JPH0511106A - Color filter manufacturing method - Google Patents

Abstract

(57) [Summary] [Structure] The portion corresponding to the colored portion of the color filter is patterned in a single exposure through a negative mask having a different light transmittance for each color, and the light transmittance is set in order. A method of manufacturing color filters that sequentially develops and colors corresponding pattern parts. [Effect] The above manufacturing method does not require high-level fine processing technology, can increase the degree of freedom in the pattern shape of the coloring layer, and can perform all patterning with a single exposure.
Furthermore, it is easy to deal with the increase in size. Therefore, the color filter can be easily mass-produced and is extremely useful industrially.

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 or the like.

[0002]

2. Description of the Related Art At present, as a color filter manufacturing method that is generally used, there are a dyeing method, a printing method, a pigment dispersion method, and the like, in which a transparent substrate is colored with a binder containing a dye or a pigment.

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 carry out a dye-proof and a photolithography step each time the color is changed, and the printing method is dye-proof. However, there is a limit to the miniaturization of the color pattern, and there is a problem that the accuracy of the printing position deteriorates as the number of colors increases. Further, although the above-mentioned pigment dispersion method allows a fine pattern, it has a drawback in that a highly accurate photolithography process must be performed each time the color is changed, and the process becomes extremely complicated.

On the other hand, in order to eliminate these drawbacks, Japanese Patent Application Laid-Open No. 59-114572 proposes a method for producing a color filter by an electrodeposition coating method. 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 a portion of the patterned transparent electrode that is colored in the same color, and the transparent electrode is placed in a colored electrodeposition bath. Electrodeposited to form a colored layer. Next, a voltage is applied only to a portion colored with another color and electrodeposition treatment is performed to form another colored layer. However, in this method, the patterning of the transparent electrode, which requires high precision, must be performed first.
Great care must be taken in handling in the subsequent process, and even if a part of the fine pattern is broken, the subsequent coloring process becomes difficult, which is not preferable in manufacturing. In addition, the patterned transparent electrode
All of the fine parts must be electrically continuous, which limits the flexibility of the pattern shape.

Further, in Japanese Patent Laid-Open No. 63-210901, exposure is carried out through a mask having a pattern of only portions colored in the same color by using a positive type photosensitive resin composition,
After developing and forming a colored layer by electrodeposition, this exposure
A method has been proposed in which the steps of development and electrodeposition are repeated a desired number of times, but this method is inferior in stability because it uses a compound having an unstable quinonediazide group. When the quinonediazide compound is exposed to an aqueous alkaline solution for further development,
The quinonediazide compound in the unexposed area also reacts with the alkaline aqueous solution to significantly change the photosensitivity, which makes subsequent exposure and development difficult.

All of the above-mentioned methods require high-precision processing technology for alignment, and thus meet the demand for a larger work size, that is, a larger screen size and a cost reduction due to multiple surfaces. Have difficulty.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above-mentioned drawbacks, to require no advanced fine processing technology, to have a large degree of freedom in the pattern shape of the coloring layer, and to increase the size. The present invention provides a method for producing a color filter, which is easy to deal with and easy to mass-produce.

[0008]

As a result of research on a method of manufacturing a color filter which has a large degree of freedom in the pattern shape of a colored layer and can cope with an increase in size, the present inventors have identified a negative photosensitive resin. It was found that a color filter having excellent performance can be obtained by a simple process of combining the above 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 thereof, and a negative mask having a pattern having at least three different light transmittances is provided through a negative mask. Corresponds to the exposure step and the operation of (B) developing and removing the photosensitive coating film on the pattern portion to form a colored layer by electrodeposition coating a colored paint on the exposed conductive layer in the order of increasing light transmittance of the negative mask. And a step of forming a colored layer by sequentially repeating the above pattern portions.

The present invention will be described in more detail below.

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

The transparent substrate having a transparent conductive layer on the surface used in the present invention is not particularly limited as long as it has a conductive layer on the surface and is a transparent plate, and for example, glass,
Examples thereof include a plastic plate and a substrate having a transparent conductive layer formed on the surface of another plate-shaped material. 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.

Examples of the material of the conductive layer include materials containing tin oxide, indium oxide, antimony oxide or the like. 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 vapor deposition method. Alternatively, a commercially available transparent substrate having a transparent conductive layer may be used. It is desirable to use a substrate having as high transparency as possible in terms of the performance of the color filter.

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

As the photosensitive coating material for forming the photosensitive coating film, a resin having film forming ability and photosensitivity (hereinafter, referred to as
Examples thereof include a resin for a photosensitive coating), a photopolymerization initiator, and optionally a dye and / or a pigment, which are dispersed or dissolved in an organic solvent or water. The photosensitive paint may or may not contain a dye and / or a pigment, etc., but it does not contain a dye and / or a pigment having a hue which is a component of the target color filter. The number of times of repeating the step (B) described later can be omitted once, which is preferable.

The photosensitive coating resin preferably used in the present invention includes a photosensitive group such as a (meth) acryloyl group such as an acryloyl group or a methacryloyl group and / or a cinnamoyl group at the molecular end and / or side chain. Examples thereof include a prepolymer or resin having a molecular weight of about 500 to 10,000.

