JP2002082448A - Method for forming resist pattern and method for manufacturing color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming resist patterns which is capable of easily removing a resist remaining in the outer peripheral part of a substrate and a method for manufacturing a color filter. SOLUTION: This method of forming resist patterns consists of forming patterns by applying resist containing a photosensitive resin by a spin coating method on the substrate, then exposing the resist through a photomask and developing the resist. In this method, a resist releasable material is at least applied at the corner parts in the outer peripheral part of the substrate and thereafter the resist is applied on the substrate. The method for manufacturing the color filter consists in using a surfactant or developer as the resist releasable material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a resist pattern and a method for manufacturing a color filter used in a color liquid crystal display device or the like, and more particularly, to a resist having improved removal properties of a resist remaining on a peripheral portion of a substrate. The present invention relates to a pattern forming method and a color filter manufacturing method.

[Prior art]

[0002] A color filter used in a color liquid crystal display device is one in which a pattern of a transparent coloring layer colored red, green, blue or the like is regularly arranged on a transparent substrate such as a glass substrate. For the formation of each colored pattern, a pigment dispersion method is widely used in which a color resist composed of a pigment, a dispersant, a binder resin, a monomer serving as a reactive diluent, a photopolymerizing agent, and a solvent is used and patterned by a so-called photolithographic method. Have been.

In the above-mentioned pigment dispersion method, after a color resist in which a color pigment is dispersed is applied on a substrate, and when the resist is a negative type, a photomask for irradiating light only to a pixel portion to be formed is provided. The method includes a step of forming a transparent colored pattern using the same, and this step is repeated at least three times for each of the red, green, and blue transparent colored layers to produce a color filter. In order to obtain a colored pattern having good spectral characteristics, it is necessary that the layer thickness is uniform. Therefore, spin coating is mainly used for applying a resist.
In the spin coating method, after supplying the color resist onto the substrate by dropping or the like, the substrate is rotated at a high speed to form a coating film having a uniform thickness.

[0004] Such a spin coating method has an advantage that a colored pattern with good spectral characteristics can be formed because the layer thickness is uniform, but there is a problem that a resist bulges on an outer peripheral portion of the substrate. is there. That is, the resist that has moved to the outer peripheral portion of the substrate due to the centrifugal force at the time of spin coating forms a rounded liquid mass due to the action of surface tension, and has a larger film thickness that rises more than other portions. In particular, a thick resist tends to remain at the corners of the substrate. Since such a resist is thick, it is not easily removed even by an appropriate developing process, and remains on the outer peripheral portion of the substrate.

On the other hand, the manufactured color filter has a T
The substrate is bonded to the substrate on which the FT is formed. However, if there is a raised resist residue on the outer peripheral portion of the substrate, stress is applied to the substrate at the time of bonding, and in some cases, cracks may occur.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method of forming a resist pattern and a method of manufacturing a color filter which can easily remove a resist from an outer peripheral portion of a substrate.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems. As a result, if the substrate is contaminated with a substance such as oil having low compatibility with the resist, the resist is repelled. Paying attention to the cause of color loss and the like, if the outer peripheral portion of the substrate is coated with a substance from which the resist is easily peeled (resist stripping substance), the outer peripheral portion is prevented from being coated with the resist. It was found that even if the resist could not be completely prevented or the resist could not be completely prevented, it was possible to easily remove the resist on the outer peripheral portion in a later step (developing step, washing step, etc.), and to complete the present invention. Reached.

That is, in the method of forming a resist pattern according to the present invention, a resist containing a photosensitive resin is applied on a substrate by spin coating, and then exposed through a photomask and developed to form a pattern. The method is characterized in that a resist-releasable substance is applied to at least a corner portion of an outer peripheral portion of a substrate, and then the resist is applied on the substrate. Examples of the resist stripping substance include substances having low compatibility with the resist and low surface tension.

The method of the present invention can be suitably applied particularly to a method for producing a color filter. That is, the method for producing a color filter according to the present invention comprises applying a color resist containing a pigment and a photosensitive resin onto a substrate by a spin coating method, exposing the resultant through a photomask, and developing the colored pattern. The method is characterized in that a surfactant or a developing solution is applied as a resist-releasable substance to at least a corner portion of an outer peripheral portion of the substrate, and then the color resist is applied on the substrate.

The use of a surfactant or a developer as a resist stripping substance is not only because the developer itself has a resist stripping property, but also a surfactant, particularly a surfactant contained in the developer, has a resist stripping property. Is focused on. Such a surfactant or developer does not adversely affect the quality of the color filter. The resist stripping substance containing a surfactant and a developing solution is preferably applied to four sides of the substrate including the corners.

[0011]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below with reference to the production of a color filter as an example. That is, the color filter first forms a black matrix on a transparent substrate, then applies a color resist containing a pigment and a photosensitive resin on the transparent substrate by a spin coating method, and then exposes and develops via a photomask. Is performed to form a colored pattern, and this process is repeated at least three times for each of the red, green, and blue transparent colored patterns to manufacture the device.

