WO2007061115A1 - 隔壁、カラーフィルタ、有機elの製造方法 - Google Patents
隔壁、カラーフィルタ、有機elの製造方法 Download PDFInfo
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- WO2007061115A1 WO2007061115A1 PCT/JP2006/323729 JP2006323729W WO2007061115A1 WO 2007061115 A1 WO2007061115 A1 WO 2007061115A1 JP 2006323729 W JP2006323729 W JP 2006323729W WO 2007061115 A1 WO2007061115 A1 WO 2007061115A1
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- partition wall
- exposure
- producing
- ethylenic double
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2022—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure
- G03F7/2024—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure of the already developed image
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
Definitions
- the present invention relates to a method for manufacturing partition walls such as partition walls of color filters, ITO electrode partitions of liquid crystal display elements, partition walls of organic EL display elements, partition walls of circuit wiring boards, etc., produced by an ink jet recording technique.
- the present invention also relates to a color filter manufacturing method and an organic EL manufacturing method.
- a resist composition has been used to produce a mask for manufacturing a circuit such as a semiconductor integrated circuit (IC), a thin film transistor (TFT) circuit for a liquid crystal display (LCD), and the like.
- the composition is also attracting attention as a material for forming a permanent film such as a partition between color filter pixels, an ITO electrode partition of a liquid crystal display element, a partition between pixels of an organic EL display element, and a partition of a circuit wiring board.
- an ink jet method for the manufacture of liquid crystal display elements, an ink jet method has been proposed in which an ITO solution is spray-coated when forming an ITO (tin-doped indium oxide) electrode.
- a resist composition is used to form an ITO electrode pattern. It is carried out by the photolithography used, and a cured film of the resist composition is used as the partition wall.
- an inkjet method has been proposed in which a hole transport material and a light emitting material solution are spray-coated to form a hole transport layer, a light emitting layer, and the like in a minute pixel.
- the pixel pattern is formed by photolithography using a resist composition, and a cured film of the resist composition is used as a partition between pixels.
- circuit wiring board For the production of a circuit wiring board, an inkjet method has been proposed in which a metal solution is spray-coated when forming circuit wiring.
- the formation of the circuit wiring pattern is also performed by photolithography with a resist composition force, and a cured film of the resist composition is used as a partition wall.
- the partition wall is required to have a property of repelling water or an organic solvent, which is an inkjet coating liquid, so-called water and oil repellency.
- Patent Document 1 discloses that a barrier rib is formed by applying a photosensitive composition onto a substrate and performing drying, exposure, development, and heat treatment.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2005-60515
- an object of the present invention is to provide a method for manufacturing a partition wall that is excellent in the uniformity of the thickness of the ink layer even when the exposure amount in the exposure step is low.
- the present invention includes a side chain having a fluoroalkyl group (provided that the fluoroalkyl group may have an etheric oxygen atom between carbon atoms) and an ethylenic double bond.
- the manufacturing method of the partition characterized by these is provided.
- the fluorine-containing polymer (A) contained in the negative photosensitive composition of the present invention has a side chain having a fluoroalkyl group, and thus exhibits surface migration, and in the vicinity of the coating film surface in the drying step. Transition. Therefore, the upper surface of the partition wall formed with the composition strength exhibits water and oil repellency (liquid repellency with respect to ink).
- the fluoropolymer (A) since the fluoropolymer (A) has a side chain having an ethylenic double bond, it can be fixed on the surface of the coating film by a curing reaction in the exposure step. However, the exposure amount in the exposure process is low! In some cases, some molecules of the fluoropolymer (A) do not undergo a curing reaction, and may remain in the partition wall without being removed from the system in the development process. . In the conventional method, it is considered that the unreacted residual molecules migrated from the partition walls to the dots and contaminated the dots in the heat treatment step performed after the development step.
- the post-exposure step is provided after the development step, the curing reaction of the fluoropolymer (A) is sufficiently performed, and unreacted residual molecules may migrate to dots. Hateful. That is, the partition wall is excellent in water and oil repellency, and the dot is excellent in hydrophilic lipophilicity. Therefore, since the dot has high wettability of the ink, the ink spreads uniformly in the dot and the thickness of the ink layer formed immediately becomes high.
- the partition walls are sufficiently cured by the post-exposure process, and are resistant to the solvent in the ink used in the ink jet method. Therefore, curing by the heat treatment process is not always necessary.
- a heat treatment step may be employed after the post-exposure step for the purpose of enhancing the heat resistance of the partition walls or for the purpose of removing the volatile components of the partition wall force.
- the fluoropolymer (A) preferably has a side chain having an acidic group.
- Some molecules of the fluoropolymer (A) that did not undergo a curing reaction in the exposure process are washed away in the partition surface force in the development process because they have side chains having acidic groups, and are fixed in the partition walls. It is difficult for the remaining molecules to be left behind. Therefore, it is possible to further reduce the number of molecules that can migrate to dots in the previous stage of the post-exposure process, which is more effective for improving the uniformity of the ink layer thickness.
- the present invention is characterized in that after the partition wall is formed on the base material by the above-described manufacturing method, the ink is injected into the region divided by the partition wall by an ink jet method to form a pixel.
- a method for manufacturing a color filter is provided.
- the present invention provides an organic EL display characterized in that, after a partition wall is formed on a substrate by the above-described manufacturing method, a pixel is formed by injecting ink into an area partitioned by the partition wall by an ink jet method.
- An element manufacturing method is provided.
- the partition wall manufacturing method of the present invention is applied to electronic device such as partition walls of color filters produced by an ink jet coating method, partition walls of ITO electrodes of liquid crystal display elements, partition walls of organic EL display elements, and partition walls of circuit wiring boards. It is suitably used for manufacturing a partition wall.
