JP4569283B2 - Manufacturing method of color filter - Google Patents

Description

  The present invention relates to a method for producing a color filter used for a color display device such as a color liquid crystal display device.

  For example, in a color filter used in a color liquid crystal display device, etc., three colored patterns of red (R), green (G), and blue (B) are regularly arranged in a dot shape or a stripe shape on a transparent substrate. Thus, between each colored layer, a lattice-shaped or stripe-shaped light shielding layer so-called black matrix serving as a partition for optically separating each colored layer is provided. In such a color filter, conventionally, each layer of a black matrix and three colored patterns is formed on a transparent substrate by using a photolithography method that repeats resist coating, exposure, and development processes. It was. When the photolithography method is used, the pattern accuracy is good, but there is a problem that the number of work steps is large and the cost is high.

  In particular, with the trend toward larger screens of display devices in recent years, there has been a demand for a method for manufacturing a color filter with good pattern accuracy at low cost even when applied to a wide area.

  For this reason, there is a method in which a black matrix is formed by a photolithography method, and a colored pattern of three colors is formed by using an ink jet method instead of the photolithography method (see, for example, Patent Document 1). However, the black matrix formed by using the photolithography method has a problem that exposure failure is likely to occur due to a light shielding component included in the black matrix.

  Therefore, a method has been proposed in which the black matrix is formed using a printing method instead of the photolithography method.

  In order to obtain a high-definition coloring pattern, the black matrix preferably has a rectangular cross section. When there are many solvent components in the ink used for printing the black matrix, the cross section of the black matrix obtained after the solvent is volatilized is rounded. It is conceivable to use reversal printing in which a high-definition pattern is obtained over a wide area with a small amount of solvent component in the ink used.

In this reversal printing, ink is uniformly applied to a blanket plate, unnecessary ink is removed using an intaglio plate, a reversal pattern is formed on the blanket plate, and then transferred onto the substrate at a time. At this time, a release agent is sufficiently added to the ink used in order to improve the release property from the blanket plate. However, this release agent may be eluted from the black matrix by baking after reversal printing and spread not only to the black matrix surface but also to the substrate surface. As a result, when a colored pattern of three colors is formed on the substrate between the partition walls by the black matrix by ink-jet printing, the ink is repelled and not sufficiently placed between the partition walls, resulting in white spots. As a result, the color filter There was a problem of causing uneven color.
JP-A-6-347637

  The present invention has been made in view of the above circumstances, and the light shielding layer and the coloring pattern can be applied to a large screen without using a photolithographic method using a mask with good dimensional accuracy and low cost. An object of the present invention is to provide a method for manufacturing a high-definition color filter that can be formed and has no color unevenness.

The color filter manufacturing method according to the first aspect of the present invention includes a first light shielding layer having a predetermined pattern on each main surface of a transparent substrate having first and second main surfaces facing each other. And a step of forming the second light shielding layer by a printing method,
Forming a positive resist layer containing an ink repellent agent on the first main surface of the transparent substrate and the first light shielding layer;
The positive resist layer is exposed from the second main surface side of the transparent substrate and then developed to selectively provide a patterned positive resist layer on the first light shielding layer. A pattern processing step of providing an opening from which the resist layer has been removed between the first light shielding layers,
After the pattern processing step, after removing the second light shielding layer, and after removing the second light shielding layer, colored ink is ejected into the opening by an ink jet method to form a colored layer. It comprises the process.

Moreover, the manufacturing method of the color filter which concerns on the 2nd viewpoint of this invention,
Forming a first light shielding layer and a second light shielding layer each having a predetermined pattern on each principal surface of the transparent substrate having the first and second principal surfaces facing each other by a printing method;
Forming a positive resist layer on the first main surface of the transparent substrate and the light shielding layer formed on the first main surface;
The positive resist layer is exposed from the second main surface side of the transparent substrate and then developed to selectively provide a patterned positive resist layer on the first light shielding layer. A pattern processing step of providing an opening from which the resist layer has been removed between the first light shielding layers,
A step of removing the second light shielding layer after the pattern processing step;
A step of forming an ink repellent layer on the patterned positive resist layer after the step of removing the second light shielding layer;
After the step of forming the ink repellent layer, a step of discharging a colored ink to the opening by an ink jet method to form a colored layer is provided.

  In the present invention, preferably, a reverse printing method can be used as the printing method.

  In the present invention, it is preferable that an ink for forming a light shielding layer containing a release agent can be used in the reversal printing method.

  In the present invention, preferably, a step of heating the printed light shielding layer may be further included before the step of forming the positive resist layer.

  In the present invention, preferably, before the step of forming the positive resist layer, at least a step of subjecting at least the first main surface of the transparent substrate on which the light shielding layer is formed to ultraviolet ozone cleaning is further provided. Can do.

  In the present invention, preferably, a step of heating the positive resist layer may be further included before the step of forming the ink repellent layer.

  In the present invention, preferably, the width of the pattern of the light shielding layer on the second main surface can be made smaller than the width of the pattern of the light shielding layer on the first main surface.

  By using the method of the present invention, the light shielding layer and the colored pattern can be formed with good dimensional accuracy and low cost that can be applied to a large screen without using a photolithography method using a mask. Therefore, a high-definition color filter without color unevenness can be obtained.

  The color filter manufacturing method according to the first aspect of the present invention includes a step of forming a light shielding layer having a predetermined pattern on a transparent substrate by a printing method, a positive resist on the transparent substrate on which the light shielding layer is formed. Step of forming a layer, opening the positive resist layer after exposure, and providing a positive resist layer selectively patterned on the light shielding layer by performing development, and opening the positive resist layer removed between the light shielding layers In a color filter manufacturing method comprising a pattern processing step of providing a portion and a step of forming a colored layer by discharging colored ink to the opening by an inkjet method, the light shielding layers are formed on both main surfaces of the transparent substrate. Then, a first light shielding layer having a predetermined pattern is provided on the first main surface, and a second light shielding layer having a predetermined pattern is provided on the second main surface, and the positive resist layer has a light-repellent property. Containing click agent, exposure is back exposed from the second major surface side of the transparent substrate, the second light-shielding layer, characterized in that it is removed after patterning process.

