JP2010217390A - Method for producing partition pattern, color filter and liquid crystal display apparatus - Google Patents

Abstract

[Problem] To solve the problem that partition walls for partitioning colored ink ejected by an ink jet cause heat dripping during the manufacture of the partition walls, resulting in "color mixing" and "white spots" of the colored layer. In addition, there is provided a means for solving the problem while maintaining a high volumetric efficiency of the partition wall.
A process for obtaining a photosensitive resin composition comprising at least a binder resin, a monomer, a pigment dispersion paste and a solvent, and a colloidal solution containing fine particles are added to the photosensitive resin composition and stirred to obtain a photosensitive resin solution. A method for producing a partition pattern comprising: a step, a step of coating the photosensitive resin solution on a transparent substrate to form a coating film; and a step of forming a partition pattern from the coating film by a photolithography method in this order. The barrier rib pattern is a method for manufacturing a barrier rib pattern characterized by containing the fine particles having a particle diameter of 10 to 15 nm at a ratio of 20 to 30% in the total solid content.
[Selection] Figure 1

Description

  The present invention relates to a color filter substrate used in a color display device or the like, and in particular, a partition for preventing color inks of different colors from being mixed when a color filter is manufactured by discharging the color ink by an inkjet method. The present invention relates to a method for manufacturing a partition wall pattern.

  In recent years, an inkjet method has been proposed as a method for producing a color filter used in a color display device such as a color liquid crystal display (for example, see Patent Documents 1 and 2). In these documents, a black matrix conventionally provided in a color filter substrate contains a fluorine-containing compound and / or a silicon-containing compound, so that ink bleeding occurs in the ink ejection process and ink is mixed between adjacent pixels. A technique for forming a partition wall for preventing color mixing is disclosed.

  However, in order to sufficiently partition a large amount of ink ejected into an opening section partitioned by a partition wall (hereinafter also referred to as partition wall), the partition wall needs to have a certain height or more. When the thickness is large, the dripping of the upper part and the edge of the partition wall due to heat tends to occur during the curing process of the partition wall. When the upper part of the partition wall is heated, ink repellent components will be present on the side walls of the partition wall, which may cause white spots due to the repelling of the colored ink, or deteriorate the in-pixel flatness of the finished color filter. Become. These defects cause color unevenness and deteriorate the appearance quality of the color filter substrate, and also adversely affect the behavior of the liquid crystal when the liquid crystal panel is formed.

  Therefore, a technique for fixing the shape of the partition walls by performing re-exposure after the exposure / development process and before the heat treatment is disclosed in order to prevent problems caused by thermal dripping (see, for example, Patent Document 3). However, this requires a device and a space for that purpose, which is a problem in terms of cost.

In addition, attempts have been made to improve thermal sag by containing filler in the partition walls, but in this case, it is necessary to disperse the filler simultaneously with the pigment dispersion to prevent the filler from aggregating (for example, see Patent Document 4). . In the method of dispersing the filler together with the pigment at the time of dispersing the pigment, it is difficult to cope with the production of a large variety of small quantities, and there is a problem that the advantages of the ink jet system that can form the partition pattern corresponding to various kinds only by switching the discharge conditions etc. there were.
Further, when the filler reduces the dispersibility of the pigment, there is a problem in that the volume resistance at the time of film formation is greatly reduced, and the usable applications are limited.

JP-A-7-35915 JP 7-35917 A JP 2007-155923 A JP 2006-284673 A

  According to the present invention, while the production of color filter substrates is diversified in small quantities, the partition walls for partitioning the colored layer are subject to thermal dripping during the manufacture of the partition walls, leading to “color mixing” and “whiteout” of the colored layer. In order to prevent this problem by dispersing fillers in the partition walls, an object of the present invention is to provide a method for manufacturing the partition walls that is suitable for small-quantity, multi-product production and can maintain a high volume resistivity of the partition walls.

  According to the first aspect of the present invention, there is provided a step of obtaining a photosensitive resin composition comprising at least a binder resin, a monomer, a pigment dispersion paste, and a solvent, and a colloidal solution containing fine particles is added to the photosensitive resin composition and stirred for photosensitivity. A partition including a step of obtaining a conductive resin solution, a step of coating the photosensitive resin solution on a transparent substrate to form a coating film, and a step of forming a partition pattern from the coating film by a photolithography method in this order A method for producing a partition, wherein the partition pattern includes the fine particles having a particle size of 10 to 15 nm at a ratio of 20 to 30% in the total solid content. is there.

  The invention according to claim 2 is the method for producing a partition pattern according to claim 1, wherein the partition pattern includes a light shielding agent.

  The invention according to claim 3 is the method for producing a partition pattern according to claim 1 or 2, wherein the partition pattern has an optical density of 3.5 or more and 6.0 or less.

  According to a fourth aspect of the present invention, the barrier rib pattern manufacturing method according to any one of the first to third aspects, wherein the barrier rib pattern has a thickness of 1.5 μm or more and 3.0 μm or less. It is a method.

  The invention according to claim 5 is the method for producing a partition pattern according to any one of claims 1 to 4, wherein the partition pattern includes an ink repellent component.

  The invention described in claim 6 is a color filter characterized by being formed by filling the opening of the partition wall pattern manufactured by the method of any one of claims 1 to 5 with colored ink. is there.

  According to a seventh aspect of the present invention, there is provided a liquid crystal display device manufactured by using the color filter according to the sixth aspect.

  According to the first aspect of the invention, since the fine particles (synonymous with the filler, hereinafter the same) are not dispersed in the black pigment dispersion paste but are added later, switching in the dispersion paste of the ink jet device is performed. By simply adjusting the discharge conditions, it is possible to efficiently and easily cope with the production of a small variety of color filter substrates.

