WO2022039028A1 - 感光性樹脂組成物、硬化物、表示装置、半導体装置及び硬化物の製造方法 - Google Patents

感光性樹脂組成物、硬化物、表示装置、半導体装置及び硬化物の製造方法 Download PDF

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WO2022039028A1
WO2022039028A1 PCT/JP2021/028917 JP2021028917W WO2022039028A1 WO 2022039028 A1 WO2022039028 A1 WO 2022039028A1 JP 2021028917 W JP2021028917 W JP 2021028917W WO 2022039028 A1 WO2022039028 A1 WO 2022039028A1
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group
resin composition
photosensitive resin
cured product
organic
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PCT/JP2021/028917
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English (en)
French (fr)
Japanese (ja)
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池田圭
小森悠佑
三好一登
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東レ株式会社
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Priority to KR1020227042069A priority Critical patent/KR20230051766A/ko
Priority to JP2021546305A priority patent/JPWO2022039028A1/ja
Priority to CN202180043115.7A priority patent/CN115698854A/zh
Publication of WO2022039028A1 publication Critical patent/WO2022039028A1/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
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/22—Exposing sequentially with the same light pattern different positions of the same surface
    • 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
    • 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
    • G09F9/33—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 being semiconductor devices, e.g. diodes
    • G09F9/335—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 being semiconductor devices, e.g. diodes being organic light emitting diodes [OLED]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • 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

Definitions

  • the present invention relates to a photosensitive resin composition, a cured product, a display device, a semiconductor device, and a method for producing a cured product.
  • organic electroluminescence hereinafter referred to as organic EL
  • display devices having a thin display such as smartphones, tablet PCs, and televisions.
  • an organic EL display device has a drive circuit, a flattening layer, a first electrode, a pixel dividing layer, a light emitting layer, and a second electrode on a substrate, and is located between the first electrode and the second electrode facing each other. It emits light by applying a voltage.
  • a photosensitive resin composition that can be patterned by ultraviolet irradiation is generally used.
  • the positive photosensitive resin compositions that have been proposed so far are those obtained by mixing an alkali-soluble resin with a photosensitive component, naphthoquinonediazide sulfonic acid ester, and using a polyimide precursor as the resin (see, for example, Patent Document 1). ), Those using a polybenzoxazole precursor (see, for example, Patent Document 2).
  • organic EL display devices are becoming stricter year by year, and the design / design of materials for flattening layers and pixel division layers, such as placing a camera directly under the display of a transmissive organic EL display or mobile terminal. From the viewpoint of diversification and further functionalization, transparency in the visible light region is required.
  • the photosensitive resin composition of the present invention has the following constitution. That is, (A) Alkaline-soluble resin, (B) Photoacid generator and (C) Compound having a phenolic hydroxyl group having an octanol / water partition coefficient (LogP) of 4.6 to 20.0 (hereinafter referred to as component (C)).
  • component (C) Compound having a phenolic hydroxyl group having an octanol / water partition coefficient (LogP) of 4.6 to 20.0.
  • component (C) Compound having a phenolic hydroxyl group having an octanol / water partition coefficient (LogP) of 4.6 to 20.0
  • component (C) Compound having a phenolic hydroxyl group having an octanol / water partition coefficient (LogP) of 4.6 to 20.0
  • a photosensitive resin composition containing, and having a transmittance of 80% or more and 99% or less at 400 nm at a thickness of 1.5 ⁇
  • the first aspect of the cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention.
  • the method for producing a cured product of the present invention includes a step of applying the photosensitive resin composition of the present invention to a substrate to form a resin film, a step of drying the resin film, a step of exposing the dried resin film, and exposure.
  • This is a method for producing a cured product which comprises a step of developing a resin film and a step of heat-treating the developed resin film to obtain a cured product.
  • a second aspect of the cured product of the present invention is a compound having a transmittance of 80% or more and 99% or less at 400 nm at a thickness of 1.5 ⁇ m, a yellow index of 0.1 or more and 7 or less, and an imide ring structure. It is a cured product containing a compound having an indene structure, a compound having a structure represented by the formula (2), and a compound having a structure represented by the formula (1).
  • R 2 , R 3 and R 4 are monovalent organic groups having 1 to 30 carbon atoms which may independently contain a hydrogen atom or a hetero atom, respectively.
  • Each R 1 is a monovalent organic group having 1 to 20 carbon atoms which may contain a hetero atom independently.
  • the organic EL display device of the present invention is an organic EL display device provided with the cured product of the present invention.
  • the semiconductor device of the present invention is a semiconductor device provided with the cured product of the present invention.
  • the photosensitive resin composition of the present invention is excellent in visible light transmission after heat curing.
  • the photosensitive resin composition of the present invention is (A) Alkaline-soluble resin, A photosensitive resin composition containing (B) a photoacid generator and (C) a compound having a phenolic hydroxyl group having an octanol / water partition coefficient (LogP) of 4.6 to 20.0, which is thermally cured.
  • the transmittance at 400 nm at a thickness of 1.5 ⁇ m is 80% or more and 99% or less, and the yellow index is 0.1 or more and 7.0 or less.
  • the photosensitive resin composition of the present invention is preferably used for the flattening layer and / or the pixel dividing layer of the organic EL display device. When used in such a layer, it becomes easy to improve the visible light transmittance of the organic EL display device.
  • the photosensitive resin composition of the present invention is used for a mobile device provided with a camera and / or a sensor directly under the active area of the organic EL display device. Since the photosensitive resin composition is used for each of the above-mentioned layers, the visible light transmittance of the organic EL display device can be easily improved. Therefore, a mobile equipped with a camera and / or a sensor directly under the active area of the organic EL display device. It will be easier to use for the device. Therefore, it becomes easy to correspond to various designs / designs such as a transmissive organic EL display.
  • the photosensitive resin composition of the present invention contains (A) an alkali-soluble resin.
  • alkali-soluble means that a solution of a resin dissolved in ⁇ -butyrolactone is applied onto a silicon wafer and prebaked at 120 ° C. for 4 minutes to form a prebaked film having a thickness of 10 ⁇ m ⁇ 0.5 ⁇ m.
  • the dissolution rate required from the decrease in film thickness when the prebake film is immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ⁇ 1 ° C. and then rinsed with pure water is 50 nm / min or more. To say.
  • alkali-soluble resin examples include polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyaminoamide, acrylic resin, cardo resin, phenol resin, cyclic olefin polymer, and polysiloxane. Not limited to this.
  • the alkali-soluble resin may contain two or more of these resins. Among these alkali-soluble resins, those having excellent heat resistance and a small amount of outgas at high temperatures are preferable. Specifically, one or more alkali-soluble resins selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, their copolymers and polysiloxane are preferable.
  • the (A) alkali-soluble resin is a polyimide, a polyimide precursor, a polybenzoxazole, a polybenzoxazole precursor, and their co-weights, because they have excellent film physical properties such as bending resistance. It is more preferable to contain one or more kinds of alkali-soluble resins selected from the group consisting of coalescing. Further, from the viewpoint of visible light transmission, exposure sensitivity and chemical resistance, one or more alkali-soluble resins selected from the group consisting of polyimide precursors, polybenzoxazole precursors and copolymers thereof are particularly preferable.
  • the alkali-soluble resin preferably has an acidic group in the structural unit of the resin and / or at the end of the main chain thereof. Having an acidic group makes it easier to obtain alkali solubility.
  • the acidic group include a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group. Of these, carboxyl groups and phenolic hydroxyl groups are preferable in that they do not contain sulfur atoms.
  • the alkali-soluble resin preferably has a fluorine atom.
  • a fluorine atom By having a fluorine atom, it is possible to impart water repellency to the interface between the film and the base material when developing with an alkaline aqueous solution, and to suppress the penetration of the alkaline aqueous solution into the interface.
  • the fluorine atom content in the alkali-soluble resin is preferably 5% by mass or more in (A) 100% by mass of the alkali-soluble resin from the viewpoint of the effect of preventing the alkaline aqueous solution from seeping into the interface, and 20 from the viewpoint of solubility in the alkaline aqueous solution. It is preferably mass% or less.
  • the alkali-soluble resin can be synthesized by a known method.