  The color filter manufacturing method according to the second aspect of the present invention includes a step of forming a light shielding layer having a predetermined pattern on a transparent substrate by a printing method, a positive resist on the transparent substrate on which the light shielding layer is formed. Step of forming a layer, opening the positive resist layer after exposure, and providing a positive resist layer selectively patterned on the light shielding layer by performing development, and opening the positive resist layer removed between the light shielding layers In a color filter manufacturing method comprising a pattern processing step of providing a portion and a step of forming a colored layer by discharging colored ink to the opening by an ink jet method, the light shielding layers are formed on both main surfaces of the transparent substrate. A first light-shielding layer having a predetermined pattern on the first main surface, and a second light-shielding layer having a predetermined pattern on the second main surface. of Back exposure is performed from the surface side, the second light shielding layer is removed after the pattern processing step, and after removing the second light shielding layer, an ink repellent layer is formed on the patterned positive resist layer. And

  According to the method of the present invention, the light shielding layer is formed by a printing method, and further, the colored layer is formed by an ink jet method, so that the resist is compared with the case where the light shielding layer or the colored layer is formed by a photolithography method. In addition, it is possible to reduce the number of materials such as a developing solution, the number of work steps, and the work time, and the cost of manufacturing a color filter can be significantly reduced.

  According to the method of the first aspect of the present invention, the partition including the light shielding layer and the positive resist layer formed on the transparent substrate has a height sufficiently higher than that of the light shielding layer alone. The positive resist layer that is the uppermost layer of the partition wall contains an ink repellent agent and has a higher ink repellency than the light shielding layer, so that the colored ink ejected by inkjet printing is repelled on the top surface of the partition wall. It is easily received in the opening, and it is possible to prevent white spots due to uneven transfer, and it is difficult for ink to move to the adjacent opening beyond the partition wall, thereby preventing color mixing.

  Further, according to the method of the second aspect of the present invention, the laminate including the light shielding layer, the positive resist layer, and the ink repellent layer formed on the transparent substrate is more than the light shielding layer alone. The ink repellent agent layer that constitutes the partition wall having a sufficiently high height and is the uppermost layer of the partition wall has higher ink repellency than the light shielding layer and the positive resist layer. For this reason, the colored ink ejected by ink jet printing is repelled on the upper surface of the partition wall and easily received in the opening, and it becomes possible to prevent white spots due to uneven transfer, and to the adjacent opening beyond the partition. It is difficult for ink to migrate, and color mixing can be prevented.

  Thus, according to the present invention, a high-definition color filter having no color unevenness can be manufactured.

  In addition, the pattern processing of the positive resist layer used in the present invention can be back-exposed from the second main surface of the transparent substrate, so that a special mask is not required, and it is low-cost and easy. The positive resist layer can be colored.

  Furthermore, in the method of the present invention, a light shielding layer is formed on both surfaces of the transparent substrate in accordance with a predetermined pattern. Therefore, even if a defect occurs in the light shielding layer on one surface during exposure, This light shielding layer can be used as a mask to compensate for this defect, so that the pattern processing accuracy of the positive resist layer becomes better than forming the light shielding layer only on one surface.

  As described above, the method of the present invention has good dimensional accuracy and is less likely to cause color unevenness. Therefore, the method of the present invention can sufficiently cope with the manufacture of a color filter having a large screen size of, for example, 360 mm × 460 mm or more.

  Hereinafter, the present invention will be described in more detail with reference to the drawings.

  1 to 8 are views for explaining an example of a color filter manufacturing method according to the first aspect of the present invention.

  In the method for manufacturing a color filter according to the first aspect of the present invention, first, as shown in FIG. 1, a transparent substrate 1 having a first main surface 2 and a second main surface 3 facing the first main surface 2 is prepared. The first light shielding layer 4 is formed on the first main surface 2 by a printing method, for example, in a lattice shape or a stripe shape. Similarly, the second light shielding layer is formed on the second main surface 3 by a printing method. 4 ′ is formed in a pattern corresponding to the pattern of the light shielding layer 4 in a region facing the light shielding layer 4 through the transparent substrate 1.

  At this time, the pattern dimension of the second light shielding layer 4 ′ is the same as the pattern dimension of the first light shielding layer 4, or the width of the pattern may be slightly narrowed as shown in FIG. it can. When the pattern width is narrowed, two kinds of pattern originals are required for printing, but the alignment of the second light shielding layer formed in the region facing the first light shielding layer is facilitated. .

  After forming the light shielding layer 4 having a predetermined pattern by the reverse printing method, or after forming the light shielding layer 4 and the light shielding layer 4 ′, heating so-called post-baking can be preferably performed. Thereby, the printed light shielding layer can be thermally cured and firmly fixed on the transparent substrate 1. The heating temperature can be, for example, 150 ° C. to 230 ° C. The light shielding layer formed by printing may contain a component that repels the ink-jet ink used when forming a colored pattern. This component may be eluted on the surface of the light shielding layer by post-baking. In such a case, this component can be removed by performing ultraviolet ozone cleaning after post-baking. Further, when this eluted component reaches the surface of the transparent substrate between the light shielding layers, it is more preferable to remove this component by ultraviolet ozone cleaning or the like.

  Next, as shown in FIG. 3, a positive resist layer 5 containing an ink repellent agent is formed on the first main surface 2 of the transparent substrate and the light shielding layer 4 formed on the first main surface 2. To do. After the positive resist layer 5 is formed, pre-baking can be performed at 90 ° C. to 110 ° C., for example, as necessary. Thereby, the positive resist layer 5 can be hardened and more firmly fixed on the first light shielding layer 4.