  When fine particles (fillers) are dispersed together during pigment dispersion, the black pigment dispersion paste must be adjusted for each type of color filter, and the amount of the dispersion paste produced at one time must be reduced. On the other hand, if the black pigment dispersion paste is a single type of filler, it can be applied to a variety of small lot color filters just by changing the amount of the filler added, and one type of the dispersion paste can be prepared in large quantities. As a result, costs can be reduced, development costs can be cut, and time can be shortened.

Conventionally, it was thought that the aggregation of the filler affects the dispersion state of the carbon-based material constituting the black pigment dispersion paste and causes a decrease in the resistance value. Therefore, the filler can be dispersed together with the pigment paste to aggregate the filler. The only way to prevent it was taken.
The present invention adjusts the filler colloidal solution with the filler particle size and addition amount optimized to easily uniform the filler in the photosensitive resin composition comprising the binder resin, monomer, pigment dispersion paste, and solvent. It was found that it could be dispersed in a photosensitive resin solution.

  The partition wall manufactured using this has no decrease in volume resistivity, and the upper part or edge of the partition wall does not sag to the side due to heat during firing. As a result, when a colored pattern containing a colored pigment is ejected into the opening to form a colored pattern, the colored pixels can be prevented from having a convex shape, and the color without white spots due to the repelling of the colored ink It can be a filter.

  According to invention of Claim 2, a partition pattern functions as a black matrix.

  According to the invention described in claim 3, the partition wall pattern functions sufficiently as a black matrix without light leakage.

  According to the fourth aspect of the present invention, it is possible to reduce the problem of color mixing that occurs when different color inks straddle the partition wall pattern.

  According to the fifth aspect of the present invention, the function of partitioning the ink is reliably ensured by the ink repellent material, and the problem of color mixing that occurs when different color inks straddle the partition wall pattern can be sufficiently reduced.

  According to the invention described in claim 6, it is possible to provide a color filter in which both color unevenness and mixed color are reduced.

  According to the seventh aspect of the present invention, it is possible to provide a liquid crystal display device with less color unevenness and improved image quality.

The figure of the cross-sectional view which illustrates typically the preferable aspect for which a colored layer occupies the inside of a partition. The figure of the cross-sectional view which illustrates typically the unpreferable aspect which a colored layer occupies the inside of a partition. 1 is an overall view of an ink jet printing apparatus according to an embodiment of the present invention. The block diagram of an inkjet head unit. The top view which shows the example of arrangement | positioning of an inkjet head. (A), (b) Schematic of the operation method of the inkjet printing apparatus which concerns on a 2nd method. Schematic of the operation method of the 1 color inkjet head of the inkjet printing apparatus which concerns on a 2nd method.

  Hereinafter, an example of the embodiment of the present invention will be described, but the present invention is not particularly limited thereto.

  FIG. 1 schematically shows how a colored layer occupies a partition pattern when ink repellency is imparted to the partition wall 100 according to the present invention, and colored ink containing a color pigment is ejected to the openings partitioned by the partition wall. FIG. The partition wall 100 is formed on the substrate 200. Since the partition wall does not sag due to the filler filling effect, the ink repellent component 300 exists only at the upper part of the partition wall, and the partition side portion does not have ink repellency. Therefore, the pixel surface shape is flat without the colored ink 400 being repelled.

  On the other hand, FIG. 2 is a schematic cross-sectional view for explaining an undesirable cross-sectional shape of the partition wall. When an appropriate amount of filler is not added, the upper part of the partition wall 100 containing the ink repellent component 300 hangs down on the side wall of the partition wall due to heat. For this reason, the colored ink 400 is repelled by the partition walls, and the flatness of the colored pixels is deteriorated.

The amount of filler contained in the partition walls is preferably 20 to 30%, more preferably 20 to 25% of the total solid content of the partition walls. If the amount of filler is less than 20% of the total solid content forming the partition walls, the shape cannot be maintained in a self-supporting manner, resulting in an unfavorable shape as shown in FIG. On the other hand, if the amount of filler is more than 30%, the volume resistance value of the partition walls may be lowered or the patterning property may be deteriorated.
Examples of the fine particles for filler that can be used in the present invention include, but are not limited to, true spherical, spherical, and polyhedral shapes such as Al2O3, TiO2, Fe2O3, ZnO, CeO2, Y2O3, Mn3O4, and SiO2.

  The line width in the Y direction of the barrier rib pattern in the present invention is preferably 5 to 100 μm. The average film thickness is preferably 1.0 to 5.0 μm. When the barrier rib pattern is provided with a light shielding property and functions as a black matrix, the line width of the Y-direction barrier rib pattern is more preferably 5 to 50 μm. When the partition pattern functions as a black matrix, the average film thickness α is more preferably 1.5 to 3.0 μm, and the optical density is preferably 3.5 to 6.0. If it is out of this range, white bright spots or light leakage may occur or the in-plane uniformity may deteriorate.

  The size of the opening in the present invention is preferably 2,000 to 150,000 μm 2.

  As for the line | wire width of the X direction of the partition pattern in this invention, 5-200 micrometers is preferable. Further, when the barrier rib pattern is provided with a light shielding property and functions as a black matrix, the line width is more preferably 50 to 150 μm. The average film thickness of the X-direction partition pattern is set to be the same as the film thickness of the Y-direction partition pattern. There may be a groove serving as an ink passage in the partition wall as long as the light shielding property is not affected.