Examples of the prepolymer or resin include prepolymers such as epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate; acrylic resin, epoxy resin, urethane resin, polybutadiene resin, and amino group. A resin in which an onium group such as ammonium, ammonium or sulfonium and the photosensitive group are introduced, and a cationic resin such as a resin which is solubilized and / or dispersed in water with an acid such as formic acid, acetic acid, propionic acid or lactic acid or an acidic substance. Resin; acrylic resin, polyester resin, maleated oil resin, polybutadiene resin,
A resin obtained by introducing a carboxyl group and the like and a photosensitive group into an epoxy resin, triethylamine, diethylamine,
Anionic resins such as resins that are solubilized and / or dispersed in water with a basic substance such as dimethylethanolamine and ammonia can be mentioned. Especially, from the viewpoint of process simplification and pollution prevention, solubilization in water is possible. The use of and / or dispersible prepolymers or resins is preferred.

In addition, low molecular weight (meth) acrylates may be added to the resin for photosensitive coatings in order to adjust the photosensitivity and viscosity of the coating film. (Meth) acrylate, 2-phenoxyethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tricyclodecane (meth)
Acrylate, hexanediol di (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, etc. are exemplified, 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 resin for photosensitive coating. If the mixing ratio of the (meth) acrylate exceeds 50 parts by weight, the coating film tends to have tackiness, which is not preferable.

The photopolymerization initiator may be a known one, and examples thereof include benzoin and its ethers, benzylalkyl ketals, benzophenone derivatives, anthraquinone derivatives, and thioxanthone derivatives. If necessary, a sensitizer may be added. Good. The addition amount of the photopolymerization initiator is preferably 0.1 to 30 parts by weight, and particularly preferably 0.5 to 2 parts by weight with respect to 100 parts by weight of the resin for photosensitive coating.
It is in the range of 0 parts by weight. Addition amount of photopolymerization initiator is 0.1
If it is less than part by weight, the photocurability is insufficient, and if it exceeds 30 parts by weight, the curing is excessively advanced, the coating film strength is insufficient, and it is uneconomical, which is not preferable.

The organic solvent used to disperse or dissolve the respective components of the photosensitive paint may be any one which 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, for example, dibutyl ether, dioxane, tetrahydrofuran, etc .; Alcohols, for example, methoxybutanol, diacetone alcohol, butanol, isopropanol, etc .; Hydrocarbons, for example, toluene, xylene, hexane, etc .; Esters,
For example, ethyl acetate, butyl acetate, 2-methoxyethyl acetate, 2-methoxypropyl acetate and the like can be mentioned, and when used, they can be used alone or as a mixture.

These organic solvents are used for facilitating solubilization and dispersion, improving bath stability, and obtaining a smooth coating film. It can also be added at the time of chemical conversion or at the time of water dispersion.

The hue of the dyes and / or pigments to be blended in the photosensitive coating, if necessary, can be appropriately selected according to the purpose, but dark ones are preferable in order to prevent light leakage.
Particularly, hues such as black, dark blue, dark purple and dark brown are preferable.

Further, it is desirable to select, as the dye and / or pigment, a dye and / or pigment that does not impair the stability of the coating, the electrodeposition characteristics, the durability of the coating film, etc., if necessary. From this viewpoint, 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. As the pigment, for example, azo lake, quinacridone, phthalocyanine, isoindolinone, anthraquinone, thioindigo organic pigments, yellow lead, iron oxide, chrome vermillion, chrome green, ultramarine blue, dark blue, cobalt blue, Inorganic pigments such as cobalt green, emerald green and carbon black are suitable. 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. For the dye and / or pigment, "COLOR INDEX" or the like may be appropriately referred to.

The proportion of the dye and / or pigment used is
Purpose, hue, type of dye and / or pigment used,
It is appropriately selected depending on the film thickness of the photosensitive coating when it is dried, etc., and is preferably 3 to 70% by weight, particularly preferably 5 to 60% by weight, based on the entire photosensitive coating.

Further, the coating film to be obtained can be made to have a light-transmitting property or a light-shielding property depending on the kind and the ratio of use of the dye and / or pigment, and can be appropriately selected depending on the purpose. For example, a black and light-shielding coating film can be obtained by using carbon black or the like as a pigment in the range of 3 to 34% by weight with respect to the entire photosensitive coating material. The black and light-shielding coating film is particularly preferable for the purpose of preventing light leakage. The color of the dye and / or pigment also includes white. Furthermore, the dyes and / or pigments used are preferably purified and used to obtain good coating films. Further, various additives such as a dispersion aid for the dye or pigment, a leveling agent for improving the smoothness of the coating film, a viscosity modifier, and a defoaming agent may be added to the photosensitive paint.

The above-mentioned photosensitive paint is prepared by using a resin for photosensitive paint, a photopolymerization initiator, an organic solvent and / or water, if necessary, a dye and / or a pigment, an acidic substance or a basic substance, a dye or a pigment. A dispersing aid, a leveling agent for improving the smoothness of the coating film, a viscosity adjusting agent, a defoaming agent and various other auxiliaries are mixed, and a commonly used dispersing machine such as a sand mill, a roll mill or an attritor is used. It can be obtained by a method of sufficiently using and dispersing. The film thickness of the photosensitive coating film formed by the photosensitive coating material thus obtained is not particularly limited and can be appropriately selected according to the performance required for the color filter, etc., but is usually 0.3 to 5 μm when dried.
m, preferably about 1 to 3 μm. To adjust the film thickness, for example, when a photosensitive coating film is formed by an electrodeposition method, it can be controlled by adjusting electrodeposition conditions such as voltage, electrodeposition time, liquid temperature, etc. It can be performed under the same conditions as the electrodeposition coating of the paint.

