WO2022172605A1 - ネガ型感光性組成物、硬化膜、有機ｅｌ表示装置および硬化膜の製造方法 - Google Patents

ネガ型感光性組成物、硬化膜、有機ｅｌ表示装置および硬化膜の製造方法 Download PDF

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WO2022172605A1
WO2022172605A1 PCT/JP2021/047273 JP2021047273W WO2022172605A1 WO 2022172605 A1 WO2022172605 A1 WO 2022172605A1 JP 2021047273 W JP2021047273 W JP 2021047273W WO 2022172605 A1 WO2022172605 A1 WO 2022172605A1
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formula
photosensitive composition
group
negative photosensitive
molecule
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French (fr)
Japanese (ja)
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石川暁宏
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Toray Industries Inc
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Toray Industries Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • 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 [2D] 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 [2D] radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional [2D] 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
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • H10K59/8792—Arrangements for improving contrast, e.g. preventing reflection of ambient light comprising light absorbing layers, e.g. black layers

Definitions

  • the present invention relates to a negative photosensitive composition, a cured film, an organic EL display device, and a method for producing a cured film.
  • An organic EL display device is a self-luminous display device that emits light by recombination energy of electrons injected from a cathode and holes injected from an anode. Pixels are formed in openings in a patterned pixel dividing layer that functions as an insulating layer.
  • Patent Document 1 discloses, for example, a negative photosensitive composition containing a (meth)acrylate compound having a fluorene skeleton or an indane skeleton, a polyimide resin, and a black pigment.
  • a (meth)acrylate compound having a fluorene skeleton or an indane skeleton a polyimide resin, and a black pigment.
  • Patent Document 1 it is possible to form a pixel division layer having both high light shielding properties and a low taper angle.
  • the negative photosensitive composition disclosed in Patent Document 2 can form a pixel dividing layer by development using a low-concentration inorganic alkaline aqueous solution, the driving voltage is high, and a black pigment is added to impart light-shielding properties. In this case, there is a problem that the driving voltage becomes higher.
  • the negative photosensitive composition disclosed in Patent Document 3 also has a problem of high driving voltage.
  • the present invention provides (a) a (meth)acrylate compound having one 9,9-bisarylfluorene skeleton in the molecule and one structure represented by formula (1) in the molecule, and an adamantane skeleton in the molecule.
  • a (meth)acrylate compound having one 9,9-bisarylfluorene skeleton in the molecule and one structure represented by formula (1) in the molecule, and an adamantane skeleton in the molecule One or more selected from the group consisting of (meth) acrylate compounds having one or two structures represented by formula (1) in the molecule, and salts thereof, and (b ) is a negative photosensitive composition containing a photopolymerization initiator.
  • R 1 represents a divalent hydrocarbon group having 2 to 8 carbon atoms. * represents a bonding site with an oxygen atom.
  • the negative photosensitive composition of the present invention it is possible to form a pixel division layer that can be developed with a low-concentration inorganic alkaline aqueous solution and that achieves both a low taper angle and a low driving voltage for an organic EL display device. can be done.
  • FIG. 4 is a cross-sectional view showing taper angles ⁇ of pixel division layers in all examples and comparative examples.
  • a numerical range represented using “to” means a range including the numerical values described before and after “to” as lower and upper limits.
  • a pixel division layer means a pixel division layer provided in an organic EL display device. Visible light means light with a wavelength of 380 nm or more and less than 780 nm, and near-ultraviolet means light with a wavelength of 200 nm or more and less than 380 nm.
  • the term “light shielding” refers to the ability to reduce the intensity of transmitted light compared to the intensity of light incident on the cured film in the vertical direction, and the term “light shielding property” refers to the extent to which visible light is shielded.
  • the photosensitive composition means an alkali-developable photosensitive composition having sensitivity to near-ultraviolet rays.
  • the weight average molecular weight (Mw) is a value analyzed by gel permeation chromatography using tetrahydrofuran as a carrier and converted using a standard polystyrene calibration curve.
  • C.I used in the names of some coloring materials is an abbreviation for Color Index Generic Name, and based on the Color Index published by The Society of Dyers and Colorists, regarding coloring materials registered in the Color Index , Color Index Generic Name represents the chemical structure and crystal form of a pigment or dye.
  • C.I. I. Carbon black classified as Pigment Black 7 is classified as an inorganic black pigment.
  • the total solid content means the proportion (% by weight) of components excluding solvent and water in the negative photosensitive composition.
  • the present inventors have made intensive studies on the structure of the photopolymerizable monomer component that contributes to the reduction of the driving voltage while taking advantage of the excellent hydrophobicity, rigidity and heat resistance of the fluorene skeleton and the adamantane skeleton. It has been found that meth)acrylate compounds are extremely effective in solving the aforementioned problems.
  • the present invention provides (a) a (meth)acrylate compound having one 9,9-bisarylfluorene skeleton in the molecule and one structure represented by formula (1) in the molecule, an adamantane skeleton having one or two in the molecule and one or more selected from the group consisting of (meth)acrylate compounds having one structure represented by formula (1) in the molecule, and salts thereof; (b) a negative photosensitive composition containing a photopolymerization initiator;
  • R 1 represents a divalent hydrocarbon group having 2 to 8 carbon atoms. * represents a bonding site with an oxygen atom.
  • the negative photosensitive composition of the present invention contains the above component (a).
  • Component (a) has three effects due to its characteristic structure.
  • the first effect is to suppress the occurrence of a gouged cross-sectional shape, that is, an undercut that can occur due to excessive dissolution of the film bottom compared to the film surface in the development process using a low-concentration inorganic alkaline aqueous solution. As a result, a developed film having a low taper angle can be obtained.
  • a second effect it is possible to form a pixel division layer that exhibits appropriate reflowability in a curing step, which will be described later, and has a taper angle that is even lower than that of the developed film.
  • As a third effect it becomes possible to reduce the driving voltage in an organic EL display device having a pixel division layer.
  • Lowering the driving voltage can reduce the burden on the light-emitting element, extend the light-emitting life, and reduce power consumption, thereby improving the value of the organic EL display device.
  • a developing solution used for manufacturing a color filter composed of a transmissive pixel portion containing red, green and blue and a black matrix is usually a low-concentration inorganic alkaline aqueous solution, and an organic EL display device comprising a color filter and a pixel dividing layer. is more economically advantageous because processes such as the type of developer, developing device and waste liquid treatment device can be shared.
  • the 9,9-bisarylfluorene skeleton possessed by the compound belonging to component (a) means the skeleton represented by formula (2).
  • Z represents an aryl group having a substituent.
  • a skeleton composed of two phenyl groups having substituents and one fluorene skeleton is preferable from the viewpoint of low driving voltage, that is, a 9,9-bisphenylfluorene skeleton is preferable.
  • the adamantane skeleton possessed by the compound belonging to component (a) means the skeleton represented by formula (37).
  • a (meth)acrylate compound means a compound having a methacryloxy group and/or an acryloxy group. Accordingly, the compounds belonging to component (a) have methacryloxy groups and/or acryloxy groups. These functional groups function as radically polymerizable groups that are crosslinked by radical active species (b) generated from the photopolymerization initiator in the exposure step described later. In other words, it is a functional group serving as a source of negative photosensitivity, which renders the exposed portion of the film insoluble in a developer and removes the unexposed portion of the film to obtain a patterned developed film.
  • the total number of methacryloxy groups and/or acryloxy groups that the compound belonging to component (a) has in one molecule is preferably 2 or more in order to suppress undercutting due to overdevelopment at the bottom of the film. It is preferably 4 or less, more preferably 2 or less, in order to obtain appropriate reflowability in the curing step described later and to form a pixel division layer with a small taper angle at the edge of the opening. That is, the negative photosensitive composition of the present invention has (a) one 9,9-bisarylfluorene skeleton in the molecule and one structure represented by formula (1) in the molecule.
  • the structure represented by formula (1) is preferably a structure derived from a dicarboxylic acid anhydride from the viewpoint of reactivity when synthesizing a compound belonging to component (a).
