JP5686014B2 - Optical element and manufacturing method thereof - Google Patents

Description

  The present invention relates to an optical element in which a functional layer ink is applied to a region partitioned by a partition pattern to form a functional layer pattern, and a manufacturing method thereof.

  2. Description of the Related Art In recent years, color liquid crystal display devices and organic EL (Electro Luminescence) display devices have been widely used as color display devices for various electrical devices such as information terminals such as flat-screen TVs, personal computers, and mobile phones, digital cameras, and video cameras. . The optical element is used in a color filter used in an organic EL display device or a color liquid crystal display device.

  A color filter used in a color liquid crystal display device or the like is an indispensable member for a color liquid crystal display device or the like, and has a role of improving the image quality of the liquid crystal display device or giving each pixel a color of each primary color. Yes. As a method for producing this color filter, a dyeing method, an electrodeposition method, a pigment dispersion method, and the like are known. From the viewpoint of reliability, a pigment dispersion method having high weather resistance is widely used. In the pigment dispersion method, a photolithography method in which a photosensitive resin composition in which a pigment is dispersed is applied onto a transparent substrate, exposed and developed, and unnecessary portions of the coating film are removed to form a pixel pattern is generally used. It is.

  However, this method eliminates the need for much of the coating film, so the material usage efficiency is low, and it is necessary to repeat at least three steps of red (R), green (G), and blue (B). Had the problem of. Recently, an ink jet method has been attracting attention, in which each color can be simultaneously printed only in a necessary portion using ink in which R, G, and B pigments are dispersed. In the method of manufacturing a pigment-dispersed color filter using an ink jet method, in order to prevent a defect (color mixture) due to mixing of ink between adjacent color pixels, a repellent function that keeps discharged ink within a desired region. An ink partition wall pattern forming technique is important.

  On the other hand, the development of organic EL display devices is accelerating as a self-luminous display that is thin, energy-saving, and has high display performance, replacing color liquid crystal display devices. In an organic EL display device, a barrier rib pattern serving as an insulating layer is formed on a transparent substrate on which circuit elements and pixel electrode patterns are formed, a hole injection layer, a transport layer, and a light emitting layer are stacked, sandwiched between electrodes, It is manufactured by sealing to block deterioration substances such as oxygen and oxygen.

  The above-described hole injection, transport layer, and light emitting layer forming methods are generally roughly classified into vapor deposition methods and coating methods. The vapor deposition method is a method in which a low molecular material is deposited on an electrode pattern through a metal mask under vacuum, and since a uniform film can be formed and a stable quality organic EL display device can be manufactured. Although this method is widely used for small and medium-sized display devices, the accuracy of vacuum equipment and metal masks has become a bottleneck, and there is a difficulty in dealing with the increase in size of substrates. In contrast, the coating method uses an ink in which the hole injection, transport layer, and light emitting layer materials are dissolved or dispersed in a solvent and is patterned by a printing method, and will be applied to future large substrates such as organic EL televisions. Is expected as a possible method. As the above printing method, an inkjet method, a nozzle printing method, a spray coating method, a slit die coating method, a relief printing method, and the like have been proposed. In particular, when ink containing a large amount of a solvent component is applied directly on a substrate, RGB In order to suppress mixing (color mixing) between inks and film thickness unevenness, it is necessary to form an ink-repellent partition wall pattern as in the case of manufacturing the ink jet color filter described above.

  Here, various methods have been proposed as a method for obtaining the ink repellent partition. For example, at least a part of the partition wall forming material contains an ink repellent component to form a partition wall pattern (for example, Patent Documents 1 to 4), and after the partition wall pattern is formed, the partition wall surface is subjected to an ink repellent treatment by plasma treatment. And a method of transferring and applying a liquid repellent component onto the partition pattern after the partition pattern is formed (for example, Patent Documents 7 and 8).

  However, although any method can impart ink repellency to the partition wall surface, if ink repellency is imparted to the opening surrounded by the partition wall or the side wall of the partition wall, The processed ink does not spread evenly over the entire opening, the functional layer thickness around the partition wall becomes thin, or white spots are partially generated, resulting in display unevenness, contrast reduction, non-light emission due to current leakage, etc. May cause display defects. Among the methods for imparting ink repellency, the method of forming the barrier rib pattern by adding the ink repellent component to the barrier rib forming material is such that the ink repellant component remains in the opening portion or in the thermosetting step of the barrier rib pattern. In some cases, the ink repellent component may move to the side wall of the partition wall or the opening, and a complicated process is required to suppress them. In addition, when ink repellency is imparted by plasma treatment after the barrier rib pattern is formed, the ink repellency is imparted to all exposed surfaces of the organic barrier ribs, so that the organic residue on the side surfaces of the barrier ribs and the openings is also ink repellant. Since the ink repellency is lowered due to the characteristic and the heat history, color mixing defects are liable to occur when a plurality of layers are laminated like an organic EL. In view of the above, the transfer method that can impart ink repellency only to the upper surface of the partition wall by a simple method after the partition pattern is formed is the most preferable method.

JP-A-6-347637 JP-A-7-35915 JP-A-9-127327 JP 2000-35511 A JP-A-11-271753 JP 2003-344640 A JP 2002-305070 A JP 2008-139378 A

  However, in the transfer method described above, a transfer material carrying an ink repellent component on a temporary support is brought into contact with the upper surface of the partition pattern on the transparent substrate, and the necessary heat pressure is applied to repel the upper surface of the partition. Ink components are transferred, but due to the increase in pixel size and the formation of complex circuit patterns due to the increase in screen size and functionality of display devices in recent years, the functional layer is printed on uneven surfaces. In addition to the upper surface of the partition wall, the transfer material touches not only the central part of the opening but also the convex part in the surface to be printed, and the ink repellent component is transferred. This causes a problem of display defects.

  Therefore, the object of the present invention is to solve the above-mentioned problems, and can be applied to a large substrate, and can be manufactured easily and inexpensively in an application method such as an ink-jet method with high material use efficiency. It is an object of the present invention to provide a high-quality color filter, an organic EL, and other optical elements free from display defects due to uneven thickness of the functional layer, white spots, mixed colors, and the like, and a manufacturing method thereof.

  In order to achieve the above object, the present invention employs the following configuration.

The present invention is an optical element in which a desired functional layer pattern is formed on a substrate that transmits light, the partition pattern separating the functional layer pattern, and the ink repellency formed on the upper surface of the partition pattern Layer, a columnar spacer formed in the opening region divided by the partition pattern, and a functional layer formed in the opening region by applying a functional layer forming ink to the opening region. When the height from the lowest part of the part to which the functional layer forming ink is applied in the opening region to the highest part of the partition pattern is 1, the lowest part to the highest part of the spacer Is in a range of 0.3 to 1.2, and the ratio of the total area of the bottom surface of the spacer to the total area of the open region is 0.0001 to 0.0. It is in the range of.

  Further, when the height from the lowest part of the part to which the functional layer forming ink is applied in the opening region to the highest part of the partition pattern is 1, the highest part of the spacer from the lowest part The height up to may be in the range of 0.5 to 1.0.

  The spacer may be formed of an affinity material having a contact angle with respect to the functional layer forming ink of 30 ° or less.

  The ink repellent layer may be a compound containing fluorine.

