JPH04324802A - Manufacture of color filter - Google Patents

Abstract

PURPOSE:To facilitate the manufacture of color filters in a large quantity, without necessity of a highly delicate fabrication technique, with a increased degree of freedom of a coloring layer pattern shape, with possibility of entire patterning in one exposure and easy formation of an opaque film furthermore, easy copying with enlargement of a scale. CONSTITUTION:A part of a color filter corresponding to a coloring part is exposed in one time, through negative mask having a different transmission per kind of color, to carry out the entire patterning, the pattern parts corresponding to the order of light transmissions are developed and colored in order, furthermore, a metallic layer is formed selectively.

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 color filter, and more particularly to a method of manufacturing a color filter suitable for use in color liquid crystal display devices.

0002

BACKGROUND OF THE INVENTION Currently, commonly used methods for manufacturing color filters include a dyeing method in which a transparent substrate is colored with a binder containing a dye or pigment, a printing method, and a pigment dispersion method.

However, since the dyeing method is a method of selectively dyeing the resin thin film on the substrate with a dye, it is necessary to carry out resist dyeing and photolithography steps every time the color is changed, and the printing method requires resist dyeing and photolithography steps. Although this is not necessary, there is a problem in that there is a limit to the miniaturization of color patterns, and as the number of colors increases, the accuracy of printing position becomes worse. Further, although the pigment dispersion method allows fine patterns to be formed, it has the disadvantage that a highly accurate photolithography process must be performed each time a color is changed, making the process extremely complicated.

On the other hand, in order to eliminate these drawbacks, Japanese Patent Application Laid-Open No. 114572/1983 proposes a method for producing color filters by electrodeposition coating. In this method, first, a transparent conductive film formed on a substrate is patterned to form a transparent electrode, and a voltage is applied only to the portions of the patterned transparent electrode that are to be colored in the same color. A colored layer is formed by electrodeposition. Next, a voltage is applied only to the portions to be colored in a different color, and electrodeposition is performed to form another colored layer. However, this method requires that the transparent electrode be patterned first, which requires high precision.
Great care is required in handling in subsequent steps, and if even a part of the fine pattern is broken, the subsequent coloring step becomes difficult, which is not desirable in terms of manufacturing. Furthermore, all of the patterned transparent electrodes must be electrically continuous even in minute portions, which limits the degree of freedom in pattern shape.

Furthermore, in Japanese Patent Application Laid-Open No. 63-210901, a positive photosensitive resin composition is exposed through a mask having a pattern of only the areas to be colored in the same color.
A colored layer is formed by developing and electrodeposition, and then this exposure and
A method has been proposed in which the steps of development and electrodeposition are repeated a desired number of times, but this method uses a compound having an unstable quinonediazide group and is therefore inferior in stability. Furthermore, when the quinonediazide compound is exposed to an alkaline aqueous solution for development,
The quinonediazide compound in the unexposed area also reacts with the alkaline aqueous solution, resulting in a significant change in photosensitivity, making subsequent exposure and development difficult.

On the other hand, due to the demand for higher performance of devices having color filters, it is desired to improve contrast and prevent deterioration of color purity, and as a solution to this, generally, a non-transparent material is provided between each pixel of a color filter. Methods of forming films are known. The method for forming the non-light-transmitting film includes, for example, forming pixels while aligning on a substrate on which a non-light-transmitting film pattern is formed in advance, or forming pixels on a substrate on which a pixel pattern is formed in advance. However, a method is used in which a non-transparent film pattern is formed.

However, in all of these methods, it is necessary to perform an alignment operation between the pixel pattern and the non-transparent film pattern. It is difficult to form a non-transparent film pattern. Furthermore, when these overlapping portions occur, a step is created on the color filter, making it difficult to manufacture a color filter with excellent flatness, which is structurally demanding.

[0008] In addition, all of the above-mentioned methods require high-precision processing technology for alignment, and are required to respond to the demand for larger workpiece sizes, that is, the demand for cost reductions due to larger screen dimensions and multi-sided mounting. is difficult.

[0009]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above-mentioned drawbacks, to eliminate the need for advanced microfabrication technology, to have a large degree of freedom in the pattern shape of the colored layer, and to provide a method that allows the color filter to have a uniform spacing between pixels. The purpose of the present invention is to provide a method for manufacturing a color filter that has no gaps, allows a non-light-transmitting metal film to be disposed, can easily handle upsizing, and is easy and simple to mass-produce.

0010

[Means for Solving the Problems] As a result of research into a manufacturing method for a color filter that has a large degree of freedom in the pattern shape of the colored layer and can handle upsizing, the present inventors identified a method for manufacturing a color filter as a negative photosensitive resin. It was discovered that a color filter with excellent performance can be obtained by a simple process of combining masks.

That is, according to the present invention, (A) a photosensitive coating film is formed on a transparent substrate having a transparent conductive layer on the surface, and is coated through a negative mask having a pattern with at least three levels of light transmittance. The process of exposing to light and (B) the operation of developing and removing the photosensitive coating film in the pattern area and electrodepositing a colored paint on the exposed conductive layer to form a colored layer are performed in descending order of the light transmittance of the negative mask. a step of forming a colored layer by sequentially repeating the pattern portions to be colored;
C) A step of selectively forming a metal layer on the conductive layer exposed by developing and removing the photosensitive coating film in at least one pattern portion and/or on the conductive layer in the portion where the colored layer is not formed. Provided is a method for producing a color filter, the method comprising:

The present invention will be explained in more detail below.

