JP2006221053A - Method of manufacturing black matrix substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a black matrix substrate having a thinned black matrix. <P>SOLUTION: The method of manufacturing the black matrix substrate has: a black matrix forming material applying step for applying a black material forming material containing a light shielding material and a photosensitive resin on a base material; an exposure step for irradiating the black matrix forming material pattern-like with energy; a development step for removing a non-exposed part of the black matrix forming material; and a post baking step for heating the black matrix forming material to obtain the black matrix. In the heating in the post baking step, the base material having the pattern-like black matrix forming material on the surface is arranged so as to be horizontal and so that the the black material forming material faces downward. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for manufacturing a black matrix substrate having a black matrix used for a color filter or the like.

  In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays, particularly color liquid crystal displays, has been increasing. As a color filter used for such a liquid crystal display or the like, a black matrix is usually formed, and a colored layer is formed in the opening of the black matrix.

  As such a black matrix, a material obtained by etching a metal thin film obtained by vacuum-depositing a metal such as chromium has been used. However, in recent years, a resin in which a black pigment or the like is dispersed is applied and photolithography is performed. Development of a resin black matrix formed by patterning by a method or the like has been promoted and put into practical use. Such a black matrix made of resin has an advantage that a process such as vacuum vapor deposition is unnecessary and can be applied to a color filter having a large area as compared with a black matrix made of a metal thin film.

  Here, in recent years, there has been a demand for higher image quality of liquid crystal displays and the like, and higher definition of color filters is desired. In the black matrix as described above, when the line width is large, the color filter cannot be made high definition, and the amount of light transmitted through the colored layer is small, so that the luminance of the liquid crystal display device is low. Become. Therefore, it is desired to provide a color filter or the like having a finer black matrix. For example, as shown in Patent Document 1 and Patent Document 2, improvement of the material surface of a resin black matrix is being promoted. However, it is difficult to perform the above thinning only on the material side, and further improvement has been desired.

  Further, when the resin black matrix as described above is formed, a heating step (post-bake step) is usually performed after the development step by the photolithography method in order to further promote curing. At that time, depending on the type of the resin black matrix, for example, as shown in FIG. 2, the black matrix forming material 2 (FIG. 2 (a)) after the development process is heated in the post-baking process to melt the resin ( Hereinafter, as a result of the melt flow, the shape of the black matrix forming material 2 is changed, and a black matrix 2 ′ (FIG. 2B) having a thick line width may be formed. In addition, when such a melt flow occurs, not only is it difficult to make a thin line, but there is also a problem that the film thickness at the end part becomes extremely thin and the light shielding property at the end part becomes low. .

  On the other hand, as a resin for forming a black matrix, a highly curable resin that does not cause a melt flow in the post-baking process and accelerates the curing of the resin before development or does not melt flow during the post-bake process. When used, it is difficult to remove the insoluble part by development, or it is difficult to adjust the line width in the development process, and thus it is difficult to make the line thin.

JP-A-9-197115 JP 2000-292615 A

  The present invention has been made in view of the above problems, and a main object of the present invention is to provide a method of manufacturing a black matrix substrate having a thinned black matrix.

  In the present invention, a black matrix forming material applying step of applying a black matrix forming material containing a light-shielding material and a photosensitive resin on a substrate, and the black matrix forming material is irradiated with energy in a pattern. And a post-baking step of heating the black matrix forming material to obtain a black matrix, and a black matrix substrate manufacturing method. When the post-baking step is heated, the base material having the patterned black matrix forming material obtained in the developing step on the surface is horizontal, and the black matrix forming material is disposed downward. A method of manufacturing a black matrix substrate is provided.

  According to the present invention, in the post-baking step, the substrate having the patterned black matrix forming material obtained in the developing step on the surface is horizontal, and the black matrix forming material is downward. By arranging, it is possible to prevent the black matrix forming material that melts when heated from spreading in the horizontal direction, and to obtain a black matrix substrate having a thinned black matrix.

  In the said invention, it is preferable that the line | wire width of the said black matrix is 4 micrometers-8 micrometers. In this case, by setting the line width of the black matrix within the above range, it is possible to increase the definition of the color filter and increase the luminance of the liquid crystal display device.

