JP3263219B2 - Image forming method of water-based paint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color liquid crystal display,
Electroluminescence display, color fluorescent display, plasma display panel, OA sensor,
The present invention relates to a method for forming an image of a water-based paint for forming a black matrix pattern of a color filter used for a solid-state imaging device or the like.

[0002]

2. Description of the Related Art A method of using graphite for a light-shielding pattern of a television picture tube has been widely used as described in, for example, JP-A-49-32926 and JP-A-53-18381. Have been. However, the formation of a light-shielding pattern in a television picture tube requires a light-shielding surface having a diameter of about 3 mm.
A hole of about 00 μm was formed, the pattern had a wide line width, and its edges were considerably uneven, and the sharpness was low. Therefore, the light-shielding pattern of graphite used for a television picture tube has not been adapted to the conditions of high definition and high sharpness required for a liquid crystal display device, a solid-state imaging device, an OA sensor and the like. The black matrix of this television picture tube is manufactured by the following method. First, a water-soluble negative photoresist is applied to a transparent substrate, exposed to ultraviolet light through a black matrix positive mask, developed and dried, and then a water-soluble paint for a black matrix is applied and dried. Then, the negative photoresist is dissolved and lifted off. In this process, since the photoresist must be water-based, even if this method is applied to a black matrix used in a liquid crystal display device or the like, there are limitations on resolution and pattern shape.

Further, a glass having a hydrophilic surface is subjected to a surface treatment with a silane coupling agent, and a positive photoresist capable of obtaining a pattern having a higher resolution is applied to form a pattern. Even if applied, the water-based paint cannot be applied uniformly, and even if an attempt is made to obtain a pattern of the water-based paint by dissolving and lifting off the positive photoresist, a pattern with a good resolution and a uniform thickness is obtained. No pattern was obtained, and the adhesion of the pattern to the substrate was not good.

On the other hand, in a means for forming a light-shielding pattern of a color filter used in a liquid crystal display device, a metal or a metal oxide is applied to a substrate in a thin film form by vacuum evaporation, sputtering or ion plating. In the method of etching the film, it is necessary to put the substrate of the color filter into and out of the vacuum system, so that the throughput (operability) is poor, and the apparatus is expensive, so that it is difficult to obtain a light-shielding pattern at low cost. Met. A method of depositing chromium, aluminum, tantalum, copper oxide, or the like with a metal has a drawback in that a thin film can be obtained, but the reflection is large when viewed from the transparent substrate side.

A black matrix formed by a photolithographic method (Japanese Patent Laid-Open No. 63-298304) using a photocurable resist in which a black pigment such as carbon black is dispersed is intended to increase the optical density. It was necessary to form a thick thin film. For example, ST
In order to obtain an optical density (absorbance) of 2.2 required for a light-shielding pattern for an N (super twisted nematic) liquid crystal display device, the film thickness needs to be 1.3 to 1.5 μm. In addition, many of these resists are generally dissolved in an organic solvent, and there is an inconvenience in handling from the viewpoint of working environment such as safety and hygiene.

On the other hand, when a light-shielding pattern is formed by a printing method using a printing ink in which a black pigment such as carbon black is dispersed in a resin (JP-A-62-153902), the sharpness of the edge of the light-shielding pattern is reduced. (Cut)
However, in order to obtain an optical density of 2.2, the film thickness had to be about 1.5 μm. In the case of dyeing the resin formed in a pattern with a dye,
In order to make the optical density 2.2, the film thickness should be 1.0 to 1.
It had to be 2 μm. Other conventional technologies include:
As described in JP-A-61-99104, a pattern is formed by applying a photoresist for lift-off on a substrate, and a coloring agent obtained by adding a coloring agent to a thermosetting resin is formed thereon. After applying and curing, there has been a method of forming a color filter pattern by peeling off the photoresist pattern together with a coloring agent on the photoresist pattern. However, it is easy to apply the photoresist uniformly to the substrate, and there is no problem in applying the photoresist uniformly because the liquid obtained by adding the colorant to the thermosetting resin is not an aqueous paint.

Further, when a water-based paint containing a pigment or a dye such as blue, green, or red is applied on a positive photoresist pattern to form a colored pattern by lift-off, the water-based paint is applied uniformly. No sharp pattern could be formed.

Japanese Patent Application Laid-Open No. 59-25223 and Japanese Patent Application Laid-Open No. 60-579 disclose a method of cleaning the surface of a substrate with ultraviolet rays.
No. 37, JP-A-60-58238, JP-A-6-58238
Although described in Japanese Patent Application Laid-Open No. 3-276003, any of the methods is for removing contamination on the substrate surface, and does not disclose the technology as in the present invention.

[0009]

Under the circumstances described above, the present invention provides a film having a thickness of 2 μm or less, preferably 1.0 μm or less.
The purpose of the present invention is to uniformly apply a water-based paint for forming a light-shielding pattern having a high optical density with a thickness of not more than μm, more preferably a small thickness of not more than 0.7 μm. In the present invention, the “pattern” refers to an image-like or uniform solid image. Another object of the present invention is to uniformly apply a water-based paint for forming a colored pattern in a film thickness of 5 μm or less, preferably 2.0 μm or less. Another object of the present invention is to provide a method for uniformly applying a water-based paint by irradiating ultraviolet rays after forming a pattern with a positive photoresist. Also, when a water-based paint is applied after forming a pattern with a positive-type photoresist, and then the positive-type photoresist is dissolved and peeled off to form a pattern of the water-based paint, so-called lift-off, It is another object of the present invention to reduce the concentration of alkali used for dissolution and to reduce the spray pressure of water used for removing unnecessary patterns to prevent the pattern of the water-based paint from being lost. Further, even if the photoresist is immersed in a stripping solution of the positive photoresist in the lift-off process, the photoresist remains as a residual film on the substrate, and the pattern of the light-shielding layer or the coloring layer formed in the opening of the photoresist is peeled off. It is also intended to prevent peeling off. Considering the conservation of the global environment in the future, it is certain that the benefits of water-based paints can be expected, and therefore the need to be able to apply water-soluble paints on any surface condition is solved. It is also intended.

