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WO2017033834A1 - Composition de résine photosensible de type négatif, film de résine durci, séparation, élément optique et procédé de fabrication associé - Google Patents

Composition de résine photosensible de type négatif, film de résine durci, séparation, élément optique et procédé de fabrication associé Download PDF

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Publication number
WO2017033834A1
WO2017033834A1 PCT/JP2016/074149 JP2016074149W WO2017033834A1 WO 2017033834 A1 WO2017033834 A1 WO 2017033834A1 JP 2016074149 W JP2016074149 W JP 2016074149W WO 2017033834 A1 WO2017033834 A1 WO 2017033834A1
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Prior art keywords
resin composition
photosensitive resin
partition
ink
negative photosensitive
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PCT/JP2016/074149
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English (en)
Japanese (ja)
Inventor
川島　正行
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旭硝子株式会社
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Publication of WO2017033834A1 publication Critical patent/WO2017033834A1/fr

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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
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an organic EL element, a quantum dot display, a negative photosensitive resin composition used for a TFT array or a thin film solar cell, a cured resin film, a partition wall and an optical element (specifically, an organic EL element, a quantum dot display,
  • the present invention relates to a TFT array and a thin film solar cell) and a method for producing the optical element.
  • an organic layer such as a light emitting layer is used as a dot by an inkjet (IJ) method.
  • IJ inkjet
  • a pattern printing method may be used. In such a method, a partition is provided along the outline of the dot to be formed, and an ink containing the material of the organic layer is injected into a partition (hereinafter also referred to as “opening”) surrounded by the partition. This is dried and / or heated to form dots having a desired pattern.
  • the upper surface of the partition wall needs to have ink repellency in order to prevent ink mixing between adjacent dots and to uniformly apply ink in dot formation.
  • the dot forming opening surrounded by the partition including the partition side surface needs to have ink affinity. Therefore, in order to obtain a partition having ink repellency on the upper surface, a method of forming a partition corresponding to a dot pattern by a photolithography method using a photosensitive resin composition containing an ink repellent agent is known. .
  • Patent Document 1 discloses that in an organic EL device or the like, at least one of hydrogen atoms is substituted with an alkali-soluble photosensitive resin having an acidic group and three or more ethylenic double bonds in the molecule.
  • An ink repellent agent comprising a polymer unit having an alkyl group having 20 or less carbon atoms (however, the alkyl group includes those having etheric oxygen) and a polymer unit having an ethylenic double bond;
  • a negative photosensitive resin composition containing a photopolymerization initiator is described.
  • As a photopolymerization initiator 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (IR907) is disclosed.
  • the present invention has been made in order to solve the above-described problem, and the top surface of the obtained partition wall has good ink repellency, and when ink is dropped onto an opening partitioned by the partition wall by inkjet.
  • An object of the present invention is to provide a negative photosensitive resin composition that has good wetting and spreading to the base material of the ink.
  • the present invention also provides an optical element having dots that are accurately formed by uniformly applying ink to openings partitioned by a partition, specifically an organic EL element, a quantum dot display, a TFT array, and a thin-film solar cell, and An object is to provide a method for producing the optical element.
  • the present invention has the gist of [1] to [9] below.
  • An alkali-soluble resin or alkali-soluble monomer (A) having photocurability, a photopolymerization initiator (B), and an ink repellent agent (C), and the photopolymerization initiator (B) Contains a photopolymerization initiator (B1) made of an ⁇ -hydroxyalkylphenone compound, and is a negative-type photosensitivity for organic EL elements, quantum dot displays, TFT arrays, or thin film solar cells Resin composition.
  • An organic EL device, a quantum dot display, a TFT array, or a thin-film solar cell characterized by being formed using the negative photosensitive resin composition according to any one of [1] to [5] Resin cured film.
  • optical element having a plurality of dots and a partition located between adjacent dots on the surface of the substrate, the optical element being an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell, Is formed of the partition walls of [7].
  • the upper surface of the obtained partition wall has good ink repellency, and has a good negative wetting and spreading to the base material of the ink when ink is dropped onto the opening partitioned by the partition wall by inkjet.
  • a photosensitive resin composition can be provided.
  • the optical element of the present invention can provide an optical element having dots that are accurately formed by uniformly applying ink to the openings partitioned by the partition walls.
  • (Meth) acryloyl group is a general term for “methacryloyl group” and “acryloyl group”.
  • the (meth) acryloyloxy group, (meth) acrylic acid, (meth) acrylate, (meth) acrylamide, and (meth) acrylic resin also conform to this.
  • the group represented by the formula (x) may be simply referred to as a group (x).
  • the compound represented by the formula (y) may be simply referred to as the compound (y).
  • the expressions (x) and (y) indicate arbitrary expressions.
  • a resin mainly composed of a certain component or “a resin mainly composed of a certain component” means that the proportion of the component occupies 50% by mass or more based on the total amount of the resin.
  • the “side chain” is a group other than a hydrogen atom or a halogen atom bonded to a carbon atom constituting the main chain in a polymer in which a repeating unit composed of carbon atoms constitutes the main chain.
  • total solid content of the photosensitive resin composition refers to a component that forms a cured film described later among the components contained in the photosensitive resin composition, and the photosensitive resin composition is heated at 140 ° C. for 24 hours. Obtained from the residue from which the solvent has been removed. The total solid content can also be calculated from the charged amount.
  • a film made of a cured product of a composition containing resin as a main component is referred to as a “resin cured film”.
  • a film coated with the photosensitive resin composition is referred to as a “coating film”, and a film obtained by drying the film is referred to as a “dry film”.
  • a film obtained by curing the “dry film” is a “resin cured film”. Further, the “resin cured film” may be simply referred to as “cured film”.
  • the resin cured film may be in the form of a partition formed in a shape that partitions a predetermined region into a plurality of sections. For example, the following “ink” is injected into the partitions partitioned by the partition walls, that is, the openings surrounded by the partition walls to form “dots”.
  • “Ink” is a generic term for liquids that have optical and / or electrical functions after drying, curing, and the like.
  • dots as various constituent elements may be pattern-printed by an ink jet (IJ) method using the ink for forming the dots.
  • IJ ink jet
  • “Ink” includes ink used in such applications.
  • “Ink repellency” is a property of repelling the above ink and has both water repellency and oil repellency.
  • the ink repellency can be evaluated by, for example, a contact angle when ink is dropped.
  • “Ink affinity” is a property opposite to ink repellency, and can be evaluated by the contact angle when ink is dropped as in the case of ink repellency.
  • the ink affinity can be evaluated by evaluating the degree of ink wetting and spreading (ink wetting and spreading property) when ink is dropped on a predetermined standard.
  • the “dot” indicates a minimum area where light modulation is possible in the optical element.
  • Perfect (%) represents mass% unless otherwise specified. Embodiments of the present invention will be described below.
  • the negative photosensitive resin composition of the present invention can be suitably used for organic EL devices, quantum dot displays, TFT arrays, or thin film solar cells.
  • the negative photosensitive resin composition of this invention is photopolymerization containing the photoinitiator (B1) which consists of alkali-soluble resin or alkali-soluble monomer (A) which has photocurability, and a specific compound.
  • An initiator (B) and an ink repellent agent (C) are contained.
  • the negative photosensitive resin composition of the present invention further comprises a photopolymerization initiator (B2), a photopolymerization initiator (B3), a crosslinking agent (D), a colorant (E), and a solvent (F) as necessary. And other optional ingredients.
  • a photopolymerization initiator B2
  • a photopolymerization initiator B3
  • a crosslinking agent D
  • a colorant E
  • F solvent
  • alkali-soluble resin or alkali-soluble monomer (A))
  • the alkali-soluble resin will be described with a symbol (AP) and the alkali-soluble monomer with a symbol (AM). In the following description, these may be collectively referred to as “alkali-soluble resin (A)”.