- a negative photosensitive composition coating film is formed on the surface of a substrate by a known coating film forming method.
- the method for forming a coating film include a spray method, a roll coating method, a spin coating method, and a bar coating method.
- the material of the substrate is not particularly limited.
- various glass plates such as polyethylene terephthalate; polyolefins such as polypropylene and polyethylene; poly (meth) acrylic resin, polycarbonate, polymethylmeta
- thermoplastic plastic sheets such as tallylate and polysulfone
- thermosetting plastic sheets such as epoxy resin and unsaturated polyester.
- glass plates and heat resistant plastics are preferably used from the viewpoint of heat resistance.
- the back exposure (base material side) force where the partition walls are not formed may be performed, it is preferable to use a transparent substrate.
- black matrix such as metal black matrix or black resin matrix is formed.
- a formed base material can also be used. In that case, it is preferable to form partition walls on the black matrix by the production method of the present invention.
- the coating film is dried (hereinafter also referred to as a pre-beta).
- the solvent is volatilized and a non-flowable coating film is obtained.
- the pre-beta conditions are different forces depending on the type of each component, the mixing ratio, etc., preferably 50 to 120 ° C and a wide range of about 10 to 2000 seconds.
- the exposure that is, the heated coating film is irradiated with light through a mask having a predetermined pattern.
- irradiation light visible light; ultraviolet light; far ultraviolet light; KrF excimer laser, ArF excimer laser, F excimer laser, Kr excimer laser, KrAr excimer laser
- Excimer laser such as Ar excimer laser; X-ray; electron beam.
- I-line (365 nm), h-line (405 nm), and g-line (436 nm) are particularly preferable. Electromagnetic waves having a distribution in the range of 300 to 500 nm are more preferable.
- a known ultra-high pressure mercury lamp, deep UV lamp, or the like can be used as the irradiation device.
- the exposure dose is preferably in the range of 5 to: LOOOmjZcm 2 , more preferably 50 to 400 mjZcm 2 . When the exposure amount is 5 mjZcm 2 or less, the partition walls are not sufficiently cured, and subsequent development may cause dissolution or peeling. When the exposure dose exceeds lOOOmiZcm 2 , high resolution tends to be lost.
- developer After the exposure step, development is performed with a developer, and unexposed portions are removed.
- the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine.
- Secondary amines such as jetylamine and di-n-propylamine; tertiary amines such as triethylamine, methyljetylamine and N-methylpyrrolidone; dimethylethanolamine and triethanolamine Alcohol amines; Tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, quaternary ammonium salts such as choline; Alkaline water that is an alkaline power of cyclic amines such as pyrrole and piperidine A liquid can be used.
- an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like to the alkaline aqueous solution is used as a developer.
- the development time is preferably 30 to 180 seconds.
- the developing method may be either a liquid piling method or a datebing method. After development, water on the substrate can be removed by washing with running water and air-drying with compressed air or compressed nitrogen.
- post exposure is performed.
- the post-exposure may be performed from either the front surface where the partition walls are formed or the back surface (base material side) where the partition walls are not formed. Moreover, you may expose from both front and back.
- a preferable exposure amount is 50 mjZcm 2 or more, more preferably 200 mjZcm 2 or more, more preferably 10OOmjZcm 2 or more, and further preferably 2000 mjZcm 2 or more.
- a known ultra-high pressure mercury lamp or high-pressure mercury lamp can be used as a light source for which ultraviolet rays are preferred. These light sources are preferably used because they emit light of 600 nm or less that contributes to the hardening of the barrier ribs, and emit less light of 200 nm or less that causes oxidative decomposition of the barrier ribs. Furthermore, it is preferable that the quartz tube glass used for the mercury lamp has an optical filter function for cutting light of 200 ⁇ m or less.
- a low-pressure mercury lamp can also be used as the light source.
- a low-pressure mercury lamp is liable to be subjected to a large amount of exposure because it tends to cause acid / sodium decomposition of the partition walls due to the generation of ozone with a high emission intensity at a wavelength of 200 nm or less.
- the exposure dose is more preferably Sig 300MjZcm 2 or less preferred is 500MiZcm 2 or less.
- the heat treatment may be performed by a heating device such as a hot plate or an oven, preferably at 150 to 250 ° C. for 5 to 90 minutes.
- a heating device such as a hot plate or an oven, preferably at 150 to 250 ° C. for 5 to 90 minutes.
- a pixel is formed in the dot between partitions using the inkjet method.
- the ink jet apparatus used for forming such pixels is not particularly limited, but a method in which charged ink is continuously ejected and controlled by a magnetic field, and ink is ejected intermittently using a piezoelectric element.
- An ink jet apparatus using various methods such as a method of heating and a method of heating ink and intermittently using the foaming thereof
- the shape of the pixel formed by the pixel formation process of the present invention may be any known arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type.
- the ink used for forming the pixel mainly includes a coloring component, a binder resin component, and a solvent component.
- the water-based ink is composed of water and, if necessary, a water-soluble organic solvent, contains a water-soluble or water-dispersible resin as a binder resin component, and various auxiliary agents as necessary. .
- the oil-based ink has an organic solvent as a solvent, and contains a resin soluble in an organic solvent as a nodder resin component, and various auxiliary agents as necessary.
- coloring component it is preferable to use pigments and dyes excellent in heat resistance and light resistance.
- Noinder resin component examples include, but are not limited to, an acrylic resin, a melamine resin, and a urethane resin, which are preferable for a transparent resin having excellent heat resistance.