  • a method of reacting a tetracarboxylic acid dianhydride with a diamine compound at a low temperature a method of reacting a tetracarboxylic acid dianhydride with a diamine compound at a low temperature, and then N, N- Dimethylformamide
  • a method of partially esterifying the amic acid structure with dimethylacetal or the like a method of obtaining a diester with a tetracarboxylic acid dianhydride and an alcohol, and then reacting with an amine in the presence of a condensing agent, a method of tetracarboxylic acid dianhydride.
  • a diester can be obtained from the compound and an alcohol, and then the remaining dicarboxylic acid can be acid chlorided and synthesized by a method of reacting with an amine.
  • polyimide for example, it can be obtained by dehydrating and ring-closing the polyimide precursor obtained by the above-mentioned method by heating in a solvent or by chemical treatment with an acid or a base.
  • a polybenzoxazole precursor it can be obtained, for example, by subjecting a bisaminophenol compound and a dicarboxylic acid to a condensation reaction.
  • a dehydration condensing agent for example, there is a method of reacting a dehydration condensing agent with an acid and adding a bisaminophenol compound to the reaction, or a method of dropping a solution of a dicarboxylic acid dichloride into a solution of a bisaminophenol compound to which a tertiary amine is added.
  • the dehydration condensing agent include dicyclohexylcarbodiimide (DCC) and the like.
  • pyridine and the like are mentioned as a tertiary amine.
  • polybenzoxazole for example, it can be obtained by dehydrating and closing the ring of the polybenzoxazole precursor obtained by the above method by heating in a solvent or by chemical treatment with an acid or a base.
  • Examples of the acid dianhydride used for polyimide, the polyimide precursor and its copolymer include pyromellitic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,3.
  • Examples of the acid component used for polybenzoxazole, polybenzoxazole precursor and its copolymer include dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid and the like.
  • Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyldicarboxylic acid, benzophenone dicarboxylic acid, triphenyldicarboxylic acid and the like.
  • Examples of the tricarboxylic acid include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid and the like.
  • Examples of the tetracarboxylic acid include aromatic tetracarboxylic acid and aliphatic tetracarboxylic acid.
  • aromatic tetracarboxylic acids are pyromellitic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 2,2', 3, 3'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenone tetracarboxylic acid, 2,2', 3,3'-benzophenone tetracarboxylic acid, 2,2-bis (3,4-dicarboxy) Phenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 1,1-bis (2,3-bis) Dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxy
  • diamines include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, and 1,4-bis (4-amino).
  • Phenoxy) benzene benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxy) biphenyl, bis ⁇ 4- (4-aminophenoxy) phenyl ⁇ Ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3' -Dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2', 3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3 ', 4,4'-Tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluor
  • R 5 and R 8 represent an oxygen atom, C (CF 3 ) 2 , or C (CH 3 ) 2 .
  • R 6 , R 7 and R 9 to R 16 independently represent a hydrogen atom or a hydroxyl group, respectively.
  • diamines can be used as diamines or as the corresponding diisocyanate compounds, trimethylsilylated diamines.
  • end-capping agents include monoamines having acidic groups, acid anhydrides, acid chlorides, monocarboxylic acids and the like.
  • the content of the terminal encapsulant is preferably 2 to 25 mol parts with respect to 100 mol parts in total of the acid and amine components constituting the resin.
  • the acrylic resin one obtained by radically polymerizing (meth) acrylic acid and (meth) acrylic acid ester is preferable.
  • the (meth) acrylic acid ester include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, cyclopropyl (meth) acrylic acid, cyclopentyl (meth) acrylic acid, and (meth) acrylic acid.
  • Aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene and ⁇ -methylstyrene may be copolymerized with the above (meth) acrylic acid and (meth) acrylic acid ester. ..
  • an ethylenically unsaturated double bond group can be introduced by an addition reaction of an epoxy compound having an ethylenically unsaturated double bond group with (meth) acrylic acid.
  • cardo resin examples include a resin having a cardo structure, that is, a skeleton structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure.
  • a common cardo structure is a fluorene ring with a benzene ring bonded to it.
  • skeleton structure in which two cyclic structures are bonded to the quaternary carbon atom constituting the cyclic structure include a fluorene skeleton, a bisphenol fluorene skeleton, a bisaminophenylfluorene skeleton, a fluorene skeleton having an epoxy group, and an acrylic group.
  • fluorene skeleton having a fluorene skeleton examples include a fluorene skeleton having a fluorene skeleton.
  • the cardo resin is formed by polymerizing the skeleton having the cardo structure by the reaction between the functional groups bonded to it.
  • the cardo resin has a structure (cardo structure) in which a main chain and a bulky side chain are connected by one element, and has a cyclic structure in a direction substantially perpendicular to the main chain.
  • the monomer having a cardo structure examples include bis (glycidyloxyphenyl) fluorene type epoxy resin, 9,9-bis (4-hydroxyphenyl) fluorene, and 9,9-bis (4-hydroxy-3-methyl).
  • Cardo-structure-containing bisphenols such as phenyl) fluorene, 9,9-bis (cyanoalkyl) fluorene such as 9,9-bis (cyanomethyl) fluorene, 9,9-bis (3-aminopropyl) fluorene, etc. Examples thereof include 9,9-bis (aminoalkyl) fluorenes.
  • the cardo resin is a polymer obtained by polymerizing a monomer having a cardo structure, but may be a copolymer with other copolymerizable monomers.
  • phenol resin examples include novolak phenol resin and resol phenol resin.
  • Phenol resins can be obtained, for example, by polycondensing various phenols alone or a mixture thereof with an aldehyde such as formalin.
  • phenols include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3, 4-Dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylenebisphenol , Methylenebis p-cresol, resorcin, catechol, 2-methylresorcin, 4-methylresorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxy Phenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isoprop
  • aldehydes include paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, and chloroacetaldehyde. These aldehydes can be used alone or as a mixture of multiple aldehydes.
  • the weight average molecular weight of the phenol resin is preferably 2000 to 50,000, and more preferably 3000 to 30,000. By setting the weight average molecular weight to 50,000 or less, developability and sensitivity are likely to be improved. Further, when the value is 2000 or more, the pattern shape, resolution, developability, and heat resistance are likely to be improved.
  • the weight average molecular weight of the phenol resin is measured by gel permeation chromatography and calculated in terms of polystyrene.
  • polysiloxane examples include polysiloxanes obtained by hydrolyzing and dehydrating and condensing one or more kinds selected from tetrafunctional organosilanes, trifunctional organosilanes, bifunctional organosilanes and monofunctional organosilanes.
  • tetrafunctional organosilane examples include tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane.
  • trifunctional organosilane examples include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3 -Methyloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ethyltrimethoxysilane, 2- (P-Hydroxy
  • bifunctional organosilane examples include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, din-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, and (3).
  • -Glysidoxypropyl) methyldiethoxysilane, di (1-naphthyl) dimethoxysilane, di (1-naphthyl) diethoxysilane and the like can be mentioned.
  • the monofunctional organosilane examples include trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane and the like. Two or more of these organosilanes may be used. Further, a silicate compound such as methyl silicate 51 manufactured by Fuso Chemical Industry Co., Ltd. and M silicate 51 manufactured by Tama Chemical Industry Co., Ltd. may be copolymerized.
  • the weight average molecular weight (Mw) of the polysiloxane is not particularly limited, but is preferably 1,000 or more in terms of polystyrene measured by GPC (gel permeation chromatography). When it is 1,000 or more, the coating film property is likely to be improved. On the other hand, from the viewpoint of solubility in a developing solution, the Mw of the polysiloxane is preferably 100,000 or less, and more preferably 50,000 or less.
  • Polysiloxane can be synthesized, for example, by hydrolyzing and partially condensing a monomer such as organosilane.
  • the partial condensation means not condensing all the Si-OH of the hydrolyzate, but leaving a part of Si-OH in the obtained polysiloxane.
  • Common methods can be used for hydrolysis and partial condensation. For example, a method of adding a solvent, water, and a catalyst as needed to the organosilane mixture and heating and stirring at 50 to 150 ° C. for about 0.5 to 100 hours can be mentioned. During stirring, the hydrolysis by-product (alcohol such as methanol) and the condensation by-product (water) may be distilled off, if necessary.
  • the catalyst is not particularly limited, but an acid catalyst and a base catalyst are preferably used.
  • the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyvalent carboxylic acid or its anhydride, ion exchange resin and the like.