In the present invention, a photosensitive coating film is first formed on a transparent substrate having a transparent conductive layer on its surface, and exposed through a negative mask having a pattern with at least three different light transmittances (hereinafter referred to as (A)). ) process).

[0014] The transparent substrate having a transparent conductive layer on its surface used in the present invention is not particularly limited as long as it has a conductive layer on its surface and is in the form of a transparent plate, such as glass,
Examples include plastic plates and other plate-shaped substrates with transparent conductive layers formed on their surfaces. It is desirable that the surface of the substrate be smooth in view of the performance of the color filter, and if necessary, the surface may be polished before use.

[0015] Examples of the material for the conductive layer include materials containing tin oxide, indium oxide, antimony oxide, or the like. Further, the method for forming the 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 evaporation method. Alternatively, a commercially available transparent substrate having a transparent conductive layer may be used. In view of the performance of the color filter, it is desirable to use a substrate with as high transparency as possible.

The method for forming the photosensitive coating film on the transparent substrate is not particularly limited, but the photosensitive coating is usually coated by a known method such as electrodeposition, spraying, dip coating, roll coating, It can be formed by coating on a substrate using a screen printing method, a coating method using a spin coater, or the like.

[0017] As the photosensitive paint for forming the photosensitive coating film, a resin (hereinafter referred to as
Examples include paints in which a photopolymerization initiator (referred to as a photosensitive paint resin), a photopolymerization initiator, and, if necessary, a dye and/or pigment are dispersed or dissolved in an organic solvent, water, or the like.

The photosensitive coating resin preferably used in the present invention has a (meth)acryloyl group such as an acryloyl group or a methacryloyl group and/or a photosensitive group such as a cinnamoyl group at the molecular terminal and/or side chain. Generally, prepolymers or resins having a molecular weight of about 500 to 10,000 can be mentioned.

Examples of the prepolymer or resin include prepolymers such as epoxy (meth)acrylate, urethane (meth)acrylate, and polyester (meth)acrylate; , ammonium, sulfonium, etc., and the above-mentioned photosensitive group are introduced, and are cationic resins that can be solubilized and/or dispersed in water with acids or acidic substances such as formic acid, acetic acid, propionic acid, and lactic acid. resins; resins in which carboxyl groups, etc. and the above-mentioned photosensitive groups are introduced into acrylic resins, polyester resins, maleated oil resins, polybutadiene resins, epoxy resins, etc., and basic substances such as triethylamine, diethylamine, dimethylethanolamine, ammonia, etc. Examples include anionic resins such as resins that can be solubilized and/or dispersed in water, and in particular, prepolymers or resins that can be solubilized and/or dispersed in water from the viewpoint of process simplification and pollution prevention. It is preferable to use

Furthermore, low molecular weight (meth)acrylates may be added to the photosensitive coating resin in order to adjust the photosensitivity and viscosity of the coating film. Specifically, 2-hydroxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, tricyclodecane (meth)acrylate
Examples include acrylate, hexanediol di(meth)acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tris(acryloyloxyethyl)isocyanurate, etc., and these may be used as a mixture. The blending ratio of these (meth)acrylates is 0 to 50 parts by weight, preferably 0 to 30 parts by weight, based on 100 parts by weight of the photosensitive coating resin. If the blending ratio of (meth)acrylates exceeds 50 parts by weight, the coating film tends to become sticky, which is undesirable.

The photopolymerization initiator may be a known one, such as benzoin and its ethers, benzyl alkyl ketals, benzophenone derivatives, anthraquinone derivatives, and thioxanthone derivatives, and if necessary, a sensitizer may be added. good. The amount of the photopolymerization initiator added is preferably 0.1 to 30 parts by weight, particularly preferably 0.5 to 2 parts by weight, relative to 100 parts by weight of the photosensitive coating resin.
It is in the range of 0 parts by weight. The amount of photopolymerization initiator added is 0.1
If it is less than 30 parts by weight, the photocurability will be insufficient, and if it exceeds 30 parts by weight, curing will proceed too much and the strength of the coating will be insufficient, which is undesirable.

The organic solvent used for dispersing or dissolving each component of the photosensitive paint may be any solvent as long as it can dissolve the above-mentioned prepolymer or resin, and 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, triethylene glycol dimethyl ether, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone,
Isophorone, etc.; Ethers, such as dibutyl ether, dioxane, tetrahydrofuran, etc.; Alcohols,
For example, methoxybutanol, diacetone alcohol,
Butanol, isopropanol, etc.; hydrocarbons, such as toluene, xylene, hexane, etc.; esters, such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, 2-methoxypropyl acetate, etc. When used, It can be used alone or as a mixture.

In addition, these organic solvents are used to dissolve the cationic or anionic resin in water in order to facilitate solubilization and dispersion, to improve bath stability, to obtain a smooth coating film, etc. It can also be added at the time of oxidation or water dispersion.

[0024] Furthermore, various auxiliary agents such as a leveling agent, a viscosity modifier, and an antifoaming agent may be added to the photosensitive paint to improve the smoothness of the coating film.