The present invention is also a method of manufacturing an optical element in which a desired functional layer pattern is formed on a substrate that transmits light, the step of forming a partition pattern that divides the functional layer pattern, and the partition pattern Forming a columnar spacer in the divided opening area; forming an ink repellent layer on the upper surface of the partition wall pattern; and applying the functional layer forming ink to the opening area. Forming a functional layer in the region, and when the height from the lowest part of the part to which the functional layer forming ink is applied in the opening region to the highest part of the partition pattern is 1, The height from the lowest part to the highest part of the spacer is in the range of 0.3 to 1.2 and occupies the total area of the open area. The ratio of the total area of the bottom surface of the spacer is in the range of 0.0001 to 0.01.

  According to the present invention, by providing at least one or more columnar spacers in the opening surrounded by the partition wall pattern, the ink repellent component can be transferred regardless of the pixel size or the unevenness in the opening. In addition, it is possible to suppress the adhesion of the ink repellent component to the printing surface, and it is possible to provide a high-quality optical element that is free from unevenness in the thickness of the functional layer and white spots at a low cost.

  Further, when the height from the lowest part of the part to which the functional layer forming ink is applied in the opening region to the highest part of the partition wall pattern is 1, the height from the lowest part to the highest part of the spacer By setting the value in the range of 0.3 to 1.2, the transfer of the ink repellent component (ink repellent layer) to the upper surface of the partition wall is prevented regardless of the pixel size and the unevenness in the opening (opening region). Without the ink-repellent component adhering to the printing surface. Furthermore, by setting the height of the columnar spacer to 0.5 to 1.0, the adhesion of the ink repellent component to the printing surface is further suppressed, and the liquid repellent component is effectively formed on the surface of the partition wall. Therefore, it is possible to provide a high-quality optical element that is free from display defects due to uneven thickness of the functional layer, white spots, or mixed colors at a low cost.

  Further, by setting the ratio of the total area of the bottom surface of the spacer to the total area of the opening region in the range of 0.0001 to 0.01, the display device can be suppressed while suppressing the adhesion of the ink repellent component to the printing surface. A high-quality optical element that exhibits its original display performance can be provided simply and inexpensively. Here, the total area of the opening region is an image obtained by photographing the partition pattern from the Z-axis direction of the substrate on which the partition pattern is formed (direction looking down on the substrate) instead of the surface area when the opening region is uneven. Represents the total area of the opening region.

  In addition, since the spacer is formed of a material having an affinity with a contact angle with respect to the functional layer forming ink of 30 ° or less, film thickness unevenness and white spots on the functional layer are less likely to occur. An element can be provided simply and inexpensively.

  In addition, since the ink repellent material is a fluorine-containing compound, it is possible to more stably suppress uneven thickness, white spots, or color mixing of the functional layer, and to provide a high-quality optical element easily and inexpensively. .

Sectional drawing which shows the ink jet type color filter which is 1st embodiment of the optical element of this invention Sectional drawing which shows the organic EL element which is 2nd embodiment of the optical element of this invention Bottom shape diagram showing an example of a columnar spacer which is an embodiment of the optical element of the present invention The schematic diagram which shows the partition pattern board | substrate of the color filter which is 1st embodiment of the optical element of this invention The schematic diagram which shows the partition pattern board | substrate with a columnar spacer of the color filter which is 1st embodiment of the optical element of this invention. The schematic diagram which shows the partition pattern board | substrate with a columnar spacer of the organic EL element which is 2nd embodiment of the optical element of this invention.

(First embodiment)
Hereinafter, an inkjet color filter 1 which is a first embodiment of the optical element of the present invention will be described with reference to FIG.

  The ink jet type color filter 1 (hereinafter sometimes simply referred to as the color filter 1) as the first embodiment of the optical element of the present invention is manufactured as follows. As can be seen from FIG. 1, first, the partition pattern 20 is formed on the transparent substrate 10, and the columnar spacer 40 is formed in the opening 30 surrounded by the partition pattern 20. Thereafter, a transfer material (not shown) carrying an ink repellent component on the temporary support is pressed against the upper surface 21 of the partition pattern 20 by using a heating roll or the like, and the temporary support is peeled off to remove the ink repellent. The sexual component (ink repellent layer) 22 is transferred. Thereafter, R, G, and B colored inks are applied to the opening (opening region) 30 surrounded by the partition wall pattern 20 using an ink jet coating apparatus, and dried and baked. The color filter 1 is obtained by the above process.

  The transparent substrate 10 may be a plastic sheet and a plastic film, such as polycarbonate, polyethersulfine, and polyacrylate, as long as transparency and mechanical strength characteristics as a color filter are satisfied. However, as the transparent substrate 10, it is more preferable to use a glass substrate that is excellent in transparency, strength, heat resistance, and weather resistance.

  A method for forming the partition pattern 20 is not particularly limited, such as a photolithography method, a printing method, a transfer method, an ink jet method, an etching method, and the like, and a conventionally known method can be used. Among them, a photolithography method capable of forming a fine pattern is particularly preferable as a method for forming the partition wall pattern 20. When the barrier rib pattern 20 is formed by a photolithography method, the photosensitive resin composition is uniformly applied on a transparent substrate, exposed through a photomask having a desired pattern, and developed to remove unnecessary portions. The partition pattern 20 can be formed.

  Moreover, it is preferable that the partition of the color filter 1 contains a colored or light-shielding material and has a function as a black matrix, thereby reducing the manufacturing process and obtaining a high-performance color filter. The height of the partition pattern 20 used in the color filter 1 of the present embodiment is preferably 0.5 to 5 μm, more preferably 1 to 3 μm. Here, the height of the partition pattern 20 is a distance from the surface of the transparent substrate 10 to the highest portion of the partition pattern 20 (see FIG. 1).

  Below, the formation method of the partition pattern 20 by the photolithographic method using a black negative photosensitive resin composition is demonstrated concretely. First, the black negative photosensitive resin composition is uniformly coated on the transparent substrate 10 using a known coating apparatus such as a slit die coater or a spin coater. Thereafter, in order to remove the solvent component, vacuum drying treatment or pre-baking treatment is performed as necessary. Then, pattern exposure and development are performed to form a predetermined black matrix pattern. Subsequently, a heat treatment at about 180 to 250 ° C. is performed to thermally cure the negative photosensitive resin composition, and the partition pattern 20 is obtained. As this heating method, a hot-air circulating oven, a hot plate, heating by infrared rays, or the like can be used, and is not particularly limited.

  The main components of the negative photosensitive resin composition are a binder resin, a compound having radical polymerizability, a photopolymerization initiator, a solvent, and a light shielding member. First, the binder resin is preferably an alkali-soluble thermosetting resin, and specific examples include cresol-novolak resin, polyvinylphenol resin, acrylic resin, and methacrylic resin. These binder resins may be used alone or in combination of two or more. In addition to these resins, a melamine derivative and a photoacid generator can also be contained. As the melamine derivative, any compound having a methylol group or a methoxymethyl group may be used, but those having high solubility in a solvent are particularly preferable.

  As the above-mentioned compound having radical polymerizability, for example, a monomer or oligomer having a vinyl group or an allyl group, or a polymer 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, Mention may be made of N-vinyl heterocycles, allyl ethers, allyl esters, and derivatives thereof.

  Examples of suitable compounds include relatively low molecular weight polyfunctional acrylates such as pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol penta and hexaacrylate. Yes, but this is not the case. These radically polymerizable compounds may be used alone or in combination of two or more. The amount of these radically polymerizable compounds can range from 1 to 200 parts by weight with respect to 100 parts by weight of the binder resin, and preferably 50 to 150 parts by weight with respect to 100 parts by weight of the binder resin. Part.

