WO2016010077A1 - ネガ型感光性樹脂組成物、樹脂硬化膜、隔壁および光学素子 - Google Patents

ネガ型感光性樹脂組成物、樹脂硬化膜、隔壁および光学素子 Download PDF

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WO2016010077A1
WO2016010077A1 PCT/JP2015/070289 JP2015070289W WO2016010077A1 WO 2016010077 A1 WO2016010077 A1 WO 2016010077A1 JP 2015070289 W JP2015070289 W JP 2015070289W WO 2016010077 A1 WO2016010077 A1 WO 2016010077A1
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Prior art keywords
resin composition
photosensitive resin
partition
negative photosensitive
acid
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PCT/JP2015/070289
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English (en)
French (fr)
Japanese (ja)
Inventor
高橋　秀幸
光太郎 山田
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旭硝子株式会社
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Priority to CN201580038938.5A priority Critical patent/CN106662815B/zh
Priority to KR1020177001713A priority patent/KR102411740B1/ko
Priority to JP2016534467A priority patent/JP6536578B2/ja
Publication of WO2016010077A1 publication Critical patent/WO2016010077A1/ja

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing

Definitions

  • the present invention is, for example, a negative photosensitive resin composition, a cured resin film, a partition wall and an optical element used in the production of an optical element such as an organic EL element, a quantum dot display, a TFT array, and a thin film solar cell.
  • the present invention relates to an organic EL element, a quantum dot display, a TFT array, a thin film solar cell, and the like.
  • the partition wall it is possible to form a fine and high-precision pattern by the partition wall by reducing the residue in the opening while maintaining good production efficiency and the top surface of the partition wall having good ink repellency. Furthermore, it is also applicable to flexible applications using plastic substrates, for example, negative photosensitive resin compositions used in the production of optical elements such as organic EL elements, quantum dot displays, TFT arrays, thin film solar cells, etc. Can provide things.
  • the cured resin film of the present invention has good ink repellency on the upper surface, and the partition wall has good ink repellency on the upper surface, and can form a fine and highly accurate pattern.
  • TFT arrays, thin film solar cells, and the like, and in particular, can be suitably used for optical elements including flexible applications using plastic substrates.
  • the group represented by the formula (x) may be simply referred to as a group (x).
  • the compound represented by the formula (y) may be simply referred to as the compound (y).
  • the expressions (x) and (y) indicate arbitrary expressions.
  • the “side chain” is a group other than a hydrogen atom or a halogen atom bonded to a carbon atom constituting the main chain in a polymer in which a repeating unit composed of carbon atoms constitutes the main chain.
  • total solid content of the photosensitive resin composition refers to a component that forms a cured film described later among the components contained in the photosensitive resin composition, and the photosensitive resin composition is heated at 140 ° C. for 24 hours. Obtained from the residue from which the solvent has been removed. The total solid content can also be calculated from the charged amount.
  • “Ink” is a general term for liquids having optical and / or electrical functions after drying, curing, and the like.
  • an optical element such as an organic EL element, a quantum dot display, a TFT array, a thin film solar cell, and a color filter
  • dots as various constituent elements are pattern-printed by ink jet (IJ) method using the ink for forming the dots.
  • IJ ink jet
  • “Ink” includes ink used in such applications.
  • “Ink repellency” is a property of repelling the above ink and has both water repellency and oil repellency.
  • the ink repellency can be evaluated by, for example, a contact angle when ink is dropped.
  • “Ink affinity” is a property opposite to ink repellency, and can be evaluated by the contact angle when ink is dropped as in the case of ink repellency.
  • the ink affinity can be evaluated by evaluating the degree of ink wetting and spreading (ink wetting and spreading property) when ink is dropped on a predetermined standard.
  • the negative photosensitive resin composition of the present invention comprises a photocurable alkali-soluble resin or alkali-soluble monomer (A), a photoradical polymerization initiator (B), a photoacid generator (C), A negative photosensitive resin composition comprising an acid curing agent (D) and an ink repellent agent (E) having a fluorine atom.
  • the acid curing agent (D) refers to a curing agent that reacts with an acidic group such as a carboxylic acid or a phenolic hydroxyl group in the presence of an acid.
  • the alkali-soluble resin or alkali-soluble monomer (A) is polymerized and cured by radicals generated from the photoradical polymerization initiator (B) in the exposed area. A cured film is formed.
  • the alkali-soluble resin or the alkali-soluble monomer (A) does not contain a fluorine atom.
  • the ink repellent agent (E) has a property of shifting to the upper surface in the process of forming a cured film by having fluorine atoms (upper surface transition property), and the ink repellent agent (E) transferred to the upper surface is fixed on the upper surface of the cured film. To do.
  • the negative photosensitive resin composition of the present invention may further comprise a compound (F) having two or more unsaturated double bonds in the molecule and having neither an acidic group nor a fluorine atom, if necessary.
  • crosslinking agent (F) thiol compound (G) having 3 or more mercapto groups in one molecule
  • thiol compound (G) thiol compound having 3 or more mercapto groups in one molecule
  • thiol compound (G) phosphoric acid compound (H)
  • Polymerization inhibitor (I) Polymerization inhibitor
  • solvent (J) colorant (K)
  • alkali-soluble resin or alkali-soluble monomer (A))
  • the alkali-soluble resin will be described with a symbol (AP) and the alkali-soluble monomer with a symbol (AM). In the following description, these may be collectively referred to as “alkali-soluble resin (A)”.