The board | substrate with which the partition pattern which concerns on this invention was formed can be utilized suitably as an optical component which comprises the display screen of a display display. In this case, the area partitioned by the partition corresponds to a unit pixel. As the optical component, for example, a color filter substrate constituting a display screen of a color liquid crystal display can be exemplified, and in this case, the colored pattern constitutes a colored layer for coloring transmitted light. Moreover, an organic electroluminescent element can also be illustrated as an optical component, and in this case, a coloring pattern is comprised from an organic luminescent material layer. Naturally, a plurality of organic light emitting material layers exhibiting different emission colors are assigned to the divided areas.
In addition, examples of the partition pattern formation according to the present invention include a circuit board, a thin film transistor, a microlens, and a biochip.

  As the transparent substrate used in the present invention, a known transparent material such as a glass substrate, a quartz substrate, TAC (triacetyl cellulose film), PEN (polyethylene naphthalate), PET, or other plastics such as acrylic resin can be used. Usually, it is desirable to use a glass substrate that is excellent in transparency, strength, heat resistance, and weather resistance.

  In the present invention, the partition pattern is formed on a transparent substrate. This is because a plurality of colors of ink are ejected into the openings partitioned by the partition pattern to provide a substantially striped colored pattern. The partition pattern also has a function of preventing ink filled in each of a large number of openings partitioned by the partition from being mixed with colored ink in adjacent openings.

  The barrier rib pattern can be formed by spin coating, die coating, roll coating, curtain coating, inkjet coating, etc., applying the composition to the entire surface of the substrate and then forming it by photolithography, screen printing, letterpress printing, gravure printing, lithographic printing. Well-known methods such as ink jet printing and transfer can be used. For example, in the case of forming by photolithography, a photosensitive resin composition imparted with photosensitivity is used. In the following, the description will be made according to the photolithographic method, but the present invention is not limited to such a method.

  When the partition pattern is provided by a photolithography method, a positive resist or a negative resist can be used. The positive resist and the negative resist can contain, for example, a binder resin, a solvent, a monomer, and a light shielding agent. In the case of a negative resist, it can further contain a photopolymerization initiator. Moreover, you may add another additive as needed.

  As the binder resin, a resin containing an amino group, an amide base, a carboxyl group, or a hydroxyl group is preferable. Specific examples include cresol-novolak resins, polyvinylphenol resins, acrylic resins, methacrylic resins, melamine resins, and the like. These resin compositions may be used alone or in combination of two or more.

  Specific examples of the solvent include dichloromethane, dichloroethane, chloroform, acetone, cyclohexanone, ethyl acetate, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-ethylethoxyacetate, 2-butoxyethyl acetate, 2 -Methoxyethyl ether, 2-ethoxyethyl ether, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, 2- (2'ethoxyethoxy) ethyl acetate, 2- (2-butoxyethoxy) Ethyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, tetrahydrofuran and the like can be used. The amount of the solvent used is desirably a coating that is uniform when printed or coated on a substrate, and can form a coating film without pinholes and uneven coating. As a content ratio of such a solvent, it is preferable to prepare such that the solvent amount is 50 to 97% by weight with respect to the total weight of the resin composition.

  As the monomer, a monomer having a vinyl group or an allyl group, an oligomer, a molecule having a vinyl group or an allyl group at the terminal or side chain can be used. Specifically, (meth) acrylic acid and salts thereof, (meth) acrylic acid esters, (meth) acrylamides, maleic anhydride, maleic acid esters, itaconic acid esters, styrenes, vinyl ethers, vinyl esters, N -Vinyl heterocycles, allyl ethers, allyl esters, and derivatives thereof. Suitable compounds include, for example, relatively low molecular weight polyfunctional acrylates such as pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol penta and hexaacrylate. it can. These monomers may be used alone or in combination of two or more. The amount of the monomer can be in the range of 1 to 200 parts by weight, preferably 50 to 150 parts by weight with respect to 100 parts by weight of the binder resin.

  Examples of the photopolymerization initiator include benzophenone compounds such as benzophenone, 4,4'-bis (dimethylamino) benzophenone, and 4,4'-bis (diethylamino) benzophenone. In addition, as photopolymerization initiators, 1-hydroxycyclohexyl acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one An acetophenone derivative such as can also be used. Further, thioxanthone derivatives such as thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone may be used. Moreover, anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and chloroanthraquinone may be used. In addition, benzoin ether derivatives such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether can also be used. Further, acylphosphine derivatives such as phenylbis- (2,4,6-trimethylbenzoyl) -phosphine oxide, 2- (o-chlorophenyl) -4,5-bis (4′-methylphenyl) imidazolyl dimer Lophine isomers such as N-arylglycine such as N-phenylglycine, organic azides such as 4,4′-diazidochalcone, 3,3 ′, 4,4′-tetra (tert-butylperoxycarboxy) Examples include benzophenone and quinonediazide group-containing compounds. These photopolymerization initiators may be used alone or in combination of two or more. The quantity of a photoinitiator can take the range of 0.1-50 weight part with respect to 100 weight part of binder resin, Preferably it is 1-20 weight part.

  As the additive, for example, a leveling agent, a chain transfer agent, a stabilizer, a sensitizing dye, a surfactant, a coupling agent and the like can be added.

  Moreover, a well-known material can be used as the light shielding agent for the partition wall pattern. Specifically, carbon black, aniline black, graphite, iron black, titanium oxide, black pigment, black dye, inorganic pigment, organic pigment, and the like can be used. These light shielding agents may be used alone or in combination of two or more.

  The partition pattern may have ink repellency. As a method for imparting ink repellency, an ink repellant material may be mixed in the resin composition or an ink repellency treatment may be performed after pattern formation.

