JP2012247643A - Black matrix substrate, color filter, and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black matrix substrate including narrow-width black matrices, which are free from collapse in which a coloring material forming a coloring layer goes beyond the black matrices to mix with another coloring material of an adjacent coloring layer.SOLUTION: A black matrix substrate includes a base, and black matrices formed on the base and made of a resin including a light-blocking material. Each black matrix is covered entirely with a cover body made of a transparent resin including a liquid-repellent material.

Description

  The present invention relates to a black matrix substrate, a color filter, and a liquid crystal display device. More specifically, for example, a black matrix substrate used for a color filter in the case where a colored layer is formed by an inkjet method, a color filter excellent in flatness of the colored layer by using this, and this color filter were used. The present invention relates to a liquid crystal display device.

  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. In response, there is an urgent need to establish means to supply more beautiful displays at reasonable prices.

  A conventional method for producing a color filter is a pigment dispersion method. In this method, first, a photosensitive resin layer in which a pigment is dispersed is formed on a substrate, and this is patterned into a desired shape by a photolithography process to obtain a monochromatic pattern, in other words, a monochromatic colored layer. By repeating this process three times, a color filter having three colored layers of R, G and B can be formed. However, in this method, in the case of forming a color filter having three colored layers of R, G, and B, it is necessary to repeat the above steps three times. Since the process is repeated, there is a problem that the yield decreases.

  Under such circumstances, for example, a method has been proposed in which a colored layer forming coating solution is applied onto a substrate by an inkjet method, thereby forming a colored layer. In this method, liquid repellency is imparted to the black matrix simultaneously with the formation of the colored layer. This is to prevent so-called breakage in which adjacent colored layers are mixed beyond the black matrix by imparting liquid repellency to the black matrix. As an example of the treatment for imparting liquid repellency to the black matrix, a plasma treatment in which a gas mixed with carbon tetrafluoride is introduced and a head electrode that generates plasma is scanned on the black matrix can be exemplified.

  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. For example, in a black matrix of a color filter in which a colored layer is formed by the ink jet method as described above, if the line width is thick, the color filter cannot be made high definition, and light that passes through the colored layer is transmitted. Therefore, the luminance of the liquid crystal display device is lowered. Therefore, it is desired to provide a color filter having a more thin black matrix. For example, as shown in Patent Document 1 and Patent Document 2, improvement of the material surface of the resin black matrix has been promoted, but it is difficult to perform the above thinning only with the material surface, and further improvement is desired. It was.

  On the other hand, however, thinning the black matrix is not simple, and if the line width of the black matrix is made too thin, the colorant that forms the colored layer mixes with the colorant of the adjacent colored layer beyond the black matrix. There is a possibility that so-called breakdown will occur. Therefore, the thinning of the black matrix has to be performed in consideration of the breakdown.

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

  The present invention has been made in such a situation. For example, when a colored layer is formed by an ink jet method, the colorant forming the colored layer is mixed with the colorant of the adjacent colored layer beyond the black matrix. It is a main object to provide a black matrix substrate on which a black matrix having a narrow line width is formed without causing breakage, and a color filter and a liquid crystal display device having high luminance and contrast.

  A first invention for solving the above problem is a black matrix substrate having a base material and a black matrix formed on the base material and containing a light-shielding material and a resin, wherein the black matrix is The surface is covered with a covering containing a liquid repellent material and a transparent resin.

  In the above invention, it is preferable that the liquid repellent material contained in the covering is distributed more on the upper surface than on the side surface of the covering.

  A second invention for solving the above-described problems is a base material, a black matrix formed on the base material and including a light-shielding material and a resin, on the base material, and formed by the black matrix. A color layer formed in the opening, wherein at least a part of the black matrix in the color filter is covered with a covering containing a liquid repellent material and a transparent resin. It is characterized by being.

  In the above invention, it is preferable that the liquid repellent material contained in the covering is distributed more on the upper surface than on the side surface of the covering.

  In the above invention, it is preferable that the black matrix having two or more colored layers and at least between the colored layers of different colors is covered with the covering.

  According to a third aspect of the present invention, there is provided a liquid crystal display device having a color filter and a counter electrode substrate facing each other and a liquid crystal layer sealed between the color filter, the base material, A black matrix formed on the base material and containing a light-shielding material and a resin; and a colored layer formed on the base material and formed in an opening formed by the black matrix. At least a part of the black matrix in the filter is characterized in that its surface is covered with a covering containing a liquid repellent material and a transparent resin.