- a protective film layer is formed as necessary.
- the protective film layer is preferably formed for the purpose of increasing the surface flatness and for blocking the eluate from the ink in the partition walls and the pixel portion from reaching the liquid crystal layer.
- a transparent electrode such as indium tin oxide (ITO) is formed on a transparent substrate such as glass by sputtering or the like, and if necessary, a desired pattern is formed.
- the transparent electrode is etched.
- the partition wall of the present invention is formed by the above method.
- a hole transport material and a light emitting material solution are sequentially applied to the dots between the barrier ribs using an inkjet method and dried to form a hole transport layer and a light emitting layer, and then an electrode such as aluminum is formed.
- Pixels of organic EL display elements can be obtained by forming them by vapor deposition.
- (meth) atalylate means attalylate and / or metatalylate.
- (meth) acrylic acid means acrylic acid and Z or methacrylic acid
- (meth) acrylamide means acrylamide and Z or methacrylamide
- (meth) acryloyl group means ataryloyl group and Z. Or means a methacryloyl group.
- the fluoropolymer (A) is composed of a side chain having a fluoroalkyl group (wherein the alkyl group may have an etheric oxygen atom between carbon atoms) and a side chain having an ethylenic double bond. And have.
- the side chain having a fluoroalkyl group may be formed directly by a polymerization reaction or may be formed by chemical conversion after the polymerization reaction. Further, the side chain having an ethylenic double bond can be formed by chemical conversion after the polymerization reaction.
- the fluoroalkyl group is an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may be linear or branched.
- the carbon number of the fluoroalkyl group is preferably 20 or less. Specific examples of the fluoroalkyl group include the following structures.
- the fluoroalkyl group is preferably a perfluoroalkyl group.
- the water / oil repellency is improved.
- it is preferably a perfluoroalkyl group having 4 to 6 carbon atoms. In this case, sufficient water and oil repellency can be imparted, and the compatibility between the fluoropolymer (A) and other components constituting the negative photosensitive composition is good. It is possible to form partition walls with a good appearance without the fluoropolymers (A) aggregating with each other.
- Examples of the ethylenic double bond include addition-polymerizable unsaturated groups such as a (meth) ataryloyl group, a aryl group, a bur group, and a vinyl ether group. Some or all of the hydrogen atoms in these groups may be substituted with hydrocarbon groups. As the hydrocarbon group, a methyl group is preferable.
- the fluorine-containing polymer (A) of the present invention is obtained by copolymerizing two or more monomers including a monomer (al) having a fluoroalkyl group and a monomer (a2) having a reactive group, It can be produced by reacting the obtained copolymer with a compound (zl) having an ethylenic double bond and a functional group capable of binding to the reactive group.
- the monomer (a1) having a fluoroalkyl group a monomer represented by the formula 1 is preferred.
- R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group
- X represents a single bond or a divalent organic group containing no fluorine atom having 1 to 6 carbon atoms
- R f represents a fluoroalkyl group.
- X is preferably an alkylene group having 2 to 4 carbon atoms from the viewpoint of availability.
- R f is preferably a perfluoroalkyl group having 4 to 6 carbon atoms because of excellent compatibility between the fluoropolymer (A) and other components constituting the negative photosensitive composition.
- Examples of the monomer represented by the above formula 1 include the following.
- R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group
- R 2 represents an alkylene group having 1 to 6 carbon atoms
- R 3 represents a hydrogen atom or a methyl group
- R f represents a fluoroalkyl group.
- R 2 examples include CH —, —CH CH one, CH (CH) —,
- Specific examples of the monomer represented by the above formula 1 include perfluorinated hexylethyl (meth) acrylate and perfluorobutyl cetyl (meth) acrylate.
- the above monomers may be used alone or in combination of two or more.
- Examples of the monomer (a2) group having a reactive group include a monomer having a hydroxyl group, an acid anhydride having an ethylenic double bond, a monomer having a carboxyl group, and a monomer having an epoxy group. Can be mentioned.
- the monomer (a2) preferably does not substantially contain a fluoroalkyl group.
- the reactive group of the monomer (a2) having a reactive group reacts with the compound (zl) having a functional group capable of binding to the reactive group described later and an ethylenic double bond after polymerization. As a result, the fluoropolymer (A) having a side chain having an ethylenic double bond is formed.
- the monomer having a hydroxyl group examples include 2 hydroxyethyl (meth) acrylate, 2 hydroxypropyl (meth) acrylate, 3 hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) Atalylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3 2 Hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2-hydroxyethyl benzylate , 4-hydroxybutyl vinylenoether, cyclohexanediol monovinino ether, 2-hydroxyethyl ether, N hydroxymethyl (meth) acrylamide, N, N bis (hydroxymethyl) (meta ) Acrylamide and the like.
- the monomer having a hydroxyl group may be a monomer having a polyoxyalkylene chain whose terminal is a hydroxyl group.
- CH CHOCH C H CH O (C H O
- H CHCOOC H 0 (C H O) H
- CH C (CH) COOC H 0 (C H O) H
- acid anhydride having an ethylenic double bond examples include maleic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, 3-methylphthalic anhydride, methyl-5-norbornene-2,3 dicarboxylic acid Examples include acid, 3,4,5,6-tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, and 2-butene-1-ylsuccinic anhydride.
- Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, bulacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, kaycin acid, and salts thereof.
- the monomer having an epoxy group examples include glycidyl (meth) acrylate and 3, 4 epoxy cyclohexyl methyl acrylate.
- the fluoropolymer (A) further has a side chain having an acidic group!
