WO2024195628A1 - 感光性樹脂組成物、硬化物、隔壁、有機電界発光素子、カラーフィルター及び画像表示装置 - Google Patents

感光性樹脂組成物、硬化物、隔壁、有機電界発光素子、カラーフィルター及び画像表示装置 Download PDF

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WO2024195628A1
WO2024195628A1 PCT/JP2024/009525 JP2024009525W WO2024195628A1 WO 2024195628 A1 WO2024195628 A1 WO 2024195628A1 JP 2024009525 W JP2024009525 W JP 2024009525W WO 2024195628 A1 WO2024195628 A1 WO 2024195628A1
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group
mass
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resin composition
ring
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French (fr)
Japanese (ja)
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聰 小野
佑樹 田中
良尚 沢井
麗華 裴
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority to CN202480017719.8A priority Critical patent/CN120883137A/zh
Priority to KR1020257028313A priority patent/KR20250162774A/ko
Priority to JP2025508338A priority patent/JPWO2024195628A1/ja
Publication of WO2024195628A1 publication Critical patent/WO2024195628A1/ja
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • 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
    • 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
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]

Definitions

  • the present invention relates to a photosensitive resin composition, a cured product, a partition wall, an organic electroluminescent device, a color filter, and an image display device.
  • Liquid crystal displays utilize the property that liquid crystal molecules change their alignment when a voltage is applied to the liquid crystal, while many of the components that make up an LCD cell are formed by methods that use photosensitive compositions, such as photolithography.
  • This photosensitive composition is being used in a wider range of applications because it is easy to form fine structures and is also easy to process on substrates for large screens.
  • Image display devices that include organic electroluminescence (also known as organic EL) devices have been attracting attention as the next generation of flat panel displays (FPDs) because they offer excellent visibility in terms of contrast and viewing angle, responsiveness, and the ability to reduce power consumption, be thin and lightweight, and have flexible display bodies.
  • FPDs flat panel displays
  • An organic electroluminescent element has a structure in which an organic layer including a light-emitting layer or various functional layers is sandwiched between a pair of electrodes, at least one of which is light-transmitting.
  • An image display device displays images by driving a panel in which an organic electroluminescent element is arranged for each pixel.
  • organic electroluminescent elements are manufactured by forming partitions (banks) on a substrate, and then laminating a light-emitting layer or various functional layers in an area surrounded by the partitions.
  • a deposition method is mainly used in which a material is sublimated in a vacuum state and deposited on a substrate to form a film.
  • methods of forming films by wet processes such as casting, spin coating, and inkjet printing have been attracting attention.
  • inkjet printing can reduce unevenness in film thickness when applied over a large area, and can also achieve high-definition displays by applying different layers during application, reduce the amount of material used, and improve yields, making it suitable as a method of forming organic layers in large panels.
  • a method for easily forming the partition wall is known to be a photolithography method using a photosensitive composition.
  • a method for imparting light-shielding properties to the partition wall and suppressing light leakage between pixels is known to be a method for incorporating a colorant into the photosensitive composition.
  • Patent Document 1 describes a photosensitive colored resin composition that uses a specific organic black pigment and a dispersant and thereby has high light-shielding properties and a low dielectric constant.
  • Patent Document 2 also describes a photosensitive colored resin composition used for partition walls of organic electroluminescent devices, which is effective in suppressing outgassing by using a specific organic black pigment and an alkali-soluble resin.
  • the process of forming the partition walls using photolithography involves a baking process in which the substrate is placed in a high-temperature chamber.
  • fumes a gas that is generated during this baking process, can adhere to the anode, causing display defects such as an increase in the drive voltage of organic electroluminescent devices and unevenness in the light-emitting surface.
  • an organic electroluminescent device when a cathode serving as a common electrode is provided by a vapor deposition method, the smaller the taper angle of the partition wall (the angle between the support and the cured product in the cross section of the cured product) is, the less likely disconnection and the like is likely to occur, and the productivity of the organic electroluminescent device is improved.
  • a good taper angle cannot be obtained during the production of the partition wall.
  • the resulting partition walls are susceptible to fluctuations in the development and baking treatment steps, and the quality thereof may be unstable.
  • the present invention has been made in consideration of the above circumstances, and aims to provide a photosensitive resin composition capable of forming partition walls that produce a small amount of fumes during baking, have a small taper angle, and have an excellent film remaining rate after baking. It also aims to provide an organic electroluminescent device and an image display device that include this partition wall.
  • the present inventors have found that the above problems can be solved by using a specific ethylenically unsaturated compound in a photosensitive resin composition, and have thus completed the present invention. That is, the gist of the present invention is as follows.
  • a photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) an ethylenically unsaturated compound,
  • the photosensitive resin composition wherein the (C) ethylenically unsaturated compound has a structure represented by the following general formula (2):
  • R 4 to R 6 each independently represent an alkylene group, and the alkylene group may be interrupted by an etheric oxygen atom.
  • R 7 to R 9 each independently represent a hydrogen atom or a methyl group.
  • R 611 and R 616 each independently represent a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
  • R 612 , R 613 , R 614 , R 615 , R 617 , R 618 , R 619 and R 620 each independently represent a hydrogen atom, a halogen atom, R 621 , COOH, COOR 621 , COO - , CONH 2 , CONHR 611 , CONR 621 R 622 , CN, OH, OR 621 , COCR 621 , OOCNH 2 , OOCNHR 621 , OOCNR 621 R 622 , NO 2 , NH 2 , NHR 621 , NR 621 R 622 , NHCOR 622 , NR 621 COR 622 , N ⁇ CH 2 , N ⁇ CHR 621 , N ⁇ CR 621 R 622 , SH, SR 621 , S
  • An organic electroluminescent device comprising the partition wall according to [12].
  • a color filter comprising luminescent nanocrystalline particles and the partition wall according to [12].
  • An image display device comprising the partition wall of [12].
  • the present invention provides a photosensitive resin composition capable of forming partition walls that produce a small amount of fumes during baking and have a small taper angle, and that have an excellent film remaining rate after baking. It also provides an organic electroluminescent device, a color filter, and an image display device that include this partition wall.
  • FIG. 1 is a schematic cross-sectional view of an example of a color filter having partition walls of the present invention.
  • (meth)acrylic means “acrylic and/or methacrylic", and the same applies to "(meth)acrylate” and "(meth)acryloyl”.
  • the term "acrylic resin” refers to a (co)polymer containing (meth)acrylic acid, or a (co)polymer containing a (meth)acrylic acid ester having a carboxy group.
  • the “total solids content” means all components other than the solvent contained in the photosensitive resin composition or the colorant dispersion liquid. Even if a component other than the solvent is liquid at room temperature, that component is not included in the solvent but is included in the total solids content.
  • (co)polymer is intended to include both homopolymers and copolymers
  • acid (anhydride) and “(anhydride)...acid” are intended to include both acids and their anhydrides.
  • monomer is the opposite of a so-called high molecular substance (polymer), and includes not only a monomer in the narrow sense, but also a dimer, trimer, and oligomer.
  • the "weight average molecular weight” refers to the weight average molecular weight (Mw) calculated in terms of polystyrene by GPC (gel permeation chromatography).
  • the "amine value” refers to the amine value calculated based on the effective solid content, and is a value expressed as the mass of KOH equivalent to the amount of base per 1 g of solid content of the dispersant. The measurement method will be described later.
  • the “acid value” refers to the acid value calculated as the effective solid content, and is calculated by neutralization titration.
  • C.I Color Index
  • the photosensitive resin composition of the present invention contains (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) an ethylenically unsaturated compound.
  • the alkali-soluble resin (A) in the present invention is not particularly limited as long as it is a resin that exhibits alkali solubility, and examples thereof include resins containing a carboxy group or a hydroxy group, and more specifically, examples thereof include epoxy (meth)acrylate resins, acrylic resins, carboxy group-containing epoxy resins, carboxy group-containing urethane resins, novolac resins, polyvinylphenol resins, and isocyanuric skeleton-containing resins.
  • (A1) epoxy (meth)acrylate resins, (A2) isocyanuric skeleton-containing resins, and (A3) acrylic copolymer resins are preferably used from the viewpoint of excellent plate-making properties. These resins can be used alone or in combination of two or more.
  • the epoxy (meth)acrylate resin (A1) in the present invention is an alkali-soluble resin (A), which is obtained by reacting an epoxy compound (epoxy resin) with an ⁇ , ⁇ -unsaturated monocarboxylic acid and/or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group in the ester moiety to generate a hydroxy group, and then reacting the hydroxy group with a compound having two or more substituents capable of reacting with a hydroxy group, such as a polybasic acid and/or an anhydride thereof.
  • A alkali-soluble resin
  • the epoxy (meth)acrylate resin (A1) also includes a resin obtained by reacting a compound having two or more substituents capable of reacting with a hydroxy group with the polybasic acid and/or anhydride thereof, prior to reacting the polybasic acid and/or anhydride with a hydroxy group, and then reacting the polybasic acid and/or anhydride with the polybasic acid and/or anhydride. Resins obtained by reacting the carboxy group of the resin obtained by the above reaction with a compound having a functional group that can further react are also included in the epoxy (meth)acrylate resin (A1).
  • Epoxy (meth)acrylate resins have substantially no epoxy groups in terms of their chemical structure, and are not limited to "(meth)acrylate", but are named in this manner according to convention because epoxy compounds (epoxy resins) are the raw material and "(meth)acrylate” is a representative example.
  • the epoxy (meth)acrylate resin (A1) used in the present invention the following epoxy (meth)acrylate resin (A1-1) and/or epoxy (meth)acrylate resin (A1-2) (hereinafter sometimes referred to as "carboxy group-containing epoxy (meth)acrylate resin") are preferably used from the viewpoints of developability and reliability.
  • the (A1) epoxy (meth)acrylate resin one having an aromatic ring in the main chain is more preferably used from the viewpoint of the residual film rate.
  • an aromatic ring in the main chain developer resistance and heat resistance are increased, so that the residual film rate of the partition wall obtained after the baking treatment tends to be high.
  • the epoxy resin includes the raw material compound before the resin is formed by thermal curing, and the epoxy resin can be appropriately selected from known epoxy resins.
  • the epoxy resin can be a compound obtained by reacting a phenolic compound with epihalohydrin.
  • the phenolic compound is preferably a compound having a divalent or more than divalent phenolic hydroxyl group, and may be a monomer or a polymer.
  • the types of epoxy resins that can be used as raw materials include, for example, cresol novolac type epoxy resins, phenol novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, trisphenolmethane type epoxy resins, biphenyl novolac type epoxy resins, naphthalene novolac type epoxy resins, epoxy resins that are reaction products of epihalohydrin with a polyaddition product of dicyclopentadiene and phenol or cresol, adamantyl group-containing epoxy resins, and fluorene type epoxy resins, and those having aromatic rings in the main chain are more preferably used.
  • Epoxy resins include, for example, bisphenol A type epoxy resins (e.g., Mitsubishi Chemical Corporation's "jER (registered trademark, the same applies below) 828," “jER1001,” “jER1002,” “jER1004,” etc.), epoxy resins obtained by reacting the alcoholic hydroxyl group of bisphenol A type epoxy resin with epichlorohydrin (e.g., Nippon Kayaku Co., Ltd.'s "NER-1302” (epoxy equivalent 323, softening point 76°C)), and bisphenol F type resins (e.g., "jER807", "EP-4001", “EP-4002", “EP-4004" and the like manufactured by Mitsubishi Chemical Corporation), epoxy resins obtained by reacting alcoholic hydroxyl groups of bisphenol F type epoxy resins with epichlorohydrin (for example, "NER-7406” (epoxy equivalent 350, softening point 66°C) manufactured by Nippon Kayaku Co., Ltd.), bisphenol S type epoxy resins, bipheny
  • an epoxy resin represented by the following general formula (A1 ⁇ ) is "XD-1000" manufactured by Nippon Kayaku Co., Ltd.
  • an epoxy resin represented by the following general formula (A1 ⁇ ) is "NA2000” and “NA2500” manufactured by Nippon Kayaku Co., Ltd.
  • an epoxy resin represented by the following general formula (A1 ⁇ ) is "E-201” manufactured by Osaka Organic Chemical Industry Co., Ltd.
  • an epoxy resin represented by the following general formula (A1 ⁇ ) is "ESF-300” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • a is an average value and represents a number from 0 to 10
  • each R 111 independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. Note that multiple R 111 present in one molecule may be the same or different.
  • b1 and b2 are average values and each independently represents a number from 0 to 10, and each R 121 independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. Note that multiple R 121 present in one molecule may be the same or different.
  • X represents a linking group represented by the following general formula (A1 ⁇ -1) or (A1 ⁇ -2).
  • the molecular structure contains one or more adamantane structures.
  • c represents 2 or 3.
  • R 131 to R 134 and R 135 to R 137 each independently represent an adamantyl group which may have a substituent, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent, and * represents a bond.
  • p and q each independently represent an integer of 0 to 4
  • R 141 and R 142 each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom
  • R 143 and R 144 each independently represent an alkylene group having 1 to 4 carbon atoms
  • x and y each independently represent an integer of 0 or more.
  • the epoxy resin it is preferable to use an epoxy resin represented by any one of formulas (A1 ⁇ ) to (A1 ⁇ ).
  • Examples of ⁇ , ⁇ -unsaturated monocarboxylic acids or ⁇ , ⁇ -unsaturated monocarboxylic acid esters having a carboxy group include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, and ⁇ -position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid; 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl adipic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxyprop
  • Examples of the monomer include acryloyloxypropyl phthalate, 2-(meth)acryloyloxypropyl maleate, 2-(meth)acryloyloxybutyl succinate, 2-(meth)acryloyloxybutyl adipic acid, 2-(meth)acryloyloxybutyl hydrophthalate, 2-(meth)acryloyloxybutyl phthalate, and 2-(meth)acryloyloxybutyl maleate; monomers obtained by adding lactones such as ⁇ -caprolactone, ⁇ -propiolactone, ⁇ -butyrolactone, and ⁇ -valerolactone to (meth)acrylic acid; monomers obtained by adding acids (anhydrides) such as (anhydrous) succinic acid, (anhydrous) phthalic acid, and (anhydrous) maleic acid to hydroxyalkyl (meth)acrylate and pentaerythritol tri(meth)acrylate; and (meth)acrylic acid
  • a known method can be used to add an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin.
  • an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group can be reacted with an epoxy resin in the presence of an esterification catalyst at a temperature of 50 to 150°C.
  • esterification catalyst used here examples include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride.
  • tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine
  • quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride.
  • the epoxy resin, the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group, and the esterification catalyst may each be used alone or in combination of two or more.
  • the amount of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group used is preferably 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group in the epoxy resin, more preferably 0.7 to 1.1 equivalents.
  • the amount of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group used is made equal to or less than the upper limit, it is possible to suppress the remaining unreacted ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group, and it is easy to make the curing characteristics good.
  • polybasic acids and/or their anhydrides examples include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and their anhydrides.
  • maleic acid succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
  • Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
  • the addition reaction of the polybasic acid and/or its anhydride can be carried out by a known method, and the target product can be obtained by continuing the reaction under the same conditions as the addition reaction of an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin.
  • the amount of the polybasic acid and/or its anhydride component added is preferably such that the acid value of the resulting carboxy-containing epoxy (meth)acrylate resin is 10 to 150 mgKOH/g, more preferably 20 to 140 mgKOH/g. By making the amount equal to or greater than the lower limit, the alkali developability tends to be good. By making the amount equal to or less than the upper limit, the curing performance tends to be good.
  • a polyfunctional alcohol such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, or 1,2,3-propanetriol may be added to introduce a multi-branched structure.
  • polyhydric alcohol such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, or 1,2,3-propanetriol
  • the polybasic acid and/or its anhydride undergoes an addition reaction with any of the hydroxy groups present in the mixture of the reaction product of the epoxy resin and ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group, and the polyfunctional alcohol.
  • the molecular weight of the epoxy (meth)acrylate resin (A1) can be increased, a branch can be introduced into the molecule, and the molecular weight and viscosity tend to be well balanced.
  • the introduction rate of an acid group into the molecule can be increased, and the sensitivity, adhesion, and other properties tend to be well balanced.
  • carboxyl group-containing epoxy (meth)acrylate resins for example, those described in Korean Patent Publication No. 10-2013-0022955 can be mentioned.
  • the weight average molecular weight (Mw) of the carboxyl group-containing epoxy (meth)acrylate resin in terms of polystyrene, measured by gel permeation chromatography (GPC), is preferably 1000 or more, more preferably 1500 or more, even more preferably 2000 or more, even more preferably 3000 or more, especially more preferably 4000 or more, and particularly preferably 5000 or more. It is also preferably 30000 or less, more preferably 20000 or less, and even more preferably 15000 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, 1000 to 30000 is preferable, 1500 to 20000 is more preferable, 1500 to 15000 is even more preferable, and 2000 to 15000 is even more preferable.