[0025] The photosensitive paint is prepared by adding a photosensitive paint resin, a photopolymerization initiator, an organic solvent and/or water, and optionally a dye and/or pigment, an acidic substance or a basic substance, and a dye or pigment. Mix various auxiliaries such as dispersion aids, leveling agents that improve the smoothness of the coating film, viscosity modifiers, antifoaming agents, etc., and use commonly used dispersing machines such as sand mills, roll mills, and attritors. It can be obtained by using a method of sufficiently dispersing the compound. The thickness of the photosensitive coating film formed from the photosensitive paint thus obtained is not particularly limited, and can be selected appropriately depending on the performance required of the color filter, but it is usually 0.3 to 20μ when dry.
m, preferably about 1 to 15 μm. To adjust the film thickness, for example, when forming a photosensitive coating film by electrodeposition, it can be controlled by adjusting the electrodeposition conditions such as voltage, electrodeposition time, and liquid temperature, but usually the coloring described below can be controlled. It can be carried out under the same conditions as electrodeposition coating of paint.

In the present invention, the photosensitive coating film must be exposed to light through a negative mask having a pattern with at least three different light transmittances. Here, the light transmittance refers to the ratio of the intensity of the light beam used for exposure before and after passing through the negative mask. Further, the number of stages of different light transmittance of the pattern of the negative mask is at least 3.
There may be any number of stages, which can be determined depending on the number of types of colored paints used, and the difference in light transmittance between each stage can be appropriately selected depending on the exposure conditions and the development conditions described below. In general, it is preferable to increase the relative difference between the respective light transmittances because it is easier to adjust the exposure amount and exposure time, but even when the difference in light transmittance is small, increasing the exposure amount is preferable. Alternatively, the same objective can be achieved by increasing the exposure time. Therefore, although the relative difference in light transmittance is not particularly limited, it is usually preferable to have a significant difference of 5% or more.

[0027] The above-mentioned exposure can usually be carried out 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, etc. can be used as a light source, and if necessary, other radiation can be used. You may. Exposure conditions can be appropriately selected depending on the photosensitive paint, exposure device, negative mask, etc. used.

In step (A) of the present invention, exposure is performed through a negative mask having a pattern with at least three different levels of light transmittance, so that the pattern of the negative mask has different levels of light transmittance. The same number of
Different exposure conditions can be created.

[0029] In the manufacturing method of the present invention, following the step (A), the photosensitive coating film in the pattern portion is developed and removed, and a colored paint is electrodeposited on the exposed conductive layer to form a colored layer. , a colored layer is formed by sequentially repeating pattern portions corresponding to decreasing light transmittance of the negative mask (hereinafter referred to as step (B)). That is, said (B)
In the process, first, the photosensitive coating film of the portion of the negative mask corresponding to the pattern with the lowest light transmittance is selectively developed and removed, and colored paint is electrodeposited on the exposed conductive layer to form a colored layer. Next, the photosensitive coating film in the portion of the negative mask corresponding to the pattern with the next smallest light transmittance is selectively developed and removed.
A colored layer can be formed by sequentially repeating the steps of electrodepositing a colored paint on the exposed conductive layer to form a colored layer.

The conditions for selectively developing and removing the photosensitive coating film include the amount of exposure of the portion to be selectively removed, the solubility of the photosensitive coating used in the developer, the type and concentration of the developer,
Furthermore, the conditions may vary depending on the development temperature and development time, and conditions suitable for the resin etc. used for preparing the photosensitive paint may be appropriately selected. Specifically, for example, when a cationic resin is used as a component of a photosensitive paint, an aqueous solution in which an acidic substance is dissolved can be used as the developer. The acidic substances include formic acid, acetic acid, propionic acid,
Examples include organic acids such as lactic acid and inorganic acids such as hydrochloric acid and phosphoric acid. For example, when lactic acid is used in a developer, the lactic acid concentration is usually 0.01 to 50% by weight, preferably 0.01 to 50% by weight.
30% by weight, temperature is usually 10 to 70°C, preferably 20°C
~50° C., and the development time may be appropriately selected from the range of usually 5 to 600 seconds. Further, when an anionic resin is used as a component of the photosensitive paint, an aqueous solution in which a basic substance is dissolved can be used as the developer. Examples of the basic substance include sodium carbonate, sodium hydrogen carbonate, sodium metasilicate, tetraalkylammonium hydroxide, sodium hydroxide, potassium hydroxide, etc. For example, when an aqueous sodium carbonate solution is used as a developer, The sodium carbonate concentration is usually 0.01 to 25% by weight, preferably 0.05 to 15% by weight, and the temperature is usually 1.
The temperature and development time may be appropriately selected from the range of 0 to 70°C, usually 5 to 600 seconds, preferably 5 to 300 seconds. Furthermore, organic solvents such as alcohols, glycol ethers, ketones, and chlorinated hydrocarbons can also be used as the developer. In addition, surfactants and antifoaming agents may be added to these developers to improve wettability and defoaming, and it is preferable to use aqueous developers in terms of toxicity and work environment friendliness. .

Next, after the development, a colored paint is electrodeposited on the exposed conductive layer to form a colored layer.