  • the alkali-soluble resin (AP) a photosensitive resin having an acidic group and an ethylenic double bond in one molecule is preferable. Since the alkali-soluble resin (AP) has an ethylenic double bond in the molecule, the exposed portion of the negative photosensitive resin composition is polymerized and cured by radicals generated from the photopolymerization initiator (B). A cured film is formed.
  • the exposed area sufficiently cured in this way is not easily removed with an alkaline developer.
  • the alkali-soluble resin (AP) has an acidic group in the molecule
  • the non-exposed portion of the uncured negative photosensitive resin composition can be selectively removed with an alkaline developer.
  • the cured film can be in the form of a partition that partitions a predetermined region into a plurality of sections.
  • Examples of the acidic group include a carboxy group, a phenolic hydroxyl group, a sulfo group, and a phosphoric acid group. These may be used alone or in combination of two or more.
  • Examples of the ethylenic double bond include double bonds having an addition polymerization property such as a (meth) acryloyl group, an allyl group, a vinyl group, a vinyloxy group, and a vinyloxyalkyl group. These may be used alone or in combination of two or more.
  • some or all of the hydrogen atoms possessed by the ethylenic double bond may be substituted with an alkyl group such as a methyl group.
  • alkali-soluble resin (AP) having an ethylenic double bond examples include a resin (A-1) having a side chain having an acidic group and a side chain having an ethylenic double bond, and an epoxy group having an acidic group and ethylene. And a resin (A-2) into which an ionic double bond is introduced. These may be used alone or in combination of two or more. As such alkali-soluble resin (AP), those described in the specification of WO2014 / 084279 can be used.
  • alkali-soluble resin (AP) peeling of the cured film during development can be suppressed, and a high-resolution dot pattern can be obtained, and the linearity of the pattern when the dots are linear is good.
  • the resin (A-2) it is preferable to use the resin (A-2).
  • the linearity of a pattern is favorable means that the edge of the partition obtained does not have a chip etc. and is linear.
  • Examples of the resin (A-2) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenolmethane type epoxy resin, epoxy resin having naphthalene skeleton, and biphenyl skeleton.
  • An epoxy resin having an acidic group and an ethylenic double bond are preferably introduced into the epoxy resin having fluorenyl-substituted bisphenol A type epoxy resin and the epoxy resin described in JP-A-2006-84985.
  • the number of ethylenic double bonds that the alkali-soluble resin (AP) has in one molecule is preferably 3 or more on average, and particularly preferably 6 or more.
  • the number of ethylenic double bonds is at least the lower limit of the above range, the alkali solubility between the exposed and unexposed portions is likely to be different, and a fine pattern can be formed with a smaller exposure amount.
  • the mass average molecular weight (Mw) of the alkali-soluble resin (AP) is preferably 1.5 ⁇ 10 3 to 30 ⁇ 10 3 , particularly preferably 2 ⁇ 10 3 to 15 ⁇ 10 3 .
  • the number average molecular weight (Mn) is preferably 500 to 20 ⁇ 10 3 , and particularly preferably 1.0 ⁇ 10 3 to 10 ⁇ 10 3 .
  • the number average molecular weight (Mn) and the mass average molecular weight (Mw) are those measured by a gel permeation chromatography method using polystyrene as a standard substance unless otherwise specified.
  • the acid value of the alkali-soluble resin (AP) is preferably 10 to 300 mgKOH / g, particularly preferably 30 to 150 mgKOH / g. When the acid value is within the above range, the developability of the negative photosensitive composition is improved.
  • alkali-soluble monomer for example, a monomer (A-3) having an acidic group and an ethylenic double bond is preferably used.
  • the acidic group and ethylenic double bond of the alkali-soluble monomer (AM) are the same as those of the alkali-soluble resin (AP).
  • the acid value of the alkali-soluble monomer (AM) is also preferably in the same range as the alkali-soluble resin (AP).
  • Examples of the monomer (A-3) include 2,2,2-triacryloyloxymethylethylphthalic acid.
  • the alkali-soluble resin or alkali-soluble monomer (A) contained in the negative photosensitive resin composition may be used alone or in combination of two or more.
  • the content of the alkali-soluble resin or alkali-soluble monomer (A) in the total solid content in the negative photosensitive resin composition is preferably 5 to 80% by mass, particularly preferably 10 to 60% by mass. When the content ratio is in the above range, the photo-curing property and developability of the negative photosensitive resin composition are good.
  • the photopolymerization initiator (B) in the present invention includes a photopolymerization initiator (B1) composed of an ⁇ -hydroxyalkylphenone compound.
  • Examples of ⁇ -hydroxyalkylphenone compounds include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2- Methyl-1-propan-1-one, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1,1 ′-(methylene-di-4,1 -Phenylene) bis [2-hydroxy-2-methyl-1-propanone].
  • a photoinitiator (B1) may be used individually by 1 type, or may use 2 or more types together.
  • the photopolymerization initiator (B1) in the present invention is preferably a compound capable of generating a plurality of single bond cleavage reactions within one molecule.
  • the ink repellency of the partition formed from the cured film obtained from the negative photosensitive resin composition of the present invention is easily exhibited even at a low exposure amount.
  • the fine line formation property at the time of image development of the partition formed from the cured film obtained from the negative photosensitive resin composition of this invention improves.
  • the ink is dropped onto the dot portion by ink jetting, wetting and spreading of the ink to the base material is improved.
  • Examples of such a photopolymerization initiator (B1) include 1,1 ′-(methylene-di-4,1-phenylene) bis [2-hydroxy-2-methyl-1-propanone].
  • the photopolymerization initiator (B) preferably contains a photopolymerization initiator (B2) and / or a photopolymerization initiator (B3) in addition to the photopolymerization initiator (B1).
  • the photopolymerization initiator (B2) in the present invention comprises a compound other than the photopolymerization initiator (B1), and has an absorbance of 0.2 or more at a wavelength of 365 nm.
  • the absorbance at a wavelength of 365 nm is a value when a methanol solution in which the concentration of the photopolymerization initiator (B2) is 1.0 ⁇ 10 ⁇ 3 mass% is measured with a 1 cm square cell.
  • “absorbance” refers to absorbance at a wavelength of 365 nm measured by the method, unless otherwise specified.
  • Examples of the photopolymerization initiator (B2) include 4,4′-bis (dimethylamino) benzophenone (absorbance; 0.8), 4,4′-bis (diethylamino) benzophenone (absorbance; 0.8), and the like. .
  • the taper angle of the partition formed from the cured film obtained from the negative photosensitive resin composition of the present invention can be increased, and the shape of the partition also changes. Hateful.
  • the taper angle of a partition means the angle which the cross section of the taper part of a partition forms with respect to a base material. The cross-sectional shape of the partition walls can be observed with a scanning electron microscope (SEM) or the like.
  • the photopolymerization initiator (B3) in the present invention is a thioxanthone compound, and the absorbance at a wavelength of 365 nm is less than 0.2.
  • the absorbance is a value measured under the same conditions as the photopolymerization initiator (B2).
  • Examples of the photopolymerization initiator (B3) include isopropylthioxanthone (absorbance: 0.1), 2,4-diethylthioxanthone (absorbance: 0.1), and the like.
  • the photopolymerization initiator (B) may contain other photopolymerization initiators other than the photopolymerization initiators (B1), (B2), and (B3).
  • Other photopolymerization initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butan-1-one, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like.
  • the content of the photopolymerization initiator (B) in the total solid content of the negative photosensitive resin composition is preferably 0.1 to 50% by mass. More preferably, it is 0.5 to 30% by mass, and further preferably 1 to 15% by mass.
  • the content of the photopolymerization initiator (B1) in the total solid content in the negative photosensitive resin composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and 1 to 15% by mass. % Is particularly preferred.
  • the content ratio of (B1) is in the above range, the shape of the partition wall of the negative photosensitive resin composition is stable even when the exposure amount is changed.
  • the content of the photopolymerization initiator (B2) in the total solid content in the composition is preferably 1 to 10% by mass.
  • the taper angle of the partition formed from the cured film obtained from the negative photosensitive resin composition of the present invention can be increased, and the partition The shape of is difficult to change.
