JPH09311214A - Production of substrate for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To industrially advantageously produce a substrate for high precision color filter which has no residual pigment particles or photosensitive resin after development and causes no redeposition of the pigment particles and the photosensitive resin component dissolved or dispersed in a developer. SOLUTION: A photosensitive resin with dispersion of a pigment is applied on a glass substrate and heat treated, exposed and brought into contact with a developer for development to obtain a color filter substrate. This production method includes a process to replace the developer on the glass substrate after the development by a diluted developer diluted with water by 2 to 200 times and a process to replace the diluted developer by water.

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 substrate for a color filter used in a color liquid crystal display or other color liquid crystal display devices, and more particularly to an improvement in a developing method in which no resist remains on the substrate.

[0002]

2. Description of the Related Art In the manufacturing process of color filters,
Various processes such as a printing method, a pigment dispersion method and a dyeing method have been developed. However, the pigment dispersion method is industrially advantageous in terms of cost, and process development by this method has been vigorously carried out. In a general color filter pattern forming process in the pigment dispersion method, first, a photosensitive resin liquid in which a pigment is dispersed is prepared in a predetermined manner on a transparent support using various coating machines such as spin coating and roll coater method. Apply to the film thickness. Next, in order to remove the solvent in the applied photosensitive resin liquid and improve the adhesion between the resin and the transparent support, heat treatment is performed at a predetermined temperature using an oven, a heater or the like. After that, the substrate is allowed to cool or a cooling process is performed using various devices. A latent image is formed by selectively irradiating the cooled support with an electromagnetic wave in a predetermined wavelength range, such as ultraviolet rays or an electron beam having a predetermined energy, at a predetermined irradiation amount according to the photosensitive resin. Next, the exposed photosensitive resin film is subjected to a development treatment with, for example, an alkaline developing solution to selectively expose the exposed portion in the case of a positive photosensitive resin and the non-exposed portion in the case of a negative photosensitive resin. It is dissolved and removed. After that, a rinsing process and a drying process are performed to form a desired pattern, and the color filter substrate is manufactured. By repeating these steps with a photosensitive resin liquid in which pigments of different colors are dispersed, a color filter pattern is formed.

[0003]

In the conventional method for developing a negative photosensitive resin, the pigment particles or the photosensitive resin is left undeveloped in the unexposed area, or is dissolved in a developing solution.
There is a problem in that the dispersed photosensitive resin component / pigment particles are redeposited on the substrate. Further, if the development time is lengthened to reduce the undeveloped portion in the unexposed area, overdevelopment occurs, resulting in peeling of the pattern area, making it impossible to manufacture a fine pattern.

Among the above problems, in order to solve the development residue of the pigment particles, the substrate provided with the photosensitive resin is dipped in a developing solution, and the pressurized developing solution is sprayed onto the substrate (Japanese Patent Laid-Open No. Hei 2).
No. 118662), or it is suggested to spray pressurized water after immersion in a developing solution (JP-A-2-106).
757). However, in recent years, there has been a demand for a color filter having a finer structure for a color liquid crystal display device having a wide viewing angle, and the pressurized developer as described above is directly sprayed on the substrate. Alternatively, the method of spraying pressurized water with the developing solution on the substrate has a problem that the fine pattern accuracy cannot be controlled. Especially when the black matrix is made of a photosensitive resin, these methods cannot be used because extremely fine pattern accuracy is required.

In particular, with respect to the undeveloped portion of the pigment particles in the peripheral portion of the substrate, a method has been proposed in which a developing solution or a chemical solution similar thereto is applied to the peripheral portion of the substrate in advance before the development, and the development is preceded (Japanese Patent Laid-Open No. Hei 10 (1999) -58242). 7-27917). However, this method cannot be applied because a pattern defect is likely to occur in the vicinity of the pattern or in an unexposed portion in the pattern, and it has not been completely solved.

Further, none of the above methods has solved the re-adhesion of pigment particles / photosensitive resin component dissolved / dispersed in a developing solution after development. In addition, a method of carrying out preliminary development before development to prevent uneven development (Japanese Patent Laid-Open No. Sho 58-58)
-4144, JP-A-62-2254, JP-A-63-84
027), a method of developing while removing with a rinse to prevent pattern deformation due to swelling (JP-A-63-1)
64217), various developing methods have been developed,
Since these methods originally have different purposes, the above problems have not been solved yet.