- Some molecules of the fluoropolymer (A) that did not undergo a curing reaction in the exposure process are washed away by the partition surface force in the development process because they have side chains having acidic groups, and are contained in the partition walls. It is difficult to leave a fixed molecule that is not fixed. Molecules that migrate to dots in the previous stage of the post-exposure process can be reduced, and the hydrophilic / lipophilicity of the inter-partition dots becomes higher.
- the acidic group is preferably one or more acidic groups that can be selected from the group power of carboxyl group, phenolic hydroxyl group, and sulfonic acid group.
- the side chain having an acidic group may be formed by a polymerization reaction of the monomer (a3) having an acidic group, or may be formed by a chemical conversion after the polymerization reaction.
- Examples of the monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene.
- one or more hydrogen atoms of these benzene rings are an alkyl group such as a methyl group, an ethyl group or an n-butyl group; an alkoxy group such as a methoxy group, an ethoxy group or an n-butoxy group; a halogen atom; A haloalkyl group in which at least one hydrogen atom of the group is substituted with a halogen atom; a nitro group; a cyano group; an amide group or the like.
- Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-hydroxy-3- (meth) aryloxypropane sulfonic acid, and (meth).
- vinyl sulfonic acid styrene sulfonic acid
- (meth) allyl sulfonic acid 2-hydroxy-3- (meth) aryloxypropane sulfonic acid
- 2-meth) acrylamide-2-methylpropane sulfonic acid etc.
- monomers used for polymerization include a monomer having a fluoroalkyl group (al), a monomer having a reactive group (a2), and a monomer having an acidic group (a3).
- Other monomers other than (a4) may be included.
- Other monomers (a4) include hydrocarbon-based olefins, butyl ethers, iso-propyl ethers, allylic ethers, butyl esters, allylic esters, (meth) acrylic acid esters, ( Examples include meth) acrylamides, aromatic bur compounds, chloroolefins, and conjugated genes.
- examples of the functional group that may contain a functional group include a carbonyl group and an alkoxy group.
- (meth) acrylic acid esters and (meth) acrylamides are preferred because the partition walls formed from the composition are excellent in heat resistance.
- R 4 and R 5 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group
- R 6 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms
- n is an integer of 1 to 200
- the fluorine-containing polymer (A) can be synthesized, for example, by the following method. First, the monomer is dissolved in a solvent and heated, and a polymerization initiator is added for copolymerization to obtain a copolymer. In the copolymerization reaction, a chain transfer agent is preferably present as necessary. Monomer, polymerization initiator, solvent and chain transfer agent may be added continuously.
- Examples of the solvent include alcohols such as ethanol, 1 propanol, 2 propanol, 1-butanol and ethylene glycol; ketones such as acetone, methyl isobutyl ketone and cyclohexanone; 2-methoxyethanol, 2 -Cellsolves such as ethoxyethanol and 2-butoxyethanol; carbitols such as 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol and 2- (2-butoxyethoxy) ethanol; methyl acetate, E chill acetate, n-butyl acetate, Echiruratateto, n - butyl Honoré rata Tate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, glycerol tri-acetate, etc. Esters diethylene glycol dimethyl ether, and diethylene glycol methyl E chill ether.
- ketones such as acetone,
- Examples of the polymerization initiator include known organic peroxides, inorganic peroxides, and azo compounds. Organic peroxides and inorganic peroxides can be used as redox catalysts in combination with reducing agents. These polymerization initiators may be used alone or in combination of two or more.
- organic peroxide examples include benzoyl peroxide, lauroyl peroxide, isoptyryl peroxide, t-butyl hydroperoxide, t-butyl-a amyl peroxide.
- Examples of inorganic peroxides include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, and percarbonate.
- Examples of the azo compound include 2,2'-azobisisobutyryl-tolyl, 1, ⁇ -azobis (cyclohexane-1-carbotolyl), 2,2'-azobis (2,4-dimethylvale- Tolyl), 2,2'-azobis (4-methoxy-1,2,4-dimethylvale-tolyl), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis (2-amidinopropane) dihydrochloride, etc. Can be mentioned.
- chain transfer agents examples include n-butyl mercaptan, n-dodecyl mercaptan, tert-butyl mercaptan, thioglycolate ethyl, 2-glycolate thioglycolate, 2-mercaptoethanol and other mercaptans; And alkyl halides such as carbon tetrachloride and carbon tetrabromide.
- the fluoropolymer (A) is produced by reacting the copolymer obtained as described above with a compound (zl) having a functional group capable of binding to a reactive group and an ethylenic double bond (zl). it can.
- Examples of the compound (zl) having a functional group capable of binding to the reactive group and an ethylenic double bond to the monomer (a2) having a reactive group include the following combinations.
- Specific examples of the acid anhydride having an ethylenic double bond include the above-described examples.
- Specific examples of the compound having an isocyanate group and an ethylenic double bond include 2- (meth) atalylooxychetyl isocyanate, 1, 1- (bis (meth) atalylooxymethyl) Examples include tilisocyanate.
- Specific examples of the compound having an acyl chloride group and an ethylenic double bond include (meth) acryloyl chloride.
- Specific examples of the compound having a hydroxyl group and an ethylenic double bond include the above-described monomers having a hydroxyl group.
- Specific examples of the compound having an epoxy group and an ethylenic double bond include the above-described monomers having an epoxy group.
- Specific examples of the compound having a carboxyl group and an ethylenic double bond include the above-described examples of the monomer having a carboxyl group.
- the solvent used for the reaction is the solvent exemplified in the synthesis of the copolymer. Can be used.