  • the alkali-soluble resin (AP) a photosensitive resin having an acidic group and an ethylenic double bond in one molecule is preferable.
  • the alkali-soluble resin (AP) has an ethylenic double bond in the molecule, and is thus polymerized by the radical generated by the photo radical polymerization initiator (B). Since the alkali-soluble resin (AP) has an acidic group in the molecule, it reacts with the acid curing agent (D) in the presence of the acid generated by the photoacid generator (C). Moreover, it is alkali-soluble by having an acidic group.
  • Examples of the acidic group include a carboxy group, a phenolic hydroxyl group, a sulfo group, and a phosphoric acid group. These may be used alone or in combination of two or more.
  • Examples of the ethylenic double bond include double bonds having an addition polymerization property such as a (meth) acryloyl group, an allyl group, a vinyl group, a vinyloxy group, and a vinyloxyalkyl group. These may be used alone or in combination of two or more.
  • some or all of the hydrogen atoms possessed by the ethylenic double bond may be substituted with an alkyl group such as a methyl group.
  • alkali-soluble resin (AP) having an ethylenic double bond examples include a resin (A-1) having a side chain having an acidic group and a side chain having an ethylenic double bond, and an epoxy group having an acidic group and ethylene. And a resin (A-2) into which an ionic double bond is introduced. These may be used alone or in combination of two or more.
  • A-2 into which an ionic double bond is introduced.
  • alkali-soluble resin (AP) peeling of the cured film during development can be suppressed, and a high-resolution dot pattern can be obtained, and the linearity of the pattern when the dots are linear is good.
  • the resin (A-2) it is preferable to use the resin (A-2).
  • the linearity of a pattern is favorable means that the edge of the partition obtained does not have a chip etc. and is linear.
  • Examples of the resin (A-2) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenolmethane type epoxy resin, epoxy resin having naphthalene skeleton, and biphenyl skeleton.
  • a resin in which an acidic group and an ethylenic double bond are introduced into an epoxy resin such as an epoxy resin or a fluorenyl-substituted bisphenol A type epoxy resin is particularly preferable.
  • the number of ethylenic double bonds that the alkali-soluble resin (AP) has in one molecule is preferably 3 or more on average, and particularly preferably 6 or more.
  • the number of ethylenic double bonds is at least the lower limit of the above range, the alkali solubility between the exposed and unexposed portions is likely to be different, and a fine pattern can be formed with a smaller exposure amount.
  • the mass average molecular weight (Mw) of the alkali-soluble resin (AP) is preferably 1.5 ⁇ 10 3 to 30 ⁇ 10 3 , particularly preferably 2 ⁇ 10 3 to 15 ⁇ 10 3 .
  • the number average molecular weight (Mn) is preferably 500 to 20 ⁇ 10 3 , and particularly preferably 1.0 ⁇ 10 3 to 10 ⁇ 10 3 .
  • the acid value of the alkali-soluble resin (AP) is preferably 10 to 300 mgKOH / g, particularly preferably 30 to 150 mgKOH / g. When the acid value is within the above range, the developability of the negative photosensitive composition is improved.
  • alkali-soluble monomer for example, a monomer (A-3) having an acidic group and an ethylenic double bond is preferably used.
  • the acidic group and the ethylenic double bond are the same as those of the alkali-soluble resin (AP).
  • the acid value of the alkali-soluble monomer (AM) is also preferably in the same range as the alkali-soluble resin (AP).
  • Examples of the monomer (A-3) include 2,2,2-triacryloyloxymethylethylphthalic acid.
  • the alkali-soluble resin or alkali-soluble monomer (A) contained in the negative photosensitive resin composition may be used alone or in combination of two or more.
  • the content of the alkali-soluble resin or alkali-soluble monomer (A) in the total solid content in the negative photosensitive resin composition is preferably 5 to 80% by mass, particularly preferably 10 to 60% by mass. When the content ratio is in the above range, the photo-curing property and developability of the negative photosensitive resin composition are good.
  • the radical photopolymerization initiator (B) in the present invention is not particularly limited as long as it is a compound having a function as a radical photopolymerization initiator that generates radicals by actinic rays.
  • the radical photopolymerization initiator (B) is also simply referred to as “photopolymerization initiator (B)”.
  • Examples of the photopolymerization initiator (B) include those described in WO2014 / 046209, for example, paragraphs [0130] and [0131], and WO2014 / 0669478, for example, in paragraphs [0089] and [0090].
  • photopolymerization initiators (B) benzophenones, aminobenzoic acids and aliphatic amines are preferably used together with other radical initiators because they may exhibit a sensitizing effect.
  • a photoinitiator (B) may be used individually by 1 type, or may use 2 or more types together.
  • the content of the photopolymerization initiator (B) in the total solid content in the negative photosensitive resin composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and 1 to 15% by mass. % Is particularly preferred. When the content ratio is in the above range, the photo-curing property and developability of the negative photosensitive resin composition are good.
  • the photoacid generator (C) is not particularly limited as long as it is a compound that decomposes to generate an acid upon irradiation with an actinic ray. Generally, any compound can be selected and used from compounds used as a photoacid generator in a photosensitive resin composition using a cationic polymerization type alkali-soluble resin. Hereinafter, the photoacid generator (C) is also simply referred to as “acid generator (C)”.
