JPH085830A - Production of color filter - Google Patents

Abstract

PURPOSE:To obtain a production method of a color filter by which any patterns of color layers can be freely selected without requiring high processing techniques, a large filter can be easily produced, and color filters can be mass- produced at a low cost. CONSTITUTION:A positive photosensitlve coating film is formed on a transparent conductive layer of a transparent substrate. The coating film is exposed to light to form exposed areas with different two levels of light quantity. The photosensitive coating film in the area with larger light quantity is developed, and then a light-shielding layer is formed by electrodeposition coating. The photosensitive coating film not developed is exposed to form exposed areas with different two levels of light quantity. The coating film in the area with larger light quantity is developed and a color layer is formed by electrodeposition coating. Further, the photosensitive coating film not developed is exposed to form exposed areas with three or more different levels of light quantity. The coating film in the area with the largest light quantity is developed and a color layer is formed by electrodeposition coating. This procedure is repeated two or more times in the order of the largest light quantity and color layers are formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a color filter, and more particularly to a method for manufacturing a color filter suitable for a color liquid crystal display device.

[0002]

2. Description of the Related Art At present, as a method for producing a color filter, a dyeing method, a printing method, a pigment dispersion method, etc., in which a transparent substrate is colored with a binder containing a dye or a pigment, are known. However, since the dyeing method is a method of selectively dyeing a resin thin film on a substrate with a dye, it is necessary to perform a dye-proofing and photolithography step each time the color is changed, which complicates the process, resulting in high manufacturing cost. There is a problem of becoming. Further, since a dye is used as a colorant, it has a drawback that heat resistance, weather resistance, chemical resistance and the like are inferior. Further, although the printing method does not require anti-staining, there is a problem in that the miniaturization of the color pattern is limited and the accuracy of the printing position becomes worse as the number of colors increases. Further, the pigment dispersion method can manufacture a fine pattern, but has a drawback that a highly accurate photolithography process must be performed each time a color change is performed, and the process becomes extremely complicated.

On the other hand, in order to eliminate these drawbacks, a method of manufacturing a color filter by an electrodeposition coating method has been proposed. For example, a transparent electrode is formed in a predetermined pattern in advance, and a voltage is applied in a tank in which a polymer containing dyes or pigments dissolved or dispersed in a solvent is ionized to form a color filter. In the filter manufacturing method, a transparent electrode for forming a color filter is required in addition to the transparent electrode for display, and the transparent electrode for forming the color filter needs to be insulated for each color, so an etching process is required. . Further, an electric short circuit occurs in the transparent electrode for display, a line defect occurs, and further the yield decreases. Further, there is a problem that it is difficult to arrange pixels other than the stripe type formed by arranging the electrodes.

Further, in JP-A-61-203403, a photosensitive film on an electrode is peeled off in a pattern by a photolithography method, an exposed portion is electrodeposited, and a photosensitive film on an adjacent region is peeled off. A method for producing a color filter for electrodeposition is disclosed in JP-A-61-272720, in which a positive photosensitive film is formed on a conductive layer, exposed and developed, and an electrodeposited portion is electrodeposited. The way is
Japanese Patent Laid-Open No. 61-279803 discloses a method in which a positive type photosensitive resin layer on a transparent electrode is exposed and developed in a mosaic shape and electrodeposited, and then another mosaic pattern is formed adjacently to electrodeposition. Are disclosed respectively. However, in these methods, it is necessary to form the colored layer in a process involving exposure and development for each color, which is a problem in that the process becomes complicated.

Therefore, recently, a method of forming different patterns in at least three steps on a photosensitive coating formed on a transparent conductive layer by one exposure, and successively repeating development and formation of a colored layer (JP-A-4-287003). Gazettes) have been proposed. In this method, the pattern can be formed by one exposure, so that the process can be simplified and the number of expensive exposure machines can be reduced. Furthermore, the photolithography method in which the colored layer is formed for each color. Compared with, there is an advantage that precise alignment is not required at the time of pattern formation. Such a method of forming all the patterns required for a color filter by one exposure is excellent in itself, but depending on the conditions etc., compared to the usual method of repeating exposure / development every time. The exposure and development conditions may become strict. In such a case, a problem may occur in the durability of the photosensitive coating film itself, and the pattern accuracy may be deteriorated.

In order to solve such a drawback, a light-shielding layer which requires the highest precision is previously formed by using the first photosensitive coating film, and the other exposure is performed by one exposure described above. A method of forming a pattern for forming a layer and a method of dividing the exposure for pattern formation into two and re-forming a second photosensitive coating film, which requires durability, again in accordance with the exposure are also proposed. Has been done. This method has the advantage of simplifying the process as compared with the conventional photolithography method of forming colored layers for each color, but since it is necessary to form at least two photosensitive coating films, There is a drawback that the material cost is higher than the method using one photosensitive coating film. Such a problem of material cost is an important factor in industrial production, and moreover, the photosensitive resin forming the photosensitive coating film occupies most of the material cost, most of which is non-reusable electrodeposition. In the manufacturing method of a color filter using painting, the most improvement is required together with the simplification of the process.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above-mentioned drawbacks, to provide a large degree of freedom in the shapes of the light-shielding layer and the colored layer, to easily cope with the increase in size, and to reduce the cost and mass production. It is to provide a manufacturing method of a color filter which is easy to produce.

Another object of the present invention is to provide a color filter for a liquid crystal color display, which has at least a coloring layer of red, green, blue or the like and a dark light shielding layer, and optionally has a transparent outer frame portion. It is an object of the present invention to provide a method for producing a color filter, which is capable of producing a filter at a low cost by a simple process.

[0009]

Means for Solving the Problems The present inventors have studied a method of manufacturing a color filter which has a large degree of freedom in the shapes of a light-shielding layer and a colored layer and can cope with an increase in size. It was found that a color filter can be obtained with good accuracy and at low cost by a simple process of combining a resist and a specific exposure method.

That is, according to the present invention, (a) a step of forming a positive type photosensitive coating film on a transparent conductive layer of a transparent substrate having a transparent conductive layer, and (b) the positive type photosensitive coating film. A step of forming exposure areas having different exposure amounts in two steps; (c) developing a photosensitive coating film having a large exposure amount in the exposure areas to expose the transparent conductive layer, and then forming a light shielding layer by electrodeposition coating. And (d) a step of forming an exposure area in which the exposure amount is different in two steps in the undeveloped photosensitive coating film in the step (c).
(e) a step of developing the photosensitive coating film having a large exposure amount in the exposed area formed in the step (d) to expose the transparent conductive layer, and then electrodepositing a colored paint to form a colored layer, f1) a step of forming an exposed area having a different exposure amount in at least three stages on the undeveloped photosensitive coating film in the step (e),
1) Repeat the operation of developing the photosensitive coating film in the exposed area to expose the transparent conductive layer, and then electrodepositing the colored paint to form the colored layer at least twice in order of increasing exposure amount in the exposed area. The method for producing a color filter (hereinafter, referred to as a first production method) is provided including the step of forming a colored layer.

Further, according to the present invention, the above (a) to (e)
And (f2) a step of forming a plurality of exposed areas having different exposure amounts in three stages on the undeveloped photosensitive coating in the above (e) step, and (g2) developing the photosensitive coating in the exposed area. The transparent conductive layer is exposed to expose the transparent conductive layer, and then the operation of forming the colored layer by electrocoating the colored coating material is repeated twice in order of increasing exposure amount of the exposed area to form the colored layer, and then the remaining exposed area is exposed. A method for producing a color filter (hereinafter referred to as a second production method), which comprises a step of developing to expose the transparent conductive layer.

The present invention will be described in more detail below. In the first and second manufacturing methods of the present invention, first, a positive type photosensitive coating film is formed on a transparent conductive layer of a transparent substrate having a transparent conductive layer (hereinafter referred to as step (a)). The transparent substrate used in the present invention is not particularly limited as long as it is a transparent plate. Examples thereof include glass, various laminated plates, various plastic plates, and other plate-shaped insulators, and glass is particularly preferable. It is desirable that the surface of the substrate is smooth in view of the performance of the color filter, and the surface can be polished before use if necessary. The thickness of the transparent substrate can be appropriately selected according to the purpose, but is usually 0.1.
It is preferably about 2 mm.