[0032] The colored paint uses, for example, a cationic or anionic resin as a film-forming component, adds a dye and/or pigment as a coloring component, and further uses an acidic or basic substance to dissolve and/or dissolve in water. Alternatively, a dispersed paint, etc. can be used, and organic solvents can be used to facilitate the dissolution and/or dispersion of the resin in the colored paint, to improve bath stability, or to obtain a smooth coating film. may be added.

Examples of the cationic resin include resins in which onium groups such as amino groups, ammonium, and sulfonium are introduced into acrylic resins, epoxy resins, urethane resins, polybutadiene resins, polyamide resins, etc., such as formic acid, acetic acid, and propionic resins. Examples include resins that are solubilized or dispersed in water with an acid such as acid or lactic acid or an acidic substance.

[0034] Examples of the anionic resin include resins such as acrylic resins, polyester resins, maleated oil resins, polybutadiene resins, and epoxy resins into which carboxyl groups are introduced, such as triethylamine, diethylamine, dimethylethanolamine, and ammonia. Examples include resins that are solubilized or dispersed in water with basic substances such as. Furthermore, the film-forming component of the colored paint may be photosensitive, and among the prepolymers and resins used for the photosensitive coating in step (A), those suitable for electrodeposition may be used. A photopolymerization initiator may be used in combination.

[0035] It is desirable that the colored paint used in the step (B) be different in type, hue, color density, and color brightness for each part with different light transmittance, but it is also possible to use the same paint twice. can.

The dye and/or pigment used in the colored paint is selected depending on the desired hue, and the transparency of the resulting paint film, the stability of the paint, the electrodeposition properties, the durability of the paint film, etc. From this point of view, it is desirable to select dyes that do not cause problems with pigments, such as oil-soluble or dispersible dyes, such as azo dyes, anthraquinone dyes, benzodifuranone dyes, condensed methine dyes, etc. For example, organic pigments such as azo lake type, quinacridone type, phthalocyanine type, isoindolinone type, anthraquinone type, thioindigo type, yellow lead, iron oxide, chrome vermilion, chrome green, ultramarine blue, navy blue, cobalt blue, cobalt green, Examples include inorganic pigments such as emerald green, titanium white, and carbon black. Depending on the desired hue, the above dyes and/or
or pigment, as long as it does not impair its properties, 2
It is also possible to use a mixture of more than one type.

The colored paint is prepared by adding a resin, a dye and/or a pigment, an acidic substance or a basic substance, and if necessary an organic solvent, a dispersion aid for the dye or pigment, a leveling agent to improve the smoothness of the coating film, Mix various auxiliary agents such as viscosity modifiers and antifoaming agents, thoroughly disperse using commonly used dispersing machines such as sand mills, roll mills, and attritors, and then mix with water to the desired concentration. This can be carried out by diluting preferably to a solid content of about 4 to 25% by weight, particularly preferably 7 to 20% by weight, to form a coating material suitable for electrodeposition. The colored paint obtained in this way is
A colored layer is formed by electrodeposition coating on the conductive layer.

The thickness of the colored layer is not particularly limited and can be appropriately selected depending on the performance required of the color filter, but it is usually 0.3 to 5 μm, preferably 1 to 3 μm when dried.
It is sufficient as long as it is of a certain extent.

The conditions for the electrodeposition coating are appropriately selected depending on the type of colored paint used and the desired thickness of the colored layer, but the voltage is usually 5 to 500 V, preferably 10 to 30 V.
It is preferable to use 0V direct current, and the electrodeposition time is usually 5 to 3
00 seconds, preferably 10-200 seconds, liquid temperature usually 10-200 seconds
Desirably, the temperature is 35°C, preferably 15-30°C. At this time, when the electrodeposition time to obtain the desired film thickness has elapsed, the electricity supply is stopped, the substrate is removed from the bath, and the excess bath solution is thoroughly washed with water and dried to form a colored layer. can.

The drying conditions can be appropriately selected depending on the conditions of the post-process, etc., but usually it is sufficient as long as the moisture on the surface can be dried, for example, 120° C. or lower, preferably 30° C.
It is desirable to dry at 00°C for usually 1 to 20 minutes, preferably 2 to 10 minutes. If the drying temperature is higher than 120°C, the photosensitive coating may be cured by heat.
This is not preferable because it makes subsequent development work difficult.

[0041] In the manufacturing method of the present invention, following the step (B), the photosensitive coating film in at least one patterned portion is developed and removed, and no colored layer is formed on the exposed conductive layer and/or A step (hereinafter referred to as step (C)) of selectively forming a metal layer on a portion of the conductive layer is performed. (
In step C), it is particularly preferable to form a metal layer in the gaps existing between the patterns of the colored layer obtained in step (B). Formation of the metal layer in this case means first (
B) After forming the colored layer in the process, the negative photosensitive coating film remaining on the substrate is removed in the same manner as the development performed before forming the colored layer, and then the exposed conductive layer is electroplated. This can be done by processing using a method such as a method or an electroless plating method. These treatments may be performed using various commonly used plating solutions, and may be appropriately selected from among the usual treatment conditions in accordance with the performance required of the color filter.

[0042] Metals that can be used for the metal layer include general metal materials that can be plated, such as copper, nickel, silver, and gold, alloys made of two or more of these metal materials, and even metals that can be plated. Examples include metals in which two or more types of metal materials are mixed in a plating solution. The thickness of the metal layer is
Although it can be selected as appropriate depending on the performance required of the color filter, it is usually 10 nm to 5 μm, preferably 10 nm.
It suffices if it is about m to 3 μm. Note that it is particularly preferable to form the metal layer so that the thickness substantially matches the coloring layer thickness, since the color filter can be significantly flattened.

