, and a 0.2 μm thick film was formed on the ITO thin film by a sol-gel method.
A TiO ₂ layer was formed. Film formation by spin coating on ITO substrate
The alkoxide of TiO ₂ is rotated 1400 times, and TiO ₂
The layers were formed. After that, heat treatment at about 480 ° C for 1 hour
_Two films were formed. Thereafter, as in the case of Example 1, annealing was performed at 360 ° C. for 20 minutes in pure nitrogen gas mixed with 4% hydrogen gas as in Example 1.

(Formation of Filter Part) In a three-electrode arrangement generally used in electrochemical, an electrodepositable polymer material-styrene-acrylic acid copolymer (molecular weight 14,000, hydrophobic group / (hydrophilic group +
(Hydrophobic group) molar ratio 69%, acid value 100, glass transition point 35
℃, flow start point 85 ° C, decomposition point 240 ° C, precipitation start point p
H5.8) and an azo red ultrafine particle pigment in a solid content ratio of 8
A mercury xenon lamp (Yamashita Denso Co., Ltd.) was used from the back side of the substrate while using a TiO ₂ electrode as a working electrode against a saturated calomel electrode in an aqueous solution containing the pigment dispersed in a ratio of 2, while applying a bias voltage of 1.7 V to the working electrode. Light intensity at a wavelength of 365 nm 50 mW /
When a pattern image was irradiated with light through a photomask for 7 seconds using a photomask (cm ² ), a mask filter pattern of a red color portion was formed only in the region where the light was irradiated on the TiO ₂ surface. Thereafter, the pattern image was immersed and washed with a pH adjusted aqueous solution having a pH value of 4.0.

Next, a TiO ₂ electrode was used as a working electrode with respect to a saturated calomel electrode in an aqueous dispersion in which the electrodepositable polymer material and the phthalocyanine green-based ultrafine particle pigment were dispersed at a solid content ratio of 8: 2. Then, the working electrode was set to 1.8 V, and a mercury xenon lamp (manufactured by Yamashita Denso, light intensity of 365 nm, light intensity 50 mW / cm ² ) was irradiated from the back side of the substrate for 8 seconds through a green color photomask, A green mask filter pattern was formed only on the region where the light was irradiated on the TiO ₂ surface. Thereafter, the plate was washed with a pH adjusted liquid having a pH value of 4.6.
Next, in the same manner, in an aqueous solution containing a pigment obtained by dispersing the electrodepositable polymer material and the phthalocyanine blue-based ultrafine particle pigment in a solid content ratio of 8 to 2, a TiO ₂ electrode was used as a working electrode with respect to a saturated calomel electrode. Using a working electrode of 1.9 V, a mercury xenon lamp (Yamashita Denso, 365 nm wavelength)
The light intensity of 50 mW / cm ² ) was irradiated for 7 seconds through the photomask of the blue part, and a blue mask filter pattern was formed only in the area of the TiO ₂ surface where the light was irradiated. A layer was formed.

(Formation of Black Matrix Part) Then, 17% by weight of the total liquid of acidic carbon black black pigment particles having a carboxylic acid group and a sulfonic acid group on the surface with an average particle diameter of 33 nm were added to the electrodepositable polymer. Material: Styrene-acrylic acid copolymer (molecular weight 14,000, hydrophobic group / (hydrophilic group +
(Hydrophobic group) molar ratio 69%, acid value 100, glass transition point 35
℃, flow start point 85 ° C, decomposition point 240 ° C, precipitation start point p
H5.8) was immersed in the above solution mixed and dispersed by propeller agitation at 0.2% by weight, and then the substrate was illuminated with a bias voltage of 2.8 V over the entire surface for 2.1 seconds while irradiating the substrate with light. Precipitate electrodeposited material while applying
As a result, a conductive film other than the colored filter film was coated with a black pigment. The film was a black electrodeposition film containing carbon black particles having a thickness of 0.56 μm, and a black matrix could be formed by this thin film.

In the color filter obtained here, the boundary portion between the filter layer and the black matrix layer was clearly optically shown at the boundary portion, and good performance was confirmed without any leakage light. Thereafter, it was washed with a pH-adjusting liquid having a pH value of 5.1 and dried by heating to complete a color filter. The completed color filter was immersed in pure water for 20 days, and the film quality was observed. However, no change was confirmed, demonstrating that the color filter exhibited sufficient robustness.

(Example 4) A quartz glass substrate having a thickness of 1 mm
A transparent conductive film of TO was formed to a thickness of 0.4 μm by sputtering, and a 0.5 μm thick TiO ₂ layer was formed on the ITO thin film by a sol-gel method. TiO ₂ is formed on the ITO substrate by spin coating.
Was rotated at a rotation speed of 1400 to form a TiO ₂ layer. Thereafter, heat treatment was performed at about 500 ° C. for 1 hour to form a TiO ₂ film. Then, as a reduction treatment, the surface of the TiO ₂ film is heated by a laser beam in pure nitrogen gas mixed with 4% hydrogen gas in the same manner as in Example 1 to increase the crystallinity of the TiO ₂ film. Obtained.