  • the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide and amino. Examples thereof include alkoxysilane having a group and an ion exchange resin.
  • the total content of the components (A) to (C) is preferably 50% by mass or more in 100% by mass of the total amount of the photosensitive resin composition excluding the organic solvent, and 80 from the viewpoint of visible light transmission and exposure sensitivity. It is more preferably 90% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more. The upper limit of the total content is not particularly limited, but is 100% by mass.
  • the total content of the components (A) to (D) is preferably 50% by mass or more, and visible light transmission and exposure. From the viewpoint of sensitivity, it is more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more.
  • the upper limit of the total content is not particularly limited, but is 100% by mass.
  • the photosensitive resin composition of the present invention contains (B) a photoacid generator.
  • the (B) photoacid generator may be simply referred to as the (B) component.
  • the (B) photoacid generator has a function of generating an acid by irradiation with light and increasing the solubility of the irradiated portion of the light in an alkaline aqueous solution.
  • the photoacid generator (B) include naphthoquinone diazide sulfonic acid ester, diaryliodonium salt, triarylsulfonium salt, oxime sulfonate compound, naphthaleneimide compound and the like.
  • (B) Light because a positive photosensitive resin precursor composition that is efficiently sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp, which is a general ultraviolet ray, can be obtained. It is preferable that the acid generator contains a naphthoquinone diazide sulfonic acid ester.
  • the (B) photoacid generator is one or more selected from the group consisting of a naphthoquinone diazide sulfonic acid ester, a diaryliodonium salt, a triarylsulfonium salt, an oxime sulfonate compound, and a naphthaleneimide compound. It is more preferable to contain and.
  • the photoacid generating material By having a structure in which the photoacid generating material is applied, the dissolution rate of the unexposed portion when developing with an alkaline aqueous solution is reduced, and the difference in solubility between the exposed portion and the unexposed portion is increased, so that the photosensitivity is highly efficient.
  • the unexposed portion is thermally decomposed by a thermosetting treatment to generate an acid, and the temperature is as low as 250 ° C. or lower. Even in curing, the cross-linking reaction of the cross-linking agent proceeds sufficiently, and the chemical resistance of the cured film can be dramatically improved.
  • the component (A) contains one or more kinds of alkali-soluble resins selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor and a copolymer thereof, the imide ring and the oxazole ring thereof. Since cyclization is promoted, the cyclization reaction proceeds sufficiently even in low temperature curing, and the chemical resistance of the cured film is improved.
  • an oxime sulfonate compound is preferable because it easily causes efficient thermal decomposition at a low temperature of 250 ° C. or lower.
  • the (B) photoacid generator contains a naphthoquinone diazide sulfonic acid ester.
  • the naphthoquinone diazide sulfonic acid ester is preferably a compound in which a sulfonic acid of naphthoquinone diazide is bonded to a compound having a phenolic hydroxyl group by an ester.
  • Compounds having a phenolic hydroxyl group include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, and BisP.
  • the naphthoquinone diazide sulfonic acid ester can be synthesized, for example, by an esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazido sulfonic acid compound.
  • Examples of the quinonediazide sulfonic acid compound include, but are not limited to, naphthoquinonediazide-4-sulfonic acid and naphthoquinonediazide-5-sulfonic acid.
  • the photosensitive resin composition further improves resolution, sensitivity, and residual film ratio by containing the above-mentioned compound having a phenolic hydroxyl group and a naphthoquinone diazide sulfonic acid ester obtained by an esterification reaction with a quinone diazido sulfonic acid compound. do.
  • the naphthoquinone diazidosulfonic acid-4-ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. Further, the naphthoquinone diazide-5-sulfonic acid ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure.
  • the photosensitive resin composition of the present invention can contain both a naphthoquinone diazide-4-sulfonic acid ester compound and a naphthoquinone diazido-5-sulfonic acid ester compound.
  • It can also contain a naphthoquinone diazide sulfonic acid ester having both a naphthoquinone diazide-4-sulfonyl group and a naphthoquinone diazide-5-sulfonyl group in the same molecule. Further, both a naphthoquinone diazide-4-sulfonic acid ester compound and a naphthoquinone diazide-5-sulfonic acid ester compound can be contained.
  • diaryliodonium salt triarylsulfonium salt, oxime sulfonate compound, and naphthaleneimide compound are shown below, but the present invention is not limited thereto.
  • diallyl iodonium salt examples include SP-130 and SP-140 (trade name, manufactured by ADEKA CORPORATION).
  • examples of the triarylsulfonium salt include WPAG-567 (trade name, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), SP-056 (trade name, manufactured by ADEKA Corporation), SI-200, SI-210, SI-220. (Product name, manufactured by Sanshin Chemical Industries, Ltd.) and the like.
  • the oxime sulfonate compound examples include PAG121, PAG103 (trade name, manufactured by BASF Japan Ltd.), PA-480, PA-411, PA-528 (trade name, manufactured by Heleus Co., Ltd.), PAI-01, PAI-.
  • PAI-106 PAI-1001, PAI-1002, PAI-1003, PAI-1004 (Midori Kagaku) and the like can be mentioned.
  • the naphthaleneimide compound include SP-082, SP-601, SP-606, SP-607, SP-612 (trade name, manufactured by ADEKA CORPORATION), NIT, MIN, ILP-110, ILP-110N, and ILP-. 118, ILP-113, PA-223, PA-298 (trade name, manufactured by Heleus Co., Ltd.), NAI-105, NAI-106, NAI-109 (trade name, manufactured by Midori Chemical Co., Ltd.), etc. Be done.
  • the content of the component (B) is preferably 3 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total amount of the (A) alkali-soluble resin. When it is 3 parts by mass or more, the exposure sensitivity is improved, and when it is 50 parts by mass or less, the visible light transmission is further improved.
  • the content of the component (B) is more preferably 5 parts by mass or more and 40 parts by mass or less, further preferably 7 parts by mass or more and 40 parts by mass or less, and 10 parts by mass or more and 35 parts by mass or less. Is particularly preferable.
  • the total content of these salts or compounds is 100 parts by mass of the total amount of the alkali-soluble resin (A).
  • 0.01 part by mass or more is preferable, and 0.1 part by mass or more is more preferable.
  • the total content of these salts or compounds is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and more preferably 2 parts by mass or less.
  • the photosensitive resin composition of the present invention contains (C) a compound having a phenolic hydroxyl group having a LogP of 4.6 to 20.0 (hereinafter, may be referred to as a component (C)).
  • the photosensitive resin composition obtained by containing the component (C) hardly dissolves in an alkaline developer before exposure, and easily dissolves in an alkaline developer when exposed, so that film loss due to development is small. And, development becomes easy in a short time. Therefore, the sensitivity is likely to be improved.
  • the molecular weight of the component (C) is preferably in the range of 90 to 2000. It is preferably 200 to 1500, and more preferably 300 to 1200.
  • the polarity of the component (C) affects the visible light transmittance of the cured film of the photosensitive resin composition.
  • the higher the polarity of the component (C) contained in the photosensitive resin composition the lower the visible light transparency when the cured product is formed, and the lower the polarity of the component (C), thereby lowering the polarity of the cured product. Visible light transmission can be improved.
  • LogP octanol / water partition coefficient
  • LogPow octanol / water partition coefficient
  • LogP is a physical property value related to the compatibility of the target substance with water, and the larger this value is, the lower the polarity is.
  • LogP is represented by the common logarithm of the concentration ratio of each phase of the target substance, targeting the case where the target substance is in an equilibrium state in a two-phase system of water and octanol (1-octanol).
  • LogP can be obtained from the structure of the compound by using the calculation function of commercially available software such as "ChemDraw” (PerkinElmer Informatics, Inc.). In the examples and comparative examples described later, the values obtained by using the built-in "Chemical properties window" in the product name "ChemDraw ver. 19.1.0.8" (manufactured by PerkinElmer Informatics, Inc.) are adopted. did.
  • the LogP value of the component (C) is 4.6 to 20.0. If the LogP value of the component (C) is less than 4.6, the visible light transmittance of the cured product tends to decrease. On the other hand, when the LogP value exceeds 20.0, the solubility in a solvent is lowered and the exposure sensitivity is lowered.
  • the LogP of the component (C) is preferably 5.5 or more, more preferably 6.0 or more, further preferably 7.0 or more, and particularly preferably 8.0 or more, from the viewpoint of improving visible light transmission.