  According to the present invention, since the entire surface of the black matrix is covered with the covering including the liquid repellent material and the transparent resin, the coloring material that forms the coloring layer can be repelled on the upper surface of the covering. As a result, the coloring material can be prevented from being mixed with other coloring material beyond the covering and the black matrix, that is, so-called breakage. Further, the present invention prevents so-called breakage by the presence of the transparent resin covering the entire surface of the black matrix, and therefore, even if the line width of the black matrix itself is reduced, it does not cause the breakage. The line width can be designed to be as thin as a desired value.

It is a schematic sectional drawing of a black matrix substrate. It is process explanatory drawing which shows the manufacturing process of a black matrix substrate. It is sectional drawing of a color filter. It is a front view of a color filter.

  Hereinafter, a black matrix substrate, a color filter, and a liquid crystal display device of the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic sectional view of a black matrix substrate.

  As shown in FIG. 1, the black matrix substrate 1 includes a base material 2 and a black matrix 3 formed on the base material 2 and including a light-shielding material 31 and a resin 32, and further, the black matrix 3, the entire surface is covered with a covering 4 including a liquid repellent material 41 and a transparent resin 42.

(Base material)
As the base material 2 of the black matrix substrate 1, it is sufficient that various configurations such as the black matrix 3, the covering 4, and further each color coloring layer can be formed thereon. Can be used.

  Specifically, for example, a resin, a laminate obtained by laminating a resin on paper, a laminate obtained by laminating a resin on a glass cloth or a glass nonwoven fabric, ceramic, metal, quartz glass, Pyrex (registered trademark) glass, non-alkali glass, etc. Can be mentioned. Moreover, the said base material 2 may be a transparent base material, On the other hand, a reflective base material and the base material colored in white may be sufficient.

(Black matrix)
The black matrix 3 formed on the substrate 2 is composed of at least a light shielding material 31 and a resin 32. The black matrix 3 may include other than the light-shielding material 31 and the resin 32 described below. In particular, the black matrix 3 of the present invention does not come into direct contact with the colorant that forms the colored layer, and therefore it is not necessary to consider compatibility with the colorant, and can be freely designed. Since materials and the like can be designed freely, blackness and the like can be improved.

(Black matrix forming coating solution)
Further, when the photolithography method is used for forming the black matrix 3 on the substrate 2, the light-shielding material 31 and the resin 32 constituting the black matrix 3, and the photopolymerization initiator are dissolved in a solvent. A black matrix forming coating solution is used.

  Hereinafter, the light-shielding material 31, the resin 32, the solvent, the photopolymerization initiator, and the like included in the black matrix 3 and the black matrix forming coating liquid will be described in detail.

-Light-shielding material As the light-shielding material 31 which comprises the black matrix 3, the material generally used for the black matrix can be selected suitably, and is not specifically limited. Specific examples include particles having light shielding properties such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments. Various dyes that dissolve in the resin 32 may be used.

Resin The resin 32 constituting the black matrix 3 is not particularly limited as long as the resin 32 can be cured in a state including the light-shielding material 31 and can form a desired pattern shape. Conventionally used resins can be appropriately selected and used in consideration of the manufacturing method and the like.

  As described above, for example, a photosensitive resin is used as the resin 32 when the black matrix 3 is manufactured by a photolithography method. More specifically, a cardo resin, an ethylene-vinyl acetate copolymer, an 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, polyetheretherketone, polyether Sulfone, polyphenylene sulfide, polyarylate, polyvinyl butyral, epoxy resins, phenoxy resins, polyimide resins, polyamide-imide resins, polyamic acid resins, polyether imide resins, phenolic resins, and urea resins.

  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- Buty (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, malein , 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 in this case, 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.

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

-Solvent As a solvent contained in the coating liquid for black matrix formation, alcohol, ether, ethylene glycol alkyl ether acetate, etc. can be used. More specifically, examples include butyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl cellosolve, 3-methoxybutyl acetate and the like.