  • dicarboxylic anhydride examples include maleic anhydride (the number of carbon atoms in R 1 in formula (1) obtained after the reaction: 2), succinic anhydride (in formula (1) obtained after the reaction, R 1 number of carbon atoms: 2), 1-cyclopentene-1,2-dicarboxylic anhydride (in formula (1) obtained after the reaction, number of carbon atoms in R 1 : 5), 1,2,3,6-tetrahydrophthalic acid anhydride (in formula (1) obtained after the reaction, carbon number of R 1 : 6), 3,4,5,6-tetrahydrophthalic anhydride (in formula (1) obtained after the reaction, carbon of R 1 number: 6), 1,2-cyclohexanedicarboxylic anhydride (carbon number of R 1 in formula (1) obtained after the reaction: 6), cis-4-cyclohexene-1,2-dicarboxylic anhydride (in the formula (1) obtained after the reaction, the number of carbon atoms in R 1 : 6), phthalic anhydride (the number of
  • At least part of component (a) may exist in the form of a salt in the negative photosensitive composition.
  • Types of salts include ammonium salts, amine salts or metal salts.
  • An ammonium salt is preferable from the viewpoint of lowering the driving voltage, and a specific example is a form in which an ammonium cation forms a salt with the carboxyl group in the structure represented by the above formula (1).
  • ammonium salts include tetramethylammonium salt, tetraethylammonium salt, tetra-n-propylammonium salt, tetraisopropylammonium salt, tetra-n-butylammonium salt, tetra-sec-butylammonium salt, tetra-tert-butylammonium salt, Tetra n-pentylammonium salt, tetra n-hexylammonium salt, tetraheptylammonium salt, trimethylmonoethylammonium salt, triethylmonoethylammonium salt, tri-n-propylmonomethylammonium salt, tri-n-propylmonoethylammonium salt, trimethyl monophenylammonium salts and trimethylmonobenzylammonium salts. These ammonium salts may be derived, for example, from te
  • a compound obtained by addition of a compound is preferred, and specifically a compound represented by formula (3) is preferred.
  • the negative photosensitive composition of the present invention has one 9,9-bisarylfluorene skeleton in the molecule as the component (a), and one structure represented by formula (1) in the molecule.
  • the component (a) preferably contains a compound represented by formula (3) and/or a salt thereof in order to reduce the driving voltage.
  • a and b are integers and each independently represents 0 or 1.
  • R2 and R3 each independently represent an ethylene group or a propylene group.
  • c and d are integers each independently representing 0 to 3;
  • R4 and R5 each independently represent a hydrogen atom or a methyl group.
  • One of R 6 and R 7 is a hydrogen atom and the other is a structure represented by formula (4).
  • R 8 and R 9 each independently represent an alkyl group having 1 to 3 carbon atoms.
  • e and f are integers each independently representing 0 to 2;
  • R 10 represents a divalent hydrocarbon group having 2 to 8 carbon atoms. * represents a bonding site with an oxygen atom.
  • the integers a, b, c, and d are all preferably 0 from the viewpoint of lowering the driving voltage. Both R4 and R5 are preferably hydrogen atoms to obtain a low taper angle. When integers c and d are 1 to 3, both R 2 and R 3 are preferably ethylene groups. Both R 8 and R 9 are preferably methyl groups.
  • Specific examples of the divalent hydrocarbon group R 10 include the same dicarboxylic anhydride-derived structure group as R 1 in the above formula (1). 2 to 6 are preferable from the viewpoint of chemical conversion, and it is more preferable to have an alicyclic structure. As a specific example in the case of a salt, the same viewpoint as described above can be applied, and an ammonium salt is preferred.
  • the negative photosensitive composition of the present invention has one 9,9-bisarylfluorene skeleton as the component (a) in the molecule, and has one structure represented by formula (1) in the molecule (
  • component (a) contains a compound represented by formula (5) and/or a salt thereof, from the viewpoint of lowering the driving voltage.
  • R 11 and R 12 each independently represent a hydrogen atom or a methyl group.
  • One of R 13 and R 14 is a hydrogen atom, and the other represents a structure represented by formula (6), a structure represented by formula (7), or a structure represented by formula (8).
  • R 15 and R 16 represent a methyl group.
  • g and h are integers each independently representing 0 to 2;
  • * represents a bonding site with an oxygen atom.
  • a salt the same viewpoint as described above can be applied, and an ammonium salt is preferred.
  • adamantane skeleton in the molecule Of the two hydroxyl groups of a (meth)acrylate compound obtained by derivatizing an adamantane compound having one or two epoxy groups and two epoxy groups in the molecule with (meth)acrylic acid, one hydroxyl group is dicarboxylic.
  • a compound obtained by adding an acid anhydride is preferable, and specifically, a compound having a structure represented by formula (38) or a structure represented by formula (39) or a salt thereof is preferable.
  • the negative photosensitive composition of the present invention has, as the component (a), one or two adamantane skeletons in the molecule and one structure represented by formula (1) in the molecule (
  • the component (a) When containing a meth) acrylate compound or a salt thereof, from the viewpoint of low driving voltage, it has one or two adamantane skeletons in the molecule and has one structure represented by formula (1) in the molecule.
  • the (meth)acrylate compound preferably has a structure represented by formula (38) or a structure represented by formula (39).
  • the negative photosensitive composition of the present invention has, as the component (a), one or two adamantane skeletons in the molecule and one structure represented by formula (1) in the molecule ( More preferably, the meth)acrylate compound has a structure represented by formula (38).
  • n1 is an integer and represents 1 or 2.
  • n2 is an integer and represents 0 or 1;
  • R 22 represents an alkyl group having 1 to 3 carbon atoms. * represents a bonding site with a carbon atom.
  • n3 and n4 are integers and represent 0 or 1.
  • R 23 and R 24 each independently represent an alkyl group having 1 to 3 carbon atoms. * represents a bonding site with a carbon atom.
  • the compound having the structure represented by formula (38) or a salt thereof may contain a compound represented by formula (40) as component (a) and/or a salt thereof, from the viewpoint of lowering the driving voltage. preferable.
  • the negative photosensitive composition of the present invention preferably contains (a) a (meth)acrylate compound represented by formula (40) and/or a salt thereof.
  • n5 and n6 are integers and each independently represents 0 or 1.
  • R25 and R26 each independently represent an ethylene group or a propylene group.
  • One of R 27 and R 28 is a hydrogen atom and the other is a structure represented by formula (41).
  • n7 is an integer and represents 1 or 2.
  • n8 is an integer and represents 0 or 1.
  • R29 and R30 each independently represent a hydrogen atom or a methyl group.
  • R 31 represents an alkyl group having 1 to 3 carbon atoms.
  • R 32 represents a divalent hydrocarbon group having 2 to 8 carbon atoms. * represents a bonding site with an oxygen atom.
  • Both R29 and R30 are preferably hydrogen atoms in order to obtain a low taper angle.
  • R25 and R26 are preferably ethylene groups from the viewpoint of low driving voltage.
  • Specific examples of the divalent hydrocarbon group R 32 include the same dicarboxylic anhydride-derived structure group as R 1 in the above formula (1). 2 to 6 are preferable from the viewpoint of chemical conversion, and it is more preferable to have an alicyclic structure.
  • a salt the same viewpoint as described above can be applied, and an ammonium salt is preferred.
  • the compounds belonging to the above component (a) may be used singly or in combination.
  • the content of component (a) is preferably 5 to 95% by weight of the total solid content in the negative photosensitive composition in order to achieve both a low taper angle and a low driving voltage.
  • the component (a) contained in the negative photosensitive composition of the present invention can be confirmed by known analytical techniques such as proton nuclear magnetic resonance spectroscopy (hereinafter, “ 1 H-NMR”), LC-MS, etc. Structure can be specified.
  • a (meth)acrylate compound having one 9,9-bisarylfluorene skeleton in the molecule and one structure represented by formula (1) in the molecule is, for example, the following two-stage can be synthesized by the reaction of
  • a starting material a fluorene compound having one 9,9-bisarylfluorene skeleton in the molecule and two epoxy groups in the molecule
  • a non-reactive solvent In an active gas atmosphere, methacrylic acid and/or acrylic acid corresponding to 2 mol are added to 1 mol of the starting material and reacted to obtain an epoxy (meth)acrylate compound having a 9,9-bisarylfluorene skeleton as an intermediate product. to obtain a solution containing
  • fluorene compounds having one 9,9-bisarylfluorene skeleton in the molecule and two epoxy groups in the molecule which are starting materials, include 9,9-bis[4-(2-glycidyloxy ethoxy)phenyl]fluorene, 9,9-bis[4-(2-glycidyloxypropoxy)phenyl]fluorene, 9,9-bis[4-(2-glycidyloxyethoxy)-3-methylphenyl]fluorene, 9, 9-bis[4-(2-glycidyloxypropoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-glycidyloxyethoxy)-3,5-dimethylphenyl]fluorene, 9,9- Bis[4-(2-glycidyloxyethoxy)-3-ethylphenyl]fluorene (all manufactured by Osaka Gas Chemicals Co., Ltd.) is preferred.