  • the acid value of the carboxyl group-containing epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, even more preferably 60 mgKOH/g or more, even more preferably 80 mgKOH/g or more, and particularly preferably 100 mgKOH/g or more. Also, it is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, even more preferably 130 mgKOH/g or less, and particularly preferably 120 mgKOH/g or less.
  • the above upper and lower limits can be arbitrarily combined.
  • 20 to 200 mgKOH/g is preferred, 60 to 150 mgKOH/g is more preferred, 80 to 130 mgKOH/g is even more preferred, and 100 to 130 mgKOH/g is even more preferred.
  • the lower limit or more the development solubility is improved and the resolution tends to be good.
  • the upper limit or less the remaining film rate tends to be good.
  • the chemical structure of the (A1) epoxy (meth)acrylate resin is not particularly limited, but from the standpoint of developability and reliability, it is preferable that the resin contains an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (A1-I) (hereinafter, may be abbreviated as "(A1-I) epoxy (meth)acrylate resin”) and/or an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (A1-II) (hereinafter, may be abbreviated as "(A1-II) epoxy (meth)acrylate resin”):
  • R 11 represents a hydrogen atom or a methyl group
  • R 12 represents a divalent hydrocarbon group which may have a substituent
  • k represents 1 or 2
  • * represents a bond.
  • the benzene ring in formula (A1-I) may be further substituted with any substituent.
  • R 13 each independently represents a hydrogen atom or a methyl group
  • R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain
  • R 15 and R 16 each independently represent a divalent aliphatic group which may have a substituent
  • m and n each independently represent an integer of 0 to 2
  • * represents a bond.
  • R 11 represents a hydrogen atom or a methyl group
  • R 12 represents a divalent hydrocarbon group which may have a substituent
  • k represents 1 or 2
  • * represents a bond.
  • the benzene ring in formula (A1-I) may be further substituted with any substituent.
  • R 12 represents a divalent hydrocarbon group which may have a substituent.
  • the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups are linked with one or more divalent aromatic ring groups.
  • the divalent aliphatic group may be a linear, branched, or cyclic aliphatic group. From the viewpoint of development solubility, a linear aliphatic group is preferred. On the other hand, from the viewpoint of reducing the penetration of the developer into the exposed area, a cyclic aliphatic group is preferred.
  • the number of carbon atoms is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more. Also, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the upper and lower limits can be arbitrarily combined. For example, 1 to 20 is preferred, 1 to 15 is more preferred, and 1 to 10 is even more preferred.
  • Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. From the viewpoint of the rigidity of the skeleton, a methylene group is preferred.
  • divalent branched aliphatic group examples include a structure in which the above-mentioned divalent linear aliphatic group has, as a side chain, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.
  • the number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Also, it is preferably 12 or less, more preferably 10 or less.
  • the above upper and lower limits can be combined in any way. For example, 1 to 12 is preferred, 1 to 10 is more preferred, and 2 to 10 is even more preferred.
  • divalent cyclic aliphatic groups include groups in which two hydrogen atoms have been removed from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a dicyclopentadiene ring, or a dicyclopentane ring. From the viewpoint of skeletal rigidity, groups in which two hydrogen atoms have been removed from a dicyclopentadiene ring, a dicyclopentane ring, or an adamantane ring are preferred.
  • the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group, a hydroxy group, a nitro group, a cyano group, and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that the divalent aliphatic group is unsubstituted.
  • the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more.
  • it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the upper and lower limits can be arbitrarily combined. For example, 4 to 20 is preferable, 5 to 15 is more preferable, and 6 to 10 is even more preferable.
  • By setting it to the lower limit value or more a strong film is easily obtained, surface roughness caused during development is unlikely to occur, and adhesion to the substrate tends to be good.
  • By setting it to the upper limit value or less deterioration of sensitivity can be suppressed, and the residual film rate after development tends to be high and resolution tends to be improved.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • divalent aromatic hydrocarbon ring groups include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, all of which have two free valences.
  • the aromatic heterocycle in the divalent aromatic heterocycle group may be a single ring or a condensed ring.
  • the divalent aromatic heterocycle group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring,
  • a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.
  • the substituent that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of solubility in development, it is preferable that the divalent aromatic ring group is unsubstituted.
  • Examples of the group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include groups in which one or more of the above-mentioned divalent aliphatic groups are linked to one or more of the above-mentioned divalent aromatic ring groups.
  • the number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the upper and lower limits can be arbitrarily combined. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 3 is even more preferable, and 2 to 3 is particularly preferable.
  • the number By making the number equal to or greater than the lower limit, a strong film is easily obtained, surface roughness during development is unlikely to occur, and adhesion to the substrate tends to be good.
  • the number By making the number equal to or less than the upper limit, deterioration of sensitivity can be suppressed, and the residual film rate after development tends to be high and resolution tends to be improved.
  • the number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the above upper and lower limits can be combined in any way. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 1 to 3 is even more preferred, and 2 to 3 is particularly preferred.
  • Examples of groups linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups include groups represented by the following formulae (A1-IA) to (A1-IF).
  • A1-IA groups represented by the following formulae (A1-IA) to (A1-IF).
  • * represents a bond. From the viewpoint of the rigidity of the skeleton and the hydrophobization of the film, the group represented by the following formula (A1-IA) is preferred.
  • k represents 1 or 2. From the viewpoints of adhesion and plate-making properties, k is preferably 1. From the viewpoint of sensitivity, k is preferably 2.
  • the epoxy (meth)acrylate (A1-I) may contain both a partial structure in which k is 1 and a partial structure in which k is 2.
  • the benzene ring in formula (A1-I) may be further substituted with any substituent. Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of the substituent is not particularly limited, and may be one or two or more.
  • the alkyl group is unsubstituted.
  • the partial structure represented by formula (A1-I) is preferably a partial structure represented by the following general formula (A1-I-1).
  • R 11 , R 12 and k are defined as in formula (A1-I), R x represents a hydrogen atom or a polybasic acid residue, and * represents a bond.
  • the benzene ring in formula (A1-I-1) may be further substituted with any substituent.
  • the polybasic acid residue means a mono- or divalent group obtained by removing one or two OH groups from a polybasic acid.
  • polybasic acid examples include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
  • benzene ring in formula (A1-I-1) may be further substituted with any substituent.
  • substituent those exemplified for the benzene ring in formula (A1-I) can be preferably used.
  • the partial structure represented by formula (A1-I-1) contained in one molecule of the epoxy (meth)acrylate resin (A1-I) may be of one type or of two or more types.
  • a structure in which R X is a hydrogen atom and a structure in which R X is a polybasic acid residue may be mixed.
  • the number of partial structures represented by formula (A1-I) contained in one molecule of the epoxy (meth)acrylate resin (A1-I) is not particularly limited, but is preferably 1 or more, more preferably 3 or more. Also, it is preferably 20 or less, and more preferably 15 or less.
  • the upper and lower limits above can be arbitrarily combined. It is preferably 1 to 20, more preferably 1 to 15, and even more preferably 3 to 15.
  • the weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (A1-I) measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, even more preferably 2000 or more, even more preferably 3000 or more, particularly preferably 4000 or more, and most preferably 5000 or more, and is preferably 30000 or less, more preferably 20000 or less, and even more preferably 15000 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, 1000 to 30000 is preferable, 1500 to 2000 is more preferable, 1500 to 15000 is more preferable, and 2000 to 1500 is even more preferable.
  • the residual film ratio tends to be good.
  • the solubility in the developer tends to be good.
  • the acid value of the epoxy (meth)acrylate resin (A1-I) is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, even more preferably 60 mgKOH/g or more, even more preferably 80 mgKOH/g or more, and particularly preferably 100 mgKOH/g or more. Also, it is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, even more preferably 130 mgKOH/g or less, and particularly preferably 120 mgKOH/g or less. The above upper and lower limits can be arbitrarily combined.
  • it is preferably 20 to 200 mgKOH/g, more preferably 60 to 150 mgKOH/g, even more preferably 80 to 130 mgKOH/g, and even more preferably 100 to 130 mgKOH/g.
  • the lower limit the development solubility is improved and the resolution tends to be good.
  • the upper limit the remaining film ratio tends to be good.
  • Specific examples of the epoxy (meth)acrylate resin (A1-I) are listed below. In the examples, * indicates a bond.
  • R 13 each independently represents a hydrogen atom or a methyl group
  • R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain
  • R 15 and R 16 each independently represent a divalent aliphatic group which may have a substituent
  • m and n each independently represent an integer of 0 to 2
  • * represents a bond.
  • the structure of formula (A1-II) is preferable in terms of light-emitting properties.
  • R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
  • the cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.
  • the number of rings in the aliphatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Also, it is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the upper and lower limits can be arbitrarily combined. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 3 is even more preferable, and 2 to 3 is particularly preferable.
  • the number of carbon atoms in the aliphatic ring group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. Also, it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and especially preferably 15 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, 4 to 40 is preferred, 4 to 30 is more preferred, 6 to 20 is even more preferred, and 8 to 15 is especially preferred.
  • Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoints of film retention rate and resolution, an adamantane ring is preferred.
  • the number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. Also, it is preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less.
  • the upper and lower limits can be arbitrarily combined. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 4 is even more preferable, and 2 to 4 is particularly preferable, and 3 to 4 is particularly preferable.
  • the lower limit By making it equal to or more than the lower limit, a strong film is easily obtained, and surface roughness caused during development tends to be less likely to occur.
  • the upper limit By making it equal to or less than the upper limit, deterioration of sensitivity can be suppressed, and the residual film rate after development tends to be high, and the resolution tends to be improved.
  • aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
  • the number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, even more preferably 10 or more, and particularly preferably 12 or more.
  • it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, 4 to 40 is preferred, 6 to 40 is more preferred, 8 to 30 is even more preferred, even more preferably 10 to 20, and particularly preferably 12 to 15.
  • Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. From the viewpoint of patterning properties, a fluorene ring is preferred.
  • the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups.
  • the divalent aliphatic group may be a linear, branched, or cyclic aliphatic group. From the viewpoint of development solubility, a linear aliphatic group is preferred, while a cyclic aliphatic group is preferred from the viewpoint of reducing the penetration of the developer into the exposed area.
  • the number of carbon atoms is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more. Also, it is preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 25 is preferred, 3 to 20 is more preferred, and 6 to 15 is even more preferred.
  • Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. From the viewpoint of the rigidity of the skeleton, a methylene group is preferable.
  • divalent branched aliphatic group examples include a structure in which the above-mentioned divalent linear aliphatic group has a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group as a side chain.
  • the number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Also, it is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the above upper and lower limits can be combined in any way. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 1 to 3 is even more preferred, and 2 to 3 is particularly preferred.
  • Examples of the divalent cyclic aliphatic group include a group in which two hydrogen atoms have been removed from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, or an adamantane ring. From the viewpoint of the rigidity of the skeleton, a group in which two hydrogen atoms have been removed from an adamantane ring is preferred.
  • Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group, a hydroxy group, a nitro group, a cyano group, and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that the divalent aliphatic group is unsubstituted.
  • Divalent aromatic ring groups include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic groups.
  • the number of carbon atoms is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. Also, it is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 4 to 30 is preferable, 5 to 20 is more preferable, and 6 to 15 is even more preferable.
  • By setting it to the lower limit or more a strong film is easily obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good.
  • By setting it to the upper limit or less deterioration of sensitivity can be suppressed, and the remaining film rate after development tends to be high and resolution tends to be improved.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • divalent aromatic hydrocarbon ring groups include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, all of which have two free valences.
  • the aromatic heterocycle in the divalent aromatic heterocycle group may be a single ring or a condensed ring.
  • the divalent aromatic heterocycle group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring,
  • the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of solubility in development, it is preferable that the divalent aromatic ring group is unsubstituted.
  • the group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include groups in which one or more of the above-mentioned divalent aliphatic groups are linked to one or more of the above-mentioned divalent aromatic ring groups.
  • the number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the above upper and lower limits can be combined in any way. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 1 to 3 is even more preferred, and 2 to 3 is particularly preferred.
  • the number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the above upper and lower limits can be combined in any way. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 1 to 3 is even more preferred, and 2 to 3 is particularly preferred.
  • Examples of the group formed by linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups include the groups represented by the above-mentioned formulae (A1-IA) to (A1-IF). From the viewpoints of the rigidity of the skeleton and the hydrophobization of the film, the group represented by formula (A1-IC) is preferred.
  • the bonding mode of the cyclic hydrocarbon group as a side chain to these divalent hydrocarbon groups is not particularly limited, but examples include a mode in which one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with a cyclic hydrocarbon group as a side chain, and a mode in which a cyclic hydrocarbon group as a side chain is formed by including one carbon atom of an aliphatic group.
  • R 15 and R 16 each independently represent a divalent aliphatic group which may have a substituent.
  • the divalent aliphatic group may be a linear, branched, or cyclic aliphatic group. From the viewpoint of development solubility, a linear aliphatic group is preferred, while a cyclic aliphatic group is preferred from the viewpoint of reducing the penetration of the developer into the exposed area.
  • the number of carbon atoms is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more. Also, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the upper and lower limits above can be arbitrarily combined. For example, 1 to 20 is preferred, 3 to 15 is more preferred, and 6 to 10 is even more preferred.
  • a strong film is easily obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good.
  • deterioration of sensitivity can be suppressed, and the remaining film rate after development tends to be high and resolution tends to be improved.
  • Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. From the viewpoint of the rigidity of the skeleton, a methylene group is preferable.
  • divalent branched aliphatic group examples include a structure in which the above-mentioned divalent linear aliphatic group has, as a side chain, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.
  • the number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Also, it is preferably 12 or less, more preferably 10 or less.
  • the above upper and lower limits can be combined in any way. For example, 1 to 12 is preferred, and 2 to 10 is more preferred.
  • Examples of the divalent cyclic aliphatic group include groups in which two hydrogen atoms have been removed from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, or a dicyclopentadiene ring. From the viewpoint of the rigidity of the skeleton, groups in which two hydrogen atoms have been removed from a dicyclopentadiene ring or an adamantane ring are preferred.
  • Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group, a hydroxy group, a nitro group, a cyano group, and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that the divalent aliphatic group is unsubstituted.
  • m and n each independently represent an integer of 0 to 2.
  • the patterning suitability becomes good and the surface roughness generated during development tends to be less likely to occur, and by making it equal to or less than the upper limit, the developability tends to be good.
  • m and n are 0.
  • m and n are 1 or more.
  • the partial structure represented by formula (A1-II) is preferably a partial structure represented by the following general formula (A1-II-1).
  • R 13 , R 15 , R 16 , m and n are the same as those in formula (A1-II), R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent, p represents an integer of 1 or more, and * represents a bond.
  • the benzene ring in formula (A1-II-1) may be further substituted with any substituent.
  • R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
  • the cyclic hydrocarbon group may be an aliphatic ring group or an aromatic ring group.
  • the number of rings in the aliphatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Also, it is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.
  • the upper and lower limits can be arbitrarily combined. For example, 1 to 6 is preferred, 1 to 4 is more preferred, 1 to 3 is even more preferred, and 2 to 3 is particularly preferred.
  • the number of carbon atoms in the aliphatic ring group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. Also, it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and especially preferably 15 or less.
  • the above upper and lower limits can be combined in any way. For example, 4 to 40 is preferred, 4 to 30 is more preferred, 6 to 20 is even more preferred, and 8 to 15 is especially preferred.
  • Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of strong film properties, an adamantane ring is preferred.
  • the number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and more preferably 3 or more. Also, it is preferably 10 or less, and more preferably 5 or less. The upper and lower limits can be arbitrarily combined.
  • 1 to 10 is preferable, 1 to 5 is more preferable, 2 to 5 is even more preferable, and 3 to 5 is particularly preferable.
  • the lower limit By making it equal to or more than the lower limit, a strong film is easily obtained, and surface roughness caused during development tends to be less likely to occur.
  • the upper limit By making it equal to or less than the upper limit, patterning characteristics tend to be good.
  • Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
  • the number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. It is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
  • the above upper and lower limits can be combined in any way. For example, 4 to 30 is preferred, 5 to 20 is more preferred, and 6 to 15 is even more preferred.
  • Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. From the viewpoint of development solubility, a fluorene ring is preferred.
  • Examples of the substituent that the cyclic hydrocarbon group may have include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, and isoamyl; alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy; hydroxyl; nitro; cyano; and carboxyl. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.
  • R ⁇ is preferably a monovalent aliphatic cyclic group, and more preferably an adamantyl group.
  • the benzene ring in formula (A1-II-1) may be further substituted with any substituent.
  • substituents include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of the substituents is not particularly limited, and may be one or two or more. From the viewpoint of patterning properties, it is preferably unsubstituted.
  • Specific examples of the partial structure represented by formula (A1-II-1) are shown below. In the following examples, * represents a bond.