[0010]

According to the present invention, in order to uniformly apply the water-based paint on the pattern of the positive photoresist, electromagnetic radiation is uniformly irradiated on the resist pattern, and then the water-based paint is applied. Solved by the method of application. By irradiating a positive photoresist pattern with electromagnetic radiation, for example, ultraviolet rays, the resist surface is made hydrophilic so that the water-based paint can be uniformly applied,
In addition, since the pattern of the positive photoresist is easily dissolved by alkali at the time of lift-off, the pattern formed by the water-based paint is sharpened, and further, there is no residue of the positive photoresist at the edges and corners of the pattern. Having.

In the present invention, the reason why the waterborne paint can be uniformly applied by irradiating the positive photoresist with electromagnetic radiation is that the quinonediazide compound used in the positive photoresist is changed to indenecarboxylic acid. When exposed to electromagnetic radiation in the presence of air, the oxygen in the air changes to ozone, generating oxygen atoms with reactive activity and cleaning the surface of the resist and substrate. It is considered that the effect of synthesizing acts synergistically to apply the water-based paint uniformly. In addition, the positive photoresist is more easily dissolved in the aqueous alkali solution, so that the adhesion of the pattern of the water-based paint to the substrate after lift-off is increased, and the edge and corner portions are likely to be cut off. Can be Further, an advantage of the present invention is that by irradiating electromagnetic radiation, a positive photoresist can be easily dissolved and peeled off at the time of lift-off, and further, dirt on a transparent substrate is decomposed.

The water-based paint is a paint characterized by containing a medium containing water as a main component, in which fine pigments and / or dyes are dispersed. The coating may include a binder or dispersant. As the pigment, for example, particles of a substance having a layered lattice structure, phthalocyanine pigments, naphthoquinone pigments, azo pigments, anthraquinone pigments, isoindolinone pigments, dioxazine pigments, condensed polycyclic pigments such as quinacridone pigments, Rhodamine B
Lakes, triphenylmethane dyes, carbon black, zinc oxide, titanium oxide, barium sulfate, and the like.

As the binder, there are a water-soluble polymer compound, a water-emulsion type compound, and a copolymer amine or an aqueous ammonia solution containing an acid component for conversion to water. Examples of the water-soluble polymer compound include gelatin, casein, polyvinyl alcohol, polyacrylate, carboxymethyl cellulose,
Examples include water-soluble polyimide. Examples of the water emulsion type include an acrylic emulsion, a vinyl acetate emulsion, and a polyester emulsion. Examples of copolymerized amine or aqueous ammonia solution containing an acid component for aqueous conversion include, for example, vinyl acetate-vinyl chloride copolymer, vinyl acetate-crotonic acid copolymer, acrylic acid-styrene copolymer , Methacrylic acid-
Methacrylic acid ester copolymers; methacrylic acid-acrylic acid copolymers; multi-component copolymers containing methacrylic acid, acrylic acid esters and methacrylic acid esters; butadiene-styrene-methacrylic acid copolymers;

Examples of the dispersant include β-naphthalene sulfonate, alkyl naphthalene sulfonate, lignin sulfonate, alkylbenzene sulfonate and the like.
The cation component of the salt is sodium, potassium, ammonium or the like. In addition, known nonionic surfactants such as alkyl or aryl ethers of polyethylene glycol can also be used. The use amount of the dispersant is appropriately 0.2 to 20% based on the weight of the particles, and if the amount of the dispersant is small, the dispersion of the particles is incomplete,
If the amount is too large, defects such as poor water resistance of the coating film and thickening of the coating film occur.

Examples of substances having a layered lattice structure that can be used as water-based paints are described in detail below. The particle diameter of the substance is 3 μm or less, the amount of particles having a particle diameter of 0.1 μm or less is 40 to 95% by weight, and the average particle diameter is 0.0
5 to 0.08 μm and an aspect ratio of 1:10 or more.

As the substance having a layered lattice structure, graphite,
There are molybdenum disulfide, tungsten disulfide, boron nitride, graphite fluoride, selenium sulfide, mica, talc, enstatite and the like, and one or more of these can be used in combination. Further, these layered lattice structural materials can be combined with pigments and dyes. Pigments and dyes are used to change the color tone of the light-shielding pattern.

The layered lattice structure material is crushed into flakes using a crusher such as a ball mill, a roll mill, and a sand mill.
The particle size distribution and the aspect ratio (the ratio between the thickness and the width of the particles) are adjusted. By pulverizing the layered lattice structure material, the layers are separated, and flaky fine particles can be obtained. The particle size distribution is a value measured using an optical particle size distribution measuring device. This particle size distribution has been determined in accordance with demands such as being as fine as possible and being obtained efficiently and economically. When a particle having a large particle diameter is used, it is necessary to make the film thick to obtain a film having a high optical density. Specifically, if the diameter of the particles of the layered lattice structure material is larger than 3 μm, the shape of the light-shielding pattern is not uniform, which is not preferable. Also, it is desirable that most of the particles have a diameter of 0.1 μm or less,
If the amount of the particle group of 0.1 μm or less is less than 40% by weight, the adhesive strength to the substrate will be weak, and if it is more than 95% by weight, the productivity will be poor, and both are not preferred. Further, as described above, the average particle diameter is preferably in the range of 0.05 to 0.08 μm. When the average particle diameter is larger than this range, the shape of the light-shielding pattern becomes non-uniform, and when it is small, the productivity is poor. It is still not preferred. The aspect ratio needs to be 1:10 or more, and this value is 1: 1.
If it is smaller than 0, the optical density of the formed film cannot be increased. Incidentally, 1:10 or more means that the width dimension is 10 or more with respect to the thickness 1 of the particles. When a paint in which such fine flaky particles are dispersed is applied to a glass substrate and dried, the particles are arranged flatly on the surface of the substrate, forming a thin and dense coating film, and have an adhesive property with a transparent substrate. Becomes better.