Examples of the transparent conductive layer formed on the transparent substrate include materials containing tin oxide, indium oxide, antimony oxide, indium-tin oxide and the like, and indium-tin oxide is particularly preferably used. To be The thickness of the transparent conductive layer is preferably 20 to 300 nm. The method for forming the transparent conductive layer is not particularly limited, and examples thereof include known methods such as a spray method, a CVD method, a sputtering method, and a vacuum vapor deposition method. The transparent conductive layer is
From the viewpoint of the performance of the color filter, it is desirable to use a filter having the highest possible transparency.

The method for forming the positive photosensitive coating film formed on the transparent conductive layer of the transparent substrate is not particularly limited, but known methods such as electrodeposition method, spraying method, dip coating method, roll coating method, A screen printing method, a method of coating with a spin coater and the like can be mentioned. The spin coater method is particularly preferable. When the spin coater method is used, it is preferable to dry the coating film after coating. The drying conditions in this case are not particularly limited, but usually the drying temperature is 50 to 150 ° C. and the drying time is about 1 to 30 minutes.

As the positive type photosensitive resin for forming the positive type photosensitive coating film, a resin having a coating film forming ability and photosensitivity can be used. The positive photosensitive resin is not particularly limited as long as the exposed portion is eluted by the developing solution, for example, a resin having a quinonediazide group, a resin having a diazomeldrum acid or a nitrobenzyl ester, or the like. Preferable examples are resin compositions containing these resins. Specifically, for example, a resin obtained by introducing an amino group or ammonium, an onium group such as sulfonium and a hydroxyl group into an acrylic resin, an epoxy resin, a urethane resin, or a polybutadiene resin, and further adding a quinonediazidesulfonic acid compound by an esterification reaction. , Cationic resins that are solubilized and / or dispersed in water with acids or acidic substances such as formic acid, acetic acid, propionic acid, lactic acid; acrylic resins, polyester resins,
Maleated oil resin, polybutadiene resin, epoxy resin, etc., a resin obtained by introducing a carboxyl group and a hydroxyl group, and further adding a quinonediazide sulfonic acid compound by an esterification reaction, and a base such as triethylamine, diethylamine, dimethylethanolamine, or ammonia. Anionic resin that is solubilized and / or dispersed in water with a volatile substance; Resin obtained by reacting a compound having a hydroxyl group such as polyhydroxybenzophenone with a quinonediazide sulfonic acid derivative, and film formation of novolac cresol resin The resin composition etc. which mixed the resin which has a function suitably can be mentioned. In particular, from the viewpoint of process simplification and prevention of pollution, it is preferable to use a resin that can be solubilized and / or dispersed in water. The mixing ratio in the resin composition can be arbitrarily selected depending on the exposure conditions and the development conditions. In addition, a positive photosensitive resin containing a compound having a group capable of generating an alkali or water-soluble group by an acid catalyst and a compound capable of generating an acid by light (photoacid generator) as essential components can also be used. it can.

In the present invention, when a positive type photosensitive coating film is formed on a transparent substrate having a transparent conductive layer, the positive type photosensitive resin is used as it is or by dispersing or dissolving it in an organic solvent and / or water. It can be used as a photosensitive paint. The organic solvent is not particularly limited,
For example, various glycol ethers such as ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monophenyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone , Cyclohexanone, isophorone, N-
Ketones such as methylpyrrolidone; ethers such as dibutyl ether, dioxane, tetrahydrofuran; alcohols such as methoxybutanol, diacetone alcohol, butanol, octanol, isopropanol; hydrocarbons such as toluene, xylene, cyclohexane, hexane; ethyl acetate , Butyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-methoxypropyl acetate, ethyl benzoate, etc .; acid amides such as dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, etc. It can be used alone or as a mixture.

Further, the organic solvent solubilizes and / or disperses the cationic resin or anionic resin in water in order to facilitate solubilization and dispersion, improve bath stability, obtain a smooth coating film, and the like. Alternatively, it can be added at the time of dispersion.

If necessary, the positive type photosensitive paint may include
Dyes and / or pigments can be added. The hue of the dye and / or pigment can be appropriately selected according to the purpose. For example, in order to improve the resolution of the positive type photosensitive coating material, it is necessary to remove long wavelength light having a large diffraction at the time of exposure.
It is desirable to incorporate a dye that absorbs light having a wavelength of 0 to 500 nm, for example, an ultraviolet absorber such as oil yellow or trihydroxybenzophenone. Further, depending on the desired hue, two or more kinds of the dyes and / or pigments may be mixed and used as long as the characteristics are not impaired. The use ratio of the dye and / or pigment is appropriately selected depending on the purpose, hue, type of dye and / or pigment used, film thickness of the positive photosensitive coating when dried, and the amount thereof is preferably positive. 1 for all photosensitive paints
It is preferably 0% by weight or less, particularly preferably 5.0% by weight or less.

The positive photosensitive coating composition is prepared by using a positive photosensitive resin, an organic solvent and / or water, if necessary, a dye and / or a pigment, an acidic substance or a basic substance, a dispersion aid of the dye or the pigment. , A leveling agent that improves the smoothness of the coating film,
By mixing various auxiliaries such as a viscosity modifier and an antifoaming agent, and sufficiently dispersing them using a commonly used disperser such as a sand mill, a roll mill and an attritor, and diluting to a desired concentration. Obtainable. The film thickness of the positive type photosensitive coating film formed by the positive type photosensitive coating material thus obtained is not particularly limited and can be appropriately selected according to the performance required for the color filter, etc. ．
It may be 3 to 20 μm, preferably 0.5 to 15 μm, and more preferably 1 to 3 μm. The film thickness can be adjusted by adjusting the electrodeposition conditions such as current, voltage, electrodeposition time, and liquid temperature when the film is formed by the electrodeposition method. It can be performed under the same conditions as the coating.

Next, in the first and second manufacturing methods of the present invention, the positive type photosensitive coating film is formed with exposure regions having two different exposure amounts (hereinafter referred to as step (b)). In the step (b), an unexposed area can be assigned as one of the exposed areas having different exposure amounts in two steps.

The shape of the exposure area is not particularly limited,
For example, a method of exposing only a required portion through a mask and forming an exposure region in which the exposure amount of an exposed portion and an unexposed portion differ in two steps, or a method in which a mask having a pattern in which light transmittance differs in two steps is used Examples include a method in which exposure is performed twice to form an exposure area having two different exposure amounts. In the latter case, it is preferable to increase the relative difference between the light transmittances because the exposure amount and the exposure time can be easily adjusted. The same purpose can be achieved by increasing the amount or increasing the exposure time. Therefore, the relative difference in light transmittance is not particularly limited, but is usually 5% or more, preferably 50% or more.
It is desirable to provide a significant difference of not less than%, most preferably 100%. When this significant difference of 100% is provided, an exposed portion and an unexposed portion are formed. However, by increasing such a relative difference in light transmittance, the exposure including the development in the next step is performed. It is most preferable because it can reduce the damage to the conductive coating film. The light transmittance refers to the ratio of the intensity of light rays used for exposure before and after passing through the mask.

Next, in the first and second production methods of the present invention, the transparent conductive layer is exposed by developing the photosensitive coating film having a large exposure amount in the exposed region, and then the light shielding layer is formed by electrodeposition coating. (Hereinafter referred to as step (c)).

The development of the photosensitive coating film having a large amount of exposure in the exposed area can be appropriately selected from the development conditions described later.

In the step (c), after the development, a light-shielding layer is formed on the exposed transparent conductive layer by electrodeposition coating. The reason why the light shielding layer is formed first is that the light shielding layer is required to have the highest precision in the color filter. If the light-shielding layer is formed in the first step that does not require alignment with other patterns, pattern alignment in other colored layer forming steps can be easily performed. Note that electrodeposition coating is a coating method in which a colored coating material is deposited only on the transparent conductive layer portion exposed by development,
It can be carried out under the electrodeposition conditions described later.

The hue of the light-shielding layer can be appropriately selected according to the purpose, but normally black or dark color is preferable.
Examples of the black or dark colorant used in the light-shielding layer include carbon black, vanadium trioxide, manganese dioxide, molybdenum disulfide, iron trioxide black, aniline black, Sudan black B, acid black, and the like. Black is preferred.