  • the acid generated from the acid generator (C) is a bond between the alkali-soluble resin (A) and the acid curing agent (D) described below. Involved.
  • the acid generator (C) decomposes upon irradiation with actinic rays to generate an acid.
  • the actinic rays include high energy rays such as ultraviolet light, X-rays, and electron beams.
  • i line (365 nm), h line (405 nm), and g line (436 nm) are used preferably for exposure.
  • the acid generator (C) it is preferable to select an acid generator (C) having a large absorbance at the wavelength of light used for exposure.
  • Those having absorption at 350 to 450 nm are preferred, and those having absorption in light including at least one of i-line (365 nm), h-line (405 nm) and g-line (436 nm) have high curability. preferable.
  • the acid generator (C) include onium salt acid generators and nonionic acid generators.
  • the onium salt acid generator include onium salts and iodonium salt compounds of a compound having a mono to triphenylsulfonium skeleton represented by the following formula (C0).
  • R a1 and R a2 each represents an optionally substituted alkyl group having 1 to 20 carbon atoms or a phenyl group, and R a3 represents a monovalent organic group.
  • w is an integer of 0 to 5.
  • a compound in which R a1 and R a2 are both phenyl groups (which may be substituted) is preferable.
  • an onium salt of a compound having a triphenylsulfonium skeleton represented by the following formula (C1) or (C2) is preferable.
  • a compound in which the hydrogen atom of the phenyl group of the triphenylsulfonium skeleton is substituted in the compound (C1) and the compound (C2) can also be used as the acid generator (C).
  • Xa - and Xb - represents an anion, specifically, X in the above formula (C0) - same anion are exemplified.
  • Xa - and Xb - as the anion of the anion and sulfonic acid salt type of phosphorus-based is preferred.
  • the cation moiety absorbs the irradiated light, and the anion moiety becomes a source of acid generation.
  • Examples of the compound (C0) include an onium salt represented by the following formula (C0-1) as an onium salt of a compound having a monophenylsulfonium skeleton. Further, in the compounds (C1) and (C2) which are onium salts of a compound having a triphenylsulfonium skeleton, for example, as a compound used for performing exposure at i-line (365 nm), the following formula (C1-1) in triphenylsulfonium nonafluorobutanesulfonate represented, triarylsulfonium, PF 6 salts and triarylsulfonium, special phosphorus-based salts represented respectively by the following formula (C2-1) and the following formula (C2-2) Can be mentioned. These compounds are preferable in that they have a large absorbance at a wavelength of 365 nm and are easily available.
  • iodonium salt compound examples include diaryl iodonium salts and triarylsulfonium salts.
  • the triarylsulfonium salt is composed of the cation moiety and the anion moiety, and is composed of a combination of one specific example of the cation moiety and one specific example of the anion moiety.
  • triphenylsulfonium trifluoromethanesulfonate is an example.
  • Such a compound include a naphthalimide skeleton and a nitrobenzene represented by the following formula (C3), the following formula (C4), the following formula (C5), the following formula (C6), and the following formula (C7), respectively.
  • a skeleton (however, when there is one nitro group, the position is the 2nd or 4th position; when there are two nitro groups, the position is the 2nd or 5th position), a diazomethane skeleton, a phenylacetophenone skeleton, Examples thereof include compounds having a thiochitosan skeleton and a structure in which alkanesulfonic acid, arylsulfonic acid or the like is bonded.
  • R b1 to R b5 , R b7 , R b9, and R b11 in formulas (C3) to (C7), (C9), (C10), and (C11) are each independently partially or completely substituted with a fluorine atom. It may be a linear, branched or cyclic (including those having a partial cyclic structure) alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 18 carbon atoms.
  • R b6 , R b8, and R b10 in formulas (C8), (C9), and (C10) each independently may have a substituent or an unsaturated bond, and may contain a heterocyclic ring. Is an organic group.
  • Specific examples of the compound having a triazine skeleton and a chlorine atom represented by the above formula (C8) include 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, the following formula (C8-1) 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2-furyl) ethenyl-bis (trichloromethyl) -1,3 5-triazine, 2- (5-methyl-2-furyl) ethenyl-4,6-bis (trichloromethyl) -1,3,5-triazine represented by the following formula (C8-2), 3) 2- (4-methoxyphenyl) ethenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-dimethoxyphenyl) ethenyl-4,6-bis shown in 3) (Trichlorome Le)
  • R 11 to R 32 are each independently a hydrogen atom, a hydroxymethyl group or an alkoxymethyl group. At least one of R 11 to R 16 , at least one of R 17 to R 20 , at least one of R 21 to R 24 , at least one of R 27 to R 30 , R 31 and R 32 At least one of them is an alkoxymethyl group.
  • R 33 to R 36 are each independently a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group, and Xc is a single bond, a methylene group or an oxygen atom.
  • the ink repellent agent (E2) is a compound having a main chain of a hydrocarbon chain and a side chain having a fluorine atom.
  • the mass average molecular weight (Mw) of the ink repellent agent (E2) is preferably from 100 to 1,000,000, particularly preferably from 5,000 to 100,000. When the mass average molecular weight (Mw) is not less than the lower limit, the ink repellent agent (E2) tends to move to the upper surface when a cured film is formed using the negative photosensitive resin composition. The opening residue is less than the upper limit, which is preferable.