(Formation of Filter Portion) Next, in a three-electrode arrangement generally used in electrochemistry, the same electrodepositable polymer material and the azo red ultrafine particle pigment as in Example 1 were used in a solid content ratio of 7%. Disperse in a weak alkaline aqueous solution to a ratio of 3 to obtain an aqueous pigment dispersion, use a TiO ₂ layer electrode as a working electrode with respect to a saturated calomel electrode, set the working electrode to 1.7 V, and use an ultraviolet light source from the back side of the substrate. The light of the signal corresponding to the red filter pixel was used to form a red filter pattern only in the region of the surface of the TiO ₂ layer where the light was irradiated. Thereafter, the pattern image was washed by immersion in a pH adjusted aqueous solution having a pH value of 5.0.

Next, in a water-based pigment dispersion in which the electrodepositable polymer material and the phthalocyanine green-based ultrafine particle pigment were dispersed at a solid content ratio of 7: 3, a Ti was applied to a saturated calomel electrode.
The O2 electrode is used as the working electrode, the working electrode is set to 1.7 V, UV light is irradiated from the back side of the substrate to the quartz substrate side in the same way as before, and only that part of the TiO ₂ layer surface that is irradiated with light is green. A filter pattern was formed. Thereafter, the pattern image was immersed and washed with a pH adjusted aqueous solution having a pH value of 4.0. Similarly, a TiO ₂ electrode is used as a working electrode for a saturated calomel electrode in an aqueous pigment dispersion in which the electrodepositable polymer material and the phthalocyanine blue-based ultrafine particle pigment are dispersed at a solid content ratio of 7: 3, When the working electrode was set to 1.7 V and UV light was irradiated from the back side of the substrate in the same manner as described above, a blue filter pattern was formed only in the light-irradiated region on the surface of the TiO ₂ layer, and a color filter layer was formed. next,
Thereafter, the pattern image was immersed and washed with a pH adjusted aqueous solution having a pH value of 4.2.

(Formation of Black Matrix Part) A phthalocyanine pigment having an average particle diameter of 93 nm was 0.8% by weight relative to the total liquid, and a carbon black pigment having an average particle diameter of 32 nm and having a carboxylic acid group on the surface was a weight based on the total liquid. % By weight, electrodepositable polymer material: styrene-acrylic acid copolymer (molecular weight 14,000, molar ratio of hydrophobic group / (hydrophilic group + hydrophobic group) 69%, acid value 100, glass transition point 35)
℃, flow start point 85 ° C, decomposition point 240 ° C, precipitation start point p
H5.8) was mixed with 0.8% by weight of the weight and pure water for the others, and the entire substrate was immersed in the above solution while being mixed and dispersed by stirring with a propeller.
8 V is applied to the entire surface while light is applied for 2.3 seconds to form a film. Then, the substrate is immersed in a plating solution at a temperature of 40 ° C. in a nickel plating solution, and the substrate is immersed in the plating solution. When 2 V was applied for 13 seconds, a black matrix layer having a two-layer structure in which a plated metal thin film was laminated on the carbon black particle-containing black electrodeposition film other than the electrodeposited portion of the filter was formed.
The thickness was 38 μm. The optical transmission density of this film is 3.
It was 7. According to this method, the composite film of the electrodeposition film and the plating thin film was formed only in the region where the color filter layer was not formed, and the black matrix layer could be formed. Thereafter, a color filter was completed by coating a polyimide protective layer on the top.

[0086]

According to the manufacturing method of the present invention, without using photolithography, a filter section having high resolution, high controllability and high translucency, and excellent uniformity and light shielding properties are obtained.
An excellent filter having a black matrix portion having a good film quality with little unnecessary light reflection can be manufactured with a small number of steps and at low cost.

[Brief description of the drawings]

FIG. 1 shows a black electrodeposition film using carbon black having no functional group, a black electrodeposition film using carbon black having a functional group of the present invention, and a nickel plating layer laminated on the black electrodeposition film of the present invention. 4 is a graph showing the relationship between the film thickness and the transmission optical density of the sample and the nickel plating layer.

2A is a schematic cross-sectional view schematically showing a black matrix and a filter layer obtained by the production method of the present invention, and FIG. 2B is a schematic view showing a conventional black matrix and a filter layer containing carbon black. FIG.

FIG. 3 is a graph showing a relationship between a pH change of an aqueous colorant liquid and a dissolution characteristic of the colorant.

FIG. 4 is a graph showing dissolution characteristics of two electrodeposited materials having different polarities and which can be used in combination with a change in pH.