  • the upper limit of LogP is preferably 15.0 or less, more preferably 13.0 or less, and particularly preferably 12.0 or less, from the viewpoint of balancing solubility and exposure sensitivity. Further, from the viewpoint of further reducing the yellow index, the LogP of the component (C) is preferably 8.0 to 15.0.
  • the content of the component (C) is preferably 5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the total amount of the (A) alkali-soluble resin.
  • the content is low, the sensitivity may be lowered, while when the content is high, the visible light transmittance after thermosetting may be lowered. Therefore, it is more preferably 10 parts by mass or more and 35 parts by mass or less. From the viewpoint of the balance between sensitivity and visible light transmission after heat curing, it is more preferably 15 parts by mass or more and 30 parts by mass or less.
  • component (C) having a LogP value in the range of 4.6 to 20.0 is shown below, but it has a phenolic hydroxyl group and has a LogP value in the range of 4.6 to 20.0. However, it is not limited to these.
  • the component (C) When the number of phenolic hydroxyl groups in the component (C) increases, the LogP value tends to decrease, and when the number of substituents and aromatic rings increases, the LogP value tends to increase. Above all, it is preferable that the component (C) has a cyclohexane ring structure because it is effective in improving the LogP value, the solubility of the component (C) in a solvent is unlikely to decrease, and the coloration in thermosetting is small. From the viewpoint of efficiently improving the LogP value and reducing coloration in thermosetting, it is more preferable that the component (C) contains a compound containing two or more cyclohexane ring structures in the molecule.
  • the structure having a hydrogen atom at the benzyl position does not contain hydrogen at the benzyl position because coloring is likely to occur during thermal curing, especially during curing in an oxygen atmosphere.
  • the component (C) is the compound represented by the formula (3) and the compound represented by the formula (4) in the photosensitive resin composition of the present invention. It is preferable to contain one or more kinds selected from the group consisting of.
  • R 17 is an independent methyl group or a group represented by formula (5), and at least one R 17 is a group represented by formula (5).
  • c is an integer of 1 to 4. * Indicates the binding position.
  • R18 is a divalent organic group having 1 to 10 carbon atoms.
  • a and b are independently integers of 0 to 4, and a + b is 1 or more.
  • the divalent organic group having 1 to 10 carbon atoms is preferably an alkyl group, an aryl group, or a group having a cyclohexane ring structure.
  • the divalent organic group having 1 to 10 carbon atoms is a divalent organic group having 1 to 10 carbon atoms. It is particularly preferable that the group has a cyclohexane ring structure.
  • the compound having a phenolic hydroxyl group may be contained in combination of two or more.
  • the LogP average value of the compound having a phenolic hydroxyl group is preferably in the range of 4.6 to 20.0.
  • the lower limit of the LogP average value is preferably 5.5 or more, more preferably 6.0 or more, further preferably 7.0 or more, and particularly preferably 8.0 or more, from the viewpoint of enhancing visible light transmission.
  • the upper limit of the LogP average value is preferably 15.0 or less, more preferably 13.0 or less, and particularly preferably 12.0 or less, from the viewpoint of balancing solubility and exposure sensitivity.
  • the LogP average value is a value obtained by multiplying the LogP value of each compound having a phenolic hydroxyl group contained in the photosensitive resin composition by the mass ratio of each phenol compound to the entire phenol compound. It is the value calculated for each phenol compound and the sum of the values.
  • the photosensitive resin composition of the present invention has a transmittance of 80% or more and 99% or less at 400 nm at a thickness of 1.5 ⁇ m after heat curing, and a yellow index of 0.1 or more and 7.0 or less. Since the transmittance and the yellow index are in the above ranges, when the cured product of the photosensitive resin composition is applied to an organic EL display device, the visible light transmittance of the organic EL display device is likely to be improved, and thus organic. It will be easier to use for mobile devices equipped with a camera and / or sensor directly under the active area of the EL display device. In addition, it is possible to easily support various designs / designs such as a transmissive organic EL display.
  • a resin film described below containing a component (C) having a large LogP and a component (D) described below may be used.
  • Examples thereof include a method of lowering the maximum heating temperature in the step of heat-treating to obtain a cured product.
  • the photosensitive resin composition of the present invention preferably contains the compound represented by the formula (D) (1) (hereinafter, may be referred to as the component (D)).
  • Each R 1 is a monovalent organic group having 1 to 20 carbon atoms which may contain a hetero atom independently.
  • the monovalent organic group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 7 carbon atoms in terms of visible light transmission. Further, from the viewpoint of improving the transparency of visible light, it is preferable that the monovalent organic group having 1 to 20 carbon atoms has a hydroxyl group and an acrylic group. On the other hand, from the viewpoint of increasing heat resistance, chemical resistance and hardness, it is preferable that the monovalent organic group having 1 to 20 carbon atoms has an epoxy group and an oxetanyl group.
  • the content of the component (D) is preferably 5 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the total amount of the (A) alkali-soluble resin.
  • the content of the component (D) is more preferably 15 parts by mass or more and 65 parts by mass or less, and further preferably 25 parts by mass or more and 60 parts by mass or less.
  • the component (D) may be contained in combination of two or more. Examples of the component (D) are shown by the following chemical formulas, but the components are not limited thereto.
  • the compound represented by the formula (1) is a compound (DA) in which at least two of R1 in the formula (1) are monovalent groups containing an epoxy group (D).
  • D an epoxy group
  • it may be simply referred to as a component (D-a) or (D-a))
  • / or at least two of R1 in the formula (D-b) (1) have an acrylic group and / or a hydroxyl group.
  • It is preferable to contain a compound which is a monovalent group to be contained hereinafter, may be simply referred to as (Db) or (Db) component).
  • the compound represented by the formula (1) contains the component (Da), in addition to further improving the transparency, a cross-linking reaction occurs during thermosetting, and the heat resistance of the film after thermosetting. Chemical resistance and hardness can be increased, the amount of outgas from the cured product can be reduced, and the long-term reliability of the organic EL display device can be improved.
  • the compound represented by the formula (1) contains the component (Db), in addition to further improving the transparency, the exposure sensitivity is likely to be improved, and the storage stability of the photosensitive resin composition is likely to be improved. Can be kept high.
  • the mass ratio (D-a) / (D-b) shall be 1/9 to 9/1. Is preferable, more preferably 1/9 to 8/2, and particularly preferably 2/8 to 7/3.
  • the compound represented by the above formula (D) (1) is a monovalent group in which at least two of R1 in the formula (DA) (1) contain an epoxy group.
  • (Db) contains a compound in which at least two of R1 in the formula (1) are a monovalent group containing an acrylic group and / or a hydroxyl group, and the mass ratio thereof (D-a). ) / (Db) is preferably 1/9 to 9/1.
  • the photosensitive resin composition of the present invention contains the component (C) and the compound represented by the formula (D) at the same time, so that the visible light transmittance can be more easily improved.
  • the total content (Cm + Dm) is 20 parts by mass or more and 110 parts by mass or less, and the content ratio (Dm / Cm) is 1/9 to 9 /. It is preferably 1.
  • the total content (Cm + Dm) is more preferably 25 parts by mass or more and 100 parts by mass or less, and particularly preferably 40 parts by mass or more and 90 parts by mass or less.
  • the content ratio (Dm / Cm) is more preferably 3/7 to 9/1, and particularly preferably 5/5 to 8/2.
  • the photosensitive resin composition of the present invention can contain a heat-crosslinking agent as long as the visible light transmittance of the cured product is not impaired.
  • the heat-crosslinking agent refers to a compound having at least two thermoreactive functional groups in the molecule. Examples of the thermoreactive functional group include an alkoxymethyl group, a methylol group, an epoxy group, an oxetanyl group and the like.
  • the resin of the component (A) or other additive components can be cross-linked to improve the heat resistance, chemical resistance and hardness of the film after heat curing, and further, outgas from the cured product. The amount can be reduced and the long-term reliability of the organic EL display device can be improved.
  • the thermal cross-linking agent may be contained in combination of two or more types.
  • the content of the thermal cross-linking agent is preferably 1% by mass or more and 30% by mass or less in 100% by mass of the total amount of the photosensitive resin composition excluding the organic solvent.