  Further, as the photopolymerization initiator contained in the black matrix forming coating liquid, 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. Can be used. Specific examples of such photopolymerization initiators 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-methylpropio Phenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal Benzoin 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-benzoy ) Oxime, Michler's ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, Naphthalenesulfonyl chloride, quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyldisulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, Adeka N1717, carbon tetrabromide, Examples include combinations of photoreducing dyes such as tribromophenylsulfone, benzoin peroxide, eosin, and methylene blue with reducing agents such as ascorbic acid and triethanolamine. In addition, these photoinitiators can be used individually by 1 type or in combination of 2 or more types.

  In addition to the above, the black matrix forming coating solution may contain a dispersant, a sensitizer, a coating property improver, a crosslinking agent, a polymerization inhibitor, a plasticizer, and a flame retardant as appropriate. Can be included.

  The shape of the black matrix 3 containing various components as described above is not particularly limited, and can be freely designed. For example, the thickness t of the black matrix 3 is preferably 1.0 to 2.5 μm. If it is thinner than 1.0 μm, the optical density (OD) may be insufficient. On the other hand, if it is thicker than 2.5 μm, wrinkles may occur. This is because the difference between the thickness of the portion combined with the body 4 and the thickness of the colored layer is increased, and there is a concern that alignment failure of the liquid crystal may occur.

  The cross-sectional shape of the black matrix 3 and the cover 4 described later is preferably a forward tapered shape. This is because if the taper is reversed, light leakage may occur.

(Coating)
The black matrix 3 is characterized in that the whole is covered with a covering 4 including a liquid repellent material 41 and a transparent resin 42. By covering the entire black matrix 3 with the covering 4 in this way, in order to prevent so-called breakage, it is possible to make the covering 4 have a certain line width or make its surface liquid-repellent. You can carry it. Since the black matrix 3 itself can be designed freely without considering so-called breakdown, the blackness and line width of the black matrix 3 can be set to a desired state.

(Coating fluid for coating formation)
Further, in the case of using the photolithography method in the same manner as the above-described black matrix 3 in forming the covering 4, the liquid repellent material 41 and the transparent resin 42 constituting the covering 4 are dissolved in a solvent. A coating liquid for forming a covering is used.

  Hereinafter, the liquid repellent material 41, the transparent resin 42, and the like included in the cover 4 and the coating liquid for forming the cover will be described in detail.

-Liquid repellent material As the liquid repellent material 41 constituting the covering 4, a fluorine-containing compound or silicone fine particles having a low surface energy is preferably used.

  Examples of the fluorine-containing compound include a polymer compound having a fluorine atom, a monomer having a hydrophilic group and / or a lipophilic group and a fluorine-containing group (low-molecular compound), or an oligomer. Examples thereof include homopolymers of vinylidene fluoride, vinyl fluoride and ethylene trifluoride, and copolymers of these with ethylene tetrafluoride and other solvent-soluble monomers. Thus, what is contained in a dissolved state or molecular order is advantageous in terms of improving patterning accuracy.

In general, a material known as a fluorosurfactant can also be used. By selecting the structure of the hydrophilic group or the lipophilic group depending on the type of the transparent resin 42, the mixed state with the photosensitive agent is improved. Can do. As the fluorine-containing group of the fluorosurfactant, a perfluoroalkyl group of CnF _{(2n + 1)} (n = 1 to 50), or one or more fluorine atoms therein is represented by CnF _{(2n + 1)} Use a branched type substituted with a chain, a type in which some or all of the hydrogen atoms of the aromatic ring are substituted with F or CnF _{(2n + 1)} , and a type in which the fluorine atom of tetrafluoroethylene is substituted with CF ₃ be able to. In the case of a perfluoroalkyl group, the carbon chain length is not limited, but preferably n <20, more preferably 3 <n <15. As the aromatic ring type, fluorobenzene, difluorobenzene, trifluorobenzene, perfluorobenzene, fluorophenol, and derivatives thereof can be used. Such fluorine-containing groups can be present alone or in a plurality in the surfactant. In particular, those containing two or more terminal CF ₃ ^- in the basic structural unit as a fluorine-containing component are more preferable in terms of ink repellency, because CF ₃ ^- is very superior to one structure. Specifically, when the monomer or oligomer is composed of repeating basic structural units, the structure including two or more linear side chains of CnF _{(2n + 1) in} the basic structural unit is Both can achieve good ink repellency.