  • the amount of solvent in the first reaction step is set so that the solid content in the reaction system is 10-70% by weight, preferably 20-60% by weight.
  • the liquid temperature is 50 to 130° C., preferably 70 to 110° C.
  • the heating time is 1 to 15 hours, preferably 2 to 10 hours
  • stirring is maintained in order to achieve both suppression of gelation and promotion of the reaction. and heat.
  • non-reactive solvents examples include propylene glycol monomethyl ether acetate, methoxybutyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, toluene, and xylene.
  • a thermal polymerization inhibitor such as hydroquinone and methoquinone may be used to suppress the self-polymerization of methacrylic acid and/or acrylic acid and the formation of dimers as intermediate products.
  • the amount of thermal polymerization inhibitor to be used is preferably 0.01 to 0.1% by weight based on the total amount of methacrylic acid and acrylic acid.
  • the reaction end point of the first reaction step is determined by liquid chromatography mass spectrometry (hereinafter "LC-MS") or infrared spectroscopy (hereinafter "IR”) of methacrylic acid and / or acrylic acid in the reaction system. It can be determined by confirming the disappearance. As a simpler method, it is also possible to use a method in which the point at which the acid value in the system falls below 1 mgKOH/g is regarded as the reaction end point. After reaching the reaction end point, the second reaction step is then carried out.
  • LC-MS liquid chromatography mass spectrometry
  • IR infrared spectros
  • the second reaction step 1 mol of dicarboxylic acid anhydride is further added to 1 mol of the intermediate product described above to proceed with the dehydration reaction to obtain a solution containing a compound belonging to component (a).
  • the dicarboxylic acid anhydride the group of compounds described above can be preferably applied.
  • the second reaction step may be carried out, if necessary, after isolating only the intermediate product from the solution containing the intermediate product obtained in the first reaction step and subjecting it to treatment such as purification. .
  • the reaction conditions in the second reaction step are a liquid temperature of 50 to 100°C, preferably 60 to 90°C, a heating time of 4 to 20 hours, preferably 8 to 15 hours, and heating while maintaining stirring.
  • a catalyst may be used as necessary in the first reaction step and the second reaction step.
  • a basic catalyst can be used, and examples include tertiary amines such as trimethylamine and triethylamine, A tetraalkylammonium halide can be mentioned.
  • a tetraalkylammonium halide is preferred because it functions as a phase transfer catalyst and can improve the yield of the component (a).
  • the reaction endpoint of the second reaction step can be determined by the disappearance of intermediates by LC-MS.
  • the remaining unreacted starting materials, catalysts and/or by-products are removed by isolation by silica gel chromatography, followed by drying under reduced pressure to remove the compound belonging to the component (a) to a high degree. Purity can be obtained.
  • a tetraalkylammonium halide or the like is added to the obtained solution containing the compound belonging to the component (a) to form a salt with the carboxyl group, and the halogen anion is removed by reprecipitation treatment and washing with water for purification.
  • At least part of the component (a) may be in the form of an ammonium salt.
  • potassium hydroxide, sodium hydroxide, or the like may be used to convert at least part of component (a) into the form of an alkali metal salt such as potassium salt or sodium salt.
  • a (meth)acrylate compound having one or two adamantane skeletons in the molecule and having one structure represented by formula (1) in the molecule is, for example, the aforementioned 9,9-bisarylfluorene
  • a fluorene compound having one skeleton in the molecule and two epoxy groups in the molecule a compound having one or two adamantyl groups in the molecule and two or three epoxy groups is used. It can be synthesized by a similar method including the above-described first reaction step and second reaction step, using as a starting material.
  • Examples of compounds having one or two adamantyl groups in the molecule and two or three epoxy groups, which are starting materials, include compounds represented by formula (42), and compounds represented by formula (43). a compound represented by the formula (44), a compound represented by the formula (45), a compound represented by the formula (46), a compound represented by the formula (47), a compound represented by the formula (48) Examples of commercially available products of these compounds include “Adamantate (registered trademark)” XE series (manufactured by Idemitsu Kosan Co., Ltd.).
  • a specific example of a (meth)acrylate compound having one 9,9-bisarylfluorene skeleton in the molecule and one structure represented by formula (1) in the molecule is represented by formula (49).
  • a compound represented by the formula (50) is preferable.
  • (meth) acrylate compounds having one or two adamantane skeletons in the molecule and having one structure represented by formula (1) in the molecule include compounds represented by formula (51) , a compound represented by the formula (52) is preferably mentioned.
  • the structure represented by formula (1) having one 9,9-bisarylfluorene skeleton in the molecule and one or two adamantane skeletons in the molecule For a (meth) acrylate compound or a salt thereof having one in the molecule, it has one 9,9-bisarylfluorene skeleton in the molecule and has one structure represented by formula (1) in the molecule ( It is defined as belonging to meth)acrylate compounds.
  • Compounds corresponding to this include, for example, compounds represented by formula (53).
  • the negative photosensitive composition of the present invention contains (b) a photopolymerization initiator.
  • Component (b) is not particularly limited as long as it produces radical active species upon exposure to actinic radiation and initiates photoradical polymerization reaction of the (meth)acrylate compound containing component (a).
  • component (b) examples include oxime ester-based photopolymerization initiators, alkylphenone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators.
  • an oxime ester-based photopolymerization initiator that is highly sensitive to near-ultraviolet rays is preferred.
  • an oxime ester photopolymerization initiator and a non-oxime ester photopolymerization initiator are used. It may be used together with an initiator to adjust the sensitivity.
  • oxime ester-based photopolymerization initiators include, for example, "Adekacruz (registered trademark)” NCI-831E (manufactured by ADEKA Corporation, hereinafter referred to as "NCI-831E”), and Japanese Unexamined Patent Application Publication No. 2008/100955.
  • NCI-831E is a compound having the same structure as NCI-831 described in Patent Document 1.
  • the content of the photopolymerization initiator is preferably 5 to 95% by weight based on the total solid content in the negative photosensitive composition in order to achieve both a low taper angle and a low driving voltage.
  • the negative photosensitive composition of the present invention preferably further contains a coloring agent.
  • the pixel division layer can be provided with a light-shielding property.
  • the coloring material known pigments and dyes can be used, and the (c) pigment is preferable from the viewpoint of the uniformity of the light shielding property of the pixel division layer in the substrate surface and the reduction of the driving voltage. That is, the negative photosensitive composition of the present invention preferably further contains (c) a pigment.
  • the term “pigment” as used herein does not include metal particles such as silver particles and copper particles.
  • Pigments include organic pigments and inorganic pigments, and organic pigments are preferred because of their high insulating properties and low dielectric constant.
  • organic pigments include organic black pigments, organic yellow pigments, organic orange pigments, organic red pigments, organic blue pigments, and organic purple pigments.
  • organic black pigments include lactam-based organic black pigments, perylene-based organic black pigments, and azomethine-based organic black pigments.
  • organic yellow pigments include C.I. I. Pigment Yellow 120, 138, 139, 151, 175, 180, 185, 181, 192, 193, 194.
  • organic orange pigments include C.I. I. Pigment Orange 13, 36, 43, 60, 61, 62, 64, 71, 72.
  • organic red pigments include C.I. I. Pigment Red 122, 123, 149, 178, 177, 179, 180, 189, 190, 202, 209, 254, 255, 264.
  • organic blue pigments include C.I. I.
  • organic purple pigments include C.I. I. Pigment Violet 19, 23, 29, 32, 37.
  • inorganic black pigments examples include carbon black, titanium nitride, titanium oxynitride, zirconium nitride, and zirconium oxynitride. When an inorganic black pigment is contained, carbon black is preferable. 1300, TPK1227.
  • the (c) pigment in the negative photosensitive composition of the present invention contains a lactam-based organic black pigment.
  • the lactam organic black pigment it is more preferable to further contain an organic red pigment having an anthraquinone skeleton and/or an organic blue pigment having an anthraquinone skeleton.
  • the lactam-based organic black pigment referred to here refers to an organic black pigment containing a compound having two lactam skeletons in the molecule.
  • Lactam-based organic black pigments include, for example, bis-oxodihydroindolylene-benzodifuranone described in WO 2009/010521. Among them, a lactam-based organic black pigment containing a compound represented by formula (9) is preferable from the viewpoint of low-voltage driving.