The coating material is prepared by mixing the above light-shielding powder with water together with a dispersant such as sodium β-naphthalenesulfonate, sodium alkylnaphthalenesulfonate, sodium ligninsulfonate and the like. The amount of the dispersing agent is 0.
If the amount of the dispersant is small, the dispersion of the particles becomes incomplete, and if the amount is too large, defects such as poor water resistance of the coating film and thickening of the coating film occur.

The content of the light-shielding powder in the water-based paint is not specified because it can be variously adjusted depending on the method of application and the size of the transparent plate to be applied, but is usually about 2 to 30% by weight, preferably about 25% by weight. It is. When the content of the light-shielding powder is small, there is a concern that the coating is too thin and the optical density becomes low. When it is too large, the coating becomes thick and the variation in thickness becomes large. The water-based paint should be used to prevent the pattern from being damaged when applied to the pattern of the positive photoresist.
It is desirable that H be 11 or less.

As the positive type photoresist, those containing a diazonium salt, a 1,2-naphthoquinonediazide derivative or a 1,2-quinonediazide derivative compound as a photosensitive group are often used. Diazonium salts are not preferred in the present invention because they change from water-soluble to oil-soluble upon light irradiation. On the other hand, a 1,2-naphthoquinone cyanazide compound or a 1,2-quinonediazide compound is a preferred photosensitive group for the present invention since it becomes soluble from an organic solvent to an aqueous alkali solution by light irradiation. Positive photoresists have 1,2-
Compounds containing naphthoquinonediazides, for example, compositions containing o-naphthoquinonediazidesulfonic acid ester (NQD) and a novolak resin are well known. The novolak resin alone is water-soluble, but becomes water-insoluble when coexisting with NQD, and NDQ is decomposed by light irradiation to generate an indenecarboxylic acid through a rearrangement reaction, thereby promoting the water solubility of the novolak resin.

Many positive photoresists are used as a composition containing a 1,2-quinonediazide compound and a novolak resin as described above.
PR series or PMER series, FPPR series, FHPR series of Fuji Pharmaceutical, Microposit series of Shipley, AZ series of Hoechst, PFR-3003 of Nippon Synthetic Rubber, WAYCOAT-HPR, WAY COAT- of Hunt Chemical
MPR and the like can be used in the method of the present invention. In addition, as the positive type photoresist, one that responds to radiant energy such as near infrared rays, electron beams, and ion beams in addition to ordinary ultraviolet rays or near ultraviolet rays can also be used.

The 1,2-quinonediazide compound contained in the positive photoresist used in the present invention is not particularly limited, but for example, 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2 Examples thereof include naphthoquinonediazide-4-sulfonic acid ester, 1,2naphthoquinonediazide-4-sulfonic acid ester, and 1,2naphthoquinonediazide-5-sulfonic acid ester. Specifically, p-cresol-1,2
1,2 (poly) hydroxybenzene such as benzoquinonediazide-4-sulfonic acid ester, resorcin-1,2-naphthoquinonediazide-4-sulfonic acid ester, pyrogallol-1,2-naphthoquinonediazide-5-sulfonic acid ester -Quinonediazidesulfonic acid esters, 2,4-dihydroxyphenyl-propyl ketone-1,2-benzoquinonediazide-4-sulfonic acid ester, 2,4-dihydroxyphenyl-n-hexylketone-1,2-naphthoquinonediazide-4 -Sulfonic acid ester, 2,4-dihydroxybenzophenone-
1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4-trihydroxyphenyl-n-hexylketone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone -1,2-naphthoquinonediazide-4-sulfonic acid ester and the like can be mentioned.

The novolak resin, which is important as a component of the positive photoresist, is synthesized by addition condensation of hydroxynaphthalenes (A) and aldehydes in the presence of an acid catalyst. Hydroxynaphthalenes can be used alone or in combination of two or more. The novolak resin used in the present invention may be a condensate with a phenol (B) that can be addition-condensed with the hydroxynaphthalene (A). The co-condensation ratio between the hydroxynaphthalenes (A) and the phenols (B) is preferably (A) / (B) = 10/90 to 100/0 in terms of molar ratio, and is preferably (A) / (B). = 30/70 to 100/0. Further, as the aldehydes, preferably, formaldehyde, acetaldehyde, benzaldehyde and the like can be mentioned. The aldehyde is used in a ratio of 0.7 to 3 mol, preferably 1.1 to 2 mol, per 1 mol of the total of the hydroxynaphthalenes (A) and the phenols (B). As the acid catalyst, inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid and organic acids such as benzenesulfonic acid, formic acid and acetic acid are used. The use amount of these acid catalysts is preferably 1 × 10 ^{-4 to} 5 × 10 ^-1 mol per 1 mol of the total of the hydroxynaphthalenes (A) and the phenols (B). In the condensation reaction, water is usually used as a reaction medium, but the hydroxynaphthalenes (A) and phenols (B) used in the condensation reaction do not dissolve in the aqueous solution of the aldehyde and become heterogeneous from the beginning of the reaction. In such a case, a hydrophilic solvent can be used as a reaction medium.

