WO2017170032A1 - Pellicule photosensible - Google Patents

Pellicule photosensible Download PDF

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Publication number
WO2017170032A1
WO2017170032A1 PCT/JP2017/011435 JP2017011435W WO2017170032A1 WO 2017170032 A1 WO2017170032 A1 WO 2017170032A1 JP 2017011435 W JP2017011435 W JP 2017011435W WO 2017170032 A1 WO2017170032 A1 WO 2017170032A1
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group
photosensitive film
resin
mol
general formula
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PCT/JP2017/011435
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English (en)
Japanese (ja)
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池田芳史
小山祐太朗
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東レ株式会社
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Priority to CN201780019777.4A priority Critical patent/CN108780275B/zh
Priority to KR1020187028914A priority patent/KR102314567B1/ko
Priority to JP2017517124A priority patent/JP6982786B2/ja
Priority to SG11201807876SA priority patent/SG11201807876SA/en
Publication of WO2017170032A1 publication Critical patent/WO2017170032A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/28—Condensation with aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor

Definitions

  • the present invention relates to a photosensitive film. More specifically, the present invention relates to a photosensitive film suitable for a surface protective film on the surface of a semiconductor element, an interlayer insulating film, and an insulating layer of an organic electroluminescent element.
  • Resins typified by polyimide and polybenzoxazole have excellent heat resistance and electrical insulation, and are therefore used for surface protective films of semiconductor elements, interlayer insulating films, insulating layers of organic electroluminescent elements, and the like.
  • surface protective films of semiconductor elements interlayer insulating films, insulating layers of organic electroluminescent elements, and the like.
  • surface protection films, interlayer insulating films, and the like are required to have a resolution of several ⁇ m level. Therefore, in such applications, a positive photosensitive polyimide resin composition and a positive photosensitive polybenzoxazole resin composition that can be finely processed are often used.
  • a semiconductor element is formed on a substrate, a photosensitive layer is formed on a passivation film typified by Si or SiN, and then heated and dried using a hot plate or the like.
  • a pattern is formed through development. After the pattern is formed, heat treatment is performed at a high temperature, and the insulating layer is formed by curing.
  • a method for forming a photosensitive layer on a substrate there are a method of applying a resin composition by a spin coating method, and a method of laminating a photosensitive film by applying heat to the substrate.
  • a method of laminating using a photosensitive film is generally used in order to increase the film thickness uniformity after the formation.
  • the positive photosensitive polyimide used for the resin composition or photosensitive film is based on polyimide (for example, Patent Document 1), based on polyhydroxystyrene (for example, Patent Document 2), and polyimide and polyhydroxy.
  • polyimide for example, Patent Document 1
  • polyhydroxystyrene for example, Patent Document 2
  • polyimide and polyhydroxy for example, Patent Document 3
  • Patent Document 4 a technique using a phenol resin as a photosensitive film
  • Patent Document 5 a technique using a polyimide having a low glass transition point
  • JP 2014-71374 A Japanese Patent Laid-Open No. 2006-154779 JP 2014-137523 A JP 2015-19006 A International Publication No. 2011/059089
  • a method of laminating with a photosensitive film is generally used in order to increase the film thickness uniformity after the formation.
  • the photosensitive film is required to have mechanical properties such as high extensibility and heat resistance in the cured film.
  • it In addition to having good pattern processability (high sensitivity), it also has good adhesion to the substrate. Properties, that is, laminate properties are required.
  • Patent Document 4 discloses a technique of using a phenol resin for the purpose of enhancing fluidity, but has a problem that the heat resistance of the cured film is low.
  • Patent Document 5 discloses a technique using a polyimide having a low softening point, but has a problem that high heat resistance cannot be obtained.
  • the present invention provides a photosensitive film which can obtain a cured film having high heat resistance, has good pattern workability (high sensitivity), and has good adhesion to a substrate, that is, laminate properties.
  • the photosensitive film of the present invention has the following constitution. That is, 1 selected from (A1) an alkali-soluble resin having a structural unit represented by the general formula (1), (A2) polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof.
  • a photosensitive film containing an alkali-soluble resin containing at least one kind (B) a photoacid generator, and (C) a thermal crosslinking agent.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • a represents 0 to 4
  • b represents an integer within the range of 1 to 3
  • R 2 represents a hydrogen atom, (Methyl group, ethyl group, or propyl group.)
  • the present invention it is possible to obtain a photosensitive film having good pattern processability (high sensitivity) and having good adhesion to a substrate, that is, laminating properties. Moreover, according to the photosensitive film of the present invention, a cured film having high elongation and high heat resistance can be obtained.
  • the present invention is selected from (A1) an alkali-soluble resin having a structural unit represented by the general formula (1), (A2) polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof.
  • (A1) resin, (A2) resin, (B) component, and (C) component may be omitted.
  • the photosensitive film of this invention contains alkali-soluble resin which has a structural unit represented by said (A1) general formula (1).
  • R 1 in the general formula (1) represents a hydrogen atom or an alkyl group having a carbon number of 1 ⁇ 5
  • a is 0 ⁇ 4
  • b represents an integer in the range of 1 ⁇ 3
  • R 2 is a hydrogen atom
  • methyl represents any of a group, an ethyl group, and a propyl group.
  • Examples of the structural unit represented by the general formula (1) include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, and o-isopropenylphenol.
  • aromatic vinyl compounds having a phenolic hydroxyl group and aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, etc., alone or in a known manner. It can be obtained by subjecting a part of the obtained polymer to an addition reaction of an alkoxy group using a known method (for example, a method described in Japanese Patent No. 5659259).
  • aromatic vinyl compound having a phenolic hydroxyl group p-hydroxystyrene and / or m-hydroxystyrene is preferably used, and styrene is preferably used as the aromatic vinyl compound.
  • the alkali-soluble resin having the structural unit represented by the general formula (1) further improves the sensitivity and adjusts the solubility in an alkali developer, so that the general formula (2) And at least one of the structural units represented by the general formula (3). Furthermore, from the viewpoint of solubility in an alkali developer, the structural unit of the general formula (3) is preferably 50 mol% or less.
  • R 3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and e represents an integer in the range of 1 to 5)
  • R 4 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • the introduction rate of alkoxyalkyl (CH 2 OR 2 ) groups in the (A1) resin is preferably an introduction rate of 10 mol% or more per 1 mol of hydroxystyrene from the viewpoint of heat resistance after curing, and is 20 mol% or more. More preferably. From the viewpoint of improving the resolution, it is preferably 70 mol% or less, and more preferably 50 mol% or less.
  • the polystyrene-reduced weight average molecular weight (Mw) of the (A1) resin is preferably 3,000 or more from the viewpoint of forming an unexposed portion pattern without eluting. Moreover, 60,000 or less is preferable from a viewpoint of maintaining the alkali solubility which can reduce the residue of an exposure part, and 25,000 or less are more preferable.
  • the polystyrene-converted weight average molecular weight (Mw) is a value calculated using GPC (gel permeation chromatography) measurement in terms of polystyrene.
  • the photosensitive film of the present invention contains an alkali-soluble resin containing at least one selected from (A2) polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof.
  • the (A2) resin may contain two or more of any one of polyimide, polybenzoxazole, polyamideimide, their precursors, and copolymers thereof, or a copolymer having two or more of these repeating units. A polymer may be included.
  • the (A2) resin preferably has a substituent that reacts with the alkoxyalkyl group of the (A1) resin.
  • the alkoxyalkyl group (A1) particularly refers to an alkoxymethyl group.
  • the structure of the resin is not particularly limited as long as it has a substituent that reacts with an alkoxyalkyl group, but a group selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group at the main chain or terminal. It is preferable to have one or more.
  • the content of (A2) resin is preferably 5 parts by mass or more and more preferably 10 parts by mass or more from the viewpoint of pattern processability with respect to 100 parts by mass of the total amount of (A1) resin and (A2) resin. Moreover, 90 mass parts or less are preferable from a viewpoint of heat resistance and a mechanical characteristic, and 70 mass parts or less are more preferable.
  • the (A2) resin preferably has at least one of the structural units represented by the general formulas (4) and (5).
  • R 5 represents a divalent to tetravalent organic group having 4 to 40 carbon atoms
  • R 6 represents a divalent organic group having 20 to 100 carbon atoms
  • n 1 represents 10 to 100. An integer in the range of 1,000.