  Thereafter, as shown in FIG. 4, exposure in the direction of the first main surface 2 from the second main surface 3 side of the transparent substrate 1 is performed so-called back exposure. At this time, since the first light shielding layer 4 and the second light shielding layer 4 ′ function like a photomask, the first light shielding layer 4 is not formed by the light transmitted through the transparent substrate 1. The positive resist layer 5 on the region is exposed, and the positive resist layer located on the region where the first light shielding layer 4 is formed is not exposed. After the exposure, development is performed to remove the exposed positive resist layer. In addition, since both the light shielding layer 4 and the light shielding layer 4 ′ having a predetermined pattern are formed on the transparent substrate 1, for example, even when a defect occurs when the first light shielding layer 4 is formed, The opposing second light shielding layer 4 ′ serves as a mask, and the resist layer can be exposed in a desired pattern, and pattern processing can be performed with good accuracy.

  Thus, as shown in FIG. 5, the positive resist layer 5a patterned according to the pattern of the first light shielding layer 4 is provided on the first light shielding layer 4, and the first light shielding layer 4 is provided. Between the light shielding layer 4, an opening from which the exposed positive resist layer is removed is provided. Since the stack of the patterned first light shielding layer 4 and the positive resist layer 5a is higher than the height of the first light shielding layer 4 alone, it is discharged onto the transparent substrate 1 by an inkjet nozzle. Provided is a partition wall having a height that can more easily receive colored pattern coating ink. Further, the positive resist layer 5a which is the uppermost layer has ink repellency, and the first light shielding layer 4 therebelow has lower ink repellency than the positive resist layer 5a. And can be well received within the aperture.

  After the formation of the positive resist layer 5a, heating so-called post-baking can be arbitrarily performed. Thereby, the positive resist 5a can be sufficiently heat-cured, and the ink repellent agent can be eluted from the surface of the positive resist layer 5a to increase the ink repellency. The heating temperature can be, for example, 150 ° C. to 230 ° C.

  Subsequently, as shown in FIG. 6, the second light shielding layer 4 ′ is removed from the second main surface.

  Thereafter, as shown in FIG. 7, the colored pattern coating ink 8 such as the red colored ink 8R, the green colored ink 8G, and the blue colored ink 8B are applied to the inkjet device, respectively, and the inkjet nozzle 7 such as the red inkjet nozzle 7R and green. The colored inks 8R, 8G, and 8B of each color are ejected in a predetermined arrangement from the inkjet nozzle 7G for blue and the inkjet nozzle 7B for blue to the opening. The colored inks 8R, 8G, and 8B of the respective colors can be received in the predetermined openings without protruding into the openings adjacent to each other by the partition walls formed of the above-described lamination. For this reason, color mixing between the colored inks 8R, 8G, and 8B of each color and black defects caused thereby are difficult to occur, and uneven coating of the colored layer (white spots) and resulting color unevenness are difficult to occur.

  In this way, as shown in FIG. 8, on the transparent substrate 1, a first light shielding layer 4 having a predetermined pattern and a positive resist layer 5a containing an ink repellent agent, and a gap between the layers. The color filter 10 according to the first aspect of the present invention including the colored pattern 11 having the red colored layer 11R, the green colored layer 11G, and the blue colored layer 11B arranged regularly is formed.

  In the method for producing a color filter according to the second aspect of the present invention, the first resist except that a positive resist layer to which no ink repellent agent is added is formed instead of the positive resist layer containing the ink repellent agent. In the same manner as in each of the manufacturing steps shown in FIGS. 1 to 6 of the color filter according to the above aspect, a patterned positive resist layer to which no ink repellent agent is added is formed on the light shielding layer 4, The second light shielding layer is removed from the main surface.

  Thereafter, as shown in FIG. 9, the ink repellent layer 12 is formed on the positive resist layer 5'a to which the ink repellent agent is not added. Since the stack of the patterned first light shielding layer 4 and the positive resist layer 5a is higher than the height of the first light shielding layer 4 alone, it is discharged onto the transparent substrate 1 by an inkjet nozzle. Provided is a partition wall having a height that can more easily receive colored pattern coating ink. Further, the ink repellent layer 12 which is the uppermost layer has ink repellency, and the first light shielding layer 4 and the positive resist layer 5 therebelow have lower ink repellency than the ink repellent layer 12, so that The ink is repelled on the top of the septum and can be well received in the opening.

  Further, as shown in FIG. 10, a colored pattern coating ink 8 such as a red colored ink 8R, a green colored ink 8G, and a blue colored ink 8B are applied to the inkjet device, respectively, and an inkjet nozzle 7 such as a red inkjet nozzle 7R or green color is applied. The colored inks 8R, 8G, and 8B of each color are ejected in a predetermined arrangement from the inkjet nozzle 7G for blue and the inkjet nozzle 7B for blue to the opening. The colored inks 8R, 8G, and 8B of the respective colors can be received in the predetermined openings without protruding into the openings adjacent to each other by the partition walls formed of the above-described lamination. For this reason, color mixing between the colored inks 8R, 8G, and 8B of each color and black defects caused thereby are difficult to occur, and uneven coating of the colored layer (white spots) and resulting color unevenness are difficult to occur.

  In this way, as shown in FIG. 11, the first light shielding layer 4, the positive resist layer 5′a, and the ink repellent agent layer 12 having a predetermined pattern are laminated on the transparent substrate 1, and this lamination is performed. The color filter 20 according to the second aspect of the present invention is formed, which includes the colored pattern 11 having the red colored layer 11R, the green colored layer 11G, and the blue colored layer 11B regularly arranged therebetween.

  As the transparent substrate, for example, a plastic sheet and a plastic film such as a glass substrate, a quartz substrate, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethersulfone, and polyacrylate can be preferably used.