  • lactam-based organic black pigments containing the compound represented by formula (9) may be used, for example, "Irgaphor (registered trademark)" Black S0100CF and Experimental Black 582 (both manufactured by BASF). be done.
  • organic red pigments having an anthraquinone skeleton include C.I. I. Pigment Red 177
  • organic blue pigments having an anthraquinone skeleton include, for example, C.I. I. Pigment Blue 60 can be mentioned.
  • the average primary particle size of the organic pigment is preferably 10-150 nm, more preferably 40-100 nm.
  • the term "average primary particle size" as used herein refers to the number average value of primary particle sizes calculated by a particle size measurement method using an image analysis type particle size distribution analyzer.
  • As a method for obtaining a finely divided organic pigment powder there is an acid paste method in which a solution obtained by dissolving a pigment crude in concentrated sulfuric acid is mixed with a large amount of water to precipitate and granulate, or an organic pigment and a water-soluble inorganic salt are mixed together.
  • a solvent salt milling method can be applied in which a water-soluble organic solvent is kneaded under heating, and wet pulverization is performed while adjusting the particle shape by crystal growth.
  • the content of the pigment (c) is preferably 10 to 40% by weight, more preferably 15 to 30% by weight, based on the total solid content of the negative photosensitive composition, from the viewpoint of achieving both light shielding properties and low driving voltage. .
  • the negative photosensitive composition of the present invention contains (c) a pigment, it preferably further contains (d) a pigment dispersant. (d) By containing a pigment dispersant, it becomes easier to control the particle size distribution of all particle components including the (c) pigment to the desired range described later, and the (c) pigment in the negative photosensitive composition It has the effect of stabilizing the dispersion state of
  • Pigment dispersants include polymer-type dispersants and non-polymer-type dispersants, and these may be mixed and used.
  • a polymer-type dispersant is a polymer chain consisting of repeating units derived from a monomer, and at least one highly polar functional group selected from a tertiary amino group, a quaternary ammonium base, a phosphoric acid group, and a sulfo group.
  • a compound having a weight average molecular weight (Mw) of 1000 or more among compounds having As the highly polar functional group, a tertiary amino group or a phosphoric acid group is preferable in order to achieve both (c) dispersion stabilization of the pigment and reduction in driving voltage.
  • polymer chains examples include polyether-based polymer chains, (meth)acrylic-based polymer chains, polyurethane-based polymer chains, polyester-based polymer chains, and polyamide-based polymer chains. From the viewpoint of conversion, a polyether polymer chain or a (meth)acrylic polymer chain is preferred.
  • a polymer-type dispersant having a polyether polymer chain and a tertiary amino group for example, a dispersant composed of a tertiary polyamine obtained by grafting a linear polyether polymer chain to an aliphatic primary amine is preferable. be done.
  • examples of polymer-type dispersants having a (meth)acrylic polymer chain and a tertiary amino group include an A block having a tertiary amino group in the side chain and a B block having no tertiary amino group in the side chain. Dispersants composed of AB block copolymers or BAB block copolymers are preferred.
  • a block examples include polymer chains containing structural units derived from N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate.
  • Polymer-type dispersants having a (meth)acrylic polymer chain and a phosphate group include, for example, structural units derived from a (meth)acrylate compound having a phosphate group and ( Random copolymers with meth)acrylate compounds are mentioned.
  • (Meth)acrylate compounds having a phosphoric acid group include, for example, 2-methacryloyloxyethyl acid phosphate, acid phosphooxyethyl (meth)acrylate, acid phosphooxypropyl (meth)acrylate, acid phosphooxypolyoxypropylene glycol ( meth)acrylates.
  • the polymer-type dispersant may be contained during the production of the pigment dispersion described below, or may be contained during the production of the negative photosensitive composition.
  • the non-polymeric dispersant means a compound that has at least one highly polar functional group selected from a tertiary amino group, a quaternary ammonium group, a phosphoric acid group, and a sulfo group, and does not belong to the aforementioned polymeric dispersants. do.
  • non-polymer dispersants examples include organic dye derivatives (synergists) obtained by derivatizing pigments or dyes, as well as triazine derivatives. From the viewpoint of low driving voltage, triazine derivatives are preferred. A compound having an organic dye residue and a triazine ring is defined as a triazine derivative.
  • the non-polymer type dispersant may be contained as a refinement accelerator when obtaining the aforementioned finely divided organic pigment powder, or may be included during the production of the pigment dispersion described below.
  • organic dye derivatives include compounds represented by formula (10) and compounds represented by formula (11).
  • the triazine derivative is preferably a compound having a 1,3,5-triazine ring and a sulfo group or an N,N-dialkylamino group from the viewpoint of low driving voltage, and has a structure represented by formula (12).
  • a compound having That is, the negative photosensitive composition of the present invention preferably further contains (d) a pigment dispersant, and the pigment dispersant contains a compound having a structure represented by formula (12).
  • a compound having a structure represented by formula (12) may be particularly effective as a technical means for setting the value of XY, which will be described later, within a desired range.
  • R 17 represents a divalent hydrocarbon group.
  • R 18 represents a sulfo group or an N,N-dialkylamino group. * represents a binding site.
  • R 17 is preferably a phenylene group.
  • R 18 is an N,N-dialkylamino group
  • R 17 is preferably an alkylene group having 1 to 5 carbon atoms.
  • Examples of compounds having a structure represented by formula (12) include compounds having a structure represented by formula (13) and compounds having a structure represented by formula (14).
  • R 19 represents an alkylene group having 1 to 5 carbon atoms.
  • R 20 and R 21 are the same as each other and represent an alkyl group having 1 to 5 carbon atoms. * represents a binding site.
  • the compound having the structure represented by formula (13) and the compound having the structure represented by formula (14) include the compound represented by formula (15) and the compound represented by formula (16).
  • the compound having the structure represented by formula (12) is not limited to anthraquinone triazine derivatives.
  • the negative photosensitive composition of the present invention may contain (e) an alkali-soluble resin.
  • the alkali-soluble resin is a polymer having a hydroxyl group and/or a carboxyl group as an alkali-soluble group, a weight average molecular weight (Mw) of 1000 or more and 150000 or less, and the components (a) to (d) described above and the components described later. It means a compound that does not belong to the (f) component.
  • Alkali-soluble resins include, for example, alkali-soluble (meth)acrylic resins, alkali-soluble epoxy (meth)acrylate resins, alkali-soluble polyimide resins, alkali-soluble polyimide precursors, and alkali-soluble polysiloxane resins.
  • the negative photosensitive composition of the present invention may contain a (meth)acrylate compound other than the (a) component as the (f) component.
  • the negative photosensitive composition of the present invention further comprises, from the viewpoint of lowering the driving voltage, It is preferable to contain a (meth)acrylate compound having a functionality of 4 or more.
  • Examples of tetrafunctional (meth)acrylate compounds include compounds represented by formula (17) and compounds represented by formula (18).
  • Pentafunctional (meth)acrylate compounds include dipentaerythritol penta(meth)acrylate.
  • examples of the hexafunctional (meth)acrylate compounds include dipentaerythritol hexaacrylate and ⁇ -caprolactone-modified hexafunctional acrylate “KAYARAD (registered trademark)” DPCA-20, DPCA-30, DPCA-60 (hereinafter referred to as “DPCA- 60”) and DPCA-120 (both manufactured by Nippon Kayaku Co., Ltd.).
  • a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate also includes "KAYARAD®" DPHA.
  • the negative photosensitive composition of the present invention preferably further contains (g) a compound represented by formula (54).
  • the content of component (g) is preferably 0.01 to 0.5% by weight based on 100% by weight of the solid content of the negative photosensitive composition.
  • n 9 to n 11 are integers and each independently represents 0 to 2.
  • R 33 to R 35 each independently represent a methyl group, an ethyl group, a methoxy group or an ethoxy group.
  • component (g) include triphenylphosphine, tris(3,5-dimethylphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(m-methoxyphenyl)phosphine, and tris(o-methoxyphenyl). phosphines.
  • the negative photosensitive composition of the present invention may further contain a solvent.
  • a solvent By containing a solvent, the viscosity, thixotropy, etc. of the negative photosensitive composition can be adjusted, and coatability can be improved.
  • the solvent from the viewpoint of dissolving power and dispersion stability, it is preferable to use an ether-based solvent or an acetate-based solvent alone or in combination.
  • ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl. ethers.