Next, in the first and second manufacturing methods of the present invention, in the above-mentioned step (c), an exposed area having two different exposure amounts is formed on the undeveloped photosensitive coating film (step (d) below). That). The step (d) can be performed by exposing in the same manner as in the step (b). At this time, the portion where the light-shielding layer has already been formed does not have photosensitivity, so that it may or may not be irradiated with light.
For example, when performing exposure for the purpose of forming a colored layer in a part of the region adjacent to the light-shielding layer, it is not necessary to precisely limit the exposure range to only the desired colored layer portion, and the light on the light-shielding layer does not always have to be exposed. Since it may be irradiated, it is not necessary to perform alignment for pattern formation with high accuracy.

Next, in the first and second manufacturing methods of the present invention, the photosensitive coating film having a large exposure amount in the exposed region formed in the step (d) is developed to expose the transparent conductive layer, and then colored. The paint is applied by electrodeposition to form a colored layer (hereinafter referred to as step (e)).

The operation of developing the photosensitive coating film having a large exposure amount in the exposed area in the step (e) to expose the transparent conductive layer can be performed in the same manner as in the step (c).
The operation of forming the colored layer by electrocoating the colored paint can be performed by using the colored paint described below and appropriately selected from the electrodeposition conditions described below.

After the formation of the light-shielding layer as described above, the next step
The steps (d) and (e) for forming a colored layer of one color in advance before forming the colored layer and the like in the step (f1), the step (g1) or the step (f2) and the step (g2). This is an essential step for limiting the use of the photosensitive coating film, which accounts for most of the material cost, to only once in the method for producing a color filter of the present invention. That is, according to the above steps (b) to (e), which can be carried out under mild exposure and development conditions, etc.,
By forming one colored layer in advance, it will be described later (f1)
The exposure conditions for pattern formation in the step or (f2) step can be relaxed, and therefore damage to the photosensitive coating during exposure, development, etc. can be reduced, and a single photosensitive coating can be used to form a color filter. Can be formed. Moreover, the production method of the present invention can be carried out by using one photosensitive coating film, and by the next step,
It is the most industrially preferable method because the process can be simplified as compared with the conventional method of forming a colored layer and the like by a photolithography method in which exposure and development are repeated for each color.

Next, in the first production method of the present invention,
An exposed area having a different exposure amount in at least three stages is formed on the undeveloped photosensitive coating film (hereinafter referred to as step (f1)). Further, in the second manufacturing method of the present invention, in the step (e), the exposed areas of the undeveloped photosensitive coating film having different exposure amounts are formed in three steps (hereinafter referred to as step (f2)). The shape of the exposed region at this time is not particularly limited and can be appropriately determined depending on the purpose as a color filter.

There is no particular limitation on the method of forming the exposure regions having different exposure amounts in at least three steps, and for example, a method of exposing at once through a mask having a pattern having different light transmittance in at least three steps, 2 There may be mentioned a method of repeating an operation of exposing through a mask having a specific pattern with different light transmittance at different stages, moving the mask, and exposing again with a different exposure amount. Especially to simplify the process,
A method in which exposure is performed once through a mask having a pattern having different light transmittances in at least three stages can be preferably used. At this time, an unexposed area can be assigned as the portion with the smallest exposure amount. In the method of exposing through a mask having a pattern having different light transmittance in at least three steps, the number of steps of different light transmittance of the mask pattern may be at least three steps, and the number of kinds of coloring paints to be used. It can be determined according to the presence or absence of the outer frame portion, and the like. The difference in light transmittance between the stages can be appropriately selected according to the exposure conditions and the development conditions described later. For example, the light transmittance in three stages is 0.1% or less, preferably 0.01% or less, considering the durability of the photosensitive coating film.
The following regions, 5 to 70%, preferably 10 to 60%, more preferably 20 to 40%, and 90% or more, preferably 99% or more are good.

Exposure is performed through a mask having a specific pattern having patterns having different light transmittances in the two steps,
The movement in the method of repeating the operation of moving the mask and re-exposing with a different exposure amount is changing the relative position between the mask and the substrate, for example, fixing the substrate and moving the mask. Both the mask and the mask may be moved. As the mask having the specific pattern, it is preferable to use a mask in which portions through which light passes (hereinafter referred to as pattern blocks) do not overlap with each other after moving a required number of times. Therefore, the gap with one pattern block needs to have a width such that the pattern blocks do not overlap at each exposure even if one pattern block is moved by the number of times of movement.

The moving direction of the mask is not particularly limited and may be on the front, back, left or right as long as it is on the same plane, and the position and relative distance of the pattern block of the mask are
It is appropriately determined according to the number of movements, the movement direction, the movement distance, and the like.

In the exposure, each time the mask is moved, the light irradiation amount is different from the light irradiation performed before that. The means for changing the light irradiation amount is not particularly limited, and various methods such as a method of changing the exposure time, a method of changing the distance of the light source, and a method of changing the output of the light source can be used. At this time, the difference in the light irradiation amount when the exposure is performed so that the light irradiation amount is different can be appropriately selected according to the exposure condition and the developing condition described later. The relative difference in light irradiation amount is not particularly limited, but it is preferable to provide a significant difference of usually 5% or more, preferably 10% or more.

In the above method, instead of moving and using one specific mask, two masks having different patterns can be replaced for each exposure and used. The same method can be used.

In the method of using at least two masks, the patterns of the masks may partially overlap with each other, and in this case, the light irradiation dose for each exposure through the masks is different. Or, even if the light irradiation amount through each mask is the same, the exposure amount of the overlapping portion of the pattern is larger than that of the non-overlapping portion. You can also Even in the case of using such at least two masks or moving one mask to perform exposure for each movement, after forming different exposure areas collectively in at least three stages, each color is exposed. Since the development and electrodeposition are performed, the process can be simplified as compared with the conventional process of repeatedly exposing and developing each color. That is, even if a different exposure region is not formed in at least three steps in one exposure through a mask having different light transmittance in at least three steps, it is possible to change the mask by simply changing or moving the mask.
Exposure can be performed using a single exposure machine, and after completion of all exposures, the original plate can be subjected to development and electrodeposition steps.

Next, in the first production method of the present invention, an operation of developing the photosensitive coating film in the exposed region to expose the transparent conductive layer, and then electrodepositing a coloring paint to form the coloring layer. Is repeated at least twice in the order of increasing exposure amount in the exposed area to form a colored layer (hereinafter referred to as step (g1)). Further, in the second production method of the present invention, the photosensitive coating film in the exposed area is developed to expose the transparent conductive layer,
Next, the operation of forming a colored layer by electrocoating a colored paint is repeated twice in the order of increasing exposure amount of the exposed area to form the colored layer, and then the remaining exposed area is developed to expose the transparent conductive layer. (Hereinafter referred to as step (g2)). In particular, the second manufacturing method which requires the step (g2) can be preferably employed for the purpose of forming a color filter having an outer frame in which the transparent conductive layer is exposed at the peripheral portion of the color filter.

Even in the first production method of the present invention, (g
After forming the colored layer at least twice in step 1), the transparent outer frame portion can be formed by electrodeposition coating the transparent coating material on the outer frame portion.

In the present invention, the light used for exposure is preferably ultraviolet light. The exposure is usually performed using a device capable of generating a large amount of ultraviolet rays. For example, a high pressure mercury lamp,
An ultra-high pressure mercury lamp, a metal halide lamp, or the like can be used as a light source, and if necessary, a radiation source other than ultraviolet rays may be used. The exposure conditions such as the exposure amount and the exposure time can be appropriately selected according to the photosensitive resin used, the exposure device, the type of mask, and the like.

In the step (g1) or the step (g2), in order to selectively repeat the development removal and the electrodeposition of portions having different exposure doses in the exposed areas, developing solutions having different solubilities in the photosensitive resin are used. It is desirable to prepare the required number of types. Depending on the case, even if the number of kinds of the developing solution is less than the required number of kinds, the development can be selectively performed by adjusting the developing time.

As the developing solution used in the present invention, an aqueous solution in which a basic substance is dissolved can be usually used. Examples of the basic substance include sodium carbonate, sodium hydrogen carbonate, sodium metacinnamate, tetraalkylammonium hydroxide, sodium hydroxide, potassium hydroxide and the like.