The present invention has been made by paying attention to the above problems, and there is no development residue of pigment particles / photosensitive resin.
Another object of the present invention is to provide a method for producing a high-definition color filter substrate without redeposition of pigment particles / photosensitive resin component dissolved / dispersed in a developing solution.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventor increased the amount of the developer remaining / adhering to the glass substrate after the development treatment to 2-200 times with water. It was found that a highly accurate color filter substrate can be easily manufactured without a problem of residual development and redeposition by replacing the diluted developing solution with water and further substituting the diluted developing solution with water. The present invention has been reached.

That is, the gist of the present invention is to manufacture a substrate for a color filter in which a photosensitive resin in which a pigment is dispersed is applied to a glass substrate, heat-treated, exposed, and then brought into contact with a developing solution for development. In the method, after the developing treatment, a step of substituting the developing solution adhering on the glass substrate with a dilute developing solution diluted 2-200 times with water, and a step of further substituting the dilute developing solution with water. The present invention also relates to a method for manufacturing a color filter substrate having the above.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
As the pigment for the photosensitive resin used in the present invention, an organic pigment or an inorganic pigment is used. As organic pigments,
C. I. Pigment Yellow 24, 31,
53, 83, 139; C.I. I. Pigment Or
ange 43; C.I. I. Pigment Red
9, 97, 105, 122, 123, 149, 168,
176, 177, 180, 192, 215; C.I. I.
Pigment Violet 14, 23, 29;
C. I. Pigment Blue 15, 15: 3,
22, 28, 60, 64; C.I. I. Pigment
Green 7, 15, 25, 36; C.I. I. Pigm
ent Brown 28; C.I. I. Pigment
Black 1, 7, etc. may be used alone or as a mixture of them in any ratio.

As described above, the present invention can be applied to various pigments, but is particularly effective for pigments used for a black matrix. The black matrix is required to have a high pigment content ratio as compared with photosensitive resins of other colors in order to have particularly high light-shielding performance, and the development residue of pigment particles in non-pixel portions tends to increase. Further, since the non-pixel portion in the black matrix also includes the RGB pixel portion, the remaining pigment here becomes a defect in the pixel. Further, it is necessary to form a finer pattern than that of RGB, so that a method that causes less damage to the pattern is required.

The photosensitive resin used in the present invention can be applied in various compositions without limitation, but it is particularly effective in a composition containing an acrylic resin, a dispersant, a photopolymerizable monomer and a photopolymerization initiator. To do. As the acrylic resin, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-
Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobornyl methacrylate, etc. A polymer of monomers or a copolymer of plural kinds of these monomers is used.

The photopolymerizable monomer includes bifunctional, trifunctional and polyfunctional monomers, and the bifunctional monomer includes
1,6-hexadiol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, and the like, and the trifunctional monomers include trimethylolpropane triacrylate, pentaerythritol acrylate, and tris (2-hydroxy). Ethyl) isocyanate and the like, and polyfunctional monomers include ditrimethylolpropane tetraacrylate, dipentaerythritol penta and hexaacrylate.

As the photopolymerization initiator, photodecomposition type, hydrogen transfer type and the like can be used. Specific examples include benzophenone, 3,3-dimethyl-4-methoxy-benzophenone, chlorobenzophenone, hydroxybenzophenone, 4,4′-dimethylaminobenzophenone, 4,
4'-diethylaminobenzophenone, Michler's ketone, 2,2-dimethoxy-2-phenylacetophenone, 2,4,6- (trihalomethyl) triazine, 2-
(2-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2,3-dichlorophenyl) -4,
Examples thereof include 5-diphenylimidazole dimer, dimethylthioxanthone, diethylthioxanthone, 2-chlorothioxanthone, 9-phenylacridine, 2,4,6-tri (trichloromethyl) triazine and the like.

The developer used in the present invention contains an alkaline agent and a surfactant. Here, the alkaline agent means lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, phosphoric acid. Inorganic alkaline compounds such as potassium dihydrogen, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, and ammonia, Tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine Organic alkali compounds such is used.

As the surface active agent used here, an anionic surface active agent, a cationic surface active agent, or a nonionic surface active agent can be used. Examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate. And the like, such as alkylaryl sulfonates.