  • the content of the photopolymerization initiator (B3) in the total solid content in the composition is preferably 1 to 10% by mass.
  • the content ratio of the photopolymerization initiator (B3) is within the above range, the ink repellency of the partition formed from the cured film obtained from the negative photosensitive resin composition of the present invention is easily developed even at a low exposure amount. .
  • the fine line formation property at the time of image development of the partition formed from the cured film obtained from the negative photosensitive resin composition of this invention improves.
  • the ink repellent agent (C) in the present invention has a fluorine atom.
  • the ink repellent agent (C) has a property of transferring to the upper surface in the process of forming a cured film using the negative photosensitive resin composition containing the same (upper surface transfer property) and ink repellency.
  • the upper layer portion including the upper surface of the obtained cured film becomes a layer in which the ink repellent agent (C) is present densely (hereinafter also referred to as “ink repellent layer”). Ink repellency is imparted to the upper surface of the cured film.
  • the content of fluorine atoms in the ink repellent agent (C) is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, and particularly preferably 10 to 30% by mass. . If the fluorine atom content of the ink repellent agent (C) is at least the lower limit of the above range, good ink repellency can be imparted to the upper surface of the cured film, and if it is less than the upper limit, the negative photosensitive resin composition Compatibility with other components in the inside is improved.
  • the ink repellent agent (C) is preferably a compound having an ethylenic double bond. Since the ink repellent agent (C) has an ethylenic double bond, radicals act on the ethylenic double bond of the ink repellent agent (C) transferred to the upper surface, and the ink repellent agent (C) or ink repellent Crosslinking by (co) polymerization with the agent (C) and other components having an ethylenic double bond contained in the negative photosensitive resin composition becomes possible.
  • the fixability in the upper layer portion of the cured film of the ink repellent agent (C), that is, the ink repellent layer can be improved.
  • the ink repellent agent (C) can be sufficiently fixed to the ink repellent layer even when the exposure amount during exposure is low.
  • the case where the ink repellent agent (C) has an ethylenic double bond is as described above.
  • the photocurable component mainly composed of the alkali-soluble resin (A) present around the ink repellent agent (C) is sufficiently cured.
  • the ink repellent agent (C) can be sufficiently fixed.
  • Examples of the ink repellent agent (C) include an ink repellent agent (C1) made of a compound in which the main chain is a hydrocarbon chain and the side chain contains a fluorine atom.
  • an ink repellent agent (C2) made of a partially hydrolyzed condensate of a hydrolyzable silane compound containing a hydrolyzable silane compound having a fluorine atom may be used.
  • the ink repellent agent (C1) and the ink repellent agent (C2) are used alone or in combination.
  • the ink repellent agent (C1) from the viewpoint of developing higher ink repellency.
  • an ink repellent agent (C2) it is preferable to use an ink repellent agent (C2).
  • the ink repellent agent (C1) is a compound having a main chain of a hydrocarbon chain and a side chain having a fluorine atom.
  • the mass average molecular weight (Mw) of the ink repellent agent (C1) is preferably from 100 to 200,000, more preferably from 1,000 to 150,000, and particularly preferably from 10,000 to 130,000.
  • Mw mass average molecular weight
  • the ink repellent agent (C1) tends to shift to the upper surface when a cured film is formed using the negative photosensitive resin composition.
  • the opening residue is less than the upper limit, which is preferable.
  • the ink repellent agent (C1) is a polymer containing a side chain comprising a fluoroalkyl group which may contain an etheric oxygen atom and / or a side chain having a fluoroalkyl group which may contain an etheric oxygen atom. Preferably there is.
  • the fluoroalkyl group may be linear or branched.
  • Specific examples of the fluoroalkyl group not containing an etheric oxygen atom include the following structures. -CF 3 , -CF 2 CF 3 , -CF 2 CHF 2 ,-(CF 2 ) 2 CF 3 ,-(CF 2 ) 3 CF 3 ,-(CF 2 ) 4 CF 3 ,-(CF 2 ) 5 CF 3 ,-(CF 2 ) 6 CF 3 ,-(CF 2 ) 7 CF 3 ,-(CF 2 ) 8 CF 3 ,-(CF 2 ) 9 CF 3 ,-(CF 2 ) 11 CF 3 ,-(CF 2 ) 15 CF 3 .
  • fluoroalkyl group containing an etheric oxygen atom examples include the following structures. -CF (CF 3 ) O (CF 2 ) 5 CF 3 , -CF 2 O (CF 2 CF 2 O) r1 CF 3, —CF (CF 3 ) O (CF 2 CF (CF 3 ) O) r 2 C 6 F 13 , And —CF (CF 3 ) O (CF 2 CF (CF 3 ) O) r3 C 3 F 7 .
  • r1 is an integer of 1 to 8
  • r2 is an integer of 1 to 4
  • r3 is an integer of 1 to 5.
  • the hydrocarbon chain constituting the main chain of the ink repellent agent (C1) specifically, a main chain obtained by polymerization of a monomer having an ethylenic double bond, —Ph—CH 2 — (however, “ Ph ”represents a benzene skeleton.) And a novolak-type main chain composed of repeating units.
  • the ink repellent agent (C1) can include one or more side chains selected from the group consisting of a side chain having an acidic group, a side chain having an ethylenic double bond, and a side chain having an oxyalkylene group.
  • One side chain may contain two or more selected from the group consisting of an acidic group, an ethylenic double bond, and an oxyalkylene group.
  • the ink repellent agent (C1) can contain side chains such as a dimethyl silicone chain, an alkyl group, a glycidyl group, an isobornyl group, an isocyanate group, and a trialkoxysilyl group.
  • the main chain of the ink repellent agent (C1) is a novolak-type main chain composed of repeating units of -Ph-CH 2-
  • the side chain having a fluorine atom in the benzene skeleton (Ph) constituting the main chain is usually used.
  • a polymer having an acidic group, an ethylenic double bond, and an oxyalkylene group are used as the ink repellent agent (C1).
  • ink repellent agent (C1) specifically, for example, in paragraphs [0080] to [0102] of International Publication No. 2014/046209 and in paragraphs [0145] to [0170] of International Publication No. 2014/0669478, for example. What has been described.
  • the ink repellent agent (C2) is a partially hydrolyzed condensate of a hydrolyzable silane compound mixture (hereinafter also referred to as “mixture (M)”).
  • the mixture (M) is a hydrolyzable silane compound having a fluoroalkylene group and / or a fluoroalkyl group and a group in which a hydrolyzable group is bonded to a silicon atom (hereinafter referred to as “hydrolyzable silane compound (s1)”).
  • hydrolyzable silane compound (s1) As an essential component, and optionally a hydrolyzable silane compound other than the hydrolyzable silane compound (s1).
  • hydrolyzable silane compound optionally contained in the mixture (M) examples include the following hydrolyzable silane compound (s2) and hydrolyzable silane compound (s3).
  • hydrolyzable silane compound (s2) is particularly preferable.
  • Hydrolyzable silane compound (s2) a hydrolyzable silane compound in which four hydrolyzable groups are bonded to a silicon atom.
  • Hydrolyzable silane compound (s3) a hydrolyzable silane compound having a group having an ethylenic double bond and a group in which a hydrolyzable group is bonded to a silicon atom, and does not contain a fluorine atom.
  • hydrolyzable silane compound (s1) include the following compounds. F (CF 2 ) 4 CH 2 CH 2 Si (OCH 3 ) 3 , F (CF 2 ) 6 CH 2 CH 2 Si (OCH 3 ) 3 , F (CF 2 ) 6 CH 2 CH 2 CH 2 Si (OCH 3 ) 3 , F (CF 2 ) 8 CH 2 CH 2 Si (OCH 3 ) 3 , F (CF 2) 3 OCF ( CF 3) CF 2 O (CF 2) 2 CH 2 CH 2 Si (OCH 3) 3, F (CF 2) 2 O ( CF 2) 2 O (CF 2) 2 CH 2 CH 2 Si (OCH 3) 3.