Examples of the solvent include alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and cyclic ethers such as tetrahydrofuran and dioxane. The amount of the reaction medium used is generally 50 to 1000 parts by weight per 100 parts by weight of the reaction raw material. The reaction temperature during the condensation reaction can be appropriately adjusted according to the reactivity of the reaction raw materials, but is usually from 10 to 150 ° C, and preferably from 70 to 130 ° C.

The positive photoresist composition of the present invention is prepared by dissolving the alkali-soluble novolak resin and a 1,2-quinonediazide compound in a solvent,
It is prepared by dissolving a compound in which a 2-quinonediazide compound is bonded to a novolak resin in a solvent. As the solvent, for example, ethylene glycol monomethyl ether, glycol ethers such as ethylene glycol monoethyl ether, methyl cellosolve acetate, cellosolve esters such as ethyl cellosolve acetate,
Examples include aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone and cyclohexanone, and esters such as ethyl acetate and butyl acetate. Further, two or more of these solvents may be used as a mixture. The compounding amount of these 1,2-quinonediazide compounds is 100% of the alkali-soluble novolak resin.
5 to 100 parts by weight, preferably 5 to 100 parts by weight
To 10 parts by weight. If the amount is less than 5 parts by weight, the 1,2-quinonediazide compound absorbs electromagnetic radiation and generates a small amount of carboxylic acid, which makes patterning difficult.
On the other hand, when the amount exceeds 100 parts by weight, all of the added 1,2-quinonediazide compound cannot be decomposed by short-time irradiation with electromagnetic radiation, and it becomes difficult to perform development with a developer composed of an alkaline aqueous solution.

Examples of the developer for the positive photoresist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, and n-propyl. Primary amines such as amines, secondary amines such as diethylamine and di-n-propylamine,
Triethylamine, tertiary amines such as methyldiethylamine, diethylethanolamine, alcoholamines such as triethanolamine, tetramethylammonium hydroxide, aqueous solutions of alkalis such as quaternary ammonium salts such as tetraethylammonium hydroxide, pyrrole, Aqueous solutions of cyclic amines such as piperidine, 1,8-diazabicyclo (5,4,0) -7-undecene and 1,5-diazabicyclo (4,3,0) -5-nonane are used and contain metals. When manufacturing an integrated circuit or a liquid crystal display device in which the use of a developer is problematic, it is preferable to use an aqueous solution of a quaternary ammonium salt or a cyclic amine. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as alcohols such as methanol and ethanol or a surfactant to the aqueous solution of the above-mentioned alkalis can also be used for the developer.

The application of the positive photoresist and the water-based paint onto the substrate is carried out by a usual coating technique, that is, a roll coating method, an air knife coating method, a doctor blade coating method, a spray coating method, a gisa coating method, or the like. Alternatively, an applicator, a bar coater, a spin coater or the like is used. In addition, coating is performed by a coating method such as screen printing or offset printing so that the film thickness after drying is preferably about 0.01 to 50 μm, particularly preferably about 0.1 to 10 μm. Normal,
This is pre-baked at about 50 to 130 ° C. using a heating means such as a hot plate or an oven, image-exposed, developed, and dried. Next, the entire surface of the positive photoresist pattern is irradiated with electromagnetic radiation such as ultraviolet rays.

Next, the method of forming the pattern of the water-based paint is as follows.
This will be described in more detail by taking graphite as an example. The substrate is a glass plate such as borosilicate glass or SiO
₂ or SiN _X thinly coated glass plate, optical resin plate (for example, polymethyl methacrylate, polystyrene,
Transparent or thinly colored members such as resin films such as cyclohexyl methacrylate), polymethyl methacrylate, polyester, polybutyral, polyamide, and polyimide. When the substrate is a film-like substance, a material having a multilayer structure instead of a single-layer structure can be used. The film-like substance can be multilayered by melt extrusion or solution coating. The coating resin applied to the unstretched film is in a state of being coated with an extremely thin film (for example, submicron) by stretching. Examples include multilayer films such as polyester films coated with polyvinylidene chloride in-line or hydrophilic polymers (terephthalic acid, adipic acid, sodium sulfoisophthalate, ethylene glycol copolymer, etc.).
As the polymer to be applied, either a water-soluble or oil-soluble polymer may be used.

The above-mentioned substrate is formed by integrally forming a light-shielding pattern with a light-shielding pattern to be applied. For example, in the case of a liquid crystal display device, a glass plate or an ITO
(Indium tin oxide) is a glass plate provided in a pattern, or a color filter element in which ITO is formed into a matrix, and in the case of a specific TFT liquid crystal element and solid-state imaging element, the light receiving surface may be used. ,
In the case of a color sensor, it is also the light receiving surface. Further, an insulating layer may be provided on the light receiving surface. First, a positive photoresist is applied to a substrate. The exposed portion of this resist is dissolved in a developing solution to form a so-called positive pattern.

After the positive photoresist layer is applied and prebaked (prebaked), the film thickness is 5 μm or less, preferably 1.5 μm or less. In the subsequent process, when applying the water-based paint uniformly on the photoresist pattern, and when removing and removing the water-based paint film by lifting off with the photoresist according to the pattern of the positive photoresist below The film thickness is an important factor for improving the sharpness of edges and the sharpness of corners of the light-shielding pattern portion and / or the colored portion. The thickness of the water-based paint is preferably 0.6 times or more and 2.0 times or less of the positive photoresist. The line width of the light-shielding pattern is 10 to 100 μm in a liquid crystal display element, but a line width of 3 to 8 μm may be required as a light-shielding pattern for alignment. In this case, it is particularly important to form the photoresist pattern accurately using a positive photoresist as in the present invention and to increase sharpness.