In the present invention, it is necessary to expose the photosensitive coating film through a negative mask having a pattern having at least three different light transmittances. Here, the light transmittance means the ratio of the intensity of light rays used for exposure before and after passing through the negative mask. Further, the number of steps of different light transmittance of the negative mask pattern is at least 3
The number of stages is sufficient, and it can be determined according to the number of types of colored paints to be used, and the difference in light transmittance between the stages can be appropriately selected according to the exposure conditions and the development conditions described below. Generally, it is preferable to increase the relative difference between the respective light transmittances because the exposure amount and the exposure time can be easily adjusted, but even if the difference in the light transmittance is small, the exposure amount is increased. Alternatively, the same purpose can be achieved by increasing the exposure time. Therefore, the relative difference in light transmittance is not particularly limited, but it is generally preferable that the relative difference is 5% or more.

The exposure can be carried out by using an apparatus capable of generating a large amount of ultraviolet rays, and for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp or the like can be used as a light source, and if necessary, other radiation is used. You may. The exposure conditions can be appropriately selected according to the photosensitive paint used, the exposure device, the negative mask, and the like.

In the step (A) of the present invention, the photosensitive coating is exposed through a negative mask having a pattern having at least three different light transmittances so that the photosensitive coating has a different light transmittance of the negative mask pattern. As many as
Different exposure conditions can be created.

In the production method of the present invention, after the step (A), the photosensitive coating film on the pattern portion is developed and removed, and a colored coating material is electrodeposited on the exposed conductive layer to form a colored layer. The colored layer is formed by sequentially repeating the pattern portions corresponding to the light transmittance of the negative mask in the ascending order (hereinafter referred to as step (B)). That is, the (B)
In the process, first, the light transmittance of the negative mask is selectively developed and removed to remove the photosensitive coating film in the portion corresponding to the pattern, and the colored layer is formed by electrocoating a colored coating on the exposed conductive layer, Then, the photosensitive coating film in the portion corresponding to the pattern having the next smallest light transmittance of the negative mask is selectively developed and removed, and the colored coating is electrodeposited on the exposed conductive layer to form the colored layer. A colored layer can be formed by repeating.

The conditions for selectively developing and removing the photosensitive coating film are as follows: the amount of exposure of the portion to be selectively removed, the solubility of the photosensitive paint used in the developer, the kind and concentration of the developer,
Further, it may vary depending on the developing temperature and the developing time, and the conditions suitable for the resin or the like used for preparing the photosensitive coating material may be appropriately selected. Specifically, for example, an aqueous solution in which an acidic substance is dissolved can be used as the developing solution when a cationic resin is used as a component of the photosensitive paint. Examples of the acidic substance include formic acid, acetic acid, propionic acid,
Examples thereof 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 developing solution, the lactic acid concentration is usually 0.01 to 50% by weight, preferably 0.01 to
30% by weight, the temperature is usually 10 to 70 ° C, preferably 20
The developing time may be appropriately selected from the range of -50 ° C and the developing time of usually 5-600 seconds. 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 a developer. Examples of the basic substance include sodium carbonate, sodium hydrogen carbonate, sodium metasilicate, tetraalkylammonium hydroxide, sodium hydroxide, potassium hydroxide and the like. For example, when an aqueous solution of sodium carbonate is used in the developing solution, 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 developing time may be appropriately selected from the range of 0 to 70 ° C. and the developing time of usually 5 to 600 seconds, preferably 5 to 300 seconds. Furthermore, organic solvents such as alcohols, glycol ethers, ketones and chlorinated hydrocarbons can be used as the developing solution. Further, a surfactant or an antifoaming agent may be added to these developers for improving wettability and defoaming, and it is preferable to use an aqueous solution type developing agent in view of toxicity and working environment. ..

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

The colored coating composition uses, for example, a cationic or anionic resin as a film forming component, a dye and / or a pigment as a coloring component, and an acidic or basic substance to dissolve and / or dissolve in water. Alternatively, a dispersed paint or the like can be used, and further, for facilitating the dissolution and / or dispersion of the resin in the colored paint, for improving bath stability or for obtaining a smooth coating film, an organic solvent, etc. May be added.

Examples of the above-mentioned cationic resin include acrylic resin, epoxy resin, urethane resin, polybutadiene resin, polyamide resin and the like into which an onium group such as amino group, ammonium or sulfonium is introduced. Formic acid, acetic acid, propion Examples thereof include resins that are solubilized or dispersed in water with an acid such as acid or lactic acid or an acidic substance.

Examples of the anionic resin include acrylic resins, polyester resins, maleated oil resins, polybutadiene resins, epoxy resins and the like having a carboxyl group introduced therein, such as triethylamine, diethylamine, dimethylethanolamine, and ammonia. Examples thereof include resins that are solubilized or dispersed in water with a basic substance such as. Furthermore, the film-forming component of the colored paint may have photosensitivity, and among the prepolymers and resins used for the photosensitive coating film in the step (A), those suitable for electrodeposition may be used. A photopolymerization initiator may be used in combination.