  • F (CF 2 ) 6 CH 2 CH 2 Si (OCH 3 ) 3 and F (CF 2 ) 3 OCF (CF 3 ) CF 2 O (CF 2 ) 2 CH 2 CH 2 Si (OCH 3 ) 3 are Particularly preferred.
  • the content of the hydrolyzable silane compound (s1) in the mixture (M) is preferably such that the content of fluorine atoms in the partial hydrolysis-condensation product obtained from the mixture is 1 to 40% by mass. More preferred is 5 to 35% by mass, and particularly preferred is 10 to 30% by mass.
  • the content ratio of the hydrolyzable silane compound (s1) is not less than the lower limit of the above range, good ink repellency can be imparted to the upper surface of the cured film. Compatibility with the decomposable silane compound is improved.
  • hydrolyzable silane compound (s2) include the following compounds. Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 , A partial hydrolysis condensate of Si (OCH 3 ) 4 , Partially hydrolyzed condensate of Si (OC 2 H 5 ) 4 .
  • the content of the hydrolyzable silane compound (s2) in the mixture (M) is preferably 0.01 to 5 mol, particularly 0.05 to 4 mol, relative to 1 mol of the hydrolyzable silane compound (s1). preferable.
  • the content ratio is not less than the lower limit of the above range, the film forming property of the ink repellent agent (C2) is good, and when it is not more than the upper limit value, the ink repellent property of the ink repellent agent (C2) is good.
  • the content of the hydrolyzable silane compound (s3) in the mixture (M) is preferably 0.1 to 5 mol, particularly 0.5 to 4 mol, relative to 1 mol of the hydrolyzable silane compound (s1). preferable.
  • the content ratio is equal to or more than the lower limit of the above range, the top transferability of the ink repellent agent (C2) is good, and the fixability of the ink repellent agent (C2) in the ink repellent layer including the top surface after shifting to the top surface. Further, the storage stability of the ink repellent agent (C2) is good.
  • the amount is not more than the upper limit, the ink repellency of the ink repellent (C2) is good.
  • the mixture (M) can optionally contain one or more hydrolyzable silane compounds other than the hydrolyzable silane compounds (s1) to (s3).
  • Other hydrolyzable silane compounds include a hydrolyzable silane compound (s4) having only a hydrocarbon group and a hydrolyzable group as a group bonded to a silicon atom, a mercapto group and a hydrolyzable silyl group, Hydrolyzable silane compound (s5) containing no fluorine atom, hydrolyzable silane compound (s6) having an epoxy group and a hydrolyzable silyl group and no fluorine atom, oxyalkylene group and hydrolyzable silyl group Hydrolyzable silane compound (s7) having no fluorine atom, hydrolyzable silane compound (s8) having sulfide and hydrolyzable silyl group, and not containing fluorine atom, ureido group and hydrolyzable silyl Hydrolyzable silane compound (s9) having
  • hydrolyzable silane compound (s4) for example, (CH 3 ) 3 —Si—OCH 3 , (CH 3 CH 2 ) 3 —Si—OC 2 H 5 , (CH 3 ) 3 —Si —OC 2 H 5 , (CH 3 CH 2 ) 3 —Si—OCH 3 , (CH 3 ) 2 —Si— (OCH 3 ) 2 , (CH 3 ) 2 —Si— (OC 2 H 5 ) 2 , ( CH 3 CH 2 ) 2 —Si— (OC 2 H 5 ) 2 , (CH 3 CH 2 ) 2 —Si— (OCH 3 ) 2 , Ph—Si (OC 2 H 5 ) 3 , Ph—Si (OCH 3) ) 3 , C 10 H 21 —Si (OCH 3 ) 3 .
  • Ph represents a phenyl group.
  • hydrolyzable silane compound (s5) for example, HS— (CH 2 ) 3 —Si (OCH 3 ) 3 , HS— (CH 2 ) 3 —Si (CH 3 ) (OCH 3 ) 2 is added with water.
  • Examples of the decomposable silane compound (s6) include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycid Xylpropylmethyldimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane are, for example, CH 3 O (C 2 H 4 O) k Si (OCH 3 ) 3 (polyoxy) as the hydrolyzable silane compound (s7).
  • Ethylene group-containing trimethoxysilane (here, k is, for example, about 10), hydrolyzable silane compound (s8) For example, bis (triethoxysilylpropyl) tetrasulfide, hydrolyzable silane compound (s9), for example, 3-ureidopropyltriethoxysilane, hydrolyzable silane compound (s10), for example, N-phenyl-3 -Aminopropyltrimethoxysilane.
  • hydrolyzable silane compound (s8) For example, bis (triethoxysilylpropyl) tetrasulfide
  • hydrolyzable silane compound (s9) for example, 3-ureidopropyltriethoxysilane
  • hydrolyzable silane compound (s10) for example, N-phenyl-3 -Aminopropyltrimethoxysilane.
  • the ink repellent agent (C2) contains a hydrolyzable silane compound (s5) or a hydrolyzable silane compound (s8)
  • the ink repellency is easily exhibited even at a low exposure amount.
  • the ink repellent agent (C2) contains a hydrolyzable silane compound (s7)
  • the dispersion stability and storage stability of the ink repellent agent (C2) are improved, which is preferable.
  • n1 of the hydrolyzable silane compound (s1), n2 of the hydrolyzable silane compound (s2), and n3 of the hydrolyzable silane compound (s3) A hydrolysis condensate is mentioned.
  • n1: n2: n3 corresponds to the charged composition of the hydrolyzable silane compounds (s1), (s2), and (s3) in the mixture (M).
  • the molar ratio of each component is designed from the balance of the effect of each component.
  • n1 is preferably 0.02 to 0.4 in such an amount that the fluorine atom content in the ink repellent agent (C2) falls within the above-mentioned preferable range.
  • n2 is preferably from 0 to 0.98, particularly preferably from 0.05 to 0.6.
  • n3 is preferably 0 to 0.8, particularly preferably 0.2 to 0.5.
  • the mass average molecular weight (Mw) of the ink repellent agent (C2) is preferably 500 or more, preferably less than 1,000,000, and particularly preferably 5000 or less.
  • Mw mass average molecular weight
  • the ink repellent agent (C2) is likely to shift to the upper surface when a cured film is formed using the negative photosensitive resin composition.
  • it is less than the upper limit the opening residue is reduced, which is preferable.
  • the mass average molecular weight (Mw) of the ink repellent agent (C2) can be adjusted by the production conditions.
  • the ink repellent agent (C2) can be produced by subjecting the above-mentioned mixture (M) to hydrolysis and condensation reaction by a known method. This reaction is catalyzed by alkali catalysts such as sodium hydroxide and tetramethylammonium hydroxide (TMAH), inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or organic acids such as acetic acid, oxalic acid and maleic acid. Can be used as Moreover, a well-known solvent can be used for the said reaction.
  • the ink repellent agent (C2) obtained by the above reaction may be blended in a negative photosensitive resin composition in the form of a solution together with a solvent.
  • ink repellent agent (C2) for example, paragraphs [0033] to [0078] of International Publication No. 2014/046209, for example, paragraphs [0027] to [0082] of International Publication No. 2014/046210. And those described in paragraphs [0095] to [0143] of International Publication No. 2014/0669478.
  • the content ratio of the ink repellent agent (C) in the total solid content in the negative photosensitive resin composition is a content ratio at which the surface satisfies the above characteristics in the partition obtained using the same.
  • the content ratio depends on the type of the ink repellent agent (C) to be used, but specifically, it is preferably 0.03 to 10% by mass, more preferably 0.05 to 5% by mass, and 0.10 to 3%. Mass% is particularly preferred.
  • the content ratio is at least the lower limit of the above range, the upper surface of the cured film formed from the negative photosensitive resin composition has excellent ink repellency. Adhesiveness of a cured film and a base material becomes it favorable that it is below the upper limit of the said range.
  • the crosslinking agent (D) optionally contained in the negative photosensitive resin composition of the present invention is a compound having two or more ethylenic double bonds in one molecule and no acidic group.