After the coated and dried positive photoresist film is exposed through a mask, it is developed with an aqueous solution containing an alkali or an acid and dried to obtain a positive photoresist pattern. The mask is formed by forming Cr, Ni, Mo, Ta, Zr, A on a transparent plate such as a glass plate.
A material having a light-shielding film formed of a metal such as g or Cu, or an oxide thereof is used. Alternatively, a photographic film mask can be used.

Next, after irradiating the entire surface of the substrate provided with the positive photoresist pattern with electromagnetic radiation, an aqueous paint is applied and dried. In addition, it prebakes as needed and forms a coating film of a water-based paint. The electromagnetic radiation preferably has a wavelength in the range of 180 to 450 nm. As an electromagnetic radiation source, one that emits light having a wavelength of at least 300 to 420 nm, which is the photosensitive wavelength of a positive photoresist, is required, and 2 to 165 to 205 nm and 235 to 275 nm are required.
Lamps that generate ultraviolet rays of various wavelengths and convert oxygen in the air into ozone can also be preferably used. Generally, when a low-pressure mercury lamp is turned on in air, the wavelength is 160 to
Ultraviolet light of 400 nm is emitted to the outside, and light of another wavelength is slightly emitted. Thus the wavelength is 160-40
It is known that oxygen in the air is converted to ozone by ultraviolet light of 0 nm, which is decomposed to generate oxygen atoms having reactive activity, and this oxygen decomposes organic components in the coating film and scatters them in a gaseous state. ing. Therefore, in the present invention, a method of irradiating ultraviolet rays as described above and simultaneously generating ozone by ultraviolet rays is also practical. As the lamp that generates ultraviolet light, a lamp that generates ultraviolet light having a wavelength of 160 to 400 nm, such as a low-pressure mercury lamp, a xenon lamp, a metal halide lamp, or a carbon arc lamp, is suitable. In addition, a laser that is coherent and capable of fine processing is preferably used. As the above-mentioned mercury lamp, a high-pressure mercury lamp mainly having a wavelength of 366 nm, a low-pressure mercury lamp which simultaneously emits light having wavelengths of 253.7 nm and 184.9 nm can be used. As a laser, an excimer laser emitting short-wavelength and high-output light can be used in addition to lasers such as Ar, He—Cd, and N ₂ . An excimer laser is preferably used because it gives high energy to a substrate in a short time and can greatly modify the substrate chemically and physically.

The irradiation amount of the electromagnetic radiation is 10 mJ /
cm ² or more and up to 2000 mJ / cm ² . 10
When the irradiation amount is less than mJ / cm ² , the surface of the positive photoresist cannot be made hydrophilic by exposing the positive photoresist. If it is more than 2000 mJ / cm ² , there is a concern that the surface of the substrate may be damaged. Further, the ozone concentration upon irradiation with electromagnetic radiation is preferably 0.001% by volume or more in order to wash the coated surface of the water-based paint without the positive photoresist, and the irradiation amount of electromagnetic radiation or the amount of electromagnetic radiation and If the ozone concentration is low, it is difficult to sufficiently exert the effects of the present invention. Irradiating the positive photoresist pattern of the present invention with electromagnetic radiation synergistically utilizes the effect of easily dissolving the positive photoresist in alkali, unlike general surface cleaning. The irradiation time of the electromagnetic radiation varies depending on the light source and the optical system, but is usually about 5 seconds to 10 minutes, preferably 10 seconds to 4 minutes.
The temperature at that time is usually 15 to 100 ° C., preferably 20 to 100 ° C.
~ 50 ° C.

The detailed reason why the pattern and the coated surface of the positive photoresist of the water-based paint are modified by the present invention is unknown. It is presumed that the former is converted to indene carboxylic acid by the chemical change due to ozone, and the latter is reformed to form hydrophilic carboxyl groups and hydroxyl groups, etc., which are taken to be hydrophilically modified. In addition, various electron beam accelerators, Cockloft-Walson type, Bande graph type, resonance transformer type and other electron beam processing are also effective. The irradiation dose is 1 to 5
About 0 Mrad is used. Further, a conventional ion beam irradiation apparatus is used for the ion treatment, and irradiation is performed partially or on a fine pattern by using a mask or a collected ion beam. Various ions can be used as the ions, and are not particularly limited. He ⁺ , Ar ⁺ , C ⁺ , and N ⁺
And the like. Further, a preferable value of the ion energy is 0.05 Kov to 500 Ko.
When the value is less than this value, the effect is small, and when the value exceeds this value, the ash of the base material remarkably progresses, which is not preferable.

The thickness of the water-based paint film is 5 μm or less. The lower limit of the thickness is determined according to the required optical density of the light-shielding pattern. In the case of a TN (twisted nematic) or STN (super twisted nematic) liquid crystal display element, the optical density of the light-shielding pattern is 1.8 or more, preferably Since it is 2.2 or more, most preferably 2.5 or more, the film thickness of the coating film is 0.16 μm or more, preferably 0.1 μm or more.
It is at least 2 μm, most preferably at least 0.25 μm.
In the case of a TFT (thin film transistor) liquid crystal display element, the optical density of the light-shielding pattern is 2.5 or more, more preferably 3.0 or more.
It is at least 3 μm, more preferably at least 0.35 μm.
In the case of a liquid crystal color filter, the upper limit of the thickness of the coating film is determined by the process of forming the RGB colored pixels in the subsequent process. And the sharpness (cut) of the edge of the colored pixel is improved.

When RGB colored pixels are formed by a photofabrication method using a pigment-containing photoresist, the thinner the coating film, the more uniformly the pigment-containing resist can be coated on the light-shielding pattern, and the more uniform the radial unevenness. There are few defects such as (striation). Further, unevenness in the unevenness of the surface of the colored pixel is reduced.