An organic solvent such as a surfactant, alcohols, glycol ethers, ketones, chlorinated hydrocarbons or a defoaming agent may be added to the developer for improving wettability and defoaming. .

The developing conditions may be appropriately selected depending on the exposure amount of the portion to be removed, the solubility of the used photosensitive resin in the developing solution, the type and concentration of the developing solution, the developing temperature, the developing time and the like. Good. For example, the concentration of the basic substance is usually 0.01 to 25% by weight, preferably 0.05 to
20% by weight, the temperature is usually 10 to 70 ° C, preferably 15
~ 50 ° C, development time is usually 2 to 600 seconds, preferably 3
It can be appropriately selected from the range of 0 to 300 seconds.
Further, the residual developing solution after the development can be washed with water and dried if necessary.

The hue of the colored paint to be electrodeposited in the steps (c) and (g1) or (g2) is usually different for each electrodeposition coating. Depending on the purpose, it is possible to use a hue that overlaps with other areas.

The hue of the colored coating material can be selected as appropriate, but red, green and blue (or indigo), which are usually called three primary colors, are preferably used. The order of color electrodeposition coating is not particularly limited, but it is preferable to introduce red, which has a large amount of ultraviolet absorption, first.

The coloring paint used in the present invention includes:
For example, a cationic or anionic resin is used as a resin component, a dye and / or a pigment is added as a coloring component,
Further, a paint or the like which is dissolved and / or dispersed in water using an acidic or basic substance can be used, and furthermore, the dissolution and / or dispersion of the resin in the colored paint is facilitated, so that the bath stability is improved. In order to obtain a smooth coating film, an organic solvent or the like may be added.

Examples of the cationic resin used as the resin component of the colored coating material include a resin obtained by introducing an onium group such as an amino group, ammonium or sulfonium into an acrylic resin, an epoxy resin, a urethane resin, a polybutadiene resin, a polyamide resin or the like. Examples thereof include resins that are solubilized and / or dispersed in water with an acid or an acidic substance such as formic acid, acetic acid, propionic acid, and lactic acid.

Examples of the anionic resin used as the resin component of the colored coating material include acrylic resins, polyester resins, maleated oil resins, polybutadiene resins, epoxy resins and the like, into which a carboxyl group or the like has been introduced.
Examples thereof include resins that are solubilized and / or dispersed in water with a basic substance such as triethylamine, diethylamine, dimethylethanolamine, and ammonia. Furthermore, the film-forming component of the colored paint may have photosensitivity. Further, as the resin component of the colored paint, an electrodeposition resin having a strong thermosetting property, for example, a mixture of acrylic resin or polyester resin and melamine resin may be used. In the present invention, among the resin components, a mixture of acrylic resin or polyester resin and melamine resin is particularly preferably used.

The dyes and / or pigments used in the colored paint are selected according to the intended hue, but the transparency of the resulting coating film, the stability of the coating material, the electrodeposition characteristics, the durability of the coating film, etc. It is desirable to select one that does not cause a problem. From this point, the dye is preferably an oil-soluble or dispersible dye, and specific examples thereof include azo type, anthraquinone type, benzodifuranone type and condensed methine type dyes. Examples of the pigment include azo lake-based, quinacridone-based, phthalocyanine-based, isoindolinone-based, anthraquinone-based, thioindigo-based organic pigments, yellow lead, iron oxide, chrome vermilion, chrome green, ultramarine blue, cobalt blue, cobalt Examples thereof include inorganic pigments such as green, emerald green, and titanium white, or a mixture thereof. For the dye and / or pigment, "COLOUR INDEX" or the like may be referred to as appropriate.

The above-mentioned colored paint is prepared by using resin, dye and / or
Alternatively, a pigment, an acidic substance or a basic substance and, if necessary, an organic solvent, a dispersion aid for a dye or a pigment, a leveling agent for improving the smoothness of a coating film, a viscosity adjusting agent, various defoaming agents, and the like are added. Mixed and commonly used sand mill,
It is sufficiently dispersed using a disperser such as a roll mill or an attritor, and then diluted with water to a predetermined concentration, for example, a solid content of about 2.5 to 25% by weight, particularly preferably 4 to 20% by weight, and an electric charge is obtained. It can be performed by a method of providing a coating suitable for wearing. The colored coating thus obtained forms a colored layer by electrodeposition coating on the transparent conductive layer. The thickness of the colored layer is not particularly limited and can be appropriately selected according to the performance required for the color filter, but it is usually 0.3 to 5 μm, preferably 1 to 3 μm when dried.

The method of electrodeposition coating in the present invention is not particularly limited, and a known method can be adopted. For example,
Examples thereof include a method of using a conductive substrate as an anode or a cathode and a stainless plate or a stainless rod as a counter electrode, or a method of using a conductive container containing an electrodeposition solution as a counter electrode.

The conditions for the electrodeposition coating are appropriately selected depending on the kind of the colored coating material used and the intended thickness of the colored layer, but the voltage is usually 5 to 500 V, preferably 10 to 30 V.
It is preferably 0 V DC, and the electrodeposition time is usually 5 to 3
00 seconds, preferably 10 to 200 seconds, the liquid temperature is usually 10
It is desirable that the temperature is 35 ° C, preferably 15 to 30 ° C.
At this time, when the electrodeposition time for obtaining the desired film thickness has elapsed, the energization is stopped, the substrate is taken out of the bath, and the excess bath solution is thoroughly washed with water or ion-exchanged water, etc. and dried to form the colored layer. Can be formed.

The drying conditions can be appropriately selected depending on the conditions of the post-process and the like, but it is important that the drying impart resistance to the electrodeposited colored layer at least to the extent that it is not damaged in the post-process, and It is important to carry out under conditions that do not impair the characteristics of the undeveloped positive photosensitive coating. For example, 15
0 ° C or lower, preferably 60 ° C to 130 ° C, usually 0.0
It is desirable to dry for 1 to 1 hour, preferably 1 to 30 minutes.

In the present invention, it is also preferable to irradiate the object to be coated with ultrasonic waves before performing the electrodeposition coating treatment. For example, the object to be coated immersed in the electrodeposition liquid is irradiated with ultrasonic waves, and then the electrodeposition coating is performed. By such ultrasonic treatment, generation of pinholes, white spots, and the like can be prevented, and a color filter of good quality without uneven coloring can be obtained. At this time, the ultrasonic wave only needs to have a frequency exceeding the audible frequency range, and is usually 16 kHz to 5 GH.
It is about z, preferably 20 kHz to 1 GHz, and more preferably about 25 kHz to 100 MHz. If the frequency range is outside this range, the desired effect cannot be obtained, or a large-scale device is required, which is not preferable. The conditions for irradiating ultrasonic waves include the frequency and output of ultrasonic waves, the size of the object to be coated, the arrangement and size of pixels, the shape and size of the tank in which the object is immersed, the amount of liquid, the temperature and the time. The temperature of the liquid during irradiation is preferably the same as the temperature at which electrodeposition is performed in view of process control, but is preferably 10 ° C or higher.
The temperature is about 40 ° C, preferably about 15 ° C to 35 ° C. If the temperature of the liquid rises significantly, appropriate cooling means may be provided so that the temperature falls within this range. The irradiation time is usually 1 second to 300 seconds, preferably 5 seconds to 200 seconds,
More preferably, it is 10 seconds to 90 seconds. Irradiation time 1
If it is less than 2 seconds, the desired effect cannot be obtained, and if it exceeds 300 seconds, the positive photosensitive coating, the light-shielding layer or the coloring layer formed in the previous step may be damaged, which is not preferable.

The ultrasonic wave is generated by a commonly used piezoelectric vibrator, electrostrictive vibrator, magnetostrictive vibrator, or the like,
As the configuration of the vibrator, throw-in type, push-in type,
Examples include adhesive type and horn type. Further, the ultrasonic irradiation method is also a direct method, that is, a method of directly immersing the vibrator in a liquid to generate ultrasonic waves, or an indirect method, that is, a tank for immersing an object to be coated is placed in another tank and placed outside. There is a method of applying ultrasonic waves to the tank.