  • ink repellent agent (E2) examples include those described in, for example, [0079] to [0102] of WO2014 / 046209 and, for example, [0144] to [0171] of WO2014 / 0669478.
  • the content of the crosslinking agent (F) in the total solid content in the negative photosensitive resin composition is preferably 10 to 60% by mass, particularly preferably 20 to 55% by mass.
  • thiol compound (G) examples include tris (2-mercaptopropanoyloxyethyl) isocyanurate, pentaerythritol tetrakis (3-mercaptobutyrate), trimethylolpropane tristhioglycolate, pentaerythritol tristhioglycol.
  • the negative photosensitive resin composition of the present invention can optionally contain a phosphoric acid compound (H) in order to improve the adhesion of the obtained cured film to a substrate, a transparent electrode material such as ITO, and the like.
  • Such a phosphoric acid compound (H) is not particularly limited as long as it can improve the adhesion of a cured film to a substrate, a transparent electrode material, etc., but the ethylenically unsaturated double molecule in the molecule.
  • a phosphoric acid compound having a bond is preferable.
  • Examples of the phosphoric acid (meth) acrylate compound used in the present invention include mono (2- (meth) acryloyloxyethyl) acid phosphate, di (2- (meth) acryloyloxyethyl) acid phosphate, and di (2-acryloyloxyethyl). Examples include acid phosphate, tris ((meth) acryloyloxyethyl) acid phosphate, mono (2-methacryloyloxyethyl) caproate acid phosphate, and the like.
  • the content is preferably 0.01 to 10% by mass with respect to the total solid content in the negative photosensitive resin composition, 0.1 to 5% by mass is particularly preferable.
  • the content ratio is in the above range, the adhesion between the obtained cured film and the substrate is good.
  • the content of the polymerization inhibitor (I) in the total solid content in the negative photosensitive resin composition is preferably 0.001 to 20% by mass, more preferably 0.005 to 10% by mass, and 0.01 to 5% by mass. % Is particularly preferred. When the content ratio is in the above range, the development residue of the negative photosensitive resin composition is reduced, and the pattern linearity is good.
  • solvent (J) When the negative photosensitive resin composition of the present invention contains a solvent (J), the viscosity is reduced, and the negative photosensitive resin composition can be easily applied to the substrate surface. As a result, a coating film of a negative photosensitive resin composition having a uniform film thickness can be formed.
  • a known solvent is used as the solvent (J).
  • a solvent (J) may be used individually by 1 type, or may use 2 or more types together.
  • Examples of the solvent (J) include alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, alcohols, and solvent naphtha. Among these, at least one solvent selected from the group consisting of alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, and alcohols is preferable.
  • the negative photosensitive resin composition of the present invention contains a colorant (K) when imparting light-shielding properties to a cured film, particularly a partition wall, depending on the application.
  • a colorant (K) in the present invention include carbon black, aniline black, anthraquinone black pigment, and perylene black pigment. I. Pigment black 1, 6, 7, 12, 20, 31 etc. are mentioned. Mixtures of organic pigments such as red pigments, blue pigments and green pigments and / or inorganic pigments can also be used.
  • the negative photosensitive resin composition of the present invention can be obtained by mixing predetermined amounts of the above components.
  • the negative photosensitive resin composition of this invention can be used for manufacture of optical elements, such as an organic EL element, a quantum dot display, a TFT array, a thin film solar cell, a color filter, for example. Specifically, the effect can be exhibited particularly when used for forming a cured film or a partition used for an optical element such as an organic EL element, a quantum dot display, a TFT array, and a thin film solar cell.
  • the negative photosensitive resin composition of the present invention it is possible to produce a cured film having good ink repellency on the upper surface, in particular, a partition wall.
  • the cured resin film of the embodiment of the present invention is formed using the above-described negative photosensitive resin composition of the present invention.
  • the cured resin film according to the embodiment of the present invention is, for example, coated with the negative photosensitive resin composition of the present invention on the surface of a substrate such as a substrate, dried as necessary to remove the solvent, and then exposed. Is obtained by curing.
  • the cured resin film according to the embodiment of the present invention is particularly effective when used for optical elements, particularly organic EL elements, quantum dot displays, TFT arrays, and thin film solar cells.
  • the partition wall of the present invention is a partition wall made of the above-described cured film of the present invention formed so as to partition the substrate surface into a plurality of sections for dot formation.
  • the partition wall is obtained by masking a portion to be a dot formation partition before exposure, developing after exposure. By development, an unexposed portion is removed by masking, and an opening corresponding to a dot forming section is formed together with a partition.
  • the partition wall according to the embodiment of the present invention exhibits a particularly remarkable effect when used in an optical element, particularly an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell.
  • the partition wall of the embodiment of the present invention does not necessarily require high-temperature treatment in the production process, and thus can be applied to flexible applications using a plastic substrate such as polyethylene terephthalate (PET) or polycarbonate. is there.
  • PET polyethylene terephthalate
  • polycarbonate polycarbonate
  • a negative photosensitive resin composition is applied to one entire main surface of the substrate 1 to form a coating film 21.
  • the ink repellent agent (E) is totally dissolved and uniformly dispersed in the coating film 21.
  • the ink repellent agent (E) is schematically shown, and does not actually exist in such a particle shape.