  • R 5 represents a divalent to tetravalent organic group having 4 to 40 carbon atoms
  • R 6 represents a divalent organic group having 20 to 100 carbon atoms
  • R 7 represents hydrogen or carbon.
  • n 2 represents an integer in the range of 10 to 100,000
  • p and q represent integers satisfying 0 ⁇ p + q ⁇ 2.
  • R 5 represents a divalent to tetravalent organic group having 4 to 40 carbon atoms and having a monocyclic or condensed polycyclic alicyclic structure.
  • the monocyclic or condensed polycyclic alicyclic structure preferably contains one or more organic groups selected from the following general formulas (6) to (9).
  • R 8 to R 53 each independently represents a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 3 carbon atoms.
  • a hydrogen atom contained in the organic group may be substituted with a halogen atom.
  • R 5 is an organic group derived from an acid dianhydride used as a raw material for the resin.
  • acid dianhydride containing a monovalent or condensed polycyclic alicyclic structure and having a C 4-40 divalent organic group used in the present invention include 1, 2 , 3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2, Examples include compounds such as 3,4-cyclobutanetetracarboxylic dianhydride and 1,2,4,5-cyclohexanetetracarboxylic dianhydride.
  • pyromellitic acid, 3, 3 is preferable as a preferable structure of a divalent to tetravalent organic group having 4 to 40 carbon atoms having 1 to 4 aromatic rings in R 5 .
  • Alicyclic structure monocyclic or fused polycyclic at R 5 is improved general formula (4) and (5) when the the R 5 100 mol% of, high elongation of the laminate against the substrate of the film If it is 10 mol% or more from the viewpoint to make it, it is more preferable if it is 30 mol% or more. From the viewpoint of obtaining an appropriate dissolution rate in the developer, it is preferably 80 mol% or less, more preferably 60 mol% or less.
  • R 5 has 70 mol% of a monocyclic or condensed polycyclic alicyclic structure with respect to 100 mol% of the total amount of repeating units in the general formulas (4) and (5), and has an aromatic ring 4
  • the monocyclic or condensed polycyclic alicyclic structure is 70 mol%.
  • R 5 has two or more monocyclic or condensed polycyclic alicyclic structures, it is calculated as 70 mol%.
  • R 6 in the general formulas (4) and (5) preferably has an organic group having a polyether structure represented by the following general formula (10).
  • R 54 to R 57 each independently represents an alkylene group having 1 to 6 carbon atoms; R 58 to R 65 each independently represents hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms, provided that The structure represented in parentheses of repeating unit x is different from the structure represented in parentheses of repeating unit y, and the structure represented in parentheses of repeating unit z is different from the structure represented in parentheses of repeating unit y.
  • X, y and z each independently represents an integer of 0 to 35.
  • R 6 in the general formulas (4) and (5) is derived from a diamine used as a raw material for the resin. Organic group.
  • diamine containing an organic group having a polyether structure used in the present invention
  • diamine containing an organic group having a polyether structure examples include “Jeffamine” (registered trademark) HK-511, ED-600, ED-900, ED-2003, EDR-148. , EDR-176, D-200, D-400, D-2000, D-4000, “Elastamine” (registered trademark) RP-409, RP-2009, RT-1000, HT-1100, HE-1000, HT- An aliphatic diamine such as 1700 (trade name, manufactured by HUNTSMAN Co., Ltd.) can be used.
  • R 6 has 70 mol% of an organic group derived from a diamine containing an organic group having a polyether structure with respect to 100 mol% of the total amount of repeating units in the general formulas (4) and (5), and an aromatic ring It is calculated that there are 70 mol% of organic groups derived from a diamine containing an organic group having a polyether structure when 30 mol% of a divalent organic group having an organic group is present. At this time, when R 6 has an organic group derived from a diamine containing an organic group having two or more polyether structures, it is calculated as 70 mol%.
  • R 5 in the general formulas (4) and (5) by further containing an organic group having a fluorine atom, water repellency is imparted to the resin, and permeation from the surface of the film is suppressed during alkali development. This is preferable. By suppressing the penetration from the surface of the film, it is possible to obtain a resin film having a high residual film ratio in which there is no development residue in the tack or processing pattern of the unexposed area. These characteristics are important in realizing thick film processing.
  • the organic group having a fluorine atom can prevent the penetration of the interface if it is 20 mol% or more, and if it is 90 mol% or less, an appropriate dissolution rate in the developer. Is preferable, and the content is more preferably 40 mol% to 60 mol%.
  • the compound having a fluorine atom examples include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, compounds in which these aromatic rings are substituted with an alkyl group or a halogen atom, and amides.
  • An aromatic acid dianhydride such as an acid dianhydride having a group can be mentioned.
  • the resin is preferably a resin including a structure derived from these compounds.
  • the photosensitive film of this invention may contain the structure derived from other acid dianhydrides and diamine in addition to the above-mentioned acid dianhydride and diamine in the range which does not reduce the above-mentioned characteristic.
  • dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetra Carboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3 '-Benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1, 1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) me
  • Examples thereof include compounds substituted with an alkyl group or a halogen atom, and acid dianhydrides having an amide group. These can be used in combination with two or more acid dianhydrides containing an alicyclic structure having 4 to 40 carbon atoms.
  • diamines include bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, and bis (3-amino-4-hydroxyphenyl) propane.
  • an aliphatic group having a siloxane structure may be introduced as long as the heat resistance is not lowered, and the adhesion to the substrate can be improved.
  • the diamine component bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, or the like is used in an amount of 100 mol% of R 6 in the general formulas (4) and (5). Examples thereof include those copolymerized by 1 to 15 mol%.
  • an aromatic diamine in an amount of 50 mol% or more of the total diamine.
  • (A2) resin has a phenolic hydroxyl group component.
  • at least one of R 5 and R 6 is an organic group having a phenolic hydroxyl group. Due to the presence of phenolic hydroxyl group, moderate solubility in alkaline developer is obtained, and it interacts with the photosensitizer to suppress solubility in the unexposed areas, thus improving the remaining film ratio and increasing sensitivity. Become.
  • the phenolic hydroxyl group also contributes to the reaction with the cross-linking agent, and thus is preferable in that high mechanical properties and chemical resistance can be obtained.
  • the compound having a phenolic hydroxyl group examples include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride or a compound in which an aromatic ring thereof is substituted with an alkyl group or a halogen atom, and Aromatic acid dianhydrides such as acid dianhydrides having amide groups, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3- Amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3 -Hydroxyl-containing diamines such as -amino-4-hydroxyphenyl) fluorene, and these Some of the hydrogen atoms of the aromatic ring, an alkyl group or
  • n 1 and n 2 represent the degree of polymerization.
  • Mw molecular weight per unit of the general formulas (4) and (5)
  • Mw weight average molecular weight of the alkali-soluble resin
  • the weight average molecular weight of the alkali-soluble resin is determined by GPC (gel permeation chromatography) as described in Examples.
  • n 1 and n 2 can be easily calculated by measuring the weight average molecular weight (Mw) by gel permeation chromatography (GPC), light scattering method, X-ray small angle scattering method or the like.
  • n Mw / M.
  • the number of repetitions n in the present invention refers to a value calculated using the simplest GPC (gel permeation chromatography) measurement in terms of polystyrene.
  • the weight average molecular weight of the resin is preferably in the range of 3,000 to 80,000, more preferably in the range of 8,000 to 50,000, in terms of polystyrene by gel permeation chromatography. preferable. If it is this range, a thick film can be formed easily.
  • the end of the resin may be capped with a terminal capping agent such as monoamine, acid anhydride, acid chloride, or monocarboxylic acid.
  • a terminal capping agent such as monoamine, acid anhydride, acid chloride, or monocarboxylic acid.
  • end-capping agent examples include monoamines such as 3-aminophenylacetylene, 4-aminophenylacetylene, 3,5-diethynylaniline, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, and 3,4-diethynyl.
  • Monocarboxylic acids such as benzoic acid and 3,5-diethynylbenzoic acid, maleic anhydride, acid anhydrides such as 5-norbornene-2,3-dicarboxylic anhydride, and the carboxyl group of the monocarboxylic acid are acid chlorided Compound, compound obtained by acid chloride of one carboxyl group of dicarboxylic acid such as maleic acid, active ester compound obtained by reaction of monoacid chloride compound with N-hydroxy-5-norbornene-2,3-dicarboximide, etc.
  • the resin having at least one of the structural units represented by the general formulas (4) and (5) can be produced according to known methods for producing polyimides and polyimide precursors.