  • the partial structure represented by formula (A1-II) is preferably a partial structure represented by the following general formula (A1-II-2) from the viewpoint of the rigidity of the skeleton and the hydrophobization of the membrane.
  • R 13 , R 15 , R 16 , m and n are defined as in formula (A1-II), R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent, and * represents a bond.
  • the benzene ring in formula (A1-II-2) may be further substituted with any substituent.
  • R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent.
  • the cyclic hydrocarbon group may be an aliphatic ring group or an aromatic ring group.
  • the number of rings in the aliphatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Also, it is preferably 10 or less, more preferably 5 or less.
  • the upper and lower limits can be arbitrarily combined. For example, 1 to 10 is preferable, and 2 to 5 is more preferable. By making it equal to or more than the lower limit, a strong film is easily obtained, and surface roughness during development tends to be less likely to occur. By making it equal to or less than the upper limit, deterioration of sensitivity can be suppressed, and the residual film rate after development tends to be high, and resolution tends to be improved.
  • the number of carbon atoms in the aliphatic ring group is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. Also, it is preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less.
  • the above upper and lower limits can be combined in any way. For example, 4 to 40 is preferred, 6 to 35 is more preferred, and 8 to 30 is even more preferred.
  • Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoints of the residual film rate after development and the resolution, the adamantane ring is preferred.
  • the number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. Also, it is preferably 10 or less, and more preferably 5 or less. The upper and lower limits can be arbitrarily combined.
  • 1 to 10 is preferable, 1 to 5 is more preferable, 2 to 5 is even more preferable, and 3 to 5 is particularly preferable.
  • the lower limit By making it equal to or more than the lower limit, a strong film is easily obtained, and surface roughness caused during development tends to be less likely to occur.
  • the upper limit By making it equal to or less than the upper limit, it is easy to suppress deterioration of sensitivity and film loss, and resolution tends to be improved.
  • the aromatic ring group examples include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and even more preferably 10 or more.
  • it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less.
  • the upper and lower limits can be arbitrarily combined. For example, it is preferably 4 to 40, more preferably 6 to 30, even more preferably 8 to 20, and particularly preferably 10 to 15.
  • By making it equal to or more than the lower limit a strong film is easily obtained, and surface roughness occurring during development tends to be less likely to occur.
  • By making it equal to or less than the upper limit it is easy to suppress deterioration of sensitivity and film loss, and resolution tends to be improved.
  • aromatic rings in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring.
  • a fluorene ring is preferred. Since the plane forming the fluorene ring is perpendicular to the bond connecting the two benzene rings, the bulkiness results in a more rigid skeleton, which is less susceptible to penetration of the developer and less susceptible to shrinkage during baking treatment, and is presumed to result in a higher residual film rate.
  • Examples of the substituents that the cyclic hydrocarbon group may have include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, and isoamyl; alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy; hydroxyl groups; nitro groups; cyano groups; and carboxy groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.
  • R ⁇ is preferably a divalent aliphatic ring group, more preferably a divalent adamantane ring group, and from the viewpoint of patterning properties, R ⁇ is preferably a divalent aromatic ring group, more preferably a divalent fluorene ring group.
  • the benzene ring in formula (A1-II-2) may be further substituted with any substituent. Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of the substituents is not particularly limited, and may be one or two or more.
  • two benzene rings may be linked via a substituent, in which case examples of the substituent include divalent groups such as --O--, --S--, --NH--, and --CH 2 --. From the viewpoint of patterning properties, it is preferably unsubstituted, and from the viewpoint of preventing film loss and the like, it is preferably substituted with a methyl group.
  • substituent include divalent groups such as --O--, --S--, --NH--, and --CH 2 --.
  • substituent include divalent groups such as --O--, --S--, --NH--, and --CH 2 --.
  • the partial structure represented by formula (A1-II-2) are shown below. In the examples, * indicates a bond.
  • the partial structure represented by formula (A1-II) is preferably a partial structure represented by the following general formula (A1-II-3).
  • R 13 , R 14 , R 15 , R 16 , m and n are defined as in formula (A1-II), and R Z represents a hydrogen atom or a polybasic acid residue.
  • the polybasic acid residue means a mono- or divalent group obtained by removing one or two OH groups from a polybasic acid. An additional OH group may be removed and shared with R Z in another molecule represented by formula (A1-II-3). In other words, a plurality of molecules represented by formula (A1-II-3) may be linked via R Z.
  • polybasic acids examples include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
  • the partial structure represented by formula (A1-II-3) contained in one molecule of the epoxy (meth)acrylate resin (A1-II) may be of one type or of two or more types. For example, one in which R Z is a hydrogen atom and one in which R Z is a polybasic acid residue may be mixed.
  • the number of partial structures represented by formula (A1-II) contained in one molecule of the epoxy (meth)acrylate resin (A1-II) is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. Also, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the above upper and lower limits can be combined in any way. For example, 1 to 20 is preferred, 1 to 15 is more preferred, and 3 to 10 is even more preferred.
  • the weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (A1-II) measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, even more preferably 2000 or more, even more preferably 3000 or more, even more preferably 4000 or more, and particularly preferably 5000 or more. Also, it is preferably 10000 or less, more preferably 8000 or less, and even more preferably 7000 or less. The above upper and lower limits can be arbitrarily combined.
  • it is preferably 1000 to 10000, more preferably 1500 to 10000, even more preferably 1500 to 8000, even more preferably 2000 to 8000, and particularly preferably 2000 to 7000.
  • the residual film ratio tends to be good.
  • the solubility in the developer tends to be good.
  • the acid value of the epoxy (meth)acrylate resin (A1-II) is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, even more preferably 60 mgKOH/g or more, even more preferably 80 mgKOH/g or more, and particularly preferably 100 mgKOH/g or more. Also, it is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, even more preferably 130 mgKOH/g or less, and particularly preferably 120 mgKOH/g or less.
  • the above upper and lower limits can be arbitrarily combined.
  • the epoxy (meth)acrylate resin (A1) may be used alone or in combination of two or more kinds.
  • the photosensitive resin composition of the present invention may use an isocyanuric skeleton-containing resin having an ethylenic double bond and a carboxy group (hereinafter, may be simply referred to as (A2) isocyanuric skeleton-containing resin).
  • (A2) isocyanuric skeleton-containing resin The presence of an isocyanuric skeleton, an ethylenic double bond, and a carboxy group improves chemical resistance and heat resistance, and reduces the amount of decomposition products during development and baking treatments, which tends to increase the current density when a voltage is applied to an organic electric field element.
  • the (A2) isocyanuric skeleton-containing resin is an (A) alkali-soluble resin and is not particularly limited as long as it has an ethylenic double bond, a carboxy group, and an isocyanuric skeleton.
  • examples thereof include the following resins (A2-1) and (A2-2).
  • (A2-1) A resin obtained by further reacting a reaction product of an epoxy group-containing compound having an isocyanuric skeleton with an ⁇ , ⁇ -unsaturated monocarboxylic acid and/or an ester compound with a polybasic acid and/or an anhydride thereof.
  • Examples of the epoxy group-containing compound having an isocyanuric skeleton include compounds represented by the following general formula (A2-1-1).
  • R 4 to R 6 each independently represent an alkylene group, and the alkylene group may be interrupted in the middle by an etheric oxygen atom.
  • the alkylene group preferably has 1 or more carbon atoms.
  • the number of carbon atoms is also preferably 6 or less, more preferably 4 or less, and even more preferably 2 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, 1 to 6 is preferred, 1 to 4 is more preferred, and 1 to 2 is even more preferred.
  • the alkylene group may have a linear or branched chain.
  • alkylene groups include methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, and n-hexylene groups, as well as ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, and n-hexylene groups interrupted by an ether oxygen atom.
  • preferred are methylene, ethylene, and n-propylene groups, and more preferred is methylene.
  • Examples of ⁇ , ⁇ -unsaturated monocarboxylic acids and/or ester compounds include monocarboxylic acids such as (meth)acrylic acid, ⁇ -position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid; 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl adipate, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxypropyl ...phthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl phthalic acid
  • polybasic acids and/or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
  • the addition reaction of the polybasic acid and/or its anhydride can be carried out in the same manner as in the case of the epoxy (meth)acrylate resin (A1).
  • Examples of the ⁇ , ⁇ -unsaturated monocarboxylic acid and/or ester compound include the same compounds as those described in the section on (A1) epoxy (meth)acrylate resin.
  • Examples of the resin (A2-2) include the resins described in JP-A-2020-75994 and intermediates thereof.
  • the weight average molecular weight (Mw) of the isocyanuric skeleton-containing resin (A2) is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, even more preferably 2000 or more, even more preferably 3000 or more, even more preferably 4000 or more, and particularly preferably 5000 or more. Also, it is preferably 10000 or less, more preferably 8000 or less, and even more preferably 7000 or less. The above upper and lower limits can be combined arbitrarily.
  • 1000 to 10000 is preferred, 1500 to 10000 is more preferred, 1500 to 8000 is even more preferred, 2000 to 8000 is even more preferred, and 2000 to 7000 is particularly preferred.
  • the lower limit or more it is possible to suppress the solubility in the developer from becoming too high.
  • the upper limit or less it is possible to easily achieve good solubility in the developer.
  • the acid value of the isocyanuric skeleton-containing resin is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, even more preferably 60 mgKOH/g or more, even more preferably 80 mgKOH/g or more, and particularly preferably 100 mgKOH/g or more. Also, it is preferably 200 mgKOH/g or less, and more preferably 150 mgKOH/g or less.
  • the above upper and lower limits can be arbitrarily combined. For example, 20 to 200 mgKOH/g is preferable, and 60 to 150 mgKOH/g is more preferable. By setting it to the lower limit or more, the development solubility is improved and the resolution tends to be good. By setting it to the upper limit or less, the remaining film rate tends to be good.
  • an acrylic copolymer resin (A3) may be used from the viewpoint of compatibility with pigments, dispersants, etc.
  • the acrylic copolymer resin (A3) for example, those described in JP 2014-137466 A can be preferably used.
  • the acrylic copolymer resin (A3) include copolymers of an ethylenically unsaturated monomer having one or more carboxy groups (hereinafter referred to as "unsaturated monomer (A3-1)") and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (A3-2)").
  • Examples of the unsaturated monomer (A3-1) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, ⁇ -chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, and mesaconic acid; mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate; mono(meth)acrylates of polymers having a carboxy group and a hydroxy group at both ends, such as ⁇ -carboxypolycaprolactone mono(meth)acrylate; and p-vinylbenzoic acid. These unsaturated monomers (A3-1) can be used
  • Examples of the unsaturated monomer (A3-2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; Aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, p-hydroxystyrene, p-hydroxy- ⁇ -methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene;
  • N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide
  • Aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, p-hydroxystyrene, p-hydroxy- ⁇ -methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene;
  • Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 2,6 ]decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, and 3-(vinyloxymethyl)-3-ethyloxetane;
  • the polymer include macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane.
  • These unsaturated monomers (A3-2) can be used alone or in combination of two or more kinds.
  • the copolymerization ratio of the unsaturated monomer (A3-1) is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass.
  • copolymers of unsaturated monomer (A3-1) and unsaturated monomer (A3-2) include the copolymers disclosed in Japanese Patent Application Publication Nos. 7-140654, 8-259876, 10-31308, 10-300922, 11-174224, 11-258415, 2000-56118, and 2004-101728.
  • the copolymer of the unsaturated monomer (A3-1) and the unsaturated monomer (A3-2) can be produced by a known method.
  • the structure, Mw, and Mw/Mn (Mn is the number average molecular weight) can be controlled by the methods disclosed in JP-A-2003-222717, JP-A-2006-259680, and WO 2007/029871.
  • the acrylic copolymer resin (A3) in addition to the above, resins described in WO 2016/194619 and WO 2017/154439 may be used.
  • the photopolymerization initiator (B) used in the present invention is a component that has a function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization active radical. If necessary, an additive such as a polymerization promoter (chain transfer agent) or a sensitizing dye may be added.
  • Examples of the photopolymerization initiator (B) include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; hexaarylbiimidazole derivatives described in JP-A-2000-56118; halomethylated oxadiazole derivatives and halomethyl-s-triazine derivatives described in JP-A-10-39503; ⁇ -aminoalkylphenone derivatives; and oxime ester compounds described in JP-A-2000-80068 and JP-A-2006-36750.
  • metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; hexaarylbiimidazole derivatives described in JP-A-2000-56118; halomethylated oxadiazole derivatives and halomethyl-s-triazine derivatives described in JP-A-10-39503
  • Metallocene compounds include, for example, dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), dicyclopentadienyltitanium bis(2,3,5,6-tetrafluorophenyl-1-yl), dicyclopentadienyltitanium bis(2,4,6-trifluorophenyl-1-yl), dicyclopentadienyltitanium These include di(2,6-difluorophenyl-1-yl), dicyclopentadienyltitanium di(2,4-difluorophenyl-1-yl), di(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), di(methylcyclopenta
  • hexaarylbiimidazole derivatives examples include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.
  • halomethylated oxadiazole derivatives examples include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2'-(6''-benzofuryl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.
  • halomethyl-s-triazine derivatives examples include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.
  • Examples of ⁇ -aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, and 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octylcarbazole.
  • an oxime ester compound is particularly effective in terms of sensitivity and plate making properties, and for example, when an alkali-soluble resin containing a phenolic hydroxy group is used, such an oxime ester compound having excellent sensitivity is particularly useful.
  • Oxime ester compounds have a high quantum yield of photoreaction and generate radicals with high activity, so that a small amount of the compound is highly sensitive and stable against thermal reactions, making it possible to obtain a highly sensitive photosensitive resin composition with a small amount of the compound.
  • the oxime ester compound include compounds represented by the following general formula (IV).
  • R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
  • R 21b represents any substituent containing an aromatic ring.
  • R 22a represents an alkanoyl group which may have a substituent, or an aroyl group which may have a substituent.
  • n represents an integer of 0 or 1.
  • the number of carbon atoms in the alkyl group in R 21a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is preferably 1 or more, more preferably 2 or more, and is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group.
  • Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxy group, a carboxy group, a halogen atom, an amino group, an amide group, a 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl group, and an N-acetyl-N-acetoxyamino group. From the viewpoint of ease of synthesis, it is preferable that the alkyl group is unsubstituted.
  • Examples of the aromatic ring group in R 21a include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive resin composition. Also, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less. For example, it is preferably 5 to 30, more preferably 5 to 20, and even more preferably 5 to 12.
  • Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. From the viewpoint of developability, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
  • Examples of the substituent that the aromatic ring group may have include a hydroxy group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group in which these substituents are linked. From the viewpoint of developability, an alkyl group, an alkoxy group, and a group in which these substituents are linked are preferred, and a linked alkoxy group is more preferred.
  • R 21a is preferably an aromatic ring group which may have a substituent, and more preferably an aromatic ring group having a linked alkoxy group as a substituent.
  • R 21b may be exemplified by an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, an optionally substituted diphenylsulfide group, an optionally substituted fluorenyl group, or an optionally substituted indolyl group.
  • an optionally substituted carbazolyl group is preferred.
  • an optionally substituted diphenylsulfide group is preferred.
  • the number of carbon atoms in the alkanoyl group in R 22a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is preferably 2 or more, and is preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, and particularly preferably 5 or less.
  • examples of the alkanoyl group include an acetyl group, a propanoyl group, and a butanoyl group.
  • Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxy group, a carboxy group, a halogen atom, an amino group, and an amide group. From the viewpoint of ease of synthesis, it is preferable that the alkanoyl group is unsubstituted.
  • the number of carbon atoms in the aroyl group in R 22a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is preferably 7 or more, more preferably 8 or more, and is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • Examples of the aroyl group include a benzoyl group and a naphthoyl group.
  • the substituent that the aroyl group may have include a hydroxy group, a carboxy group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of ease of synthesis, it is preferable that the aroyl group is unsubstituted.
  • R 22a is preferably an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.
  • photopolymerization initiators described in Japanese Patent Publication No. 4454067, International Publication No. 2002/100903, International Publication No. 2012/45736, International Publication No. 2015/36910, International Publication No. 2006/18973, International Publication No. 2008/78678, Japanese Patent Publication No. 4818458, International Publication No. 2005/80338, International Publication No. 2008/75564, International Publication No. 2009/131189, International Publication No. 2009/131189, International Publication No. 2010/133077, International Publication No. 2010/102502, and International Publication No. 2012/68879 can be used.
  • the photopolymerization initiator described in JP 2016-133574 A can also be suitably used because it reduces contamination by colorants.
  • the photopolymerization initiator may be used alone or in combination of two or more kinds.
  • the photopolymerization initiator may contain a sensitizing dye and a polymerization promoter according to the wavelength of the image exposure light source, if necessary, for the purpose of increasing the sensitivity.