It is desirable that the colored paint used in the step (B) has different kinds, hues, color densities, and light and shades for different portions having different light transmittances, but the same thing may be used repeatedly. it can.

The hue of the colored paint can be appropriately selected according to the purpose. For example, for the photosensitive coating used in the step (A), the colored coating used in the step (B), and each colored coating used when the step of electrodeposition coating the colored coating in the step (B) is performed a plurality of times. Can have different hues.

The dyes and / or pigments used in the colored paint are selected according to the desired 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 a dye that does not cause a problem with this point, and as the dye, oil-soluble or dispersible dyes, specifically, for example, azo-based, anthraquinone-based, benzodifuranone-based, condensed methine-based dyes, etc. Examples of organic pigments such as azo lake type, quinacridone type, phthalocyanine type, isoindolinone type, anthraquinone type, thioindigo type, yellow lead, iron oxide, chrome vermillion, chrome green, ultramarine blue, dark blue, cobalt blue, cobalt green, Inorganic pigments such as emerald green, titanium white and carbon black can be mentioned. Further, depending on the desired hue, the dye and / or
Alternatively, the pigment may be used as long as it does not impair its properties.
It is also possible to use a mixture of more than one type.

For the preparation of the above-mentioned colored paint, 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 the pigment, a leveling agent for improving the smoothness of the coating film, Viscosity modifier, various auxiliaries such as defoaming agents, etc. are mixed and sufficiently dispersed using a commonly used sand mill, roll mill, disperser such as attritor, and then a predetermined concentration with water, The solid content is preferably about 4 to 25% by weight, particularly preferably 7 to 20% by weight, and a coating suitable for electrodeposition can be obtained by such a method. The colored paint obtained in this way is
The 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 according to the performance required for the color filter, but is usually 0.3 to 5 μm, preferably 1 to 3 μm when dried.
It may be about m.

The conditions for the electrodeposition coating are appropriately selected according to the kind of the colored coating used and the thickness of the desired 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 excessively adhered bath liquid is thoroughly washed with water or the like and dried to form the colored layer. it can.

The drying conditions can be appropriately selected depending on the conditions of the post-process and the like, but it is usually required that the surface moisture can be dried, for example, 120 ° C. or less, preferably 30 ° C. to 1
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 film may be cured by heat,
It is not preferable because the subsequent developing work becomes difficult.

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

The process 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 an embodiment of the present invention, and FIG. 2 is an enlarged schematic view of a negative mask of the embodiment of the negative mask used in the present invention in which the light transmittance differs in four stages. 1 is a portion corresponding to a light-shielding film having a light transmittance of 100%,
2 is a portion corresponding to the first color having a light transmittance of 5%, 3 is a light transmittance of 2
A portion corresponding to the second color of 5%, and 4 indicates a portion corresponding to the third color having a light transmittance of 80%.

First, a black photosensitive coating film (which becomes a light-shielding film) is formed on a transparent substrate having a transparent conductive layer on its surface, and the dried substrate is exposed through, for example, a negative mask shown in FIG. The first development is carried out, the conductive layer of the portion corresponding to the first color equivalent portion 2 where the light transmittance of the negative mask is 5% is exposed, and the negative electrode is electroplated in the electrodeposition bath containing the colored paint of the first color. After coating, wash with water.

Next, the second development (the conditions are different from those of the first development) is performed, and the light transmittance of the negative mask is 25.
% Of the portion corresponding to the second color corresponding portion 3, the conductive layer is exposed, and electrodeposition coating is performed in an electrodeposition bath containing a coloring paint of the second color, followed by washing with water.

Further, the third development (the conditions are different from those of the first and second development) is performed, and the conductivity of the portion corresponding to the third color corresponding portion 4 having the light transmittance of the negative mask of 80% is obtained. The color filter of the present invention can be obtained by exposing the layer, performing electrodeposition coating in an electrodeposition bath containing a colored coating material of the third color, washing with water and drying to form a colored layer having a light-shielding film. it can.

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

[0050]

The method for producing the color filter of the present invention is
The degree of freedom of the pattern shape of the colored layer can be increased without the need for advanced fine processing technology, all patterning can be performed with a single exposure, and it is easy to deal with larger size. Therefore, the color filter can be easily mass-produced and is extremely useful industrially.

[0051]

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

[0052]

[Synthesis Example 1] Synthesis of photosensitive resin (A-1) Synthesis of amine-added epoxidized polybutadiene (a-1) Epoxidized liquid polybutadiene (Nippon Petrochemical Co., Ltd.)
Product name "E-1000-8", number average molecular weight 1,0
00, oxirane oxygen amount 8%) 1,000 g was charged into a 2 liter separable flask equipped with a thermometer, a stirrer and a reflux condenser, the system was replaced with nitrogen, and then 231.2 g of methylethanolamine was added. In addition, 17
The reaction was carried out at 0 ° C for 5 hours. Then, unreacted methylethanolamine was distilled off under reduced pressure to obtain an amine value of 230.4 mmol.
/ 100 g of amine-added epoxidized polybutadiene (a
-1) was obtained.