  • a method of reacting a tetracarboxylic dianhydride having an R 5 group, a diamine compound having an R 6 group, and a monoamino compound as a terminal blocking agent under low temperature conditions (II) an R 5 group A diester obtained by having a tetracarboxylic dianhydride and an alcohol, and then reacting in the presence of a diamine compound having an R 6 group, a monoamino compound as a terminal blocking agent and a condensing agent, (III) R 5 group A diester is obtained by using tetracarboxylic dianhydride and alcohol, and then the remaining two carboxyl groups are acid chlorideed to react with a diamine compound having an R 6 group and a monoamino compound as a terminal blocking agent. be able to.
  • a diamine compound having an R 6 group is dissolved in a polymerization solvent.
  • a tetracarboxylic dianhydride having an R 5 group which is substantially equimolar with the diamine compound, is gradually added.
  • the mixture is stirred at ⁇ 20 to 100 ° C., preferably 10 to 50 ° C. for 0.5 to 100 hours, more preferably 2 to 24 hours.
  • the mixture is stirred at ⁇ 20 to 100 ° C., preferably 10 to 50 ° C. for 0.1 to 24 hours, and then the end capping agent is gradually added. You may add and you may make it react at once.
  • the polymerization solvent is not particularly limited as long as it can dissolve the raw material monomers tetracarboxylic dianhydride and diamine.
  • the reaction is performed without precipitation of raw materials and resins. If it is 1900 parts by mass or less, the reaction proceeds rapidly, and 150 to 950 parts by mass is more preferable.
  • the photosensitive film of this invention has photosensitivity by containing the (B) photo-acid generator. That is, (B) the photoacid generator has a characteristic that an acid is generated when irradiated with light, and the solubility of the light irradiated portion in an alkaline aqueous solution is increased.
  • (B) Photoacid generators include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, and the like.
  • (A1) an alkali-soluble resin having a structural unit represented by the general formula (1)
  • (A2) polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof.
  • a quinonediazide compound is preferably used in that it exhibits an excellent dissolution inhibiting effect when used in combination with an alkali-soluble resin containing one or more selected types.
  • the quinonediazide compound has a quinonediazide sulfonic acid bonded to a polyhydroxy compound with an ester, a quinonediazide sulfonic acid bonded to a polyamino compound, and a quinonediazide sulfonic acid bonded to the polyhydroxypolyamino compound with an ester bond or sulfonamide bond. And those in which a sulfonic acid of quinonediazide is ester-bonded and sulfonamide-bonded to a polyhydroxypolyamino compound.
  • Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP -IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-B P, TML- Q, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (
  • Polyamino compounds include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl Examples thereof include, but are not limited to, sulfhydrides.
  • examples of the polyhydroxypolyamino compound include 2,2-bis (3-amino-4-) hydroxyphenyl) hexafluoropropane, 3,3′-dihydroxybenzidine, and the like, but are not limited thereto.
  • quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group.
  • the 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
  • the 5-naphthoquinonediazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure.
  • a naphthoquinone diazide sulfonyl ester compound can be obtained by using a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound. Can also be used as a mixture.
  • the molecular weight of the quinonediazide compound of the present invention is preferably in the range of 300 to 3,000.
  • the molecular weight of the quinonediazide compound is larger than 5,000, the quinonediazide compound is not sufficiently thermally decomposed in the subsequent heat treatment, so that the heat resistance of the resulting film is lowered, the mechanical properties are lowered, the adhesiveness is lowered, etc. Problems can arise.
  • the quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, there is a method in which 5-naphthoquinonediazide sulfonyl chloride and a phenol compound are reacted in the presence of triethylamine. Examples of the method for synthesizing a phenol compound include a method in which an ⁇ - (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst.
  • those that moderately stabilize the acid component generated by exposure are preferably sulfonium salts, phosphonium salts, or diazonium salts. Since the photosensitive film of the present invention is used as a permanent film, it is not environmentally preferable that phosphorus and the like remain, and it is necessary to consider the color tone of the film, and among these, a sulfonium salt is preferably used. . Particularly preferred is a triarylsulfonium salt, which can suppress changes in the color tone of the film.
  • the content of the photoacid generator is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the total amount of (A1) resin and (A2) resin.
  • the quinonediazide compound is preferably in the range of 3 to 40 parts by mass.
  • the compound selected from sulfonium salt, phosphonium salt and diazonium salt is preferably in the range of 0.05 to 40 parts by mass, more preferably in the range of 0.1 to 30 parts by mass.
  • the photosensitive film of the present invention contains (C) a thermal crosslinking agent.
  • a thermal crosslinking agent a compound having an alkoxymethyl group is preferable, and a compound represented by the general formula (11) is particularly preferable.
  • R 66 represents a 1 to 10 valent organic group.
  • the plurality of R 67 may be the same or different, and each represents an alkyl group having 1 to 4 carbon atoms. Represents an integer of 5.
  • s represents an integer of 1 to 10.
  • the alkoxymethyl group causes a thermal crosslinking reaction at 160 ° C. or higher. Therefore, a cross-linking reaction occurs in the step of thermosetting the photosensitive film, and a good pattern shape can be obtained.
  • the number of alkoxymethyl groups is preferably 2 or more in order to improve the crosslinking density, and more preferably 4 or more in order to improve chemical resistance.
  • the compound represented by the general formula (11) functions as a thermoplastic agent at a temperature lower than 160 ° C. that causes a thermal crosslinking reaction. Lamination is preferably performed at a temperature of 150 ° C. or lower. At this time, the photosensitive layer is heated and melted, and the contact area with the substrate is increased. Therefore, it is presumed that the adhesion between the two is improved.
  • thermal crosslinking agent examples include the following compounds, but are not limited thereto. Moreover, you may contain 2 or more types of these.
  • the content of the thermal crosslinking agent is to improve the crosslinking density, chemical resistance, and adhesion to the substrate in the resulting cured film, so that the total amount of (A1) resin and (A2) resin is 100 parts by mass.
  • the amount is preferably 1 part by mass or more, and more preferably 5 parts by mass or more.
  • it is preferable that it is 70 mass parts or less, and it is more preferable that it is 50 mass parts or less.
  • the weight average molecular weight (Mw) of the thermal crosslinking agent is preferably 100 or more, and more preferably 300 or more, in order to improve the mechanical properties of the cured film after the heat treatment. Moreover, in order to improve laminating property, it is preferable that it is 2,500 or less, and it is more preferable that it is 2,000 or less.
  • the photosensitive film of the present invention preferably contains a thermal crosslinking agent having a structural unit represented by the following general formula (12).
  • a thermal crosslinking agent having a structural unit represented by the following general formula (12).
  • R 69 and R 70 each independently represent a hydrogen atom or a methyl group.
  • R 68 is a divalent organic group having an alkylene group having 2 or more carbon atoms, and is linear.
  • R 68 may be an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, or a carbonyl group.
  • thermal crosslinking agent itself has a flexible alkylene group and a rigid aromatic group, it is possible to improve the elongation while having heat resistance and laminating properties.
  • the crosslinking group include, but are not limited to, an acrylic group, a methylol group, an alkoxymethyl group, and an epoxy group.
  • an epoxy group is preferred because it can react with the phenolic hydroxyl group of (A1) resin and (A2) resin to improve the heat resistance of the cured film and can react without dehydration. .
  • Examples of the compound represented by the general formula (12) include, but are not limited to, the following structures.
  • n is an integer of 1 to 5, and m is 1 to 20.
  • n is preferably 1 to 2 and m is preferably 3 to 7 from the viewpoint of achieving both heat resistance and improvement in elongation.
  • the amount of the compound represented by the general formula (12) is preferably 2 to 35 parts by mass, more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the total amount of the (A1) resin and the (A2) resin. preferable.
  • the addition amount is 2 parts by mass or more, the effect of improving the elongation is sufficiently obtained, and when the addition amount is 35 parts by mass or less, the sensitivity reduction of the photosensitive film before curing can be suppressed.
  • the photosensitive film of the present invention may contain (D) an acrylate compound as necessary.
  • the (D) acrylate compound refers to a compound having an acryloyl group or a methacryloyl group.
  • the acrylate compound includes a monofunctional acrylate and a polyfunctional acrylate.
  • the monofunctional acrylate refers to a compound having at least one of acryloyl group and methacryloyl group.
  • acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide, etc. can be mentioned.