  According to the present invention, it is possible to manufacture a black matrix substrate having a thinned black matrix by using a simple method.

  The present invention relates to a method for manufacturing a black matrix substrate having a black matrix used for a color filter or the like. Hereinafter, the manufacturing method of the black matrix substrate of the present invention will be described in detail.

  The method for producing a black matrix substrate of the present invention includes a black matrix forming material applying step of applying a black matrix forming material containing a light-shielding material and a photosensitive resin on a base material, and the black matrix forming material. , An exposure step of irradiating energy in a pattern, a development step of removing the non-exposed portion of the black matrix forming material, and a post baking step of heating the black matrix forming material to obtain a black matrix, When heating in the post-baking step, the substrate having the pattern-shaped black matrix forming material obtained in the developing step on the surface is horizontal and the black matrix forming material is disposed downward. It is a feature. Here, the horizontal in the present invention includes not only strictly horizontal but also includes that the base material having the black matrix forming material is within a range of ± 5 ° from the horizontal plane.

  For example, as shown in FIG. 1, the method for producing a black matrix substrate of the present invention comprises a coating step (FIG. 1 (a)) for applying the black matrix forming material 2 on a substrate 1, and the formation of the black matrix. An exposure process (FIG. 1 (b)) in which the material 2 is irradiated with energy 4 in a pattern through, for example, a photomask 3, and a black matrix forming material in a portion where the energy 4 is not irradiated in the exposure process A developing step (FIG. 1C) for removing 2 and a substrate 1 having a patterned black matrix forming material 2 obtained by the developing step on the surface, and the black matrix forming material 2 And a post-baking step (FIG. 1 (d)) in which the black matrix 2 'is formed on the substrate 1. The black matrix substrate was a method of producing a (FIG. 1 (e)).

  In the conventional method for manufacturing a black matrix substrate, after the development step, the post-baking step is performed with the black matrix forming material facing upward, so that when the melt flow occurs, the molten black matrix forming material becomes the base material. Spread on the surface. For this reason, the line width of the black matrix after completion of the post-baking process is thicker than before the post-baking process, or the film thickness at the end of the black matrix is reduced, and the light shielding property at the end is reduced. Etc.

  On the other hand, in the present invention, heating is performed in a state where the base material having the patterned black matrix forming material on the surface is horizontal and the black matrix forming material is disposed downward in the post-baking step. . Therefore, when the black matrix forming material is melted, it can be prevented from spreading in the horizontal direction, and at the same time, the film thickness at the edge of the black matrix can be prevented from being thinned. Can keep. Here, the line width in the present invention refers to the distance from the end of the black matrix to the opposite end.

Therefore, according to the method for manufacturing a black matrix substrate of the present invention, it is possible to manufacture a black matrix substrate that can be used for various applications such as a high-definition color filter.
Hereafter, each process in the manufacturing method of the black matrix substrate of this invention is demonstrated in detail.

1. Black Matrix Forming Material Application Step First, the black matrix forming material application step in the method for manufacturing a black matrix substrate of the present invention will be described. The black matrix forming material application step in the present invention is a step of applying a black matrix forming material containing a light-shielding material and a photosensitive resin to a substrate, and the black matrix forming material can be applied. If it is a method, the application | coating method etc. will not be specifically limited. For example, a black matrix forming material, which will be described later, is dissolved in a solvent, and known spin coating, spray coating, dip coating, roll coating, bead coating, etc. used for application of a general black matrix forming material. It can carry out by apply | coating with the apply | coating method.

The black matrix forming material used in the present invention is not particularly limited as long as it contains a light shielding material and a photosensitive resin and can form a black matrix. From the viewpoint of thinning the matrix, it is particularly preferable that the material is not a material that can be completely cured by the energy irradiated in the exposure process described later. This is because, by using such a material, as will be described later, it is possible to achieve finer lines by adjusting the shower pressure, the developing time, the developer concentration, the developing temperature, and the like in the developing step.
As such a black matrix forming material, a material obtained by adding a monomer, a photoinitiator, or the like to a light shielding material or a photosensitive resin can be used.

  As the light-shielding material, materials generally used for black matrices can be used, and examples thereof include light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments.