  The light shielding layer can be printed using an ink composition for printing a light shielding layer. The ink composition may contain an ink binder resin and a black light shielding material.

  The black light shielding material can be selected from the group consisting of black pigment, black dye, carbon black, aniline black, graphite, and iron black, for example. This ink composition can further contain titanium oxide, an inorganic pigment, and an organic pigment.

  The light shielding layer can be formed, for example, in a stripe or lattice pattern. The width of these patterns can be set to 5 μm to 50 μm, for example. The thickness of the light shielding layer can be 0.5 μm to 1.5 μm.

  Examples of the printing method include a reverse printing method, a letterpress printing method, and a flat printing method. Preferably, the reverse printing method can be used.

  FIGS. 12 to 14 are views for explaining an example of the light shielding layer forming process using the reverse printing method.

  In the figure, 22 is a coating unit for applying a constant amount of light shielding layer forming ink, 24 is a rotatable cylindrical blanket cylinder that receives the light shielding layer forming ink from the coating unit 22 and supports the ink layer 23, 32. Denotes a blanket installed on the blanket cylinder, and 25 denotes a peeling member having a concave pattern corresponding to the reversal pattern of the light shielding layer and for removing unnecessary portions from the ink layer 23 on the blanket 32.

  First, as shown in FIG. 12, the blanket cylinder 24 is rotationally moved to receive ink from the coating unit 22 and apply a uniform ink layer 23 on the blanket 32.

  Next, as shown in FIG. 13, the peeling member 25 is brought into contact with the ink layer 23, unnecessary portions are removed from the ink layer 23, and a light shielding layer reversal pattern 31 is formed on the blanket 24.

  Thereafter, as shown in FIG. 14, the transparent substrate 27 is brought into contact with the blanket 24 on which the reverse pattern 31 is formed, and the reverse pattern 31 is transferred onto the transparent substrate 27 to form the light shielding layer 26.

  Further, a light shielding layer can be similarly formed on the other main surface of the transparent substrate 27. When changing the width of the light shielding layer pattern on the other main surface, the peeling member can be replaced with a peeling member having the same concave pattern except that the width is narrowed.

  As the coating unit, a coating device such as a slit coater and a die coater can be used.

  The ink composition for forming a light shielding layer used for reversal printing may contain the black light shielding material, the ink binder resin, a release agent, a solvent, a dispersant, and the like.

  As the binder resin for ink, for example, casein, gelatin, polyvinyl alcohol, carboxymethyl acetal, polyimide resin, acrylic resin, epoxy resin, and melamine resin can be selected. When heat resistance and light resistance are required, for example, an acrylic resin can be preferably used. The content of the binder resin for ink is preferably 5% by weight to 50% by weight with respect to the total weight of the ink composition.

  As the solvent, those appropriately selected in consideration of the coating property of the ink composition, the stability of the dispersant, and the like can be used. Examples thereof include toluene, xylene, ethyl cellosolve, ethyl cellosolve acetate, diglyme, and cyclohexanone. . The content of the solvent is preferably 5% by weight to 50% by weight with respect to the total weight of the ink composition.

  As the release agent, for example, a material containing silicon and / or fluorine atoms such as a fluororesin-based member and a silicone resin-based member is used. As the fluororesin-based member, a fluorine-containing monomer or oligomer (low molecular compound), silicone As the resin-based member, a silicon-containing monomer or oligomer (low molecular compound) can be used. The content of the release agent is preferably 0.01% to 5% by weight, more preferably 0.1% to 0.5% by weight, based on the total weight of the ink composition.

  Examples of the dispersant include nonionic surfactants such as polyoxyethylene alkyl ethers, ionic surfactants such as sodium alkylbenzene sulfonate, poly fatty acid salts, fatty acid salt alkyl phosphates, tetraalkyl ammonium salts, and the like. Examples thereof include organic pigment derivatives and polyester. These dispersants can be used alone or in admixture of two or more. The content of the dispersant is preferably 1% to 20% by weight.

  The peeling member is preferably a material having moderate hardness, dimensional stability, and workability, and may be selected from, for example, glass, metal, and plastic. The blanket is preferably selected in combination with the light shielding layer forming ink composition, and is preferably a material having a certain degree of hardness and flexibility such as a polymer film or rubber. Acrylate, silicone resin, polycarbonate, polyolefin, polymethyl methacrylate, polyethylene terephthalate, polyamide, polyvinyl chloride, polyvinylidene chloride, ethylene-vinyl acetate copolymer, polyethersulfone, silicone elastomer, fluorine elastomer, butyl rubber, ethylene Propylene rubber or a mixture thereof is used.

  In this reversal printing method, an ink for forming a light shielding layer containing a release agent is preferably used in order to easily peel the ink layer from the blanket plate during transfer. When a light shielding layer formed by reversal printing is used, the release agent is eluted from the light shielding layer by post-baking after the light shielding layer is formed, and the upper surface, side surfaces, and the openings between the light shielding layers are transparent. There is a tendency to spread on the substrate surface. When such a releasing agent is present on the side surface and the opening of the light shielding layer, the colored pattern coating ink is repelled and not received in the opening, so-called white spots occur, and as a result, uneven color tends to occur. For this reason, after the post-baking, the light shielding layer formed on the first principal surface and the first principal surface of the transparent substrate is subjected to ultraviolet ozone cleaning to remove the release agent eluted from the light shielding layer. be able to. Thereafter, a positive resist layer may be applied.

  In the ultraviolet ozone cleaning, for example, the concentration of the ozone atmosphere is set to several tens to several tens of thousands ppm, and the ultraviolet rays are irradiated at an exposure amount of 5 to 1000 mW for 1 to 10 minutes. Thereby, organic substance can be decomposed | disassembled. In addition, as a UV lamp to be used, for example, a low / medium output (50 to 200 mW) or a high output (500 to 5000 mW) can be used.