Examples of cationic surfactants include quaternary ammonium salts such as stearylamine hydrochloride, lauryltrimethylammonium chloride and alkylbenzenedimethylammonium chloride. Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene allyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester. , Polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

Of these, nonionic surfactants are preferable from the viewpoint of image forming ability, and specifically, polyoxyethylene allyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, and polyoxyethylene derivative are preferable. . The content of the alkaline agent and the surfactant is 1: as a content ratio in the developer.
5-1: 40 is still preferable in terms of image forming ability.

The replacement treatment is carried out with a dilute developing solution diluted with water. If the concentration is high, the photosensitive resin in the exposed area will be dissolved and the pattern will be greatly damaged. Redeposition of the pigment particles and photosensitive resin component dissolved / dispersed in the solution will occur. Further, if the concentration is low, it almost becomes a state of being replaced by water, resulting in poor development and re-deposition. Therefore, in the present invention, the diluted developer is prepared by diluting the developer with water 2-200 times.
The dilution ratio is preferably 4 to 60 times in order to further reduce the development residue and redeposition of the pigment particles and the photosensitive resin without damaging the pattern.

The dilute developer on the substrate is further subjected to displacement treatment with water. In this displacement treatment, substantially no pressure is applied, that is, a pressure greatly exceeding the pressure due to the depth of water is applied. It is preferable to replace untreated water by naturally dropping it from a low place of 1 m or less, preferably 50 cm or less and usually about 20 to 30 cm on the substrate. Further, after this, it is more preferable to perform a rinse treatment by spraying pressurized water from the nozzle.

[0021]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. [Example 1] A commercially available black resist (trade name: Color Mosaic K: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was applied on a glass substrate by a spin coating method so as to have a thickness of about 1 µm, and 100 ° C for 1 minute on a hot plate. I prebaked it. Polyvinyl alcohol was applied thereon by spin coating, and prebaking was performed on a hot plate at 100 ° C. for 1 minute, and a mask was applied to expose with ultraviolet intensity of 100 mJ / cm ² . This was immersed for 1.5 minutes in a developer containing 0.1% potassium carbonate and 0.5% polyoxyethylene alkyl ether type nonionic surfactant (“Emulgen NC-150” manufactured by Lion Corporation). After development, the developing solution on the substrate was subjected to a displacement treatment by spraying a developing solution diluted with pure water 50 times on the substrate by a spray method. Further, pure water is sprinkled on the substrate on which the diluted developing solution is placed, by using a device having a slit-shaped outlet as shown in FIG. 1 so that the solution can be sprinkled on the substrate at a low pressure. The replacement process was performed. [Example 2] C.I. I. Pigment Red 177
10g and BYK manufactured by Big Chemie Co., Ltd. as a dispersant
5 g of -161 and 18 g of polyethylene glycol monomethyl ether acetate were mixed and shaken with a paint conditioner for 10 hours to prepare a red paste. Similarly, C.I. I. Pigment Yell
ow 139 10g, BYK-161 5g, polyethylene glycol monomethyl ether acetate 5
1 g was mixed and shaken with a paint conditioner for 10 hours to prepare a yellow paste.

31.7 g of red paste and yellow paste
A resin having a repeating unit represented by the following formula (I) 8.5 was mixed with 19.9 g of the acrylic resin.
g, 4.2 g of dipentaerythritol hexaacrylate as a photopolymerizable monomer, 0.5 g of mercaptobenzothiazole, and 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer of 0.6 as a photopolymerization initiator
g, 4,4′-bis (diethylamino) benzophenone (0.4 g) and polyethylene glycol monomethyl ether acetate (29.4 g) were added and mixed with stirring to obtain a photosensitive resin liquid.

[0023]