In the manufacturing method of the present invention, a metal layer is formed by plating or the like on the exposed conductive layer in step (C), so the metal layer is formed in a self-aligned manner between the colored layers. be able to. In addition to improving contrast and color purity as described above, such color filters can also function as electrode auxiliary lines, reducing signal delays and heat generation inside cells in large-screen displays. have an effect.

[0044] The above steps (A), (B) and (C)
) The desired color filter can be manufactured by the process, but if necessary, further heating/curing or photo-curing can be performed to further improve weather resistance, chemical resistance, etc. When heating and curing, the temperature is usually 100 to 250°C, preferably 150 to 250°C, and the heating and curing is carried out for 5 minutes to 1 hour, preferably 15 to 40 minutes.

The steps of the present invention will be described below with reference to FIGS. 1 and 2, but the present invention is not limited thereto.

FIG. 1 is a process diagram showing one embodiment of the present invention, and FIG. 2 is an enlarged schematic diagram of a negative mask having four levels of light transmittance among the embodiments of the negative mask used in the present invention. , 1 is a portion equivalent to a light shielding film with a light transmittance of 100%,
2 is the part corresponding to the first color with a light transmittance of 5%, 3 is the light transmittance 2
5% is the second color equivalent portion, and 4 is the third color equivalent portion with a light transmittance of 80%.

First, a photosensitive coating film is formed on a transparent substrate having a transparent conductive layer on the surface, and the dried substrate is coated as shown in FIG.
After exposure through the negative mask shown in , a first development is performed to expose the conductive layer in the part corresponding to the first color corresponding part 2 with a light transmittance of 5% on the negative mask. After electrodepositing in an electrodeposition bath containing colored paint, wash with water.

Next, a second development (conditions are different from the first development) is performed, and the light transmittance of the negative mask is 25.
% of the conductive layer corresponding to the second color corresponding portion 3 is exposed, electrocoated with an electrodeposition bath containing a colored paint of the second color, and washed with water.

Further, a third development (conditions are different from the first and second development) is carried out, and the conductivity of the part corresponding to the third color corresponding part 4 where the light transmittance of the negative mask is 80% is The layer is exposed and electrodeposited using an electrodeposition bath containing a colored paint of a third color, followed by washing with water and drying to form a colored layer.

Next, the fourth development (first and second development)
The conditions are different from the first and third development).
The color filter of the present invention can be obtained by exposing the conductive layer in the portion of the negative mask corresponding to the light-shielding film where the light transmittance is maximum, and forming a metal layer by plating or the like.

In the present invention, a coating in which a cationic resin is dissolved and/or dispersed in water is used as a photosensitive coating, and coating is performed by an electrodeposition method, and a colored layer is formed using a colored coating prepared using an anionic resin. or conversely, a method in which an anionic resin is dissolved and/or dispersed in water as a photosensitive paint, and a colored layer is formed using a colored paint prepared with a cationic resin. Particularly preferred.

[0052]

[Effect of the invention] The method for producing a color filter of the present invention is as follows:
It does not require advanced microfabrication technology, allows for a greater degree of freedom in the pattern shape of the colored layer, allows for all patterning with a single exposure, makes it easy to form non-transparent films, and furthermore It is also easy to handle larger sizes. Therefore, color filters can be easily mass-produced, making them extremely useful industrially.

[0053]

EXAMPLES The present invention will be specifically explained below using synthesis examples and examples, but the present invention is not limited thereto.

[0054]

[Synthesis Example 1] Synthesis of photosensitive resin (A-1) Synthesis of amine-added epoxidized polybutadiene (a-1) Epoxidized liquid polybutadiene (manufactured by Nippon Petrochemical Co., Ltd., product name "E-1000-8", Number average molecular weight 1,00
0, oxirane oxygen content 8%) 1,000g with a thermometer,
The mixture was charged into a 2-liter separable flask equipped with a stirrer and a reflux condenser, and after purging the system with nitrogen, 231.2 g of methylethanolamine was added, and the mixture was reacted at 170° C. for 5 hours. Next, unreacted methylethanolamine was distilled off under reduced pressure, and the amine value was 230.4 mmol/
100 g of amine-added epoxidized polybutadiene (a-
1) was obtained.

Synthesis of Isocyanate Compounds Containing Unsaturated Groups In a heatable and coolable 2 liter round bottom flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel, two
, 4-tolylene diisocyanate and 266.1 g of diethylene glycol dimethyl ether were charged and heated to 40° C., and then 362.8 g of 2-hydroxyethyl acrylate was added dropwise from the dropping funnel. At this time, 200 ppm of parabenzoquinone was also added. Although heat generation was observed due to the dropwise addition of 2-hydroxyethyl acrylate, the temperature was maintained at the same temperature by cooling as necessary. After the dropwise addition of 2-hydroxyethyl acrylate was completed, the temperature was raised to 70°C, and the reaction was allowed to proceed at the same temperature for 3 hours. Infrared absorption spectrum analysis showed that the absorption intensity of the isocyanate group was approximately 1/2 of that before the start of the reaction. After confirmation, the mixture was cooled to obtain an unsaturated group-containing isocyanate compound (a-2).