  As the ink repellent material, for example, a compound having compatibility with the water repellent portion and the resin binder of the partition pattern can be used. The site having water repellency can use a fluoroalkyl group, and more preferably a perfluoroalkyl group. As a site exhibiting compatibility with the resin binder, a known lipophilic polymer such as an alkyl group, an alkylene group, or polyvinyl alcohol can be used. Since the ink repellent material includes the ink repellent and ink-philic portions, it acts as a surfactant in the ink. In addition, a material containing fluorine or silicon atoms can be used. For example, fluorinated resins such as vinylidene fluoride, vinyl fluoride, ethylene trifluoride, and copolymers thereof can be used. In particular, a fluorine-containing copolymer having a mass average molecular weight of 10,000 to 100,000 is preferable, and specific examples include a fluorine-containing copolymer. Examples of the silicon compound include organic silicon in the main chain or side chain, and include silicon resins and silicone rubbers containing a siloxane component. These silicon-containing compounds can be used alone or in combination of two or more. Further, the fluorine-containing compound and the silicon-containing compound, or other ink repellent components may be used in combination. These ink repellent materials can be used alone or in combination of two or more. For example, when an ink repellent material is mixed in a resin composition to form a partition pattern, a resin composition in which an ink repellent material in an amount of 0.1 wt% to 10 wt% is mixed with respect to the total weight part is used. be able to.

  As the ink repellent treatment, the ink repellent treatment can be performed by performing plasma or corona treatment using a gas that can exhibit ink repellency such as a fluorine-containing gas.

  As the ink repellency on the surface of the partition wall pattern in the present invention, the result of performing negative ion analysis on the surface of the partition wall pattern after forming the partition wall pattern with a time-of-flight secondary ion mass spectrometer (TOF-SIMS) The partition wall pattern is formed so that the detected intensity of fluorine ions is 0.2 to 0.6 when the total detected intensity of negative ions is 1 (normalized). For example, when an ink repellent material is mixed in a resin composition to form a partition pattern, a resin composition in which an ink repellent material in an amount of 0.1 wt% to 10 wt% is mixed with respect to the total weight part is used. be able to.

The coloring pattern of this invention can be comprised from the composition containing the pigment | dye which consists of a resin binder and a coloring pigment or dye, for example. The color pigments are different for each color, and red pigments include C.I. I. Pigment Violet 19, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 29, C.I. I. PigmentViolet 30, C.I. I. Pigment Violet 37, C.I. I. Pigment Violet 40, C.I. I. Pigment Violet 50, C.I. I. Pigment Red 7, C.I. I. Pigment Red 9, C.I. I. Pigment Red 14, C.I. I. Pigment Red 41, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 48: 2, C.I. I. Pigment Red 48: 3, C.I. I. Pigment Red 48: 4, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 146, C.I. I. Pigment Red 149, C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 180, C.I. I. Pigment 184, C.I. I. Pigment Red 185, C.I. I. PigmentRed 187, C.I. I. Pigment Red 192, C.I. I. Pigment Red 200, C.I. I. Pigment Red 202, C.I. I. Pigment Red 208, C.I. I. Pigment Red 210, C.I. I. Pigment Red 216, C.I. I. Pigment Red 220, C.I. I. Pigment Red 221, C.I. I. Pigment Red 223, C.I. I. Pigment Red 226, C.I. I. Pigment Red 227, C.I. I. Pigment Red 240, C.I. I. Pigment Red 246, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, C.I. I. Pigment Red 272 and the like. Furthermore, C.I. I. Pigment Red 254 and C.I. I. A mixture of Pigment Red 177 can be used.

  Examples of the green coloring pigment include C.I. I. Pigment Green 7, C.I. I. Pigment Green 36 can be used. Furthermore, C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 139 or C.I. I. A mixture with Pigment Yellow 13 can be used.

Examples of the blue coloring pigment include C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60 and the like. Moreover, you may use the pigment mentioned to these 2 types or more in mixture.
As the resin binder, polyimide resin, acrylic resin, epoxy resin, melamine resin, or the like is used, and is appropriately selected in relation to the pigment. Furthermore, these may be used in combination of two or more.

  In the case of manufacturing an organic EL element, ink containing an organic light emitting material is used and discharged from an ink jet printing apparatus to an opening of a partition pattern. The ink can contain an organic light emitting material, a solvent, and a resin binder as necessary.

  Organic light-emitting materials such as coumarin, perylene, pyran, anthrone, porphyrene, quinacridone, N, N'-dialkyl substituted quinacridone, naphthalimide, N, N'-diaryl substituted pyrrolopyrrole, iridium complex Organic light-emitting materials that are soluble in organic solvents such as those dispersed in polymers such as polystyrene, polymethyl methacrylate, polyvinyl carbazole, polyarylene-based, polyarylene vinylene-based, polyfluorene-based, etc. And a high molecular organic light emitting material.

  Various coating methods can be used for forming the colored pattern in the present invention. For example, patterning from the beginning such as spin coating, die coating, roll coating, curtain coating, etc., by applying the composition to the entire surface and then forming by photolithography, screen printing, letterpress printing, gravure printing, planographic printing, ink jet method, transfer method, etc. It can form by the method of performing.

  The present invention has a particularly advantageous effect when applied to a method employing the latter “method of forming by patterning from the beginning”. Hereinafter, the case of the ink jet method will be described as an example, but the present invention is not limited to the method.

  Hereinafter, a case where a color filter is manufactured by ejecting colored ink containing a color pigment by inkjet will be described as an example.