As the hydrophilic group, OH group, carboxylic acid, sulfonic acid, phosphoric acid and its salt, ammonium salt, ethylene oxide, polyethylene oxide and the like are effective. As the lipophilic group, all structures showing hydrophobicity such as chain hydrocarbons and aromatic rings can be used. In the case of an oligomer, a structure in which these fluorine-containing group, hydrophilic group, and lipophilic group are pendant on the main chain is more effective. Among these, the fluorine-containing compound is preferably a monomer or oligomer having a fluorine-containing group and a hydrophilic group and / or a lipophilic group. A monomer or oligomer having a fluorine-containing group and a hydrophilic group and / or a lipophilic group is represented by the general formula Rf-X-Rf ', or the general formula (Rf-XR) -Y- (Rf'-X'-Rf). It is preferable that the compound represented by ') is included. Here, Rf and Rf ′ represent a fluoroalkyl group, R and R ′ represent an alkylene group, and Rf and Rf ′ or R and R ′ may be the same or different. X, X ′, and Y are —COO—, —OCOO—, —CONR ″ —, —OCONR ″ —, —SO ₂ NR ″ —, —SO ₂ —, —SO ₂ O—, —O—, —NR ″ —, —S—, —CO—, —OSO ₂ O—, —OPO (OH) O—, where X, X ′, and Y are the same or different It may be. R ″ represents an alkyl group or hydrogen.

Transparent resin The transparent resin 42 constituting the covering 4 is not particularly limited as long as it is a resin that can be cured in a state including the liquid repellent material 41 and can form a desired pattern shape. As the transparent resin 42 in the case of manufacturing the cover 4 by the lithography method, a photosensitive resin is used. Specifically, the transparent resin 42 is the same as the resin 32 used when the black matrix 3 is formed by the photolithography method. Things can be used.

  When the covering 4 is formed by photolithography using a covering forming coating liquid, the content of the liquid repellent material 41 with respect to the covering forming coating liquid is particularly limited. It is only necessary to ensure the desired liquid repellency. Specifically, it is preferably in the range of 0.005% by mass to 50% by mass, and particularly preferably in the range of 0.01% by mass to 25% by mass.

  The liquid repellent material 41 is preferably present in the vicinity of the upper surface 43 of the covering 4 and not in the vicinity of the side surface 44 thereof. Thereby, when a colored layer is formed on the base material 2, the flatness of the colored layer can be improved. In order to prevent so-called breakage, it is sufficient that the upper surface 43 portion of the covering 4 has liquid repellency, and it is sufficient to prevent the coloring agent from being placed on the portion. Since the colored layer of the color filter is a part formed, if the part has liquid repellency, the colorant may be repelled in this part, which may adversely affect the flatness of the colored layer. is there. In addition, as a method for confirming that the liquid repellent material is present on the upper surface rather than the side surface, it is performed by measuring the amount of fluorine present solely in the covering due to the liquid repellent material. The fluorine content is measured by measuring the upper part of the black matrix of the color filter with TOF-SIMS (Time Of Flight-Secondary Ionization Mass Spectrometer), and the upper surface of the cover and forward taper. Can be measured.

  As described above, the method for causing the liquid repellent material 41 to be unevenly distributed only in the vicinity of the upper surface 43 of the covering 4 is not particularly limited, and various methods can be appropriately employed. For example, according to the photolithography method described later, the liquid-repellent material in the transparent resin 42 is unevenly distributed on the surface during the pre-baking process, and unnecessary portions are deleted in the subsequent exposure process and development process. It is preferable that the liquid repellent material 41 is not present on the side wall portion of the body 4.

  The shape of the covering 4 is not particularly limited as long as the shape can cover the entire upper surface and side surfaces of the black matrix 3. Specifically, as described above, the combined shape of the black matrix 3 and the cover 4 is preferably a forward tapered shape whose cross-sectional shape is shorter at the top side than at the bottom side, as shown in FIG.

  Moreover, although the thickness T of the said covering 4 is not limited, For example, it is preferable that it is 1.0-2.5 micrometers. This is because if the thickness is less than 1.0 μm, the liquid repellency of the side wall portion may be strengthened. This is because there is a concern that the difference between the thickness of the combined portion and the thickness of the colored layer is increased, resulting in poor alignment of the liquid crystal.

  As for the liquid repellency of the covering body 4, it is sufficient that the upper surface 43 portion has a liquid repellency sufficient to prevent so-called breakage. Specifically, the contact angle with water is 85 ° or more, Alternatively, the contact angle with a liquid having a surface tension of 20 to 40 mN / m is preferably 30 to 65 °.