  Examples of the photosensitive resin include cardo resin, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polystyrene, acrylonitrile-styrene copolymer, ABS resin, polymethacrylic acid. Resin, ethylene-methacrylic acid resin, polyvinyl chloride resin, chlorinated vinyl chloride, polyvinyl alcohol, cellulose acetate propionate, cellulose acetate butyrate, nylon 6, nylon 66, nylon 12, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, Polyvinyl acetal, polyether ether ketone, polyether sulfone, polyphenylene sulfide, polyarylate, polyvinyl butyral, epoxy resin, phenoxy resin, polyimide resin Polyamide-imide resins, polyamic acid resins, polyetherimide resins, and phenolic resin, urea resin and the like.

  Further, polymerizable monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert- Butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, styrene, α- One or more selected from methylstyrene, N-vinyl-2-pyrrolidone, and glycidyl (meth) acrylate, and a dimer of (meth) acrylic acid and acrylic acid (for example, M- manufactured by Toagosei Co., Ltd.) 5600), itaconic acid, crotonic acid, male Acid, fumaric acid, vinyl acetate, polymers or copolymers comprising one or more selected from among these anhydrides can also be exemplified. Moreover, although the polymer etc. which added the ethylenically unsaturated compound which has a glycidyl group or a hydroxyl group to said copolymer can be illustrated, it is not limited to these.

  Among the above examples, a resin containing an ethylenically unsaturated bond is particularly preferably used because it forms a cross-linked bond with the monomer and provides excellent strength.

  Moreover, as a monomer which can be used for this invention, a polyfunctional acrylate monomer is mentioned, for example, The compound which has two or more ethylenically unsaturated bond containing groups, such as an acryl group and a methacryl group, can be used. Specifically, ethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) Acrylate, hexane di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol diacrylate, penta Erythritol (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Ruhekisa (meth) acrylate can be exemplified dipentaerythritol penta (meth) acrylate.

  You may use a polyfunctional acrylate monomer in combination of 2 or more types. In the present invention, (meth) acryl means either acryl or methacryl, and (meth) acrylate means either an acrylate group or methacrylate.

  In addition, as a photoinitiator that can be used in the present invention, a photoradical polymerization initiator that can be activated by ultraviolet rays, ionizing radiation, visible light, or other wavelengths, particularly energy rays of 365 nm or less, should be used. Can do. Specific examples of such a photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino acetophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpro Piophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, Nzoin methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis ( p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione 2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) Oxime, Michler's ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, naphthalene Sulfonyl chloride, quinoline sulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, Adeka N1717, carbon tetrabromide, tri Examples include combinations of photoreducing dyes such as bromophenyl sulfone, benzoin peroxide, eosin, and methylene blue with reducing agents such as ascorbic acid and triethanolamine. In the present invention, these photopolymerization initiators can be used alone or in combination of two or more.

In addition, the base material used in the present invention is not particularly limited as long as the black matrix can be formed, and is appropriately selected according to the type and application of the black matrix substrate. In addition, transparency and flexibility are appropriately selected.
As a base material used for such a black matrix substrate, for example, a resin laminate of a paper base, a resin laminate of a glass cloth / glass non-woven base, ceramic, metal or the like can be used.

  Examples of the solvent used in this step include butyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl cellosolve, and 3-methoxybutyl acetate. Normally, after coating by the above method, the solvent is volatilized using a hot plate or the like to form a layer.

  Here, the film thickness of the black matrix forming material after the black matrix forming material is applied by this process, and the solvent is evaporated and dried depends on the use of the black matrix substrate to be manufactured. Usually, about 0.5 μm to 2.0 μm, and more preferably about 0.8 μm to 1.2 μm.

2. Exposure Step Next, the exposure step in the present invention will be described. The exposure step in the present invention is not particularly limited as long as it is a step of irradiating the black matrix forming material applied on the base material with energy in a pattern forming a black matrix. Usually, it can be performed by irradiating energy using a photomask or the like.