  Ink is ejected into the opening of the partition pattern formed on the transparent substrate using an ink jet printing apparatus to form a color filter. Below, the manufacturing method of the color filter provided with the colored ink layer of RGB is demonstrated.

  As a color filter by an ink jet printing apparatus, a method (first method) is known in which ink is ejected while the direction of the ink applied in stripes is parallel to the main scanning direction of the ink jet head. In addition, a method (second method) is known in which ink is ejected while the direction of the ink applied in stripes is perpendicular to the main scanning direction. Any method may be used in the present invention. An outline of a method for producing a color filter using the second method is shown in FIG.

  Inkjet heads 42 for discharging RBG three color inks are arranged (total of three). The inkjet head 42 is arranged such that the nozzles are substantially perpendicular to the main scanning direction (second direction 44).

  These three inkjet heads are inseparably integrated to form a single inkjet head unit. The inkjet head unit is scanned on the substrate 41 in parallel with the second direction to form the RBG three-color colored ink layer 43 (FIG. 6A). The colored ink layer 43 is formed in a stripe shape so that each of the three colors is parallel to the first direction. The colored ink layer 43 may be formed in a lattice shape parallel to the first direction. If the partition walls described above are provided in advance on the substrate 41 as necessary, color mixing of colored inks can be effectively prevented. In addition, an image receiving layer made of a transparent resin can be provided on the substrate 41 in advance. Subsequently, the ink jet head unit can perform sub-scanning along the first direction, and then further perform main scanning in the opposite direction (FIG. 6B).

  FIG. 7 shows the operation of the inkjet head when attention is paid to the operation of the one-color inkjet head. The ink-jet head is scanned along the second direction (the direction of the arrow in the figure) on the substrate 51, and ink is ejected from the nozzles 54 at regular time intervals. 53 is formed.

The ink jet apparatus used for forming the colored pattern can be selected from a piezo conversion method and a heat conversion method mainly due to the difference in the ink discharge method. When applying a color filter as a pattern forming substrate, a piezo conversion method is particularly suitable.
Further, an apparatus in which the ink particleization frequency is about 5 to 100 KHz, the nozzle diameter is about 5 to 80 μm, three heads are arranged, and 60 to 500 nozzles are incorporated in one head is preferable. After ink is ejected to the openings partitioned by the partition pattern by the ink jet method, the solvent is evaporated, and then the resin in the ink is cured by UV irradiation or heat to form a colored pattern. Hereinafter, an example will be described in detail.

  FIG. 3 shows an overall view of an example of an inkjet printing apparatus and peripheral equipment that can be used in the practice of the present invention. The ink jet printing apparatus includes a substrate transport stage 2, an ink jet head unit 14, an ink jet head unit moving shaft 4, a main controller 10, and a discharge controller 9. The ink jet head unit is equipped with a single ink jet head or a plurality of ink jet heads. FIG. 4 shows an example of an inkjet head unit 14 equipped with a plurality of inkjet heads. The ink jet head includes a large number of nozzles (not shown) that are substantially arranged in a specific direction.

  A substrate to be coated is mounted on the substrate transfer stage 2. Examples of the substrate include optical elements such as color filters and organic electroluminescence elements, as well as elements having fine patterns such as wiring circuit boards and biochips. The substrate transfer stage 2 moves along a predetermined substrate transfer stage transfer direction 11. The substrate transport stage transport direction 11 is parallel to the main scanning direction.

  The inkjet head unit 14 moves on the inkjet head unit moving shaft 4 along the main scanning direction. The inkjet head unit moving shaft 4 is orthogonal to the scanning direction 11 of the inkjet head unit. The ink jet head unit is sub-scanned along the ink jet head unit moving axis.

  Hereinafter, the direction in which the inkjet head unit is sub-scanned is defined as a first direction, and the direction of main scanning of the inkjet head unit is defined as a second direction. The substrate transfer stage 2 includes a vacuum suction hole for fixing the substrate 1, and can fix the substrate without protruding from the substrate surface. As a result, the gap between the substrate 1 and the inkjet head 13 can be brought to a minimum.

  The ejection control unit 9 includes a storage unit (not shown) that stores a measurement value of linearity of the locus of movement of the inkjet head unit. Accordingly, the linearity at an arbitrary position on the first direction axis of the ink jet head unit can be grasped, and even if the ink jet head unit 14 is not straight with respect to the first direction axis at a desired position. The coating accuracy can be corrected by changing the nozzle discharge timing in accordance with the linearity (deviation) at that position.

  FIG. 4 shows details of the inkjet head unit 14 and its peripheral mechanism diagram.

The inkjet head unit 14 includes a plurality of inkjet heads. The inkjet head includes a plurality of nozzles that eject ink. The nozzles are arranged so that the positions along the first direction are at predetermined equal intervals.
The deviation of the orientation of the inkjet head from a predetermined orientation is referred to as the rotational deviation of the inkjet head. For this reason, the inkjet coating apparatus includes a θ adjustment mechanism 15 for correcting a shift in the rotation direction (hereinafter also referred to as the θ direction). The θ adjustment mechanism 15 can adjust the general direction of the plurality of inkjet heads when the inkjet head unit is mounted with a plurality of inkjet heads. In addition, the inkjet head may be tilted and a vertical displacement (third direction) may occur. In order to correct the deviation in the third direction, it is effective to provide a gap adjusting mechanism (not shown).