  • the polyfunctional acrylate compound refers to a compound having at least one of acryloyl group and methacryloyl group.
  • the photosensitive film of the present invention is heat-treated after pattern processing.
  • the acrylate compound When used as a positive-type photosensitive film, the acrylate compound reacts with the heat-polymerized or alkali-soluble resin between the acrylate compounds and crosslinks to improve the elongation of the cured film.
  • the acrylates When used as a negative photosensitive resin film, the acrylates are photopolymerized by exposure during pattern processing, thereby forming a network structure with the alkali-soluble resin.
  • the curing of the film by the crosslinking reaction does not proceed sufficiently and the effect of improving the elongation is low, so that it is preferably a polyfunctional acrylate.
  • Light Acrylate (registered trademark) series 3EG-A, 4EG-A, 9EG-A, 14EG-A, TMGA-250, NP-A, MPD-A, 1.6HX-A manufactured by Kyoeisha Chemical Co., Ltd.
  • “KAYARAD” registered trademark
  • acrylate compounds having a molecular weight of 100 or more and 2,000 or less are preferable.
  • a cured film having a high elongation can be obtained when the molecular weight is 100 or more, and a resin composition having moderate alkali solubility and high compatibility with an alkali-soluble resin can be obtained when the molecular weight is 2,000 or less.
  • alkali-soluble resins may be contained within a range not impairing the heat resistance of the cured film obtained by the heat treatment.
  • acrylic polymers copolymerized with acrylic acid, siloxane resins, novolak resins, resole resins, polyhydroxystyrene resins and other phenol resins, and cross-link groups such as methylol groups, alkoxymethyl groups and epoxy groups. Examples thereof include introduced resins and copolymers thereof.
  • Such a resin is soluble in an aqueous alkali solution such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate.
  • an aqueous alkali solution such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate.
  • a phenol resin is preferable from the viewpoint of sensitivity.
  • a phenol resin is obtained by polycondensing phenols and aldehydes by a known method. You may contain combining the resin which has 2 or more types of phenolic hydroxyl groups.
  • phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3 , 5-trimethylphenol, 3,4,5-trimethylphenol and the like.
  • phenol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol or 2,3,5-trimethylphenol are preferable. Two or more of these phenols may be used in combination.
  • the resin having a phenolic hydroxyl group preferably includes an m-cresol residue or a cresol novolak resin containing an m-cresol residue and a p-cresol residue.
  • the molar ratio of m-cresol residue to p-cresol residue (m-cresol residue / p-cresol residue, m / p) in the cresol novolak resin is preferably 1.8 or more. If it is this range, the moderate solubility to an alkali developing solution will be shown, and favorable sensitivity will be obtained. More preferably, it is 4 or more.
  • aldehydes include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, salicylaldehyde and the like. Of these, formalin is particularly preferred. Two or more of these aldehydes may be used in combination.
  • the amount of the aldehyde used is preferably 0.6 mol or more, more preferably 0.7 mol or more, per 1 mol of phenols. Moreover, 3 mol or less is preferable and 1.5 mol or less is more preferable.
  • an acidic catalyst is usually used.
  • the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, p-toluenesulfonic acid, and the like.
  • the amount of these acidic catalysts used is usually 1 ⁇ 10 ⁇ 5 to 5 ⁇ 10 ⁇ 1 mol per 1 mol of phenols.
  • water is usually used as a reaction medium. However, when a heterogeneous system is formed from the beginning of the reaction, a hydrophilic solvent or a lipophilic solvent is used as the reaction medium.
  • hydrophilic solvent examples include alcohols such as methanol, ethanol, propanol, butanol and propylene glycol monomethyl ether; and cyclic ethers such as tetrahydrofuran and dioxane.
  • lipophilic solvent examples include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. The amount of these reaction media used is usually 20 to 1,000 parts by mass per 100 parts by mass of the reaction raw material.
  • the reaction temperature of the polycondensation can be appropriately adjusted according to the reactivity of the raw material, but is usually 10 to 200 ° C.
  • phenols, aldehydes, acidic catalysts, etc. are charged all at once and reacted, or phenols, aldehydes, etc. are added as the reaction proceeds in the presence of acidic catalysts, etc. Can be adopted as appropriate.
  • the reaction temperature is generally increased to 130 to 230 ° C., and volatile components are reduced under reduced pressure. The resin having a phenolic hydroxyl group is removed.
  • the polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) of the phenol resin is preferably 1,000 or more, and more preferably 2,000 or more. Moreover, 20,000 or less is preferable and 10,000 or less is more preferable. If it is this range, it will be excellent in the workability
  • the content of the other alkali-soluble resin is preferably 1 part by mass or more and more preferably 5 parts by mass or more from the viewpoint of sensitivity with respect to 100 parts by mass of the total amount of (A1) resin and (A2) resin. From the viewpoint of mechanical properties and heat resistance, it is preferably 70 parts by mass or less, and more preferably 50 parts by mass or less.
  • the resin containing the structure represented by the general formulas (4) and (5) is preferably 30% by mass or more.
  • (E) Compounds having a phenolic hydroxyl group include, for example, Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP -EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Tetrakis P-DO-BPA), TrisP-HAP , TrisP-PA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP
  • Preferred (E) compounds having a phenolic hydroxyl group are Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisCP- IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F, etc. .
  • Particularly preferred (E) compounds having a phenolic hydroxyl group are Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR-BIPC-F. It is.
  • (E) By containing a compound having a phenolic hydroxyl group, it is hardly soluble in an alkali developer before exposure, but is easily dissolved in an alkali developer at the time of exposure. Can be obtained.
  • the content of the compound having a phenolic hydroxyl group is preferably 1 to 50 parts by mass, more preferably 3 to 40 parts by mass with respect to 100 parts by mass of the total amount of (A1) resin and (A2) resin. Is within the range.
  • the photosensitive film of the present invention may contain (F) a solvent.
  • Solvents include polar aprotic solvents such as ⁇ - butyrolactone, ethers such as tetrahydrofuran, dioxane, propylene glycol monomethyl ether, and dialkylenes such as dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether.
  • Glycol dialkyl ethers acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, ketones such as N, N-dimethylformamide, N, N-dimethylacetamide, acetates such as 3-methoxybutyl acetate and ethylene glycol monoethyl ether acetate , Esters such as ethyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate, Aromatic hydrocarbons such as ethylene and xylene can be used alone or in combination.
  • (F) 0.0001 mass part or more is preferable with respect to 100 mass parts of total amounts of (A1) resin and (A2) resin, and, as for content of a solvent, 50 mass parts or less are preferable.
  • the photosensitive film of the present invention can contain (G) a silane compound and can be used as an adhesion aid for improving the adhesion to the base substrate.
  • a silane compound include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, and N-phenyl.
  • silane compound is not limited thereto. Two or more of these may be contained.
  • the content of (G) silane compound is preferably 0.01 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the total amount of (A1) resin and (A2) resin. Within this range, a sufficient effect as an adhesion aid can be obtained while maintaining the heat resistance of the positive photosensitive film.
  • esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, tetrahydrofuran, dioxane, etc.
  • the ethers may be included.
  • inorganic particles such as silicon dioxide and titanium dioxide, polyimide powder, and the like can also be contained.
  • the photosensitive film of the present invention preferably contains (H) a compound represented by the following general formula (13) (hereinafter referred to as component (H)).
  • component (H) a compound represented by the following general formula (13)
  • the adhesion between the laminated film and the metal material, particularly copper is remarkably improved. This is due to the fact that the S and N atoms of the compound represented by the general formula (13) interact with the metal surface, and further have a three-dimensional structure that easily interacts with the metal surface. To do.
  • R 71 to R 73 each represents an O atom, an S atom, or an N atom, and at least one of R 71 to R 73 represents an S atom.
  • l represents 0 or 1
  • R 71 represents an oxygen atom or a sulfur atom when l is 0, and represents a nitrogen atom when l is 1.
  • m and n represent 1 or 2.
  • R 74 to R 76 each independently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.
  • R 74 to R 76 include a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, alkyl ether group, alkylsilyl group, alkoxysilyl group, aryl group, aryl ether group, carboxyl group, carbonyl group, allyl group, vinyl A group, a heterocyclic group, a combination thereof, and the like, and may further have a substituent.
  • the addition amount of the component (H) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the (A1) resin and the (A2) resin.
  • the addition amount is 0.1 parts by mass or more, the effect of improving the adhesion after lamination to the metal material can be sufficiently obtained, and when the addition amount is 10 parts by mass or less, the photosensitive film used in the present invention can be obtained.