(Black matrix substrate manufacturing method)
Next, a method for manufacturing the black matrix substrate 1 will be described with reference to the drawings.

  FIG. 2 is a process explanatory view showing the manufacturing process of the black matrix substrate.

  The manufacturing method of the black matrix substrate 1 is not particularly limited, and any method can be adopted as long as the black matrix substrate 1 described with reference to FIG. 1 can be manufactured. However, among various methods, the method of forming the black matrix 3 and the covering 4 separately in this order by using the photolithography method shown in FIG. 2 and repeating this twice is preferable. This is because the photolithography method has been conventionally used frequently for the production of black matrix substrates and can therefore be carried out simply and at low cost.

  In the production of the covering 4, it is particularly preferable to use a photolithography method. The photolithography method includes a pre-baking step, and by performing this step, the liquid repellent material 41 in the transparent resin 42 can be moved to the vicinity of the surface 43 of the covering 4, and as a result, This is because the liquid repellency of the upper surface 43 portion can be made higher than that of the side surface 44.

  As shown in FIG. 2 (a), a black matrix coating step of coating the base material 2 with the black matrix forming coating solution containing the light shielding material 31 and the resin 32 described above is performed. The process may be any method that can apply the black matrix-forming coating solution with a uniform thickness, and known coating methods such as spin coating, spray coating, dip coating, roll coating, and bead coating. Coating may be performed by

  Next, as shown in FIG.2 (b), a prebaking process is performed as needed. In performing the prebaking process, a so-called hot plate H or the like can be used, and it may be performed at 60 to 120 ° C. for 0.5 to 5 minutes. In addition, it may replace with a prebaking process and a vacuum drying process may be performed, and both of these may be performed.

  As shown in FIG. 2C, after the pre-baking process or the like, an exposure process is performed in which energy is irradiated from above the mask M using the mask M having an opening having a desired shape. The exposure process may be any method that can form a black matrix pattern only in a desired region, and a conventionally used method can be appropriately selected. For example, proximity exposure may be performed in which the mask M is arranged and exposed with a distance of about several tens of μm from the surface of the black matrix forming coating solution coated on the substrate 2. When a negative photosensitive resin is used as the resin by this exposure, a curing reaction occurs at the exposed portion, and when a positive photosensitive resin is used, an acid generation reaction occurs at the exposed portion.

  As a light source used for exposure, a light source generally used for forming a black matrix can be used, and examples thereof include an ultrahigh pressure mercury lamp, a low pressure mercury lamp, and a metal halide lamp. it can.

  As shown in FIG. 2D, after the exposure step, a development step is performed in which the unexposed portion is removed using an alkaline developer and the black matrix 3 is developed. Although it does not specifically limit as an alkaline substance used for an alkaline developing solution, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n- Primary amines such as propylamine, secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, and tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH) , Quaternary ammonium salts such as choline, triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, diethylaminoethanol and other alcohol amines, pyrrole, piperidine, 1,8-dia Organic alkalis such as cyclic amines such as bicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane, morpholine, etc., ethanol, γ- A water-soluble organic solvent such as butyrolactone, dimethylformamide, or N-methyl-2-pyrrolidone may be added as appropriate.

  As shown in FIG. 2E, a post-baking process is performed after the developing process. This process is not particularly limited and may be performed in the same manner as in the past. Specifically, for example, the temperature may be 150 to 300 ° C, preferably 150 to 250 ° C.

  At this point, the black matrix 3 is completed.

  Next, as shown in FIGS. 2 (f) to 2 (j), a covering 4 is formed so as to cover the surface of the black matrix 3 formed on the substrate 2. In forming the covering 4, in the same manner as the formation of the black matrix 3 described above, a coating forming coating liquid coating step (FIG. 2 (f)), a reduced pressure drying step and / or a prebaking step ( 2 (g)), an exposure process (FIG. 2 (h)), a development process (FIG. 2 (i)), and a post-baking process (FIG. 2 (j)) may be performed in order, and the description thereof is omitted here.

  The black matrix substrate 1 is completed through the above steps.

(Color filter)
Next, a color filter using the black matrix substrate 1 of the present invention will be described.

  FIG. 3 is a cross-sectional view of the color filter 30.

  FIG. 4 is a front view of the color filter 30.