After forming the coating film of the water-based paint, the non-light-shielding pattern portion is dissolved or / stripped together with the photoresist pattern to form a light-shielding pattern by dipping or spraying in a positive photoresist stripping solution or an etching solution. I do. In the case of a positive type photoresist, a so-called organic alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or tetraalkylammonium hydroxide (an alkyl group such as methyl, ethyl, or isopropyl) is dissolved in water. A dissolved alkaline aqueous solution is used. The alkaline aqueous solution has an alkali concentration of 0.1 to 4% by weight. When the positive photoresist is hardly soluble in alkali, re-exposure to make the positive photoresist more soluble in an alkaline aqueous solution and then applying a stripping solution may have an effect. Alternatively, an etching solution containing 1 to 20% by volume of an organic solvent, for example, an alcohol such as acetone, ethyl alcohol, or isopropyl alcohol, ethyl cellosolve or ethyl cellosolve monoacetate may be effective.

According to the method of forming a pattern coating film of the present invention,
A coating film can be formed uniformly using an aqueous paint. In the case of a light-shielding coating film, a coating thickness of 0.15 μm shows an absorbance of 2.0 or more, and a coating thickness of 0.3 μm shows an absorbance of 3.0 or more. good. for that reason,
In a liquid crystal color display device, malfunction due to external light or stray light of a TFT can be eliminated. In contrast, in the case of a conventional light-shielding film made of carbon black, in order to obtain the same light-shielding rate as that of the light-shielding film of the present invention, the thickness of the coating film must be increased three to four times.

The light reflectance of the light-shielding film when irradiated with light at an angle of 45 ° from the glass surface side using a variable-angle gloss measuring device (Model VP-1001DP) manufactured by Nippon Denshoku Industries Co., Ltd. is standard. The black plate is 84, and the conventional carbon black is 2
52, and 756 for the metal chromium vapor-deposited film, and 87 for the graphite coating film of the light-shielding film of the present invention, which is extremely low in reflection. Note that the image display surface provided with each coating of graphite, molybdenum disulfide, tungsten disulfide, boron nitride, graphite fluoride, selenium sulfide, mica, talc, enstatite, etc. has a unique color tone. You can choose.

The paint used in the method of the present invention uses water as a medium, has no danger of fire in the coating film forming process, has no effect on the human body, and is safe and sanitary. Furthermore, the cost of solvent recovery equipment and disposal equipment required when using conventional organic solvent type paints is greatly reduced, and ordinary water can be used for cleaning equipment and diluting paints. You can save money.

[0041]

【Example】

<Embodiment 1> The present invention will be further described below with reference to embodiments. Natural flaky graphite with a particle size of about 5 μm
It was placed in a 0%, 5 liter ball mill and ground at 40 revolutions per minute for 30 hours. The particle size measured by a light transmission type particle size distribution analyzer was 1 μm or less in particle size, the amount of particles having a particle size of 0.1 μm or less was 85% by weight, and the average particle size was 0.06 μm. A paint was prepared using this graphite. The above graphite particles 1
0% by weight, 1% by weight of aqueous ammonia as a binder (1% by weight of sodium β-naphthalenesulfonate as a dispersant, concentration of 28% by weight), and the remaining water were blended, and these were mixed with a high-speed stirrer [special machine Chemical Industry Co., Ltd., homomixer M type]
For about 3 hours to prepare a graphite paint. P of this paint
H was 10.8.

Next, a positive photoresist (PME manufactured by Tokyo Ohka Co., Ltd.) was applied to a glass plate treated with a silane coupling agent.
R-6020EK) with a spinner and dried to form a film having a thickness of 0.9 μm. An ozone-less ultra-high pressure mercury lamp was irradiated with an i-line sensor at 40 mJ / cm ² through a shadow mask having a circular hole, developed with a 0.7% aqueous sodium hydroxide solution, washed with water, and washed to a thickness of about 0.2 μm. A disc-shaped stencil was formed. Next, after irradiation with an ozone-less ultra-high pressure mercury lamp at 500 mJ / cm ² , the above coating material was applied on a glass plate on which a stencil was formed, and dried to form a coating film having a coating thickness of 0.6 μm. After immersing the glass plate on which the coating is formed in a positive resist stripping solution containing 1.5% sodium hydroxide at a temperature of 25 ° C.,
Pure water at a pressure of 5 kgf / cm ² was sprayed on the coating surface to remove the resist layer of the stencil together with the coating film thereon, thereby completing a black paint layer in a circular hole. After the prepared samples were fired at 250 ° C. for 1 hour, each sample was immersed in a solution of various chemicals for 1 hour, and the state of missing coating films was observed. The chemical solution used for the durability test was a 1N aqueous sodium hydroxide solution,
There are six types of aqueous hydrochloric acid, acetone, isopropyl alcohol (IPA), normal methylpyrrolidone (NMP), and ethyl carbitol acetate (ECA). After immersion for 30 minutes in general, a cross-cut test was performed. The sample using the coating material according to the present invention did not show any change in any of the chemicals without peeling off the tape for cross-cutting.

Further, durability was evaluated. The sample was boiled in boiling water for 60 minutes and then dried, and an adhesive tape was stuck to the surface of the coating film and separated, and the state of peeling of the coating film was observed. This tape peeling test is based on JIS K5631 (oil-based paint for steel ship outer panel). No peeling was observed in any of the samples, indicating that the samples exhibited water resistance. Next, of the coating composition using the graphite particles, a coating material was prepared by replacing the graphite particles with carbon black, and a coating film was formed on a glass plate in the same manner as in the sample preparation described above to obtain a comparative sample. The thickness of the coating is 2 μm
It is. Further, the optical densities of the light shielding films of both samples were compared.
The optical density of the light-shielding film (thickness: 0.7 μm) of the sample of the present invention was 3.0, and the optical density of the light-shielding film (thickness: 2 μm) of the comparative sample using carbon black was 2.1. In addition, the light-shielding property of the coating film using the graphite particles was excellent.