The output for the generation of ultrasonic waves is appropriately selected depending on the size of the article to be coated, the shape and size of the dipping tank, the direct method or the indirect method, etc. It is 1W to 2kW, preferably 5W to 1kW, and more preferably 10W to 500W. If the output range is outside this range, the desired effect cannot be obtained, and the ultrasonic wave may cause a marked increase in the liquid temperature, which is not preferable. Further, by irradiating ultrasonic waves, there is also a secondary effect that hydrogen and oxygen generated by electrodeposition dissolved in the electrodeposition liquid are easily removed.

(A) to (g) in the above first manufacturing method
1) Steps (a) to (g2) in the second manufacturing method
Although the desired color filter can be produced by the process, it is also possible to further improve the weather resistance, the chemical resistance and the like by further performing heating / curing or photocuring as necessary. When the heating / curing is performed, for example, the temperature is usually 100 to 270 ° C, preferably 120 to 250 ° C.
The time may be 5 minutes to 1 hour, preferably 15 to 40 minutes. In the present invention, not only the colored layer and the light-shielding layer, but also the outer frame portion of the color filter, which is transparent and has conductivity on the surface, can be manufactured without performing a special process.

[0058]

EFFECTS OF THE INVENTION The method for producing a color filter of the present invention does not require a high level of fine processing technology, has a high degree of freedom in the pattern shape of the colored layer, is easy to deal with a large size, and is inexpensive and large in volume. Since the method is easy to produce, it is industrially very useful. Further, in the present invention, a light-shielding layer, a coloring layer and, if necessary, a transparent outer frame portion can be formed on the color filter by a simple method.

[0059]

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

[0060]

[Synthesis Example 1] Synthetic colored resin ( R-1) (G-1) (B-1) of black paint (BK-1) synthetic acrylic resin (manufactured by Toa Gosei Kagaku Co., Ltd., trade name "Aron S-" 4030 ") was neutralized with triethylamine until the pH became about 8, and deionized water was added to this to prepare an aqueous resin solution (S). Next, carbon black, azo metal salt red pigment, phthalocyanine green, and phthalocyanine blue were added to the resin aqueous solution (S) under stirring to prepare black, red, green, and blue pigment dispersions, respectively. Separately from this, a mixture of the acrylic resin and a melamine resin (Sumitomo Chemical Co., Ltd., trade name “M-66B”) was neutralized with triethylamine until the pH reached 8, and then deionized water was added. An aqueous resin solution (T) was prepared by adding.

By adding a resin aqueous solution (T) to the pigment dispersion of each color, a black paint (BK-1) and a colored paint (R-1, G-1,
B-1) was obtained. The obtained black paint (BK-1)
The colored paints (R-1, G-1, B-1) are thermosetting and have anionic electrodeposition.

[0062]

[Table 1]

[0063]

Example 1 A positive type photoresist (manufactured by Tokyo Ohka Co., Ltd., trade name “OFPR-”) was formed on a 0.7 mm thick Pyrex glass substrate having an ITO film of 100 nm thickness on the surface.
800 ") was applied by a spin coater and dried at 80 ° C for 10 minutes to form a positive photosensitive coating film having a film thickness of 2.5 µm (hereinafter referred to as" original plate 1 "). Next, through a mask (mask having a pattern corresponding to the portion 1 corresponding to the light shielding layer) shown in FIG. 1, a UV exposure apparatus having a high pressure mercury lamp (manufactured by Oak Manufacturing Co., Ltd., trade name "JL-3300")
Was irradiated with ultraviolet rays of 100 mJ / cm ² and then developed with an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.4% by weight. The exposed area, that is, the mask had a light transmittance of 100%. The positive photosensitive coating film in the portion corresponding to the portion 1 was selectively removed, and the transparent conductive film (ITO film) was exposed. After washing and drying, original plate 1
Is used as an anode, and a stainless steel beaker containing black paint (BK-1) is used as a cathode.
It was electrodeposited for 20 seconds under the condition of 5 ° C. The original plate 1 was washed with ion-exchanged water and then dried at 120 ° C. for 10 minutes to form a black light-shielding layer.

Then, a UV exposure apparatus (manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp is inserted through a mask (mask having a pattern corresponding to the portion 3 corresponding to the colored layer of the first color) shown in FIG. "JL-3300")
Was irradiated with ultraviolet rays of 100 mJ / cm ² and then developed with an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.4% by weight. The exposed area, that is, the mask had a light transmittance of 100%. The positive photosensitive coating film in the portion corresponding to the portion 3 was selectively removed, and the transparent conductive layer (ITO film) was exposed. At this time, no change was observed in the black light shielding layer. Next, after washing with water and drying, the first coating was carried out in the same manner as the electrodeposition of the black paint (BK-1).
The colored (red) colored paint (R-1) was electrodeposited, washed with ion-exchanged water, and dried at 120 ° C. for 10 minutes. No change was observed in the black light shielding layer formed earlier, and the first colored layer was formed.

Then, a UV exposure apparatus (manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp is put through the mask shown in FIG.
100 mJ / using the product name "JL-3300")
After irradiating with cm ² of ultraviolet rays and developing with a tetramethylammonium hydroxide aqueous solution having a concentration of 2.4% by weight, a region having the largest exposure amount, that is, a portion corresponding to the portion 5 having the highest light transmittance of the mask, The positive type photosensitive coating film was selectively removed, and the transparent conductive layer (ITO film) was exposed. After washing with water and drying, the original plate 1 was used as an anode, and a stainless steel beaker containing the second color (green) colored paint (G-1) was used as a cathode, and electrodeposition was performed for 20 seconds under conditions of a DC voltage of 28 V and 25 ° C. . The original plate 1 was washed with ion-exchanged water and then dried at 120 ° C. for 10 minutes to form a second color (green) colored layer.

Next, when developed with a 3.5% by weight aqueous solution of tetramethylammonium hydroxide, the region having the second largest amount of exposure, that is, the light transmittance of the mask is 2
The positive type photosensitive coating film in the portion corresponding to the next highest portion 6 was selectively removed, and the transparent conductive layer (ITO film) was exposed. Next, after washing with water and drying, the third color (blue) colored paint (B-1) is electrodeposited in the same manner as the electrodeposition of the colored paint (G-1) and washed with ion-exchanged water, It was dried at 120 ° C. for 10 minutes. No change was observed in the black light shielding layer and the colored layers of the first color and the second color, which were previously formed, and the colored layer of the third color was formed. Next, 200 mJ on the entire surface of original plate 1.
/ Cm ² of ultraviolet rays were irradiated, the residual positive photosensitive coating film was removed with a 3.5% by weight aqueous solution of tetramethylammonium hydroxide, washed with water and dried. At this time, the transparent conductive layer in the outer frame portion of the color filter was exposed. Then, it was heated at 180 ° C. for 30 minutes to cure the light-shielding layer and the coloring layer, and the film thickness was 2 μm ±
A uniform and highly transparent color filter having a black light shielding layer of 0.1 μm, a colored layer and a transparent outer frame was obtained.

[0067]

[Example 2] In Example 1, after exposing the transparent conductive layer in the outer frame portion of the color filter, a transparent coating material (resin aqueous solution T) was electrodeposited in the same manner as the colored coating material, and ion-exchanged water was used. It was washed and dried at 120 ° C. for 10 minutes. No change was observed in the black light-shielding layer and the colored layers of the first color, the second color and the third color, which were previously formed, and a transparent outer frame was formed. After that, it was heated at 180 ° C. for 30 minutes to cure the light-shielding layer and the coloring layer. As a result, it had a black light-shielding layer, a coloring layer and a transparent outer frame having a film thickness of 2 μm ± 0.1 μm which did not show tackiness at room temperature. A uniform and excellent color filter was obtained.

[0068]

Example 3 A positive type photoresist (manufactured by Tokyo Ohka Co., Ltd., trade name “OFPR-”) was formed on a 0.7 mm thick Pyrex glass substrate having an ITO film of 100 nm thickness on the surface.
800 ") was applied by a spin coater and dried at 80 ° C for 10 minutes to form a positive photosensitive coating film having a film thickness of 2.5 µm (hereinafter referred to as" original plate 2 ").