  As shown in FIG. 3, the color filter 30 has a configuration in which a colored layer 40 is formed in the opening 33 provided in the black matrix 3 by, for example, an ink jet method. The colored layer 40 formed in the opening 33 is not particularly limited, and may be composed of, for example, a red colored layer 40R, a green colored layer 40G, and a blue colored layer 40B.

  Here, in the color filter 30 of the present invention, it is not necessary that the covering 4 is provided on all the black matrices 3, and as shown in FIG. 3 and FIG. May be provided only. For example, in the case of the black matrix 3 existing between the colored layers of the same color, that is, in the case of the black matrix 3 ′ existing between the blue colored layers 40B in FIG. 3, it is assumed that the breakdown occurs and the colored layers are mixed. However, since it is the same color, there is no problem with the color. In such a case, it is not always necessary to cover the black matrix 3 in the portion with the covering 4. Therefore, in the case shown in FIG. 4, that is, when the colored layers of the same color are arranged vertically, the black matrix 3 extending in the vertical direction is preferably covered with the covering 4, while the black matrix 3 extending in the horizontal direction. In ', it is not always necessary to form the covering 4.

  The color filter manufacturing method is not particularly limited, but the colored layer 40 may be formed in the opening 33 provided in the black matrix 3 by an inkjet method. In this case, the colored layer forming coating liquid is used as an inkjet head. A colored layer is formed by discharging from a plurality of nozzles. The inkjet head used here is not particularly limited as long as it has a desired number of nozzles depending on the area of the color filter, the shape of the opening, and the like. Adopt it. Also, the discharge method when the inkjet head discharges the coating liquid for forming the colored layer is not particularly limited as long as it is a method capable of discharging a predetermined amount of the coating liquid. Specifically, for example, a method of continuously discharging a charged colored layer forming coating liquid and controlling the discharge amount by a magnetic field, a method of intermittently discharging using a piezoelectric element, and the like can be given. Among these, as a discharge method, it is preferable to use a method of intermittent discharge using a piezoelectric element. This is because a very small amount of discharge can be controlled with relatively high accuracy according to this method.

  Further, even in the above colored layer forming coating solution, those generally used when forming a colored layer by an ink jet method can be appropriately selected and used. Further, as shown in the drawing, in order to form colored layers of three colors of red, green, and blue, a coating solution for forming a colored layer of each color is required.

(Liquid crystal display device)
The black matrix substrate 1 and the color filter 30 of the present invention described above can be used for various display devices. For example, the color filter 30 of the present invention and the TFT array substrate (liquid crystal driving side substrate) are opposed to each other, and the inner peripheral side peripheral portions thereof are bonded together with a sealant, so that they are stuck in a state where a cell gap of a predetermined distance is maintained. Combined. An active matrix liquid crystal display device, which is a typical example of a liquid crystal display device, is obtained by filling the gap with a liquid crystal and sealing it.

  Hereinafter, the present invention will be specifically described using examples and comparative examples.

Example 1
1. Formation of Black Matrix Substrate A 0.7 mm thick, 100 mm wide, 100 mm long EAGLE 2000 made by Corning, which is used as a base material constituting the black matrix substrate, was prepared, washed with an alkaline aqueous solution, and then UV ozone. Treated. On this glass substrate, the black matrix forming coating solution was coated with a spin coater to a film thickness of 1.4 μm. Thereafter, it was dried under reduced pressure, and prebaked at 80 ° C. for 3 minutes on a hot plate.
Using a predetermined photomask, mask exposure was carried out with a UV exposure apparatus, followed by alkaline development, followed by rinsing with pure water, and post baking at 160 ° C. for 30 minutes in an oven. As a result, a black matrix substrate in which a grid-like black matrix having a line width of 7 μm and a plurality of openings of 170 μm × 510 μm was formed on a glass substrate was obtained.

  Next, on the glass substrate on which the black matrix is formed, a coating forming liquid containing a liquid repellent material and a transparent resin is coated with a film thickness of 1.4 μm from the upper surface of the black matrix (the film thickness combined with the black matrix 2.8 μm) was applied with a spin coater. Then, it dried under reduced pressure and pre-baked for 3 minutes at 80 degreeC with the hotplate.

