WO2017209176A1 - Procédé de fabrication de stratifié, procédé de fabrication d'élément semi-conducteur, et stratifié - Google Patents

Procédé de fabrication de stratifié, procédé de fabrication d'élément semi-conducteur, et stratifié Download PDF

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Publication number
WO2017209176A1
WO2017209176A1 PCT/JP2017/020249 JP2017020249W WO2017209176A1 WO 2017209176 A1 WO2017209176 A1 WO 2017209176A1 JP 2017020249 W JP2017020249 W JP 2017020249W WO 2017209176 A1 WO2017209176 A1 WO 2017209176A1
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Prior art keywords
resin composition
photosensitive resin
group
metal layer
layer
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PCT/JP2017/020249
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English (en)
Japanese (ja)
Inventor
犬島　孝能
慶 福原
ステファン ヴァンクロースター
勝志 伊藤
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富士フイルム株式会社
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Priority to CN201780032974.XA priority Critical patent/CN109313397B/zh
Priority to JP2018520955A priority patent/JP6845848B2/ja
Priority to KR1020187034311A priority patent/KR102147108B1/ko
Publication of WO2017209176A1 publication Critical patent/WO2017209176A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
    • H01L25/03—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes
    • H01L25/04—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers
    • H01L25/07—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L29/00
    • H01L25/073—Apertured devices mounted on one or more rods passed through the apertures
    • 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
    • G03F7/20—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
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • 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
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
    • H01L25/03—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes
    • H01L25/04—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers
    • H01L25/065—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L27/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
    • H01L25/03—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes
    • H01L25/04—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers
    • H01L25/065—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L27/00
    • H01L25/0657—Stacked arrangements of devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
    • H01L25/03—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes
    • H01L25/04—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers
    • H01L25/07—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L29/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
    • H01L25/18—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different subgroups of the same main group of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16135—Disposition the bump connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip
    • H01L2224/16145—Disposition the bump connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip the bodies being stacked
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector

Definitions

  • the present invention relates to a laminate manufacturing method, a semiconductor element manufacturing method, and a laminate.
  • Resins such as polyimide resins and polybenzoxazole resins are excellent in heat resistance and insulation, and are therefore used for insulating layers of semiconductor elements.
  • a cured film of a resin having excellent heat resistance and insulation such as polyimide resin or polybenzoxazole resin
  • the cured film and the metal layer are laminated to rewiring the semiconductor element.
  • Making the layer is done.
  • the present inventors examined laminating a cured film and a metal layer of a resin having excellent heat resistance and insulating properties such as a polyimide resin and a polybenzoxazole resin, the adhesion between the cured film and the metal layer was insufficient. It was found that delamination occurred between the cured film and the metal layer.
  • a material constituting the wiring layer is formed on the substrate by providing a barrier metal film between the substrate and the wiring layer made of copper (Cu) or the like. It is known to prevent the deterioration of wiring caused by diffusion (see Patent Document 1).
  • Patent Document 1 a substrate having fine holes or grooves formed on the surface is prepared, and titanium or a titanium compound is formed on the substrate in a state where the temperature of the substrate is set in a range of 150 ° C. or more and 500 ° C. or less.
  • a barrier metal film forming method for forming a barrier metal film made of is described.
  • Patent Document 1 by using the method for forming a barrier metal film having the above-described configuration, an overhang (a diameter of the opening is smaller than that of the bottom) with respect to a high aspect ratio pattern or the like. It is described that generation can be reduced.
  • Patent Document 1 pays attention only when a silicon oxide film is formed on the surface of a silicon wafer as a substrate. That is, Patent Document 1 did not pay attention to delamination when a cured film of a resin excellent in heat resistance and insulation, such as a polyimide resin or a polybenzoxazole resin, and a metal layer are laminated.