  • the positive type is preferable because it can suppress a decrease in sensitivity of the photosensitive film due to the interaction with the photosensitive agent.
  • R 71 to R 73 each represents an O atom, an S atom, or an N atom, and at least one of R 71 to R 73 is S An atom is preferred.
  • the sensitivity may be impaired due to the interaction between the photosensitizer and the N atom-containing compound. The effect of improving the adhesion can be obtained without lowering.
  • Examples of the compound represented by the general formula (13) include the following, but are not limited to the following structures.
  • A1 an alkali-soluble resin having a structural unit represented by the general formula (1)
  • A2 a polyimide, polybenzoxazole, polyamideimide having a substituent that reacts with the (A1) alkali-soluble resin
  • An alkali-soluble resin having at least one selected from their precursors and their copolymers
  • B) a photoacid generator
  • C a thermal crosslinking agent
  • F a solvent
  • Examples thereof include a method of stirring and dissolving in a glass flask or stainless steel container with a mechanical stirrer, a method of dissolving with ultrasonic waves, a method of stirring and dissolving with a planetary stirring deaerator.
  • the viscosity of the composition containing (A1) resin, (A2) resin, (B) photoacid generator, (C) thermal crosslinking agent, (F) solvent and the like is preferably 200 to 10,000 mPa ⁇ s. Further, in order to remove the foreign matter, it may be filtered through a filter having a pore size of 0.1 ⁇ m to 5 ⁇ m.
  • the photosensitive film of the present invention preferably has a support film.
  • a composition containing (A1) resin, (A2) resin, (B) photoacid generator, (C) thermal crosslinking agent, (F) solvent, etc. is applied onto a support film and then dried to support it.
  • a photosensitive film having a photosensitive layer on the film can be obtained.
  • the support film is not particularly limited, but various commercially available films such as a polyethylene terephthalate (PET) film, a polyphenylene sulfide film, and a polyimide film can be used.
  • PET polyethylene terephthalate
  • the bonding surface between the support film and the photosensitive film may be subjected to a surface treatment such as silicone, a silane coupling agent, an aluminum chelating agent, or polyurea in order to improve adhesion and peelability.
  • the thickness of the support film is not particularly limited, but is preferably in the range of 10 to 100 ⁇ m from the viewpoint of workability.
  • the photosensitive film of the present invention may have a protective film on the film in order to protect the surface.
  • the photosensitive film surface can be protected from contaminants such as dust and dust in the atmosphere.
  • protective films examples include polyolefin films and polyester films.
  • the protective film preferably has a small adhesive force with the photosensitive film.
  • a method for forming a photosensitive layer by applying a composition containing (A1) resin, (A2) resin, (B) photoacid generator, (C) thermal crosslinking agent, (F) solvent, etc. examples thereof include spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, slit die coater and the like.
  • the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but it is usually preferable that the film thickness of the photosensitive layer obtained after drying is 0.5 ⁇ m or more and 100 ⁇ m or less. Moreover, it is more preferable that they are 3 micrometers or more and 40 micrometers or less.
  • Oven, hot plate, infrared, etc. can be used for drying.
  • the drying temperature and the drying time may be in a range where the solvent can be volatilized, and it is preferable to appropriately set a range in which the resin film material for a semiconductor is in an uncured or semi-cured state. Specifically, it is preferable to carry out from 1 minute to several tens of minutes in the range of 40 ° C to 120 ° C. Moreover, you may heat up in steps combining these temperatures, for example, you may heat-process at 50 degreeC, 60 degreeC, and 70 degreeC for 1 minute each.
  • thermocompression bonding can be performed by a heat press process, a heat laminating process, a heat vacuum laminating process, or the like.
  • the temperature for thermocompression bonding and lamination is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of adhesion to the substrate and embedding.
  • the temperature of thermocompression bonding is preferably 150 ° C. or less, and preferably 120 ° C. or less. More preferred. Moreover, you may carry out under reduced pressure in order to remove a bubble at the time of thermocompression bonding.
  • the support film is peeled off from the photosensitive film in a temperature range of 0 ° C. or higher and 100 ° C. or lower.
  • Examples of the substrate to be used include, but are not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit substrates, inorganic circuit substrates, and substrates on which circuit constituent materials are arranged.
  • Examples of organic circuit boards include glass-based copper-clad laminates such as glass cloth / epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven fabrics / epoxy copper-clad laminates, polyetherimide resin substrates, Examples include heat-resistant / thermoplastic substrates such as ether ketone resin substrates and polysulfone resin substrates, polyester copper-clad film substrates, and polyimide copper-clad film substrates.
  • Examples of the inorganic circuit board include ceramic substrates such as an alumina substrate, an aluminum nitride substrate, and a silicon carbide substrate, and metal substrates such as an aluminum base substrate and an iron base substrate.
  • circuit materials include conductors containing metals such as gold, silver and copper, resistors containing inorganic oxides, low dielectrics containing glass materials, resins, etc., resins and high dielectric constants Examples thereof include high dielectric materials containing inorganic particles and insulators containing glass-based materials.
  • the photosensitive film formed by the above method is exposed to actinic radiation through a mask having a desired pattern.
  • actinic radiation used for exposure there are ultraviolet rays, visible rays, electron beams, X-rays and the like.
  • the exposure may be performed after peeling the support film from the photosensitive film, or the exposure may be performed without peeling. .
  • the support film is peeled after exposure and before development.
  • Developers include tetramethylammonium aqueous solution, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl
  • An aqueous solution of a compound showing alkalinity such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable.
  • these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone, dimethylacrylamide, methanol, ethanol, Contains alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone alone or in combination of several kinds Good.
  • polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone, dimethylacrylamide, methanol, ethanol, Contains alcohols such as isopropanol, esters such as ethy
  • Development can be performed by spraying the developer on the surface with the photosensitive coating, immersing in the developer, applying ultrasonic waves while immersing, or spraying the developer while rotating the substrate. It can.
  • the development conditions such as the development time and the temperature of the development step developer may be any conditions that allow the unexposed areas to be removed. In order to process fine patterns and remove residues between patterns, unexposed areas It is preferable to perform further development after the removal.
  • Rinsing with water may be performed after development.
  • alcohols such as ethanol and isopropyl alcohol
  • esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.
  • a step of performing a baking process before development can be incorporated.
  • This temperature is preferably in the range of 50 to 180 ° C, more preferably in the range of 60 to 120 ° C.
  • the time is preferably 5 seconds to several hours.
  • a cured film is obtained by applying a temperature of 120 ° C. to 400 ° C.
  • This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature.
  • heat treatment is performed at 130 ° C. and 200 ° C. for 30 minutes each.
  • a method such as linearly raising the temperature from room temperature to 250 ° C. over 2 hours can be mentioned.
  • the heating temperature is preferably 150 ° C. or higher and 300 ° C. or lower, and more preferably 180 ° C. or higher and 250 ° C. or lower.
  • the thickness of the cured film is preferably 0.5 ⁇ m or more and more preferably 2 ⁇ m or more in order to improve the insulation. Further, from the viewpoint of reducing the warpage of the substrate due to residual stress, 100 ⁇ m is preferable, and 40 ⁇ m or less is more preferable.
  • the cured film obtained by curing the photosensitive film of the present invention is suitably used for applications such as a semiconductor passivation film, a semiconductor protective film, an interlayer insulating film of a multilayer wiring for high-density mounting, and an insulating layer of an organic electroluminescent element.
  • cured the photosensitive film of this invention can be used for a semiconductor device in the state in which the relief pattern layer of this cured film was formed.
  • the cured film is disposed on the substrate with a film thickness of 2 to 40 ⁇ m as described above, and after the copper wiring is disposed thereon, the cured film is further formed to have a film thickness of 2 to 40 ⁇ m as an insulating film between the copper wirings.
  • a semiconductor device can also be manufactured.
  • FIG. 1 shows an example of a suitable structure of a semiconductor device in which a cured film obtained by curing the photosensitive film of the present invention is disposed.
  • a passivation film 2 is formed on the semiconductor element 1.
  • the photosensitive film according to the present invention is laminated on the passivation film 2 by thermocompression bonding, heat-dried using a hot plate or the like, and a pattern of the photosensitive film is formed through exposure and development. After the pattern formation of the photosensitive film, a high temperature treatment process by curing is performed to form the cured film 3.