  • Acetate-based solvents include, for example, propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA”), 3-methoxybutyl acetate (hereinafter referred to as "MBA”), butyl acetate, and ethylene glycol monomethyl ether acetate. , ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate.
  • PGMEA propylene glycol monomethyl ether acetate
  • MSA 3-methoxybutyl acetate
  • butyl acetate butyl acetate
  • ethylene glycol monomethyl ether acetate ethylene glycol monoethyl ether acetate
  • ethylene glycol monobutyl ether acetate diethylene glycol monomethyl ether acetate
  • diethylene glycol monoethyl ether acetate
  • the water content in the negative photosensitive composition of the present invention is preferably 1% by weight or less, more preferably 0.5% by weight or less, from the viewpoint of lowering the driving voltage.
  • the negative photosensitive composition of the present invention may further contain, as other components, a thermal cross-linking agent, a surfactant, a leveling agent, an antioxidant, an ultraviolet absorber, and the like.
  • a method for preparing the negative photosensitive composition of the present invention includes a method of mixing and stirring components (a) and (b). Further, when the components (c) to (g) are included, for example, the components (c), (d), (e) and a solvent are mixed to prepare a pigment dispersion by wet dispersion treatment, and then ( A) component, (b) component, (f) component, (g) component, solvent and other components may be mixed with a pigment dispersion, stirred, and optionally filtered through a filter. .
  • a wet media dispersing machine or a wet medialess dispersing machine may be used. preferred to use.
  • wet media dispersion machines include "Revomill (registered trademark)” (manufactured by Asada Iron Works), “Nano Getter (registered trademark)” (manufactured by Ashizawa Finetech), “DYNO-MILL (registered trademark)” (Willy A Bachofen), “Spike Mill (registered trademark)” (manufactured by Inoue Seisakusho), “Sand Grinder (registered trademark)” (manufactured by DuPont), “Ultra Apex Mill Advance (registered trademark)” (manufactured by ) manufactured by Hiroshima Metal & Machinery) and “NEO-Alpha Mill (registered trademark)” (manufactured by AIMEX Co., Ltd.).
  • Zirconia beads and zircon beads are examples of media used for wet media dispersion treatment.
  • the diameter of the media is preferably 0.03 to 0.5 mm ⁇ , and the higher the sphericity, the better.
  • Preferable examples of commercially available products include "Torayceram (registered trademark)” (manufactured by Toray Industries, Inc.) and "YTZ (registered trademark)” (manufactured by Nikkato Corporation).
  • the particle size distribution of all particle components (c) including the pigment preferably satisfies the following relationship from the viewpoint of lowering the driving voltage. That is, in the particle size distribution of all particle components contained in the negative photosensitive composition measured by the dynamic light scattering method, the cumulative 50% particle diameter X (nm) based on the light scattering intensity and the volume based It is preferable that the cumulative 50% particle size Y (nm) satisfies the relationship of 10 nm ⁇ XY ⁇ 30 nm. More preferably, the relationship 10 nm ⁇ XY ⁇ 20 nm is satisfied.
  • the cumulative 50% particle size X (nm) based on the light scattering intensity and the cumulative 50% particle size Y (nm) based on the volume are indices indicated by two different standards for one sample. , can be measured using a dynamic light scattering particle size distribution analyzer “SZ-100 (manufactured by HORIBA, Ltd.)”.
  • the light source of the measuring device has a wavelength of 532 nm/10 mW (semiconductor-excited solid-state laser), and near-ultraviolet rays are not irradiated during the measurement.
  • Cumulative 50% means a particle size corresponding to 50% cumulatively from the smaller particle size side to the larger particle size side in the cumulative particle size distribution curve (0%).
  • the diluting solvent the same solvent as the solvent contained in the negative photosensitive composition is used.
  • the value of the solvent viscosity required for measurement the value of the viscosity of the dilution solvent used for dilution at 25° C. (under atmospheric pressure) is entered.
  • the cured film of the present invention is a cured film containing a cured product of a negative photosensitive composition.
  • the cured film of the present invention is, for example, a pixel division layer and a TFT planarization layer of an organic EL display device, a black matrix and a black column spacer of a liquid crystal display device, a near-infrared highly transparent black film of a solid-state imaging device, and a touch panel. It can be used as a near-infrared highly transparent black film for bezels, and the application is not particularly limited.
  • the cured product means a cured product obtained through a step including at least a curing step in which the negative photosensitive composition is heated at a temperature of 200°C or higher and 400°C or lower under atmospheric pressure for 10 minutes or longer.
  • a cured film can be obtained by a forming method including at least a coating step and a curing step.
  • the negative photosensitive composition of the present invention is applied to the surface of a substrate using a spin coater as a coating device, and then heated at 230° C. for 30 minutes under atmospheric pressure using a hot air oven as a heating device. and obtain a solid cured film.
  • the method for producing the cured film of the present invention includes a coating step of applying a negative photosensitive composition to obtain a coating film, and pattern exposure to actinic radiation to form an exposed portion and an unexposed portion in the surface.
  • a cured film comprising an exposure step for obtaining an exposed film, a developing step for obtaining a developed film by developing with an alkaline developer containing potassium hydroxide, and a curing step for obtaining a cured film by heat curing by heating. Manufacturing methods are more preferred.
  • a spin coater or a slit coater can be preferably used as a coating device used in the coating process because of its excellent thin film coating properties.
  • pin gap pre-baking or contact pre-baking may be performed.
  • the prebaking temperature is preferably 50 to 150° C.
  • the prebaking time is preferably 30 seconds to 5 minutes.
  • Examples of exposure apparatuses used in the exposure process include steppers, mirror projection mask aligners (MPA), and parallel light mask aligners (PLA).
  • the actinic radiation irradiated during exposure is preferably j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm) or g-line (wavelength 436 nm) of a mercury lamp, and a mixed line containing at least i-line. more preferred.
  • a negative type exposure mask for example, a thin film having a shielding property made of a metal such as chromium is formed in a pattern on one surface of a substrate such as glass, quartz, or film that is translucent at the exposure wavelength.
  • An exposed film having an exposed portion and an unexposed portion in the plane can be obtained by performing pattern exposure by transmitting actinic rays only through the openings of the mask.
  • exposed portion refers to a portion that has been exposed
  • unexposed portion refers to a portion that has not been exposed.
  • the developing method includes, for example, a method of immersing the exposed film for 10 seconds to 3 minutes by a method such as showering, dipping, or puddle.
  • the paddle method is preferable from the viewpoint of in-plane uniformity of the opening width.
  • a low-concentration inorganic alkaline aqueous solution is preferable from the viewpoint of economic advantage as described above.
  • a low-concentration alkaline aqueous solution means an alkaline aqueous solution with a concentration of 1% by weight or less.
  • a high-concentration alkaline aqueous solution means an alkaline aqueous solution with a concentration exceeding 1% by weight.
  • the alkali component include tetramethylammonium hydroxide and potassium hydroxide, and from the viewpoint of being more economically advantageous, a 0.01 to 1% by weight potassium hydroxide aqueous solution is preferred.
  • commercially available high-concentration stock solutions for developers include "CD-150CR (registered trademark)" (manufactured by JSR Corporation) containing potassium hydroxide and a surfactant, and the concentration of potassium hydroxide is It can be diluted with deionized water to preferably 0.01 to 1% by weight, more preferably 0.03 to 0.1% by weight. After the development step, washing treatment by showering with deionized water and/or draining treatment by blowing air may be added.
  • the developed film is thermally cured by heating, and at the same time, moisture is volatilized to obtain a cured film.
  • Heating devices include, for example, hot air ovens and IR ovens.
  • the heating temperature is preferably 200 to 300°C, more preferably 220 to 260°C under atmospheric pressure.
  • the optical density (OD) per 1.0 ⁇ m film thickness is 0.00 to suppress external light reflection and increase the value as a display device. 5 or more is preferable, and 0.7 or more is more preferable. From the viewpoint of low driving voltage, it is preferably 1.5 or less, more preferably 1.3 or less.
  • the optical density per 1.0 ⁇ m film thickness is the optical density meter (manufactured by X-Rite; X-Rite 361T) for a cured film formed on a transparent substrate so as to have a film thickness of 1.5 ⁇ m. ) is used to measure the incident light intensity and the transmitted light intensity, and the value calculated from the following formula is divided by 1.5, which is the value of the film thickness.
  • a transparent glass substrate "Tempax (manufactured by AGC Techno Glass Co., Ltd.)" can be preferably used.