- a polymerization inhibitor a publicly known polymerization inhibitor can be used, and specifically, 2, 6-dibutyl-p-cresol can be mentioned.
- a catalyst or a neutralizing agent may be added.
- a tin compound or the like can be used.
- the tin compound include dibutyltin dilaurate, dibutyltin di (maleic acid monoester), dioctyltin dilaurate, dioctyltin di (monoester maleate), and dibutyltin diacetate.
- a basic catalyst When a copolymer having a hydroxyl group is reacted with a compound having an acyl chloride group and an ethylenic double bond, a basic catalyst can be used.
- the basic catalyst include triethylamine, pyridine, dimethylamine, tetramethylurea and the like.
- the fluorine atom content of the fluoropolymer (A) of the present invention is preferably 5 to 35 mass%.
- the fluorine atom content is too high And there exists a possibility that the adhesiveness of a partition and a base material may become low.
- the lower limit of the fluorine atom content in the fluoropolymer (A) is more preferably 10% by mass, and the upper limit is more preferably 30% by mass.
- the fluoropolymer (A) preferably has 2 or more and 100 or less ethylenic double bonds in the molecule. More preferably, it is 6 or more and 50 or less. Within this range, the fixing property of the fluorine-containing polymer (A) to the partition walls and the developability will be good.
- the acid value of the fluoropolymer (A) is preferably 100 (mgKOH / g) or less, more preferably 10 to 50 (mgKOH / g). Within this range, residual molecules that have not been fixed in the exposure process are easily washed away in the development process.
- the acid value is the mass (unit: mg) of potassium hydroxide required to neutralize greaves lg. In this specification, the unit is described as mg KOHZg.
- the weight average molecular weight of the fluoropolymer (A) is preferably from 1000 to less than 30000, more preferably from 2000 to less than 20000. Within this range, alkali solubility and developability are good.
- the proportion of the fluoropolymer (A) in the total solid content of the negative photosensitive composition of the present invention is preferably 0.1 to 30% by mass with respect to the total solid content.
- the fluoropolymer (A) is excellent in the effect of lowering the surface tension of the partition wall to be formed, and imparts high water and oil repellency to the partition wall.
- the ratio is too high, the adhesion between the partition walls and the substrate may be lowered.
- the lower limit of the proportion of the fluoropolymer (A) in the total solid content of the composition is preferably 0.15% by mass, and the upper limit is preferably 20% by mass.
- the negative photosensitive composition in the present invention preferably contains an alkali-soluble photosensitive resin (B) having an acidic group and an ethylenic double bond in one molecule. It is preferable that the photosensitive resin (B) does not substantially contain a fluoroalkyl group! /.
- the photosensitive resin (B) for example, two or more types of monomers having an ethylenic double bond having a side chain having an acidic group and a side chain having an ethylenic double bond may be used.
- B-1 Novolak rosin derivative with acidic group and ethylenic double bond in one molecule
- B-2 Novolak rosin derivative with acidic group and ethylenic double bond in one molecule
- B 3 Epoxy rosin with acidic group and ethylenic double bond in one molecule Derivative
- the copolymer (B-1) should be produced by the same method except that the fluoropolymer (A) does not use the monomer (al) having a fluoroalkyl group. Can do.
- the novolak resin in the novolak resin derivative (B-2) is obtained by polycondensation of phenols with aldehydes.
- phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3 xylenol, 2,5 xylenol, 3,5 xylenol, 2,3,5 trimethylphenol, catechol, resorcinol, Hydroquinone, methylhydroquinone, pyrogallol, phloroglicinol and the like can be mentioned.
- the aldehyde formaldehyde is preferable.
- Examples thereof include phenol'formaldehyde resin, talesol'formaldehyde resin, phenol.cresol.formaldehyde co-condensate resin, and the like.
- phenol'formaldehyde resin talesol'formaldehyde resin
- phenol.cresol.formaldehyde co-condensate resin and the like.
- the wettability to the ink on the substrate surface from which the resin has been removed by development is preferable.
- Examples of a method for introducing an ethylenic double bond into the above-mentioned rosin include a method in which a part of a phenolic hydroxyl group is reacted with a compound having an epoxy group and an ethylenic double bond.
- the epoxy group after reacting a part or all of the phenolic hydroxyl group with epichlorohydrin and introducing an epoxy group into the novolac resin, the epoxy group has a carboxyl group and an ethylenic double bond.
- the method of making a compound react is mentioned.
- the hydroxyl group produced by this reaction can be reacted with an acid anhydride to introduce a carboxyl group into the molecule.
- the epoxy rosin derivative (B-3) is preferably derived from a bisphenol epoxy compound represented by the formula (3).
- R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and Y is CO—, —SO 1, C (
- n represents an integer of 0 to L0.
- examples of the bisphenol type epoxy compound that gives the epoxy resin derivative (B-3) include the following.
- the average value of n in the formula (1) is 0 to 10, preferably 0 to 2. If it is within the range, there will be no problem with the performance of the present resin composition.
- a method for introducing an ethylenic double bond group into the resin include a reaction of a carboxyl group and a carboxyl group of a compound having an ethylenic double bond with an epoxy group of a bisphenol epoxy compound. The method of letting it be mentioned. Furthermore, a hydroxyl group generated by this reaction can be reacted with an acid anhydride to introduce a carboxyl group into the molecule.
- the acid value of the photosensitive resin (B) is preferably 10 to 300 mgKOHZg, more preferably 30 to 150 mgKOH / g. Within this range, alkali solubility and developability are good.