Embedded image

The photosensitive resin was applied onto a glass substrate by spin coating so as to have a thickness of 1 μm, and prebaked at 70 ° C. for 3 minutes on a hot plate. A mask was applied and exposure was performed with an ultraviolet intensity of 50 mJ / cm 2. this,
After developing by dipping in a developer containing potassium hydroxide and a nonionic surfactant of polyoxyethylene derivative for 1 minute, the developer on the substrate is diluted 5 times with pure water and sprayed with a spray method. The replacement process was carried out. Further, using the apparatus as shown in FIG. 1, pure water was poured on the substrate on which the above-mentioned diluted developing solution was placed to carry out a substitution process with water. [Example 3] Carbon black (manufactured by Mitsubishi Chemical Corporation "M
A-220 ″) 10 g and BYK-161 4.6 g,
Resin 1.6 having a repeating unit represented by the above formula (I)
g and polyethylene glycol monomethyl ether acetate (16.6 g) were mixed and shaken in a paint conditioner for 10 hours to prepare a black paste. The same operation as in Example 2 was performed except that a black paste was used instead of the red and yellow pastes. [Example 4] After developing, except that the developing solution deposited on the substrate was replaced with a developing solution diluted three times with pure water, instead of being replaced with a developing solution diluted three times with pure water. Example 3
The same operation was carried out. [Embodiment 5] After development, the developing solution deposited on the substrate was replaced with a developing solution diluted with pure water by a factor of 5 instead of a developing solution diluted with pure water by a factor of 5 was replaced. Performed the same operation as in Example 3. [Comparative Example 1] The same operation as in Example 2 was carried out except that the replacement treatment with a dilute developer after development was not carried out. [Comparative Example 2] The same operation as in Example 3 was carried out except that the replacement treatment with a dilute developer after development was not carried out. [Comparative Example 3] After developing, except that the developing solution on the substrate was replaced with a developing solution diluted with pure water by a factor of 5 instead of with a developing solution diluted by 300 times with pure water. Performed the same operation as in Example 3. [Comparative Example 4] After development, instead of replacing the developing solution on the substrate with a developing solution diluted 5 times with pure water, a replacement processing with a developing solution diluted 1.5 times with pure water was carried out. The same operation as in Example 3 was carried out except that the above was performed.

In each of the above Examples and Comparative Examples, the residual development and the pattern accuracy were evaluated by the following methods. The results are shown in Table 1. Development residual evaluation method Halogen lamp (MHF-150, manufactured by Moritex Co., Ltd.)
L) was used to irradiate the non-pixel portion on the glass substrate with light from a direction of 45 °, and the reflection state by the pigment particles attached to the surface of the glass substrate was visually observed, and evaluated according to the following criteria.

A: A state where no development residue of pigment particles can be confirmed over the entire surface of the substrate. B: A state in which a development residue of pigment particles can be confirmed on a part of the substrate (30% or less of the substrate). C: A state in which the development residue of pigment particles can be confirmed on most of the substrate (30 to 90% of the substrate).

D: Pigment on the entire surface of the substrate (90% or more of the substrate)
The state in which the undeveloped particles can be confirmed. Pattern accuracy evaluation method Sankei on the optical microscope XD-20 manufactured by Nikon Corporation
CCD color camera CS572B and Fove made by
1 Installed Measure Unit MC-50 manufactured by Co., Ltd.
Wear it, measure the line width of each pattern, and
The difference from the line width of the disc was evaluated according to the following criteria.

A: Line width difference is within 0.5 μm. B: Line width difference is within 0.5 to 1 μm. C: Line width difference is 1 μm or more.

[0029]

[Table 1]

[0030]

As described above, the present invention has the following effects. It is possible to industrially manufacture a defect-free color filter substrate by removing the development residue of pigment particles in the pixel portion or non-pixel portion on the substrate without damaging the pixel pattern of the color filter substrate. .

[Brief description of drawings]

FIG. 1 is a schematic perspective view of an apparatus used to replace a dilute developer on a substrate with pure water according to an embodiment of the present invention. 1 ... Outflow port 3 ... Liquid supply pipe 2 ... Tip part 4 ... Liquid flowing down

Claims (6)

[Claims] 1. A method for producing a substrate for a color filter, which comprises coating a glass substrate with a photosensitive resin having a pigment dispersed therein, heat-treating it, exposing it to light, and then contacting it with a developing solution to develop it. After that, the method further comprises a step of substituting the developing solution adhering on the glass substrate with a dilute developing solution diluted 2-200 times with water, and a step of further substituting the dilute developing solution with water. Method for manufacturing color filter substrate. 2. The method for producing a substrate for a color filter according to claim 1, wherein the diluted developing solution is diluted 4 to 60 times with water. 3. The method for manufacturing a color filter substrate according to claim 1, wherein the pigment contained in the photosensitive resin is carbon black. 4. The developing solution contains an alkaline agent and an anionic, cationic or nonionic surfactant in a developing solution content ratio of 1: 5 to 1:40. A method for producing a substrate for a color filter as described above. 5. The method for manufacturing a color filter substrate according to claim 1, wherein the photosensitive resin contains an acrylic resin, a dispersant, a photopolymerizable monomer, and a photopolymerization initiator. 6. The method for producing a substrate for a color filter according to claim 1, wherein the substitution treatment with water is carried out by naturally dropping water which is not pressed onto the substrate.