  • the coating film 21 is dried to form a dry film 22.
  • the drying method include heat drying, reduced pressure drying, and reduced pressure heat drying.
  • the heating temperature is preferably 50 to 120 ° C.
  • the ink repellent agent (E) moves to the upper layer of the dry film.
  • the upper surface transfer of an ink repellent agent (E) is similarly achieved within a coating film.
  • the exposure method includes full-surface batch exposure, scan exposure, and the like. You may expose in multiple times with respect to the same location. At this time, the multiple exposure conditions may or may not be the same.
  • the acid generator (C) in the exposed portion, the acid generator (C) generates an acid by exposure in parallel with radical polymerization of the alkali-soluble resin (A) during exposure.
  • the acid curing agent (D) reacts with an acidic group such as a carboxylic acid of the alkali-soluble resin (A).
  • the cured film in particular, the curing property of the alkali-soluble resin (A) on the upper surface of the cured film and the fixing property of the ink repellent agent (E) are improved.
  • a membrane is obtained.
  • a cured film having a curability equivalent to that of a conventional cured film, in particular, a curability on the upper surface can be obtained even with a low exposure amount.
  • FIG. 1D shows a state after the non-exposed portion 23B is removed by development.
  • the non-exposed portion 23B is dissolved and removed by an alkali developer in a state where the ink repellent agent (E) has moved to the upper layer portion and the ink repellent agent (E) is hardly present in the lower layer. Therefore, the ink repellent agent (E) hardly remains in the opening 5.
  • the uppermost layer including the upper surface is the ink repellent layer 4A.
  • the ink repellent agent (E) does not have a side chain having an ethylenic double bond
  • the ink repellent agent (E) is present in a high concentration as it is in the uppermost layer and becomes an ink repellent layer.
  • the alkali-soluble resin (A) present around the ink repellent agent (E) is strongly photocured with the acid curing agent (D), particularly in the presence of an acid generated by the acid generator (C).
  • the ink repellent agent (E) is fixed to the ink repellent layer.
  • the negative photosensitive resin composition optionally contains the thiol compound (G)
  • the reaction by the ethylenic double bond is promoted, and the ink repellent layer is cured more firmly.
  • the ink-repellent layer 4A has mainly an alkali-soluble resin (A), an acid curing agent (D), and an optionally contained thiol compound (G), and other photocuring components.
  • A alkali-soluble resin
  • D acid curing agent
  • G thiol compound
  • other photocuring components are photocured by radical polymerization by radicals generated by the photopolymerization initiator (B) and cationic polymerization in the presence of acid generated by the acid generator (C), and the layer hardly contains the ink repellent agent (E). 4B is formed.
  • the ink repellent agent (E) is sufficiently fixed to the partition including the ink repellent layer 4A and the lower layer 4B, and therefore hardly migrates to the opening during development.
  • the surface and the inside of the cured film are sufficiently cured by combining the radical polymerization reaction by light and the curing reaction in the presence of acid by light. . Therefore, the hardened portion which is the exposed portion has resistance to erosion and peeling by the alkaline developer during development. Therefore, the exposed portion is not easily affected by long-time development, which is advantageous for removing the residue at the opening.
  • the partition 4 may be further heated after development.
  • the heating temperature is preferably 80 to 250 ° C.
  • the partition 4 is hardened by heating.
  • the ink repellent agent (E) is more firmly fixed in the ink repellent layer 4A.
  • the composition of the present invention can exhibit high liquid repellency even when cured at low temperature, and can also have high liquid repellency even after being immersed in a chemical such as an acid or an organic solvent.
  • the heating temperature needs to be set low.
  • the heating temperature is preferably set to 150 ° C. or lower, particularly preferably 120 ° C. or lower.
  • the composition of the present invention maintains liquid repellency and has excellent chemical resistance even when heated at a low temperature as described above.
  • the cured resin film and the partition 4 of the present invention thus obtained have good ink repellency on the upper surface even when exposure is performed at a low exposure amount.
  • the ink repellent (E) hardly exists in the opening 5 after development, and the uniform coating property of the ink in the opening 5 can be sufficiently ensured.
  • the substrate 1 with the partition walls 4 may be subjected to ultraviolet / ozone treatment.
  • the width of the partition formed from the negative photosensitive resin composition of the present invention is preferably 100 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
  • the distance between adjacent partition walls (pattern width) is preferably 300 ⁇ m or less, and particularly preferably 100 ⁇ m or less.
  • the height of the partition wall is preferably 0.05 to 50 ⁇ m, particularly preferably 0.2 to 10 ⁇ m.
  • the partition formed from the negative photosensitive resin composition of the present invention has few irregularities in the edge portion when formed to the above width, and is excellent in linearity.
  • the high linearity in the partition walls is particularly remarkable when a resin (A-2) in which an acidic group and an ethylenic double bond are introduced into an epoxy resin is used as the alkali-soluble resin.
  • A-2 a resin in which an acidic group and an ethylenic double bond are introduced into an epoxy resin
  • an epoxy resin is used as the alkali-soluble resin.
  • the partition of the present invention can be used as a partition having the opening as an ink injection region when pattern printing is performed by the IJ method.
  • pattern printing is performed by the IJ method
  • the partition wall of the present invention is formed and used so that the opening thereof coincides with a desired ink injection region, the partition top surface has good ink repellency. It is possible to suppress ink from being injected into an undesired opening, that is, an ink injection region beyond the partition wall.