  Moreover, said photoinitiator produces | generates a radical by exposure and bridge | crosslinks binder resin through the compound which has radical polymerizability. Examples of the photopolymerization initiator include benzophenone compounds such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 1-hydroxycyclohexylacetophenone, 2,2-dimethoxy- Acetophenone derivatives such as 2-phenylacetophenone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2 -Thioxanthone derivatives such as chlorothioxanthone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, anthraquinone derivatives such as chloroanthraquinone, benzoin methyl ether, benzoin ethyl Benzoin ether derivatives such as ether and benzoin phenyl ether, acylphosphine derivatives such as phenylbis- (2,4,6-trimethylbenzoyl) -phosphine oxide, 2- (o-chlorophenyl) -4,5-bis (4 Lophine dimers such as '-methylphenyl) imidazolyl dimer, N-aryl glycines such as N-phenylglycine, organic azides such as 4,4'-diazidochalcone, 3,3', 4,4 Examples include '-tetra (tert-butylperoxycarboxy) benzophenone and quinonediazide group-containing compounds.

  These photopolymerization initiators may be used alone or in combination of two or more. The amount of these photopolymerization initiators can range from 0.1 to 50 parts by weight with respect to 100 parts by weight of the binder resin, and preferably 1 to 20 parts by weight with respect to 100 parts by weight of the binder resin. Part.

  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 these solvents used is preferably a coating that is uniform when coated on a substrate and can form a coating film with no pinholes or uneven coating. The amount of solvent relative to the total weight of the photosensitive resin composition Is preferably prepared so as to be 50 to 97% by weight.

  Further, the light shielding member (black light shielding member) imparts light shielding properties to the black matrix and improves the contrast of the color filter. As an example of the black light shielding member, a black pigment, a black dye, carbon black, aniline black, graphite, iron black, titanium oxide, an inorganic pigment, and an organic pigment can be used. These black light shielding members may be used alone or in combination of two or more.

  In addition, the negative photosensitive resin composition used for forming the partition wall pattern may have compatible additives as necessary, for example, a leveling agent, a chain transfer agent, a stabilizer, a sensitizing dye, a surfactant, a cup A ring agent or the like can be added.

  Next, a method for forming the columnar spacer 40 will be described. As a method for forming the columnar spacer 40, similarly to the partition wall pattern 20, conventionally known methods such as a photolithography method, a printing method, a transfer method, an ink jet method, and an etching method can be used. One or more columnar spacers 40 are disposed in the opening 30 surrounded by the partition wall pattern 20, and when one column spacer 40 is disposed, as illustrated in FIG. 1, the opening 30 surrounded by the partition wall pattern 20. It is preferable to arrange them at substantially the center, and it is preferable that they are arranged in substantially the same shape and pattern without variation between pixels. In order to increase the contrast of the liquid crystal display device, it is preferable that the columnar spacer 40 also has a light shielding property by containing a colored or light shielding material. Furthermore, the pattern of the columnar spacer 20 may be drawn on the photomask when the partition pattern 20 is formed, and may be formed simultaneously with the partition pattern 20. Accordingly, the columnar spacer 40 can be formed in the same manner as the partition wall pattern 20 is formed by the photolithography method using the negative photosensitive resin composition described above. Here, the columnar spacer 40 is preferably formed of a material having an affinity with a contact angle with respect to a color layer forming ink (functional layer forming ink) to be described later of 30 ° or less, and does not include a component exhibiting ink repellency. preferable.

  The shape of the bottom surface of the columnar spacer 40 is not particularly limited. As long as the object of the present embodiment can be achieved, a circular shape, an elliptical shape, a rectangular shape, and a multiplicity as shown in FIGS. It can be formed in various shapes such as a square shape, a cross shape, and a shape obtained by combining them. Further, a plurality of columnar spacers 40 of several types may be arranged. In the present embodiment, when the total opening area to be the printing surface is 1, the ratio of the bottom area of the entire columnar spacer 40 to the total opening area is in the range of 0.0001 to 0.01. preferable. When the ratio of the bottom area of the columnar spacer 40 to the entire opening area is smaller than 0.0001, the function as a spacer for preventing defective transfer into the opening 30 during the transfer process of the ink repellent component can be sufficiently exerted. However, when the ratio is larger than 0.01, the light extraction efficiency decreases with a decrease in the aperture ratio, and the brightness of the liquid crystal display device decreases. This leads to an increase in energy consumption.

  Further, the distance between the partition pattern 20 and the columnar spacer 40 is preferably within 300 μm, more preferably within 200 μm, and even more preferably within 100 μm. By setting the interval between the partition pattern 20 and the columnar spacer 40 within the above range, the effect of preventing defective transfer of the ink repellent component into the opening 30 can be further enhanced (see FIG. 1).

  Subsequently, the transfer material in which the ink repellent component is supported on the temporary support on the substrate on which the partition pattern 20 and the columnar spacer 40 are formed is in a state where the upper surface 21 of the partition pattern 20 and the ink repellent component layer 22 are in contact with each other. After the ink repellent component 22 is transferred to the upper surface 21 of the partition wall pattern 20, the temporary support is peeled off to impart ink repellency to the upper surface 21 of the partition wall pattern 20 (see FIG. 1). ).

  Here, the pressure bonding refers to contact by applying pressure as in a laminate, for example, with a roller or flat plate obtained by heating and / or pressing a transfer material carrying an ink repellent component on a temporary support. The ink repellent component can be attached to the upper surface of the partition wall pattern by pressure bonding or thermocompression bonding. For the pressure bonding, a known laminator method or a known laminator can be used. Moreover, as a pressure bonding condition, the pressure during pressure bonding is preferably 0.1 MPa to 2.0 MPa, and more preferably 0.5 MPa to 1.5 MPa. The temperature during pressure bonding is preferably 40 ° C to 150 ° C, more preferably 60 ° C to 120 ° C.

  As a temporary support used for the transfer material, it is possible to uniformly carry an ink repellent component, withstands the heat pressure at the time of pressure bonding, and from the viewpoint of good adhesion to the upper surface 21 of the partition wall pattern 20. It is preferable to use a plastic film having moderate flexibility. For example, a film made of a material such as polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, or polyester can be used as appropriate. As thickness of a temporary support body, 10-300 micrometers is preferable and 10-150 micrometers is more preferable. Among these, a temporary support having a material of polyethylene terephthalate and a thickness of 15 μm to 50 μm is particularly preferable.

  The ink repellent component 22 is formed in a layer on the temporary support, and is pressure-bonded to the upper surface 21 of the partition pattern 20 so that all or part of the ink repellency component 22 is transferred to the upper surface 21 of the partition pattern 20. Thus, it has a role of imparting ink repellency to the upper surface 21 of the partition wall pattern 20. The ink repellent component 22 is an ink repellent compound, other resin (binder polymer or the like), other monomer, and a surfactant or the like can be appropriately added. The method for forming the ink repellent component layer on the temporary support is not particularly limited. For example, a composition liquid containing the ink repellent component is prepared, and a known coating method such as slit coating or micro gravure coating is used. It can form by apply | coating on a temporary support body. Also, it is possible to provide another layer between the temporary support and the ink repellent component layer as long as the effects of the present embodiment are not hindered. Further, the thickness of the ink repellent component 22 is preferably 1 nm to 1000 nm, and more preferably 10 nm to 100 nm.