  • sensitizing dye examples include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarin dyes having a heterocycle described in JP-A-3-239703 and JP-A-5-289335, 3-ketocoumarin compounds described in JP-A-3-239703 and JP-A-5-289335, pyrromethene dyes described in JP-A-6-19240, JP-A-47-2528, JP-A-54-155292, and JP-A-54-155293.
  • Examples of dyes having a dialkylaminobenzene skeleton include those described in JP-B-45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69, JP-A-57-168088, JP-A-5-107761, JP-A-5-210240, and JP-A-4-288818.
  • an amino group-containing sensitizing dye is preferred, and a compound having an amino group and a phenyl group in the same molecule is more preferred.
  • benzophenone compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,
  • p-Dialkylaminophenyl group-containing compounds such as (p-nyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, and (p-diethylaminophenyl)pyrimidine are preferred, with 4,4'-dialkylaminobenzophenone being particularly preferred.
  • the sensitizing dyes may be used alone or in combination of two or more kinds.
  • the polymerization accelerator include aromatic amines such as ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, and 4-dimethylaminopropiophenone, and aliphatic amines such as n-butylamine, N-methyldiethanolamine, and 2-dimethylaminoethyl benzoate.
  • aromatic amines such as ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, and 4-dimethylaminopropiophenone
  • aliphatic amines such as n-butylamine, N-methyldiethanolamine, and 2-dimethylaminoethyl benzoate.
  • the photosensitive resin composition of the present invention contains an ethylenically unsaturated compound (C) represented by the following general formula (2).
  • R 4 to R 6 each independently represent an alkylene group, and the alkylene group may be interrupted by an etheric oxygen atom.
  • R 7 to R 9 each independently represent a hydrogen atom or a methyl group.
  • the compound has a hydroxy group
  • the boiling point is increased and the amount of fumes, which are gases generated during the baking treatment of the photosensitive resin composition of the present invention, tends to be reduced.
  • an acid anhydride is added to a hydroxy group
  • the decomposition of the acid anhydride tends to occur easily, and the amount of fumes tends to increase.
  • the increase in the carboxyl group tends to decrease the development resistance.
  • an organic electroluminescence device When an organic electroluminescence device is formed using a partition wall obtained by curing a photosensitive resin composition due to the small taper angle, the organic material can be uniformly deposited, and disconnection and the like are less likely to occur, improving the productivity of the device.
  • a high residual film rate tends to prevent decomposition products, by-products, uncured materials, etc. in the composition from remaining on the anode or from adhering again.
  • a low amount of fumes can reduce the amount of decomposition products adhering to and contaminating the inner wall surface of the chamber.
  • the boiling point becomes higher than that of a compound having one or two hydroxyl groups, and the boiling point of the thermal decomposition product during baking also becomes higher, and the amount of fumes tends to decrease. Also, by containing (meth)acryloyloxy groups in three side chains, the exposure sensitivity becomes higher, and the amount of fumes tends to decrease.
  • the alkylene group in R 4 to R 6 preferably has 1 or more carbon atoms.
  • the alkylene group preferably has 6 or less carbon atoms, more preferably 4 or less carbon atoms, and even more preferably 2 or less carbon atoms.
  • the alkylene group may be linear or branched.
  • alkylene groups include methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, and n-hexylene groups, as well as ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, and n-hexylene groups interrupted by an ether oxygen atom.
  • preferred are methylene, ethylene, and n-propylene groups, and more preferred is methylene.
  • the molecular weight of the ethylenically unsaturated compound (C) is not particularly limited, but is preferably 500 or more. It is also preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less.
  • the above upper and lower limits can be combined in any way. For example, 500 to 1000 is preferred, 500 to 800 is more preferred, and 500 to 600 is even more preferred.
  • the boiling point tends to be high and fumes tend to be suppressed.
  • the exposure sensitivity tends to be high and development resistance and remaining film rate tend to be improved.
  • the double bond equivalent of the ethylenically unsaturated compound (C) is not particularly limited, but is preferably 170 or more, more preferably 180 or more. Also, it is preferably 240 or less, more preferably 220 or less, and even more preferably 200 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 170 to 240, more preferably 170 to 220, and even more preferably 180 to 200. By making it equal to or more than the lower limit, fumes tend to be suppressed. By making it equal to or less than the upper limit, development resistance and film remaining rate tend to be improved.
  • Examples of the ethylenically unsaturated compound (C) include structures represented by the following formulas (C1-1) and (C1-4) to (C1-8).
  • the ethylenically unsaturated compound (C) a structure represented by formula (C1-1) is preferable from the viewpoint of exposure sensitivity.
  • the method for producing the ethylenically unsaturated compound (C) is not particularly limited.
  • the ethylenically unsaturated compound can be obtained by adding (meth)acrylic acid to an epoxy resin represented by the following formula (3).
  • an ethylenically unsaturated compound other than the (C) ethylenically unsaturated compound (C2) may be contained.
  • the (C2) ethylenically unsaturated compound is a compound having at least one ethylenically unsaturated group in the molecule, other than the (C) ethylenically unsaturated compound, and specifically includes, for example, (meth)acrylic acid, (meth)acrylic acid alkyl ester, acrylonitrile, styrene, a carboxylic acid having one ethylenically unsaturated bond, and a monoester of a polyhydric or monohydric alcohol.
  • the ethylenically unsaturated compound (C2) when the ethylenically unsaturated compound (C2) is contained, it is preferable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule.
  • the number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is not particularly limited, but is preferably two or more, more preferably four or more, even more preferably five or more, and preferably eight or less, and more preferably seven or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 2 to 8 are preferable, 2 to 7 are more preferable, 4 to 7 are even more preferable, and 5 to 7 are particularly preferable.
  • polyfunctional ethylenic monomers examples include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; and esters obtained by esterification reactions between polyhydric hydroxy compounds, such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, and unsaturated carboxylic acids and polybasic carboxylic acids.
  • Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include, for example, acrylic acid esters of aliphatic polyhydroxy compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate; methacrylic acid esters in which these acrylates are replaced with methacrylates; itaconic acid esters in which these acrylates are replaced with itaconates; crotonic acid esters in which these acrylates are replaced with crotonates; and maleic acid esters in which these acrylates are replaced with maleates
  • esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate.
  • Esters obtained by the esterification reaction of polybasic carboxylic acids and unsaturated carboxylic acids with polyhydric hydroxy compounds are not necessarily single compounds, but examples include condensates of acrylic acid, phthalic acid, and ethylene glycol, condensates of acrylic acid, maleic acid, and diethylene glycol, condensates of methacrylic acid, terephthalic acid, and pentaerythritol, and condensates of acrylic acid, adipic acid, butanediol, and glycerin.
  • urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylic acid ester
  • epoxy acrylates
  • urethane (meth)acrylates examples include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, and UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, and UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Mitsubishi Chemical Corporation).
  • the (C2) ethylenically unsaturated compound a urethane (meth)acrylate obtained by reacting a (meth)acrylic acid alkyl ester, a polyisocyanate compound with a hydroxy group-containing (meth)acrylic acid ester, or a polyisocyanate compound with a polyol and a hydroxy group-containing (meth)acrylic acid ester, and it is more preferable to use a polyisocyanate compound and a hydroxy group-containing (meth)acrylic acid ester.
  • a urethane (meth)acrylate obtained by reacting a (meth)acrylic acid alkyl ester, a polyisocyanate compound with a hydroxy group-containing (meth)acrylic acid ester, or a polyisocyanate compound with a polyol and a hydroxy group-containing (meth)acrylic acid ester, and it is more preferable to use a polyisocyanate compound and a hydroxy group-
  • the photosensitive resin composition of the present invention preferably contains a colorant (D).
  • a colorant (D) By containing the colorant (D), appropriate light absorption properties can be obtained, particularly appropriate light shielding properties when used for forming a light shielding member such as a partition wall.
  • the colorant (D) in the present invention preferably contains an organic black pigment (D-1). By including the organic black pigment (D-1), the insulating properties tend to be improved.
  • Examples of the organic black pigment (D-1) include perylene-based black pigments, aniline-based black pigments, and benzodifuranone-based black pigments.
  • Examples of perylene-based black pigments include Lumogen Black (registered trademark) FK4281, K0087, and Paliogen Black (registered trademark) EH0788 (all manufactured by BASF).
  • aniline-based black pigments examples include Paliotol Black (registered trademark) L0080, D0080, and K0080 (all manufactured by BASF).
  • organic black pigment (D-1) from the viewpoints of light-shielding properties, dispersibility, developability, and light-emitting properties, a benzodifuranone-based black pigment is preferred.
  • R 611 and R 616 each independently represent a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
  • R 612 , R 613 , R 614 , R 615 , R 617 , R 618 , R 619 and R 620 each independently represent a hydrogen atom, a halogen atom, R 621 , COOH, COOR 621 , COO - , CONH 2 , CONHR 621 , CONR 621 R 622 , CN, OH, OR 621 , COCR 621 , OOCNH 2 , OOCNHR 621 , OOCNR 621 R 622 , NO 2 , NH 2 , NHR 621 , NR 621 R 622 , NHCOR 622 , NR 621 COR 622 , N ⁇ CH 2 , N ⁇ CHR 621 , N ⁇ CR 621 R 622 , SH, SR 621 , S
  • Compound (D-1-1) and the geometric isomers of compound (D-1-1) have the following core structure (substituents in the structural formula are omitted), with the trans-trans isomer being likely the most stable.
  • compound (D-1-1) When compound (D-1-1) is anionic, it is preferably a salt whose charge is compensated by any known suitable cation, such as a metal, organic, inorganic or metal-organic cation, specifically an alkali metal, an alkaline earth metal, a transition metal, a primary ammonium, a secondary ammonium, a tertiary ammonium such as a trialkylammonium, a quaternary ammonium such as a tetraalkylammonium, or an organometallic complex. Also, when a geometric isomer of compound (D-1-1) is anionic, it is preferably a similar salt.
  • a metal, organic, inorganic or metal-organic cation specifically an alkali metal, an alkaline earth metal, a transition metal, a primary ammonium, a secondary ammonium, a tertiary ammonium such as a trialkylammonium, a quaternary ammoni
  • R 612 , R 614 , R 615 , R 617 , R 619 and R 620 each independently represent preferably a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.
  • R 613 and R 618 are each independently preferably a hydrogen atom, NO 2 , OCH 3 , OC 2 H 5 , a bromine atom, a chlorine atom, CH 3 , C 2 H 5 , N(CH 3 ) 2 , N(CH 3 )(C 2 H 5 ), N(C 2 H 5 ) 2 , ⁇ -naphthyl, ⁇ -naphthyl, SO 3 H or SO 3 -- , more preferably a hydrogen atom or SO 3 H, and particularly preferably a hydrogen atom.
  • R 611 and R 616 each independently represent preferably a hydrogen atom, CH 3 or CF 3 , more preferably a hydrogen atom.
  • At least one combination selected from the group consisting of R 611 and R 616 , R 612 and R 617 , R 613 and R 618 , R 614 and R 619 , and R 615 and R 620 is the same, more preferably, R 611 is the same as R 616 , R 612 is the same as R 617 , R 613 is the same as R 618 , R 614 is the same as R 619 , and R 615 is the same as R 620 .
  • alkyl group having 1 to 12 carbon atoms examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a 2-methylbutyl group, an n-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2,2-dimethylpropyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 1,1,3,3-tetramethylbutyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.
  • Cycloalkyl groups having 3 to 12 carbon atoms include, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, trimethylcyclohexyl, thujyl, norbornyl, bornyl, norcaryl, caryl, menthyl, norpinyl, pinyl, adamantan-1-yl, and adamantan-2-yl groups.
  • alkenyl groups having 2 to 12 carbon atoms include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadiene-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadiene-3-yl, hexenyl, octenyl, nonenyl, decenyl, and dodecenyl.
  • Cycloalkenyl groups having 3 to 12 carbon atoms include, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadiene-1-yl, 1-p-menthen-8-yl, 4(10)-thujein-10-yl, 2-norbornen-1-yl, 2,5-norbornadiene-1-yl, 7,7-dimethyl-2,4-norcaradien-3-yl, or camphenyl.
  • the alkynyl group having 2 to 12 carbon atoms is, for example, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyne-6-yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyne-8-yl, 1-nonyne-9-yl, 1-decyn-10-yl, or 1-dodecyn-12-yl.
  • the halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • the organic black pigment represented by formula (D-1-1) is preferably an organic black pigment containing at least one selected from the group consisting of a compound represented by the following general formula (D-1-2) (hereinafter, also referred to as "compound (D-1-2)”) and a geometric isomer of compound (D-1-2):
  • the compound (D-1-2) is the trade name Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF).
  • This organic black pigment is preferably dispersed using a dispersant, a solvent, and a method described below before use.
  • a sulfonic acid derivative of the compound (D-1-1), particularly a sulfonic acid derivative of the compound (D-1-2) is present during dispersion, dispersibility and storage stability may be improved, so it is preferable that the organic black pigment contains these sulfonic acid derivatives.
  • the colorant (D) that can be used in the photosensitive resin composition of the present invention may be used in combination with a colorant other than the organic black pigment (D-1).
  • the colorant that can be used in combination is not particularly limited, and a pigment or a dye may be used. From the viewpoint of durability, it is preferable to use a pigment.
  • the organic color pigment include organic color pigments other than organic black pigments, and inorganic pigments. Examples of the organic color pigment include red pigments, orange pigments, blue pigments, purple pigments, green pigments, and yellow pigments.
  • an organic coloring pigment From the viewpoints of suppressing absorption of ultraviolet light, improving curability, and making it easier to control the shape of the cured product, it is preferable to use an organic coloring pigment.
  • the organic coloring pigment to be used in combination with the organic black pigment may be used alone or in combination of two or more. In particular, it is more preferable to use a combination of organic coloring pigments that exhibit a color close to black when combined with the organic black pigment.
  • organic coloring pigments are not particularly limited, but examples include azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. Specific examples of pigments that can be used are shown below with their pigment numbers.
  • the "C.I.” in “C.I. Pigment Red 2" and other examples below stands for color index.
  • Red pigments include, for example, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123 , 144, 146, 147, 149, 151, 166 , 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193,
  • the photosensitive resin composition is cured with ultraviolet light, it is preferable to use a red pigment with a low ultraviolet absorption rate, and from this viewpoint, it is more preferable to use C.I. Pigment Red 254 and 272.
  • Orange pigments include, for example, C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79. From the viewpoint of dispersibility and light blocking properties, it is preferable to use C.I. Pigment Orange 13, 43, 64, and 72. When the photosensitive resin composition is cured with ultraviolet light, it is preferable to use an orange pigment with a low ultraviolet light absorption rate, and from this viewpoint, it is more preferable to use C.I. Pigment Orange 64 and 72.
  • blue pigments examples include C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. From the viewpoint of light-blocking properties, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60 are preferred, and C.I. Pigment Blue 15:6 is even more preferred. From the viewpoint of dispersibility and light-blocking properties, C.I. It is preferable to use C.I. Pigment Blue 15:6, 16, or 60. When the photosensitive resin composition is cured with ultraviolet light, it is preferable to use a blue pigment with a low ultraviolet absorption rate, and from this viewpoint, it is more preferable to use C.I. Pigment Blue 60.
  • Examples of purple pigments include C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. From the viewpoint of light-shielding properties, C.I. Pigment Violet 19, 23, and 29 are preferred, and C.I. Pigment Violet 23 is even more preferred. From the viewpoint of dispersibility and light-shielding properties, it is preferable to use C.I. Pigment Violet 23 and 29. When the photosensitive resin composition is cured with ultraviolet light, it is preferable to use a purple pigment with a low ultraviolet light absorption rate, and from this viewpoint, it is more preferable to use C.I. Pigment Violet 29.
  • Green pigments include, for example, C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, and 59.
  • C.I. Pigment Green 7 and 36 are preferred.
  • yellow pigments examples include C.I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 13 8, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185
  • Red pigment C.I. Pigment Red 177, 254, 272
  • Orange pigment C.I. Pigment Orange 43, 64, 72
  • Blue pigment C.I. Pigment Blue 15:6, 60 Purple pigment: C.I. Pigment Violet 23, 29
  • the combination of the organic color pigments is not particularly limited. From the viewpoint of light-shielding properties, however, it is preferable to contain at least one selected from the group consisting of a red pigment and an orange pigment, and at least one selected from the group consisting of a blue pigment and a purple pigment.
  • the color combination is not particularly limited, but from the viewpoint of light blocking properties, examples of the combination include a red pigment and a blue pigment, a blue pigment and an orange pigment, and a blue pigment, an orange pigment and a purple pigment.
  • the inorganic pigment it is preferable to use an inorganic black pigment from the viewpoint of higher light-shielding properties.
  • inorganic black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black. From the viewpoint of light-shielding properties and image characteristics, carbon black can be preferably used. Examples of carbon black include the following carbon blacks.