  • the opening surrounded by the partition wall has good ink wetting and spreading properties, it is possible to print the ink uniformly without causing white spots or the like in a desired region.
  • the barrier rib of the present invention is an optical element having a barrier rib positioned between a plurality of adjacent dots on a substrate surface on which dots are formed by the IJ method, particularly an organic EL element, a quantum dot display, a TFT array, and a thin film solar. It is useful as a battery partition.
  • optical element of the present invention in particular, an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell is an optical element having a plurality of dots and a partition wall of the present invention located between adjacent dots on the substrate surface. is there.
  • the dots are preferably formed by the IJ method.
  • An organic EL element has a structure in which a light emitting layer of an organic thin film is sandwiched between an anode and a cathode. It can be used for partitioning applications.
  • the organic TFT array element is a semiconductor layer including a plurality of dots arranged in a matrix in plan view, each pixel having a pixel electrode and a TFT as a switching element for driving it, and including a TFT channel layer.
  • the organic TFT array element is provided as a TFT array substrate in, for example, an organic EL element or a liquid crystal element.
  • ink 10 is dropped from the inkjet head 9 into the opening 5 surrounded by the partition wall 4 and a predetermined amount of ink 10 is injected into the opening 5.
  • known inks for organic EL elements are appropriately selected and used in accordance with the function of dots.
  • the optical element of the embodiment of the present invention uses the partition wall of the present invention, so that an ink is formed in an opening partitioned by the partition wall in the manufacturing process.
  • an optical element having dots formed with high accuracy in particular, an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell.
  • an organic EL element can be manufactured as follows, for example, it is not limited to this.
  • a light-transmitting electrode such as tin-doped indium oxide (ITO) is formed on a plastic light-transmitting substrate such as glass or PET by sputtering or the like.
  • the translucent electrode is patterned as necessary.
  • partition walls are formed in a lattice shape in plan view along the outline of each dot by photolithography including coating, exposure and development.
  • the materials of the hole injection layer, the hole transport layer, the light emitting layer, the hole blocking layer, and the electron injection layer are applied and dried in the dots by the IJ method, and these layers are sequentially stacked.
  • the kind and number of organic layers formed in the dots are appropriately designed.
  • a reflective electrode such as aluminum is formed by vapor deposition or the like.
  • the quantum dot display can be manufactured, for example, as follows, but is not limited thereto.
  • a light-transmitting electrode such as tin-doped indium oxide (ITO) is formed on a plastic light-transmitting substrate such as glass or PET by sputtering or the like.
  • the translucent electrode is patterned as necessary.
  • partition walls are formed in a lattice shape in plan view along the outline of each dot by photolithography including coating, exposure and development.
  • the materials of the hole injection layer, the hole transport layer, the quantum dot layer, the hole blocking layer, and the electron injection layer are respectively applied and dried in the dots by the IJ method, and these layers are sequentially stacked. .
  • the kind and number of organic layers formed in the dots are appropriately designed.
  • a reflective electrode such as aluminum or a translucent electrode such as ITO is formed by vapor deposition or the like.
  • a nanoparticle solution that converts blue light into green light by the IJ method, a nanoparticle solution that converts blue light into red light, and a blue color ink as necessary are coated in the dots and dried. Is made.
  • a liquid crystal display with excellent color reproducibility can be obtained by using a light source that emits blue as a backlight and using the module as a color filter alternative.
  • the TFT array can be manufactured, for example, as follows, but is not limited thereto.
  • a gate electrode such as aluminum or an alloy thereof is formed on a light-transmitting substrate made of plastic such as glass or PET by a sputtering method or the like. This gate electrode is patterned as necessary.
  • a gate insulating film such as silicon nitride is formed by a plasma CVD method or the like.
  • a source electrode and a drain electrode may be formed over the gate insulating film.
  • the source electrode and the drain electrode can be formed by forming a metal thin film such as aluminum, gold, silver, copper, or an alloy thereof by, for example, vacuum deposition or sputtering.
  • a resist is coated, exposed and developed to leave the resist in a portion where the electrode is to be formed, and then exposed with phosphoric acid or aqua regia. There is a method of removing the metal and finally removing the resist.
  • the source electrode and the drain electrode may be formed by a method such as ink jet using a metal nanocolloid such as silver or copper.
  • partition walls are formed in a lattice pattern in plan view along the outline of each dot by photolithography including coating, exposure and development.
  • a semiconductor solution is applied in the dots by the IJ method, and the solution is dried to form a semiconductor layer.
  • an organic semiconductor solution or an inorganic coating type oxide semiconductor solution can also be used.
  • the source electrode and the drain electrode may be formed by using a method such as inkjet after forming the semiconductor layer.
  • a transparent electrode such as ITO is formed by sputtering or the like, and a protective film such as silicon nitride is formed.
  • Examples 1 to 10 are examples, and examples 11 to 13 are comparative examples.
  • the column is maintained at 37 ° C., tetrahydrofuran is used as the eluent, the flow rate is 0.2 mL / min, and a 0.5% tetrahydrofuran solution of the measurement sample is used. 40 ⁇ L was injected.
  • fluorine atom content The content of fluorine atoms was calculated by 19 F NMR measurement using 1,4-ditrifluoromethylbenzene as a standard substance.