  • the curability of the negative photosensitive resin composition at the time of exposure is improved, and a cured film can be formed even with a low exposure amount.
  • At least one of the crosslinking agents (D) has 7 or more ethylenic double bonds.
  • the crosslinking agents (D) has 7 or more ethylenic double bonds.
  • a monomer having a urethane skeleton bonded with (10 functional) is preferred.
  • the number of ethylenic double bonds of the crosslinking agent (D) is more preferably 9 or more, and particularly preferably 10 or more.
  • the content of the crosslinking agent (D) in the total solid content in the negative photosensitive resin composition is preferably 10 to 60% by mass, particularly preferably 20 to 55% by mass.
  • the negative photosensitive resin composition of this invention contains a coloring agent (E), when providing light-shielding property to a cured film, especially a partition, according to a use.
  • a coloring agent (E) in the present invention include various inorganic pigments or organic pigments such as carbon black, aniline black, anthraquinone black pigment, perylene black pigment, and azomethine black pigment.
  • preferred organic pigments include 2-hydroxy-4-n-octoxybenzophenone, methyl-2-cyanoacrylate, 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4 -Dibutoxyphenyl) -1,3,5-triazine, C.I. I. Pigment black 1, 6, 7, 12, 20, 31, C.I. I. Pigment Blue 15: 6, Pigment Red 254, Pigment Green 36, Pigment Yellow 150, and the like.
  • Coloring agent (E) may be used alone or in combination of two or more.
  • the content of the colorant (E) in the total solid content is preferably 15 to 65% by mass, and 20 to 50%. Mass% is particularly preferred. Further, 15 to 1500% by mass is preferable, and 20 to 1000% by mass is more preferable with respect to 100% by mass of the alkali-soluble resin or the like (A).
  • the negative photosensitive resin composition obtained when the colorant (E) is within the above range has good sensitivity, and the formed partition has excellent light shielding properties.
  • solvent (F) When the negative photosensitive resin composition of the present invention contains the solvent (F), the viscosity is reduced, and the negative photosensitive resin composition can be easily applied to the substrate surface. As a result, a coating film of a negative photosensitive resin composition having a uniform film thickness can be formed.
  • a known solvent is used as the solvent (F).
  • a solvent (F) may be used individually by 1 type, or may use 2 or more types together.
  • Examples of the solvent (F) include alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, alcohols, solvent naphtha, and water.
  • at least one solvent selected from the group consisting of alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, and alcohols is preferable.
  • More preferred is at least one solvent selected from the group consisting of monoethyl ether acetate and 2-propanol.
  • a solvent (F) contains water
  • content of water is 10 mass% or less of the whole solvent (F).
  • the water content is more preferably 1 to 10% by mass.
  • the content ratio of the solvent (F) in the negative photosensitive resin composition is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and particularly preferably 65 to 90% by mass with respect to the total amount of the composition. Further, 0.1 to 3000% by mass is preferable, and 0.5 to 2000% by mass is more preferable with respect to 100% by mass of the alkali-soluble resin or the like (A).
  • the thiol compound (G) optionally contained in the negative photosensitive resin composition of the present invention is a compound having two or more mercapto groups in one molecule. If the negative photosensitive resin composition of this invention contains a thiol compound (G), the radical of a thiol compound (G) will produce
  • This ene-thiol reaction is different from the usual radical polymerization of ethylenic double bonds, and is not subject to reaction inhibition by oxygen, so it has high chain mobility and also undergoes crosslinking at the same time as polymerization.
  • the shrinkage rate is low, and there is an advantage that a uniform network can be easily obtained.
  • the negative photosensitive resin composition of the present invention contains a thiol compound (G), it can be sufficiently cured even at a low exposure amount as described above, and includes a partition upper surface that is particularly susceptible to reaction inhibition by oxygen. Since the photocuring is sufficiently performed also in the upper layer portion, it is possible to impart good ink repellency to the upper surface of the partition wall.
  • G thiol compound
  • the mercapto group in the thiol compound (G) is preferably contained 2 to 10 in one molecule, more preferably 2 to 8 and even more preferably 2 to 5. From the viewpoint of storage stability of the negative photosensitive resin composition, 3 is particularly preferable.
  • the molecular weight of the thiol compound (G) is not particularly limited.
  • the mercapto group equivalent represented by [molecular weight / number of mercapto groups] is preferably 40 to 1,000, more preferably 40 to 500, and more preferably 40 to 250, from the viewpoint of curability at low exposure. Is particularly preferred.
  • thiol compound (G) examples include tris (2-mercaptopropanoyloxyethyl) isocyanurate, pentaerythritol tetrakis (3-mercaptobutyrate), trimethylolpropane tristhioglycolate, pentaerythritol tristhioglycol.
  • the content ratio is a mercapto group with respect to 1 mol of the ethylenic double bond of the total solid content in the negative photosensitive resin composition. Is preferably 0.0001 to 1 mol, more preferably 0.0005 to 0.5 mol, and particularly preferably 0.001 to 0.5 mol. Further, the amount is preferably 0.1 to 1200% by mass, more preferably 0.2 to 1000% by mass with respect to 100% by mass of the alkali-soluble resin (A). When the content ratio of the thiol compound (G) is within the above range, the photo-curability and developability of the negative photosensitive resin composition are good even at a low exposure amount.
  • the negative photosensitive resin composition of the present invention can optionally contain a phosphoric acid compound (H) in order to improve the adhesion of the obtained cured film to a substrate, a transparent electrode material such as ITO, and the like.
  • Such a phosphoric acid compound (H) is not particularly limited as long as it can improve the adhesion of a cured film to a substrate, a transparent electrode material, etc., but the ethylenically unsaturated double molecule in the molecule.
  • a phosphoric acid compound having a bond is preferable.
  • a compound having a (meth) acryloyl group which is an ethylenically unsaturated double bond or a vinyl phosphate compound is preferred.
  • Examples of the phosphoric acid (meth) acrylate compound used in the present invention include mono (2- (meth) acryloyloxyethyl) acid phosphate, di (2- (meth) acryloyloxyethyl) acid phosphate, and di (2-acryloyloxyethyl). Examples include acid phosphate, tris ((meth) acryloyloxyethyl) acid phosphate, mono (2-methacryloyloxyethyl) caproate acid phosphate, and the like.
  • phosphoric acid compound (H) phenylphosphonic acid and the like can be used in addition to the phosphoric acid compound having an ethylenically unsaturated double bond in the molecule.
  • the negative photosensitive resin composition of the present invention may contain, as the phosphoric acid compound (H), one kind of compound classified as such, or may contain two or more kinds.
  • the content is preferably 0.01 to 10% by mass with respect to the total solid content in the negative photosensitive resin composition, 0.1 to 5% by mass is particularly preferable. Further, 0.01 to 200% by mass is preferable and 0.1 to 100% by mass is more preferable with respect to 100% by mass of the alkali-soluble resin (A).
  • the content ratio of the phosphoric acid compound (H) is in the above range, the adhesion between the obtained cured film and the substrate is good.
  • the negative photosensitive resin composition in the present invention may further include a polymerization inhibitor, a thermal crosslinking agent, a polymer dispersant, a dispersion aid, a silane coupling agent, fine particles, a curing accelerator, a thickener, if necessary.
  • You may contain 1 or more types of other additives chosen from the group which consists of a plasticizer, an antifoamer, a leveling agent, and a repellency inhibitor.
  • the negative photosensitive resin composition of the present invention can be obtained by mixing predetermined amounts of the above components.
  • the negative photosensitive resin composition of the present invention is for an organic EL element, a quantum dot display, a TFT array or a thin film solar cell.
  • it is used for an organic EL element, a quantum dot display, a TFT array or a thin film solar cell.
  • the negative photosensitive resin composition of the present invention it is possible to produce a cured film having good ink repellency on the upper surface, in particular, a partition wall.