  • Printex (registered trademark, the same applies below) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, Special lBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, C color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S17 0
  • Cabot Corporation Monarch (registered trademark, hereinafter the same) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark, hereinafter the same) Same below.) 99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL550R, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark, same below), XC72R, ELFTEX (registered trademark)-8
  • RAVEN registered trademark, same below
  • RAVEN 14 RAVEN 15, RAVEN 16, RAVEN 22, RAVEN 30, RAVEN 35, RAVEN 40, RAVEN 410, RAVEN 420, RAVEN 450, RAVEN 500, RAVEN 780, RAVEN 850, RAVEN 890H
  • RAVEN 10 00, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVE N5000, RAVEN5250, RAVEN5750, RAVEN7000
  • Carbon black whose surface has been treated with an acid may be used.
  • the carbon black described in Japanese Patent Publication No. 3674086 can be preferably used.
  • Carbon black coated with resin may also be used.
  • the use of resin-coated carbon black has the effect of improving adhesion to glass substrates and volume resistivity.
  • the carbon black described in Japanese Patent Publication No. 09-71733 can be preferably used as resin-coated carbon black.
  • resin-coated carbon black is preferably used.
  • the average particle size of the pigment is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.25 ⁇ m or less, where the average particle size is determined by the number of pigment particles.
  • the average particle size of the pigment is a value determined from the pigment particle size measured by dynamic light scattering (DLS). The particle size measurement is performed on a sufficiently diluted photosensitive resin composition (usually diluted to a pigment concentration of about 0.005 to 0.2% by mass; however, if there is a concentration recommended by the measuring instrument, this concentration should be followed) at 25°C.
  • dyes may also be used.
  • dyes that can be used as colorants include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
  • Azo dyes include, for example, C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive Red 17, C.I. Reactive Red 120, C.I. Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Examples include Mordant Red 7, C.I. Mordant Yellow 5, and C.I. Mordant Black 7.
  • anthraquinone dyes examples include C.I. Bat Blue 4, C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, and C.I. Disperse Blue 60.
  • An example of a phthalocyanine dye is C.I. Vat Blue 5.
  • quinoneimine dyes examples include C.I. Basic Blue 3 and C.I. Basic Blue 9.
  • examples of quinoline dyes include C.I. Solvent Yellow 33, C.I. Acid Yellow 3, and C.I. Disperse Yellow 64.
  • Examples of nitro dyes include C.I. Acid Yellow 1, C.I. Acid Orange 3, and C.I. Disperse Yellow 42.
  • the photosensitive resin composition of the present invention may contain a dispersant (E) in order to finely disperse the colorant (D) and stabilize the dispersed state.
  • a dispersant (E) dispersant a polymer dispersant having a functional group is preferred, and furthermore, from the viewpoint of dispersion stability, a polymer dispersant having a functional group such as a carboxy group, a phosphoric acid group, a sulfonic acid group, or a base thereof, a primary, secondary or tertiary amino group, a quaternary ammonium group, or a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine is preferred.
  • a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group, a quaternary ammonium group, or a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine is particularly preferred from the viewpoint of being able to disperse the pigment with a small amount of dispersant.
  • polymeric dispersants examples include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants consisting of monomers and macromonomers with amino groups, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene diester-based dispersants, polyether phosphate-based dispersants, polyester phosphate-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified polyester-based dispersants.
  • Examples of such dispersants include, by trade name, EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK-Chemie), DISPARLON (registered trademark, manufactured by Kusumoto Chemical Industries, Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and AJISPER (registered trademark, manufactured by Ajinomoto Co., Inc.).
  • the polymer dispersing agent may be used alone or in combination of two or more kinds.
  • the dispersant (E) preferably contains either one or both of a urethane-based polymer dispersant having a functional group and an acrylic-based polymer dispersant, and it is particularly preferable that the dispersant contains an acrylic-based polymer dispersant.
  • polymer dispersants having a basic functional group and either or both of a polyester bond and a polyether bond are preferred.
  • urethane-based and acrylic-based polymer dispersants examples include DISPERBYK-160 to 167 and 182 series (all urethane-based), DISPERBYK-2000, 2001, and BYK-LPN21116 (all acrylic-based) (all manufactured by BYK-Chemie).
  • the amine value of the polymer dispersant having a basic functional group is not particularly limited, but is preferably 1 mgKOH/g or more, more preferably 10 mgKOH/g or more, even more preferably 20 mgKOH/g or more, even more preferably 40 mgKOH/g or more, and particularly preferably 50 mgKOH/g or more. Also, it is preferably 140 mgKOH/g or less, more preferably 120 mgKOH/g or less, even more preferably 100 mgKOH/g or less, even more preferably 90 mgKOH/g or less, and particularly preferably 80 mgKOH/g or less.
  • the above upper and lower limits can be arbitrarily combined.
  • 1 to 140 mgKOH/g is preferred, 10 to 120 mgKOH/g is more preferred, 20 to 100 mgKOH/g is more preferred, 40 to 90 mgKOH/g is even more preferred, and 50 to 80 mgKOH/g is particularly preferred.
  • the dispersibility tends to be good.
  • compatibility with the alkali-soluble resin (A) tends to be good.
  • the acrylic dispersant is preferably an A-B or B-A-B block copolymer composed of an A block having the above-mentioned functional group and a B block not having the above-mentioned functional group.
  • the A block in addition to the partial structure derived from the unsaturated group-containing monomer containing the above-mentioned functional group, the A block may contain a partial structure derived from the unsaturated group-containing monomer not having the above-mentioned functional group, and these may be contained in the A block in either the form of random copolymerization or block copolymerization.
  • the content ratio of the partial structure not having a functional group in the A block is preferably 80 mass% or less, more preferably 50 mass% or less, even more preferably 30 mass% or less, even more preferably 10 mass% or less, and particularly preferably 0 mass%.
  • the B block is composed only of partial structures derived from unsaturated group-containing monomers that do not contain the above-mentioned functional groups, and partial structures derived from two or more types of monomers may be contained in one B block, and these may be contained in the B block in either a random copolymerization or block copolymerization form.
  • the AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below.
  • Living polymerization methods include anionic living polymerization methods, cationic living polymerization methods, and radical living polymerization methods. Of these, in anionic living polymerization methods, the active species for polymerization is an anion, and is represented, for example, by the following scheme.
  • Ar 1 is a monovalent organic group
  • Ar 2 is a monovalent organic group different from Ar 1
  • M is a metal atom
  • s and t are each an integer of 1 or more.
  • the active species for polymerization is a radical, and for example, it is shown in the following scheme.
  • Ar 1 is a monovalent organic group
  • Ar 2 is a monovalent organic group different from Ar 1
  • j and k are each an integer of 1 or more
  • R a is a hydrogen atom or a monovalent organic group
  • R b is a hydrogen atom or a monovalent organic group different from R a .
  • the acrylic dispersant that can be used in the present invention may be an A-B block copolymer or a B-A-B block copolymer, and the A block/B block ratio that constitutes the copolymer is not particularly limited, but is preferably 1/99 to 80/20 (mass ratio), and more preferably 5/95 to 60/40 (mass ratio). By keeping it within this range, it tends to be easier to ensure a balance between dispersibility and storage stability.
  • the amount of quaternary ammonium groups in 1 g of the A-B block copolymer or B-A-B block copolymer that can be used in the present invention is preferably 0.1 to 10 mmol. By keeping it within this range, good dispersibility tends to be easily ensured.
  • Such an acrylic dispersant may contain an amino group.
  • the amine value of the acrylic dispersant is preferably 1 mgKOH/g or more, more preferably 10 mgKOH/g or more, even more preferably 20 mgKOH/g or more, even more preferably 40 mgKOH/g or more, and particularly preferably 50 mgKOH/g or more. Also, it is preferably 140 mgKOH/g or less, more preferably 120 mgKOH/g or less, even more preferably 100 mgKOH/g or less, even more preferably 90 mgKOH/g or less, and particularly preferably 80 mgKOH/g or less.
  • the above upper and lower limits can be arbitrarily combined.
  • 1 to 140 mgKOH/g is preferred, 10 to 120 mgKOH/g is more preferred, 20 to 100 mgKOH/g is more preferred, 40 to 90 mgKOH/g is even more preferred, and 50 to 80 mgKOH/g is particularly preferred.
  • the dispersibility tends to be good.
  • compatibility with the alkali-soluble resin (A) tends to be good.
  • the amine value of the acrylic dispersant is expressed as the mass of KOH equivalent to the amount of base per gram of solids excluding the solvent in a dispersant sample, and is measured by the following method. Weigh out 0.5 to 1.5 g of the dispersant sample into a 100 mL beaker and dissolve it in 50 mL of acetic acid. Using an automatic titrator equipped with a pH electrode, neutralize this solution with a 0.1 mol/L HClO4 acetic acid solution. The inflection point of the titration pH curve is set as the titration end point, and the amine value is calculated using the following formula.
  • Amine value [mg KOH/g] (561 x V) / (W x S) (W: weight of dispersant sample [g], V: titration amount at the end of titration [mL], S: solids concentration of dispersant sample [mass %].)
  • the weight average molecular weight (Mw) of the acrylic dispersant is not particularly limited, but is preferably 1000 or more, more preferably 3000 or more, even more preferably 4000 or more, and particularly preferably 5000 or more. Also, it is preferably 50,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.
  • the above upper and lower limits can be combined in any manner. For example, 1000 to 50,000 is preferred, 3000 to 50,000 is more preferred, 4000 to 20,000 is more preferred, and 5000 to 15,000 is particularly preferred.
  • the acrylic dispersant preferably has a tertiary amino group and/or a quaternary ammonium group.
  • the acrylic dispersant has a quaternary ammonium group as a functional group
  • the chemical structure of the repeating unit containing the quaternary ammonium group is not particularly limited. From the viewpoint of dispersibility, it is preferable that the acrylic dispersant has a repeating unit represented by the following general formula (V) (hereinafter, sometimes referred to as "repeating unit (V)").
  • R 31 to R 33 are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and two or more of R 31 to R 33 may be bonded to each other to form a cyclic structure.
  • R 34 is a hydrogen atom or a methyl group.
  • X is a divalent linking group, and Y ⁇ is a counter anion.
  • the alkyl groups which may have a substituent in R 31 to R 33 of formula (V) may be either linear or branched. They may also have a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
  • the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, more preferably 10 or less, more preferably 6 or less, even more preferably 4 or less, and particularly preferably 2 or less.
  • 1 to 10 is preferred, 1 to 6 is more preferred, 1 to 4 is even more preferred, and 1 to 2 is particularly preferred.
  • alkyl group examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups, with methyl, ethyl, propyl, butyl, pentyl, and hexyl groups being preferred, methyl, ethyl, propyl, and butyl groups being more preferred, and methyl and ethyl groups being even more preferred.
  • the number of carbon atoms of the aryl group which may have a substituent in R 31 to R 33 of formula (V) is not particularly limited, but is preferably 6 or more, and is preferably 16 or less, and more preferably 12 or less. For example, 6 to 16 is preferable, and 6 to 12 is more preferable.
  • aryl group examples include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group, with a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, and a diethylphenyl group being preferable, and a phenyl group, a methylphenyl group, and an ethylphenyl group being more preferable.
  • the number of carbon atoms in the aralkyl group which may have a substituent in R 31 to R 33 in formula (V) is not particularly limited, but is preferably 7 or more, and is also preferably 16 or less, more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less.
  • 7 to 16 is preferable, 7 to 12 is more preferable, 7 to 10 is even more preferable, and 7 to 8 is particularly preferable.
  • Examples of the aralkyl group include a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group, with a phenylmethyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group being preferable, and a phenylmethyl group and a phenylethyl group being more preferable.
  • R 31 to R 33 are each independently an alkyl group or an aralkyl group, and it is preferable that R 31 to R 33 are each independently a methyl group or a phenylmethyl group.
  • examples of Y ⁇ include Cl ⁇ , Br ⁇ , I ⁇ , ClO 4 ⁇ , BF 4 ⁇ , CH 3 COO ⁇ and PF 6 ⁇ .
  • aromatic dicarboxylic acid imide anions aromatic sulfonic acid anions, aromatic phosphonic acid anions, and aromatic carboxylate anions described in WO 2018/079659; and alkyl sulfate anions and alkyl sulfonate anions described in WO 2019/107020; may also be suitably used.
  • the polymer dispersant has a tertiary amine as a functional group, from the viewpoints of dispersibility and light-emitting properties, it preferably has a repeating unit represented by the following general formula (VI) (hereinafter sometimes referred to as "repeating unit (VI)").
  • R 35 and R 36 are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and R 35 and R 36 may be bonded to each other to form a cyclic structure.
  • R 37 is a hydrogen atom or a methyl group.
  • Z is a divalent linking group.
  • alkyl group which may have a substituent in R 35 and R 36 in formula (VI) those exemplified as R 31 to R 33 in formula (V) can be preferably used.
  • aryl group which may have a substituent in R 35 and R 36 in formula (VI) those exemplified as R 31 to R 33 in formula (V) can be preferably used.
  • R 35 and R 36 each independently represent an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.
  • Examples of the substituent that the alkyl group, aralkyl group or aryl group in R 31 to R 33 in formula (V) and R 35 and R 36 in formula (VI) may have include a halogen atom, an alkoxy group, a benzoyl group and a hydroxy group.
  • Examples of X in formula (V) and Z in formula (VI) each include an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a -CONH-R 43 - group, or a -COOR 44 - group (wherein R 43 and R 44 are single bonds, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms), preferably a -COO-R 44 - group, and more preferably a -COO-C 2 H 4 - group.
  • the compound has the repeating unit (V), and from the viewpoint of light-emitting properties, it is preferable that the compound has both the repeating unit (V) and the repeating unit (VI).
  • the content ratio of the repeating unit (V) in the total repeating units of the dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, and particularly preferably 8 mol% or more. Also, it is preferably 50 mol% or less, more preferably 30 mol% or less, even more preferably 20 mol% or less, and particularly preferably 15 mol% or less.
  • the content ratio of repeating unit (VI) in the total repeating units of the dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, and particularly preferably 20 mol% or more. It is also preferably 60 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, and particularly preferably 25 mol% or less.
  • the acrylic dispersant has a repeating unit represented by the following general formula (VII) (hereinafter sometimes referred to as "repeating unit (VII)").
  • R 40 is an ethylene group or a propylene group
  • R 41 is an alkyl group which may have a substituent
  • R 42 is a hydrogen atom or a methyl group
  • n is an integer of 1 to 20.
  • the alkyl group which may have a substituent in R 41 of formula (VII) may be either linear or branched. It may also include a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
  • the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. It is also preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
  • Methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group are preferred, and methyl group, ethyl group, propyl group, and butyl group are more preferred.
  • n is preferably 1 or more, more preferably 2 or more, from the viewpoint of compatibility and dispersibility in an alkali-soluble resin component such as a solvent. It is also preferably 10 or less, more preferably 5 or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 10 is preferred, and 2 to 5 is more preferred.
  • the content ratio of repeating unit (VII) in all repeating units of the dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 4 mol% or more. Also, it is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 30 mol% is preferred, 2 to 20 mol% is more preferred, and 4 to 10 mol% is even more preferred. Within the above range, it tends to be easier to achieve both compatibility with alkali-soluble resin components such as solvents and dispersion stability.
  • the acrylic dispersant has a repeating unit represented by the following general formula (VIII) (hereinafter sometimes referred to as "repeating unit (VIII)").
  • R 38 is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent
  • R 39 is a hydrogen atom or a methyl group.
  • the alkyl group which may have a substituent in R 38 of formula (VIII) may be either linear or branched. It may also include a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
  • the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 4 or more. It is also preferably 10 or less, and more preferably 8 or less.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a 2-ethylhexyl group.
  • a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a 2-ethylhexyl group are preferred, and a methyl group, an ethyl group, a propyl group, a butyl group, and a 2-ethylhexyl group are more preferred.
  • the number of carbon atoms of the aryl group which may have a substituent in R 38 of formula (VIII) is not particularly limited, but is preferably 6 or more. It is also preferably 16 or less, more preferably 12 or less, and even more preferably 8 or less. For example, 6 to 16 is preferable, 6 to 12 is more preferable, and 6 to 8 is even more preferable.
  • aryl group examples include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group, of which a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, and a diethylphenyl group are preferable, and a phenyl group, a methylphenyl group, and an ethylphenyl group are more preferable.
  • the number of carbon atoms in the aralkyl group which may have a substituent in R 38 of formula (VIII) is not particularly limited, but is preferably 7 or more, and is also preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less. For example, it is preferably 7 to 16, more preferably 7 to 12, and even more preferably 7 to 10.
  • aralkyl group examples include a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group, and is preferably a phenylmethyl group, a phenylethyl group, a phenylpropyl group, or a phenylbutyl group, and more preferably a phenylmethyl group or a phenylethyl group.