  • optical density log10 ( I0 /I) I 0 : incident light intensity I: transmitted light intensity.
  • the film thickness of the pixel dividing layer is usually 1 to 3 ⁇ m, and the taper angle at the edge of the opening of the developed film obtained after the developing process is 90° or less in order to improve the in-plane uniformity of the opening width after the curing process.
  • the taper angle at the edge of the opening of the pixel dividing layer obtained after the curing process is preferably 50° or less, more preferably 40° or less, and even more preferably 35° or less, in order to suppress non-lighting of pixels.
  • the angle is preferably 10° or more, more preferably 15° or more, and even more preferably 20° or more in order to suppress deterioration of the light-shielding properties of the edge portion.
  • the pixel division layer is patterned into a partition so as to cover at least part of the surface of an electrode made of ITO (indium-tin oxide) or the like. .
  • the organic EL display device of the present invention is an organic EL display device comprising the cured film of the present invention, and has the technical feature of being able to obtain high luminance with a low driving voltage.
  • An ITO film was formed on the entire surface of a non-alkali glass substrate of 150 mm ⁇ 150 mm by sputtering, and annealed at 200° C. for 30 minutes in a dry nitrogen atmosphere to obtain a substrate having an ITO film of 10 nm thickness.
  • the negative photosensitive composition of Example or Comparative Example was applied to the surface of the ITO film by adjusting the rotation speed so that the thickness of the cured film finally obtained was 1.5 ⁇ m, using a spin coater. A membrane was obtained. Using a hot plate (SCW-636; manufactured by Dainippon Screen Mfg. Co., Ltd.), the coating film was prebaked at 100° C.
  • a double-sided alignment single-sided exposure device (mask aligner PEM-6M; manufactured by Union Optics Co., Ltd.) was passed through a grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International) and an ultra-high pressure mercury lamp. A pattern exposure was carried out with g, h and i mixed lines to obtain an exposed film.
  • a small developing device for photolithography AD-2000; manufactured by Takizawa Sangyo Co., Ltd.
  • Developed with The puddle method as used herein refers to a method in which a developing solution is shower-coated on the surface of an exposed film for 10 seconds, and then the substrate is allowed to stand still until a predetermined developing time is reached for development.
  • the development time was determined by multiplying the time required for the unexposed portion of the film to dissolve and remove in the film depth direction by 1.5. Further, after rinsing with deionized water by a shower method for 30 seconds, the substrate was idled at 200 rpm for 30 seconds and dried to obtain a developed film-formed substrate having a patterned developed film.
  • the developed film was observed using an FPD inspection microscope (MX-61L; manufactured by Olympus Co., Ltd.), and a negative exposure mask with a line and space of 1:1 (light shielding portion 40.0 ⁇ m, transmission portion 40.0 ⁇ m). ), the exposure amount (mJ/cm 2 : i-line conversion value) when the mask bias is -2.0 ⁇ m (opening width 38.0 ⁇ m, development film width 42.0 ⁇ m) is It was taken as the optimum exposure amount (exposure sensitivity) of the negative photosensitive composition.
  • Measuring device Dynamic light scattering method Particle size distribution measuring device “SZ-100 (manufactured by HORIBA, Ltd.)”
  • Light source wavelength 532 nm/10 mW (semiconductor pumped solid-state laser)
  • Liquid temperature of measurement sample 25 ⁇ 1 ° C (under atmospheric pressure)
  • Data analysis mode monodisperse mode (particle size distribution analyzer "SZ-100")
  • Calculation method Calculate the average value of three measurements of the cumulative 50% particle diameter based on the light scattering intensity, and round the value to the first decimal place, "Cumulative 50% particle diameter X based on the light scattering intensity (nm)”.
  • the developed films before the curing process obtained in Examples 1 to 15 and Comparative Examples 1 to 5 and 7 to 11 were observed in the same manner, and when the taper angle of the pattern cross section of the developed film exceeded 90°. , the evaluation was given as F regardless of the result of the taper angle of the pixel division layer, and the result was disqualified. It should be noted that in none of the examples and comparative examples, the taper angle of the pixel division layer did not fall below 20°.
  • C The taper angle of the pixel division layer is 40° or more and less than 50°.
  • D The taper angle of the pixel division layer is 50° or more and less than 80°.
  • E The taper angle of the pixel division layer is 80° or more.
  • F The taper angle of the developed film exceeds 90°.
  • the term "per unit area” as used herein means per unit area of the light-emitting pixel portion, and the area of the pixel division layer forming portion is not included in the conversion described above.
  • the driving voltage was calculated by rounding off to the second decimal place. The lower the drive voltage, the better, and evaluation was made based on the following criteria, with AA and A to C passing, and D to E failing. If one or more non-lighting pixels occurred, it was difficult to make a proper evaluation, so it was rated as F and rejected.
  • B: The driving voltage is 4.5V or more and less than 5.0V.
  • C Drive voltage is 5.0V or more and less than 5.5V.
  • D The driving voltage is 5.5V or more and less than 6.0V.
  • E Drive voltage is 6.0 V or higher.
  • F One or more non-lit pixels occurred.
  • S0100 "Irgaphor (registered trademark)" Black S0100CF. It corresponds to a lactam-based organic black pigment containing a compound represented by formula (9).
  • Non-polymer dispersant 1 a compound represented by formula (10). Anthraquinone sulfonic acid derivative. It does not correspond to a compound having a structure represented by formula (12).
  • Non-polymer dispersant 2 a compound represented by formula (15). Anthraquinone triazine derivative having a sulfo group. It corresponds to a compound having a structure represented by formula (12).
  • Non-polymer dispersant 3 a compound represented by formula (16). Anthraquinone triazine derivatives having an N,N-dialkylamino group. It corresponds to a compound having a structure represented by formula (12).
  • Polymer Dispersant A Pigment Dispersant 1 (solid content: 100% by weight) disclosed in Synthesis Example 2 of JP-A-2020/70352. It is a polymer-type dispersant having a linear polyalkyleneamine structure and a polyether polymer chain.
  • ZCR-1569H PGMEA solution of alkali-soluble epoxy acrylate resin having a biphenyl skeleton in the main chain (manufactured by Nippon Kayaku Co., Ltd.: acid value of solid content excluding solvent 98 mgKOH / g, weight average molecular weight 3900, solid content 70 weight%).
  • Binder resin-3 Resin solution synthesized by the same method as the synthesis method disclosed in Synthesis Example 1 (synthesis of binder resin-3) of Patent Document 3 (acid value of solid content excluding solvent 110 mgKOH / g, weight Average molecular weight 4000. Methoxybutyl acetate solution with a solids content of 50% by weight). It is an alkali-soluble epoxy acrylate resin having repeating units derived from an acrylate compound having an adamantane skeleton and biphenyltetracarboxylic dianhydride.
  • Showa Denko KK solid content 42% by weight, weight average molecular weight (Mw) 7300, acid value of solid content excluding solvent 75 mgKOH/g).
  • Fruorene acrylate solution A PGMEA solution of the compound represented by formula (19) (solid content: 50% by weight). It is the component (a) and corresponds to the compound represented by the formula (3).
  • Fruorene acrylate solution B PGMEA solution of the compound represented by formula (20) (solid content: 50% by weight). It is the component (a) and corresponds to the compound represented by the formula (3).
  • Fruorene acrylate solution C PGMEA solution of the compound represented by formula (21) (solid content: 50% by weight). It is the component (a) and corresponds to the compound represented by the formula (5).
  • Fruorene acrylate solution D PGMEA solution of the compound represented by formula (22) (solid content: 50% by weight). It is the component (a) and corresponds to the compound represented by the formula (5).
  • Fruorene methacrylate solution E PGMEA solution of the compound represented by formula (23) (solid content: 50% by weight). It is the component (a) and corresponds to the compound represented by the formula (5).
  • Fruorene acrylate solution F PGMEA solution of the compound represented by formula (24) (solid content: 50% by weight). It is the component (a) and corresponds to the compound represented by the formula (5).
  • Component (a) corresponds to a mixture of the compound represented by formula (5) and the ammonium salt of the compound represented by formula (5).
  • Fruorene acrylate solution H PGMEA solution of the compound represented by formula (26) (solid content: 50% by weight). It is the component (a) and corresponds to the compound represented by the formula (5).