Although a glass substrate is often used as the transparent substrate, a plastic sheet or the like may be used. As a black matrix, a film having a two-layer structure of metal chromium and chromium oxide is formed, and then patterned by a photolithographic method, or a black light-shielding material such as carbon black is dispersed in a photosensitive resin. A pattern formed using a so-called black resist in the same manner as the transparent coloring pattern can be employed.

After the formation of the black matrix, a first colored pattern is formed. At this time, a surfactant or a developer is applied in advance to the outer peripheral portion of the substrate, particularly to the four corners. As the surfactant, those contained in a developer for removing the resist can be used. For example, polyoxyethylene octyl phenyl ether, polyoxyethylene decyl phenyl ether, polyoxyethylene pentadecyl phenyl ether, polyoxyethylene Polyoxyethylene alkyl aryl ethers such as ethylene octadecyl phenyl ether, polyoxyethylene octyl phenyl ether, and polyoxyethylene nonyl phenyl ether; polyoxyethylene octyl ether, polyoxyethylene dodecyl ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether Polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; Ethylene polystyrylphenyl ether and the like, in particular made of Kao Corporation "Emulgen A-60", "Emulgen A-9
0 "," Emulgen B-66 "," Emulgen L-
40, "Emulgen A-500" and "Newcol 740" manufactured by Nippon Emulsifier Co., Ltd. can be used.

Further, polyethyleneoxy-β-naphthyl ether (“Newcol B-1” manufactured by Nippon Emulsifier Co., Ltd.)
0, polyethyleneoxy-β-naphthyl ether (“Newcol B-18” manufactured by Nippon Emulsifier Co., Ltd.), polyethylene alkyl phenyl ether (“Nicol Chemicals”
P-10 ", sodium alkylnaphthalenesulfonate (" Perex NBL ", manufactured by Kao Corporation), sodium dodecylbenzenesulfonate (" Neoperex No.
25 "), sodium polyoxyethylene lauryl ether acetate (" AKYPO RLM 1 "manufactured by Nikko Chemicals Co., Ltd.)
[00 NV]), a surfactant such as lauryltrimethylammonium chloride, diethanolamine, tetramethylammonium hydroxide, ethylene glycol, potassium carbonate and potassium hydroxide can also be used.

Further, sorbitan monostearate, sorbitan monolaurate, sorbitan monopalmirate, sorbitan monooleate, sorbitan distearate, sorbitan tristearate, sorbitan trioleate, polyoxyethylene sorbitan monostearate, polyoxyethylene Sorbitan monooleate,
Polyhydric alcohol type nonionic surfactants such as polyoxyethylene sorbitan tristearate, glycerol monostearate, alkyl alkanolamide, polyethylene glycol ether type such as polyoxyethylene polyhydric alcohol fatty acid ester, and other polyoxyethylene derivatives Nonionic surfactants, polyethylene glycol ester type nonionic surfactants such as polyethylene glycol monolaurate, polyethylene glycol monooleate, and polyethylene glycol distearate; pluronic type nonionic interface of oxyethylene-oxypropylene block copolymer Other polyethylene glycol-type nonionic surfactants such as surfactants, polyoxyethylene alkylamines and polyoxyethylene alkylamide ethers And the like.

The surfactant may be used by dissolving or dispersing it in a solvent such as water, or may be used as a stock solution. When used in the form of a solution, the surfactant concentration is preferably 0.01% by weight or more, and preferably 0.1% by weight or more.
% By weight or more.

The developer used in the developing step may be used as it is, or may be appropriately diluted or concentrated as needed. Examples of the developer include those in which an alkaline substance and a surfactant are dissolved in water.

The alkaline substance is not particularly limited.
For example, hydroxides or carbonates of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, calcium carbonate,
Inorganic alkalis such as sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; triethylamine and methyldiethylamine Tertiary amines, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH), quaternary ammonium salts such as choline, triethanolamine, diethanolamine,
Alcoholamines such as monoethanolamine, dimethylaminoethanol and diethylaminoethanol, pyrrole, piperidine, 1,8-diazabicyclo [5,4
0] -7-undecene, 1,5-diazabicyclo [4,
Organic alkalis such as cyclic amines such as 3,0] -5-nonane and morpholine are exemplified.

The concentration of the alkaline substance is 0.01 to 5
0% by weight, preferably 0.05 to 10% by weight. The concentration of the surfactant is 0.01 to 20% by weight, preferably 0.1 to 5% by weight.

For the application of the surfactant or the developing solution to the outer peripheral portion of the substrate, any means such as brushing, spraying and dipping can be adopted. The application site is 5 to 2 from the outer edge of the four sides of the substrate.
Suitably, the area is up to 5 mm. Further, not the entire outer peripheral portion of the substrate, but only the short side or the long side of the substrate, or only the corner portion of the substrate may be used.