  • R 38 is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group, a butyl group, a 2-ethylhexyl group or a phenylmethyl group.
  • examples of the substituent that the alkyl group may have include a halogen atom and an alkoxy group.
  • examples of the substituent that the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, and an alkoxy group.
  • the chain alkyl group represented by R 38 includes both linear and branched chain alkyl groups.
  • the content of repeating unit (VIII) in all repeating units of the dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 50 mol% or more. Also, it is preferably 80 mol% or less, and more preferably 70 mol% or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 30 to 80 mol% is preferable, 40 to 80 mol% is more preferable, and 50 to 70 mol% is even more preferable.
  • the acrylic dispersant may have repeating units other than the repeating units (V), (VI), (VII) and (VIII).
  • repeating units include styrene-based monomers such as styrene and ⁇ -methylstyrene; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide-based monomers such as (meth)acrylamide and N-methylolacrylamide; and repeating units derived from monomers such as vinyl acetate, acrylonitrile, allyl glycidyl ether, crotonic acid glycidyl ether and N-methacryloylmorpholine.
  • the acrylic dispersant is preferably a block copolymer having an A block having repeating units (V) and (VI) and a B block having no repeating units (V) and (VI).
  • the block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer.
  • the B block has a repeating unit (VII), and more preferably has a repeating unit (VIII).
  • the repeating unit (V) and the repeating unit (VI) may be contained in either a random copolymerization or block copolymerization manner.
  • two or more types of each of the repeating unit (V) and the repeating unit (VI) may be contained in one A block, and in that case, each repeating unit may be contained in the A block in either a random copolymerization or block copolymerization manner.
  • Repeat units other than repeat unit (V) and repeat unit (VI) may be contained in the A block, and examples of such repeat units include the repeat units derived from the (meth)acrylic acid ester monomers described above.
  • the content of repeat units other than repeat unit (V) and repeat unit (VI) in the A block is preferably 0 to 50 mol %, more preferably 0 to 20 mol %, and it is particularly preferable that such repeat units are not contained in the A block.
  • Repeating units other than the repeating unit (VII) and the repeating unit (VIII) may be contained in the B block, and examples of such repeating units include styrene-based monomers such as styrene and ⁇ -methylstyrene, (meth)acrylate-based monomers such as (meth)acrylic acid chloride, (meth)acrylamide-based monomers such as (meth)acrylamide and N-methylolacrylamide, and repeating units derived from monomers such as vinyl acetate, acrylonitrile, allyl glycidyl ether, crotonic acid glycidyl ether, and N-methacryloylmorpholine.
  • styrene-based monomers such as styrene and ⁇ -methylstyrene
  • (meth)acrylate-based monomers such as (meth)acrylic acid chloride
  • (meth)acrylamide-based monomers such as (meth)acrylamide and N-methyl
  • the content of repeating units other than the repeating unit (VII) and the repeating unit (VIII) in the B block is preferably 0 to 50 mol %, more preferably 0 to 20 mol %, and it is particularly preferable that such repeating units are not contained in the B block.
  • These acrylic dispersants may be used alone or in combination of two or more kinds.
  • the photosensitive resin composition of the present invention may appropriately contain additives such as an adhesion improver such as a silane coupling agent, a surfactant, a pigment derivative, a photoacid generator, a crosslinking agent, a mercapto compound, and a polymerization inhibitor.
  • an adhesion improver such as a silane coupling agent, a surfactant, a pigment derivative, a photoacid generator, a crosslinking agent, a mercapto compound, and a polymerization inhibitor.
  • the photosensitive resin composition of the present invention may contain an adhesion improver in order to improve adhesion to a substrate.
  • an adhesion improver a silane coupling agent or a phosphoric acid group-containing compound is preferred.
  • silane coupling agent for example, various types such as epoxy-based, (meth)acrylic-based, and amino-based agents may be used alone or in combination of two or more.
  • silane coupling agent examples include (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, epoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, and isocyanatesilanes such as 3-isocyanatepropyltriethoxysilane.
  • epoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane
  • 3-glycidoxypropyltrimethoxysilane 3-glycidoxypropylmethyldiethoxysilane and 3-g
  • Epoxysilane silane coupling agents are particularly preferred.
  • (meth)acryloyl group-containing phosphates are preferred, and those represented by the following general formula (g1), (g2) or (g3) are preferred.
  • R 51 represents a hydrogen atom or a methyl group
  • l and l′ each represents an integer of 1 to 10
  • m is 1, 2 or 3.
  • These phosphoric acid group-containing compounds may be used alone or in combination of two or more.
  • the photosensitive resin composition of the present invention may contain a surfactant in order to improve the coatability.
  • a surfactant various types of surfactants can be used, such as anionic, cationic, nonionic, amphoteric surfactants, etc. It is preferable to use a nonionic surfactant because it is less likely to adversely affect various properties, and fluorine-based or silicone-based surfactants are more preferable in terms of coatability.
  • surfactants examples include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie), KP340 (manufactured by Shin-Etsu Silicones), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC), SH7PA (manufactured by Dow Corning Toray Co., Ltd.), DS-401 (manufactured by Daikin Industries, Ltd.), L-77 (manufactured by Nippon Unicar Co., Ltd.), and FC4430 (manufactured by 3M).
  • the surfactant may be used alone or in combination of two or more kinds.
  • the photosensitive resin composition of the present invention may contain a pigment derivative as a dispersing aid in order to improve dispersibility and storage stability.
  • pigment derivatives include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, dioxazine-based, anthraquinone-based, indanthrene-based, perylene-based, perinone-based, diketopyrrolopyrrole-based, and dioxazine-based derivatives, with phthalocyanine-based and quinophthalone-based derivatives being preferred.
  • substituents of the pigment derivative include sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxy groups, carboxy groups, and amide groups that are bonded to the pigment skeleton directly or via, for example, an alkyl group, an aryl group, or a heterocyclic group, and the preferred is a sulfonic acid group.
  • a single pigment skeleton may be substituted with multiple substituents, or may be substituted with multiple types of substituents.
  • pigment derivatives include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, and sulfonic acid derivatives of dioxazine. These may be used alone or in combination of two or more.
  • a mercapto compound can be added as a polymerization accelerator and to improve adhesion to the substrate.
  • Examples of mercapto compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, ethylene glycol bis (3-mercaptobutyrate), butanediol bis(3-
  • the photosensitive resin composition of the present invention may contain a polymerization inhibitor from the viewpoint of controlling the shape of the cured product. It is considered that the inclusion of a polymerization inhibitor inhibits the radical polymerization of the lower layer of the coating film, and therefore the taper angle (the angle between the support and the cured product in the cross section of the cured product) can be controlled.
  • polymerization inhibitors examples include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). From the viewpoint of shape control, 2,6-di-tert-butyl-4-cresol is preferred. From the viewpoint of particularly excellent safety to the human body, hydroquinone monomethyl ether and methylhydroquinone are preferred.
  • the polymerization inhibitor may be used alone or in combination of two or more kinds.
  • a polymerization inhibitor may be contained in the resin, and this may be used as the polymerization inhibitor of the present invention.
  • a polymerization inhibitor that is the same as or different from the polymerization inhibitor may be added during the production of the photosensitive resin composition.
  • the content ratio is not particularly limited, but is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, and is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and even more preferably 0.1% by mass or less, based on the total solid content of the photosensitive resin composition.
  • the above upper and lower limits can be arbitrarily combined. For example, 0.0005% by mass to 0.3% by mass is preferred, 0.001% by mass to 0.2% by mass is more preferred, and 0.01% by mass to 0.1% by mass is even more preferred.
  • the photosensitive resin composition of the present invention preferably contains a solvent. By containing a solvent, the colorant can be dispersed or dissolved in the solvent, and coating becomes easy.
  • the photosensitive resin composition of the present invention is used in a state where, for example, (A) an alkali-soluble resin, (B) a photopolymerization initiator, (D) a colorant, (E) a dispersant, and various other materials used as necessary are dissolved or dispersed in a solvent. From the viewpoints of dispersibility and coatability, an organic solvent is preferred.
  • an organic solvent with a boiling point of 100 to 300°C, and more preferably 120 to 280°C.
  • the boiling point referred to here means the boiling point at a pressure of 1013.25 hPa, and the same applies to all boiling points below.
  • Such organic solvents include, for example, glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;
  • glycol monoalkyl ethers such as ethylene
  • Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;
  • Glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;
  • Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether;
  • Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl pentanone; monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, and benzyl alcohol;
  • Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl; Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Chain or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, buty
  • Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; Halogenated hydrocarbons such as butyl chloride and amyl chloride; Ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile;
  • organic solvents that can be used include, for example, mineral spirits, Valsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso #150, Shell TS28 Solvent, Carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("Cellosolve” is a registered trademark; the same applies below), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diglyme (all trade names).
  • organic solvents may be used alone or in combination of two or more kinds.
  • the organic solvent to be selected has a boiling point of preferably 100 to 240°C, more preferably 120 to 200°C, and even more preferably 120 to 170°C.
  • glycol alkyl ether acetates are preferred because they have a good balance of application properties, surface tension, etc., and the solubility of the components in the composition is relatively high.
  • the glycol alkyl ether acetates may be used alone or in combination of two or more kinds.
  • Glycol alkyl ether acetates may be used alone, or may be used in combination with other organic solvents.
  • organic solvent to be used in combination glycol monoalkyl ethers are preferred.
  • propylene glycol monomethyl ether is preferred.
  • Glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment is likely to aggregate, and the storage stability tends to decrease, for example, the viscosity of the photosensitive resin composition obtained later increases. Therefore, the ratio of glycol monoalkyl ethers to the total mass of the solvent is preferably 5 to 30 mass%, and more preferably 5 to 20 mass%.
  • the photosensitive resin composition becomes harder to dry, but since this has the effect of preventing the uniform dispersion of the pigment in the composition from being destroyed by rapid drying, high boiling point solvents may be used in combination. For example, this has the effect of preventing the occurrence of foreign matter defects caused by the precipitation and solidification of colorants at the tip of the slit nozzle.
  • diethylene glycol mono-n-butyl ether diethylene glycol mono-n-butyl ether acetate, or diethylene glycol monoethyl ether acetate in combination.
  • the content of the high-boiling point solvent in the organic solvent is preferably 3 to 50 mass%, more preferably 5 to 40 mass%, and particularly preferably 5 to 30 mass%.
  • the content is preferably 3 to 50 mass%, more preferably 5 to 40 mass%, and particularly preferably 5 to 30 mass%.
  • the high boiling point solvent may be a glycol alkyl ether acetate or a glycol alkyl ether, in which case it is not necessary to separately contain a high boiling point solvent.
  • Preferred high boiling point solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, and triacetin.
  • the content ratio of the colorant (D) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, based on the total solid content of the photosensitive resin composition. Also, it is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, even more preferably 15 to 30% by mass, even more preferably 15 to 25% by mass, and particularly preferably 15 to 20% by mass.
  • the content of the organic black pigment (D-1) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, based on the total solid content of the photosensitive resin composition. Also, it is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less.
  • the above upper and lower limits can be arbitrarily combined. For example, 5 to 40% by mass is preferred, 10 to 30% by mass is more preferred, 15 to 30% by mass is even more preferred, 15 to 25% by mass is even more preferred, and 15 to 20% by mass is particularly preferred.
  • the content ratio is not particularly limited, but is preferably 1 mass% or more, more preferably 5 mass% or more, and even more preferably 10 mass% or more, based on the total solid content of the photosensitive resin composition. Also, it is preferably 30 mass% or less, and more preferably 20 mass% or less.
  • the above upper and lower limits can be arbitrarily combined. For example, 1 to 30 mass% is preferred, 5 to 20 mass% is more preferred, and 10 to 20 mass% is even more preferred.
  • the content of (E) the dispersant is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, relative to the total solid content of the photosensitive resin composition, and is also preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and even more preferably 7% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 20% by mass is preferred, 2 to 15% by mass is more preferred, 3 to 10% by mass is even more preferred, and 3 to 7% by mass is particularly preferred.
  • the content ratio of (E) dispersant relative to 100 parts by mass of (D) colorant is not particularly limited, but is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and preferably 50 parts by mass or less, and more preferably 30 parts by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 5 to 50 parts by mass is preferred, 10 to 50 parts by mass is more preferred, and 15 to 30 parts by mass is even more preferred.
  • the content of the alkali-soluble resin (A) is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 40% by mass or more, based on the total solid content of the photosensitive resin composition, and is also preferably 85% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 55% by mass or less.
  • the above upper and lower limits can be arbitrarily combined.
  • 5 to 80% by mass is preferred, 10 to 70% by mass is more preferred, 20 to 60% by mass is even more preferred, 30 to 60% by mass is even more preferred, 30 to 55% by mass is even more preferred, and 40 to 55% by mass is even more preferred.
  • the lower limit or more it is possible to suppress the decrease in the solubility of the unexposed part in the developer and to suppress development defects.
  • the upper limit or less it is possible to maintain the appropriate sensitivity, suppress dissolution of the exposed part in the developer, and tend to reduce the taper angle.
  • the content ratio of the epoxy (meth)acrylate resin (A1) is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, particularly preferably 30% by mass or more, and particularly preferably 40% by mass or more, and is preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 55% by mass or less, based on the total solid content of the photosensitive resin composition of the present invention.
  • the above upper and lower limits can be arbitrarily combined.
  • the solubility of the unexposed portion in the developer tends to be ensured.
  • the value at or below the upper limit appropriate sensitivity can be maintained, dissolution of exposed areas by the developer can be suppressed, and deterioration of the sharpness and adhesion of the pattern can be suppressed.
  • the content of the (A1) epoxy (meth)acrylate resin in the (A) alkali-soluble resin is not particularly limited, but is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, and is preferably 100% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 20 to 100% by mass is preferred, 30 to 90% by mass is more preferred, and 40 to 80% by mass is even more preferred.
  • the solubility of the unexposed portion in the developer tends to be ensured.
  • the appropriate sensitivity can be maintained, dissolution of the exposed portion in the developer can be suppressed, and a decrease in the sharpness and adhesion of the pattern can be suppressed.
  • the content of the isocyanuric skeleton-containing resin (A2) contained in the alkali-soluble resin (A) is not particularly limited, but is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 20 to 90% by mass is preferred, 30 to 80% by mass is more preferred, and 40 to 70% by mass is even more preferred.
  • the content of the (B) photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, and particularly preferably 3% by mass or more, based on the total solid content of the photosensitive resin composition of the present invention, and is also preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 8% by mass or less, and particularly preferably 6% by mass or less.
  • the above upper and lower limits can be arbitrarily combined.
  • 0.1 to 15% by mass is preferred, 0.5 to 15% by mass is more preferred, 1 to 10% by mass is even more preferred, 2 to 8% by mass is even more preferred, and 3 to 6% by mass is particularly preferred.
  • the content of the polymerization accelerator is not particularly limited, but is preferably 0.05% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, based on the total solid content of the photosensitive resin composition of the present invention.
  • 0.05 to 10% by mass is preferred, and 0.05 to 5% by mass is more preferred.
  • the polymerization accelerator is preferably used in an amount of 0.1 to 50 parts by mass, and more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the (B) photopolymerization initiator.
  • the content of the sensitizing dye is not particularly limited, but from the viewpoint of sensitivity, it is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total solid content in the photosensitive resin composition.
  • the total content ratio of the (C) ethylenically unsaturated compound and the (C2) ethylenically unsaturated compound is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 15% by mass or more, and is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less, based on the total solid content of the photosensitive resin composition of the present invention.
  • the upper and lower limits above can be arbitrarily combined.
  • 1 to 50% by mass is preferred, 1 to 30% by mass is more preferred, 5 to 25% by mass is even more preferred, 10 to 25% by mass is even more preferred, and 15 to 20% by mass is particularly preferred.
  • the content is set at or above the lower limit, it is possible to maintain appropriate sensitivity, suppress dissolution of the exposed portion by the developer, and also tend to suppress deterioration of the sharpness and adhesion of the pattern.
  • the content is set at or below the upper limit, it is possible to suppress high penetration of the developer into the exposed portion, and it tends to be easier to obtain a good image.
  • the content of the ethylenically unsaturated compound (C) is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and particularly preferably 15% by mass, and is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less, based on the total solid content of the photosensitive resin composition.
  • the upper and lower limits above can be arbitrarily combined. For example, 1 to 50% by mass is preferred, 1 to 30% by mass is more preferred, 5 to 25% by mass is even more preferred, 10 to 25% by mass is even more preferred, and 15 to 20% by mass is particularly preferred.
  • the content ratio of the (C) ethylenically unsaturated compound is not particularly limited, but is preferably 4% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 40% by mass or more, based on the total amount of the (C) ethylenically unsaturated compound and the (C2) ethylenically unsaturated compound. It is also preferably 100% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less. The above upper and lower limits can be arbitrarily combined.