  • the ink repellent agent (C) is sufficiently fixed on the ink repellent layer, and the ink repellent agent (C) present at a low concentration in the partition wall below the ink repellent layer has sufficient partition walls. Since it is photocured, the ink repellent agent (C) is difficult to migrate into the opening surrounded by the partition wall during development, so that an opening where the ink can be applied uniformly can be obtained.
  • the mechanism is not clear, but the photopolymerization initiator (B1) is less susceptible to polymerization inhibition due to oxygen. Therefore, the crosslink density of the surface ink repellent layer in the coating film can be improved, and a stronger ink repellent layer can be formed.
  • molecules that have not reacted have a hydroxyl group, and are therefore less likely to remain in the opening partitioned by the partition during development.
  • the photopolymerization initiator (B1) is decomposed by subsequent heating, and the photo-curing alkali-soluble resin (A) or The ink repellent agent (C) component reacts to form a residue that cannot be decomposed by UV ozone later.
  • the photopolymerization initiator (B1) of the present invention is washed away from the opening during development, when the ink is dropped into the opening by inkjet, the ink spreads to the base material better. it is conceivable that.
  • the cured resin film of the embodiment of the present invention is formed using the above-described negative photosensitive resin composition of the present invention.
  • the cured resin film according to the embodiment of the present invention is, for example, coated with the negative photosensitive resin composition of the present invention on the surface of a substrate such as a substrate, dried as necessary to remove the solvent, and then exposed. Is obtained by curing.
  • the cured resin film of the embodiment of the present invention exhibits a particularly remarkable effect when used for an optical element, particularly an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell.
  • the partition wall of the present invention is a partition wall made of the above-described cured film of the present invention formed so as to partition the substrate surface into a plurality of sections for dot formation.
  • the partition wall is obtained by masking a portion to be a dot formation partition before exposure, developing after exposure. By development, an unexposed portion is removed by masking, and an opening corresponding to a dot forming section is formed together with a partition.
  • the partition wall according to the embodiment of the present invention is particularly effective when used for an optical element, particularly an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell.
  • the manufacturing method of the partition wall is not limited to the following.
  • the following manufacturing methods are demonstrated as a negative photosensitive resin composition containing a solvent (F).
  • a negative photosensitive resin composition is applied to one entire main surface of the substrate 1 to form a coating film 21.
  • the ink repellent agent (C) is totally dissolved and uniformly dispersed in the coating film 21.
  • the ink repellent agent (C) is schematically shown, and does not actually exist in such a particle shape.
  • the coating film 21 is dried to form a dry film 22.
  • the drying method include heat drying, reduced pressure drying, and reduced pressure heat drying.
  • the heating temperature is preferably 50 to 120 ° C. in the case of heat drying.
  • the ink repellent agent (C) moves to the upper layer of the dry film.
  • the upper surface transfer of an ink repellent agent (C) is similarly achieved within a coating film.
  • the dry film 22 is exposed to light through a photomask 30 having a masking portion 31 having a shape corresponding to the opening surrounded by the partition walls.
  • the film after the dry film 22 is exposed is referred to as an exposure film 23.
  • the exposed portion 23 ⁇ / b> A is photocured, and the non-exposed portion 23 ⁇ / b> B is in the same state as the dry film 22.
  • excimer laser such as visible light; ultraviolet light; far ultraviolet light; KrF excimer laser light, ArF excimer laser light, F 2 excimer laser light, Kr 2 excimer laser light, KrAr excimer laser light, and Ar 2 excimer laser light.
  • Examples include light; X-ray; electron beam.
  • the light to be irradiated is preferably light having a wavelength of 100 to 600 nm, more preferably light having a wavelength of 300 to 500 nm, particularly preferably light containing i-line (365 nm), h-line (405 nm) or g-line (436 nm). Moreover, you may cut light below 330 nm as needed.
  • the exposure method includes full-surface batch exposure, scan exposure, and the like. You may expose in multiple times with respect to the same location. At this time, the multiple exposure conditions may or may not be the same.
  • Exposure amount In any of the above exposure method, for example, preferably 5 ⁇ 1,000mJ / cm 2, more preferably 5 ⁇ 500mJ / cm 2, more preferably 5 ⁇ 300mJ / cm 2, 5 ⁇ 200mJ / cm 2 is particularly preferable, and 5 to 50 mJ / cm 2 is most preferable.
  • the exposure amount is appropriately optimized depending on the wavelength of light to be irradiated, the composition of the negative photosensitive resin composition, the thickness of the coating film, and the like.
  • the exposure time per unit area is not particularly limited, and is designed from the exposure power of the exposure apparatus to be used, the required exposure amount, and the like. In the case of scan exposure, the exposure time is determined from the light scanning speed.
  • the exposure time per unit area is usually about 1 to 60 seconds.
  • FIG. 1D shows a state after the non-exposed portion 23B is removed by development.
  • the non-exposed portion 23B is dissolved and removed with an alkali developer in a state where the ink repellent agent (C) is transferred to the upper layer portion and the ink repellent agent (C) is hardly present in the lower layer. Therefore, the ink repellent agent (C) hardly remains in the opening 5.
  • the uppermost layer including the upper surface is the ink repellent layer 4A.
  • the ink repellent agent (C) does not have a side chain having an ethylenic double bond
  • the ink repellent agent (C) is present in a high concentration as it is in the uppermost layer and becomes an ink repellent layer.
  • the alkali-soluble resin or the like (A) present in the vicinity of the ink repellent agent (C), the thiol compound (G) optionally contained, and other photocuring components are strongly photocured and ink repellent.
  • the agent (C) is fixed to the ink repellent layer.
  • the ink repellent agent (C) When the ink repellent agent (C) has a side chain having an ethylenic double bond, the ink repellent agent (C) is mutually and / or alkali-soluble resin (A), and further optionally contains a thiol compound (G) or It is photocured together with other photocuring components to form an ink repellent layer 4A in which the ink repellent agent (C) is firmly bonded.
  • the ink repellent layer 4A has an ink-repellent layer on the lower side of the ink-repellent layer 4A, in which mainly the alkali-soluble resin (A) and the thiol compound (G) optionally contained, and other photocurable components are photocured.
  • a layer 4B containing almost no agent (C) is formed. In this manner, the ink repellent agent (C) is sufficiently fixed to the partition including the ink repellent layer 4A and the lower layer 4B, and therefore hardly migrates to the opening during development.
  • the partition 4 may be further heated after development.
  • the heating temperature is preferably 130 to 250 ° C.
  • the partition 4 is hardened by heating. Further, the ink repellent agent (C) is more firmly fixed in the ink repellent layer 4A.
  • the cured resin film and the partition 4 of the present invention thus obtained have good ink repellency on the upper surface even when exposure is performed at a low exposure amount.
  • the ink repellent (C) hardly exists in the opening 5 after development, and the uniform coating property of the ink in the opening 5 can be sufficiently secured.
  • the substrate 1 with the partition walls 4 may be subjected to ultraviolet / ozone treatment.
  • the width of the partition formed from the negative photosensitive resin composition of the present invention is preferably 100 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
  • the distance between adjacent partition walls (pattern width) is preferably 300 ⁇ m or less, and particularly preferably 100 ⁇ m or less.
  • the height of the partition wall is preferably 0.05 to 50 ⁇ m, particularly preferably 0.2 to 10 ⁇ m.
  • the partition formed from the negative photosensitive resin composition of the present invention has few irregularities in the edge portion when formed to the above width, and is excellent in linearity.
  • the high linearity in the partition walls is particularly remarkable when a resin (A-2) in which an acidic group and an ethylenic double bond are introduced into an epoxy resin is used as the alkali-soluble resin.
  • A-2 a resin in which an acidic group and an ethylenic double bond are introduced into an epoxy resin
  • the partition of the present invention can be used as a partition having the opening as an ink injection region when pattern printing is performed by the IJ method.
  • pattern printing is performed by the IJ method
  • the partition wall of the present invention is formed and used so that the opening thereof coincides with a desired ink injection region, the partition top surface has good ink repellency. It is possible to suppress ink from being injected into an undesired opening, that is, an ink injection region beyond the partition wall.