Synthesis of photosensitive resin (A-1) In a 2-liter separable flask, 500 g of (a-1) was dissolved in 166.7 g of diethylene glycol dimethyl ether, and 713.4 g of (a-1) ((a- 1) 4 equivalents of isocyanate group per 1 equivalent of hydroxyl group in
It was added dropwise at 0°C, and further reacted at the same temperature for 1 hour. It was confirmed by infrared absorption spectrum analysis that the isocyanate group had disappeared, and the photosensitive resin (a-2) was added to (a-1). A-1) was obtained.

[0057]

[Synthesis Example 2] Synthesis of polyamine (A-2) solution “Nisseki Polybutadiene B-1000” (Nippon Petrochemical Co., Ltd.
Co., Ltd., product name, number average molecular weight 1,000, iodine value 43
1,000 g of 0,1,2-bonds (65%), 554 g of maleic anhydride, 10 g of xylene and 3.0 g of trimethylhydroquinone were placed in a 3 liter separable tube equipped with a thermometer, stirrer, reflux condenser and nitrogen blowing tube. The mixture was charged into a flask and reacted at 190° C. for 5 hours under nitrogen. Next, unreacted maleic anhydride and xylene were distilled off to obtain maleated polybutadiene with a total acid value of 400 mgKOH/g.

Next, the maleated polybutadiene 1,
000g, ethylene glycol monobutyl ether 43
After charging 3g and dissolving it uniformly, add 1g under a nitrogen stream.
While maintaining the temperature at 35°C, 364.3 g of N,N-dimethylaminopropylamine was added dropwise over 1 hour. The temperature was further maintained for 5 hours to obtain a polyamine (A-2) solution having tertiary amino groups and imide groups. The obtained polyamine (A-2) solution contained 206 mmol of tertiary amine per 100 g of solution, and the nonvolatile content was 75.0% by weight.

[0059]

[Synthesis Example 3] Synthesis of half-esterified product (A-3) solution “Nisseki Polybutadiene B-1000” (Nippon Petrochemical Co., Ltd.
Co., Ltd., product name, number average molecular weight 1,000, iodine value 43
1,000 g of 0,1,2-bonds (65%), 554 g of maleic anhydride, 10 g of xylene and 3.0 g of trimethylhydroquinone were placed in a 3 liter separable tube equipped with a thermometer, stirrer, reflux condenser and nitrogen blowing tube. The mixture was charged into a flask and reacted at 190° C. for 5 hours under nitrogen. Next, unreacted maleic anhydride and xylene were distilled off to obtain maleated polybutadiene with a total acid value of 400 mgKOH/g.

Next, the maleated polybutadiene 1,
000g, diethylene glycol dimethyl ether 46
1.8 g, N,N-dimethylbenzylamine 3.0 g, and benzyl alcohol 385.5 g were charged, uniformly dissolved, and reacted at 120°C for 2 hours under a nitrogen stream to obtain a half-esterified product (A-3). A solution was obtained. The total acid value of the obtained half-esterified product (A-3) solution was 109.3 mg
KOH/g, and the nonvolatile content was 75.0% by weight.

[0061]

[Synthesis Example 4] Synthesis of Resin (A-4) 400 g of maleated polybutadiene obtained in Synthesis Example 3
, diethylene glycol dimethyl ether 188.5g
and 0.4 g of hydroquinone in a tube with a reflux condenser.
The mixture was placed in a liter separable flask, heated to 80°C, and stirred to make it homogeneous. Next, 165.6 g of 2-hydroxyethyl acrylate and 20 g of triethylamine were added and reacted at the same temperature for 2 hours to obtain a solution of half-esterified maleated polybutadiene (A-4). The total acid value of the obtained half-esterified product (A-4) solution was 105 mgK
OH/g, and the nonvolatile content was 75.0% by weight.

[0062]

[Synthesis Example 5] Preparation of photosensitive paint (B-1) To 500 g of the photosensitive resin (A-1) obtained in Synthesis Example 1,
"Irgacure 907" (
Manufactured by Civer Geigy, product name) 27.0g and “KA
After adding 3.0 g of "YACURE DETX" (manufactured by Nippon Kayaku Co., Ltd., trade name) with stirring and mixing, 16.7 g of acetic acid as a neutralizing agent was added, thoroughly stirred, and homogenized again.
While slowly adding deionized water, the mixture was dispersed in water while stirring vigorously with a high-speed mixer to prepare a photosensitive paint (B-1) aqueous solution (cationic electrodeposition type) having a solid content concentration of 15% by weight.

[0063]

[Synthesis Example 6] Preparation of photosensitive paint (B-2) Half-esterified product (A-4) solution obtained in Synthesis Example 4 50
0g of "Irgacure 90" as a photopolymerization initiator.
7" (manufactured by Civer Geigy, trade name) and 3.0 g of "KAYACURE DETX" (manufactured by Nippon Kayaku Co., Ltd., trade name) were added with stirring, and after mixing, 33.7 g of triethylamine was added as a neutralizing agent. was added and thoroughly stirred to make it homogeneous again. Then, slowly add deionized water and disperse it in water while vigorously stirring with a high-speed mixer. A mold was prepared.