5A is a schematic diagram showing a semiconductor energy band in the case of a Schottky junction, and FIG. 5B is a schematic diagram showing an energy band of a semiconductor in the case of a PIN junction.

FIG. 6 is a graph showing a change in the amount of electrodeposition of the electrodeposition material when the conductivity is changed.

FIG. 7 is a schematic diagram illustrating an image recording apparatus used for image recording according to the first embodiment.

FIGS. 8A to 8D are schematic cross-sectional views illustrating a manufacturing process of a color filter.

[Explanation of symbols]

 Reference Signs List 1 electrodeposition liquid bath 3 light-transmitting substrate 4 potentiostat power supply 5 counter (counter) electrode 6 control electrode 12 transparent substrate 14 transparent conductive film 14 16 semiconductor thin film 18 light-transmitting substrate (transparent substrate) 30 colored electrodeposition film (color) (Filter layer) 32 Black electrodeposition film (Black matrix layer)

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Keiji Shimizu 430 Sakai, Nakagawa-cho, Ashigara-gun, Kanagawa Green Tech Nakai F-term in Fuji Xerox Co., Ltd. 2H042 AA06 AA08 AA26 AA29 2H048 BA62 BB02 BB14 BB42 BB46 2H091 FA02Y FA35Y FB08 FB12 FB12 FC01 FC06 FC10 GA03 GA12 GA13 LA12

Claims (9)

[Claims] 1. A color material capable of electrochemically depositing an electrodeposited film on a light-transmitting substrate having a light-transmitting conductive film and a light-transmitting semiconductor thin film formed on predetermined portions on a light-transmitting substrate. Is disposed so as to be in contact with an aqueous electrodeposition solution containing a photo-deposition material containing, a current is generated in a predetermined area of the light-transmitting substrate, and the photo-deposition material including the coloring material is electrochemically used. A process of depositing an electrodeposited film to form a filter portion, and then supplying a current to the light-transmitting substrate, and applying a colorant to the electrode portion formed on the unformed portion of the electrodeposited film as a functional material on the surface. Depositing a black electrodeposited film containing at least 75% by weight of a carbon black pigment having a group to form a black matrix portion, and a method for producing a filter. 2. A coloring material capable of electrochemically depositing an electrodeposited film on a light-transmitting substrate formed by sequentially forming a light-transmitting conductive film and a semiconductor thin film having a photovoltaic function on a light-transmitting substrate. Is disposed so as to be in contact with an aqueous electrodeposition solution containing a photo-deposition material containing, and a predetermined region of the light-transmissive substrate is exposed to light so that only the light-irradiated portion is energized in the aqueous electrodeposition solution to form the color. Forming a filter portion by selectively depositing an electrodeposited film on the light-irradiated portion using a photo-deposited material containing a material; Forming a black matrix portion by depositing a black electrodeposition film containing at least 75% by weight of a carbon black pigment having a functional group on the surface as a coloring material for the electrode portion formed on the formation portion. A method for producing a filter, comprising: 3. The step of forming the black matrix portion comprises applying 75% by weight of a carbon black pigment having a functional group on a surface of an unformed portion of the electrodeposition film by applying a bias voltage to the entire surface of the light transmitting substrate. The method for producing a filter according to claim 1 or 2, wherein a black matrix portion is formed by depositing a black electrodeposition film containing at least 10% by weight of the black electrodeposition film. 4. The carbon black pigment having a functional group on the surface thereof has an average particle size in a range of 5.0 nm to 0.7 μm. Manufacturing method of filter. 5. The method for producing a filter according to claim 1, wherein the functional group of the carbon black pigment having a functional group on the surface includes a carboxyl group. 6. The thickness of the black matrix portion obtained by the step of forming the black matrix portion is as follows:
The method for producing a filter according to any one of claims 1 to 5, wherein the thickness is in a range of 0.2 µm to 3 µm. 7. The semiconductor thin film having a photovoltaic function contains at least one material selected from the group consisting of titanium oxide, silicon carbide, lead oxide, zinc oxide, nickel oxide, tin oxide, and molybdenum oxide. Compound optical semiconductor, or
6. An organic optical semiconductor comprising at least one material selected from the group consisting of metal phthalocyanine pigments, perylene pigments, azo pigments, and polyvinyl carbazole. A method for producing a filter according to any one of the preceding claims. 8. The method according to claim 2, wherein after forming the black matrix portion by the step of forming the black matrix portion, a metal thin film is laminated on the black matrix portion by a metal plating method. A method for producing a filter according to any one of the preceding claims. 9. A metal plating material for forming a metal thin film to be laminated on the black matrix portion is Ni,
9. The method according to claim 8, wherein the filter is selected from a metal selected from Cr, Cu, Au, Ag, Mo, Sn, Zn, and Co and a mixture or alloy thereof.