Synthesis of Unsaturated Group-Containing Isocyanate Compound In a heatable and coolable 2 liter round bottom flask equipped with a thermometer, stirrer, reflux condenser and dropping funnel,
After charging 435.5 g of 2,4-tolylene diisocyanate and 266.1 g of diethylene glycol dimethyl ether and heating to 40 ° C., 362.8 g of 2-hydroxyethyl acrylate was added dropwise from a dropping funnel. At this time, 200 ppm of parabenzoquinone was also added. Although heat generation was observed by the dropwise addition of 2-hydroxyethyl acrylate, it was cooled and kept at the same temperature as needed. After the completion of the dropwise addition of 2-hydroxyethyl acrylate, the temperature was raised to 70 ° C., the reaction was carried out at the same temperature for 3 hours, and it was confirmed by infrared absorption spectrum analysis that the absorption intensity of the isocyanate group was almost half that before the reaction was started. After confirmation, the mixture was cooled to obtain an unsaturated group-containing isocyanate compound (a-2).

Synthesis of Photosensitive Resin (A-1) (a-1) 50 in a 2-liter separable flask.
0 g of diethylene glycol dimethyl ether 166.
(A-1) 713.4 g ((a-1) 1 equivalent of the hydroxyl group to the isocyanate group 0.
(8 equivalent) was added dropwise at 40 ° C., and the mixture was further reacted at the same temperature for 1 hour, and it was confirmed by infrared absorption spectrum analysis that the isocyanate group had disappeared, and (a-1) was added to (a-2).
To obtain a photosensitive resin (A-1).

[0055]

[Synthesis Example 2] Synthesis of polyamine (A-2) solution "Nisseki Polybutadiene B-1000" (manufactured by Nippon Petrochemical Co., Ltd., trade name, number average molecular weight 1,000, iodine value 4
3,1,2-bond 65%) 1,000 g, maleic anhydride 554 g, xylene 10 g and trimethylhydroquinone 3.0 g were added to a 3 liter separable tube equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen blowing tube. The mixture was placed in a flask and reacted under nitrogen at 190 ° C. for 5 hours. Then, unreacted maleic anhydride and xylene were distilled off to obtain maleated polybutadiene having a total acid value of 400 mgKOH / g.

Next, in a 3 liter separable flask equipped with a reflux condenser, the maleated polybutadiene 1,
000g, ethylene glycol monobutyl ether 43
Charge 3 g and dissolve it uniformly, then under nitrogen flow 1
While maintaining the temperature at 35 ° C., 364.3 g of N, N-dimethylaminopropylamine was added dropwise over 1 hour. Further, the temperature was maintained for 5 hours to obtain a polyamine (A-2) solution having a tertiary amino group and an imide group. The obtained polyamine (A-2) solution contained 206 mmol of tertiary amine per 100 g of the solution, and the nonvolatile content was 75.0% by weight.

[0057]

[Synthesis Example 3] Synthesis of semi-esterified product (A-3) solution "Nisseki Polybutadiene B-1000" (manufactured by Nippon Petrochemical Co., Ltd., trade name, number average molecular weight 1,000, iodine value 4
3,1,2-bond 65%) 1,000 g, maleic anhydride 554 g, xylene 10 g and trimethylhydroquinone 3.0 g were added to a 3 liter separable tube equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen blowing tube. The mixture was placed in a flask and reacted under nitrogen at 190 ° C. for 5 hours. Then, unreacted maleic anhydride and xylene were distilled off to obtain maleated polybutadiene having a total acid value of 400 mgKOH / g.

Next, in a 3 liter separable flask equipped with a reflux condenser, 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 and uniformly dissolved, and then reacted at 120 ° C. for 2 hours under a nitrogen stream to give 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 mgK.
It was OH / g, and the nonvolatile content was 75.0% by weight.

[0059]

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

[0060]

[Synthesis Example 5] Preparation of black photosensitive coating (B -1) To 500 g of the photosensitive resin (A-1) obtained in Synthesis Example 1,
27.0 g of "Irgacure 907" (manufactured by Chiver Geigy Co., Ltd.) as a photopolymerization initiator, "KAYAC"
URE DETX "(manufactured by Nippon Kayaku Co., Ltd., trade name) 3.
0 g and 37.5 g of carbon black # 5B (product of Mitsubishi Kasei Co., Ltd.) were added with stirring and mixed, and then the carbon black particle size was 0.3 μm or less with a laboratory three-roll mill (manufactured by Kodaira Seisakusho). Dispersed until. The particle size was measured using Coulter Counter N4 (manufactured by Coulter Counter).

To the above dispersion mixture, acetic acid 1 was added as a neutralizing agent.
After adding 6.7 g and thoroughly stirring to homogenize again, deionized water was slowly added and stirred vigorously with a high speed mixer to disperse in water to disperse the water in a black photosensitive paint (B-1) having a solid content concentration of 15% by weight. An aqueous solution (cationic electrodeposition type) was prepared.