FIG. 5 is a plan view illustrating an example of the arrangement of the inkjet heads in an inkjet head unit including a plurality of inkjet heads.
The inkjet heads 13 are arranged in parallel along the first direction. Further, since the width of the ink jet head main body is wider than the nozzle range, adjacent ink jet heads are arranged in a staggered manner shifted along the second direction. For this reason, by changing the discharge timing of the nozzles belonging to the ink jet head according to the distance in the second direction generated between the ink jet head and the adjacent ink jet head, the ink discharge can be accurately linearized. it can.

Examples of the present invention will be specifically described below.

<Formation of partition walls>
Non-alkali glass was used as the transparent substrate. Photosensitive black resin composition having an optical density (OD value) of 2.5 per 1 μm and having a light shielding property (acrylic resin, cyclohexanone, carbon pigment, dispersant, radical polymerizable compound trimethylolpropane triacrylate, photopolymerization start Ink repellent component is added to the mixture, and colloidal silica having an average particle size of 10 to 15 nm is added in an amount such that the silica fine particles are 20% of the total solids, and the mixture is stirred and mixed. The photosensitive resin solution is applied on a transparent substrate by a spin coating method so as to have a thickness of 2.5 μm, the solvent is dried on a hot plate, and then passed through a photomask prepared so that a lattice-like partition wall pattern is formed. Exposure, development with aqueous alkali solution, heat baking in a predetermined temperature oven, to obtain a partition pattern as a black matrix It was.
It was confirmed that the partition wall pattern had an average film thickness of 2.0 μm, an optical density of 4.2, and had a low contrast reduction due to white bright spots and light leakage. Further, it was confirmed that the volume resistance value of the partition wall was 10 ¹³ or more. Further, when negative ion analysis is performed on the surface of the partition wall pattern by a time-of-flight secondary ion mass spectrometer (TOF-SIMS), when the total detected intensity of all negative ions is set to 1 (normalized), fluorine ions It was found that a large amount of fluorine-containing compound as an ink repellent material was present on the partition pattern surface. With this value, it was possible to prevent color mixing between the colored patterns of adjacent openings when filling with ink. When the cross section of the partition wall pattern was observed with a scanning electron microscope (SEM), it was confirmed that the shape of the partition wall upper surface was free from thermal sagging.

<Formation of colored pattern>
The ink is applied to this substrate using a red, blue and green colored ink (adjusted to the total mass of the total solid content of the ink excluding the solvent to 50% by mass and adjusted to the required spectral characteristics. The total solid concentration to be fastened to the ink was adjusted to be 30% by mass), and was discharged to the openings partitioned by the partition pattern, and then heat-cured to obtain a color filter. The color filter substrate thus obtained had no color mixing or repelling, and the thickness of each pixel on which a colored pattern was formed was measured. It was a color filter substrate with excellent properties and little variation in density. Furthermore, when a liquid crystal display device was produced using this color filter, good display without unevenness or white bright spots could be achieved.

  A partition wall pattern was prepared in the same manner as in Example 1 except that the silica fine particles added to the photosensitive resin composition were 30% of the total solid content.

<Formation of partition walls>
Non-alkali glass was used as the transparent substrate. Photosensitive resin composition having an optical density (OD value) of 2.5 per 1 μm and having a light shielding property (acrylic resin, cyclohexanone, carbon pigment, dispersant, radical polymerizable compound trimethylolpropane triacrylate, photopolymerization initiator In addition, an ink-repellent component is added to the mixture, and colloidal silica having an average particle size of 10 to 15 nm is added in an amount such that the silica fine particles are 30% of the total solids, and the mixture is stirred and mixed. The resin solution is applied on a transparent substrate by a spin coating method so as to have a thickness of 2.5 μm, the solvent is dried on a hot plate, and then exposed through a photomask prepared so that a grid-like partition wall pattern is formed. Then, development was performed with an alkaline aqueous solution, followed by heating and baking in an oven at a predetermined temperature to obtain a partition wall pattern as a black matrix.
It was confirmed that this partition wall pattern had an average film thickness of 2.0 μm, an optical density of 3.8, and had a low contrast reduction due to white bright spots and light leakage. Further, it was confirmed that the volume resistance value of the partition wall was 10 ¹³ or more. Furthermore, when the total detection intensity of all negative ions is normalized to 1 in the negative ion analysis by the time-of-flight secondary ion mass spectrometer (TOF-SIMS) on the surface of the partition wall pattern, the detection intensity of fluorine ions is About 0.4, the fluorine-containing compound, which is an ink repellent material, is present on the surface of the partition wall pattern, and when the ink is filled, it is possible to prevent color mixture between the colored patterns in adjacent openings. It confirmed that it was a partition pattern. When the cross section of the partition wall pattern was observed with a scanning electron microscope (SEM), it was confirmed that the shape of the partition wall upper surface was free from thermal sagging.

<Formation of colored pattern>
The ink is applied to this substrate using a red, blue and green colored ink (adjusted to the total mass of the total solid content of the ink excluding the solvent to 50% by mass and adjusted to the required spectral characteristics. The total solid concentration to be fastened to the ink was adjusted to be 30% by mass), and was discharged to the openings partitioned by the partition pattern, and then heat-cured to obtain a color filter. The color filter substrate thus obtained had no color mixing or repelling, and when the film thickness of each pixel on which a colored pattern was formed was measured, the difference in film thickness within one partition was 300 nm or less, and the flatness within the pixel It was a color filter substrate with excellent properties and little variation in density. Furthermore, when a liquid crystal display device was produced using this color filter, good display without unevenness or white bright spots could be achieved.

(Comparative Example 1)
A partition wall pattern was prepared in the same manner as in Example 1 except that the partition wall was formed without adding colloidal silica to the photosensitive resin composition.