  • the problem to be solved by the present invention is to provide a method for producing a laminate that can suppress delamination when a substrate, a cured film, and a metal layer are laminated. Moreover, the subject which this invention tends to solve is providing the manufacturing method of a semiconductor element containing the manufacturing method of a laminated body. Moreover, the subject which this invention tends to solve is providing the laminated body which can suppress delamination at the time of laminating
  • a vapor phase film formation such as a sputtering method is performed at a temperature lower than the glass transition temperature of a cured resin film having excellent heat resistance and insulation properties such as polyimide resin and polybenzoxazole resin. It has been found that the above-mentioned problems can be solved by forming a metal layer using The present invention, which is a means for solving the above problems, and preferred embodiments of the present invention are as follows.
  • a photosensitive resin composition layer forming step of applying a photosensitive resin composition to a substrate to form a layer An exposure step of exposing the photosensitive resin composition layer applied to the substrate; A development processing step of performing development processing on the exposed photosensitive resin composition layer; A curing step for curing the photosensitive resin composition layer after development; Including performing a metal layer forming step of forming a metal layer by vapor phase film formation on the surface of the photosensitive resin composition layer after the curing step, in the order described above, The manufacturing method of a laminated body whose temperature of the photosensitive resin composition layer after the hardening process at the time of forming a metal layer is less than the glass transition temperature of the photosensitive resin composition layer after a hardening process.
  • Production method. [3] The method for producing a laminate according to [1] or [2], wherein the photosensitive resin composition has a crosslinked structure built by exposure and the solubility in an organic solvent decreases.
  • the photosensitive resin composition includes at least one resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole.
  • [5] The method for manufacturing a laminated body according to any one of [1] to [4], further including a second metal layer forming step of forming a second metal layer on the surface of the metal layer.
  • [6] The method for manufacturing a laminate according to [5], wherein the second metal layer includes copper.
  • [8] The method for manufacturing a laminated body according to any one of [1] to [7], wherein the metal layer formed in the metal layer forming step has a thickness of 50 to 2000 nm.
  • the curing step includes a temperature raising step for raising the temperature of the photosensitive resin composition layer, and a holding step for holding at a holding temperature equal to the final temperature reached in the temperature raising step.
  • the temperature of the photosensitive resin composition layer when forming the metal layer is 30 ° C. or more lower than the glass transition temperature of the photosensitive resin composition layer, according to any one of [1] to [11]
  • a manufacturing method of a layered product is 30 ° C. or more lower than the glass transition temperature of the photosensitive resin composition layer, according to any one of [1] to [11]
  • a manufacturing method of a layered product is 30 ° C. or more lower than the glass transition temperature of the photosensitive resin composition layer, according to any one of [1] to [11]
  • a manufacturing method of a layered product is 30 ° C. or more lower than the glass transition temperature of the photosensitive resin composition layer, according to any one of [1] to [11]
  • a manufacturing method of a layered product is 30 ° C. or more lower than the glass transition temperature of the photosensitive resin composition layer, according to any one of [1] to [11]
  • a manufacturing method of a layered product is 3 ° C. or more lower than the glass transition temperature
  • the pattern cured film contains polyimide or polybenzoxazole,
  • invasion length to the pattern cured film of the metal which comprises the metal layer located in the surface of a pattern cured film is 130 nm or less from the surface of a pattern cured film.
  • [15] A laminate produced by the laminate production method according to any one of [1] to [12].
  • [16] A semiconductor device manufactured by the method for manufacturing a semiconductor device according to [13].
  • the present invention it is possible to provide a method for manufacturing a laminate that can suppress delamination when a substrate, a cured film, and a metal layer are laminated. Moreover, according to this invention, the manufacturing method of a semiconductor element including the manufacturing method of the laminated body of this invention can be provided. Moreover, according to this invention, the laminated body which can suppress delamination at the time of laminating
  • the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams.
  • the light used for the exposure generally includes an active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays or electron beams.
  • an active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays or electron beams.
  • EUV light extreme ultraviolet rays
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • (meth) acrylate represents both and / or “acrylate” and “methacrylate”
  • (meth) allyl means both “allyl” and “methallyl”
  • (Meth) acryl” represents either “acryl” and “methacryl” or any one
  • “(meth) acryloyl” represents both “acryloyl” and “methacryloyl”, or Represents either.