[0062]

[Synthesis Example 6] Preparation of black photosensitive coating (B-2) Half-esterified product (A-4) solution 50 obtained in Synthesis Example 4
0 g as a photopolymerization initiator "Irgacure 90
7 "(Ciba Geigy, trade name) 27.0 g," K
AYACURE DETX "(manufactured by Nippon Kayaku Co., Ltd., trade name) 3.0 g and carbon black # 5B (Mitsubishi Kasei Kogyo Co., Ltd. product) 37.5 g were added under stirring and mixed,
The carbon black was dispersed with a laboratory three-roll mill (manufactured by Kodaira Seisakusho) until the particle size of carbon black was 0.3 μm or less.
The particle size was measured using Coulter Counter N4 (manufactured by Coulter Counter).

To the above dispersion mixture, 33.7 g of triethylamine was added as a neutralizing agent, and the mixture was thoroughly stirred and homogenized again. Then, deionized water was slowly added to the dispersion mixture while stirring vigorously with a high-speed mixer to disperse in water to obtain a solid content concentration. A 15% by weight black photosensitive coating (B-2) aqueous solution (anion electrodeposition type) was prepared.

[0064]

[Synthesis Example 7] Preparation of black photosensitive coating (B-3 ) To 500 g of the photosensitive resin (A-1) obtained in Synthesis Example 1,
27.0 g of "Irgacure 907" (manufactured by Chiver Geigy Co., Ltd.) as a photopolymerization initiator, "KAYAC"
URE DETX "(manufactured by Nippon Kayaku Co., Ltd., trade name) 3.
0 g and 37.5 g of carbon black # 5B (product of Mitsubishi Kasei Co., Ltd.) were added with stirring and mixed, and then the carbon black particle size was 0.3 μm or less with a laboratory three-roll mill (manufactured by Kodaira Seisakusho). Dispersed until. The particle size was measured using Coulter Counter N4 (manufactured by Coulter Counter).

The above dispersion mixture was diluted with methyl ethyl ketone to a solid content concentration of 40% by weight to prepare a black photosensitive coating solution (B-3).

[0066]

[Synthesis Example 8] Preparation of colored coating materials (C-1, C-2, C-3) The half-esterified product (A-3) solution and the pigment were mixed under stirring, and a laboratory three-roll mill (manufactured by Kodaira Seisakusho) ),
The pigment was dispersed until the particle diameter became 0.3 μm or less. The particle size was measured using Coulter Counter N4 (manufactured by Coulter Counter). Next, triethylamine, which is a neutralizing agent, was added to the obtained dispersion mixture, and the mixture was thoroughly stirred and homogenized again. Then, deionized water was slowly added to the dispersion mixture while stirring vigorously with a high-speed mixer to disperse the water to a solid content concentration of 10% by weight. % Of colored paints (C-1, C-2, C-3) were prepared. Obtained three-color paint (cationic electrodeposition type)
The composition of the aqueous solution is shown in Table 1 (all numerical values in Table 1 are parts by weight).

[0067]

[Table 1]

[0068]

[Synthesis Example 9] Preparation of colored paint (C-4, C-5, C-6) The polyamine (A-2) solution and the pigment were mixed under stirring, and the mixture was placed in a laboratory three-roll mill (manufactured by Kodaira Seisakusho). And dispersed until the pigment particle size was 0.3 μm or less. The particle size was measured using Coulter Counter N4 (manufactured by Coulter Counter). Acetic acid, which is a neutralizing agent, was added to the obtained dispersion mixture, and the mixture was thoroughly stirred and homogenized again. Then, deionized water was slowly added to the dispersion mixture while vigorously stirring with a high-speed mixer to disperse the water to a solid content concentration of 10 Weight percent colored paints (C-4, C-5, C-6) were prepared. Table 2 shows the composition of the resulting three-colored colored coating solution (anionic electrodeposition type).
(The values in Table 2 are all parts by weight).

[0069]

[Table 2]

[0070]

Example 1 Stainless steel containing an aqueous solution of a black photosensitive paint (B-1) using a 1.1 mm thick Pyrex glass substrate having an ITO (indium-tin oxide) film having a thickness of 80 nm on the surface as a cathode. With the beaker made as an anode,
Electrodeposition was performed for 3 minutes under the conditions of a DC voltage of 30 V and 25 ° C. After the glass substrate was washed with ion-exchanged water, dried at 80 ° C. for 5 minutes and cooled, and a black uniform coating film having a film thickness of 2 μm and having no tackiness was formed. Then, a negative mask having a pattern in which the light transmittance shown in FIG. 2 has four different levels is adhered onto the coating film, and a UV exposure device having a high pressure mercury lamp (manufactured by Oak Manufacturing Co., Ltd., trade name “JL-3300”) Was irradiated with an ultraviolet ray of 500 mJ / cm ² .

Next, when the film was developed with an aqueous solution of lactic acid having a concentration of 0.05% by weight, the black photosensitive paint in the portion of the negative mask having the lowest light transmittance was selectively removed, and the ITO film was exposed. After washing with water and drying, electrodeposition was performed for 3 minutes under the conditions of a DC voltage of 25 V and 25 ° C., using a glass substrate as an anode and a stainless steel beaker put in the colored coating material (C-1) as a cathode. After washing the glass substrate with deionized water, 80 ℃
And dried for 5 minutes to form a red colored layer having a film thickness of 2 μm and showing no tackiness at room temperature. When developed with a 0.5 wt% aqueous lactic acid solution, no change was observed in the portions corresponding to the red colored layer and the light-shielding layer, and the black photosensitivity of the portion of the negative mask having the second lowest light transmittance was observed. The paint was selectively removed.