<Formation of partition walls>
Non-alkali glass was used as the transparent substrate. Photosensitive resin composition having a light shielding property with an optical density (OD value) of 2.5 per 1 μm (acrylic resin, cyclohexanone, carbon pigment, dispersant, radical polymerizable compound trimethylolpropane triacrylate, photopolymerization start Ink repellent component is added to the substrate) and applied on a transparent substrate by a spin coat method so as to have a thickness of 2.5 μm, and the solvent is dried by a hot plate so that a lattice-like partition wall pattern is formed. It exposed through the produced photomask, developed with aqueous alkali solution, and heat-baked in oven, and obtained the black matrix-like partition wall pattern.
It was confirmed that the partition wall pattern had an average film thickness of 1.9 μm, an optical density of 5.0, and had a low contrast reduction due to white spots and light leakage. Further, it was confirmed that the volume resistance value of the partition wall was 10 ¹⁴ or more. Furthermore, in the negative ion analysis by the time-of-flight secondary ion mass spectrometer (TOF-SIMS) on the surface of the partition wall pattern, when the total detection intensity of all negative ions is 1 (normalized), the detection of fluorine ions The strength is about 0.4, and there are many fluorine-containing compounds that are ink repellent materials on the surface of the partition wall pattern. It was confirmed that the barrier rib pattern can be prevented. When the cross section of the partition wall pattern was observed with a scanning electron microscope (SEM), it was confirmed that the top surface of the partition wall had a crack-like shape with heat dripping on the side.

<Formation of colored pattern>
The ink is applied to this substrate using a red, blue and green colored ink (adjusted to the total mass of the total solid content of the ink excluding the solvent to 50% by mass and adjusted to the required spectral characteristics. The total solid concentration to be fastened to the ink was adjusted to be 30% by mass), and was discharged to the openings partitioned by the partition pattern, and then heat-cured to obtain a color filter. In the color filter substrate thus obtained, color mixing was observed in some places because the tapered portion of the partition wall was gentle. In addition, since the liquid repellent component is present even on the glass of the opening, repellency was observed in some places, and when the film thickness of each pixel on which the colored pattern was formed was measured, the difference in film thickness within the pixel was 1 μm. As described above, the color filter substrate was poor in flatness in pixels and had many variations in density. Furthermore, when a liquid crystal display device was produced using this color filter, problems such as light leakage from white bright spots and a decrease in contrast occurred.

(Comparative Example 2)
A partition wall pattern was prepared in the same manner as in Example 1 except that the silica fine particles added to the photosensitive resin composition were 18% of the total solid content.

<Formation of partition walls>
Non-alkali glass was used as the transparent substrate. Photosensitive resin composition having an optical density (OD value) of 2.5 per 1 μm and having a light shielding property (acrylic resin, cyclohexanone, carbon pigment, dispersant, radical polymerizable compound trimethylolpropane triacrylate, photopolymerization initiator In addition, an ink-repellent component is added to the mixture, and colloidal silica having an average particle diameter of 10 to 15 nm is added in an amount such that the silica fine particles are 18% of the total solids, and the mixture is stirred and mixed. The resin solution is applied on a transparent substrate by a spin coating method to a thickness of 2.5 μm, the solvent is dried by a hot plate, and exposed through a photomask prepared so that a grid-like partition wall pattern is formed. Development was performed with an aqueous solution, followed by baking in an oven to obtain a black matrix-like partition wall pattern.
It was confirmed that the partition wall pattern had an average film thickness of 2.0 μm, an optical density of 4.2, and had a low contrast reduction due to white bright spots and light leakage. Further, it was confirmed that the volume resistance value of the partition wall was 10 ¹³ or more. Furthermore, in the negative ion analysis by the time-of-flight secondary ion mass spectrometer (TOF-SIMS) on the surface of the partition wall pattern, when the total detection intensity of all negative ions is 1 (normalized), the detection of fluorine ions The strength is about 0.4, and there are many fluorine-containing compounds that are ink repellent materials on the surface of the partition wall pattern. It was confirmed that the barrier rib pattern can be prevented. When the cross section of the partition wall pattern was observed with a scanning electron microscope (SEM), it was confirmed that the top surface of the partition wall had a crack-like shape with heat dripping on the side.

<Formation of colored pattern>
The ink is applied to this substrate using a red, blue and green colored ink (adjusted to the total mass of the total solid content of the ink excluding the solvent to 50% by mass and adjusted to the required spectral characteristics. The total solid concentration to be fastened to the ink was adjusted to be 30% by mass), and was discharged to the openings partitioned by the partition pattern, and then heat-cured to obtain a color filter. The color filter substrate thus obtained was found to be repelled in some places because the liquid repellent component was present on the glass of the opening, and when the film thickness of each pixel forming the colored pattern was measured, The difference in film thickness in one partition was 1 μm or more, the flatness in the pixel was poor, and the color filter substrate had many density variations. Furthermore, when a liquid crystal display device was produced using this color filter, problems such as light leakage from white bright spots and a decrease in contrast occurred.

(Comparative Example 3)
A partition wall pattern was prepared in the same manner as in Example 1 except that the silica fine particles added to the photosensitive resin composition were 32% of the total solid content.