  The ink repellent component 22 is not particularly limited as long as it is a compound that causes the upper surface 21 to repel ink when it is present on the upper surface 21 of the partition wall pattern 20, but a fluorine-containing compound containing fluorine. Is more preferable because it can impart particularly high ink repellency. As the fluorine-containing compound, either a fluorine-containing monomer described later or a fluorine-containing polymer (fluorine-containing resin) composed of these fluorine-containing monomers may be used, or these may be used in combination. Moreover, as a fluorine-containing polymer, 1 or more types of the fluorine-containing monomer mentioned later may be included and a copolymer with a non-fluorine monomer may be sufficient.

Specific examples of the fluorine-containing monomer are given below. For example, CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCOCH ═CH ₂ , CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH (OH) CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH (OH) CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₃ CH ₂ CH (OH) CH ₂ OCOCH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₂ OCOCH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₄ (CH ₂ ) ₂ OCOCH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₂ (CH ₂ ) ₂ OCOCH═CH ₂ , CF ₃ CH ₂ OCOCH═CH _{2, CF 3 (CF 2)} 4 CH 2 CH 2 OCOC (CH 3) = C _{2, C 7 F 15 CON (} C 2 H 5) CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) CH 2 CH 2 OCOCH = CH 2, CF 3 ( CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH═CH ₂ , C ₂ F ₅ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₃ OCOCH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₁₀ (CH ₂ ) ₃ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) _{4 CH (CH 3) OCOC (CH} 3) = CH 2, CF 3 (CF 2) 4 OCH 2 CH 2 OCOC (CH 3) = CH 2, C 2 F 5 CON (C 2 H 5) CH 2 OCOCH = CH ₂ , CF ₃ (CF ₂ ) ₂ CON (CH ₃ ) CH (CH ₃ ) CH ₂ OCOCH═CH ₂ , H (CF ₂ ) ₆ CH ( C ₂ H ₅ ) OCOC (CH ₃ ) ═CH ₂ , H (CF ₂ ) ₈ CH ₂ OCOCH═CH ₂ , H (CF ₂ ) ₄ CH ₂ OCOCH═CH ₂ , H (CF ₂ ) CH ₂ OCOC (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₁₀ OCOCH = CH ₂ , C ₂ F ₅ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ) ₄ OCOCH═CH ₂ , C ₂ F ₅ SO ₂ N (C ₂ H ₅ ) C (C ₂ H ₅ ) HCH ₂ OCOCH═CH _{2 and} other perfluoroalkyl acrylates, C ₃ F ₇ CH═CH ₂ , C _{4 F 9 CH = CH 2,} C 10 F 21 CH = CH 2, C 3 F 7 OCF = CF 2, C 7 F 15 OCF = CF 2及Fluoroalkyl olefin such as _{C 8 F 17 OCF = CF 2} , more _{CH 2 = CHCOOCH 2 (CF 2} ) 3 CH 2 OCOCH = CH 2, CH 2 = CHCOOCH 2 CH (CH 2 C 8 F 17) OCOCH = _{CH 2, CF 3 CH 2 OCH} 2 CH 2 OCOCH = CH 2, C 2 F 5 (CH 2 CH 2 O) 2 CH 2 OCOCH = CH 2, (CF 3) 2 CFO (CH 2) 5 OCOCH = CH 2 Etc.

Among the above, particularly preferred fluorine-containing monomers include CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH (OH) CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH (OH) CH ₂ OCOCH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₂ OCOCH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₄ (CH ₂ ) ₂ OCOCH═CH ₂ , and the like.

  Subsequently, colored inks of red (R), green (G), and blue (B) are ejected to the opening 30 surrounded by the partition pattern 20 imparted with ink repellency by an inkjet device, and a predetermined amount is filled. To do. At this time, the upper surface 21 of the partition wall pattern 20 has sufficient ink repellency, and the entire opening portion 30 including the side surface 23 of the partition wall pattern 20 serving as a printing surface is maintained in ink affinity. Therefore, the colored ink is uniformly spread on the surface to be printed and does not run on the upper surface of the partition pattern 20 and overflow to the adjacent pixels. Thereafter, the solvent component in the colored ink is volatilized and the resin component is cured to form the RGB colored layer 50, whereby the color filter 1 of this embodiment is obtained (see FIG. 1).

  As the ink jet device to be used, there are a piezo conversion method and a heat conversion method depending on the ink discharge method, and the piezo conversion method is particularly preferable. A device in which the ink particleization frequency is about 5 to 100 KHz, the nozzle diameter is about 5 to 80 μm, a plurality of heads are arranged, and 60 to 500 nozzles are incorporated in one head is suitable.

  As the colored ink, known materials such as a colorant, a binder component, and a solvent can be used. If necessary, additives such as a dispersant, a stabilizer, and a leveling agent can be added and prepared. . As the colorant, a dye or a pigment can be used, but a pigment dispersion type is particularly preferable in terms of reliability such as heat resistance and weather resistance. Moreover, as a solvent, although an aqueous system and an organic solvent system can be utilized, the organic solvent system which is excellent in the solubility of many materials is preferable. Furthermore, the solvent is appropriately selected in consideration of stability over time and drying properties. Several kinds of mixed solvents may be used.

  As the pigment of the coloring ink material, it is preferable to use a pigment having excellent weather resistance. Specifically, C.I. I. Pigment Red 9, 19, 38, 43, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 208, 215, 216, 217, 220, 223, 224, 226, 227, 228 240, 254, C.I. I. Pigment Blue 15, 15: 6, 16, 22, 29, 60, 64, C.I. I. Pigment Green 7, 36, 58, C.I. I. Pigment Yellow 20, 24, 86, 81, 83, 93, 108, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 168, 185, C.I. I. Pigment Orange 36, C.I. I. Pigment Violet 23 or the like can be used. Furthermore, in order to obtain a desired hue, two or more kinds of materials can be mixed and used.

  As the binder component, any of a resin having no polymerization reactivity per se and a resin having a polymerization reactivity per se may be used, or two or more binders may be used in combination. The binder component is the main component, and if necessary, polyfunctional monomers and oligomers, monofunctional monomers and oligomers, photopolymerization initiators activated by ionizing radiation, sensitizers, etc., are blended and ionized. A radiation curable binder system may be constructed.

  As the non-polymerizable binder, for example, a copolymer composed of two or more of the following monomers can be used. Acrylic acid, methacrylic acid, trimellitic acid, methyl acrylate, caprolactone, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, polystyrene macromonomer, and polymethyl methacrylate macromonomer .

  More specifically, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, benzyl methacrylate / styrene copolymer, benzyl methacrylate macromonomer / styrene copolymer, benzyl methacrylate / styrene macromonomer A copolymer etc. can be illustrated.

  On the other hand, when a resin having a thermally polymerizable functional group is used as a binder component, for example, a homopolymer obtained by polymerizing one or more monomers containing an ethylenically unsaturated bond and an epoxy group as shown below. Alternatively, a copolymer can be used. Glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4- (Meth) such as epoxybutyl, methacrylic acid-4,5-epoxypentyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl Acrylates: o-vinylphenyl glycidyl ether, m-vinylphenyl glycidyl ether, p-vinylphenyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 2,3-diglycidyl Xylstyrene, 3,4-diglycidyloxystyrene, 2,4-diglycidyloxystyrene, 3,5-diglycidyloxystyrene, 2,6-diglycidyloxystyrene, 5-vinyl pyrogallol triglycidyl ether, 4-vinyl pyrogallol Triglycidyl ether, vinylphloroglicinol triglycidyl ether, 2,3-dihydroxymethylstyrene diglycidyl ether, 3,4-dihydroxymethylstyrene diglycidyl ether, 2,4-dihydroxymethylstyrene diglycidyl ether, 3,5-dihydroxy Methyl styrene diglycidyl ether, 2,6-dihydroxymethyl styrene diglycidyl ether, 2,3,4-trihydroxymethyl styrene triglycidyl ether, and 1,3,5-trihi Glycidyl ethers such as droxymethylstyrene triglycidyl ether; and melamines such as methylated melamine, butylated melamine, mixed etherified melamine, methylated benzoguanamine and mixed etherified benzoguanamine.