The energy irradiation amount irradiated in such an exposure step is appropriately selected depending on the type of the black matrix forming material and the like, but as described above, saturation that completely cures the black matrix forming material. It is preferable that the exposure amount is smaller. This is because it is possible to reduce the thickness of the black matrix forming material in the development step described later. Specifically, such an energy irradiation amount is preferably in the range of 10 to 200 mJ / cm ² , particularly in the range of 40 to 100 mJ / cm ^{2 in} terms of i-line. If the amount of energy irradiation is larger than the above-mentioned energy irradiation amount, the black matrix forming material is hardened, and it may be difficult to develop in the development process described later, or it may be difficult to make a thin line in the development process. is there. Further, when the amount is less than the above-mentioned energy irradiation amount, the curing is weak and it may be difficult to develop into a target shape in the development step described later.

  Further, the energy irradiated at this time is appropriately selected depending on the type of the photoinitiator and the like, and any energy can be used as long as it can cure the black matrix forming material. Here, the energy referred to in the present invention includes any energy ray irradiation, and is not limited to visible light irradiation. Usually, as such energy, ultraviolet light can be used, and in particular, light having a wavelength of about 250 nm to 300 nm can be used.

  In the present invention, the line width of an opening such as a photomask used for exposure is preferably about 3 μm to 9 μm, and more preferably about 5 μm to 7 μm. This is because a black matrix having a line width of about 4 to 8 μm, especially about 4 to 6 μm can be formed by using a photomask having such an opening.

3. Development Step Next, the development step in the present invention will be described. The development step in the present invention is a step of removing the non-exposed portion of the black matrix forming material, and the method is not particularly limited as long as the non-exposed portion can be removed. It can be performed by a method similar to a general black matrix developing method.

  Here, in the present invention, it is preferable to develop the black matrix forming material so that the line width is narrower than the width of the region irradiated with energy in the exposure step. In the above exposure process, since the black matrix forming material is not completely cured, the line width can be made narrower than the width of the region irradiated with energy by, for example, the pressure of a shower applying the developer. This is because the formed black matrix can be made thinner.

  As a method of making the line width of the black matrix forming material narrower than the exposed width in this way, for example, a method of adjusting the shower pressure of the developer, a method of adjusting the length of the development time, the developer concentration And a method for adjusting the development temperature.

4). Post-bake process Next, the post-bake process in the present invention will be described. The post-baking step in the present invention is a step of heating the black matrix forming material formed in a pattern by the above developing step, and the base having the patterned black matrix forming material obtained by the above developing step on the surface. The black matrix forming material is disposed so that the material is horizontal and the black matrix forming material faces downward.

  Here, as described above, the black matrix forming material used in the present invention is preferably a material that is not completely cured by the energy irradiated in the exposure step. This is because thinning can be achieved by adjusting shower pressure, development time, developer concentration, development temperature, and the like in the development step. As described above, it is preferable to use a black matrix forming material having the above properties for thinning. However, the black matrix forming material having the above properties generally causes a melt flow in a post-bake process. There is a tendency. For this reason, in the conventional post-bake process, the black matrix forming material thinned in the development process may be melted by heat to form a black matrix having a wide line width. In such a case, by arranging the base material having the black matrix forming material on the surface to be horizontal and the black matrix forming material to face downward, the line width is not widened even if melt flow occurs, and the wire is thinned. A black matrix can be obtained.

The shape of the black matrix forming material in this step is preferably such that the maximum line width of the black matrix forming material is approximately the same as the line width on the ground plane between the substrate and the black matrix forming material. More preferably, it is less than about (tapered).
In the present invention, the black matrix forming material can be usually heated by heating within a range of 200 ° C. to 250 ° C. for about 20 minutes to 60 minutes, and a post for forming a general black matrix. It can be performed in the same manner as the baking process.

  Further, after completion of this step, the line width of the formed black matrix is preferably 4 μm to 8 μm, and more preferably 4 μm to 6 μm. This is because a black matrix substrate that can be used for various applications such as a high-definition color filter can be obtained.

5. Others The black matrix substrate obtained by the present invention is suitably used for a color filter as described above. Such a color filter is formed by laminating a colored layer, a transparent electrode layer, and the like on the black matrix substrate. Hereinafter, such a color filter will be described for each configuration.
(Colored layer)
The colored layer is not particularly limited as long as the colored layer covers a part of the light-shielding portion by the black matrix and is formed in the opening of the light-shielding portion. For example, red (R) Using a composition for forming colored layers of three colors of green (G) and blue (B), for example, a known arrangement such as a stripe type, a mosaic type, a triangle type, and a four-pixel arrangement type can be obtained. The coloring area can be arbitrarily set. The said opening part means the area | region in which the light-shielding part on a board | substrate is not formed. Moreover, as a formation method of the said colored layer, it can be set as the method used in the case of manufacture of a general color filter, such as a photolithographic method and an inkjet method, for example.