<Formation of partition walls>
Non-alkali glass was used as the transparent substrate. Photosensitive resin composition having an optical density (OD value) of 2.5 per 1 μm and having a light shielding property (acrylic resin, cyclohexanone, carbon pigment, dispersant, radical polymerizable compound trimethylolpropane triacrylate, photopolymerization initiator In addition, an ink repellant component is added to the mixture, and colloidal silica having an average particle size of 10 to 15 nm is added in an amount so that the silica fine particles are 32% of the total solids. The resin solution is applied on a transparent substrate by a spin coat method so as to have a thickness of 2.5 μm, the solvent is dried on a hot plate, and exposed through a photomask prepared so that a grid-like partition pattern is formed, Development was carried out with an alkaline aqueous solution, followed by baking in an oven to obtain a black matrix partition wall pattern.
It was confirmed that this partition wall pattern had an average film thickness of 2.0 μm, an optical density of 3.8, and had a low contrast reduction due to white bright spots and light leakage. Moreover, it confirmed that the volume resistance value of this partition was ¹⁰ <10 ^> or less. Furthermore, in the negative ion analysis by the time-of-flight secondary ion mass spectrometer (TOF-SIMS) on the surface of the partition wall pattern, when the total detection intensity of all negative ions is 1 (normalized), the detection of fluorine ions The strength is about 0.4, and there are many fluorine-containing compounds that are ink repellent materials on the surface of the partition wall pattern. It was confirmed that the barrier rib pattern can be prevented. When the cross section of the partition wall pattern was observed with a scanning electron microscope (SEM), the shape of the top surface of the partition wall was not drooped, but the linearity of the pattern was poor.

<Formation of colored pattern>
The ink is applied to this substrate using a red, blue and green colored ink (adjusted to the total mass of the total solid content of the ink excluding the solvent to 50% by mass and adjusted to the required spectral characteristics. The total solid concentration to be fastened to the ink was adjusted to be 30% by mass), and was discharged to the openings partitioned by the partition pattern, and then heat-cured to obtain a color filter. The color filter substrate thus obtained had no color mixing or repelling, and when the film thickness of each pixel on which a colored pattern was formed was measured, the difference in film thickness in the pixel was 300 nm or less, and the flatness in the pixel However, it was a color filter substrate with many variations in density due to the bad linearity of the partition wall pattern. Further, when a liquid crystal display device was produced using this color filter, the liquid crystal was poorly aligned due to its low resistance value, resulting in problems such as display unevenness.

The cross section of the partition wall pattern of the example had a shape without heat sagging, and the liquid repellent component was present only in the upper part of the partition wall. For this reason, the color filter of the embodiment is a color filter substrate with excellent density and flatness within the pixel without color mixing and repelling, and a liquid crystal display device using this color filter has no unevenness or white bright spots. It was a good liquid crystal display device.
The cross section of the barrier rib pattern of Comparative Examples 1 and 2 had a crumpled shape in which the upper surface of the barrier ribs was dripped to the side. For this reason, the color filter of the comparative example is a color filter substrate in which color mixing or white spots occur in some places, the flatness in the pixels is poor, and there are many variations in density. A liquid crystal display device using this color filter has white bright spots. Caused problems such as light leakage from the camera and a decrease in contrast. The cross section of the partition pattern of Comparative Example 3 had a shape without thermal sagging, but since the volume resistance value was reduced, the liquid crystal display device using this partition pattern had a liquid crystal alignment defect, and display unevenness, etc. Caused a problem.
As shown in Table 1, by adding the fine particles to the resin composition and adding 20 to 30% of the fine particles in the partition walls, the partition walls can have specific shapes and characteristics specifically, An excellent color filter can be produced.

DESCRIPTION OF SYMBOLS 1 ... Board | substrate 2 ... Board | substrate conveyance stage 3 ... Maintenance station 4 ... Inkjet head unit moving axis (1st direction)
5 ... Linear scale 6 ... Inkjet head unit moving base 7 ... Inverted microscope 8 ... Transport stage controller 9 ... Discharge controller 10 ... Main controller 11 ... Substrate transport stage transport direction (second direction)
12. Inkjet head unit moving direction (first direction)
13 ... Inkjet head 14 ... Inkjet head unit 15 ... θ adjustment mechanism (θ axis)
16 ... Elevating mechanism (third direction)
17 ... 3rd direction 18 ... theta direction 19 ... inkjet head base plate 20 ... alignment mark 41 ... substrate 42 ... inkjet head 43 ... colored ink layer 44 ... 2nd direction 45 ... 1st direction 51 ... substrate 52 ... inkjet Head 53 ... Colored ink layer 54 ... Nozzle 100 ... Partition 200 ... Transparent substrate 300 ... Ink-repellent component-containing portion 400 in the partition ... Colored portion of the color filter

Claims (7)

At least a step of obtaining a photosensitive resin composition comprising a binder resin, a monomer, a pigment dispersion paste, and a solvent;
Adding a colloidal solution containing fine particles to the photosensitive resin composition and stirring to obtain a photosensitive resin solution;
Applying the photosensitive resin solution on a transparent substrate to form a coating film;
Forming a barrier rib pattern from the coating film by a photolithography method in this order, the barrier rib pattern manufacturing method comprising:
A method for producing a partition wall pattern, comprising the fine particles having a particle diameter of 10 to 15 nm at a ratio of 20 to 30% in the total solid content.   The method for manufacturing a partition pattern according to claim 1, wherein the partition pattern includes a light shielding agent.   3. The method for producing a partition wall pattern according to claim 1, wherein an optical density of the partition wall pattern is 3.5 or more and 6.0 or less.   4. The method for manufacturing a partition wall pattern according to claim 1, wherein a thickness of the partition wall pattern is 1.5 μm or more and 3.0 μm or less. 5.   The method for manufacturing a partition pattern according to any one of claims 1 to 4, wherein the partition pattern includes an ink repellent component.   6. A color filter formed by filling colored ink in an opening of a partition wall pattern manufactured by the method according to claim 1.   A liquid crystal display device manufactured using the color filter according to claim 6.

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