  • the opening surrounded by the partition wall has good ink wetting and spreading properties, it is possible to print the ink uniformly without causing white spots or the like in a desired region.
  • the barrier rib of the present invention is an optical element having a barrier rib positioned between a plurality of adjacent dots on the surface of a substrate on which dots are formed by the IJ method, particularly an organic EL element, a quantum dot display, a TFT array, or a thin film solar. It is useful as a battery partition.
  • an organic EL element As an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell as an optical element of the present invention, an organic EL element having a plurality of dots and a partition wall of the present invention located between adjacent dots on the substrate surface, Quantum dot display, TFT array or thin film solar cell.
  • the dots are preferably formed by the IJ method.
  • the organic EL element has a structure in which a light emitting layer of an organic thin film is sandwiched between an anode and a cathode.
  • the partition wall of the present invention is used for a partition wall separating an organic light emitting layer, a partition wall partition separating an organic TFT layer, and a coating type oxide semiconductor. It can be used for partitioning applications.
  • the organic TFT array element is a semiconductor layer including a plurality of dots arranged in a matrix in plan view, each pixel having a pixel electrode and a TFT as a switching element for driving it, and including a TFT channel layer.
  • the organic TFT array element is provided as a TFT array substrate in, for example, an organic EL element or a liquid crystal element.
  • an organic EL element for example, an organic EL element, an example in which dots are formed in the opening by the IJ method using the partition obtained above will be described below.
  • the formation method of the dot in optical elements is not limited to the following. 2A and 2B schematically show a method of manufacturing an organic EL element using the partition walls 4 formed on the substrate 1 shown in FIG. 1D.
  • the partition 4 on the substrate 1 is formed such that the opening 5 matches the dot pattern of the organic EL element to be manufactured.
  • ink 10 is dropped from the inkjet head 9 into the opening 5 surrounded by the partition wall 4 and a predetermined amount of ink 10 is injected into the opening 5.
  • known inks for organic EL elements are appropriately selected and used in accordance with the function of dots.
  • An optical element (an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell) according to an embodiment of the present invention uses the partition wall of the present invention so that ink is unevenly distributed in an opening partitioned by the partition wall in the manufacturing process. It is an optical element (organic EL element, quantum dot display, TFT array, or thin film solar cell) having dots that are formed with high precision.
  • an organic EL element can be manufactured as follows, for example, it is not limited to this.
  • a light-transmitting electrode such as tin-doped indium oxide (ITO) is formed on a light-transmitting substrate such as glass by a sputtering method or the like.
  • the translucent electrode is patterned as necessary.
  • partition walls are formed in a lattice shape in plan view along the outline of each dot by photolithography including coating, exposure and development.
  • the materials for the hole injection layer, the hole transport layer, the light emitting layer, the hole blocking layer, and the electron injection layer are respectively applied and dried in the dot formation openings by the IJ method.
  • Laminate The kind and number of organic layers formed in the opening for forming dots are appropriately designed.
  • a reflective electrode such as aluminum or a translucent electrode such as ITO is formed by vapor deposition or the like.
  • the quantum dot display can be manufactured, for example, as follows, but is not limited thereto.
  • a light-transmitting electrode such as ITO is formed on a light-transmitting substrate such as glass by a sputtering method or the like.
  • the translucent electrode is patterned as necessary.
  • partition walls are formed in a lattice shape in plan view along the outline of each dot by photolithography including coating, exposure and development.
  • the materials for the hole injection layer, the hole transport layer, the quantum dot layer, the hole blocking layer, and the electron injection layer are applied and dried in the dot formation openings by the IJ method. Laminate sequentially. The kind and number of organic layers formed in the opening for forming dots are appropriately designed.
  • a reflective electrode such as aluminum or a translucent electrode such as ITO is formed by vapor deposition or the like.
  • optical element of the embodiment of the present invention can be applied to, for example, a blue light conversion type quantum dot display manufactured as follows.
  • the negative photosensitive resin composition of the present invention is used for a light-transmitting substrate such as glass, and partition walls are formed in a lattice shape in plan view along the outline of each dot.
  • a liquid crystal display having excellent color reproducibility can be obtained by using a light source that emits blue light as a backlight and using the module as a color filter alternative.
  • the TFT array can be manufactured, for example, as follows, but is not limited thereto.
  • a gate electrode such as aluminum or an alloy thereof is formed on a light-transmitting substrate such as glass by a sputtering method or the like. This gate electrode is patterned as necessary.
  • a gate insulating film such as silicon nitride is formed by a plasma CVD method or the like.
  • a source electrode and a drain electrode may be formed over the gate insulating film.
  • the source electrode and the drain electrode can be produced by forming a metal thin film such as aluminum, gold, silver, copper, or an alloy thereof by, for example, vacuum deposition or sputtering.
  • a resist is coated, exposed and developed to leave the resist in a portion where the electrode is to be formed, and then exposed with phosphoric acid or aqua regia. There is a method of removing the metal and finally removing the resist.
  • the source electrode and the drain electrode may be formed by a method such as ink jet using a metal nanocolloid such as silver or copper.
  • partition walls are formed in a lattice pattern in plan view along the outline of each dot by a photolithography method including coating, exposure, and development.
  • a semiconductor solution is applied in the dot forming openings by the IJ method, and the semiconductor layer is formed by drying the solution.
  • this semiconductor solution an organic semiconductor solution or an inorganic coating type oxide semiconductor solution can also be used.
  • the source electrode and the drain electrode may be formed by using a method such as inkjet after forming the semiconductor layer.
  • a transparent electrode such as ITO is formed by sputtering or the like, and a protective film such as silicon nitride is formed.
  • Examples 1 to 10 are examples, and examples 11 to 15 are comparative examples.
  • PGMEA is an abbreviation for propylene glycol monomethyl ether acetate.
  • A-1 A resin obtained by reacting a cresol novolac type epoxy resin with acrylic acid and then with 1,2,3,6-tetrahydrophthalic anhydride to introduce a acryloyl group and a carboxyl group, and purifying the resin with hexane, solid content 70% by mass, acid value 60 mgKOH / g.
  • A-2 A resin in which a carboxyl group and an ethylenic double bond are introduced into a bisphenol A type epoxy resin, solid content 70% by mass, acid value 60 mgKOH / g.
  • A-3 A resin in which a carboxyl group and an ethylenic double bond are introduced into a bisphenol F type epoxy resin, solid content 70% by mass, acid value 60 mgKOH / g.
  • A-4 A resin in which an ethylenic double bond and an acidic group are introduced into an epoxy resin having a biphenyl skeleton represented by the following formula (Aa), solid content: 50% by mass, acid value 60 mgKOH / g.
  • B1-1 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one.
  • B1-2 1,1 ′-(methylene-di-4,1-phenylene) bis [2-hydroxy-2-methyl-1-propanone].
  • Photopolymerization initiator (B2)) B2-1 4,4′-bis (diethylamino) benzophenone.
  • MAA methacrylic acid.
  • 2-HEMA 2-hydroxyethyl methacrylate.
  • V-65 2,2′-azobis (2,4-dimethylvaleronitrile).
  • n-DM n-dodecyl mercaptan.
  • BEI 1,1- (bisacryloyloxymethyl) ethyl isocyanate.
  • DBTDL Dibutyltin dilaurate.
  • TBQ t-butyl-p-benzoquinone.
  • MEK 2-butanone.
  • D-1 Dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate.
  • D-2 Monomer (10 functional) having a urethane skeleton in which HDI (hexamethylene diisocyanate) is bonded to dipentaerythritol pentaacrylate.
  • PGME Propylene glycol monomethyl ether.
  • PGMEA Propylene glycol monomethyl ether acetate.
  • EDGAC Diethylene glycol monoethyl ether acetate.
  • EDM Diethylene glycol ethyl methyl ether.