  • Alkali-soluble resin (A) Alkali-soluble resin (A1) composition: A cresol novolac epoxy resin is reacted with acrylic acid and then 1,2,3,6-tetrahydrophthalic anhydride, and a resin into which an acryloyl group and a carboxy group are introduced is purified with hexane Composition (alkali-soluble resin (A1), acid value 60 mgKOH / g) (solid content 70% by mass, PGMEA 30% by mass)
  • Alkali-soluble resin (A2) composition a composition (alkali-soluble resin (A2) having an acid value of 100 mgKOH / g) in which a carboxyl group and an ethylenic double bond are introduced into a bisphenol A type epoxy resin (solid content: 70% by mass) , PGMEA 30% by mass).
  • Alkali-soluble resin (A3) composition a resin in which an ethylenic double bond and an acidic group are introduced into an epoxy resin having a biphenyl skeleton represented by the following formula (A-2a) (alkali-soluble resin (A3), acid value) 70 mg KOH / g) (solid content 70% by mass, PGMEA 30% by mass).
  • v is an integer of 1 to 50, preferably an integer of 2 to 10.
  • the hydrogen atoms of the benzene ring are each independently an alkyl group having 1 to 12 carbon atoms or a halogen atom. Or a part of hydrogen atoms may be substituted with a phenyl group which may be substituted with a substituent.
  • Alkali-soluble resin (AR-1) A reaction tank having an internal volume of 1 L equipped with a stirrer was charged with acetone (555 g), AA (acrylic acid) (36.0 g), 2-HEMA (108.0 g), IBMA (72.0 g), chain transfer agent DSH (9.7 g) and polymerization initiator V-70 (5.1 g) were charged and polymerized at 40 ° C. for 18 hours with stirring under a nitrogen atmosphere to obtain an alkali-soluble resin ( A solution of AR-1) was obtained.
  • alkali-soluble resin (AR-1) Water is added to the acetone solution of the obtained alkali-soluble resin (AR-1) to effect reprecipitation purification, then reprecipitation purification with petroleum ether, vacuum drying, and alkali-soluble resin (AR-1) 235 g was obtained.
  • the number average molecular weight (Mn) of the alkali-soluble resin (AR-1) was 5,000, and the acid value of the alkali-soluble resin (AR-1) was 119 mgKOH / g.
  • IR907 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name IRGACURE907, manufactured by BASF).
  • OXE02 Ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (manufactured by BASF, trade name: OXE02).
  • EAB 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.).
  • PAG-A 2- (5-methyl-2-furyl) ethenyl-4,6-bis (trichloromethyl) -1,3,5-triazine (a compound represented by the above formula (C8-2)).
  • PAG-B 2- [2- (n-propylsulfonyloxyimino) thiophene-3 (2H) -ylidene] -2- (2-methylphenyl) acetonitrile (among the compounds represented by the above formula (C11), R a compound wherein b11 is an n-propyl group).
  • WPAG199 bis (p-toluenesulfonyl) diazomethane.
  • SI-150L sulfonium aromatic represented by the formula (C0-1) SbF 6 - salt (Sanshin Chemical Industry Co., Ltd., trade name: San-Aid SI-150L).
  • Epoxy A an epoxy compound containing a dicyclopentane ring represented by the above formula (De1).
  • Epoxy B a naphthalene ring-containing epoxy compound represented by the above formula (De2).
  • Melamine A 2,4,6-tris [bis (methoxymethyl) amino] -1,3,5-triazine (compound represented by the above formula (D1-1)).
  • Melamine B 1,3,4,6-tetrakis (methoxymethyl) glycoluril (compound represented by the above formula (D3-1)).
  • V-65 (2,2′-azobis (2,4-dimethylvaleronitrile))
  • V-70 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile)
  • DSH n-dodecyl mercaptan
  • BEI 1,1- (bisacryloyloxymethyl) ethyl isocyanate)
  • AOI 2-acryloyloxyethyl isocyanate
  • DBTDL Dibutyltin dilaurate TBQ: t-butyl-p-benzoquinone
  • MEK 2-butanone
  • the agent was inactivated to obtain a solution (solid content concentration: 30% by mass) of a copolymer (ink repellent agent (E-1)).
  • This solution was used for the production of a negative photosensitive resin composition described later.
  • the negative photosensitive resin composition in the state of the solution. Used in the manufacture of the product.
  • the ink repellent agent (E-1) has a number average molecular weight of 14,200, a mass average molecular weight of 21,500, a fluorine atom content of 31.4% by mass, and an acid value of 32.6 (mgKOH / g )Met.
  • the ink repellent agent (E-2) has a number average molecular weight of 7,540, a mass average molecular weight of 16,200, a fluorine atom content of 14.8% by mass, and an acid value of 35.1 (mgKOH / g )Met.
  • the ink repellent agent (E-3) has a number average molecular weight of 14,850, a mass average molecular weight of 22,700, a fluorine atom content of 31.4% by mass, and an acid value of 32.6 (mgKOH / g )Met.
  • ink repellent (E-4)
  • the ink repellent agent (E-4) had a number average molecular weight of 5,700, a mass average molecular weight of 8,800, and a fluorine atom content of 19.0% by mass.