  • the content of the thermal cross-linking agent is 1% by mass or more and 30% by mass or less, the chemical resistance and hardness of the film after firing or curing can be increased, and the amount of outgas from the cured product can be reduced.
  • the long-term reliability of the organic EL display device can be enhanced, and the storage stability of the photosensitive resin composition is also excellent.
  • the photosensitive resin composition of the present invention preferably contains an organic solvent. As a result, it can be made into a varnish state, and the coatability can be improved.
  • organic solvents include polar aprotic solvents such as ⁇ -butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Ethers such as propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tetrahydrofuran, dioxane, acetone , Methyl ethyl ketone, Diisobutyl ketone, Cyclohexanone, 2-Heptanone, 3-Heptanone, Diacetone alcohol and other ketones, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl
  • the content of the organic solvent is not particularly limited, but is preferably 100 to 3000 parts by mass, and more preferably 150 to 2000 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive resin composition excluding the organic solvent. preferable.
  • the proportion of the organic solvent having a boiling point of 180 ° C. or higher in the total amount of the organic solvent is preferably 20% by mass or less, more preferably 10% by mass or less.
  • the photosensitive resin composition of the present invention can contain an adhesion improver.
  • adhesion improver include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, and the like.
  • silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, aromatic amine compounds and alkoxy groups. Examples thereof include a compound obtained by reacting a silicon compound. Two or more of these may be contained.
  • adhesion improvers it is possible to improve the adhesion to a base material such as a silicon wafer, ITO, SiO2, or silicon nitride when developing a resin film.
  • the content of the adhesion improver is preferably 0.1 to 10% by mass based on 100% by mass of the total amount of the photosensitive resin composition excluding the organic solvent.
  • the photosensitive resin composition of the present invention may contain a surfactant, if necessary.
  • a surfactant By containing a surfactant, the wettability with the substrate can be improved.
  • Commercially available compounds can be used as the surfactant.
  • silicone-based surfactants SH series, SD series, ST series of Toray Dow Corning Silicone, BYK series of Big Chemie Japan, KP series of Shinetsu Silicone, Disform series of Nippon Oil & Fats, Toshiba Silicone
  • fluorine-based surfactants include the TSF series of Dainippon Ink Industry Co., Ltd., the "Megafuck (registered trademark)” series of Dainippon Ink Industry Co., Ltd., the Florard series of Sumitomo 3M Co., Ltd., and "Surflon (registered trademark)” of Asahi Glass Co., Ltd.
  • the content of the surfactant is preferably 0.001 to 1% by mass in 100% by mass of the total amount of the photosensitive resin composition excluding the organic solvent.
  • the photosensitive resin composition of the present invention may contain inorganic particles.
  • the inorganic particles include, but are not limited to, silicon oxide, titanium oxide, barium titanate, alumina, and talc.
  • the primary particle diameter of these inorganic particles is preferably 100 nm or less, more preferably 60 nm or less.
  • the content of the inorganic particles is preferably 5 to 50% by mass in 100% by mass of the total amount of the photosensitive resin composition excluding the organic solvent.
  • the photosensitive resin composition of the present invention may contain a thermoacid generator as long as it does not impair visible light transmission.
  • the thermal acid generator generates an acid by heating to promote the crosslinking reaction of the thermal cross-linking agent, and when the resin of the component (A) has an unclosed ring imide ring structure or an oxazole ring structure, these It is possible to promote cyclization and further improve the mechanical properties of the cured film.
  • the thermal decomposition start temperature of the thermal acid generator used in the present invention is preferably 50 ° C to 270 ° C, more preferably 250 ° C or lower. Further, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after applying the photosensitive resin composition of the present invention to the substrate, and final heating (cure: about) after patterning in subsequent exposure and development. It is preferable to select a substance that generates an acid at 100 to 400 ° C. because it can suppress a decrease in sensitivity during development.
  • the acid generated from the thermal acid generator used in the present invention is preferably a strong acid, for example, aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid and butane sulfonic acid.
  • aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid
  • methane sulfonic acid methane sulfonic acid
  • ethane sulfonic acid propane sulfonic acid and butane sulfonic acid
  • Alkyl sulfonic acid such as and haloalkyl sulfonic acid such as trifluoromethyl sulfonic acid are preferable.
  • These can be used as acid protected compounds such as alkyl esters. Two or more of these may
  • the content of the thermal acid generator used in the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more in 100% by mass of the total amount of the photosensitive resin composition excluding the organic solvent.
  • the content is 0.01% by mass or more, the cross-linking reaction and the cyclization of the unclosed ring structure of the resin are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved.
  • 5% by mass or less is preferable, 3% by mass or less is more preferable, and 2% by mass or less is more preferable.
  • the method for producing the photosensitive resin composition of the present invention will be described.
  • the components (A) to (C), the component (D) if necessary, and the other components are suspended in a solvent and stirred until dissolved. Can be manufactured with.
  • the melting temperature is preferably 5 ° C. or higher and 60 ° C. or lower from the viewpoint of solubility and suppression of the reaction of the components.
  • the stirring step is preferably performed in an atmosphere of an inert gas such as nitrogen.
  • the photosensitive resin composition of the present invention is suitably used for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating film of an organic EL element, a flattening film of a thin film transistor (TFT) substrate, and the like.
  • TFT thin film transistor
  • the first aspect of the cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention.
  • the transmittance at 400 nm at a thickness of 1.5 ⁇ m is 80% or more and 99% or less. From the viewpoint of design / design diversification such as arranging a camera directly under the display of a transmissive organic EL display or a mobile terminal, high visible light transmission is preferable, 85% or more is more preferable, and 90% or more is particularly preferable. ..
  • the upper limit of the transmittance is not particularly limited, but may be, for example, 99%, 98%, or 97%.
  • the yellow index at a thickness of 1.5 ⁇ m is 0.1 or more and 7.0 or less.
  • the yellow index is preferably low, more preferably 5.0 or less, and particularly preferably 3.0 or less. ..
  • the lower limit of the yellow index is not particularly limited, but may be, for example, 0.1, 0.2, or 0.3.
  • the method for producing a cured product of the present invention includes a step of applying the photosensitive resin composition of the present invention to a substrate to form a resin film, a step of drying the resin film, a step of exposing the dried resin film, and exposure. It includes a step of developing a resin film and a step of heat-treating the developed resin film to obtain a cured product.
  • the photosensitive resin composition can be applied to a substrate by, for example, a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method, or the like to obtain a coating film of the photosensitive resin composition.
  • the substrate to which the photosensitive resin composition is applied may be pretreated with the above-mentioned adhesion improving agent in advance.
  • a solution in which the adhesion improver is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate in an amount of 0.5 to 20% by mass is used.
  • a method of treating the surface of the base material can be mentioned. Examples of the method for treating the surface of the base material include methods such as spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.
  • a metal, glass, resin film, or the like that is preferable for supporting a display device or transporting a post-process can be appropriately selected. If it is a glass substrate, soda lime glass, non-alkali glass, or the like can be used. The thickness of the substrate may be sufficient to maintain the mechanical strength. As for the material of the glass, non-alkali glass is preferable because it is preferable that the amount of elution ions from the glass is small, but soda lime glass having a barrier coat such as SiO 2 can also be used.
  • the resin film preferably contains a resin material selected from polyimide, polyamide, polybenzoxazole, polyamideimide, and poly (p-xylylene), and these resin materials may be contained alone.
  • a plurality of species may be combined.
  • a polyamic acid including a partially imidized polyamic acid
  • a solution containing a soluble polyimide is applied to a support substrate and fired. It can also be formed with.
  • the resin After coating, the resin is dried, and if necessary, dried under reduced pressure, and then heat-treated in the range of 50 ° C to 180 ° C for 1 minute to several hours using, for example, a hot plate, an oven, or infrared rays.
  • a membrane can be obtained.
  • the chemical beam can be irradiated through a mask having a desired pattern on the resin film.
  • the chemical beam used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. Above all, it is preferable to use the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of the mercury lamp.
  • the exposed part can be removed using, for example, a developing solution.
  • the developing solution includes tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, and dimethyl.
  • An aqueous solution of an alkaline compound such as aminoethylmethacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine is preferable.
  • these alkaline aqueous solutions are mixed with polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, ⁇ -butyrolactone and dimethylacrylamide, methanol and ethanol.
  • polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, ⁇ -butyrolactone and dimethylacrylamide, methanol and ethanol.