(Transparent electrode layer)
The transparent electrode layer can be the same as the transparent electrode layer used in general color filters, such as indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), and the like. Using an alloy or the like, it can be formed by a general film forming method such as a sputtering method, a vacuum evaporation method, or a CVD method.

(Color filter)
The color filter using the black matrix substrate obtained by the present invention is not particularly limited as long as it has the black matrix substrate, the colored layer, and the transparent electrode layer. Other members such as an insulator may be included.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

[Example 1]
(1) Preparation of carbon black dispersion ink 50 parts by weight of carbon black MA-220 (manufactured by Mitsubishi Chemical Co., Ltd.), 5 parts by weight of BYK-182 (polymer dispersant made by BYK Chemie) in solid content, and further propylene glycol monomethyl Ether dispersion was added to adjust the dispersion so that the solid concentration was 50 wt%. 50 g of the dispersion was collected by weight, and premixed by thoroughly stirring with a stirrer. Next, the dispersion process was performed in the range of 25-45 degreeC with the paint shaker for 6 hours. As beads, 0.5 mmφ zirconia beads were used, and the same weight as the dispersion was added. After the completion of dispersion, the beads and the dispersion were separated by a filter to obtain a dispersion ink.
(2) Preparation of photosensitive black resin composition Next, 25 g of a binder component having the following composition was added to 100 g of the carbon black dispersion ink described above and mixed using a stirrer to obtain a photosensitive black resin composition. It was.
(Composition of binder component)
-Bisphenol A epoxy acrylate (acid adduct) ... 60 parts by weight-Dipentaerythritol pentaacrylate ... 18 parts by weight-Trimethylolpropane triacrylate ... 7 parts by weight-Irgacure 907 ... 10 parts by weight ( Ciba Specialty Chemicals)
-Biimidazole ... 5 parts by weight (3) Formation of black matrix Each photosensitive black resin composition described above is applied onto a glass substrate with a spin coater, dried, and then irradiated with ultraviolet rays of 60 mJ / cm ² through a mask. And exposure was performed. Thereafter, development was performed with an alkaline solution to remove unexposed portions. Baking was performed at 200 ° C. for 30 minutes so that the film surface was horizontally downward, and a black matrix was formed. The line width and film thickness of this black matrix were measured, and the results are shown in Table 1 below.

[Comparative Example 1]
(1) Formation of black matrix Each photosensitive black resin composition similar to that of Example 1 was applied onto a glass substrate by a spin coater, dried, and then exposed to ultraviolet rays 60 mJ / cm ² through a mask for exposure. . Thereafter, development was performed with an alkaline solution to remove unexposed portions. Baking was performed at 200 ° C. for 30 minutes so that the film surface was horizontally upward, and a black matrix was formed. The line width and film thickness of this black matrix were measured, and the results are shown in Table 1 below.

It is process drawing which showed the manufacturing method of the black matrix substrate of this invention. It is explanatory drawing for demonstrating the manufacturing method of the conventional black matrix substrate.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Black matrix formation material 2 '... Black matrix 3 ... Photomask 4 ... Energy

Claims (2)

A black matrix forming material application step of applying a black matrix forming material containing a light-shielding material and a photosensitive resin on a substrate; and an exposure step of irradiating the black matrix forming material with energy in a pattern. A black matrix substrate manufacturing method comprising: a developing step of removing a non-exposed portion of the black matrix forming material; and a post baking step of heating the black matrix forming material to obtain a black matrix,
During heating in the post-baking step, the substrate having the patterned black matrix forming material obtained in the developing step on the surface is horizontal and the black matrix forming material is disposed downward. A method for manufacturing a black matrix substrate. The black matrix substrate manufacturing method according to claim 1, wherein the black matrix has a line width of 4 μm to 8 μm.

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