  • “Fluorene acrylate solution I” PGMEA solution of the compound represented by formula (27) (solid content: 50% by weight, Ogusol EA-0250P (manufactured by Osaka Gas Chemicals Co., Ltd.)). It is a compound having the same structure as A-BPEF (manufactured by Shin-Nakamura Chemical Co., Ltd.) disclosed in Patent Document 1 and Ogsol 0200A (manufactured by Osaka Gas Chemicals Co., Ltd.) disclosed in Patent Document 2, and (a ) is a compound that does not belong to the component.
  • A-BPEF manufactured by Shin-Nakamura Chemical Co., Ltd.
  • Ogsol 0200A manufactured by Osaka Gas Chemicals Co., Ltd.
  • Fluorene acrylate solution J PGMEA solution of the compound represented by formula (28) (solid content: 50% by weight). It is the same compound as FLN-5 disclosed in Patent Document 1 and does not belong to component (a).
  • Fruorene acrylate solution K PGMEA solution of the compound represented by formula (29) (solid content: 50% by weight).
  • Fluorene acrylate solution L PGMEA solution of the compound represented by formula (30) (solid content: 50% by weight). It is a fluorene compound that does not have a 9,9-bisarylfluorene skeleton and does not belong to the component (a).
  • a mixture of acid phosphooxyethyl methacrylate (0.10 mol), 26.43 g of benzyl methacrylate (0.15 mol), and 8.21 g of azobisisobutyronitrile was added dropwise over 30 minutes, and A methacrylic copolymer having a weight average molecular weight (Mw) of 9500 and a phosphoric acid group in a side chain is cooled after proceeding with a thermal polymerization reaction by stirring for 1 hour while maintaining the liquid temperature at 100 ° C. of PGMEA solution was obtained.
  • a polymer-type dispersant solution B was obtained by diluting this with PGMEA so that the solid content was 30% by weight.
  • Alkali-soluble polyimide resin B was powdery with a solid content of 100% and had a weight average molecular weight (Mw) of 27,000.
  • a toluene solution containing only the compound represented by formula (56) was obtained by passing through silica gel chromatography and dried under reduced pressure for 10 hours to obtain a white powdery compound represented by formula (56).
  • a PGMEA solution (solid content: 50% by weight) of the compound represented by the formula (56) was prepared as adamantane acrylate solution 1.
  • the compound represented by formula (56) is component (a) and corresponds to the compound represented by formula (40).
  • a PGMEA solution solid content: 50% by weight of the compound represented by the formula (63) was prepared as a fluorene acrylate solution M.
  • the compound represented by formula (63) is not a compound belonging to component (a).
  • the pre-stirring liquid was sent to a bead mill filled with 0.4 mm ⁇ zirconia beads in a vessel at a filling rate of 75% by volume, and a wet media dispersion treatment was performed in a circulation system at a peripheral speed of 8 m/s for 1 hour. Furthermore, zirconia beads of 0.05 mm ⁇ were fed to a bead mill filled in a vessel with a vessel filling rate of 75% by volume, and subjected to wet media dispersion treatment in a circulation system at a peripheral speed of 8 m / s for 4 hours. 00% by weight Pigment Dispersion 1 was prepared.
  • Table 1 shows the blending weight of each raw material.
  • Pigment Dispersion Liquid 2 A pigment dispersion 2 was obtained in the same manner as in Preparation Example 2, except that the non-polymer dispersant 2 was used instead of the non-polymer dispersant 1.
  • Pigment Dispersion Liquid 3 having a solid content of 20.00% by weight.
  • Table 1 shows the blending weight of each raw material.
  • Preparation Example 4 Preparation of Pigment Dispersion Liquid 4 S0100 was not used, and (c) 60.00 g of C.I. I. Pigment Red 177 and 60.00 g of C.I. I. Pigment Dispersion 4 was prepared in the same manner as in Preparation Example 1, except that Pigment Blue 60 was used.
  • Pigment Dispersion Liquid 5 Preparation of Pigment Dispersion Liquid 5
  • 34.50 g of SOLSPERSE 20000 manufactured by Lubrizol, 100% by weight solids
  • a polymeric dispersant 782.00 g
  • MBA a solvent
  • the mixture was stirred for 30 minutes, and subjected to wet media dispersion treatment using a horizontal bead mill filled with zirconia beads of 0.40 mm so that the number average particle diameter was 100 nm.
  • Pigment Dispersion Liquid 5 has a solid content of 15.00% by weight, and the ratio of organic pigment/polymer type dispersant is 75/25 (weight ratio).
  • Table 1 shows the blending weight of each raw material. Based on the method described in Patent Document 1, the number average particle size of the pigment contained in the pigment dispersion 5 was measured using a zeta potential/particle size/molecular weight measuring device "Zetasizer Nano ZS" (manufactured by Sysmex Corporation). As a result of measurement, it was 100 nm.
  • Example 1 Under a yellow light, 0.38 g of NCI-831E, which is a photopolymerization initiator (b), was added to a mixed solvent of 6.38 g of MBA and 19.01 g of PGMEA, and dissolved by stirring for 10 minutes. rice field. To this, 1.27 g of fluorene acrylate solution A as component (a), 5.14 g of SPC-3410 as component (e), and 0.95 g of DPCA-60 as component (f) (solid content 100% by weight) was added and stirred to obtain a mixed solution. 16.88 g of Pigment Dispersion Liquid 1 was mixed with this prepared liquid and stirred for 30 minutes to prepare negative photosensitive composition 1 having a solid content of 15.00% by weight. Table 2 shows the blending weight of each raw material. The particle size distribution of the negative photosensitive composition 1 was measured by the method described above, and the XY values were calculated. Table 3 shows the results.
  • Negative photosensitive composition 1 was applied to the surface of a transparent glass substrate Tempax (manufactured by AGC Techno Glass Co., Ltd.) so that the thickness of the cured film finally obtained was 1.5 ⁇ m.
  • a coating film was obtained by coating with a spin coater while adjusting the number of coatings, and pre-baking the coating film at 100° C. under atmospheric pressure for 120 seconds using a hot plate (SCW-636; manufactured by Dainippon Screen Mfg. Co., Ltd.).
  • the entire surface of the pre-baked film was exposed without using a negative type exposure mask with the optimum exposure amount determined by the above-described method for g, h, and i mixed lines of an ultra-high pressure mercury lamp. Then, development, rinsing and drying were carried out in the same manner as in calculating the optimum exposure dose to obtain a solid developed film.
  • High-temperature inert gas oven IH-9CD-S; Koyo Thermosystem Co., Ltd.
  • the developed film was heated at 230° C. for 30 minutes in air to obtain a substrate for optical density evaluation having a solid cured film with a thickness of 1.5 ⁇ m.
  • the optical density (OD/ ⁇ m) was evaluated by the method, and the evaluation results are shown in Table 3.
  • a pixel division layer composed of a cured film containing a cured product of the negative photosensitive composition 1 and a bottom emission type organic EL display device having the pixel division layer were produced by the following method.
  • FIG. 1 shows the manufacturing process of an organic EL display device, including the process of forming a pixel division layer.
  • a silver alloy (99.00% by weight silver and 1.00% by weight copper alloy) was deposited on the entire surface of the non-alkali glass substrate 1 with a length of 70 mm and a width of 70 mm by sputtering.
  • etching was performed by immersing in a silver alloy etching solution SEA-1 at a liquid temperature of 30° C. to obtain a patterned silver alloy film 2 with a film thickness of 50 nm. Further, an ITO film was formed over the entire surface by a sputtering method.
  • An alkali-soluble novolac positive resist was immersed in a 5% by weight oxalic acid aqueous solution at a liquid temperature of 50°C for 5 minutes, washed with deionized water for 2 minutes in a shower, dried by air blowing, and dried at 200°C and 30°C in a dry nitrogen atmosphere. After heating for 10 minutes, an ITO film 3 having the same pattern and a thickness of 10 nm was obtained. Through the above steps, a first electrode-forming substrate having a first electrode formed of a laminated pattern of silver alloy film/ITO film on the surface of the non-alkali glass substrate was obtained.
  • Negative photosensitive composition 1 is applied to the surface of the first electrode forming substrate using a spin coater while adjusting the number of rotations so that the thickness of the finally obtained pixel division layer is 1.5 ⁇ m. Then, a coating film was obtained. Furthermore, using a hot plate, the coating film was prebaked at 100° C. under atmospheric pressure for 120 seconds to obtain a prebaked film. Using a double-sided alignment single-sided exposure apparatus, the pre-baked film is pattern-exposed through a negative exposure mask (220 openings of 260 ⁇ m in length and 70 ⁇ m in width) with the optimum exposure amount obtained by the above-described method. A membrane was obtained.