Next, after washing with water and drying, the glass substrate was used as an anode, and a stainless steel beaker containing the colored coating material (C-2) was used as a cathode, and electrodeposition was carried out for 3 minutes under conditions of a DC voltage of 25 V and 25 ° C. When the glass substrate was washed with ion-exchanged water, no change was observed in the portions corresponding to the red colored layer and the light-shielding layer formed earlier, and the green colored layer was formed. Dry at 80 ° C for 5 minutes, then 3.0% by weight
When developed with the aqueous lactic acid solution, no change was observed in the red and green colored layers, and no change was observed in the part that becomes the light-shielding film. The black photosensitivity of the part where the light transmittance of the negative mask was the third lowest The paint was selectively removed.

After washing with water and drying, the glass substrate was used as an anode, and a stainless steel beaker containing the colored coating material (C-3) was used as a cathode, and electrodeposition was carried out for 3 minutes under the conditions of a DC voltage of 25 V and 25 ° C. When the glass substrate was washed with ion-exchanged water, no change was observed in the red and green colored layers and the light-shielding layer formed earlier, and a blue colored layer was formed. After drying at 80 ° C. for 5 minutes, baking was performed at 175 ° C. for 30 minutes in order to complete the curing. The thickness of each of the colored layers and the light shielding layer after curing was 1.9 μm, and a color filter having a uniform colored layer excellent in transparency was obtained.

[0074]

Example 2 The same glass substrate as used in Example 1 was used as an anode, a stainless steel beaker containing an aqueous solution of the black photosensitive coating (B-2) was used as a cathode, and a DC voltage of 25 V and a temperature of 25 ° C. were used. It was electrodeposited for 3 minutes. After the glass substrate was washed with ion-exchanged water and dried at 80 ° C. for 5 minutes, a black uniform coating film having a film thickness of 1.8 μm and having no tackiness was formed.

Then, a negative mask having different patterns of light transmittance shown in FIG. 2 having four steps was adhered onto the coating film, and 800 mJ / cm ² was applied using the UV exposure device used in Example 1.
Of the ultraviolet rays. When developed with an aqueous solution of sodium carbonate having a concentration of 0.1% by weight, the black photosensitive paint in the portion of the negative mask where the light transmittance is minimum is selectively removed.
The TO film was exposed.

Next, after washing with water and drying, the glass substrate was used as a cathode, and the stainless steel beaker containing the colored coating material (C-4) was used as an anode, and electrodeposition was carried out for 3 minutes at a DC voltage of 30 V and 25 ° C. 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 developed with a 0.75% by weight aqueous solution of sodium carbonate, no change was observed in the red colored layer, and the black photosensitive paint in the portion having the second lowest light transmittance of the negative mask was selectively removed. Was done.

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

After washing with water and drying, electrodeposition was performed for 3 minutes under the conditions of a DC voltage of 30 V and 25 ° C. using a glass substrate as a cathode and a stainless steel beaker containing a colored coating material (C-6) as an anode. When the glass substrate was washed with ion-exchanged water, no change was observed in the red and green colored layers and the light-shielding layer formed earlier, and a blue colored layer was formed. After drying at 80 ° C. for 5 minutes, baking was performed at 170 ° C. for 30 minutes in order to complete the curing. The thickness of each of the colored layers and the light-shielding layer after curing was 1.8 μm, and a color filter having a uniform colored layer excellent in transparency was obtained.

[0079]

[Example 3] The same glass substrate as used in Example 1 was spray-coated with a black photosensitive coating solution (B-3), air-dried, and dried at 80 ° C for 5 minutes. A black uniform coating of 1.5 μm was formed.

Next, a UV exposure apparatus (manufactured by Oak Manufacturing Co., Ltd., trade name "JL-3300" having a high-pressure mercury lamp in contact with a negative mask having a pattern in which the light transmittance shown in FIG. )), 500m
It was irradiated with UV of J / cm ² . When developed with an aqueous solution of lactic acid having a concentration of 0.05% by weight, the black photosensitive paint in the portion of the negative mask where the light transmittance is minimum is selectively removed.
The TO film was exposed.

Next, after washing with water and drying, the glass substrate was used as an anode, and a stainless steel beaker containing the colored coating material (C-1) was used as a cathode, and electrodeposition was performed for 3 minutes under the conditions of a DC voltage of 25 V and 25 ° C. The glass substrate was washed with ion-exchanged water and then dried at 80 ° C. for 5 minutes to form a red colored layer. When developed with 0.5% by weight lactic acid aqueous solution, no change was observed in the red colored layer, and the black photosensitive paint in the portion having the second lowest light transmittance of the negative mask was selectively removed. It was

After washing with water and drying, electrodeposition was performed for 3 minutes under the conditions of a DC voltage of 25 V and 25 ° C., using a glass substrate as an anode and a stainless steel beaker containing a colored coating material (C-2) as a cathode. When the glass substrate was washed with ion-exchanged water, no change was observed in the red colored layer formed earlier, and a green colored layer was formed. When dried at 80 ° C for 5 minutes and then developed with a 3.0% by weight aqueous lactic acid solution, no change was observed in the red and green colored layers, and no change was observed in the part serving as the light-shielding film. The black photosensitive paint in the portion having the third lowest light transmittance was removed selectively.