  • Example 1 Production of negative photosensitive resin composition and production of cured resin film and partition wall] (Manufacture of negative photosensitive resin composition) 0.12 g of (C-1) obtained in Synthesis Example 1 above, 19.3 g of A-1 (solid content is 14.2 g, the rest is EDGAC as a solvent), 1.2 g of B1-2, D- 9.5 g of No. 1 and 68.9 g of PGME were placed in a 200 cm 3 stirring vessel and stirred for 5 hours to produce a negative photosensitive resin composition.
  • Table 1 shows the solid content concentration, the content (composition) of each component in the solid content, and the content (composition) of each component in the solvent.
  • the negative photosensitive resin composition was applied to the cleaned ITO substrate surface using a spinner and then dried on a hot plate at 100 ° C. for 2 minutes to form a dry film having a thickness of 2.4 ⁇ m. .
  • a photomask having an opening pattern opening portions 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20,
  • the exposure power (exposure output) in terms of 365 nm is 25 mW / cm 2 through a pattern of 30, 40, 50 ⁇ m ⁇ 1000 ⁇ m (with a pattern spacing of 50 ⁇ m repeated in a 20 mm ⁇ 20 mm range).
  • the entire surface was irradiated with UV light from an ultra-high pressure mercury lamp. During the exposure, light of 330 nm or less was cut.
  • the distance between the dry film and the photomask was 50 ⁇ m.
  • the exposure conditions are evaluated such that when the exposure amount is 50 mJ / cm 2 , the exposure time is 2 seconds, and when the exposure amount is 80 mJ / cm 2 , the exposure time is 3.2 seconds. Changed according to the content.
  • the ITO substrate after the exposure treatment was developed by immersing it in a 0.4 mass% tetramethylammonium hydroxide aqueous solution for 40 seconds, and the non-exposed portion was washed away with water and dried.
  • an ITO substrate with a cured film (partition wall) having a pattern corresponding to the opening pattern of the photomask was obtained by heating on a hot plate at 230 ° C. for 60 minutes.
  • a dry film is formed on the ITO substrate surface in the same manner as described above, and a photomask (a light shielding portion size: 100 ⁇ m ⁇ 200 ⁇ m and an opening width: 20 ⁇ m is repeated in a range of 20 mm ⁇ 20 mm).
  • the exposure condition is 150 mJ / cm 2 , and then the development is performed under the same conditions as the above development conditions.
  • the film is heated on a hot plate at 230 ° C. for 60 minutes to obtain a line width of 20 ⁇ m.
  • An ITO substrate with a cured resin film 2 was obtained in a pattern that surrounded the opening for dot formation (100 ⁇ m ⁇ 200 ⁇ m) with the partition walls.
  • Examples 2 to 15 A negative photosensitive resin composition, a cured resin film, and a partition wall were produced in the same manner as in Example 1 except that the negative photosensitive resin composition was changed to the compositions shown in Tables 1 and 2.
  • Liquid epoxy ME-562 (Nippon Pernox) (6.25 g), curing agent HV-562 (Nippon Pernox) (6.25 g), diethyl adipate (12.5 g) and diethyl malonate (25.0 g) ) was stirred and mixed using a stirrer for 1 hour to prepare an ink.
  • the PGMEA contact angle of the partition wall upper surface exposure amount was obtained in 50 mJ / cm 2 and 80 mJ / cm 2 with the resin cured film 1 were measured by the above method.
  • Photomask having an opening pattern of the cured resin film 1 (openings are 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 30, 40, respectively. , 50 ⁇ m ⁇ 1000 ⁇ m), the partition wall obtained with an exposure dose of 150 mJ / cm 2 is observed with a microscope, and when a line with a mask width of less than 10 ⁇ m remains, a line with a width of 10 ⁇ m or more and less than 20 ⁇ m remains. A when the line is 20 ⁇ m or more and less than 50 ⁇ m remains B, and C is when the pattern is not larger than 50 ⁇ m.
  • the negative photosensitive resin composition of the present invention can be suitably used as a composition for forming barrier ribs when performing pattern printing by the IJ method in organic EL elements, quantum dot displays, TFT arrays, or thin film solar cells. it can.
  • the barrier ribs of the present invention are barrier ribs (banks) for pattern printing of organic layers such as light-emitting layers by the IJ method in organic EL elements, or quantum dot layers and hole transport layers in the quantum dot display by the IJ method. It can be used as a partition (bank) for pattern printing.
  • the partition wall of the present invention can also be used as a partition wall for printing a conductor pattern or a semiconductor pattern by the IJ method in a TFT array.
  • the partition wall of the present invention can be used as a partition wall for pattern printing of the organic semiconductor layer, the gate electrode, the source electrode, the drain electrode, the gate wiring, the source wiring, and the like forming the channel layer of the TFT by the IJ method.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne : une composition de résine photosensible de type négatif destinée à un élément optique, présentant une bonne aptitude à repousser l'encre et permettant de réduire la formation de résidus dans une ouverture ; un film de résine durci destiné à un élément optique et présentant une bonne aptitude à repousser l'encre ; une séparation destinée à un élément optique et permettant de former un motif d'une grande précision ; et un élément optique comprenant la séparation. La composition de résine photosensible de type négatif renferme une résine photodurcissable soluble dans les alcalis ou un monomère photodurcissable soluble dans les alcalis, un initiateur de photopolymérisation comprenant un composé α-hydroxyalkylphénone et un agent repoussant l'encre. La présente invention porte également sur un film durci formé à l'aide de la composition de résine photosensible de type négatif, une séparation, un élément électroluminescent organique comprenant une pluralité de points et la séparation placée entre des points adjacents sur une surface formant substrat, un affichage à points quantiques, une matrice TFT et une cellule solaire en couches minces.
PCT/JP2016/074149 2015-08-21 2016-08-18 Composition de résine photosensible de type négatif, film de résine durci, séparation, élément optique et procédé de fabrication associé WO2017033834A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009048200A (ja) * 2002-11-06 2009-03-05 Asahi Glass Co Ltd 撥インク剤
JP2009053445A (ja) * 2007-08-27 2009-03-12 The Inctec Inc カラーフィルタ保護膜用樹脂組成物、及びカラーフィルタ
JP2011128239A (ja) * 2009-12-16 2011-06-30 Jsr Corp 着色組成物、カラーフィルタおよびカラー液晶表示素子
JP2013209636A (ja) * 2012-03-02 2013-10-10 Fujifilm Corp 撥液性処理剤、撥液性膜、撥水性領域と親水性領域とを有する部材及びその製造方法、並びに機能性材料のパターンが形成された部材の製造方法
WO2014084279A1 (fr) * 2012-11-28 2014-06-05 旭硝子株式会社 Composition de résine photosensible négative, film de résine durci, cloison de séparation et élément optique
WO2014132928A1 (fr) * 2013-02-28 2014-09-04 富士フイルム株式会社 Composition destinée à former une couche de résine transparente, couche de résine transparente, élément d'imagerie à semi-conducteurs et dispositif optoélectronique

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009048200A (ja) * 2002-11-06 2009-03-05 Asahi Glass Co Ltd 撥インク剤
JP2009053445A (ja) * 2007-08-27 2009-03-12 The Inctec Inc カラーフィルタ保護膜用樹脂組成物、及びカラーフィルタ
JP2011128239A (ja) * 2009-12-16 2011-06-30 Jsr Corp 着色組成物、カラーフィルタおよびカラー液晶表示素子
JP2013209636A (ja) * 2012-03-02 2013-10-10 Fujifilm Corp 撥液性処理剤、撥液性膜、撥水性領域と親水性領域とを有する部材及びその製造方法、並びに機能性材料のパターンが形成された部材の製造方法
WO2014084279A1 (fr) * 2012-11-28 2014-06-05 旭硝子株式会社 Composition de résine photosensible négative, film de résine durci, cloison de séparation et élément optique
WO2014132928A1 (fr) * 2013-02-28 2014-09-04 富士フイルム株式会社 Composition destinée à former une couche de résine transparente, couche de résine transparente, élément d'imagerie à semi-conducteurs et dispositif optoélectronique

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