  As the above-mentioned compound having radical polymerizability, for example, a monomer or oligomer having a vinyl group or an allyl group, or a polymer 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, Mention may be made of 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 pentaacrylate, and hexaacrylate. Yes, but not this. These radically polymerizable compounds may be used alone or in combination of two or more. The amount of these radically polymerizable compounds can range from 1 to 200 parts by weight with respect to 100 parts by weight of the binder component, and preferably 50 to 150 parts by weight with respect to 100 parts by weight of the binder component. Part.

  Moreover, said photoinitiator produces | generates a radical by exposure and bridge | crosslinks binder resin through the compound which has radical polymerizability. Examples of the photopolymerization initiator include benzophenone compounds such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 1-hydroxycyclohexylacetophenone, 2,2-dimethoxy- Acetophenone derivatives such as 2-phenylacetophenone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2 -Thioxanthone derivatives such as chlorothioxanthone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, anthraquinone derivatives such as chloroanthraquinone, benzoin methyl ether, benzoin ethyl Benzoin ether derivatives such as ether and benzoin phenyl ether, acylphosphine derivatives such as phenylbis- (2,4,6-trimethylbenzoyl) -phosphine oxide, 2- (o-chlorophenyl) -4,5-bis (4 Lophine dimers such as '-methylphenyl) imidazolyl dimer, N-aryl glycines such as N-phenylglycine, organic azides such as 4,4'-diazidochalcone, 3,3', 4,4 Examples include '-tetra (tert-butylperoxycarboxy) benzophenone and quinonediazide group-containing compounds. These photopolymerization initiators may be used alone or in combination of two or more. The amount of the photopolymerization initiator can range from 0.1 to 50 parts by weight with respect to 100 parts by weight of the binder component, preferably 1 to 20 parts by weight with respect to 100 parts by weight of the binder component. is there.

  The dispersant is blended in the ink composition as necessary in order to disperse the pigment satisfactorily. Examples of the dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, polymer surfactants (polymer dispersants) as exemplified below are preferable.

  That is, in the polymer dispersant, polyoxyethylene alkyl ethers such as xylethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether and other polyoxyethylene alkyl ethers. Polymeric surfactants such as ethylene alkylphenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes are preferably used.

  The solvent used for the colored ink is not particularly limited, and can be selected according to the quality, etc. required for the pigment, binder, and ink used. Examples of the solvent to be used include 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 1,3-butanediol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate. , Diethylene glycol dibutyl ether, diethyl adipate, dibutyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, and diethyl succinate. Two or more kinds of the above-mentioned solvents can be mixed and used.

  In the colored ink of the present embodiment, when a pigment is used as a colorant, the pigment is mixed with a dispersant in advance in a part of the solvent in the total amount used to impart dispersibility, and the resulting pigment dispersion (that is, In many cases, the pigment dispersion (high concentration) is charged into the remaining solvent together with other blending components and mixed to obtain a colored ink. In order to prepare the pigment dispersion, it is preferable to use a solvent that easily disperses the pigment, such as 3-methoxybutyl acetate or propylene glycol monomethyl ether acetate (PGMEA).

  In addition, by adjusting the viscosity of the colored ink in the range of 1 to 20 mPa · s, it is possible to stabilize the discharge performance in the ink jet method and to efficiently produce a color filter with good quality.

  A known heating device such as a hot air circulation oven, an IR oven, a hot plate, or the like is filled in the opening 30 surrounded by the partition wall pattern 20 with a colored ink by ink jet, and is dried under reduced pressure or ultraviolet irradiation as necessary. Can be used to cure the colored layer 50 by post-baking at a temperature of 200 to 250 ° C. for 3 to 60 minutes to obtain the inkjet color filter 1 of the present embodiment (see FIG. 1).

  As described above, according to the present embodiment, the columnar spacer 40 is appropriately disposed in the opening 30 surrounded by the partition wall pattern 20, so that it has conventionally been repelled on a part of the printing surface. Even under the condition where the ink component has been transferred, transfer of the ink repellent component to unnecessary portions can be suppressed, and effective ink repellency can be imparted to the upper surface 21 of the partition pattern 20. .

  The ink jet color filter 1 of the present embodiment may further form a protective layer as necessary. Further, if necessary, a transparent conductive layer, a liquid crystal alignment division protrusion, a photo spacer, and an alignment film layer are sequentially stacked, and for example, a liquid crystal display device is placed through a liquid crystal layer so as to face a counter substrate on which an electrode such as a thin film transistor is formed. Can be configured.

(Second embodiment)
Hereinafter, a coating-type organic EL element 2 which is a second embodiment of the optical element of the present invention will be described with reference to FIG.

  The coating method organic EL element 2 (hereinafter sometimes simply referred to as the organic EL element 2) as the second embodiment of the optical element of the present invention is manufactured as follows. As can be seen from FIG. 2, first, a circuit element layer is formed on the transparent substrate 100 using a known film forming technique (not shown). Subsequently, an anode 110 made of, for example, ITO (Indium Tin Oxide) is formed on the circuit element layer. Subsequently, an insulating layer (pixel separation film) 120 is formed on the circuit element layer and the anode 110. Subsequently, a partition pattern 130 is formed on the insulating layer 120. Further, a columnar spacer 150 is formed in an opening (opening region) 140 surrounded by the partition pattern 130, and a transfer material in which an ink-repellent component is supported on a temporary support is applied to the upper surface of the partition pattern 130. Then, the ink repellent component (ink repellent layer) 132 is transferred by pressing with a heating roll or the like and peeling the temporary support.

  Thereafter, the functional liquid containing the material of the hole injection layer is applied to the opening 140 surrounded by the partition wall pattern 130 to which ink repellency is imparted by a known coating means (for example, an ink jet apparatus or a nozzle printing apparatus). Coating and heat treatment are performed, and the solvent is volatilized, dried, and solidified to form the hole injection layer 160. Further, the functional liquid containing the material of the light emitting layer is applied onto the hole injection layer 160 by the same coating means as described above, heat treatment is performed, and the solvent is volatilized, dried, and solidified to form the light emitting layer. 170 is obtained. Further, a cathode 180 is formed on substantially the entire element substrate on which the light emitting layer 170 is formed, for example, by vapor deposition. Subsequently, for example, an adhesive and a barrier property such as a glass substrate and a metal plate are provided on the cathode 180. The organic EL element 2 is completed by forming the sealing layer 190 using the base material which has.

  The transparent substrate 100 may be a plastic sheet and a plastic film such as polycarbonate, polyethersulfine, and polyacrylate as long as the transparency, heat resistance, dimensional stability, and mechanical strength characteristics are satisfied. May be. However, as the transparent substrate 100, it is preferable to use a glass substrate that is excellent in transparency, strength, heat resistance, and weather resistance.