[0064]

[Synthesis Example 7] Preparation of photosensitive paint (B-3) To 500 g of the photosensitive resin (A-1) obtained in Synthesis Example 1,
"Irgacure 907" (
Manufactured by Civer Geigy, product name) 27.0g and “KAY
3.0g of ``ACURE DETX'' (manufactured by Nippon Kayaku Co., Ltd., trade name) was added with stirring, mixed, diluted with methyl ethyl ketone so that the solid content concentration was 40% by weight, and a photosensitive paint solution (B- 3) was prepared.

[0065]

[Synthesis Example 8] Preparation of colored paint (C-1, C-2, C-3) The half-esterified product (A-3) solution and pigment were mixed with stirring, and a three-roll mill for laboratory use (manufactured by Kodaira Manufacturing Co., Ltd.) was used. ) until the pigment particle size became 0.3 μm or less. Measure the particle size using Coulter Counter N4 (manufactured by Coulter Counter)
was used. Next, triethylamine as a neutralizing agent was added to the resulting dispersion mixture and thoroughly stirred to make it homogeneous again. Deionized water was then slowly added and vigorously stirred with a high-speed mixer for water dispersion to achieve a solid concentration of 10% by weight. % colored paints (C-1, C-2, C-3) were prepared. The compositions of the three colored paint (anionic electrodeposition type) aqueous solutions obtained are shown in Table 1 (all values in Table 1 are parts by weight).

[0066]

[Table 1]

[0067]

[Synthesis Example 9] Preparation of colored paints (C-4, C-5, C-6) Polyamine (A-2) solution and pigment were mixed with stirring and placed in a laboratory three-roll mill (manufactured by Kodaira Seisakusho). When the pigment particle size is 0.
It was dispersed until it became 3 μm or less. The particle size was measured using Coulter Counter N4 (manufactured by Coulter Counter). To the resulting dispersion mixture, acetic acid as a neutralizing agent was added, thoroughly stirred, and homogenized again. Deionized water was then slowly added and dispersed in water while vigorously stirring with a high-speed mixer to obtain a solid content concentration of 10. % by weight of colored paint (C-4
, C-5, C-6) were prepared. The composition of the obtained three-color colored paint (cationic electrodeposition type) aqueous solution is shown in Table 2 (Table 2
(All numbers are parts by weight.)

[0068]

[Table 2]

[0069]

[Example 1] A 1.1 mm thick Pyrex glass substrate with an 80 nm thick ITO (indium-tin oxide) film on the surface was used as the cathode, and was made of stainless steel containing a photosensitive paint (B-1) aqueous solution. Electrodeposition was carried out for 3 minutes at a DC voltage of 30 V and a temperature of 25° C. using a beaker as an anode. After washing the glass substrate with ion-exchanged water, it was dried at 80° C. for 5 minutes and cooled to form a uniform coating film with a thickness of 2 μm without stickiness. Next, a negative mask having a pattern with four levels of light transmittance as shown in FIG. using 20
Ultraviolet light of 0 mJ/cm2 was irradiated.

Next, when the film was developed with an aqueous lactic acid solution having a concentration of 0.05% by weight, the photosensitive paint in the portion of the negative mask with the lowest light transmittance was selectively removed, and the ITO film was exposed. After washing with water and drying, the glass substrate is used as an anode, and colored paint (C
Electrodeposition was carried out for 3 minutes at a DC voltage of 25 V and a temperature of 25° C. using a stainless steel beaker containing -1) as a cathode. After washing the glass substrate with ion exchange water, it was heated at 80℃ for 5 minutes.
After drying for minutes, a red colored layer having a thickness of 2 μm and showing no stickiness at room temperature was formed. Next, when it was developed with a 0.5% by weight lactic acid aqueous solution, no change was observed in the photosensitive paint portion corresponding to the red colored layer and light-shielding film, and the area with the second lowest light transmittance of the negative mask was detected. The photosensitive paint was selectively removed.

Next, after washing with water and drying, electrodeposition was carried out for 3 minutes at a DC voltage of 25 V and 25° C. using the glass substrate as an anode and a stainless steel beaker containing colored paint (C-2) as a cathode. When the glass substrate was washed with ion-exchanged water, no change was observed in the previously formed red colored layer and the photosensitive paint portion corresponding to the light-shielding film, and a green colored layer was formed. Dry at 80°C for 5 minutes, then 3.
When developed with a 0% by weight lactic acid aqueous solution, no change was observed in the red and green colored layers, and no change was observed in the photosensitive paint part that becomes the light-shielding film, and the light transmittance of the negative mask was the third highest. The photosensitive paint in the lower areas was selectively removed.

After washing with water and drying, electrodeposition was carried out for 3 minutes at a DC voltage of 25 V and 25° C. using the glass substrate as an anode and a stainless steel beaker containing colored paint (C-3) as a cathode. When the glass substrate was washed with ion-exchanged water, no change was observed in the previously formed red and green colored layers and the photosensitive coating in the portion that would become the light-shielding film, and a blue colored layer was formed. Thereafter, it was dried at 80°C for 5 minutes. When the film was then developed with a 7.0% by weight aqueous lactic acid solution, no change was observed in the colored layer, and only the remaining photosensitive coating film in the portion corresponding to the light-shielding film was selectively removed. Using the exposed ITO surface as a cathode, electroplating was performed in a 45° C. nickel plating bath at a current density of 0.1 A/cm 2 for 3 minutes. The substrate was washed with water and dried to obtain a substrate having a non-transparent (light-shielding) nickel layer and a colored layer.