  • the ink repellent agent (E-5) has a number average molecular weight of 8,000, a mass average molecular weight of 10,600, a fluorine atom content of 28.0% by mass, and an acid value of 93.3 (mgKOH / g). )Met.
  • the ink repellent agent (E-6) had a number average molecular weight of 9,000, a mass average molecular weight of 11,700, a fluorine atom content of 14.7% by mass, and an acid value of 65 mgKOH / g.
  • the ink repellent agent (E-7) had a number average molecular weight of 4,500, a mass average molecular weight of 5,590, a fluorine atom content of 12.5% by mass, and an acid value of 33 mgKOH / g.
  • Table 1 summarizes the raw material compositions and properties of the ink repellent agents (E-1) to (E-7) obtained or prepared above.
  • Table 2 shows the amount of raw material hydrolyzable silane compound used in the production of the obtained ink repellent agents ((E-8) to (E-10)).
  • the silane compound means a hydrolyzable silane compound.
  • the number average molecular weight (Mn), mass average molecular weight (Mw), and fluorine atom content (% by mass) of the obtained ink repellent agents ((E-8) to (E-10)) were measured. Table 2 shows.
  • Example 1 Production of negative photosensitive resin composition and production of cured film and partition wall (pattern film)] (Manufacture of negative photosensitive resin composition)
  • the negative photosensitive resin composition 1 was manufactured by stirring for 3 hours.
  • the entire surface of the obtained dried film was irradiated with UV light from an ultrahigh pressure mercury lamp having an exposure power (exposure output) in terms of 365 nm of 300 mW / cm 2 .
  • exposure power exposure output
  • two types of cured films were produced by adjusting the irradiation time so that the exposure amount was 30 mJ / cm 2 or 50 mJ / cm 2 . In all cases, light of 330 nm or less was cut during the exposure.
  • the glass substrate after the exposure treatment was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution for 10 seconds, washed away with water, and then dried. Subsequently, this was heated on a hot plate at 230 ° C. for 60 minutes to obtain a cured film having no opening.
  • the distance between the dry film and the photomask was 50 ⁇ m.
  • the glass substrate after the exposure treatment was developed by immersing in a 2.38% tetramethylammonium hydroxide aqueous solution for 40 seconds, and the non-exposed portion was washed away with water and dried. Next, this was heated on a hot plate at 230 ° C. for 60 minutes to obtain a pattern film 1 as a cured film having an opening corresponding to the masking portion of the photomask.
  • the distance between the dry film and the photomask was 50 ⁇ m.
  • the glass substrate after the exposure treatment was developed by immersing it in a 2.38% tetramethylammonium hydroxide aqueous solution for 200 seconds, and the non-exposed portion was washed with 1.5 MPa high-pressure water for 10 seconds and dried. Next, this was heated on a hot plate at 230 ° C. for 60 minutes to obtain a pattern film 2 as a cured film having an opening corresponding to the masking portion of the photomask.
  • the glass substrate after the exposure treatment was developed by immersing in a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 40 seconds, and the non-exposed portion was washed away with water and dried.
  • a pattern film 3 was obtained as a cured film having a pattern corresponding to the opening pattern of the photomask.
  • the PGMEA contact angle on the upper surface of the cured film obtained above was measured by the following method to evaluate ink repellency.
  • PGMEA droplets were placed on the upper surface of the cured film by the sessile drop method, and each PGMEA droplet was measured.
  • the droplet was 2 ⁇ L / droplet, and the measurement was performed at 20 ° C.
  • the contact angle was determined from the average value of 3 measurements.
  • the PGMEA contact angle on the upper surface of the cured film obtained above was measured by the above method.
  • the pattern forming property was evaluated according to the following criteria.
  • the line width of the line portion where the line / space was 20 ⁇ m / 50 ⁇ m was measured.
  • Example 2 In Example 1, except that the negative photosensitive resin composition was changed to the composition shown in Table 3, Table 4 or Table 5, a negative photosensitive resin composition, a partition, and a cured film were produced in the same manner. Evaluation similar to Example 1 was performed. The evaluation results of each example are shown in Table 3, Table 4, and Table 5 together with the composition of the negative photosensitive resin composition.
  • Examples 1 to 10 corresponding to the examples of the negative photosensitive resin composition of the present invention, an alkali-soluble resin or alkali-soluble monomer (A) having an unsaturated double bond, a photopolymerization initiator (B), Since the acid generator (C) and the acid curing agent (D) are contained, high liquid repellency was obtained even when the exposure amount was as low as 30 mJ / cm 2 . Further, even when the exposure amount is 50 mJ / cm 2, the line width is not easily increased, and the pattern formability is good.
  • Example 11 and 12 corresponding to the comparative examples since either one of the photopolymerization initiator (B) and the acid generator (C) is not contained, the exposure amount is as low as 30 mJ / cm 2 . In some cases, the liquid repellency was insufficient. For this reason, the upper surface of the cured film has insufficient ink repellency. In Example 13 corresponding to the comparative example, the amount of the photopolymerization initiator (B) was increased, so that the liquid repellency was sufficient. However, since the acid generator (C) was not contained, the exposure amount was 30 mJ / cm 2 . Even in the case of a low exposure amount, the line width tends to be thick, and the pattern formability is insufficient.

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WO2018155016A1 (ja) * 2017-02-21 2018-08-30 日本ゼオン株式会社 ネガ型感光性樹脂組成物
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