  The positive resist layer can be formed by applying the positive resist composition using an application method such as a bar coater, a roll coater, a spin coater, a die coater, or a gravure coater. For example, the thickness of the positive resist layer can be 0.5 μm to 5.0 μm.

  In the positive resist composition used in the present invention, for example, an alkali-soluble novolak resin is used as the film forming substance. Examples of the alkali-soluble novolac resin include reaction products of phenols and aldehydes.

  Phenols include phenol, O-, m-, P-cresol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,3,5-trimethylphenol, 4-t-butylphenol, 2 -T-butylphenol, 3-t-butylphenol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 3-methyl-6-t-butylphenol, 4-methyl-2-t-butylphenol, 2-naphthol, Aromatic hydroxy compounds such as 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene and 1,7-dihydroxynaphthalene are exemplified.

  Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propyl aldehyde, benzaldehyde, and phenylaldehyde.

  The reaction of phenols and aldehydes is carried out in the presence of a catalyst and can be carried out in bulk or in a solvent. Catalysts include organic acids such as formic acid, oxalic acid, P-toluenesulfonic acid, and trichloroacetic acid, inorganic acids such as phosphoric acid, hydrochloric acid, sulfuric acid, and perchloric acid, and divalent metal salts such as zinc acetate and magnesium acetate. Can be mentioned.

  In the positive resist composition used in the present invention, a quinonediazide group-containing compound can be used as the photosensitive component. Examples of the quinonediazide group-containing compound include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,3,4,4′-tetrahydroxybenzophenone, and naphthoquinone-1,2-diazide-5-sulfonic acid. Alternatively, a complete ester compound with naphthoquinone-1,2-diazide-4-sulfonic acid, or a partial ester compound thereof can be used.

  In addition, other quinonediazide group-containing compounds such as orthobenzoquinonediazide, orthonaphthoquinonediazide, orthoanthraquinonediazide, orthonaphthoquinonediazidesulfonic acid esters and the like, and further substituted with orthonaphthoquinonesulfonylsulfonyl and a hydroxyl group or amino group. Compounds such as phenol, p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphthol, carbinol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, and hydroxylated esterification Alternatively, a reaction product with etherified gallic acid, aniline, P-aminodiphenylamine, or the like can also be used. These may be used alone or in combination of two or more. These quinonediazide group-containing compounds include, for example, the polyhydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfonyl chloride or naphthoquinone-1,2-diazido-4-sulfonyl chloride in a suitable solvent such as dioxane. It can be produced by condensation in the presence of an alkali such as triethanolamine, alkali carbonate, alkali hydrogen carbonate, etc., and complete esterification or partial esterification.

  The compounding ratio of the alkali-soluble novolak resin and the quinonediazide group-containing compound in the positive resist composition used in the present invention is preferably 5 to 40 parts by weight of the quinonediazide group-containing compound with respect to 100 parts by weight of the alkali-soluble novolak resin. Is in the range of 10 to 30 parts by weight.

  Further, as a solvent used in the positive resist composition used in the present invention, ketones such as 2-heptanone, acetone, methyl ethyl ketone, 1,1,1-trimethylacetone, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol Or polyhydric alcohols such as dimethyl glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and derivatives thereof, cyclic ethers such as dioxane, ethyl lactate, methyl acetate, acetic acid Examples include esters such as ethyl, butyl acetate, methyl propionate, ethyl pyruvate, methyl 3-methoxypropionate, and methyl 3-ethoxypropionate. These can be used alone or in combination of two or more. The amount of the solvent used is not particularly limited as long as it is a coating that can form a uniform coating film without pinholes and uneven coating on the substrate. It can be prepared such that the amount of solvent is, for example, 50 to 97% by weight based on the total weight of the resist composition.

  To the positive resist composition, preferably 0.01% by weight to 10% by weight of the ink repellent agent is added with respect to the total weight of the positive resist.

  Further, the positive resist composition used in the present invention further has a compatible additive as necessary, for example, a resin, a plasticizer, a stabilizer, a surfactant for improving the performance of the resist layer, Additives such as a dye for improving the visibility of the resist pattern after development and a sensitizer for improving the sensitization effect can be contained.

  Examples of the ink repellent agent used in the positive resist composition include a fluorine-based resin, a silicon-based resin, a copolymer oligomer having a perfluoroalkyl group-containing acrylate or methacrylate as a main component, and the like. Preferably, for example, a block copolymer of a compatible segment and a fluorine segment, and a block copolymer of a compatible segment and a silicon-based segment can be used. These block copolymers have good modification effect sustainability. Specifically, for example, random oligomers manufactured by Seimi Chemical Co., Ltd., trade name Surflon, grafted oligomers manufactured by Toagosei Chemical Co., Ltd., trade name Aron G, and block type oligomer Modiper F manufactured by Nippon Oil & Fats Co., Ltd. can be mentioned.

  As the exposure means for the positive resist layer, for example, those that expose light having a wavelength with which a radically polymerizable compound reacts, such as an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon lamp, and a halogen lamp can be used.

  As the developer for the positive resist layer, a solution capable of dissolving the positive resist in the exposed portion, for example, an alkaline aqueous solution such as sodium hydroxide or sodium carbonate can be used.

  The second light shielding layer can be removed by, for example, alkali cleaning or polishing with a polishing machine.

  As the alkaline cleaning liquid, for example, an aqueous sodium carbonate solution, an aqueous tetramethylammonium hydroxide solution, an aqueous alkanolamine solution, or the like can be used.

  As an application method of the alkaline cleaning liquid, various development methods used in photolithography can be substituted. Examples of such development methods include immersion development, swing development, dip development, shower spray development, and paddle development.

  Further, as the polishing machine, for example, an Oscar type polishing machine can be used.