  As the circuit element layer, a known TFT (Thin Film Transistor) driving circuit or the like can be used. The circuit element layer includes a scanning line, a signal line, a power supply line, a switching TFT, a storage capacitor (not shown). And the like, and is formed by a known manufacturing method. The TFT may have a single gate structure, a double gate structure, or a multi-gate structure having three or more gate electrodes. Moreover, you may have a LDD structure and an offset structure. Further, two or more thin film transistors may be arranged in one pixel.

  Examples of the material of the anode 110 include metal composite oxides such as ITO, indium zinc composite oxide, and zinc aluminum composite oxide, metal materials such as gold and platinum, and fine particles of these metal oxides and metal materials made of epoxy resin, A single layer or a laminate of fine particle dispersed films dispersed in an acrylic resin or the like can be used. In particular, as the material of the anode 110, it is preferable to select a material having a high work function such as ITO. In addition, as a material for the anode 110, in the case of a so-called bottom emission structure in which light is extracted from below, it is necessary to select a light-transmitting material. As a patterning method of the anode 110, an existing patterning method such as a mask vapor deposition method, a photolithography method, a wet etching method, or a dry etching method can be used depending on a material or a film forming method. In the case of using a substrate on which a TFT is formed as a substrate, it is formed so that conduction can be achieved corresponding to a lower pixel.

The insulating layer 120 is formed by, for example, forming an insulating layer including a silicon oxide film (SiO ₂ ) or a silicon nitride film (SiN) so as to cover the circuit element layer and the anode by a CVD (Chemical Vapor Deposition) method or the like. The opening 140 is formed in a region corresponding to the light emitting region by using a photolithography method and an etching method.

  A method for forming the partition pattern 130 is not particularly limited and may be a known method such as a photolithography method, a printing method, a transfer method, an ink jet method, an etching method, and the like. Among these, a photolithography method capable of forming a fine pattern is particularly preferable. When the barrier rib pattern 130 is formed by photolithography, a photosensitive resin composition is applied on the insulating layer 120 and the anode 110 by a known method, exposed through a photomask having a desired pattern, and developed. By removing unnecessary portions, the partition pattern 130 can be formed. The height of the partition pattern 130 is 1 to 10 μm, more preferably 2 to 5 μm. The height of the barrier rib pattern referred to here is the distance from the lowest surface of the opening 140 surrounded by the barrier rib pattern 130, that is, the surface of the anode 110 to the highest portion of the barrier rib pattern 130. The thickness is included.

  The photosensitive resin composition is prepared from a polyimide precursor, acrylate, methacrylate, novolac resin, acrylic resin, and the like, and a photosensitive agent, a sensitizer, an additive, a solvent, and the like. The photosensitive resin composition is not particularly limited as long as it has heat resistance, solvent resistance, and insulation and does not adversely affect the light emission characteristics of the light emitting material. Even available.

  Subsequently, as a method for forming the columnar spacer 150, similarly to the partition wall pattern 130, a conventionally known method such as a photolithography method, a printing method, a transfer method, an ink jet method, an etching method, or the like can be used. One or more columnar spacers 150 are disposed in the opening 140 surrounded by the partition wall pattern 130, and in the case where one columnar spacer 150 is disposed, it is preferably disposed substantially at the center of the opening 140 surrounded by the partition wall pattern 130. It is preferable that they are arranged in substantially the same shape and pattern without variation between pixels (see FIG. 2). Alternatively, the columnar spacer 150 may be formed simultaneously with the partition wall pattern 130 by drawing the pattern of the columnar spacer 150 on the photomask when the partition wall pattern 130 is formed. As a material for forming the columnar spacer 150, the same material as the material for forming the partition pattern 130 can be used, and it has heat resistance, solvent resistance, and insulating properties, and does not adversely affect the light emission characteristics of the light emitting material. The material is preferable, and further, it is desirable that the contact angle with respect to the coating material for forming the hole injection layer 160 and the light emitting layer 170 described later is an affinity material having an affinity of 30 ° or less.

  The shape of the bottom surface of the columnar spacer 150 is not particularly limited, and can be formed in various shapes as shown in FIG. 3 shown in the first embodiment of the present invention. Further, a plurality of columnar spacers 150 of several types may be arranged.

  In the present embodiment, the opening 140 surrounded by the barrier rib pattern 130 includes a light emitting region in which the surface of the anode 110 is exposed and a non-light emitting region in which the insulating layer 120 is stacked on the circuit element layer. In the transfer process of the ink repellent component described later, the column spacer 150 is provided in any of the above regions within a range that can achieve the purpose of preventing the ink repellent component from being transferred to locations other than the upper surface of the partition wall pattern 130. It may be formed. When the columnar spacer 150 is provided in the light emitting region on the surface of the anode 110, when the height of the partition pattern 130 (the height from the lowest surface of the opening 140 to the highest portion of the partition pattern 130) is 1, It is preferable that the ratio of the height of the columnar spacer 150 (the height from the lowest surface of the opening 140 to the highest portion of the columnar spacer 150) be 0.3 to 1.2. When this ratio is lower than 0.3, the function as a spacer is not exhibited, and when this ratio is higher than 1.2, transfer of the ink repellent component to the partition pattern 130 in the vicinity of the columnar spacer 150 is hindered, and the functional layer The ink runs up to the upper part of the partition wall or overflows to the adjacent pixels, causing defects such as color mixing and uneven light emission.

  More preferably, the effect can be further enhanced by setting this ratio to 0.5 to 1.0. On the other hand, when the columnar spacer 150 is provided in the non-light emitting region on the surface of the insulating layer 120, the height of the columnar spacer 150 is 0.3-1. Is preferably 2, more preferably 0.5 to 1.0. Note that since the surface of the insulating layer 120 is higher than the light emitting region by the thickness of the circuit element layer (not shown) and the insulating layer 120, the ink-repellent component is easily transferred. More preferably, a columnar spacer 150 is provided.

  In the present embodiment, it is preferable that the ratio of the bottom area of all the columnar spacers 150 occupying the entire area of the opening region 140 serving as the printing surface is in the range of 0.0001 to 0.01. When the ratio of the bottom area of all the columnar spacers 150 occupying the entire area of the opening region 140 is smaller than 0.0001, the function as a spacer for preventing defective transfer into the opening 140 during the transfer process of the ink repellent component is achieved. Insufficient film thickness and white spots in RGB pixels are likely to occur, and conversely, if this ratio is greater than 0.01, the light emitting area is reduced, resulting in a decrease in luminance of the organic EL display device and driving voltage. As a result, the emission lifetime is reduced.

  Further, the distance between the partition pattern 130 and the columnar spacer 150 is preferably within 300 μm, more preferably within 200 μm, and even more preferably within 100 μm. By setting the interval between the partition pattern 130 and the columnar spacer 150 within the above range, the effect of preventing defective transfer of the ink repellent component into the opening 140 can be further enhanced.

  Subsequently, an upper surface of the partition pattern 130 and the ink repellent component layer 132 are in contact with a transfer material in which an ink repellent component is supported on a temporary support on the substrate 100 on which the partition pattern 130 and the columnar spacer 150 are formed. After pressure bonding in a state, the ink repellent component is transferred to the upper surface of the partition pattern 130, the temporary support is peeled off, and the ink repellent component layer 132 is formed on the upper surface of the partition pattern 130. Here, the step of applying the ink repellent component is performed in the same manner as in the first embodiment, and the same transfer material can be used.