  • the pixel The split layer forming substrate is rotated, and first, the compound (HT-1) represented by the formula (31) is deposited to 10 nm as the hole injection layer, and the compound (HT-1) represented by the formula (32) is deposited as the hole transport layer. -2) was deposited to a thickness of 50 nm.
  • the compound (GH-1) represented by the formula (33) as a host material and the compound (GD-1) represented by the formula (34) as a dopant material are applied to a thickness of 40 nm on the light-emitting layer. evaporated.
  • the compound (ET-1) represented by the formula (35) and the compound (LiQ) represented by the formula (36) were laminated at a volume ratio of 1:1 to a thickness of 40 nm. .
  • a silver/magnesium alloy (volume ratio: 10:1) was vapor-deposited to a thickness of 150 nm to form the second electrode 6 .
  • an epoxy resin-based adhesive was used to adhere a cap-shaped glass plate for sealing, thereby obtaining an organic EL display device.
  • the layer constituting the organic EL layer 5 is much thinner than the pixel division layer described above, and a stylus-type film thickness measuring device cannot obtain high measurement accuracy, it is suitable for thin films of less than 100 nm.
  • Each thickness was measured using a film thickness monitor, and the value obtained by rounding off the average value of three in-plane points to the first decimal place was taken as the thickness of the film.
  • the driving voltage of the manufactured organic EL display device was evaluated by the method described above. Table 3 shows the evaluation results.
  • Examples 2-8) Using fluorene acrylate solutions B to D, fluorene methacrylate solution E, and fluorene acrylate solutions F to H instead of fluorene acrylate solution A, negatives were produced in the same manner as in Example 1 at the blending amounts shown in Tables 2 and 4.
  • Type photosensitive compositions 2 to 8 were prepared, respectively, and the optical density of the cured film, the XY value, the taper angle of the pixel dividing layer, and the driving voltage of the organic EL display device were evaluated. Evaluation results are shown in Tables 3 and 5.
  • Fluorene acrylate solution D was used instead of fluorene acrylate solution A, pigment dispersions 2 to 4 were used instead of pigment dispersion 1, and the amounts shown in Table 4 were used.
  • Photosensitive compositions 9 to 11 were prepared, respectively, and the optical density of the cured film, the XY value, the taper angle of the pixel dividing layer, and the driving voltage of the organic EL display device were evaluated. Table 5 shows the evaluation results.
  • Negative photosensitive compositions 12 to 16 were prepared in the same manner as in Example 1, using fluorene acrylate solutions I to L instead of fluorene acrylate solution A, and using the blending amounts shown in Table 6. The optical density, the XY value, the taper angle of the pixel dividing layer, and the driving voltage of the organic EL display device were evaluated. Table 7 shows the evaluation results.
  • negative photosensitive composition 17 was evaluated using 0.04% by weight potassium hydroxide, which is a low-concentration inorganic alkaline aqueous solution, as a developer, and the pixel division layer could not be formed due to insufficient solubility.
  • Negative photosensitive composition 17 was prepared in the same manner as in Example 1, except that a 2.38% by weight tetramethylammonium hydroxide aqueous solution was used instead of the 0.04% by weight aqueous potassium hydroxide solution. The density, the XY value, the taper angle of the pixel dividing layer, and the driving voltage of the organic EL display device were evaluated. Table 9 shows the evaluation results. That is, in comparison with Comparative Example 6, negative photosensitive composition 17 was evaluated using a 2.38% by weight tetramethylammonium hydroxide aqueous solution, which is a high-concentration organic alkaline aqueous solution, as a developer. A pixel division layer could be formed by the change.
  • Negative photosensitive compositions 19 to 22 were prepared in the same manner as in Example 1 using adamantane acrylate solutions 1 to 3 in place of the fluorene acrylate solution A at the formulation amounts shown in Table 10, and cured films were obtained. , the XY value, the taper angle of the pixel dividing layer, and the driving voltage of the organic EL display device. Table 11 shows the evaluation results. Only negative photosensitive composition 22 was prepared by blending triphenylphosphine corresponding to the compound represented by formula (54).
  • negative photosensitive composition 23 was prepared in the same manner as in Example 1 at the blending amounts shown in Table 12, and the optical density of the cured film, X The value of -Y, the taper angle of the pixel division layer, and the drive voltage of the organic EL display device were evaluated. Table 13 shows the evaluation results.
  • Example 10 A negative photosensitive composition 24 was prepared in the same manner as in Example 1 with the formulation amounts shown in Table 12 without using the fluorene acrylate solution A, and the optical density of the cured film, the XY value, and the pixel division layer and the driving voltage of the organic EL display device were evaluated. Table 13 shows the evaluation results.
  • Example 11 A negative photosensitive composition 25 was prepared in the same manner as in Example 1 with the formulation amounts shown in Table 12 without using the fluorene acrylate solution A, and the optical density of the cured film, the XY value, and the pixel division layer was evaluated. Table 13 shows the evaluation results. In addition, one or more non-lighting pixels occurred, and it was difficult to properly evaluate the driving voltage of the organic EL display device.
  • Examples 1 to 15 by photolithography including a development step using a low-concentration inorganic alkaline aqueous solution, an organic EL display device was obtained while obtaining a developed film without undercut and a pixel division layer with a low taper angle. , the driving voltage required to obtain the desired emission luminance is low, which is superior to Comparative Examples 1 to 11. From the above results, it can be seen that the negative photosensitive composition of the present invention is useful.
  • non-alkali glass substrate 2 silver alloy film 3: ITO film 4: pixel division layer 5: organic EL layer 6: second electrode 7: non-alkali glass substrate 8: ITO film/silver alloy film 9: pixel division layer

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20230144970A (ko) * 2022-04-08 2023-10-17 제이에스알 가부시끼가이샤 렌즈의 제조 방법, 감방사선성 조성물, 표시 소자, 표시 장치, 고체 촬상 소자, 촬상 장치 및 화합물

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014118479A (ja) * 2012-12-17 2014-06-30 Toyo Ink Sc Holdings Co Ltd 黄色着色剤とその製造方法およびそれを用いたカラーフィルタ
JP2016177190A (ja) * 2015-03-20 2016-10-06 三菱化学株式会社 着色スペーサー形成用感光性着色組成物、硬化物、着色スペーサー、画像表示装置
WO2018061525A1 (ja) * 2016-09-30 2018-04-05 東レ株式会社 ネガ型感光性樹脂組成物、硬化膜、硬化膜を具備する素子及び表示装置、並びにその製造方法
JP2019203963A (ja) * 2018-05-22 2019-11-28 日鉄ケミカル＆マテリアル株式会社 感光性樹脂組成物、その硬化物および当該硬化物を含む表示装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014118479A (ja) * 2012-12-17 2014-06-30 Toyo Ink Sc Holdings Co Ltd 黄色着色剤とその製造方法およびそれを用いたカラーフィルタ
JP2016177190A (ja) * 2015-03-20 2016-10-06 三菱化学株式会社 着色スペーサー形成用感光性着色組成物、硬化物、着色スペーサー、画像表示装置
WO2018061525A1 (ja) * 2016-09-30 2018-04-05 東レ株式会社 ネガ型感光性樹脂組成物、硬化膜、硬化膜を具備する素子及び表示装置、並びにその製造方法
JP2019203963A (ja) * 2018-05-22 2019-11-28 日鉄ケミカル＆マテリアル株式会社 感光性樹脂組成物、その硬化物および当該硬化物を含む表示装置

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20230144970A (ko) * 2022-04-08 2023-10-17 제이에스알 가부시끼가이샤 렌즈의 제조 방법, 감방사선성 조성물, 표시 소자, 표시 장치, 고체 촬상 소자, 촬상 장치 및 화합물
JP2023155216A (ja) * 2022-04-08 2023-10-20 Jsr株式会社 レンズの製造方法、感放射線性組成物、表示素子、表示装置、固体撮像素子、撮像装置及び化合物
JP7646722B2 (ja) 2022-04-08 2025-03-17 Jsr株式会社 レンズの製造方法
JP2025093994A (ja) * 2022-04-08 2025-06-24 Jsr株式会社 レンズ製造用感放射線性組成物、表示素子、表示装置、固体撮像素子及び撮像装置
KR102841535B1 (ko) 2022-04-08 2025-07-31 제이에스알 가부시키가이샤 렌즈의 제조 방법

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