- the photosensitive resin (B) preferably has 3 or more ethylenic double bonds in one molecule, and more preferably has 6 or more ethylenic double bonds in one molecule. As a result, there is a difference in alkali solubility between the exposed part and the unexposed part, and it becomes possible to form a fine pattern with a smaller exposure amount immediately.
- the number average molecular weight of the photosensitive resin (B) is preferably 1000 or more and less than 100,000, more preferably 400 or more and less than 60,000. Within this range, alkali solubility and developability are good.
- the photosensitive resin (B) preferably further has a carboxyl group and Z or a hydroxyl group as a group capable of undergoing a crosslinking reaction.
- the negative photosensitive composition of the present invention further contains a thermosetting agent (G) which is a compound having two or more groups capable of reacting with a carboxyl group and Z or a hydroxyl group, the photosensitive composition is exposed to heat treatment after development. This is because a crosslinking reaction with the conductive resin (B) increases the cross-linking density of the coating film and improves the heat resistance.
- a carboxyl group and a phenolic hydroxyl group which are acidic groups are groups which can undergo a crosslinking reaction.
- the photosensitive resin (B) has a sulfonic acid group or a phosphoric acid group as an acidic group, it has at least one of a carboxyl group, a phenolic hydroxyl group, and an alcoholic hydroxyl group as a group capable of crosslinking reaction. It is preferable.
- the proportion of the photosensitive resin (B) in the total solid content of the negative photosensitive composition is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, based on the total solid content. Within this range, the negative photosensitive composition has good alkali developability.
- the negative photosensitive composition in the present invention preferably contains a photopolymerization initiator (C).
- the photopolymerization initiator (C) is preferably composed of a compound that generates radicals by light.
- the photopolymerization initiator (c) include ⁇ -diketones such as benzyl, diacetyl, methylphenol glyoxylate, and 9, 10 phenanthrenequinone; acyloines such as benzoin; benzoin methyl ether, benzoin ether Acylo ethers such as benzoin isopropyl ether; thixanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4 dimethylthioxanthone, isopropylthioxanthone, 2,4 jetylthioxanthone, 2,4 diclonal thixanthone, 2, 4 Thioxanetones such as diisopropylthioxanthone and th,
- photopolymerization initiators may be used alone, or two or more thereof may be used in combination.
- the aminobenzoic acids, the benzophenones, etc. may be used together with other photo radical generators to exhibit a sensitizing effect.
- triethanolamine, methyljetanolamine, triisopropanolamine, n-butylamine, N Aliphatic amines such as -methyljetanolamine and jetylaminoethylmetatalylate may also be used together with a photoradical generator to develop a sensitizing effect.
- the proportion of the photopolymerization initiator (C) in the total solid content of the negative photosensitive composition is preferably 0.1 to 50 mass% with respect to the total solid content, and 0.5 to 30 mass% is preferable. More preferred. Within such a range, the negative photosensitive composition has good alkali developability.
- the negative photosensitive composition in the present invention preferably contains Sarako and a radical crosslinking agent (D).
- the radical crosslinking agent (D) is preferably a compound that is insoluble in alkali and has two or more ethylenic double bond groups. However, it does not substantially have a fluoroalkyl group.
- Specific examples include diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 9- nonanediol Di (meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, dipenta erythritol hex ( And (meth) acrylate. These may be used alone or in combination of two or more.
- the proportion of the radical crosslinking agent (D) in the total solid content of the negative photosensitive composition is preferably 10 to 60 mass%, more preferably 15 to 50 mass%, based on the total solid content. Within this range, the alkali developability of the negative photosensitive composition will be good.
- the negative photosensitive composition in the present invention preferably contains a thermosetting agent (E) as necessary. Thereby, the heat resistance and water permeability of the photosensitive resin may be improved.
- thermosetting agent (E) examples include amino resin, a compound having two or more epoxy groups, a compound having two or more hydrazino groups, a polycarpoimide compound, and two or more oxazolines.
- thermosetting agents (E) in order to improve the chemical resistance of the formed partition wall, in particular, it has amino resin, a compound having two or more epoxy groups, or two or more oxazoline groups. Are preferred.
- the proportion of the thermosetting agent (E) in the total solid content of the negative photosensitive composition is preferably 1 to 50 mass%, more preferably 5 to 30 mass%, based on the total solid content. Within such a range, the negative photosensitive composition has good alkali developability.
- the negative photosensitive composition in the present invention preferably contains a silane coupling agent (F) as necessary. Thereby, adhesiveness with a base material can be improved.
- F silane coupling agent
- silane coupling agent examples include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloro Examples include oral propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, heptadecafluorooctyltrimethoxysilane, polyoxyalkylene chain-containing triethoxysilane, and imidazolesilane. These may be used alone or in combination of two or more.
- Diluent (G) can be used in the negative photosensitive composition of the present invention.
- the diluent (G) include the polymerizable monomers exemplified in the explanation of the fluoropolymer (A).
- the solvents exemplified in the description of the solvent used when synthesizing the fluoropolymer (A) can be mentioned.
- Other examples include chain hydrocarbons such as n-butane and n-hexane, cyclic saturated hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene, xylene and benzyl alcohol. These may be used alone or in combination of two or more.
- a colorant (H) can be used as necessary.
- the partition walls can be colored.
- the black photosensitive coloring composition for forming the black matrix (BM) includes, for example, bonbon black, aniline black, anthraquinone black pigment, perylene black pigment, specifically CI pigment black 1 6, 7, 12, 20, 31 etc. can be used.
- a mixture of an organic pigment such as a red pigment, a blue pigment, and a green pigment and an inorganic pigment can also be used.
- Carbon black is the preferred black pigment because of its price and light shielding properties.