Next, through a mask (mask having a pattern corresponding to the portion 1 corresponding to the light shielding layer) shown in FIG. 1, a UV exposure apparatus having a high pressure mercury lamp (manufactured by Oak Manufacturing Co., Ltd., trade name "JL-") is used. 3300 ") and use 100
After irradiation with ultraviolet rays of mJ / cm ² , the concentration is 2.4% by weight.
When developed with an aqueous solution of tetramethylammonium hydroxide, the positive type photosensitive coating film in the exposed region, that is, the portion corresponding to the portion 1 where the light transmittance of the mask is 100% is selectively removed, and the transparent conductive film is formed. The layer (ITO film) was exposed. Subsequently, after washing with water and drying, the original plate 2 was used as an anode, and a stainless steel beaker containing a black paint (BK-1) was used as a cathode, under conditions of a DC voltage of 28 V and 25 ° C.
It was electrodeposited for 0 seconds. After washing the original plate 2 with ion-exchanged water,
It was dried at 120 ° C. for 10 minutes to form a black light shielding layer.

Then, a UV exposure device (manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp is provided through a mask shown in FIG. 2 (a mask having a pattern corresponding to the portion 3 corresponding to the colored layer of the first color). "JL-3300")
Was irradiated with ultraviolet rays of 100 mJ / cm ² and then developed with an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.4% by weight. The exposed area, that is, the mask had a light transmittance of 100%. The positive photosensitive coating film in the portion corresponding to the portion 3 was selectively removed, and the transparent conductive layer (ITO film) was exposed. At this time, no change was observed in the black light shielding layer. Next, after washing with water and drying, the first coating was carried out in the same manner as the electrodeposition of the black paint (BK-1).
The colored (red) colored paint (R-1) was electrodeposited, washed with ion-exchanged water, and dried at 120 ° C. for 10 minutes. No change was observed in the black light shielding layer formed earlier, and the first colored layer was formed.

Then, through a mask (having a sufficient length in the moving direction) shown in FIG. 4, UV having a high pressure mercury lamp is used.
Exposure equipment (manufactured by Oak Manufacturing Co., Ltd., trade name "JL-33"
00 ”) was used to irradiate ultraviolet rays of 100 mJ / cm ² (hereinafter referred to as“ first exposure ”). Next, by moving the mask by the direction and distance shown in FIG. 4, 75 mJ / cm ²
Of ultraviolet rays (hereinafter referred to as "second exposure"). Subsequently, when developed with a tetramethylammonium hydroxide aqueous solution having a concentration of 2.4% by weight, the positive type photosensitive coating film in the region having the largest exposure amount, that is, the part exposed by the first exposure is selectively removed, The transparent conductive layer (ITO film) was exposed. After washing with water and drying, the original plate 2 was used as an anode, a stainless steel beaker containing the second color (green) colored paint (G-1) was used as a cathode, and a DC voltage of 28 V and 25 ° C.
Electrodeposition was carried out for 20 seconds under the above conditions. The original plate 2 was washed with ion-exchanged water and then dried at 120 ° C. for 10 minutes to form a second color (green) colored layer. Subsequently, it was developed with a 3.5% by weight aqueous solution of tetramethylammonium hydroxide, and the positive type photosensitive coating film in the region having the second largest exposure amount, that is, the part exposed by the second exposure was selectively removed. The transparent conductive layer (ITO film) was exposed. Next, wash with water,
After drying, the third step is carried out in the same manner as the electrodeposition of the colored paint (G-1).
The colored paint (B-1) of the color (for example, blue) was electrodeposited, washed with ion-exchanged water, and dried at 120 ° C. for 10 minutes. No change was observed in the black light shielding layer and the colored layers of the first color and the second color, which were previously formed, and the colored layer of the third color was formed.

Next, the remaining positive type photosensitive coating film was removed with a 2% by weight aqueous sodium hydroxide solution, washed with water and dried.
At this time, the transparent conductive layer in the outer frame portion of the color filter was exposed. Then, when the light-shielding layer and the coloring layer were cured by heating at 180 ° C. for 30 minutes, the black light-shielding layer having a film thickness of 2 μm ± 0.1 μm, the coloring layer, and the transparent outer frame, which are not tacky at room temperature, are provided. A uniform and excellent color filter was obtained.

[0073]

Example 4 A positive photoresist (manufactured by Tokyo Ohka Co., Ltd., trade name “OFPR-”) was formed on a 0.7 mm thick Pyrex glass substrate having an ITO film of 100 nm thickness on the surface.
800 ") was applied by a spin coater and dried at 80 ° C for 10 minutes to form a positive photosensitive coating film having a film thickness of 2.5 µm (hereinafter referred to as" original plate 3 "). Then, through a mask (mask having a pattern corresponding to the portion 1 corresponding to the light-shielding layer) shown in FIG. 1, a UV exposure device having a high-pressure mercury lamp (manufactured by Oak Manufacturing Co., Ltd., trade name “JL-330”).
0 ") was irradiated with ultraviolet rays of 100 mJ / cm ² and then developed with an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.4% by weight. As a result, the light transmittance of the exposed area, that is, the mask was 100%. % That is part 1
The positive type photosensitive coating film in the portion corresponding to was selectively removed, and the transparent conductive layer (ITO film) was exposed. Then wash with water,
After drying, the original plate 3 was used as an anode, and a stainless steel beaker containing a black paint (BK-1) was used as a cathode. Master 3
Was washed with ion-exchanged water and then dried at 120 ° C. for 10 minutes to form a black light-shielding layer.

Then, a UV exposure apparatus (manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp is put through the mask shown in FIG.
100 mJ / using the product name "JL-3300")
After irradiation with ultraviolet rays of cm ² and development with a tetramethylammonium hydroxide aqueous solution having a concentration of 2.4% by weight, the exposed area, that is, the light transmittance of the mask was 1
The positive type photosensitive coating film in the portion corresponding to the portion 3 which is 00% was selectively removed, and the transparent conductive layer (ITO film) was exposed. Then, after washing with water and drying, the original plate 3 is used as an anode, a stainless steel beaker containing a transparent coating material (resin aqueous solution T) is used as a cathode, and a DC voltage of 28 V and a temperature of 25 ° C.
It was electrodeposited for 0 seconds. After washing the original plate 3 with ion-exchanged water,
It dried at 120 degreeC for 10 minute (s), and formed the transparent outer frame.

Next, a UV exposure apparatus (manufactured by Oak Manufacturing Co., Ltd.) having a high pressure mercury lamp is put through the mask shown in FIG.
100 mJ / using the product name "JL-3300")
After irradiation with ultraviolet rays of cm ² and development with a tetramethylammonium hydroxide aqueous solution having a concentration of 2.4% by weight, a region having the largest exposure amount, that is, a portion corresponding to the portion 14 having the highest light transmittance of the mask, The positive type photosensitive coating film was selectively removed, and the transparent conductive layer (ITO film) was exposed. After washing with water and drying, the first color (red) colored paint (R-1) was electrodeposited in the same manner as the electrodeposition of the black paint (BK-1), washed with ion-exchanged water, and at 10 ° C at 10 ° C. Dry for minutes. No change was observed in the black light shielding layer and the outer frame formed earlier, and the colored layer of the first color was formed. Subsequently, it was developed with a 3.5% by weight aqueous solution of tetramethylammonium hydroxide. As a result, a region having the second largest exposure amount, that is, a portion 15 having the second highest light transmittance of the mask
The positive type photosensitive coating film in the portion corresponding to was selectively removed, and the transparent conductive layer (ITO film) was exposed. After washing with water and drying, a DC voltage of 2 was applied using a stainless steel beaker containing the second color (green) colored paint (G-1) as a cathode.
Electrodeposition was carried out for 20 seconds under the conditions of 8V and 25 ° C. The original plate 3 was washed with ion-exchanged water and then dried at 120 ° C. for 10 minutes to form a second color (green) colored layer.