  • Metal wiring is formed on the cured film 3 by a technique such as sputtering, vapor deposition, electroless plating, or electrolytic plating.
  • the photosensitive film according to the present invention is laminated by thermocompression bonding, heat-dried using a hot plate or the like, and a pattern is formed through exposure and development. After the pattern formation of the photosensitive film, a high-temperature treatment process by curing is performed to form the cured film 5.
  • a highly flat semiconductor device having high adhesion between the cured films and high adhesion between the cured film and the metal wiring can be provided.
  • FIG. 2 is a cross-sectional view of a coil component having the cured film of the present invention.
  • an insulating film 7 is formed on the substrate 6, and a cured film 8 is formed thereon as a pattern.
  • the photosensitive film of the present invention may be used for either the cured film 7 or the cured film 8.
  • a metal film 9 (Cr, Ti, etc.) is formed in the opening of this pattern, and a metal wiring 10 (Ag, Cu, etc.) is formed thereon by plating.
  • the metal wiring 10 (Ag, Cu, etc.) is formed on the spiral. A function as a coil can be provided by repeating the steps 7 to 10 a plurality of times and laminating them. Finally, the metal wiring 10 (Ag, Cu, etc.) is connected to the electrode 12 by the metal wiring 11 (Ag, Cu, etc.) and sealed with the sealing resin 13.
  • FIG. 3 is an example of a cross-sectional view of a hollow portion of an elastic wave device using the photosensitive film of the present invention.
  • an IDT (Inter Digital Transducer) electrode 15 composed of a pair of comb-shaped electrodes each having a plurality of electrode fingers interleaved with each other is bonded to the substrate 14, and bonding for electrical conduction.
  • a pad 16 is formed.
  • examples of the substrate 14 include lithium niobate, potassium niobate, lithium tantalate, crystal, langasite, ZnO, PZT, and lithium borate.
  • examples of the material of the electrode 15 and the bonding pad include metals such as Al, Pt, Cu, Au, Ti, Ni, Cr, W, Pd, Co, and Mn.
  • a relief pattern layer of a cured film of the photosensitive resin composition is formed as a support material 18 on the piezoelectric substrate 14 in order to secure the hollow portion 17.
  • examples of the photosensitive resin composition include polyimide resins, epoxy resins, acrylic resins, and phenol resins.
  • the covering material 19 is provided on the substrate 15 via the support material 17 so as to cover the electrode 15.
  • the photosensitive film of the present invention is used for the covering material 19, it may be used for the support material 17.
  • the thickness of the covering material 19 is, for example, 20 ⁇ m.
  • the protection member 20 is provided so as to cover the substrate 14, the support material 18, and the covering material 19.
  • the thickness of the protective member 20 on the covering material 19 is, for example, 30 ⁇ m.
  • the protective member is an insulating material such as epoxy resin, benzocyclobutene resin, silicon resin, SOG (Spin On Glass), and the like.
  • Via conductors 21 may be provided inside the support member 17 and the covering member 19 so as to penetrate in the thickness direction. Solder bumps 22 are connected and formed on the via conductors 21.
  • FIG. 4 is an enlarged cross-sectional view of a pad portion of a semiconductor device having a cured film of the present invention, and has a structure called a fan-out wafer level package (fan-out WLP).
  • the silicon wafer 23 on which the Al pad 24 and the passivation film 25 are formed is diced and cut into chips, and then sealed with a resin 26.
  • heat treatment is performed, and the shrinkage of the resin 26 causes a (T-1) step between the chip 23 and the resin 26.
  • the (T-1) step consisting of the (S-1) upper step on the surface of the chip 23 and the (S-2) lower step on the surface of the resin 26 is 2 to 40 ⁇ m.
  • a cured film 27 is formed as a pattern of the photosensitive film of the present invention over each of (S-1) the upper stage and (S-2) the lower stage, and (S-1) is disposed on the upper stage.
  • the (T-2) step difference between the cured film and the cured film disposed on the (S-2) lower step is 5 ⁇ m or less.
  • the fan-out WLP is provided with an extended portion using a sealing resin such as epoxy resin around the semiconductor chip, rewiring from the electrode on the semiconductor chip to the extended portion, and mounting a solder ball on the extended portion. This is a semiconductor package that secures the necessary number of terminals.
  • wiring is installed so as to straddle the boundary line formed by the main surface of the semiconductor chip and the main surface of the sealing resin.
  • an interlayer insulating film is formed on a base material made of two or more materials such as a semiconductor chip provided with metal wiring and a sealing resin, and wiring is formed on the interlayer insulating film.
  • wiring is installed so as to straddle the boundary line between the main surface of the semiconductor chip and the main surface of the printed circuit board.
  • an interlayer insulating film is formed on a base material made of two or more materials, and wiring is formed on the interlayer insulating film.
  • the cured film obtained by curing the photosensitive film of the present invention is disposed on a substrate made of two or more kinds of materials, the level difference on the substrate can be reduced and the flatness of the cured film can be maintained. Therefore, it is suitably used as an interlayer insulating film provided on a substrate made of two or more materials.
  • ⁇ Measuring method of film thickness> A Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. was used, and the film after pre-baking and development was measured at a refractive index of 1.629 based on polyimide.
  • NMP N-methylpyrrolidone
  • This film was divided in half, and one side was placed in an inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.), raised to a curing temperature of 350 ° C. over 30 minutes, and subjected to heat treatment at 350 ° C. for 60 minutes. Then, it annealed until the inside of oven became 50 degrees C or less, and obtained the cured film.
  • the obtained cured film (A) and the film before curing (B) were measured for infrared absorption spectra using a Fourier transform infrared spectrophotometer FT-720 (manufactured by Horiba, Ltd.). The peak intensity around 1377 cm ⁇ 1 due to CN stretching vibration of the imide ring was determined, and the value of “peak intensity of the film (B) before curing / peak intensity of the cured film (A)” was defined as the imidization ratio.
  • the protective film of the photosensitive film produced by each Example and comparative example which are mentioned later was peeled.
  • the release surface was then laminated on a silicon wafer or a copper substrate.
  • a substrate (copper plating substrate) having a metal material layer formed by sputtering titanium and copper on a silicon wafer to a thickness of 100 nm and then forming a copper plating film with a thickness of 2 ⁇ m by electrolytic plating was used.
  • Lamination was performed using a laminating apparatus (manufactured by Takatori Co., Ltd., VTM-200M) under conditions of a stage temperature of 80 ° C., a roll temperature of 80 ° C., a vacuum of 150 Pa, a sticking speed of 5 mm / sec, and a sticking pressure of 0.2 MPa.
  • the photosensitive coating was cut in a grid pattern in the center of the film on the substrate using a cutter guide so that 100 squares were formed at intervals of 2 mm ⁇ 2 mm.
  • the cellophane tape was applied to the grid-like portion, it was pulled and peeled off at an angle of 90 ° with respect to the substrate.
  • the number of the photosensitive coatings that were peeled out of the 100 when it was peeled off was counted. When the number of peeling is small, it indicates that the adhesiveness is high, and when it is large, it indicates that the adhesiveness is low. It is preferably 50 or less, more preferably 20 or less, and even more preferably 10 or less.
  • the evaluation of the laminating property was performed on a silicon wafer, and the condition 1 was performed on a copper substrate.
  • the membrane was exposed at 10 mJ / cm 2 steps at 0 ⁇ 1000mJ / cm 2 exposure amount using an i-line stepper (NIKON NSR i9). After exposure, development is performed for 90 seconds with a 2.38 mass% aqueous solution of tetramethylammonium (TMAH) (manufactured by Mitsubishi Gas Chemical Co., Ltd., ELM-D), followed by rinsing with pure water, and development with an isolated space of 5 ⁇ m. Membrane A was obtained.
  • TMAH tetramethylammonium
  • the exposure amount (hereinafter referred to as the minimum exposure amount Eth) at which the exposed portion of the isolated space of 5 ⁇ m was not completely eluted after exposure and development was defined as sensitivity. If Eth is 400 mJ / cm 2 or less, it can be determined that the sensitivity is high. 300 mJ / cm 2 and more preferably less, more preferably 250 mJ / cm 2 or less.
  • the protective film of the photosensitive film produced in each Example and Comparative Example was peeled off, and the stage temperature was 80 ° C. and the roll temperature was 120 ° C. on a silicon wafer using a laminating apparatus (manufactured by Takatori Co., Ltd., VTM-200M).