  As the functional liquid of the hole injection layer 160, for example, a mixture (PEDOT / PSS) in which polystyrene sulfonic acid (PSS) as a dopant is added to a polythiophene derivative such as polyethylenedioxythiophene (PEDOT) can be used. As an example of the PEDOT-PSS dispersion, a PEDOT / PSS weight ratio of 1:10, a solid content concentration of 0.5%, a diethylene glycol content of 50%, and a remaining amount of pure water is used. be able to.

  Subsequently, the functional liquid is dried to form the hole injection layer 160. Specifically, the hole injection layer 160 is formed in the opening 140 by drying or baking the functional liquid in a high temperature environment to evaporate the solvent and solidify PEDOT-PSS contained in the functional liquid. As a drying condition, for example, it is left in an environment of 200 ° C. for 10 minutes. The film thickness of the hole injection layer 160 is, for example, 50 nm.

  As the functional liquid of the light emitting layer 170, for example, a solution in which a red fluorescent material, a green fluorescent material, a blue fluorescent material, or the like is dissolved in a solvent can be used. The light emitting material may be either a low molecular material or a high molecular material. As the solvent, aromatic solvents such as toluene, xylene, anisole, tetralin, 4-methylanisole and cyclohexylbenzene are preferably used. The solid content concentration can be adjusted to about 0.5% to 3% within the range of dissolution.

  Subsequently, the functional liquid is dried or baked in a high temperature environment to evaporate the solvent, thereby forming the light emitting layer 170. As a condition for drying, for example, it is left in an environment of 120 ° C. for 1 hour. The film thickness of the formed light emitting layer 170 is preferably adjusted to a film thickness that maximizes the light emission efficiency and the light emission lifetime for each material, and is, for example, 50 to 100 nm.

As the cathode 180, an alkaline earth metal such as calcium, strontium, and barium, an alkali metal fluoride such as sodium fluoride, potassium fluoride, and lithium fluoride, aluminum, and the like in this order, such as an evaporation method and a sputtering method, are used. It is formed by laminating by a known method. The film thickness of the alkaline earth metal or alkali metal fluoride is, for example, 5 nm, and the film thickness of aluminum is, for example, 300 nm. Further, as the sealing 190, a protective layer such as a silicon oxide film (SiO ₂ ) or a silicon nitride film (SiN) is formed as necessary, and an adhesive and a glass substrate, a metal plate, or a water vapor barrier property, oxygen It is formed by pasting together the entire cathode with a resin sheet having a barrier property.

  Specific examples of the present invention are shown below. In addition, this invention is not limited by this Example.

<Example of color filter>
A black negative photosensitive resin composition (“V259-BK739P” manufactured by Nippon Steel Chemical Co., Ltd.) is applied on a transparent glass substrate (Corning “1737”) and pre-baked on a hot plate at 100 ° C. for 2 minutes. Thereafter, exposure, development, and post-baking for 30 minutes in a hot air baking furnace at 230 ° C. were performed, and the partition pattern substrate shown in FIG. 4 was produced.

  Subsequently, the black negative photosensitive resin composition was applied to the partition pattern substrate, and a partition pattern substrate with columnar spacers shown in FIG. 5 was produced by the same photolithography method. Table 1 shows the measurement results of the height and bottom area of the columnar spacer.

  Further, a fluorine-based coating agent (“Novec EGC-1720” manufactured by Sumitomo 3M) was applied to one side of a 20 μm-thick polyethylene terephthalate film (“AT301” manufactured by Teijin DuPont Co., Ltd.). A transfer film having an ink component layer formed thereon was prepared. The transfer film is overlaid on the partition pattern substrate with the columnar spacers so that the ink repellent component layer and the surface of the partition pattern are in contact with each other, and the roll temperature is 140 ° C. with a thermal laminator (VA400-III manufactured by Taisei Laminator). The ink repellent component was transferred onto the upper surface of the partition pattern under the conditions of cylinder pressure 0.4 MPa, linear pressure 6 kgf / cm, and laminating speed 2 m / min. Here, the contact angle on the partition wall pattern with respect to the RGB ink described later was 45 °, which was 5 ° before the transfer process.

Subsequently, an ink jet equipped with a piezo type, nozzle resolution 180 dpi head using an ink composition prepared by blending the following composition ratios as RGB colored inks and dispersing for 3 hours while cooling with a bead mill disperser. Using the recording apparatus, RGB 3 color inks were filled in the openings surrounded by the partition pattern. Subsequently, pre-baking was performed by heating on a hot plate at 100 ° C. for 3 minutes, followed by ultraviolet irradiation treatment at 3000 mJ / cm ² with a high-pressure mercury lamp, followed by post-baking treatment at 240 ° C. for 30 minutes in a hot air firing furnace, The color filters of Examples 1 to 4 in Table 1 and Comparative Examples 1 to 5 were obtained.

[Red ink composition]
-Red pigment C.I. I. Pigment Red254 “Irga Four Red B-CF” (Ciba Specialty Chemical Co., Ltd.): 20 parts by weight Diethylene glycol monobutyl ether acetate: 100 parts by weight Acrylic resin (20 parts by weight of methacrylic acid, 15 parts by weight of hydroxyethyl methacrylate, 10 parts by weight of methyl methacrylate) Part, butyl methacrylate 55 parts by weight copolymer): 23 parts by weight methylated melamine resin “Nicalac MW-30” (manufactured by Sanwa Chemical Co., Ltd.): 5 parts by weight pentaerythritol tetraacrylate “Allonics M-450” ( Toagosei Co., Ltd.): 5 parts by weight Photopolymerization initiator “Irgacure 907” (manufactured by Ciba Specialty Chemicals): 1 part by weight

[Green ink composition]
Green pigment C.I. I. Pigment Green 36 “Lionol Green 6YK” (Toyo Ink Manufacturing Co., Ltd.): 20 parts by weight • Diethylene glycol monobutyl ether acetate: 100 parts by weight • Acrylic resin (methacrylic acid 20 parts by weight, hydroxyethyl methacrylate 15 parts by weight, methyl methacrylate 10 parts by weight Copolymer of 55 parts by weight of butyl methacrylate): 23 parts by weight. Methylated melamine resin “Nicalac MW-30” (manufactured by Sanwa Chemical Co., Ltd.): 5 parts by weight. Pentaerythritol tetraacrylate “Aronics M-450” (Toago) 5 parts by weight / photopolymerization initiator “Irgacure 907” (manufactured by Ciba Specialty Chemicals): 1 part by weight

[Blue ink composition]
-Blue pigment C.I. I. Pigment Blue 15: 6 “Heliogen Blue” (manufactured by BASF): 20 parts by weight • Diethylene glycol monobutyl ether acetate: 100 parts by weight • Acrylic resin (20 parts by weight of methacrylic acid, 15 parts by weight of hydroxyethyl methacrylate, 10 parts by weight of methyl methacrylate, Copolymer of 55 parts by weight of butyl methacrylate): 23 parts by weight. Methylated melamine resin “Nicalak MW-30” (manufactured by Sanwa Chemical Co., Ltd.): 5 parts by weight. Pentaerythritol tetraacrylate “Aronics M-450” (Toagosei Co., Ltd.) 5 parts by weight / photopolymerization initiator “Irgacure 907” (manufactured by Ciba Specialty Chemicals): 1 part by weight

  When the color filters of Examples 1 to 4 and Comparative Examples 1 to 5 in Table 1 were checked for the presence of white spots and color mixing using a defect inspection machine, the color filters of Comparative Examples 1 to 5 were white spots or While color mixing defects were detected, none of the color filters of the examples detected white spots / color mixing defects.