  The ink repellent agent layer can be preferably formed using the reverse printing method.

  For example, an ink for forming an ink repellent agent layer containing an ink repellent agent and a solvent is prepared, and an ink repellent agent layer having a thickness of 0.01 μm to 1 μm is uniformly formed on a blanket plate in the same manner as in the step shown in FIG. Then, a transparent substrate having a light shielding layer and a positive resist layer patterned according to the pattern of the light shielding layer is introduced, and the positive resist layer is brought into contact with the ink repellent agent layer to form a positive resist. An ink repellent agent layer having a thickness of 0.01 μm to 0.5 μm can be transferred onto the layer. After the transfer, it can be baked preferably at 50 to 150 ° C. for 1 to 10 minutes.

  Examples of the ink repellent agent preferably used in the ink repellent agent layer include a fluorine-based resin, a silicon-based resin, a copolymer oligomer having a perfluoroalkyl group-containing acrylate or methacrylate as a main component, and the like. Preferably, for example, a block copolymer of a compatible segment and a fluorine segment, and a block copolymer of a compatible segment and a silicon-based segment can be used. These block copolymers have good modification effect sustainability. Specifically, for example, random oligomers manufactured by Seimi Chemical Co., Ltd., trade name Surflon, grafted oligomers manufactured by Toagosei Chemical Co., Ltd., trade name Aron G, and block type oligomer Modiper F manufactured by Nippon Oil & Fats Co., Ltd. can be mentioned.

  Moreover, the ink repellent agent used for an ink repellent agent layer can be mixed with a solvent as needed. Examples of the solvent include methanol, ethanol, toluene, xylene, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve, methyl cellosolve acetate, diglyme, cyclohexanone, ethylbenzene, isoamyl acetate, N-amyl acetate, propylene glycol monomethyl ether (acetate), propylene Glycol monoethyl ether (acetate), diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, dipropylene Glycol, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, ethyl lactate, and ethyl ethoxypropionate and the like are used, these solvents may be used alone or in combination of two or more.

  For example, when the ink repellent agent layer is formed by a reversal printing method, the ink for forming the ink repellent agent layer may preferably contain 0.01 to 10% by weight of the ink repellent agent.

  The color pattern coating ink contains a colorant such as a dye and a pigment, an ink binder resin, a dispersant, and a solvent.

  Specific examples of the pigment used in the coloring pattern coating ink include Pigment Red 9, 19, 38, 43, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 215. 216, 208, 216, 217, 220, 223, 224, 226, 227, 228, 240, Pigment Blue 15, 15: 6, 16, 22, 29, 60, 64, Pigment Green 7, 36, Pigment Red 20, 24, 86, 93, 108, 109, 110, 117, 125, 137, 138, 139, 147, 148, 153, 154, 166, 168, 185, Pigment Orange 36, Pigment Violet 23, etc. 2 or more It can be mixed with use.

  As the solvent for the color pattern coating ink, a solvent having a surface tension within a range suitable for the ink jet system, for example, 40 mN / m or less and a boiling point of 130 ° C. or more can be preferably used. If the surface tension exceeds 40 mN / m, the dot shape stability during ink jet discharge tends to be significantly adversely affected. If the boiling point is less than 130 ° C., the drying property near the nozzle becomes extremely high. Therefore, there is a tendency to cause defects such as nozzle clogging. Suitable solvents include, for example, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl ether, 2- (2- And ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethyl acetate, 2- (2-butoxyethoxy) ethyl acetate, 2-phenoxyethanol, and diethylene glycol dimethyl ether. If necessary, they can be used alone or in admixture of two or more. In addition to solubility, the solvent is required to be stable over time, dryness, and the like, and is appropriately selected according to the properties of the colorant and binder resin used.

  Examples of the binder resin that can be used in the colored pattern coating ink include casein, gelatin, polyvinyl alcohol, carboxymethyl acetal, polyimide resin, acrylic resin, epoxy resin, and melamine resin, and the like, depending on the colorant used. Can be selected. For example, acrylic resin is preferable when heat resistance and light resistance are required.

  In order to improve the dispersion of the pigment in the binder resin, a dispersant can be added to the colored pattern coating ink. Examples of the dispersant include a nonionic surfactant such as polyoxyethylene alkyl ether, and examples of the ionic surfactant include sodium alkylbenzene sulfonate, poly fatty acid salt, fatty acid salt alkyl phosphate, and tetra In addition to alkylammonium salts, organic pigment derivatives, polyesters, and the like can be given. A dispersing agent can be used individually or in mixture of 2 or more types.

  Moreover, the colored layer of each color can be formed with a thickness of 1 μm to 2 μm, for example.

Examples Hereinafter, the present invention will be specifically described with reference to Examples.

Example 1
Production of Light Shielding Layer A non-alkali glass substrate 1737 manufactured by Corning was prepared as a transparent substrate.

  The following ink composition materials for light shielding layer printing were prepared.

Ink composition ink binder resin for light shielding layer printing
Polyimide precursor manufactured by Toray Industries, Inc .: “Semicofine SP-510”
10 parts by weight black shading agent carbon black 7.5 parts by weight solvent N-methyl-2-pyrrolidone (NMP) 130 parts by weight dispersant copper phthalocyanine derivative 5 parts by weight release agent fluorinated low molecular weight compound
BYK333 manufactured by BYK Japan Japan Co., Ltd. 0.5 part by weight The ink material having the above composition was charged into a bead mill disperser and dispersed for 3 hours while cooling to prepare an ink composition for printing a light shielding layer.

  The obtained ink composition was subjected to the reverse printing method in the same manner as in the steps shown in FIGS. 7 to 9, and a light shielding layer was formed as follows. In the reverse printing, a metal roll having a surface coated with a silicone resin was used as the blanket plate. Moreover, the flat glass which processed the surface into the uneven pattern according to the inversion pattern of the light shielding layer pattern was used as a peeling member.