  • the film was laminated so that the film thickness T1 was 11 ⁇ m under the conditions of a degree of vacuum of 150 Pa, a sticking speed of 5 mm / second, and a sticking pressure of 0.2 Mpa.
  • the laminated substrate was pre-baked on a hot plate at 120 ° C.
  • the cured film obtained by this method was cut out with a single blade so as to be 7 ⁇ 1 cm, and this was pulled at 50 mm / min with a Tensilon universal testing machine (RTM-100, manufactured by Orientec Corp.). A value obtained by dividing the amount of elongation at this time by the sample length was obtained. This measurement was performed on 10 samples, and the maximum value was defined as the elongation.
  • the elongation is preferably 10% or more, more preferably 20% or more, and even more preferably 40% or more.
  • ⁇ 5% weight loss temperature measurement (evaluation of heat resistance)>
  • a cured film obtained by the same method as in the above ⁇ evaluation of high extensibility> was subjected to a rate of 10 ° C./min in a nitrogen stream at 80 mL / min using a thermogravimetry measuring instrument (TGA50 manufactured by Shimadzu Corporation). The temperature was raised and measured.
  • the 5% weight loss temperature is preferably 260 ° C or higher, more preferably 300 ° C or higher, and further preferably 340 ° C or higher.
  • Synthesis Example 1 Synthesis of quinonediazide compound (a) Under a nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 26.86 g of 5-naphthoquinonediazidesulfonyl acid chloride (0.10 mol) and 13.43 g (0.05 mol) of 4-naphthoquinonediazide sulfonyl chloride were dissolved in 50 g of 1,4-dioxane and brought to room temperature.
  • TrisP-PA trade name, manufactured by Honshu Chemical Industry Co., Ltd.
  • Synthesis Example 2 Synthesis of polyhydroxystyrene resin (a0-1) 500 ml of tetrahydrofuran and 0.01 mol of sec-butyllithium as an initiator were added to a mixed solution of pt-butoxystyrene and styrene at a molar ratio of 3: 1. A total of 20 g was added in a proportion and polymerized with stirring for 3 hours. The polymerization termination reaction was performed by adding 0.1 mol of methanol to the reaction solution. Next, in order to purify the polymer, the reaction mixture was poured into methanol, and the precipitated polymer was dried to obtain a white polymer.
  • Synthesis Example 3 Synthesis of polyhydroxystyrene resin (a0-2) The same procedure as in Synthesis Example 2 was conducted except that mt-butoxystyrene was used instead of pt-butoxystyrene.
  • the obtained copolymer of m-hydroxystyrene and styrene (hereinafter referred to as (a0-2)) has a weight average molecular weight (Mw) of 5000 (in terms of GPC polystyrene) and a dispersity of (Mw / Mn) 3 by GPC analysis. .20.
  • Synthesis Example 4 Synthesis of polyhydroxystyrene resin (a0-3) The same procedure as in Synthesis Example 2 was carried out except that styrene was not added.
  • the obtained p-hydroxystyrene resin (hereinafter referred to as (a0-3)) had a weight average molecular weight (Mw) of 3000 (in terms of GPC polystyrene) and a dispersity of (Mw / Mn) of 1.60 according to analysis by GPC. .
  • Synthesis Example 5 Synthesis of alkali-soluble resin (a1-1) Polyhydroxystyrene resin (a0-1) was dissolved in a solution of 80 g (2.0 mol) of sodium hydroxide in 800 g of pure water. After complete dissolution, 686 g of a 36-38 mass% formalin aqueous solution was added dropwise at 20-25 ° C. over 2 hours. Thereafter, the mixture was stirred at 20 to 25 ° C. for 17 hours. This was neutralized by adding 98 g of sulfuric acid and 552 g of water, and allowed to stand for 2 days. The white solid formed in the solution after standing was washed with 100 mL of water. This white solid was vacuum-dried at 50 ° C. for 48 hours.
  • the white solid thus obtained was dissolved in 300 mL of methanol, 2 g of sulfuric acid was added, and the mixture was stirred at room temperature for 24 hours.
  • 15 g of an anionic ion exchange resin (Rohman Haas, Amberlyst IRA96SB) was added and stirred for 1 hour, and the ion exchange resin was removed by filtration.
  • GBL500mL was added, methanol was removed with the rotary evaporator, and it was set as the GBL solution.
  • Synthesis Example 6 Synthesis of Alkali-Soluble Resin (a1-2) Synthesis was performed in the same production method except that (a0-2) was used instead of (a0-1) in Synthesis Example 5.
  • the obtained alkali-soluble resin (hereinafter referred to as (a1-2)) which is an alkoxylated polyhydroxystyrene resin, has a weight average molecular weight (Mw) of 7500 (in terms of GPC polystyrene) as analyzed by GPC, and the introduction rate of alkoxy groups was 55 mol% per mol of hydroxystyrene.
  • Synthesis Example 7 Synthesis of Alkali-Soluble Resin (a1-3) Synthesis was performed in the same production method except that (a0-3) was used instead of (a0-1) in Synthesis Example 5.
  • the obtained alkali-soluble resin (hereinafter referred to as (a1-3)), which is an alkoxylated polyhydroxystyrene resin, has a weight average molecular weight (Mw) of 3500 (in terms of GPC polystyrene) as analyzed by GPC, and has an alkoxy group introduction rate.
  • Mw weight average molecular weight
  • a novolac resin (e) polymer solid was obtained. It was confirmed by GPC analysis that the weight average molecular weight (Mw) was 3,500. ⁇ -Butyrolactone (GBL) was added to the obtained novolak resin (e) to obtain a novolak resin (e) solution having a solid content concentration of 43% by mass.
  • Synthesis Example 15 Synthesis of already-closed polyimide resin (G) Under a dry nitrogen stream, 8.82 g (0.045 mol) of CBDA was dissolved in 100 g of NMP. To this was added 1.09 g (0.010 mol) of 3-aminophenol together with 20 g of NMP. Further, 15.57 g (0.043 mol) of BAHF, 1.00 g (0.005 mol) of DAE and 0.62 g (0.003 mol) of SiDA were added together with 20 g of NMP and reacted at 60 ° C. for 1 hour, and then at 180 ° C. for 4 hours. Stir. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (G).
  • Synthesis Example 16 Synthesis of already-closed polyimide resin (H) 13.96 g (0.045 mol) of ODPA was dissolved in 100 g of NMP under a dry nitrogen stream. To this was added 1.09 g (0.010 mol) of 3-aminophenol together with 20 g of NMP. Furthermore, BAHF11.90g (0.033mol), DAE1.00g (0.005mol), ED600 6.0g (0.010mol), SiDA0.62g (0.003mol) were added with NMP20g, and at 60 degreeC. The reaction was carried out for 1 hour and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (H).
  • Synthesis Example 18 Synthesis of already-closed polyimide resin (J) In a dry nitrogen stream, 19.99 g (0.045 mol) of 6FDA was dissolved in 100 g of NMP. To this was added 1.09 g (0.010 mol) of 3-aminophenol together with 20 g of NMP. Furthermore, BAHF11.90g (0.033mol), DAE1.00g (0.005mol), ED600 6.0g (0.010mol), SiDA0.62g (0.003mol) were added with NMP20g, and at 60 degreeC. The reaction was carried out for 1 hour and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (J).
  • Synthesis Example 20 Synthesis of polyimide precursor resin (L) Under a dry nitrogen stream, 4,4′-diaminophenyl ether (hereinafter referred to as DAE) 7.51 g (0.038 mol), SiDA 1.86 g (0.007 mol), 1.09 g (0.010 mol) of 3-aminophenol was dissolved in 100 g of NMP. To this, 13.96 g (0.045 mol) of ODPA was added together with 20 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours.
  • DAE 4,4′-diaminophenyl ether
  • Synthesis Example 21 Synthesis of Polyimide Resin (M) Under a dry nitrogen stream, 8.11 g (0.04 mol) of DAE and 1.09 g (0.010 mol) of 3-aminophenol were dissolved in 100 g of NMP. To this, 13.96 g (0.045 mol) of ODPA was added together with 20 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, the mixture was stirred at 180 ° C. for 5 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed 3 times with water, and then dried for 20 hours in a vacuum dryer at 80 ° C. to obtain a polyimide resin (M).