<Example 2> After a silane coupling agent was adsorbed on a glass plate having a silicon dioxide film formed on a blue plate glass, a positive photoresist (ZP manufactured by Zeon Corporation: ZP) was used.
P-1700) with a spinner, followed by drying.
A μm coating film was formed. The i-line is 40 mJ / through a mask (negative mask) where the black matrix is transparent.
After irradiation with cm ² , the film was developed with a 0.4% aqueous sodium hydroxide solution at 23 ° C., washed with water, and dried at 90 ° C. to form a reverse pattern of a black matrix. This was irradiated with ultraviolet light including light of 185 nm and 253 nm from the back surface of the glass for 90 seconds by a UV cleaning device. Next, the black aqueous coating composition of Example 1 was applied on the pattern of the positive photoresist and then dried to form a coating having a coating thickness of 0.6 μm. The glass plate on which the coating is formed is immersed in a positive resist stripping solution containing 1.5% sodium hydroxide at a temperature of 25 ° C., and pure water at a pressure of 3 kgf / cm ² is sprayed on the coating surface to form a positive photoresist. The layer was removed along with the coating thereon to complete the black matrix. After baking the above sample at 250 ° C for 1 hour, in a solution of various chemicals,
Each sample was immersed for one hour, and the state of lack of the coating film was observed. The chemical solution used for the durability test is the same as the chemical used in Example 1. After immersion for 30 minutes by a conventional method, a cross cut test was performed. The black matrix did not peel off on the cross-cut tape in any of the chemicals, and no change was observed. Further, a durability evaluation test was performed as in Example 1. No peeling was observed in any of the samples, indicating that the samples exhibited water resistance.

Example 3 A borosilicate glass was coated with a positive photoresist (PMER-6020E manufactured by Tokyo Ohka Co., Ltd.).
K) was applied and dried using a spinner to form a film having a thickness of 0.8 μm. The i-line is 30 m through a transparent mask (negative mask) with a 20-micron wide black matrix.
After irradiation with J / cm ² , the film was developed with a 0.5% aqueous sodium hydroxide solution at 23 ° C., washed with water, and dried at 110 ° C. for 10 minutes to form an inverse pattern of a black matrix. UV cleaning equipment (Takizawa Sangyo Co., Ltd. dry cleaner)
185 nm, 253.7 nm, 282.1 nm,
Ultraviolet light including light of 302.2 nm, 313.2 nm, and 365.0 nm was irradiated on the pattern of the positive photoresist for 120 seconds. Next, a water-based paint containing a water-dispersible phthalocyanine pigment in an amount of 5% by weight of graphite was prepared in the black water-based paint used in Example 1, applied on a positive photoresist pattern, and then dried. A coating of 0.6 μm was formed. The glass plate on which this coating was formed was heated at a temperature of 2
After dipping in a positive resist stripper containing 1.5% sodium hydroxide at 5 ° C., pure water with a pressure of 4 kgf / cm ² was sprayed on the coating surface to remove the positive photoresist layer together with the coating thereon. , Completed the black matrix. The black matrix had sharp patterns formed at the edges and corners, and had an optical density of 3.2.

Comparative Example 1 A borosilicate glass was coated with a positive photoresist (PMER-6020E manufactured by Tokyo Ohka Co., Ltd.).
K) is applied with a spinner and dried, and the film thickness is 0.8 μm
Was formed. A portion of a 20 μm-wide black matrix is exposed to 30 i-lines through a transparent mask (negative mask).
After irradiation with mJ / cm ^{2, the} film was developed with a 0.5% aqueous sodium hydroxide solution at 23 ° C., washed with water, and dried at 110 ° C. for 10 minutes to form a reverse pattern of a black matrix. At that time, no ultraviolet light was applied, and an aqueous paint containing the water-dispersible phthalocyanine pigment in an amount of 5% by weight of graphite was applied to the black aqueous paint of Example 3 on a positive photoresist pattern, dried, and dried. Of 0.6 μm was formed. However, the coating film of the water-based paint was uneven in some places, and the outermost periphery was not coated with the water-based paint, and the film thickness on the inner side was thick. The glass plate on which the coating is formed is immersed in a positive resist stripping solution containing sodium hydroxide at a temperature of 25 ° C. and 1.5% at a temperature of 25 ° C. Then, pure water at a pressure of 4 kgf / cm ² is sprayed on the coating surface to form a positive-type photo resist. The resist layer was removed together with the coating thereon to prepare a black matrix. In the thick film portion of the black matrix, sharp patterns are not formed at the edges and corners, there is a residual film at the corners, and the black film of the portion to be removed by lift-off partially remains. I was The optical density of the uniformly applied portion was 3.2.

Example 4 Fastogen Blue GNPS
10 parts by weight (manufactured by Dainippon Ink and Chemicals, Inc .: copper phthalocyanine blue pigment) were mixed with a resin solution in which 12 parts by weight of casein was dissolved in 88 parts by weight of a 1% aqueous ammonia solution, and the resulting mixture was sand-milled. After mixing and dispersing in
The mixture was centrifuged at 0 rpm and filtered through a 1 μm glass filter. The obtained colored resin solution was spin-coated at a film thickness of 1 μm on a positive photoresist pattern produced in the same manner as in Example 3, and then dried at 90 ° C. for 10 minutes. Then
After immersion in a 1% aqueous solution of potassium hydroxide for 30 seconds, the positive photoresist was selectively removed by spray development to form a blue matrix image. This blue matrix image has a light transmittance of 1 at a wavelength of 560 to 700 nm.
% Or more, the transmittance at 440 to 520 nm was 85% or more. When the particle size of the pigment was measured,
Particles having a particle size of 0.01 to 0.3 μm are 9% of all particles.
It was 0%.