  First, the ink composition was applied on a blanket plate by a slit coater method to form a uniform ink layer.

  Next, unnecessary portions were removed by a peeling member, and an inverted pattern of the light shielding layer pattern was formed on the blanket plate.

  Thereafter, one main surface of the transparent substrate was brought into contact with the blanket plate on which the reverse pattern was formed, the reverse pattern was transferred onto the main surface, and the first light shielding layer was transferred.

  Next, the transparent substrate on which the first light shielding layer was formed was placed in an oven and post-baked at 230 ° C. for 1 hour. The upper part of the first light shielding layer was flat and the film thickness was 1.5 μm.

  Thereafter, a reversal pattern is formed in the same manner on the blanket plate, the blanket plate is disposed with the reversal pattern facing the other main surface side of the transparent substrate, and the reversal pattern passes through the transparent substrate to the first The blanket plate was aligned so as to face the light shielding layer, the reverse pattern was transferred onto the other main surface, and the second light shielding layer was transferred.

  Subsequently, similarly, the transparent substrate on which the second light shielding layer was formed was put in an oven and post-baked at 230 ° C. for 1 hour. The upper part of the second light shielding layer was flat and the film thickness was 1.5 μm.

  Further, when the contact angle of, for example, the light shielding layer used for inkjet printing of the colored pattern described later on the surface of the light shielding layer was measured, it was 30 °. The ink repellency was confirmed. Moreover, since the OD value (optical density) of the light shielding layer is 3, which has a sufficient light shielding property, it was confirmed that it can be used as a light shielding layer.

The OD value was obtained from the following formula from the incident light intensity I ₀ and transmitted light intensity I of a 1 μm sample.

OD = −log (I / I ₀ )
Thereafter, the transparent substrate on which the light shielding layer was formed was subjected to an ultraviolet ozone cleaning treatment under the conditions of an illuminance of 50 mW, an exposure amount of 500 mJ / cm ² and an ozone concentration of 100,000 ppm.

  When the contact angle of the ink with respect to the surface of the light shielding layer after the cleaning treatment was measured, it was 35 °, and it was confirmed that the cleaned light shielding layer surface had reduced ink repellency with respect to the colored pattern coating ink. .

Preparation of ink-repellent-containing positive resist layer Positive resist “LC100-10cp” manufactured by Rohm and Haas Electronic Materials Co., Ltd. 5% by weight of ink repellent “F179” manufactured by Dainippon Ink & Chemicals, Inc. A mixed positive resist composition was prepared. A positive resist composition was applied to a thickness of 3.0 μm with a spin coater on a glass substrate on which a light shielding layer was formed, to obtain a positive resist layer.

  The obtained positive resist layer was pre-baked at 110 ° C. for 120 seconds.

  Thereafter, the positive resist layer was so-called back-exposed from the surface of the glass substrate opposite to the surface coated with the positive resist layer through the glass substrate using an ultrahigh pressure mercury lamp as a light source. The exposure amount at that time was 50 to 150 mJ.

  Further, by developing the positive resist layer with a 2.5% by weight sodium carbonate solution, a partition composed of a light shielding layer and a positive resist layer similarly patterned on the light shielding layer is formed. Then, an opening was obtained between the partition walls.

  Thereafter, a post-bake treatment was performed on the positive resist layer at 230 ° C. for 10 minutes.

  The obtained positive resist layer had a thickness of 2 μm.

Removal of second light shielding layer The second light shielding layer on the other main surface was polished and removed using an Oscar-type polishing machine.

Preparation of colored ink 20 parts of methacrylic acid, 10 parts of methyl methacrylate, 55 parts of butyl methacrylate and 15 parts of hydroxyethyl methacrylate are dissolved in 300 g of butyl lactate, and 0.75 part of azobisisobutylnitrile is added under a nitrogen atmosphere at 70 ° C. Acrylic copolymer resin was obtained by reaction for 5 hours. The obtained acrylic copolymer resin was diluted with propylene glycol monomethyl ether acetate so that the resin concentration was 10% by weight to obtain a diluted solution of the acrylic copolymer resin.

  19.0 g of pigment and 0.9 g of polyoxyethylene alkyl ether as a dispersant were added to 80.1 g of this diluted solution, and kneaded with three rolls to obtain red, green and blue colored varnishes. . As a red pigment, Pigment Red 177, Pigment Green 36 as a green pigment, and Pigment Blue 15 as a blue pigment were used.

  Propylene glycol monomethyl ether acetate is added to each colored varnish so that the pigment concentration is 12 to 15% by weight and the viscosity is 15 cps, and red, green, and blue colored inks are obtained. It was.

Production of color filter Red (R), Green (G), and Blue (B) are respectively printed by inkjet printers using 12 pl and 180 dpi heads using red, green, and blue colored inks for the partition wall openings. A color filter according to the first aspect of the present invention was obtained. The color filter thus obtained had good smoothness, and ΔEab in the pixel was measured. As a result, it was found that the color filter was less than 1 and was a good color filter with little color unevenness. ΔEab (color difference) was measured with a microanalyzer.

Example 2
A positive resist having the same composition as in Example 1 except that the first light-shielding layer and the second light-shielding layer were prepared on both surfaces of the glass substrate, and no ink repellent was added. Was used to form a patterned positive resist layer. Thereafter, similarly, the second light shielding layer was polished and removed.

Formation of ink repellent agent layer Using N-methyl-2-pyrrolidone as a solvent, forming an ink repellent agent layer containing 5% by weight of an ink repellent agent perfluoro group-containing oligomer "F179" manufactured by Dainippon Ink & Chemicals, Inc. An ink was prepared.

  As a blanket plate, a metal roll coated with a silicone resin is prepared, and ink for forming an ink repellent layer is introduced into the slit coater in the same manner as shown in FIG. The layer was applied with a thickness of 1 μm.