  • 4 to 100% by mass is preferred, 4 to 90% by mass is more preferred, 20 to 90% by mass is even more preferred, 30 to 90% by mass is even more preferred, and 40 to 80% by mass is particularly preferred.
  • the taper angle tends to be smaller.
  • the upper limit or less the amount of fumes, which are gases generated during the firing process, tends to be suppressed.
  • the content ratio of the alkali-soluble resin (A) relative to 100 parts by mass of the total amount of the ethylenically unsaturated compound (C) and the ethylenically unsaturated compound (C2) is not particularly limited, but is preferably 100 parts by mass or more, more preferably 200 parts by mass or more, even more preferably 250 parts by mass or more, even more preferably 300 parts by mass or more, and particularly preferably 350 parts by mass or more. Also, it is preferably 700 parts by mass or less, more preferably 500 parts by mass or less, even more preferably 450 parts by mass or less, and particularly preferably 400 parts by mass or less. The above upper and lower limits can be arbitrarily combined.
  • it is preferably 100 to 700 parts by mass, more preferably 200 to 700 parts by mass, even more preferably 250 to 500 parts by mass, even more preferably 300 to 450 parts by mass, and particularly preferably 350 to 400 parts by mass.
  • the lower limit there is a tendency for an appropriate dissolution development state without peeling, etc. to be achieved.
  • the upper limit or less it is likely that an appropriate dissolution time in the developer can be obtained.
  • an adhesion enhancer When an adhesion enhancer is used, its content is not particularly limited, but is preferably 0.1 to 5 mass %, more preferably 0.2 to 3 mass %, and even more preferably 0.4 to 2 mass %, based on the total solid content of the photosensitive resin composition. By making the content equal to or greater than the lower limit, there is a tendency for the adhesion improving effect to be sufficiently obtained. By making the content equal to or less than the upper limit, there is a tendency for the sensitivity to decrease and for residues remaining after development that cause defects to be suppressed.
  • a surfactant When a surfactant is used, its content is not particularly limited, but is preferably 0.001 to 10 mass%, more preferably 0.005 to 1 mass%, even more preferably 0.01 to 0.5 mass%, and particularly preferably 0.03 to 0.3 mass%, relative to the total solid content of the photosensitive resin composition.
  • the content By making the content equal to or greater than the lower limit, the smoothness and uniformity of the coating film tends to be easily achieved.
  • the content By making the content equal to or less than the upper limit, the smoothness and uniformity of the coating film tends to be easily achieved, and deterioration of other properties also tends to be suppressed.
  • the photosensitive resin composition of the present invention is prepared by using a solvent so that the total solids content is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less.
  • the above upper and lower limits can be combined in any manner.
  • the composition is prepared so that the total solids content is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, and even more preferably 15 to 25% by mass.
  • the optical density (OD) per 1 ⁇ m of the coating film of the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.2 or more, more preferably 0.5 or more, even more preferably 0.7 or more, even more preferably 0.9 or more, and is preferably 4.0 or less, more preferably 3.0 or less, even more preferably 2.0 or less, and particularly preferably 1.5 or less.
  • the upper and lower limits can be arbitrarily combined. For example, 0.2 to 4.0 is preferred, 0.5 to 4.0 is more preferred, 0.5 to 3.0 is even more preferred, 0.5 to 2.0 is even more preferred, 0.7 to 2.0 is even more preferred, and 0.9 to 1.5 is particularly preferred.
  • the optical density (OD) per 1 ⁇ m of the coating film may be measured using a coating film obtained by curing the photosensitive resin composition of the present invention, and can be measured using a coating film having a thickness of about 0.5 to 1.5 ⁇ m that has been heat-cured at 230° C. for 20 minutes.
  • the optical density refers to the transmission optical density in which the spectral sensitivity characteristics of the light receiving part are indicated by the ISO visual density in the ISO 5-3 standard.
  • the light source used is the A light source defined by the CIE (International Commission on Illumination).
  • An example of a measuring device that can be used to measure the transmission optical density is the X-Rite 361T(V) manufactured by Sakata Inx Engineering Co., Ltd.
  • the components constituting the colorant dispersion liquid in the present invention and the composition thereof will be described below.
  • the colorant dispersion in the present invention contains a colorant (D), a dispersant (E), and an alkali-soluble resin (A), and in particular, the colorant (D) contains an organic black pigment (D-1), and further contains an ethylenically unsaturated compound (C). It is preferable that the colorant dispersion contains a solvent.
  • the constituent components of the colorant dispersion in the present invention those exemplified in the same item for the photosensitive resin composition of the present invention can be preferably used.
  • the content of the colorant (D) is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 55% by mass or more, based on the total solid content in the colorant dispersion. Also, it is usually 100% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less.
  • the photosensitive resin composition can be produced at an appropriate solid content concentration, and by making it equal to or less than the upper limit, the dispersibility tends to be good.
  • the upper and lower limits can be arbitrarily combined. For example, 10 to 80% by mass is preferable, 20 to 80% by mass is more preferable, 30 to 70% by mass is more preferable, 40 to 70% by mass is even more preferable, 50 to 65% by mass is particularly preferable, and 55 to 65% by mass is most preferable.
  • the content of the organic black pigment (D-1) is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 55% by mass or more, based on the total solid content in the colorant dispersion. Also, it is usually 100% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less. By setting it to the lower limit or more, the photosensitive resin composition can be produced with an appropriate solid content concentration, and by setting it to the upper limit or less, the dispersibility tends to be good.
  • the upper and lower limits can be arbitrarily combined. For example, 10 to 80% by mass is preferable, 20 to 80% by mass is more preferable, 30 to 70% by mass is more preferable, 40 to 70% by mass is even more preferable, 50 to 65% by mass is particularly preferable, and 55 to 65% by mass is most preferable.
  • the content of the dispersant (E) is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more, based on the total solid content in the colorant dispersion. It is also preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less.
  • the upper and lower limits can be arbitrarily combined. For example, 2 to 50% by mass is preferable, 5 to 40% by mass is more preferable, 5 to 30% by mass is even more preferable, 5 to 20% by mass is even more preferable, and 8 to 15% by mass is particularly preferable.
  • the content of the acrylic dispersant is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more, based on the total solid content in the colorant dispersion. It is also preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less.
  • the dispersibility becomes good and the pattern adhesion during development of the cured product tends to be good
  • the upper limit By making it equal to or less than the upper limit, the developability of the photosensitive resin composition obtained tends to be good.
  • the upper and lower limits can be arbitrarily combined. For example, 2 to 50% by mass is preferable, 5 to 40% by mass is more preferable, 5 to 30% by mass is even more preferable, 5 to 20% by mass is even more preferable, and 10 to 15% by mass is particularly preferable.
  • the content of the alkali-soluble resin (A) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, and particularly preferably 25% by mass or more, based on the total solid content in the colorant dispersion. It is also preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.
  • the upper and lower limits can be arbitrarily combined. For example, 5 to 50% by mass is preferable, 10 to 40% by mass is more preferable, 15 to 35% by mass is even more preferable, 20 to 35% by mass is even more preferable, and 25 to 35% by mass is particularly preferable.
  • the colorant dispersion in the present invention is prepared using the above-mentioned organic solvent so that the solid content concentration is preferably 5 to 50% by mass, more preferably 10 to 30% by mass.
  • the viscosity of the colorant dispersion is preferably 1 MPa ⁇ s or more, more preferably 3 MPa ⁇ s or more, and even more preferably 5 MPa ⁇ s or more. Also, it is preferably 15 MPa ⁇ s or less, and even more preferably 10 MPa ⁇ s or less.
  • the viscosity can be measured, for example, by a rotational viscometer.
  • the colorant dispersion in the present invention is produced in accordance with a conventional method.
  • the colorant (D) is preferably previously subjected to a dispersion treatment using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, etc.
  • the colorant (D) is finely divided by the dispersion treatment, which tends to improve the coating properties of the photosensitive resin composition and reduce the surface roughness.
  • the dispersion treatment is preferably carried out in a system in which the (D) colorant, (E) dispersant, and solvent are used in combination with part or all of the (A) alkali-soluble resin, or in which the (D) colorant, (E) dispersant, and solvent are used in combination with part or all of the (A) alkali-soluble resin.
  • the use of a polymer dispersant as the (E) dispersant is preferred because it inhibits thickening over time of the resulting colorant dispersion and photosensitive resin composition, i.e., it provides excellent dispersion stability.
  • the (D) colorant, (E) dispersant, and solvent that can be used in the colorant dispersion those that can be used in the photosensitive resin composition can be preferably used.
  • a dispersion treatment is performed on a liquid containing all the components to be blended in the photosensitive resin composition, the heat generated during the dispersion treatment may cause denaturation of highly reactive components. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
  • the temperature is preferably 0°C to 100°C, more preferably room temperature to 80°C.
  • the appropriate dispersion time varies depending on the composition of the liquid and the size of the dispersion treatment device, and is adjusted appropriately.
  • the guideline for dispersion is to control the gloss of the colorant dispersion liquid so that the 20-degree specular gloss (JIS Z8741) of the photosensitive resin composition is in the range of 50 to 300.
  • the dispersion treatment is often insufficient and coarse colorant particles remain, which may result in insufficient developability, adhesion, resolution, surface roughness, etc. If the dispersion treatment is performed until the gloss value exceeds the above range, the colorant is crushed to generate a large number of ultrafine particles, which tends to impair the dispersion stability.
  • the particle size of the colorant dispersed in the colorant dispersion is preferably 0.03 to 0.3 ⁇ m, and can be measured by a dynamic light scattering method.
  • the photosensitive resin composition of the present invention is prepared by mixing the various components contained therein to form a uniform solution or dispersion.
  • the photosensitive resin composition of the present invention contains a colorant (D)
  • the colorant dispersion obtained by the above dispersion treatment is mixed with other components contained in the photosensitive resin composition to form a uniform solution or dispersion. Since fine dust may be mixed into the liquid during the production process of the photosensitive resin composition, it is desirable to filter the obtained photosensitive resin composition using a filter or the like.
  • the cured product of the present invention can be obtained by curing the photosensitive resin composition of the present invention.
  • the cured product obtained by curing the photosensitive resin composition of the present invention can be suitably used as a black matrix, an insulating film, or a partition wall, and can be more suitably used as a partition wall.
  • the film thickness of the cured product is preferably 0.5 ⁇ m or more, more preferably 0.7 ⁇ m or more, and even more preferably 0.9 ⁇ m or more. It is also preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less. For example, it is preferably 0.5 to 15 ⁇ m, more preferably 0.7 to 10 ⁇ m, and even more preferably 0.9 to 5 ⁇ m.
  • the optical density (OD) per 1 ⁇ m of the cured product of the present invention is preferably 0.2 or more, more preferably 0.5 or more, even more preferably 0.7 or more, and particularly preferably 0.9 or more, from the viewpoint of light-shielding properties. It is also preferably 4.0 or less, more preferably 3.0 or less, even more preferably 2.0 or less, and particularly preferably 1.5 or less. For example, it is preferably 0.2 to 4.0, more preferably 0.5 to 4.0, even more preferably 0.5 to 3.0, even more preferably 0.5 to 2.0, even more preferably 0.7 to 2.0, and particularly preferably 0.9 to 1.5.
  • the optical density (OD) is a value measured by the method described below. Next, the cured product obtained by using the photosensitive resin composition of the present invention will be described along with its production method.
  • the material of the support for forming the cured product is not particularly limited as long as it has a suitable strength.
  • a substrate is mainly used, and examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, thermosetting resin sheets such as epoxy resins, unsaturated polyester resins, and poly(meth)acrylic resins, and various glasses. From the viewpoint of heat resistance, glass and heat-resistant resins are preferred.
  • a transparent electrode such as ITO or IZO, or a metal electrode such as silver, gold, platinum, aluminum, or magnesium may be formed on the surface of the substrate.
  • the support may be subjected to, for example, corona discharge treatment, ozone treatment, or thin film formation treatment with a silane coupling agent or various resins such as urethane resins in order to improve surface properties such as adhesiveness.
  • the thickness of the support is preferably in the range of 0.05 to 10 mm, more preferably 0.1 to 7 mm.
  • the thickness of the film is preferably in the range of 0.01 to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m.
  • the photosensitive resin composition is applied in the form of a film or pattern by coating or other methods onto the support on which the cured product is to be formed, and the solvent is then dried.
  • a pattern is formed by a method such as photolithography, which involves exposure and development.
  • a cured product is formed on the substrate by performing additional exposure or heat curing treatment as necessary.
  • the photosensitive resin composition of the present invention is preferably supplied onto the support in a state dissolved or dispersed in a solvent.
  • the supplying method can be a conventionally known method, such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, or a spray coating method. It may also be supplied in a pattern shape, for example, by an inkjet method or a printing method.
  • the die coating method is preferable from an overall viewpoint, since it significantly reduces the amount of coating solution used, is completely free of the influence of mist or the like that adheres when using a spin coating method, and suppresses the generation of foreign matter.
  • the amount of coating varies depending on the application, but the coating is preferably applied so that the dry film thickness is 0.5 to 10 ⁇ m, more preferably 1 to 9 ⁇ m, and particularly preferably 1 to 7 ⁇ m. It is important that the dry film thickness or the height of the finally formed cured product is uniform over the entire support. By reducing the variation, the light blocking properties within the support become uniform, and when used as a partition wall, the light emitting layer can be produced uniformly, and display defects during light emission can be suppressed. When the photosensitive resin composition of the present invention is used to collectively form cured products having different heights by a photolithography method, the heights of the finally formed cured products will differ.
  • the photosensitive resin composition is preferably dried after being supplied onto the support by a drying method using a hot plate, an IR oven, or a convection oven. It may also be combined with a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.
  • the drying conditions can be appropriately selected depending on the type of solvent component, the performance of the dryer used, etc.
  • the drying time is preferably selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 130°C, more preferably in the range of 30 seconds to 3 minutes at a temperature of 50 to 110°C, depending on the type of solvent component, the performance of the dryer used, etc.
  • Exposure is performed by superposing a negative mask pattern on the coating film of the photosensitive resin composition, and irradiating the film with a light source of ultraviolet or visible light through the mask pattern.
  • the exposure mask may be placed close to the coating film of the photosensitive resin composition, or the exposure mask may be placed at a position away from the coating film of the photosensitive resin composition, and exposure light may be projected through the exposure mask.
  • a scanning exposure method using laser light without using a mask pattern may also be used.
  • exposure may be performed in a deoxygenated atmosphere, or after forming an oxygen-blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer.
  • an exposure mask When photolithography is used to simultaneously form cured products of different heights, for example, an exposure mask is used that has a light-shielding area (light transmittance 0%) and multiple openings, which have openings with a lower average light transmittance (intermediately transparent openings) than the openings with the highest average light transmittance (fully transparent openings).
  • light transmittance 0% light-shielding area
  • multiple openings which have openings with a lower average light transmittance (intermediately transparent openings) than the openings with the highest average light transmittance (fully transparent openings).
  • a method is known in which the intermediate transmission opening is fabricated by, for example, a matrix-shaped light-shielding pattern having minute polygonal light-shielding units, and a method is known in which the absorber is fabricated by controlling the light transmittance using, for example, a film of a chromium-based, molybdenum-based, tungsten-based, or silicon-based material.
  • the light source used for exposure is not particularly limited.
  • the light source examples include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arcs, and fluorescent lamps, and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers.
  • lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arcs, and fluorescent lamps
  • laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers.
  • an optical filter can also be used
  • the optical filter may be, for example, a thin film type capable of controlling the light transmittance at the exposure wavelength, and in this case, examples of the material include Cr compounds (Cr oxides, nitrides, oxynitrides, fluorides, etc.), MoSi, Si, W, and Al.
  • the exposure dose is not particularly limited, but is preferably 1 mJ/ cm2 or more, more preferably 5 mJ/cm2 or more, and even more preferably 10 mJ/ cm2 or more, and is preferably 300 mJ/cm2 or less , more preferably 200 mJ/cm2 or less , and even more preferably 150 mJ/ cm2 or less.
  • an image pattern can be formed on the support by development using an aqueous solution of an alkaline compound or an organic solvent.
  • the aqueous solution of an alkaline compound may further contain, for example, a surfactant, an organic solvent, a buffer, a complexing agent, a dye, or a pigment.
  • alkaline compounds include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide; and organic alkaline compounds such as mono-, di-, or triethanolamine, mono-, di-, or trimethylamine, mono-, di-, or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di-, or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline.
  • TMAH tetramethylammonium hydroxide
  • Surfactants include, for example, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate salts; and amphoteric surfactants such as alkyl betaines and amino acids.
  • nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters
  • anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfon
  • organic solvent examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. These organic solvents may be used in combination of two or more.
  • the organic solvent may be used alone or in combination with water or an aqueous solution of an alkaline compound.