- the black may be surface-treated with rosin or the like.
- a blue pigment and a purple pigment can be used together with a black photosensitive coloring composition.
- carbon black having a specific surface area by the BET method of 50 to 200 m 2 Zg is preferable.
- carbon black with a specific surface area of less than 50 m 2 Zg is used, the black matrix shape is deteriorated.
- carbon black with a specific surface area of more than 200 m 2 Zg is used, the dispersion aid is excessively adsorbed on the carbon black. This is because it is necessary to add a large amount of a dispersion aid in order to express various physical properties.
- carbon black having an oil absorption of 120 ccZlOOg or less is more preferable from the viewpoint of sensitivity.
- the average primary particle diameter of carbon black observed with a transmission electron microscope is preferably 20 to 50 nm. If the average primary particle size is too small, it may be difficult to disperse at a high concentration, and it is difficult to obtain a photosensitive black composition having good stability over time, and if the average primary particle size is too large. This is because the black matrix shape may be deteriorated.
- CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 80, etc. can be used if f row! it can.
- the green pigment for example, CI Pigment Green 7, 36, etc. can be used.
- a curing accelerator a thickener, a plasticizer, an antifoaming agent, a leveling agent, a repellency inhibitor, an ultraviolet absorber and the like may be used as necessary. it can.
- the weight average molecular weight is a value measured by gel permeation chromatography using polystyrene as a standard substance.
- the content of fluorine atoms contained in the fluoropolymer (A) was measured by the following method.
- the obtained fluorine-containing resin was completely burnt and decomposed at 1200 ° C, and the generated gas was absorbed in 50 g of water.
- the amount of fluoride ions in the obtained aqueous solution was quantified, and the content of fluorine atoms contained in the fluoropolymer (A) was calculated.
- the acid value (mgKOHZg) and the number of ethylenic double bonds in one molecule are theoretical values calculated from the blending ratio of the monomer as a raw material.
- DMS Metatalylate containing dimethyl silicone chain (trade name X—22-174DX, manufactured by Shin-Etsu Chemical Co., Ltd.),
- MAA methacrylic acid
- V70 2, 2'-azobis (4-methoxy-2,4-dimethylvale-tolyl) (trade name V-70, manufactured by Wako Pure Chemical Industries, Ltd.)
- DBTDL Dibutyltin dilaurate
- BHT 2, 6—di-t-butinole p-creso-nore
- IR907 Radical initiator (trade name: IRGACURE, manufactured by Ciba Specialty Chemicals) — 907),
- IR369 Radical initiator (product name: IRGACURE, manufactured by Ciba Specialty Chemicals)
- OXE01 1, 2—octanedione, 1— [4— (Fuerthio) 1, 2— (o Benzyloxime)] (Ciba Specialty Chemicals, trade name OXE01),
- OXE02 Ethanone 1— [9 Ethyl 6- (2-Methylbenzoyl) 9H-Carbazoyl-3-yl] —1— (o Acetyloxime) (Ciba Specialty Chemicals, trade name OXE02),
- DETX-S Isopropylthioxanthone (Nippon Kayaku Co., Ltd., trade name DETX-S), D310: Dipentaerythritol pentaatrate (Nippon Kayaku Co., Ltd., trade name KAYAR AD D-310),
- CCR1115 Crezo-novolak-type epoxy acrylate (trade name C CR-1115: solid content 60% by mass; manufactured by Nippon Gyaku Co., Ltd.),
- ZFR1492H Bisphenol F-type epoxy acrylate (Nippon Kayaku Co., Ltd., trade name ZFR 1492H: solid content 65% by mass)
- 157S65 Bisphenol A novolak type (Japan Epoxy Resin, trade name Epi Coat 157S65),
- KBM403 3-Glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-403),
- a 1L autoclave equipped with a stirrer was charged with 556.
- Og of HEMA, 43.2 g of MMA, chain transfer agent 2—ME 6.2 g of the polymerization initiator and 4.5 g of the polymerization initiator V-70 were charged and polymerized at 40 ° C. for 18 hours with stirring in a nitrogen atmosphere to obtain a solution of copolymer 1.
- the weight average molecular weight of the copolymer 1 was 5600.
- a 500 mL glass flask equipped with a thermometer, stirrer, and heating device was charged with 100 g of copolymer 1, 47.7 g of MOI, 0.19 g of DBTDL, 2.4 g of BHT, and 100 g of acetone. While charging and stirring, polymerization was carried out at 30 ° C. for 18 hours to obtain a solution of the fluoropolymer (A-1). Water was added to the acetone solution of the obtained fluoropolymer (A-1) to reprecipitate and purified, followed by reprecipitation with petroleum ether, vacuum drying, and 135 g of fluoropolymer (A-1). Got. The weight average molecular weight was 8800.
- Copolymers 2 to 7 were obtained by the same polymerization reaction except that the composition of raw materials (unit: g) was changed as shown in Table 1 in the synthesis of copolymer 1.
- the fluoropolymer (A-1) side chains having an ethylenic double bond were obtained by the same reaction except that the blending of raw materials (unit: g) was changed as shown in Table 2.
- Fluoropolymers (A-2) to (A-6) having the above, and fluorinated polymer (R-1) having no side chain having an ethylenic double bond were obtained.
- partition walls were formed on the substrate by the methods shown in Examples 1 to 13 below.
- the base material on which each partition wall was formed was measured and evaluated for developability, water / oil repellency, chemical resistance, ink jetting) and coating properties by the following methods. These results are summarized in Table 4.
- the water / oil repellency was evaluated by the contact angle (degree) of water and xylene on the surface of the coating film formed on the glass substrate.