Example 5 Chromophthal Red BRN
3 parts by weight (red pigment manufactured by Ciba-Geigy) are mixed with 10 parts by weight of a 10% aqueous solution of polyvinyl alcohol having an average degree of polymerization of 500 and a saponification degree of 88 mol%. The obtained mixture is mixed by a sand mill, and then centrifuged at 10,000 rpm. Separated and filtered through a 1 μm glass filter. Next, 2 parts by weight of the obtained aqueous adhesive and 88 mol% of saponified polyvinyl alcohol (degree of polymerization 1700) were added to N-ethyl-γ-
A red photosensitive resin composition was prepared by sufficiently mixing with 10 parts by weight of a photosensitive resin into which 1.5 mol% of (p-formylstyryl) -pyridinium methosulfate was introduced. Further, the substrate prepared by applying a positive photoresist to glass to a thickness of 0.7 μm through a transparent chrome mask through a transparent chrome mask is exposed to 35 mJ / cm ² from an i-line lamp and developed. A 1.5 μm-thick film was coated on the positive photoresist pattern by a spinner, dried at 70 ° C. for 30 minutes, and then dried with a UV cleaner (Takizawa Sangyo Co., Ltd. dry cleaner). After irradiating the entire surface for 60 seconds, the red photosensitive composition was applied to a thickness of 1.5 μm and dried. After being immersed in a 1% aqueous solution of potassium hydroxide for 60 seconds, water is sprayed to selectively remove portions of the positive photoresist,
Heating at 0 ° C. for 30 minutes formed a red image. This red image was excellent in transparency, and the edge shape was almost the same as that of the conventional negative-type red photoresist.

Example 6 4.4 parts by weight of polyoxyethylene nonyl phenyl ether was added to 15 parts by weight of carbon black having a maximum particle size of 0.3 μm or less and an average particle size of 0.04 μm, and mixed well. After that, pure water 80.6
The mixture was placed in a weight part and stirred with a high-speed stirrer (Homomixer M type manufactured by Tokushu Kiko Co., Ltd.) for about 3 hours to obtain an aqueous carbon paint. A positive photoresist (PMER-6020EK manufactured by Tokyo Ohka Co., Ltd.) was applied to borosilicate glass with a spinner and dried to form a 0.8 μm-thick film. 20
After irradiating 30 mJ / cm ^{2 of} i-line through a transparent mask (negative mask) except a part of a black matrix having a micron width, the film was developed with a 0.5% aqueous sodium hydroxide solution at 23 ° C., washed with water, and washed at 110 ° C. For 10 minutes to form a reverse pattern of a black matrix. 185 UV-cleaning equipment (Takizawa Sangyo Co., Ltd. dry cleaner)
nm, 253.7 nm, 282.1 nm, 302.2 n
Ultraviolet rays including light of m, 313.2 nm and 365.0 nm were irradiated on the positive photoresist pattern for 120 seconds. Next, this was applied on the reverse pattern of the black matrix and dried to form a coating film having a thickness of 4 μm.
The glass plate on which this coating film was formed was heated at a temperature of 25 ° C. for 1.5 times.
%, Sodium hydroxide, then immersed in a positive photoresist stripper, spraying pure water at a pressure of 3 kgf / cm ² on the coating surface to remove the positive photoresist layer together with the coating thereon, thereby removing the black matrix. completed. After the prepared samples were fired at 250 ° C. for 1 hour, each sample was immersed in a solution of various chemicals for 1 hour, and the state of missing coating films was observed. The chemical solution used in the durability test was the same as the chemical used in Example 1. After immersion for 30 minutes in a conventional manner, a cross cut test was performed. Black matrix is
In any of the chemicals, no change was observed without peeling off the tape for cross-cutting. However, the optical density of this light-shielding film was 2.9, which was lower than that of Example 3.

[0050]

The light-shielding pattern formed by the paint of the present invention is formed after forming a positive photoresist pattern.
Irradiation with ultraviolet light makes it easy to apply the water-based paint uniformly, and has a feature that the edges and corners of the pattern of the water-based paint can be sharpened after lift-off. In addition, the adhesion between the transparent substrate and the water-based paint film and the weather resistance and chemical resistance of the paint film are good, and since they have excellent light-shielding properties and low light reflectivity,
Image quality of a color liquid crystal display device or the like can be further improved. In addition, since it is a water-based paint, it is easier to handle, more hygienic, and can be provided at lower cost than a conventional paint using an organic solvent.

Continuing from the front page (72) Inventor Tomasa Tsuboi 6-15, Minamishinagawa, Shinagawa-ku, Tokyo Toyo Paper Industry Co., Ltd. (72) Inventor Shinichi Tatezono 1519 Mito, Takomachi, Katori-gun, Chiba 56) References JP-A-4-131857 (JP, A) JP-A-1-217303 (JP, A) (58) Fields studied (Int. Cl. ⁷ , DB name) G02B 5/20 101 G02F 1 / 1335 505

Claims (3)

(57) [Claims] 1. A pattern is formed on a substrate using a positive photoresist, and after irradiating electromagnetic radiation having a wavelength of 180 to 450 nm , a water-based paint is applied and dried, followed by drying. A method for forming an image of a water-based paint, comprising dissolving or stripping a pattern of a positive photoresist with a photoresist stripper. 2. The image forming method according to claim 1, wherein an aqueous paint in which a fine particle pigment and / or a dye is dispersed in a medium containing water as a main component is used as the aqueous paint. Wherein irradiation injection amount of the electromagnetic radiation 10 to 200
The image forming method according to claim 1 which is 0 mJ / cm ^2.