[0073] To ensure complete curing, baking was performed at 175°C for 30 minutes. The thickness of each colored layer and the nickel layer after curing was 1.9 μm, and a color filter having a uniform colored layer with excellent transparency was obtained.

[0074]

[Example 2] The same glass substrate used in Example 1 was used as an anode, and a stainless steel beaker containing an aqueous solution of photosensitive paint (B-2) was used as a cathode, and a DC voltage of 2
Electrodeposition was carried out for 3 minutes at 5V and 25°C. When the glass substrate was washed with ion-exchanged water and dried at 80° C. for 5 minutes, a uniform coating film with a thickness of 1.8 μm without stickiness was formed.

Next, a negative mask having a pattern with four different light transmittances as shown in FIG.
2 ultraviolet rays were irradiated. When developed with a sodium carbonate aqueous solution with a concentration of 0.1% by weight, the photosensitive paint in the areas of the negative mask with the lowest light transmittance was selectively removed, and the IT
The O membrane was exposed.

Next, after washing with water and drying, electrodeposition was carried out for 3 minutes at a DC voltage of 30 V and a temperature of 25° C. using the glass substrate as a cathode and a stainless steel beaker containing colored paint (C-4) as an anode. After washing the glass substrate with ion-exchanged water, it was dried at 80° C. for 5 minutes to form a red colored layer. When it was then developed with a 0.75% by weight aqueous sodium carbonate solution, no change was observed in the red colored layer, and the photosensitive paint in the area of the negative mask with the second lowest light transmittance was selectively removed. Ta.

Next, after washing with water and drying, electrodeposition was carried out for 3 minutes at a DC voltage of 30 V and a temperature of 25° C. using the glass substrate as a cathode and a stainless steel beaker containing colored paint (C-5) as an anode. When the glass substrate was washed with ion-exchanged water, no change was observed in the previously formed red colored layer, and a green colored layer was formed. When it was dried at 80°C for 5 minutes and then developed with a 5% by weight sodium metasilicate aqueous solution, no change was observed in the red and green colored layers, and no change was observed in the photosensitive paint portion that becomes the light-shielding film. First, the photosensitive paint in the portion of the negative mask with the third lowest light transmittance was selectively removed.

After washing with water and drying, electrodeposition was carried out for 3 minutes at a DC voltage of 30 V and 25° C. using the glass substrate as a cathode and a stainless steel beaker containing colored paint (C-6) as an anode. When the glass substrate was washed with ion-exchanged water, no change was observed in the previously formed red and green colored layers and the photosensitive coating in the portion that would become the light-shielding film, and a blue colored layer was formed. Thereafter, it was dried at 80°C for 5 minutes. When the film was then developed with a 7.0% by weight aqueous sodium metasilicate solution, no change was observed in the colored layer, and only the remaining photosensitive coating film in the portion corresponding to the light-shielding film was selectively removed. The exposed ITO surface was used as a cathode, and the current density was 2.5 at a current density of 0.1 A/cm2 in a nickel plating bath at 45°C.
Electroplating was carried out for 1 minute. By washing with water and drying, a substrate having a non-transparent (light-shielding) copper layer and a colored layer was obtained.

[0079] To ensure complete hardening, baking was performed at 175°C for 30 minutes. The thickness of each colored layer and copper layer after curing was 1.8 μm, and a color filter having uniform colored layers with excellent transparency was obtained.

[0080]

[Example 3] A photosensitive paint solution (B-3) was spray-coated on the same glass substrate as used in Example 1, air-dried, and dried at 80°C for 5 minutes.
．． A uniform coating film of 9 μm was formed.

Next, a negative mask having a pattern with four levels of light transmittance as shown in FIG. ”), 200m
It was irradiated with ultraviolet rays of J/cm2. The subsequent development, electrodeposition, and plating steps were carried out in the same manner as in Example 1 to obtain a color filter having a uniform colored layer with excellent transparency and a thickness of 1.9 μm.

[Brief explanation of the drawing]

FIG. 1 is a process diagram showing one embodiment of the present invention.

FIG. 2 is an enlarged schematic diagram of a negative mask used in an example of the present invention.

[Explanation of symbols]

Claims (2)

[Claims] 1. (A) forming a photosensitive coating film on a transparent substrate having a transparent conductive layer on its surface, and exposing the film to light through a negative mask having a pattern with at least three levels of light transmittance; (B) The operation of developing and removing the photosensitive coating film on the pattern portion and electrodepositing a colored paint on the exposed conductive layer to form a colored layer is performed sequentially on the pattern portions corresponding to the negative mask in descending order of light transmittance. A step of forming a colored layer by repeating the process, and (C) on the conductive layer exposed by developing and removing the photosensitive coating film in at least one patterned part and/or on the conductive layer in the part where the colored layer is not formed. A method for producing a color filter, comprising the steps of: selectively forming a metal layer. 2. The method of manufacturing a color filter according to claim 1, wherein the metal layer in the step (C) is selectively formed in gaps existing between patterns of the colored layer.