  • the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
  • solid content concentration is the mass percentage of the other component except a solvent with respect to the gross mass of a composition.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene converted values by gel permeation chromatography (GPC measurement) unless otherwise specified.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel. It can be determined by using Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
  • the eluent is measured using THF (tetrahydrofuran).
  • detection is performed using a UV ray (ultraviolet) wavelength 254 nm detector.
  • the method for producing a laminate of the present invention comprises a photosensitive resin composition layer forming step in which a photosensitive resin composition is applied to a substrate to form a layer, An exposure step of exposing the photosensitive resin composition layer applied to the substrate; A development processing step of performing development processing on the exposed photosensitive resin composition layer; A curing step for curing the photosensitive resin composition layer after development; Including performing a metal layer forming step of forming a metal layer by vapor phase film formation on the surface of the photosensitive resin composition layer after the curing step, in the order described above, The temperature of the photosensitive resin composition layer after the curing step when forming the metal layer is lower than the glass transition temperature of the photosensitive resin composition layer after the curing step.
  • a metal layer is formed on the surface of a cured film (a cured film means a photosensitive resin composition layer after the curing process) on a substrate by vapor-phase film formation such as sputtering, usually the metal layer The substrate (and the cured film) is heated to control the film quality.
  • a metal layer is formed using a sputtering method at a high temperature, it has been estimated that metal atoms can be implanted into a cured film, and as a result, the occurrence of delamination can be suppressed.
  • the present inventors have sputtered at a high temperature. It has been found that when the metal layer is formed using the method, the phenomenon of penetration of metal into the surface of the cured film occurs. However, it has been found that when the metal layer is formed by sputtering at a high temperature, delamination occurs when the substrate, the cured film, and the metal layer are laminated.
  • TEM transmission electron microscope
  • the glass transition temperature is hereinafter also referred to as Tg (glass transition temperature).
  • the manufacturing method of the laminated body of this invention may include the process of filtering the photosensitive resin composition, before applying the photosensitive resin composition to a board
  • the filter pore diameter is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
  • a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable.
  • a filter that has been washed in advance with an organic solvent may be used.
  • a plurality of types of filters may be connected in series or in parallel.
  • filters having different pore diameters and / or materials may be used in combination. Moreover, you may filter multiple times using each kind of material, and the process filtered several times may be a circulation filtration process. Further, pressure filtration may be performed, and the pressure applied in the case of pressure filtration is preferably 0.05 MPa or more and 0.3 MPa or less.
  • impurities may be removed by filtration using an adsorbent, or filtration may be performed using a combination of filter filtration and adsorbent.
  • known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
  • the manufacturing method of the laminated body of this invention includes the photosensitive resin composition layer formation process which applies the photosensitive resin composition to a board
  • coating is preferable.
  • a spin coating method, a slit coating method, a spray coating method, and an ink jet method are more preferable.
  • a desired photosensitive resin composition layer can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the means to be applied.
  • the coating method can be appropriately selected depending on the shape of the substrate, and a spin coat method, a spray coat method, an ink jet method or the like is preferable for a circular substrate such as a wafer, and a slit coat method, a spray coat method, an ink jet method or the like for a rectangular substrate. The method is preferred.
  • the spin coating method for example, it can be applied at a rotational speed of 500 to 2000 rpm (revolutions per minute) for about 10 seconds to 1 minute.
  • the thickness of the photosensitive resin composition layer (cured film after the curing step) is preferably applied to be 0.1 to 100 ⁇ m after exposure, and is preferably applied to be 1 to 50 ⁇ m. More preferred. Moreover, as shown in FIG. 2, the thickness of the photosensitive resin composition layer formed does not necessarily need to be uniform. In particular, when a photosensitive resin composition layer is provided on an uneven surface, cured films having different thicknesses will be obtained as shown in FIG. In particular, when a plurality of cured films are laminated, a concave portion having a deep depth may be formed as the concave portion, but the present invention has a technical value in that it can more effectively suppress delamination between layers. high. When the laminated body has cured films having different thicknesses, it is preferable that the thickness of the cured film at the thinnest portion is the above thickness.