  • Alcohols such as isopropanol, esters such as ethyl lactate and monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone, alone or in combination of several types. May be good.
  • Examples of the developing method include methods such as spraying, paddle, dipping, and ultrasonic
  • distilled water For example, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to distilled water for rinsing.
  • alcohols such as ethanol and isopropyl alcohol
  • esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to distilled water for rinsing.
  • the method for producing a cured product of the present invention there may be a step of irradiating the developed resin film with ultraviolet rays.
  • the (B) photoacid generator is decomposed by irradiation with ultraviolet rays, and the degassing component can be efficiently removed in the heat treatment step described later.
  • the component (B) is a naphthoquinone diazide sulfonic acid ester, it changes to an indene carboxylic acid compound.
  • the inden carboxylic acid compound further promotes the removal of sulfur dioxide derived from the sulfonic acid ester structure from the film in the heat treatment step described later.
  • the ultraviolet light is preferably light containing any one of the wavelengths of the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of the mercury lamp.
  • the irradiation amount of ultraviolet rays is preferably in the range of 50 to 10000 mJ / cm 2 .
  • the (A) alkali-soluble resin contained in the photosensitive resin composition of the present invention contains a polyimide precursor, a polybenzoxazole precursor, or a copolymer thereof
  • the imide ring and the oxazole ring are heat-treated. Therefore, heat resistance and chemical resistance can be improved, and when a heat-crosslinking agent is contained, the heat-crosslinking reaction can be promoted by heat treatment, and heat resistance and chemical resistance are improved. be able to.
  • the temperature may be gradually raised and then maintained at the maximum heating temperature, or continuously raised and then maintained at the maximum heating temperature, or may be maintained at the maximum heating temperature from the beginning.
  • the maximum heating temperature refers to the highest temperature among the temperatures experienced by the resin film due to heating, after confirming the temperature range in which the resin film experiences a cumulative total of 1 minute or more. From the viewpoint of visible light transmission of the cured film, it is preferable that the maximum heating temperature is low. On the other hand, from the viewpoint of improving heat resistance and chemical resistance, it is preferable that the maximum heating temperature is high. In consideration of the balance of these characteristics, the maximum heating temperature is preferably 200 ° C. to 350 ° C., more preferably 220 ° C.
  • the holding time at the maximum heating temperature is not particularly limited, but is preferably 15 minutes or longer, more preferably 30 minutes or longer, and even more preferably 45 minutes or longer. Further, from the viewpoint of productivity, 180 minutes or less is preferable, 150 minutes or less is more preferable, and 120 minutes or less is further preferable.
  • an organic EL display device for example, an organic EL display having a step of forming a flattening layer, a first electrode, a pixel division layer, an organic EL layer, and a second electrode on a substrate in this order.
  • the method for manufacturing the apparatus is a step of applying the photosensitive resin composition of the present invention to a substrate to form a resin film, the resin.
  • a method that is a method for producing a cured product which comprises a step of drying the film, a step of exposing the dried resin film, a step of developing the exposed resin film, and a step of heat-treating the developed resin film to obtain a cured product.
  • a method for producing a cured product which comprises a step of drying the film, a step of exposing the dried resin film, a step of developing the exposed resin film, and a step of heat-treating the developed resin film to obtain a cured product.
  • a second aspect of the cured product of the present invention is a compound having a transmittance of 80% or more and 99% or less at 400 nm at a thickness of 1.5 ⁇ m, a yellow index of 0.1 or more and 7 or less, and an imide ring structure. It contains a compound having an indene structure, a compound having a structure represented by the formula (2), and a compound having a structure represented by the formula (1).
  • R 2 , R 3 and R 4 are monovalent organic groups having 1 to 30 carbon atoms which may independently contain a hydrogen atom or a hetero atom, respectively.
  • Each R 1 is a monovalent organic group having 1 to 20 carbon atoms which may contain a hetero atom independently.
  • a preferred embodiment of R 1 is as described above.
  • examples of the monovalent organic group having 1 to 30 carbon atoms which may contain the heteroatom include an alkyl group, an alkenyl group, an alkynyl group, an aryl group and the like.
  • the alkyl group may be linear, branched or cyclic.
  • the number of carbon atoms of the linear and branched alkyl groups is usually 1 to 30, preferably 1 to 20 from the viewpoint of maintaining high visible light transmission, and more preferably 1 to 10.
  • the number of carbon atoms of the cyclic alkyl group is usually 3 to 30, preferably 3 to 20 from the viewpoint of maintaining high visible light transmittance, and more preferably 3 to 10.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group and an octyl group.
  • Nonyl group, decyl group and the like can be mentioned.
  • the alkenyl group may be linear, branched or cyclic.
  • the number of carbon atoms of the linear and branched alkenyl groups is usually 2 to 30, preferably 2 to 20 from the viewpoint of maintaining high visible light transmission, and more preferably 2 to 10.
  • the number of carbon atoms of the cyclic alkenyl group is usually 3 to 30, preferably 3 to 20 from the viewpoint of maintaining high visible light transmittance, and more preferably 3 to 10.
  • alkenyl group examples include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, a butenyl group, a pentenyl group, a hexenyl group, a nonenyl group, a decenyl group and the like.
  • the alkynyl group may be linear, branched or cyclic.
  • the number of carbon atoms of the linear and branched alkynyl groups is usually 2 to 30, preferably 2 to 20 from the viewpoint of maintaining high visible light transmission, and more preferably 2 to 10.
  • the number of carbon atoms of the cyclic alkynyl group is usually 3 to 30, preferably 3 to 20 from the viewpoint of maintaining high visible light transparency, and more preferably 3 to 10.
  • Examples of the alkynyl group include an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group and the like.
  • the aryl group is the remaining atomic group obtained by removing one hydrogen atom directly bonded to the carbon atom constituting the aromatic ring from the aromatic hydrocarbon, and comprises a hydroxy group, the alkyl group, the alkenyl group, and the alkynyl group. Including those having as a functional group.
  • the number of carbon atoms of the aryl group is usually 6 to 30, preferably 6 to 20.
  • Examples of the aryl group include a phenyl group, a hydroxyphenyl group, an alkylphenyl group, an alkylhydroxyphenyl group and the like.
  • a hydroxyphenyl group or an alkyl hydroxyphenyl group is preferable from the viewpoint of balancing visible light transmission and heat resistance.
  • alkylphenyl group examples include a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a propylphenyl group, a methylethylphenyl group, a propylphenyl group, an isopropylphenyl group, a butylphenyl group, an isobutylphenyl group, and a tert-butylphenyl group.
  • alkyl hydroxyphenyl group examples include a methyl hydroxyphenyl group, an ethyl hydroxyphenyl group, a dimethyl hydroxyphenyl group, a propyl hydroxyphenyl group, a methyl ethyl hydroxyphenyl group, a propyl hydroxyphenyl group, an isopropyl hydroxyphenyl group, and a butyl hydroxyphenyl group.
  • Examples thereof include isobutyl hydroxyphenyl group, tert-butyl hydroxyphenyl group, pentyl hydroxyphenyl group, hexyl hydroxyphenyl group, cyclohexyl hydroxyphenyl group, heptyl hydroxyphenyl group, octyl hydroxyphenyl group, nonyl hydroxyphenyl group, decyl hydroxyphenyl group and the like. ..
  • R 2 , R 3 , and R 4 is an alkyl group, an alkenyl group, an alkynyl group, or an aryl group. More preferably, it contains both an alkyl group and a hydroxyphenyl group and / or an alkyl hydroxyphenyl group.
  • the cured product has a compound having an imide ring structure, a compound having an indene structure, a compound having a structure represented by the formula (2), and a compound having a structure represented by the formula (1), so that the thickness is 1.5 ⁇ m. It becomes easy to obtain a cured product having a transmittance of 80% or more and 99% or less at 400 nm and a yellow index of 0.1 or more and 7.0 or less at a thickness of 1.5 ⁇ m.
  • the second aspect of the cured product of the present invention is that the transmittance at 400 nm at a thickness of 1.5 ⁇ m is 80% or more and 99% or less. From the viewpoint of design / design diversification such as arranging a camera directly under the display of a transmissive organic EL display or a mobile terminal, it is preferable that the visible light transmission is high. Specifically, the visible light transmittance of the cured product is more preferably 85% or more, more preferably 88% or more, and particularly preferably 90% or more. The upper limit of the transmittance is not particularly limited, but may be, for example, 99%, 98%, or 97%.