Next, the entire surface of the original plate 3 was irradiated with ultraviolet rays of 200 mJ / cm ² , the residual positive photosensitive coating film was removed with a 3.5% by weight aqueous solution of tetramethylammonium hydroxide, washed with water and dried. . At this time, the black light shielding layer, the outer frame,
The portion of the transparent conductive layer other than the colored layers of the first color and the second color, that is, the portion corresponding to the third colored layer was exposed.
After washing with water and drying, the third color (blue) colored paint (B-1) is electrodeposited in the same manner as the electrodeposition of the colored paint (R-1).
It was washed with ion-exchanged water and dried at 120 ° C. for 10 minutes.
No change was observed in the black light-shielding layer, the outer frame, and the colored layers of the first color and the second color, which were previously formed, and the colored layer of the third color was formed. Then, it was heated at 180 ° C. for 30 minutes to cure the light-shielding layer, the outer frame, and the coloring layer. As a result, a black light-shielding layer, a coloring layer, and a transparent layer having a film thickness of 2 μm ± 0.1 μm that does not exhibit adhesiveness at room temperature were formed. A uniform and highly transparent color filter having an outer frame was obtained.

[0077]

Comparative Example 1 In the same manner as in Example 1, a positive photoresist was applied to a Pyrex glass substrate and dried to form a positive photosensitive coating film having a thickness of 2.5 μm (master plate 1).
Next, through the mask shown in FIG. 2 (mask having a pattern corresponding to the portion 3 corresponding to the colored layer of the first color), using the same UV exposure apparatus as in Example 1, 100 mJ / c
After irradiation with m ² of ultraviolet rays, development was performed with a tetramethylammonium hydroxide aqueous solution having a concentration of 2.4% by weight.
The positive type photosensitive coating film in the portion corresponding to 0% portion 3 was selectively removed, and the transparent conductive film (ITO film) was exposed. After washing with water and drying, the original plate 1 is used as an anode and the red paint (R-
Using a stainless steel beaker containing 1) as a cathode, electrodeposition was performed for 20 seconds under conditions of a DC voltage of 28 V and 25 ° C. After washing master plate 1 with ion-exchanged water,
After drying for 0 minutes, a red colored layer was formed.

Then, through the mask shown in FIG. 3, 100
After irradiation with ultraviolet rays of mJ / cm ² , the concentration is 2.4% by weight.
When developed with an aqueous solution of tetramethylammonium hydroxide, the positive type photosensitive coating film in the region having the largest exposure amount, that is, the portion corresponding to the portion 5 having the highest light transmittance of the mask is selectively removed, and the transparent conductive film is formed. Layer (ITO film)
Was exposed. After washing with water and drying, the original plate 1 was used as an anode, and a stainless steel beaker containing the second color (green) colored paint (G-1) was used as a cathode, and a DC voltage of 28 V, 25
It was electrodeposited for 20 seconds under the condition of ° C. The original plate 1 was washed with ion-exchanged water and then dried at 120 ° C. for 10 minutes to form a second color (green) colored layer.

Then, the film was developed with a 3.5% by weight aqueous solution of tetramethylammonium hydroxide. As a result, the area of the second largest exposure amount, that is, the area corresponding to the area 6 having the second highest light transmittance of the mask, was positive type. The photosensitive coating film was selectively removed, and the transparent conductive layer (ITO film) was exposed.
Next, after washing with water and drying, the third color (blue) colored paint (B-1) is electrodeposited in the same manner as the electrodeposition of the colored paint (G-1) and washed with ion-exchanged water, It was dried at 120 ° C. for 10 minutes. No change was observed in the colored layers of the first color and the second color formed earlier, and the colored layer of the third color was formed.

Next, through the mask (mask having a pattern corresponding to the portion 1 corresponding to the light shielding layer) shown in FIG. 1, 1
After irradiating with ultraviolet light of 00 mJ / cm ² , it is developed with an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.4% by weight, and the positive photosensitive coating of the portion corresponding to the portion 1 in which the light transmittance of the mask is 100%. The film was removed to expose the transparent conductive film (ITO film). After washing with water and drying, the original plate 1 was used as an anode, and a stainless steel beaker containing a black paint (BK-1) was used as a cathode, and a DC voltage of 28 V and 25 ° C.
Electrodeposition was carried out for 20 seconds under the above conditions. The original plate 1 was washed with ion-exchanged water and then dried at 120 ° C. for 10 minutes to form a black light-shielding layer. Subsequently, the entire surface of the original plate 1 is irradiated with ultraviolet rays of 200 mJ / cm ² , the remaining positive photosensitive film is removed with a 3.5% by weight aqueous solution of tetramethylammonium hydroxide, washed with water, and dried to remove the color filter. The transparent conductive layer on the outer frame portion was exposed. Then, the light-shielding layer and the coloring layer were cured by heating at 180 ° C. for 30 minutes. The obtained color filter had a poor sharpness of the light-shielding layer in contact with the coloring layer, and a part of the outer frame portion which should be transparent was used. There were defects such as remaining photoresist and coloring of the paint, and the fineness was remarkably lacking. As a result, it is understood that when the light-shielding layer in the step (c) of the present invention is formed after the formation of the colored layer, defects are generated in the obtained color filter.

[0081]

Comparative Example 2 In the same manner as in Example 1, a positive photoresist was applied to a Pyrex glass substrate and dried to form a positive photosensitive coating film having a thickness of 2.5 μm (master plate 1).
Next, through a mask (mask having a pattern corresponding to the portion 1 corresponding to the light shielding layer) shown in FIG. 1, 100 mJ / c
After irradiation with m ² of ultraviolet rays, development was performed with a tetramethylammonium hydroxide aqueous solution having a concentration of 2.4% by weight.
The positive photosensitive coating film in the portion corresponding to 0% portion 1 was selectively removed, and the transparent conductive film (ITO film) was exposed. After washing with water and drying, the original plate 1 is used as an anode and a black paint (BK
Using a stainless steel beaker containing -1) as a cathode, electrodeposition was performed for 20 seconds under conditions of a DC voltage of 28 V and 25 ° C. After washing master plate 1 with ion-exchanged water,
It was dried for 0 minutes to form a black light shielding layer.

Then, 100 through the mask shown in FIG.
After irradiation with ultraviolet rays of mJ / cm ² , the concentration is 2.4% by weight.
When developed with an aqueous solution of tetramethylammonium hydroxide, the positive type photosensitive coating film in the region having the largest exposure amount, that is, the portion corresponding to the portion 5 having the highest light transmittance of the mask is selectively removed, and the transparent conductive film is formed. Layer (ITO film)
Was exposed. After washing with water and drying, the original plate 1 was used as an anode, and a stainless steel beaker containing the first color (red) colored paint (R-1) was used as a cathode, and a DC voltage of 28 V, 25
It was electrodeposited for 20 seconds under the condition of ° C. The original plate 1 was washed with ion-exchanged water and then dried at 120 ° C. for 10 minutes to form a first-color (red) colored layer.

Then, the film was developed with a 3.5% by weight aqueous solution of tetramethylammonium hydroxide. As a result, the area of the second largest exposure amount, that is, the area corresponding to the area 6 having the second highest light transmittance of the mask, was positive type. The photosensitive coating film was selectively removed, and the transparent conductive layer (ITO film) was exposed.
Next, after washing with water and drying, the second color (green) colored paint (G
-1) is electrodeposited, washed with ion-exchanged water, and 1 at 120 ° C.
Dry for 0 minutes.

Next, the mask shown in FIG. 2 (mask having a pattern corresponding to the portion 3 corresponding to the third color layer)
The via was irradiated with ultraviolet rays at 100 mJ / cm ^2, the concentration 2.4 was developed in weight% aqueous solution of tetramethyl ammonium hydroxide, the exposed areas, i.e. part 3 the light transmittance of the mask is 100% The positive type photosensitive coating film in the portion corresponding to is removed and the transparent conductive film (ITO
The membrane) was exposed. After washing with water and drying, the original plate 1 was used as an anode, and a stainless steel beaker containing the blue paint (B-1) was used as a cathode, and a DC voltage of 28 V and a temperature of 25 ° C. were applied for 20 times.
It was electrodeposited for a second. After washing the original plate 1 with ion-exchanged water, 1
It was dried at 20 ° C. for 10 minutes to form a blue colored layer. Subsequently, the entire surface of the original plate 1 is irradiated with ultraviolet rays of 200 mJ / cm ² , the remaining positive photosensitive coating film is removed with a 3.5% by weight aqueous solution of tetramethylammonium hydroxide, and washed with water.
It was dried to expose the transparent conductive layer in the outer frame portion of the color filter. Then, the light-shielding layer and the colored layer were cured by heating at 180 ° C. for 30 minutes, but the obtained color filter could not be used for a liquid crystal display because there were some pinholes in the blue pixel. . As a result,
It has been found that when the steps (d) and (e) of the present invention are performed after the steps (f) and (g), defects are generated in the obtained color filter.