  • the conditions for the development treatment are not particularly limited, and the development temperature is preferably from 10 to 50° C., more preferably from 15 to 45° C., and further preferably from 20 to 40° C.
  • the development method can be, for example, an immersion development method, a spray development method, a brush development method, or an ultrasonic development method.
  • the substrate after development may be subjected to re-exposure by a method similar to the above-mentioned exposure method, if necessary.
  • a heat curing treatment also called a baking treatment
  • the heat curing treatment conditions are preferably a temperature of 100 to 280°C, more preferably 150 to 250°C, and a time of 5 to 60 minutes.
  • the photosensitive resin composition of the present invention can be suitably used for forming a partition wall, particularly a partition wall for partitioning an organic layer of an organic electroluminescent device.
  • the organic layer used in an organic electroluminescent device include an organic layer used as a hole injection layer, a hole transport layer, or a hole transport layer on a hole injection layer, as described in JP 2016-165396 A.
  • the present invention is used as a partition wall, the size, shape, etc. are appropriately adjusted depending on the specifications of the organic electroluminescent device to which it is applied, but the film thickness and optical density (OD) per ⁇ m of the partition wall formed from the photosensitive resin composition of the present invention are similar to those of the cured film.
  • the organic electroluminescent device of the present invention includes a cured product, such as a partition wall, formed from the photosensitive resin composition of the present invention.
  • a cured product such as a partition wall
  • various organic electroluminescence elements are manufactured by using a substrate having a partition pattern manufactured by the above-mentioned method.
  • the organic electroluminescence element is preferably manufactured by forming an organic layer such as a pixel by a wet process such as a deposition method in which a functional material is sublimated in a vacuum state and deposited in an area surrounded by the partition on the substrate to form a film after the partition pattern is formed on the substrate by the above-mentioned method, a casting method, a spin coating method, or an inkjet printing method.
  • a wet process such as a deposition method in which a functional material is sublimated in a vacuum state and deposited in an area surrounded by the partition on the substrate to form a film after the partition pattern is formed on the substrate by the above-mentioned method, a casting method, a spin coating method, or an inkjet printing method.
  • the types of organic electroluminescent devices include bottom emission types and top emission types.
  • a bottom-emission type is fabricated, for example, by forming a partition on a glass substrate on which a transparent electrode is laminated, and laminating a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode layer in an opening surrounded by the partition
  • a top-emission type is fabricated, for example, by forming a partition on a glass substrate on which a metal electrode layer is laminated as a reflective layer, and laminating an electron transport layer, a light-emitting layer, a hole transport layer, and a transparent electrode layer in an opening surrounded by the partition.
  • each of the hole transport layer and the electron transport layer may have a laminate structure consisting of two or more layers from the viewpoint of luminous efficiency.
  • the thickness of each layer is not particularly limited, but is preferably 1 to 500 nm from the viewpoint of luminous efficiency and brightness.
  • the organic electroluminescent element may be formed with each RGB color separated for each opening, or two or more colors may be laminated in one opening.
  • the organic electroluminescent element may have a sealing layer from the viewpoint of improving reliability.
  • the sealing layer has the function of preventing moisture in the air from being adsorbed to the organic electroluminescent element and reducing the light-emitting efficiency.
  • the organic electroluminescent element may have a low-reflection film at the interface with the air from the viewpoint of improving the light extraction efficiency. By disposing the low-reflection film at the interface between the air and the element, it is expected that the refractive index gap can be reduced and reflection at the interface can be suppressed. For example, moth-eye structure and super multilayer film technology can be applied to such a low-reflection film.
  • an organic electroluminescent element When an organic electroluminescent element is used as a pixel of an image display device, it is necessary to prevent light from the light-emitting layer of a pixel from leaking to other pixels. Furthermore, when electrodes or the like are made of metal, it is necessary to prevent degradation of image quality due to reflection of external light. For these reasons, it is preferable to impart light-shielding properties to the partitions constituting the organic electroluminescent element.
  • the partition wall since it is necessary to provide electrodes on the upper and lower surfaces of the partition wall, the partition wall preferably has high resistance and low dielectric constant from the viewpoint of insulation. Therefore, when a colorant is used to provide the partition wall with light-shielding properties, it is preferable to use the organic pigment having high resistance and low dielectric constant.
  • the color filter containing the luminescent nanocrystalline particles according to the present invention is not particularly limited as long as it has the partition walls of the present invention, and examples thereof include a color filter having pixels formed in regions partitioned by the partition walls.
  • Fig. 1 is a schematic cross-sectional view of an example of a color filter including a partition wall of the present invention.
  • the color filter 100 includes a substrate 10, a partition wall 20 provided on the substrate, a red pixel 30, a green pixel 40, and a blue pixel 50.
  • the red pixel 30, the green pixel 40, and the blue pixel 50 are arranged in a lattice pattern so as to be repeated in this order.
  • the partition wall 20 is provided between these adjacent pixels. In other words, the adjacent pixels are separated from each other by the partition wall 20.
  • the red pixel 30 contains red-emitting nanocrystal particles 2
  • the green pixel 40 contains green-emitting nanocrystal particles 1.
  • the blue pixel 50 is a pixel that transmits blue light from the light source. These nanocrystalline particles are nano-sized crystals that absorb excitation light and emit fluorescence or phosphorescence, and are, for example, crystals whose maximum particle size as measured by a transmission electron microscope or a scanning electron microscope is 100 nm or less.
  • Luminescent nanocrystal particles are capable of absorbing light of a specific wavelength and emitting light (fluorescence or phosphorescence) of a wavelength different from the absorbed wavelength.
  • red-luminescent nanocrystal particles 2 emit light with a peak emission wavelength in the range of 605 to 665 nm (red light)
  • green-luminescent nanocrystal particles 1 emit light with a peak emission wavelength in the range of 500 to 560 nm (green light).
  • the wavelength (emission color) of light emitted by a luminescent nanocrystal particle depends on the size (e.g., particle diameter) of the luminescent nanocrystal particle according to the solution of the Schrödinger wave equation of the well-type potential model, but also on the energy gap of the luminescent nanocrystal particle. Therefore, the emission color can be selected by changing the constituent material and size of the luminescent nanocrystal particle used. Examples of luminescent nanocrystal particles include quantum dots.
  • the method for producing a color filter containing luminescent nanocrystal particles but an example is a method in which a substrate having partition walls formed from the cured product of the present invention is prepared, and a layer containing luminescent nanocrystal particles is formed in an area partitioned by the partition walls.
  • the method for forming a layer containing luminescent nanocrystal particles but for example, the layer can be produced by a method in which an ink composition containing luminescent nanocrystal particles is selectively applied by an inkjet method, and the ink composition is cured by irradiation with active energy rays or heating.
  • the image display device of the present invention is provided with the partition wall of the present invention, and an example of the image display device of the present invention is an organic EL display device having an organic electroluminescence element provided with the partition wall of the present invention.
  • the organic EL display device is not particularly limited in type or structure of the image display device as long as it includes the above-mentioned organic electroluminescent element, and can be assembled, for example, by a conventional method using an active-drive organic electroluminescent element.
  • it can be formed by a method such as that described in "Organic EL Display” (Ohmsha, published on August 20, 2004, by Tokito Shizuo, Adachi Chihaya, and Murata Hideyuki).
  • an organic electroluminescent element that emits white light may be combined with a color filter to display an image, or organic electroluminescent elements with different luminescent colors such as RGB may be combined to display an image.
  • XD1000 polyglycidyl ether of dicyclopentadiene-phenol polymer, epoxy equivalent 252
  • 87 parts by weight of acrylic acid 0.2 parts by weight of p-methoxyphenol, 5 parts by weight of triphenylphosphine, and 255 parts by weight of propylene
  • an alkali-soluble resin (I) having a solid content of 50% by weight, an acid value of 106 mgKOH/g, and a weight average molecular weight (Mw) of 2600 in terms of polystyrene measured by GPC.
  • ⁇ Ethylenically unsaturated compound-II> A-9300: Tris-(2-acryloxyethyl)isocyanurate manufactured by Shin-Nakamura Chemical Co., Ltd. ⁇ Ethylenically Unsaturated Compound-III> TAIC: Triallyl isocyanurate manufactured by Shinryo Corporation. ⁇ Ethylenically Unsaturated Compound-IV> DA-314: Denacol acrylate manufactured by Nagase ChemteX Corporation. ⁇ Ethylenically Unsaturated Compound-V> TEPIC-S: Triglycidyl isocyanurate manufactured by Nissan Chemical Industries, Ltd.
  • optical density per unit film thickness was measured by the following procedure.
  • the photosensitive resin composition of each Example and Comparative Example was applied to a glass substrate using a spinner so that the thickness would be 1.5 ⁇ m after heat curing treatment (baking treatment).
  • the composition was then dried for 60 seconds in a vacuum dryer.
  • the composition was then heated and dried for 100 seconds on a hot plate heated to 100° C.
  • the obtained coating film was exposed to light without using an exposure mask.
  • a mirror projection type exposure machine (MPA-600FA) manufactured by Canon Inc. was used as the irradiation light source, and exposure was performed for 20 seconds so that the exposure amount was 80 mJ/ cm2 .
  • the illuminance was 500 mW/ cm2 .
  • the resist-coated substrate 1 was then obtained by heating and curing in an oven at 230°C for 30 minutes.
  • the optical density (OD value) of the obtained resist-coated substrate 1 was measured using a 361T(V) transmission densitometer manufactured by X-Rite (color temperature of illumination light source: about 2850K (equivalent to CIE standard light source A), spectral sensitivity characteristic of the light receiving part: ISO visual density according to ISO 5-3 standard), and the film thickness was measured using a non-contact surface/layer cross-sectional shape measurement system VertScan(R) 2.0 manufactured by Ryoka Systems Co., Ltd., and the optical density (unit OD value) per unit film thickness (1 ⁇ m) was calculated from the optical density (OD value) and film thickness.
  • the OD value is a value indicating the light-shielding ability, and a larger value indicates a higher light-shielding ability.
  • the photosensitive color resin composition of each Example and Comparative Example was applied to the glass substrate using a spinner so that the thickness would be 1.5 ⁇ m after heat curing treatment (baking treatment). Then, a drying treatment was performed for 60 seconds in a vacuum dryer. Then, the coating was dried for 100 seconds on a hot plate heated to 100 ° C. to obtain a coating substrate. Next, the obtained coating was exposed to light without using an exposure mask.
  • a high-pressure mercury lamp with an intensity of 40 mW/cm 2 at a wavelength of 365 nm was used as the irradiation light source, and the exposure amount was 40 mJ/cm 2.
  • the weight W2 (mg) of the substrate at this time was measured.
  • the substrate was baked in an oven at 230 ° C. for 30 minutes to obtain a substrate for measuring the amount of fume.
  • the weight W3 (mg) of the substrate at this time was measured.
  • the amount of fumes was evaluated as follows, with A being the best. A: Fume amount less than 13% B: Fume amount 13% or more and less than 17% C: Fume amount 17% or more
  • A Fume amount less than 13%
  • B Fume amount 13% or more and less than 17%
  • C Fume amount 17% or more
  • the fume amount indicates the ratio of the amount of gas during baking treatment to the amount of coating, and the smaller the better.
  • the photosensitive resin composition of each Example and Comparative Example was applied to a substrate having an indium tin oxide (ITO) film formed on the surface of a glass substrate having a thickness of 0.7 mm using a spinner so that the thickness would be 1.5 ⁇ m after heat curing treatment (baking treatment). Then, a drying treatment was performed for 60 seconds in a vacuum dryer. Next, the coating was dried by heating for 100 seconds on a hot plate heated to 100° C. to obtain a coating substrate.
  • ITO indium tin oxide
  • the thickness of the heated and dried coating film was measured by the method described later to determine the thickness T1 ( ⁇ m).
  • the obtained coating substrate was exposed to light using a photomask.
  • a mirror projection type exposure machine (MPA-600FA) manufactured by Canon was used, and exposure was performed for 20 seconds so that the exposure amount was 80 mJ/ cm2 .
  • the illuminance was 500 mW/ cm2 , and the slit width was 1.6 mm.
  • the photomask used was a mask with lattice-shaped openings (having a square-shaped covered portion of 50 ⁇ m and having a plurality of the covered portions via exposed portions of 50 ⁇ m).
  • shower development was performed at 24°C with a water pressure of 0.05 MPa, and then the developer was flushed with pure water to stop the development, and the film was washed with a water washing spray for 10 seconds.
  • the shower development time was 1.6 times the time it took for the unexposed parts of the coating film to be dissolved and removed. Since the photosensitive resin composition was flushed away from the parts corresponding to the square light-shielding parts after development, the ITO substrate was exposed, and a hole part was formed. This substrate was subjected to a heat curing treatment (baking treatment) in an oven at 230° C. for 30 minutes to obtain a patterned substrate for measuring patterning properties, and the film thickness T2 ( ⁇ m) at this time was measured.
  • a heat curing treatment baking treatment
  • the calculated film remaining rate was judged as follows: A indicates the highest film remaining rate and is favorable, and a film remaining rate of 60% or more tends to be satisfactory for practical use.
  • ⁇ Taper angle measurement> The cross-sectional shape of the partition wall of the evaluation substrate was observed at 10,000 times magnification using a scanning electron microscope (SEM), and the angle between the substrate and the partition wall was measured as the taper angle. The smaller the taper angle, the more preferable it is.
  • Examples 1 to 6, Comparative Examples 1 to 6 In Examples 1 to 6 and Comparative Examples 1 to 6, each component was added so that the solid content ratio of each component in the total solid content was the value shown in Tables 2 to 3, and a solvent was further added so that PGMEA/MB was 80/20 and the total solid content was 17 mass%, and the mixture was stirred and dissolved to prepare the photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 6.
  • the evaluation results of the optical density per unit film thickness, the remaining film rate, the taper angle, and the amount of fume are shown in Tables 2 and 3.
  • Example 1 shows that the photosensitive resin composition using the ethylenically unsaturated compound (C-1) has a small taper angle, a high residual film rate, and a small amount of fumes.
  • the ethylenically unsaturated compound (C-1) is thought to produce fewer vaporized and thermally decomposed products during the baking process due to the development resistance derived from the isocyanuric ring, the high boiling point derived from the hydroxyl group in the molecule, and the high exposure sensitivity derived from the acrylate group.
  • the ethylenically unsaturated compound-II has an isocyanuric ring and an acrylate group but does not have a hydroxyl group, so it vaporizes during baking at 230° C., producing a large amount of fumes.
  • the ethylenically unsaturated compound-III has an isocyanuric ring, but does not have an acrylate group, and is an allyl group, so the exposure sensitivity is low and the residual film rate is low.
  • it does not have a hydroxyl group it vaporizes during baking at 230°C, and the amount of fumes is large.
  • the ethylenically unsaturated compound-IV has a hydroxy group and an acrylate group, but does not have an isocyanuric ring, and therefore has low development resistance and a large taper angle.
  • the ethylenically unsaturated compounds V and VI have an isocyanuric ring but no acrylate group, and are instead epoxy or allyl groups, so that the exposure sensitivity is low and the residual film rate is low.
  • the ethylenically unsaturated compound-VII has an acrylate group, but since it does not have an isocyanuric ring, it has low development resistance, a large taper angle, and since it does not have a hydroxyl group, it produces a large amount of fumes.
  • Comparative Example 7 shows that ethylenically unsaturated compound-VIII has acrylate and isocyanuric rings, but has few hydroxyl groups and an acid anhydride is added, which makes the acid anhydride more likely to decompose and produces a large amount of fumes. Furthermore, the increased carboxyl groups result in low development resistance and a reduced residual film rate.
  • Green light-emitting nanocrystal particle 2 Red light-emitting nanocrystal particle 10
  • Substrate 20 Partition wall 30
  • Red pixel 40 Green pixel 50 Blue pixel 100 Color filter

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JPH04194942A (ja) * 1990-11-27 1992-07-14 Sanyo Chem Ind Ltd 着色画像形成用材料および着色画像の形成法
WO2019087985A1 (ja) * 2017-10-31 2019-05-09 東レ株式会社 ネガ型感光性樹脂組成物、硬化膜、並びに有機ｅｌディスプレイ及びその製造方法
WO2021111860A1 (ja) * 2019-12-02 2021-06-10 東レ株式会社 感光性組成物、ネガ型感光性組成物、画素分割層および有機ｅｌ表示装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04194942A (ja) * 1990-11-27 1992-07-14 Sanyo Chem Ind Ltd 着色画像形成用材料および着色画像の形成法
WO2019087985A1 (ja) * 2017-10-31 2019-05-09 東レ株式会社 ネガ型感光性樹脂組成物、硬化膜、並びに有機ｅｌディスプレイ及びその製造方法
WO2021111860A1 (ja) * 2019-12-02 2021-06-10 東レ株式会社 感光性組成物、ネガ型感光性組成物、画素分割層および有機ｅｌ表示装置

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