  • the second aspect of the cured product of the present invention is that the yellow index at a thickness of 1.5 ⁇ m is 7.0 or less. From the viewpoint of design / design diversification such as placing the camera directly under the transmissive organic EL display or the display of the mobile terminal, it is preferable that the yellow index of the cured product is low, specifically 5.0 or less. preferable.
  • the yellow index of the cured product is particularly preferably 3.0 or less.
  • the lower limit of the yellow index is not particularly limited, but may be, for example, 0.1, 0.2, or 0.3.
  • the second aspect of the cured product of the present invention is represented by a compound having an imide ring structure, a compound having an indene structure, a compound having a structure represented by the formula (2), and a compound represented by the formula (1).
  • a compound having such a structure it is possible to easily maintain high visible light transmission of the cured product.
  • the compound contained in the second aspect of the cured product of the present invention will be described.
  • the compound having an imide ring structure is derived from, for example, (A) a structure derived from a polyimide resin or a residue thereof, and the compound having an inden structure is derived from, for example, (B) a naphthoquinone diazide sulfonic acid ester contained as a photoacid generator.
  • the compound having the structure or its residue, the structure represented by the formula (2) is, for example, the structure derived from the component (C) or its residue, and the compound having the structure represented by the formula (1) is, for example.
  • (D) can be obtained as a structure derived from the compound represented by the formula (1) or a residue thereof.
  • the cured product of the present invention can be used for organic EL display devices, semiconductor devices, multilayer wiring boards, and the like. More preferably, an insulating layer of an organic EL display device, a flattening layer of a substrate with a drive circuit of an organic EL display device, an interlayer insulating film between rewiring of a semiconductor device, a semiconductor passive film, a protective film of a semiconductor device, and a high height. It is used in applications such as interlayer insulating films for multi-layer wiring for density mounting, wiring protection insulating layers for circuit boards, on-chip microlenses for solid-state imaging devices, and flattening layers for various displays and solid-state imaging devices.
  • the organic EL display device of the present invention comprises the cured product of the present invention.
  • the organic EL display device of the present invention has at least a substrate, a first electrode, a second electrode, an organic EL layer, a flattening layer and a pixel dividing layer, and the cured product of the present invention is a flattening layer and / or a pixel dividing layer. It is preferable to include it in.
  • a TFT thin film transistor
  • a flattening layer is provided so as to cover the unevenness, and a display element is further provided on the flattening layer.
  • the display element and the wiring are connected via a contact hole formed in the flattening layer. Since the cured product of the present invention has excellent visible light transmission, it is preferably used for a flattening layer and / or a pixel dividing layer. In particular, in recent years, the flexibility of organic EL display devices has become mainstream, and the substrate having the above-mentioned drive circuit may be an organic EL display device made of a resin film.
  • the organic EL display device of the present invention is preferably used for a mobile device provided with a camera and / or a sensor directly under the active area of the organic EL display device. Since the organic EL display device of the present invention includes the cured product of the present invention, the visible light transmittance of the organic EL display device is improved, and visible light is efficiently passed through the active area of the organic EL display device. It can be suitably used for a mobile device having a camera and / or a sensor directly under the active area. In addition, it becomes easy to support various designs / designs such as a transmissive organic EL display.
  • the flattening layer and the pixel dividing layer are each composed of a single layer or a plurality of layers, and at the laminated interface of the cured product of each layer forming the flattening layer and the pixel dividing layer.
  • the difference in refractive index with respect to the wavelength of 550 nm between the cured products forming the laminated interface is 0.3 or less at all the laminated interfaces.
  • the difference in refractive index is more preferably 0.2 or less, further preferably 0.1 or less, and particularly preferably 0.05 or less. Furthermore, it is most preferable that there is no difference in refractive index.
  • the flattening layer and the pixel dividing layer have a multi-layer structure.
  • the difference in refractive index between the cured products forming the laminated interface at the laminated interface of the cured product of each layer forming the flattening layer and the pixel dividing layer shall be within the above range.
  • reflection at the interface is less likely to occur, so that the visible light transparency of the organic EL display device is more likely to be improved.
  • a method such as arranging the types of resins contained in the curing forming the laminated interface can be mentioned, and most preferably, the cured product forming each layer is produced by using the same photosensitive resin composition. How to do it.
  • the organic EL display device of the present invention can be provided with a cured product of a photosensitive resin composition containing polysiloxane.
  • the cured product of the photosensitive resin composition containing polysiloxane is, for example, the photosensitive resin composition containing at least the polysiloxane and the photoacid generator (B) by the method described in the method for producing the cured product. It is a cured product obtained by curing.
  • the flattening layer and the pixel dividing layer are each composed of a single layer or a plurality of layers, and the flattening layer contains the cured product.
  • the pixel dividing layer contains a cured product of a photosensitive resin composition containing polysiloxane. Since a cured product of a photosensitive resin composition containing a polysiloxane generally tends to enhance visible light transmission, a cured product of the photosensitive resin composition containing the polysiloxane is provided as the pixel dividing layer. It is easy to improve the transparency of visible light of the organic EL display device.
  • the organic EL display device is provided with the first preferred embodiment in which the flattening layer contains the cured product. It is easy to improve the transparency of the visible light of the EL display device, and it is possible to further increase the flexibility of the organic EL display device.
  • a second preferred embodiment of the organic EL display device of the present invention is that the flattening layer and the pixel dividing layer are each composed of a single layer or a plurality of layers, and the flattening layer is photosensitive including polysiloxane.
  • the cured product of the resin composition is contained, and the pixel dividing layer contains the cured product.
  • the cured product of the photosensitive resin composition containing polysiloxane is generally located on the side of the TFT of the organic EL display device and the TFT, and tends to have a high performance of flattening the unevenness of the wiring connected to the TFT.
  • the second preferred embodiment it is easy to improve the visible light transparency of the organic EL display device, and the TFT of the organic EL display device is located on the side of the TFT and is connected to the TFT. It is possible to improve the flatness of the unevenness of the wiring.
  • a third preferred embodiment of the organic EL display device of the present invention is that the flattening layer and the pixel dividing layer are each composed of a single layer or a plurality of layers, and the flattening layer and the pixel dividing layer are the same.
  • the flattening layer contains the cured product, the flexibility of the organic EL display device can be enhanced, and the TFT of the organic EL display device and the wiring located on the side of the TFT and connected to the TFT.
  • the flatness of the unevenness of the surface can be appropriately increased.
  • the semiconductor device of the present invention comprises the cured product of the present invention.
  • the semiconductor device of the present invention preferably contains the cured product of the present invention in the insulating film and / or the protective film.
  • Examples of the semiconductor device include a semiconductor device having a known structure. Since the cured product of the present invention has excellent visible light transmittance, it is preferably used for the above-mentioned insulating film and / or protective film.
  • the developing film was subjected to a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo System Co., Ltd.) under a nitrogen atmosphere (oxygen concentration: 100 ppm or less) to 250 ° C. at 5 ° C./min.
  • a thermosetting step of raising the temperature and heat-treating at 250 ° C. for 1 hour was performed to prepare a cured product of varnish.
  • the thickness of the cured product was about 1.5 ⁇ m.
  • a thermosetting step was performed in which the temperature was raised to 230 ° C. at 5 ° C./min and heat-treated at 230 ° C. for 1 hour to prepare a cured product of varnish.
  • the cured product of the varnish produced above was measured and evaluated at a wavelength of 300 nm to 800 nm using a spectrophotometer (“Double Beam Spectrophotometer U-2900” manufactured by Hitachi, Ltd.). From the measurement results, the transmittance at a wavelength of 400 nm was read and the visible light transmittance was evaluated. Unless otherwise specified, for each measurement result, the transmittance in the wavelength range of 400 nm to 800 nm is the lowest at 400 nm, and is higher than the transmittance at 400 nm in the region of 401 nm or more and less than 800 nm. Transmittance was obtained. The transmittance at 400 nm obtained was determined according to the following criteria. C or higher was rated as "pass” with good transmittance, and D or lower was rated as "fail".