  Further, a transparent electrode made of ITO (Indium Tin Oxide) is formed on the surface of the color filters of Examples 1 to 4 and Comparative Examples 1 to 5 by sputtering, an alignment film made of polyimide is provided, and a liquid crystal is dropped. Then, a liquid crystal cell was formed by bonding to the opposing TFT substrate. Polarizers were attached to both surfaces of the obtained liquid crystal cell, and a backlight using a cold cathode tube was provided to obtain a liquid crystal display device. When the display state was evaluated with this liquid crystal display device, the liquid crystal display devices of the examples were all in a good display state.

<Examples of organic EL elements>
An active matrix substrate having a thin film transistor functioning as a switching element on a transparent glass substrate and a pixel electrode formed thereabove is used, a silicon nitride film is formed thereon by CVD, and etching is performed. A grid-like insulating layer pattern was formed so as to cover the end of each. Further, a stripe-shaped partition wall pattern as shown in FIG. 6 was formed on the insulating layer pattern by photolithography using a positive photosensitive resin composition (“ZWD 6216-6” manufactured by Nippon Zeon Co., Ltd.).

  Subsequently, the positive photosensitive resin composition was applied to the partition pattern substrate, and columnar spacers shown in FIG. 6 were formed by the same photolithography method. Table 2 shows the measurement results of the height and bottom area of the columnar spacer. Here, the height of the partition wall and the height of the columnar spacer are measured from the lowest part of the opening part surrounded by the partition pattern to the highest part of the partition wall and the highest part of the columnar spacer.

  Further, using the ink repellent transfer film used in the color filter examples, the ink repellent component layer was transferred onto the upper surface of the partition wall pattern in the same manner. The transfer conditions were a thermal laminator (VA400-III manufactured by Taisei Laminator Co., Ltd.) under the conditions of a roll temperature of 140 ° C., a cylinder pressure of 0.4 MPa, a linear pressure of 6 kgf / cm, and a lamination speed of 2 m / min. Here, the contact angle on the barrier rib pattern with respect to the hole injection layer ink described later was 20 ° before the transfer treatment, but became 80 °.

  Subsequently, as an ink for forming the hole injection layer, a mixture (PEDOT / PSS) in which polystyrene sulfonic acid (PSS) is added as a dopant to polyethylenedioxythiophene (PEDOT) has a solid content concentration of 0.5%. Using an aqueous solution dispersed in a 1: 1 solution of pure water and diethylene glycol, the ink is applied to the opening surrounded by the partition wall pattern and heated on a hot plate at 200 ° C. for 10 minutes. Thus, a hole injection layer having a thickness of 50 nm was formed.

  After that, using an ink in which polyvinylcarbazole derivative, which is an interlayer material, is dissolved in tetralin so as to have a concentration of 0.5%, coating is similarly performed by an ink jet method, and on a hot plate at 200 ° C. in a nitrogen atmosphere. And an interlayer having a thickness of 10 nm was formed.

  Next, using organic light emitting inks of RGB three colors in which polyphenylene vinylene derivative, which is an organic light emitting material, is dissolved in tetralin so as to have a concentration of 1%, coating is similarly performed by an ink jet method, and dried under a nitrogen atmosphere. An RGB light emitting layer having a thickness of 80 nm was formed.

  Thereafter, a calcium film having a thickness of 10 nm was formed as an electron injection layer by a vacuum deposition method, and then an aluminum film having a thickness of 150 nm was formed as a counter electrode.

  Thereafter, a glass plate was placed as a sealing material so as to cover the entire light emitting region, and sealing was performed by thermosetting the adhesive at about 90 ° C. for 1 hour. Thus, an organic EL device of this example was obtained.

  A voltage was applied between the electrodes of the organic EL elements of Examples 5 to 8 and Comparative Examples 6 to 10 in Table 2 thus obtained, and the light emission state was evaluated. In the organic EL elements of Comparative Examples 6 to 8, there is a portion where the ink repellent component is transferred in the opening, and the hole injection layer ink, the interlayer ink, and the light emitting layer ink are repelled to form a white portion. As a result, a non-light emitting pixel is generated or the light emitting state in the pixel is biased, resulting in a dark and uneven display state. In the organic EL elements of Comparative Examples 9 and 10, unevenness occurred in the transfer state of the ink repellent component onto the partition pattern, and the hole injection layer ink, interlayer ink, and light emitting layer ink overflowed from the partition pattern. As a result, the display color deteriorated due to changes in emission color or uneven emission. On the other hand, all the organic EL elements of Examples 5 to 8 obtained uniform light emission and were in a good display state.

  According to the present invention, since a uniform ink-repellent partition wall pattern can be formed by a simple transfer method, it is possible to apply a coating method such as an ink-jet method with high material use efficiency and easy adaptation to a large substrate. A high-quality color filter or organic EL display device free from display defects can be manufactured at low cost. Thus, it can be used for large display devices such as large-screen liquid crystal televisions and organic EL televisions.

DESCRIPTION OF SYMBOLS 1 ... Color filter 10 ... Transparent substrate 20 ... Partition pattern 21 ... Upper surface 22 of partition pattern ... Ink-repellent component layer 23 ... Side wall pattern 30 ... Opening 40 surrounded by partition pattern ... Columnar spacer 50R ... Red colored layer 50G ... Green colored layer 50B ... Blue colored layer 2 ... Coating organic EL
DESCRIPTION OF SYMBOLS 100 ... Transparent substrate 110 ... Anode 120 ... Insulating layer 130 ... Partition pattern 132 ... Ink-repellent component layer 140 ... Opening 150 surrounded by partition pattern ... Columnar spacer 160 ... Hole injection / transport layer 170 ... Light emitting layer 180 ... Cathode 190 ... Sealing

Claims (5)

An optical element having a desired functional layer pattern formed on a substrate that transmits light,
A partition wall pattern for dividing the functional layer pattern;
An ink repellent layer formed on the upper surface of the partition pattern;
Columnar spacers formed in the opening region divided by the partition pattern,
A functional layer formed in the opening region by applying a functional layer forming ink to the opening region ;
When the height from the lowest part of the part to which the functional layer forming ink is applied in the opening region to the highest part of the partition wall pattern is 1, the distance from the lowest part to the highest part of the spacer The height ranges from 0.3 to 1.2;
The ratio of the total area of the bottom surface of the spacer to the total area of the opening region is in the range of 0.0001 to 0.01 .   When the height from the lowest part of the part to which the functional layer forming ink is applied in the opening region to the highest part of the partition wall pattern is 1, the distance from the lowest part to the highest part of the spacer The optical element according to claim 1, wherein the height is in a range of 0.5 to 1.0.   The optical element according to claim 1, wherein the spacer is formed of a material having an affinity with a contact angle with respect to the functional layer forming ink of 30 ° or less.   The optical element according to claim 1, wherein the ink repellent layer is a compound containing fluorine. A method of manufacturing an optical element in which a desired functional layer pattern is formed on a substrate that transmits light,
Forming a barrier rib pattern for dividing the functional layer pattern;
Forming a columnar spacer in an opening region divided by the partition pattern;
Forming an ink repellent layer on the upper surface of the partition pattern;
Forming a functional layer in the opening region by applying a functional layer forming ink to the opening region;
When the height from the lowest part of the part to which the functional layer forming ink is applied in the opening region to the highest part of the partition wall pattern is 1, the distance from the lowest part to the highest part of the spacer The height ranges from 0.3 to 1.2;
The ratio of the total area of the bottom surface of the spacer to the total area of the opening region is in the range of 0.0001 to 0.01 .

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