  Thereafter, a glass substrate on which the first light shielding layer and the patterned positive resist layer were formed was prepared, and the uniform ink repellent agent layer was brought into contact with the positive resist layer for transfer.

  After the transfer, baking was performed in an oven at 230 ° C. for 10 minutes.

  The obtained ink repellent agent layer had a thickness of 0.5 μm.

  In this way, partition walls composed of a laminate of the first light shielding layer, the patterned positive resist layer, and the ink repellent agent layer were formed on the glass substrate, and openings were obtained between the partition walls.

  In this opening, red, green, and blue colored inks were used in the same manner as in Example 1, and a colored layer was formed by an inkjet printing apparatus to obtain a color filter according to the second aspect of the present invention. When smoothness was good and ΔEab in the pixel was measured, it was found to be less than 1 and a good color filter with little color unevenness.

  The partition wall of Example 2 is composed of a 1.5 μm light shielding layer, a 2 μm thick positive resist layer, and an 0.5 μm thick ink repellent layer, and has a thickness of 0.5 μm. The ink repellent agent layer contains an ink repellent component. Compared with the partition wall of Example 1, which is composed of a 1.5 μm light shielding layer and a 2 μm thick positive resist layer, and the 2 μm thick positive resist layer contains an ink repellent component, Example 2 This partition has the advantage that the ink repellent component layer is further required, but the ink repellent component is less likely to elute to the side wall of the partition and the colored ink is more easily received in the opening.

The figure for demonstrating an example of the manufacturing method of the color filter which concerns on the 1st viewpoint of this invention. The figure for demonstrating an example of the manufacturing method of the color filter which concerns on the 1st viewpoint of this invention. The figure for demonstrating an example of the manufacturing method of the color filter which concerns on the 1st viewpoint of this invention. The figure for demonstrating an example of the manufacturing method of the color filter which concerns on the 1st viewpoint of this invention. The figure for demonstrating an example of the manufacturing method of the color filter which concerns on the 1st viewpoint of this invention. The figure for demonstrating an example of the manufacturing method of the color filter which concerns on the 1st viewpoint of this invention. The figure for demonstrating an example of the manufacturing method of the color filter which concerns on the 1st viewpoint of this invention. The figure for demonstrating an example of the manufacturing method of the color filter which concerns on the 1st viewpoint of this invention. The figure for demonstrating an example of the manufacturing method of the color filter which concerns on the 2nd viewpoint of this invention. The figure for demonstrating an example of the manufacturing method of the color filter which concerns on the 2nd viewpoint of this invention. The figure for demonstrating an example of the manufacturing method of the color filter which concerns on the 2nd viewpoint of this invention. The figure for demonstrating the formation process of the light-shielding layer using a reverse printing method The figure for demonstrating the formation process of the light-shielding layer using a reverse printing method The figure for demonstrating the formation process of the light-shielding layer using a reverse printing method

Explanation of symbols

      DESCRIPTION OF SYMBOLS 1,27 ... Transparent substrate, 2 ... 1st main surface, 3 ... 2nd main surface, 4,26 ... Light shielding layer, 5 ... Positive resist layer, 7 ... Inkjet nozzle, 8 ... Color pattern coating ink, 10 DESCRIPTION OF SYMBOLS ... Color filter, 11 ... Colored layer, 23 ... Ink layer for light shielding layer formation, 24 ... Blanket plate, 25 ... Release member, 31 ... Reverse pattern, 32 ... Blanket

Claims (8)

Forming a first light shielding layer and a second light shielding layer each having a predetermined pattern on each principal surface of the transparent substrate having the first and second principal surfaces facing each other by a printing method;
Forming a positive resist layer containing an ink repellent agent on the first main surface of the transparent substrate and the first light shielding layer;
The positive resist layer is exposed from the second main surface side of the transparent substrate and then developed to selectively provide a patterned positive resist layer on the first light shielding layer. A pattern processing step of providing an opening from which the resist layer has been removed between the first light shielding layers,
After the pattern processing step, after removing the second light shielding layer, and after removing the second light shielding layer, colored ink is ejected into the opening by an ink jet method to form a colored layer. A process for producing a color filter comprising the steps. Forming a first light shielding layer and a second light shielding layer each having a predetermined pattern on each principal surface of the transparent substrate having the first and second principal surfaces facing each other by a printing method;
Forming a positive resist layer on the first main surface of the transparent substrate and the light shielding layer formed on the first main surface;
The positive resist layer is exposed from the second main surface side of the transparent substrate and then developed to selectively provide a patterned positive resist layer on the first light shielding layer. A pattern processing step of providing an opening from which the resist layer has been removed between the first light shielding layers,
A step of removing the second light shielding layer after the pattern processing step;
After the step of removing the second light shielding layer, a step of forming an ink repellent layer on the patterned positive resist layer; and a step of forming the ink repellent layer after the step of forming the ink repellent layer, coloring ink is applied to the opening by an inkjet method. A process for producing a color filter, comprising the step of forming a colored layer.   The method according to claim 1, wherein a reverse printing method is used as the printing method.   The method according to claim 3, wherein the reversal printing method uses an ink for forming a light shielding layer containing a release agent.   5. The method according to claim 1, further comprising a step of heating the printed light-shielding layer before the step of forming the positive resist layer.   6. The method according to claim 1, further comprising a step of subjecting at least the first main surface of the transparent substrate on which the light shielding layer has been formed to ultraviolet ozone cleaning before the step of forming the positive resist layer. 2. The method according to item 1. The method according to claim 2 , further comprising a step of heating the positive resist layer before the step of forming the ink repellent layer.   The width of the pattern of the light shielding layer on the second main surface is narrower than the width of the pattern of the light shielding layer on the first main surface. The method described in 1.

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