[0085]

Fifth Embodiment A positive photoresist (trade name “OFPR-8” manufactured by Tokyo Ohka Co., Ltd.) is formed on a 0.7 mm thick Pyrex glass substrate having an ITO film of 100 nm thickness on the surface.
00 ") was applied by a spin coater and dried at 80 ° C for 10 minutes to form a positive photosensitive coating film having a film thickness of 2.5 µm (hereinafter referred to as" original plate 4 "). Next, through the mask (mask having a pattern corresponding to the portion 1 corresponding to the light-shielding layer) shown in FIG. 1, a UV exposure apparatus having a high-pressure mercury lamp, manufactured by Oak Manufacturing Co., Ltd., trade name “JL-3300”) After using, after irradiating with 100 mJ / cm ² of ultraviolet rays,
When developed with an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.4% by weight, the positive type photosensitive coating film in the exposed region, that is, the portion corresponding to the portion 1 where the light transmittance of the mask is 100% is selectively formed. Then, the transparent conductive film (ITO film) was exposed. After washing with water and drying, the stainless steel beaker in which the original plate 4 was immersed in the black paint (BK-1) kept at 25 ° C. was placed in an ultrasonic cleaner (Honda Electronics Co., Ltd.) to obtain the black paint (BK-1). ) After irradiating an ultrasonic wave of 100 kHz per liter with an output of 100 W for 30 seconds, the original plate 4 is used as an anode, a stainless steel beaker containing black paint (BK-1) is used as a cathode, and a DC voltage of 28 V and 25 ° C. is used. It was electrodeposited for 20 seconds. The original plate 4 was washed with ion-exchanged water and then dried at 120 ° C. for 10 minutes to form a black light-shielding layer.

Then, after irradiating with ultraviolet rays of 100 mJ / cm ² through the mask shown in FIG. 2 (mask having a pattern corresponding to the portion 3 corresponding to the colored layer of the first color), the concentration is 2.4% by weight. When developed with an aqueous solution of tetramethylammonium hydroxide, the positive photosensitive coating film on the exposed region, that is, the portion corresponding to the portion 3 where the light transmittance of the mask is 100% is selectively removed, and the transparent conductive film is formed. The layer (ITO film) was exposed. At this time, no change was observed in the black light shielding layer. Next, after washing with water and drying, a stainless steel beaker in which the original plate 4 was immersed in a colored paint (R-1) kept at 25 ° C. was placed in an ultrasonic cleaner (Honda Electronics Co., Ltd.) to obtain a black paint (BK After the ultrasonic irradiation in the same manner as in -1), a black paint (BK-1)
Similar to the electrodeposition of No. 1, the first color (red) colored paint (R
-1) is electrodeposited, washed with ion-exchanged water, and 1 at 120 ° C.
Dry for 0 minutes. No change was observed in the black light shielding layer formed earlier, and the first colored layer was formed.

Next, 100 m through the mask shown in FIG.
After irradiation with ultraviolet rays of J / cm ² , the film was developed with an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.4% by weight. As a result, the region having the highest exposure amount, that is, the portion 5 having the highest light transmittance of the mask was obtained. The positive photosensitive coating film on the part was selectively removed, and the transparent conductive film (ITO film) was exposed. Colored paint (G
The stainless steel beaker in which the original plate 4 was immersed in -1) was placed in an ultrasonic cleaner (manufactured by Honda Electronics Co., Ltd.), and the original plate 4 was irradiated with ultrasonic waves in the same manner as in the case of the black paint (BK-1). As the anode, the second color (green) colored paint (G-1)
With a stainless steel beaker containing as a cathode,
Electrodeposition was performed for 20 seconds under conditions of a DC voltage of 28 V and 25 ° C. The original plate 4 was washed with ion-exchanged water and then dried at 120 ° C. for 10 minutes to form a second color (green) colored layer.

Next, when developed with a 3.5% by weight aqueous solution of tetramethylammonium hydroxide, a positive type of a region corresponding to the region 6 having the second largest exposure amount, that is, the region 6 having the second highest light transmittance of the mask The photosensitive coating film was selectively removed, and the transparent conductive layer (ITO film) was exposed.
Next, after being washed with water and dried, the colored paint (B-
The stainless steel beaker in which the original plate 4 was immersed in 1) was placed in an ultrasonic cleaner (manufactured by Honda Electronics Co., Ltd.), and the colored paint (G Similarly to the electrodeposition of -1), the third color (blue) colored paint (B-1) is electrodeposited and washed with ion-exchanged water,
It was dried at 120 ° C. for 10 minutes. No change was observed in the black light shielding layer and the colored layers of the first color and the second color, which were previously formed, and the colored layer of the third color was formed. Then, the entire surface of the original plate 4 is irradiated with ultraviolet rays of 200 mJ / cm ² , and 3.
The remaining positive photosensitive coating film was removed with a 5% by weight aqueous solution of tetramethylammonium hydroxide, washed with water and dried. At this time, the transparent conductive layer in the outer frame portion of the color filter was exposed. As a result of microscopic observation, no defects such as pinholes were found in the colored layer. Then 30 at 180 ℃
When the light shielding layer and the coloring layer are cured by heating for a minute,
A uniform and highly transparent color filter having a black light-shielding layer, a coloring layer, and a transparent outer frame with a film thickness of 2 μm ± 0.1 μm that does not exhibit tackiness at room temperature and has no defects such as pinholes. Was obtained.

[Brief description of drawings]

FIG. 1 is a schematic view showing masks having different light transmittances in two stages used in Examples.

FIG. 2 is a schematic view showing another mask used in the examples and having two different light transmittances.

FIG. 3 is a schematic view showing masks having different light transmittances in three stages used in Examples.

FIG. 4 is a schematic view showing a moving mask having two different light transmittances used in Examples.

FIG. 5 is a schematic view showing another mask used in the examples and having three different light transmittances.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Otsuki 332-4 Nobamachi, Konan-ku, Yokohama-shi, Kanagawa No. 403, Kaminagaya Flower Mansion No.403 (72) Inhito Hitoshi 2060-21 Kamigocho, Sakae-ku, Yokohama-shi, Kanagawa

Claims (2)

[Claims] 1. A step of: (a) forming a positive photosensitive coating on a transparent conductive layer of a transparent substrate having a transparent conductive layer; and (b) exposing the positive photosensitive coating in two steps. And (c) developing a photosensitive coating film having a large exposure amount in the exposed area to expose the transparent conductive layer, and then forming a light-shielding layer by electrodeposition coating. d) a step of forming an exposure area having two different exposure amounts on the undeveloped photosensitive coating film in the step (c); Of the conductive coating film to expose the transparent conductive layer and then electrodeposition coating of a colored paint to form a colored layer, and (f1) the undeveloped photosensitive coating film in step (e) above is exposed to light. A step of forming different exposed areas in at least three steps, and (g1) developing the photosensitive coating film in the exposed areas to form a transparent conductive layer. At least 2 was issued, then the colored coating electrodeposition coating to an operation of forming a colored layer, in order exposure amount is large in the exposure region
And a step of forming a colored layer by repeating the process repeatedly. 2. A step of: (a) forming a positive photosensitive coating on the transparent conductive layer of a transparent substrate having a transparent conductive layer; and (b) exposing the positive photosensitive coating in two steps. And (c) developing a photosensitive coating film having a large exposure amount in the exposed area to expose the transparent conductive layer, and then forming a light-shielding layer by electrodeposition coating. d) a step of forming an exposure area having two different exposure amounts on the undeveloped photosensitive coating film in the step (c); Of the conductive coating film to expose the transparent conductive layer and then electrodeposition coating of a colored paint to form a colored layer, and (f2) the undeveloped photosensitive coating film in step (e) above is exposed to light. Step of forming a plurality of different exposure areas in three steps, and (g2) developing the photosensitive coating film in the exposure areas to expose the transparent conductive layer. Then, the operation of forming a colored layer by electrocoating with a colored coating material is repeated twice in order of increasing exposure amount of the exposed area to form a colored layer, and then the remaining exposed area is developed to form a transparent conductive layer. And a step of exposing the color filter.