  • M Polyimide resin
  • Synthesis example 23 Synthesis
  • Synthesis Example 24 Synthesis of Novolak Resin (f) M-cresol 108.0 g, methanol 108.0 g, and sodium hydroxide 40.0 g were charged in a nitrogen-substituted three-necked flask 1000 ml and heated to 67 ° C. with stirring. The reflux reaction was performed for 30 minutes. Thereafter, the reaction solution was cooled to 40 ° C., charged with 65.2 g of 92% by mass paraformaldehyde, heated again to 67 ° C., and then refluxed for 5 hours. After completion of the reaction, the reaction solution was cooled to 30 ° C.
  • the temperature of the reaction solution was raised to 60 ° C., and an alkoxylation reaction was performed at 60 ° C. for 3 hours. After completion of the reaction, the reaction solution is cooled to 30 ° C. or lower, and a 10% by mass aqueous sodium hydroxide solution is added over 30 minutes until the pH of the reaction solution reaches 9.0 so that the temperature of the reaction solution does not exceed 35 ° C. It was dripped. Methyl isobutyl ketone (MIBK) 216.0 g and ion-exchanged water 324.0 g as a separation solvent for washing were added to the reaction solution, stirred at 30 ° C. for 20 minutes, allowed to stand for 20 minutes, and the separated aqueous layer was removed.
  • MIBK Methyl isobutyl ketone
  • the obtained novolak resin solution (f) had a weight average molecular weight (Mw) of 7000 (GPA polystyrene conversion) and a dispersity (Mw / Mn) of 7.5 according to analysis by GPC.
  • Mw weight average molecular weight
  • Mw / Mn dispersity
  • Example 1 6. 10.5 g of the alkali-soluble resin (a1-1), 10.5 g of the resin (A) obtained in Synthesis Example 9, 3.0 g of the quinonediazide compound (a) obtained in Synthesis Example 1, and the crosslinking agent MX-270 2 g of KBM-403 1.0 g was added to 25 g of GBL to obtain varnish A of a positive photosensitive resin composition.
  • the obtained varnish was applied onto a PET film having a thickness of 38 ⁇ m using a comma roll coater, dried at 80 ° C. for 8 minutes, and then laminated with a PP film having a thickness of 10 ⁇ m as a protective film. A characteristic film was obtained. The film thickness of the photosensitive film was adjusted to 10 ⁇ m.
  • the obtained photosensitive film was used to evaluate each of laminate property to a silicon substrate, high elongation, 5% weight loss temperature (heat resistance), and pattern workability.
  • Examples 2 to 33, Comparative Examples 1 to 8 The addition amounts of (A1) alkali-soluble resin, (A2) alkali-soluble resin, other additives, (B) photoacid generator and (C) crosslinking agent are as shown in Table 1, Table 2-1, and Table 2-2.
  • a varnish was prepared in the same manner as in Example 1 except that the varnish was changed. Using the obtained photosensitive film, each evaluation of the laminate property to a silicon substrate, high extensibility, 5% weight loss temperature (heat resistance), and pattern processability was performed.

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Abstract

L'invention concerne une pellicule photosensible qui peut produire une pellicule traitée thermiquement présentant une haute résistance à la chaleur, et qui montre une bonne capacité de traitement de motif (haute sensibilité) et qui présente simultanément une bonne adhésion à un substrat, c.-à-d. de bonnes propriétés de stratification. Cette pellicule photosensible contient : une résine soluble dans un alcalin (A1) dont une unité structurelle est représentée par la formule générale (1) ; une résine soluble dans un alcalin (A2) qui comprend au moins un organe sélectionné parmi les polyimides, les polybenzooxazoles, les imides de polyamide, leurs précurseurs, et leurs copolymères ; un générateur photoacide (B) ; et un agent réticulant thermique (C). (Dans la formule générale (1), R1 représente un atome d'hydrogène ou un groupe alkyle comportant 1 à 5 atomes de carbone ; a représente un entier compris entre 0 et 4, et b représente un entier compris entre 1 et 3 ; et R2 représente un atome d'hydrogène, un groupe méthyle, un groupe éthyle, ou un groupe propyle.)
PCT/JP2017/011435 2016-03-28 2017-03-22 Pellicule photosensible WO2017170032A1 (fr)

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CN201780019777.4A CN108780275B (zh) 2016-03-28 2017-03-22 感光性膜
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JP2017517124A JP6982786B2 (ja) 2016-03-28 2017-03-22 感光性フィルム
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Cited By (11)

* Cited by examiner, † Cited by third party
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JP2020042222A (ja) * 2018-09-13 2020-03-19 日立化成株式会社 感光性樹脂組成物、感光性フィルム、デバイス及びレジストパターンの形成方法
WO2020189354A1 (fr) * 2019-03-15 2020-09-24 日本化薬株式会社 Résine d'acide polyamique, résine de polyimide et composition de résine les comprenant
JP2020160331A (ja) * 2019-03-27 2020-10-01 東レ株式会社 感光性樹脂組成物、感光性樹脂組成物フィルムおよびこれらを用いた半導体装置
CN111936552A (zh) * 2018-03-22 2020-11-13 东丽株式会社 碱溶性树脂、感光性树脂组合物、感光性片材、固化膜、层间绝缘膜或半导体保护膜、固化膜的浮凸图案的制造方法、电子部件或半导体器件
WO2021059843A1 (fr) * 2019-09-24 2021-04-01 東レ株式会社 Composition de résine, film de composition de résine, film durci, structure creuse utilisant ce dernier et dispositif semi-conducteur
EP3951498A1 (fr) 2020-08-04 2022-02-09 Shin-Etsu Chemical Co., Ltd. Composition de résine photosensible positive, film sec photosensible positif, procédé de production de film sec photosensible positif, procédé de formation de motifs, procédé de formation d'un film durci, film d'isolation intercouche, film de protection de surface et composant électronique
US11456266B2 (en) 2019-10-31 2022-09-27 Taiwan Semiconductor Manufacturing Co., Ltd. Bump structure and method of manufacturing bump structure
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JP7375761B2 (ja) 2019-09-24 2023-11-08 東レ株式会社 ネガ型感光性樹脂組成物、ネガ型感光性樹脂組成物フィルム、硬化膜、これらを用いた中空構造体、および電子部品
JPWO2021059843A1 (fr) * 2019-09-24 2021-04-01
US11456266B2 (en) 2019-10-31 2022-09-27 Taiwan Semiconductor Manufacturing Co., Ltd. Bump structure and method of manufacturing bump structure
US11923326B2 (en) 2019-10-31 2024-03-05 Taiwan Semiconductor Manufacturing Company, Ltd. Bump structure and method of manufacturing bump structure
JP2022029198A (ja) * 2020-08-04 2022-02-17 信越化学工業株式会社 ポジ型感光性樹脂組成物、ポジ型感光性ドライフィルム、ポジ型感光性ドライフィルムの製造方法、パターン形成方法、硬化被膜形成方法、層間絶縁膜、表面保護膜、及び電子部品
KR20220017361A (ko) 2020-08-04 2022-02-11 신에쓰 가가꾸 고교 가부시끼가이샤 포지티브형 감광성 수지 조성물, 포지티브형 감광성 드라이 필름, 포지티브형 감광성 드라이 필름의 제조 방법, 패턴 형성 방법, 경화 피막 형성 방법, 층간 절연막, 표면 보호막, 및 전자 부품
JP7431696B2 (ja) 2020-08-04 2024-02-15 信越化学工業株式会社 ポジ型感光性樹脂組成物、ポジ型感光性ドライフィルム、ポジ型感光性ドライフィルムの製造方法、パターン形成方法、硬化被膜形成方法、層間絶縁膜、表面保護膜、及び電子部品
EP3951498A1 (fr) 2020-08-04 2022-02-09 Shin-Etsu Chemical Co., Ltd. Composition de résine photosensible positive, film sec photosensible positif, procédé de production de film sec photosensible positif, procédé de formation de motifs, procédé de formation d'un film durci, film d'isolation intercouche, film de protection de surface et composant électronique
EP4063954A2 (fr) 2021-03-23 2022-09-28 Shin-Etsu Chemical Co., Ltd. Composition de résine photosensible positive, film sec photosensible positif, procédé de production de film sec photosensible positif, procédé de formation de motifs, procédé de formation d'un film durci, film d'isolation intercouche, film de protection de surface et composant électronique
WO2023149398A1 (fr) * 2022-02-02 2023-08-10 東レ株式会社 Stratifié, procédé de fabrication de stratifié, structure creuse et composant électronique

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CN108780275B (zh) 2022-11-08
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