- the contact angle is the angle between the solid surface and the tangent to the liquid surface at the point where the solid and the liquid contact, and is defined as the angle containing the liquid. The larger the angle, the better the water / oil repellency of the coating film.
- the contact angle of water is expressed as ⁇ when the contact angle is 95 degrees or more, ⁇ when it is 90 degrees or more and less than 95 degrees, and X when it is less than 90 degrees.
- a contact angle of xylene of 40 degrees or more is denoted as ⁇ , 35 degrees or more and less than 40 degrees as ⁇ , and less than 35 degrees as X.
- an ink-jet device was used to inject UV curable ink containing RGB color pigments into the region partitioned by the partition, thereby forming an ink layer.
- a pixel was formed.
- the pixel pattern thus obtained was observed with an ultradeep shape measuring microscope (manufactured by Keyence Corporation). Yes, there is no mixed color or blur between adjacent pixels, and a white pixel pattern with no ink layer thickness unevenness in the pixel is obtained, but there is no mixed color or blur between pixels, The film thickness unevenness of the coating film is indicated by ⁇ , and the color mixture or blur between pixels is indicated by X.
- the substrate was developed with a 0.1% by mass tetramethylammonium hydroxide aqueous solution containing a surfactant at 25 ° C. for 40 seconds, washed with water, and dried.
- the substrate was irradiated with 1500 mi / C m 2 from the back side of the partition wall formation surface using an ultra-high pressure mercury lamp, and further subjected to heat treatment at 200 ° C. for 1 hour to obtain a substrate on which a pattern was formed.
- the substrate was developed with a 0.1% by mass tetramethylammonium hydroxide aqueous solution containing a surfactant at 25 ° C. for 40 seconds, washed with water, and dried.
- 2000 miZcm 2 was irradiated from the partition forming surface side with an ultrahigh pressure mercury lamp, and further heat-treated at 200 ° C. for 1 hour to obtain a substrate on which a pattern was formed.
- the substrate was developed with a 0.1% by mass tetramethylammonium hydroxide aqueous solution containing a surfactant at 25 ° C. for 40 seconds, washed with water, and dried.
- 3000 n3j / cm 2 was irradiated from the back side of the partition forming surface with an ultrahigh pressure mercury lamp, and further heat-treated at 200 ° C. for 1 hour to obtain a substrate on which a pattern was formed.
- the substrate was developed with a 0.1% by mass tetramethylammonium hydroxide aqueous solution containing a surfactant at 25 ° C. for 40 seconds, washed with water, and dried.
- 3000 miZcm 2 was irradiated from the partition forming surface side with an ultrahigh pressure mercury lamp, and further heat-treated at 200 ° C. for 1 hour to obtain a substrate on which a pattern was formed.
- the negative photosensitive composition 6 After applying the negative photosensitive composition 6 on a glass substrate using a spinner, it was pre-betaned on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 2.0 m.
- the substrate was developed with a 0.1% by mass tetramethylammonium hydroxide aqueous solution containing a surfactant at 25 ° C. for 40 seconds, washed with water, and dried.
- BM lattice-like black matrix
- the substrate was developed with a 0.1% by mass tetramethylammonium hydroxide aqueous solution containing a surfactant at 25 ° C. for 40 seconds, washed with water, and dried.
- the base material containing a surfactant was added in an amount of 0.1% by mass tetramethyla. Development was performed at 25 ° C for 40 seconds using an aqueous ammonium hydroxide solution, washed with water, and dried.
- the substrate was developed with a 0.1% by mass tetramethylammonium hydroxide aqueous solution containing a surfactant at 25 ° C. for 40 seconds, washed with water, and dried.
- the substrate was developed with a 0.1% by mass tetramethylammonium hydroxide aqueous solution containing a surfactant at 25 ° C. for 40 seconds, washed with water, and dried.
- the substrate was developed with a 0.1 mass% tetramethyl ammonium hydroxide aqueous solution containing a surfactant at 25 ° C. for 40 seconds, washed with water, Dried.
- Example 10 since the film was not post-exposure and heat-cured, the oil repellency, chemical resistance and ink jet coatability of the coating film were poor.
- Example 11 no ink exposure was performed because no post-exposure was performed.
- Example 12 shows a fluoropolymer having no side chain having an ethylenic double bond. Therefore, the oil repellency and chemical resistance are slightly inferior, and the ink jet coating property is inferior. Since Example 13 does not contain a fluorine-containing polymer, water / oil repellency and inkjet coating properties are inferior. Industrial applicability
- the partition wall manufacturing method of the present invention is a method for partition walls of electronic devices such as partition walls of color filters, ITO electrode partitions of liquid crystal display elements, partition walls of organic EL display elements, partition walls of circuit wiring boards, and the like. It is suitably used for production.
- the entire contents of the description, claims and abstract of Japanese Patent Application No. 2005-342278 filed on November 28, 2005 are incorporated herein by reference. Incorporate.
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KR101420470B1 (ko) | 2007-05-29 | 2014-07-16 | 아사히 가라스 가부시키가이샤 | 감광성 조성물, 격벽, 블랙 매트릭스 |
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ITBS20130110A1 (it) * | 2013-07-22 | 2015-01-23 | Guarniflon S P A | Polimero fluorurato |
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Also Published As
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US20080233493A1 (en) | 2008-09-25 |
TW200735700A (en) | 2007-09-16 |
JPWO2007061115A1 (ja) | 2009-05-07 |
KR20080073302A (ko) | 2008-08-08 |
CN101317132A (zh) | 2008-12-03 |
JP4930378B2 (ja) | 2012-05-16 |
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