After washing with water and drying, the glass substrate was used as an anode, and a stainless steel beaker containing the colored coating material (C-3) was used as a cathode, and electrodeposition was performed for 3 minutes under the conditions of a DC voltage of 25 V and 25 ° C. When the glass substrate was washed with ion-exchanged water, no change was observed in the red and green colored layers and the light-shielding layer formed earlier, and a blue colored layer was formed. After drying at 80 ° C. for 5 minutes, baking was performed at 175 ° C. for 30 minutes in order to complete the curing. The thickness of each of the colored layers and the light-shielding layer after curing was 1.5 μm, and a color filter having a uniform colored layer excellent in transparency was obtained.

[Brief description of drawings]

FIG. 1 is a process drawing showing an embodiment of the present invention.

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

[Explanation of symbols]

 1 Light-shielding film equivalent part (light transmittance 100%) 2 First color equivalent part (light transmittance 5%) 3 Second color equivalent part (light transmittance 25%) 4 Third color equivalent part (light transmission) 80%)

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] March 2, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0054

[Correction method] Change

[Correction content]

Synthesis of Photosensitive Resin (A-1) (a-1) 50 in a 2-liter separable flask.
0 g of diethylene glycol dimethyl ether 166.
It was dissolved in 7 g, and (a- 2 ) 713.4 g (0.
(8 equivalent) was added dropwise at 40 ° C., and the mixture was further reacted at the same temperature for 1 hour, and it was confirmed by infrared absorption spectrum analysis that the isocyanate group had disappeared, and (a-1) was added to (a-2).
To obtain a photosensitive resin (A-1).

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0066

[Correction method] Change

[Correction content]

[0066]

[Synthesis Example 8] Preparation of colored coating materials (C-1, C-2, C-3) The half-esterified product (A-3) solution and the pigment were mixed under stirring, and a laboratory three-roll mill (manufactured by Kodaira Seisakusho) ),
The pigment was dispersed until the particle diameter became 0.3 μm or less. The particle size was measured using Coulter Counter N4 (manufactured by Coulter Counter). Next, triethylamine, which is a neutralizing agent, was added to the obtained dispersion mixture, and the mixture was thoroughly stirred and homogenized again. Then, deionized water was slowly added to the dispersion mixture while stirring vigorously with a high-speed mixer to disperse the water to a solid content concentration of 10% by weight. % Of colored paints (C-1, C-2, C-3) were prepared. Obtained three-colored paint ( anion electrodeposition type)
The composition of the aqueous solution is shown in Table 1 (all numerical values in Table 1 are parts by weight).

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0068

[Correction method] Change

[Correction content]

[0068]

[Synthesis Example 9] Preparation of colored paint (C-4, C-5, C-6) The polyamine (A-2) solution and the pigment were mixed under stirring, and the mixture was placed in a laboratory three-roll mill (manufactured by Kodaira Seisakusho). And dispersed until the pigment particle size was 0.3 μm or less. The particle size was measured using Coulter Counter N4 (manufactured by Coulter Counter). Acetic acid, which is a neutralizing agent, was added to the obtained dispersion mixture, and the mixture was thoroughly stirred and homogenized again. Then, deionized water was slowly added to the dispersion mixture while vigorously stirring with a high-speed mixer to disperse the water to a solid content concentration of 10 Weight percent colored paints (C-4, C-5, C-6) were prepared. Table 2 shows the composition of the resulting aqueous solution of the three-color coloring paint ( cationic electrodeposition type).
(The values in Table 2 are all parts by weight).

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0071

[Correction method] Change

[Correction content]

Next, when the film was developed with an aqueous solution of lactic acid having a concentration of 0.05% by weight, the black photosensitive paint in the portion of the negative mask having the lowest light transmittance was selectively removed, and the ITO film was exposed. After washing with water and drying, the glass substrate as an anode and a stainless steel beaker containing a colored coating (C-1) as a cathode, and 3 minutes electrodeposition under conditions of DC voltage 25V, 25 ° C.. After washing the glass substrate with deionized water, 80 ℃
And dried for 5 minutes to form a red colored layer having a film thickness of 2 μm and showing no tackiness at room temperature. When developed with a 0.5 wt% aqueous lactic acid solution, no change was observed in the portions corresponding to the red colored layer and the light-shielding layer, and the black photosensitivity of the portion of the negative mask having the second lowest light transmittance was observed. The paint was selectively removed.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hitoshi Yuasa 8 Chidori-cho, Naka-ku, Yokohama-shi Kanagawa Japan Central Oil Research Institute (72) Inventor Yu Otsuki 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Address: Central Research Institute of Nippon Oil Co., Ltd.

Claims (1)

Claims: (A) A photosensitive coating film is formed on a transparent substrate having a transparent conductive layer on the surface thereof, and a light transmittance of at least 3 is obtained.
A step of exposing through a negative mask having a different pattern at different stages, and (B) an operation of developing and removing the photosensitive coating film on the pattern portion and electrodepositing a colored coating material on the exposed conductive layer to form a colored layer. And a step of forming a colored layer by sequentially repeating the pattern portions corresponding to the light transmittance of the negative mask in the ascending order of light transmittance.