  • the pattern of the obtained developing film was observed with an FDP microscope MX61 (manufactured by Olympus Corporation) at a magnification of 20 times, and the minimum required exposure amount at which the opening diameter of the contact hole reached 10 ⁇ m was obtained, and this was determined by the exposure sensitivity. And said. C or higher was regarded as good exposure sensitivity and was regarded as "pass”, and D or lower was regarded as "fail".
  • Chemical resistance evaluation ⁇ Preparation of cured product> A photosensitive resin composition (varnish) according to each of the examples and comparative examples described later was applied onto a 4-inch silicon wafer by a spin coating method, and a hot plate (DIGITAL HOT PLATE HP-18A) at 120 ° C. was applied to AS ONE Co., Ltd. ) Made) for 2 minutes. This membrane was developed with 2.38 mass% TMAH aqueous solution and rinsed with pure water.
  • the developing film was subjected to a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo System Co., Ltd.) under a nitrogen atmosphere (oxygen concentration: 100 ppm or less) to 250 ° C. at 5 ° C./min.
  • a thermosetting step of raising the temperature and heat-treating at 250 ° C. for 1 hour was performed to prepare a cured product of varnish.
  • the thickness of the cured product was about 2.0 ⁇ m.
  • a thermosetting step was performed in which the temperature was raised to 230 ° C. at 5 ° C./min and heat-treated at 230 ° C. for 1 hour to prepare a cured product of varnish.
  • composition analysis of cured product Although a method for analyzing the components contained in the cured product is shown, it is not limited to the described method as long as it is a method capable of composition analysis.
  • ⁇ Preparation of cured product for composition analysis> The photosensitive resin composition obtained in each Example and Comparative Example was coated on an 8-inch silicon wafer by a spin coating method using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Limited), and at 120 ° C. Bake on a hot plate for 3 minutes. Then, it was developed with the 2.38 mass% TMAH aqueous solution using the ACT-8 developing apparatus, rinsed with distilled water, and then shaken off to dry.
  • ACT-8 coating and developing apparatus
  • the developing film was subjected to a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo System Co., Ltd.) under a nitrogen atmosphere (oxygen concentration: 100 ppm or less) to 250 ° C. at 5 ° C./min.
  • a thermosetting step of raising the temperature and heat-treating at 250 ° C. for 1 hour was performed to prepare a cured product of varnish.
  • the thickness of the cured film was about 3.0 ⁇ m.
  • the temperature was raised to 320 ° C., the inlet temperature was 300 ° C., the column flow rate was 1.5 mL / min, the ionization method was the EI (electron ionization) method, the mass number range was m / z 10 to 800, and the scanning speed was 0.
  • the analysis was performed at 5 sec / scan.
  • Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF) 18.3 g (0.05 mol), 100 mL of acetone, propylene oxide 17 It was dissolved in 0.4 g (0.3 mol) and cooled to ⁇ 15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After completion of the dropping, the reaction was carried out at ⁇ 15 ° C. for 4 hours, and then the temperature was returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.
  • BAHF 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane
  • Synthesis Example 2 Synthesis of polyimide precursor (A-1) 31.0 g (0.10 mol) of 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter referred to as ODPA) under a dry nitrogen stream. was dissolved in 500 g of NMP.
  • ODPA 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride
  • Synthesis Example 3 Synthesis of polyimide (A-2) Under a dry nitrogen stream, 29.3 g (0.08 mol) of BAHF, 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane. As an end-capping agent, 3.27 g (0.03 mol) of 3-aminophenol was dissolved in 150 g of NMP. To this, 31.0 g (0.1 mol) of ODPA was added together with 50 g of NMP, and the mixture was stirred at 20 ° C. for 1 hour and then at 50 ° C. for 4 hours. Then, 15 g of xylene was added, and the mixture was stirred at 150 ° C.
  • Synthesis Example 4 Synthesis of polybenzoxazole precursor (A-3) Under a dry nitrogen air flow, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of glycidylmethyl ether to prepare a solution. The temperature was cooled to ⁇ 15 ° C. Here, 7.4 g (0.025 mol) of diphenyl ether dicarboxylic acid dichloride (manufactured by Nippon Agricultural Chemicals Co., Ltd.) and 5.1 g (0.025 mol) of isophthalic acid chloride (manufactured by Tokyo Kasei Co., Ltd.) are added to ⁇ -butyrolactone (GBL).
  • GBL ⁇ -butyrolactone
  • Synthesis Example 5 Synthesis of polysiloxane (A-4) In a 500 ml three-necked flask, 44.86 g (0.200 mol) of p-styryltrimethoxysilane (St) and 39.66 g (0) of phenyltrimethoxysilane (Ph) were added.
  • B-2 PAG-103 (trade name, manufactured by BASF Japan Ltd.)
  • C-1 TekP-4HBPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.)
  • C-2 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • C-3 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • C-4 TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.)
  • C-5 Bisphenol P (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • C-6 Bisphenol M (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • C-7 1,1,1-Tris (4-hydroxyphenyl) ethane (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • C-8 4,4', 4'-
  • D-1 "Aronix (registered trademark)" M-923 (trade name, manufactured by Toagosei Co., Ltd.)
  • D-2 A-9300 (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
  • D-3 TEPIC-L (trade name, manufactured by Nissan Chemical Industries, Ltd.)
  • D-4 TEPIC-VL (trade name, manufactured by Nissan Chemical Industries, Ltd.)
  • E-1 HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.)
  • E-2 "Techmore (registered trademark)” VG3101L (trade name, manufactured by Printec Co., Ltd.)
  • Example 1 10.0 g of the polyimide precursor (A-1), 1.7 g of (B-1), 0.9 g of (C-7) and 1.5 g of (D-3) obtained in Synthesis Example 2 were added to 56.4 g of PGME. And ⁇ -butyrolactone (hereinafter referred to as GBL) in 14.1 g, and then filtered through a 0.2 ⁇ m polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) to obtain a photosensitive resin composition A. rice field.
  • GBL ⁇ -butyrolactone
  • Example 27 The IR spectrum of the cured film of the photosensitive resin composition T was measured by the method described in ⁇ Composition analysis by FT-IR>. From the obtained IR spectra, peaks derived from the expansion and contraction vibration of the carbonyl group in the imide ring structure were obtained at 1775 to 1780 cm -1 and 1720 to 1725 cm -1 . In addition, peaks derived from the expansion and contraction vibration of the carbonyl group in the structure represented by the formula (1) were obtained at 1695 to 1705 cm -1 and 1430 to 1475 cm -1 .
  • the thermally decomposed product of the cured film of the photosensitive resin composition T was analyzed by the method described in the above ⁇ Composition analysis by thermal decomposition GC / MS>.
  • the structure obtained in the cured film is shown below, which is attributed to the peak (450 to 455 seconds) attributed to the inden represented by the formula (6) and the imide ring structure represented by the formula (7). Peaks (840 to 850 seconds) and peaks attributed to the structure represented by the formula (8) (1035-145 seconds) were obtained.
  • the cured film of the photosensitive resin composition T contained an imide ring structure, an indene structure, a structure represented by the formula (2) and a structure represented by the formula (1). ..

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WO2009136557A1 (ja) * 2008-05-09 2009-11-12 旭化成イーマテリアルズ株式会社 ポリイミド前駆体、感光性ポリイミド前駆体組成物、感光性ドライフィルム及びそれらを用いたフレキシブルプリント配線基板
JP2012185291A (ja) * 2011-03-04 2012-09-27 Nof Corp 感光性樹脂組成物およびその用途
JP2013174774A (ja) * 2012-02-27 2013-09-05 Nof Corp 感光性樹脂組成物およびその用途
JP2014199312A (ja) * 2013-03-29 2014-10-23 東京応化工業株式会社 ポジ型レジスト組成物

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WO2009136557A1 (ja) * 2008-05-09 2009-11-12 旭化成イーマテリアルズ株式会社 ポリイミド前駆体、感光性ポリイミド前駆体組成物、感光性ドライフィルム及びそれらを用いたフレキシブルプリント配線基板
JP2012185291A (ja) * 2011-03-04 2012-09-27 Nof Corp 感光性樹脂組成物およびその用途
JP2013174774A (ja) * 2012-02-27 2013-09-05 Nof Corp 感光性樹脂組成物およびその用途
JP2014199312A (ja) * 2013-03-29 2014-10-23 東京応化工業株式会社 ポジ型レジスト組成物

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