  Using a predetermined photomask, align the photomask so that the opening of the photomask overlaps the black matrix, perform mask exposure with a UV exposure device, then perform alkali development, then rinse with pure water, Furthermore, the front surface and the back surface were additionally exposed, and further post-baked at 160 ° C. for 30 minutes in an oven. As a result, a black matrix substrate of Example 1 of the present invention was obtained in which the surface of the black matrix was covered with a coating on a glass substrate. The line width of the covering was 8.5 μm.

  When the liquid repellency of the black matrix substrate of Example 1 of the present invention was evaluated, the contact angle with a liquid having a surface tension of 40 mN / m was 50 ° on the upper surface of the black matrix covered with the coating, and 10 ° on the glass surface. It was the following.

2. Formation of Color Filter A colored layer forming coating solution was applied to the opening of the black matrix substrate of Example 1 of the present invention using an inkjet head. The coating liquid used was a pigment-dispersed ink for each color of RGB comprising a color filter pigment and a thermosetting resin. At this time, the amount of ink was changed so that the thickness of the colored layer after drying was −0.3 μm for RG and −0.1 μm for B than the thickness of the black matrix after drying.

  In this case, the ink jet apparatus uses a Dimatix material printer DMP-2831 manufactured by Fujifilm, and the coating is performed so that one nozzle is arranged per one opening (one pixel) of the black matrix, and the ink is used. The discharge droplets landed in the opening. Next, it was dried under reduced pressure, prebaked at 100 ° C. for 20 minutes using an oven, and further heated at 230 ° C. for 40 minutes in the oven to form the color filter of Example 1 of the present invention.

(Comparative Example 1)
The step of forming the black matrix substrate is different from that of Example 1 described above, and liquid repellency was imparted by plasma treatment without performing the step of forming the covering. Specifically, it is as follows.

1. Formation of Black Matrix Substrate Under the same conditions as in Example 1, a black matrix substrate of Comparative Example 1 was obtained so as to have a film thickness of 2.8 μm. The line width at this time was 7 μm. Next, the black matrix surface was subjected to atmospheric pressure plasma irradiation with fluorine gas introduced to impart liquid repellency to the black matrix surface. When the liquid repellency of this black matrix substrate was evaluated, the contact angle with a liquid having a surface tension of 40 mN / m was 52 ° on the upper surface of the black matrix and 10 ° or less on the glass surface.

2. Formation of Color Filter A colored filter of Comparative Example 1 was obtained by forming a colored layer on the black matrix substrate of Comparative Example 1 under the same conditions as in Example 1.

(Evaluation)
The surfaces of the color filters obtained in Example 1 and Comparative Example 1 were observed with an optical microscope, and it was confirmed whether the colored layer forming coating solution broke down and penetrated into other pixels beyond the black matrix. .

(result)
As a result, no breakage occurred in the color filter of Example 1 of the present invention in which the surface of the black matrix was covered with the covering, whereas the black matrix was not covered with the covering. In 1 color filter, breakage occurred. Thus, although the line width of the black matrix is the same, the breakage in Example 1 does not occur as compared with Comparative Example 1, and it is considered that the break margin is wide.

1 Black matrix substrate 2 Base material 3 Black matrix 4 Cover 30 Color filter

Claims (6)

A substrate;
A black matrix formed on the substrate and including a light-shielding material and a resin;
A black matrix substrate having:
The black matrix substrate, wherein the surface of the black matrix is covered with a covering containing a liquid repellent material and a transparent resin.   2. The black matrix substrate according to claim 1, wherein the liquid repellent material contained in the covering is distributed more on the upper surface than on the side surface of the covering. 3. A substrate;
A black matrix formed on the substrate and including a light-shielding material and a resin;
A color filter having a colored layer formed on an opening formed by the black matrix on the substrate,
At least a part of the black matrix in the color filter has a surface covered with a covering containing a liquid repellent material and a transparent resin.
  The color filter according to claim 3, wherein the liquid repellent material contained in the covering is distributed more on the upper surface than on the side surface of the covering.   5. The color filter according to claim 3, wherein the color filter has two or more colored layers, and at least a black matrix existing between the colored layers of different colors is covered with the covering. In a liquid crystal display device having a color filter and a counter electrode substrate facing each other, and a liquid crystal layer sealed between the two,
The color filter is formed on a base material, a black matrix formed on the base material and including a light-shielding material and a resin, and a color formed on an opening portion formed on the base material by the black matrix. And a surface of at least a part of the black matrix in the color filter is covered with a covering containing a liquid repellent material and a transparent resin.

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