The surfactant or the developer may be dried after being applied to the outer peripheral portion of the substrate. Alternatively, the color resist may be immediately applied to the transparent substrate by spin coating without drying. In any case, since a coating film of a surfactant or a developing solution is formed on the outer peripheral portion of the substrate, the color resist forms a thick swell on the coating film. The application of the color resist by the spin coater is suitably performed at a rotation speed of 400 to 2000 rpm for 10 to 30 seconds.

After the color resist is applied, it is temporarily cured according to a conventional method, and then a photomask having a predetermined pattern is overlaid on the substrate surface to perform exposure. Thereafter, the developer is sprayed to develop, and further washed with water to wash out the developer. Thereby, the resist raised on the outer peripheral portion of the substrate can be almost completely removed together with the coating film under the resist. Thereafter, the resist is thermally cured to obtain a first color pattern (pixel).

Next, the second and third color patterns are formed in the same manner as above, and a protective layer is formed on the upper surface to form a color filter.

The method for forming a resist pattern according to the present invention comprises:
The present invention can be applied not only to the production of a color filter but also to the formation of various patterns using a photolithographic method. When the method of forming a resist pattern according to the present invention is applied to products other than color filters, oils such as silicone oil can be used as the resist stripping material as long as the quality of the product is not adversely affected.

[0025]

EXAMPLES Hereinafter, the method of the present invention will be described in detail with reference to Examples and Comparative Examples.

Example 1 A 1% by weight aqueous solution of "Emulgen A-60" manufactured by Kao Corporation was applied as a surfactant to an outer peripheral portion 20 mm from an end of a glass substrate (100 mm x 100 mm x 0.7 mm). Then, a resist (“FFO CB-8100L” manufactured by Fuji Film Ohlin Co., Ltd.) was placed in the center of the substrate at 1.7.
The solution was dropped at 2 g / time and shaken off with a spin coater. Spin coater conditions are 800 rpm for 10 seconds. After the application, the substrate was heated at 70 ° C. for about 2 minutes using a hot plate to temporarily cure the resist. For development, a 100-fold diluted solution of a stock solution of CD150CR (manufactured by JSR) was used as a developing solution, and about 20 mm of the end of the substrate was immersed in the diluted solution.
After leaving it to stand for 0 seconds and 30 seconds, it was immediately washed away with pure water. Next, the remaining resist on the outer periphery of the substrate was visually observed. As a result, irrespective of the standing time, no resist residue was observed on the outer peripheral portion of the substrate.

Example 2 A treatment was carried out in the same manner as in Example 1 except that the concentration of the surfactant was changed to 10% by weight. As a result, regardless of the standing time, the resist remained on the outer peripheral portion of the substrate and was not recognized.

Example 3 The outer periphery of the substrate was treated using a diluent obtained by diluting a stock solution of a developer having the following composition 6-fold with water instead of the surfactant. (Ingredient) (Blending amount) Sodium carbonate 3.0% by weight Sodium bicarbonate 1.8% by weight Surfactant 3.6% by weight Water 91.6% by weight The surfactant used was polyoxyethylene polystyryl phenyl ether. It is. The processing conditions are as follows. Glass substrate: 100 mm x 100 mm x 0.7 mm Resist: "FFO CR" manufactured by Fuji Film Ohlin
-8100L "Resist coating amount: 20 g / sheet Spin coating condition: 1020 rpm x 7 seconds Preliminary curing: 70 ° C x 110 seconds (non-contact with the heating plate for 50 seconds, then contact with the heating plate for 60 seconds) Developer: Developer with the same composition as above Others are the same as the first embodiment. As a result, no resist residue was found on the outer peripheral portion of the substrate.

[0029]

According to the present invention, the resist remaining on the outer peripheral portion of the substrate can be easily removed, which greatly contributes to a reduction in the defective rate at the time of forming a resist pattern in the production of a color filter or the like. There is an effect that can be.

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Claims (4)

[Claims] 1. A method of forming a resist pattern, comprising applying a resist containing a photosensitive resin onto a substrate by spin coating, exposing the resist through a photomask, and developing the resist to form a pattern. A method for forming a resist pattern, comprising: applying a resist-releasable substance to at least a corner portion of a portion, and then applying the resist on a substrate. 2. The method according to claim 1, wherein the resist stripping material is applied to four sides including a corner portion of an outer peripheral portion of the substrate. 3. A method for producing a color filter, comprising: applying a color resist containing a pigment and a photosensitive resin onto a substrate by spin coating, exposing through a photomask, and developing to form a colored pattern. A method of manufacturing a color filter, comprising: applying a surfactant or a developer as a resist-releasable substance to at least a corner portion of the outer peripheral portion of the substrate, and then coating the color resist on the substrate. 4. The method according to claim 3, wherein the surfactant or the developer is applied to four sides including a corner portion of the outer peripheral portion of the substrate.