  • the type of the substrate can be appropriately determined according to the application, but a semiconductor production substrate such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film , Reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate and the like.
  • a semiconductor manufacturing substrate is particularly preferable, and silicon is more preferable.
  • a cured film or a metal layer may be used as a board
  • the photosensitive resin composition preferably contains a compound that forms a crosslinked structure by exposure, more preferably for negative development, and the crosslinked structure is constructed by exposure to organic. It is particularly preferred that the solubility in a solvent is reduced, and most preferred is a negative photosensitive resin developed with an organic solvent.
  • the photosensitive resin composition may contain components other than these, and these components are not essential.
  • the photosensitive resin composition used in the present invention contains a resin.
  • the resin is not particularly limited, and a known resin can be used.
  • the resin is preferably a high heat resistant resin.
  • the photosensitive resin composition used in the present invention preferably contains at least one resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole.
  • the photosensitive resin composition contains a polyimide precursor or a polybenzoxazole precursor, and it is further more preferable that a polyimide precursor is included.
  • the photosensitive resin composition used in the present invention may contain only one kind of polyimide precursor, polyimide, polybenzoxazole precursor and polybenzoxazole, or may contain two or more kinds. Moreover, two or more types of resins having the same structure, such as two types of polyimide precursors, and having different structures may be included.
  • the content of the resin in the photosensitive resin composition used in the present invention is preferably 10 to 99% by mass, more preferably 50 to 98% by mass, and more preferably 70 to 96% by mass based on the total solid content of the photosensitive resin composition. Further preferred.
  • the resin preferably contains a polymerizable group.
  • the photosensitive resin composition contains a polymerizable compound.
  • a three-dimensional network is formed in the exposed area, forming a strong cross-linked film, and the photosensitive resin composition layer (cured film) is not damaged by the surface activation treatment described later, and the surface activity By the chemical treatment, the adhesion between the cured film and the metal layer or the adhesion between the cured films is more effectively improved.
  • the resin includes a partial structure represented by —Ar—L—Ar—.
  • Ar is each independently an aromatic group
  • L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—. , —SO 2 — or —NHCO—, and a group consisting of a combination of two or more of the above.
  • Ar is preferably a phenylene group
  • L is an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S— or —SO 2 —.
  • the aliphatic hydrocarbon group here is preferably an alkylene group.
  • the polyimide precursor is not particularly defined with respect to its type and the like, and preferably includes a repeating unit represented by the following formula (2).
  • a 1 and A 2 each independently represent an oxygen atom or NH
  • R 111 represents a divalent organic group
  • R 115 represents a tetravalent organic group
  • R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group.
  • a 1 and A 2 in Formula (2) are preferably an oxygen atom or NH, and more preferably an oxygen atom.
  • R 111 in the formula (2) represents a divalent organic group.
  • the divalent organic group include a straight chain or branched aliphatic group, a group containing a cyclic aliphatic group and an aromatic group, a straight chain or branched aliphatic group having 2 to 20 carbon atoms, a carbon number A group consisting of a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
  • R 111 in the formula (2) is exemplified by a group represented by —Ar—L—Ar—.
  • Ar is each independently an aromatic group
  • L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—. , —SO 2 — or —NHCO—, and a group consisting of a combination of two or more of the above.
  • R 111 in formula (2) is preferably derived from a diamine.
  • the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamine.
  • One type of diamine may be used, or two or more types may be used.
  • a linear or branched aliphatic group having 2 to 20 carbon atoms a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof.
  • a diamine containing is preferable, and a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms is more preferable.
  • the following aromatic groups are mentioned as an example of an aromatic group.
  • A represents a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C ( ⁇ O) —, —S—. , —S ( ⁇ O) 2 —, —NHCO— and a group selected from a combination thereof, a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, It is more preferably a group selected from —O—, —C ( ⁇ O) —, —S—, —SO 2 —, —CH 2 —, —O—, —S—, —SO 2 —, More preferably, it is a divalent group selected from the group consisting of —C (CF 3 ) 2 — and —C (CH 3 ) 2 —.
  • diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4- Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; meta and paraphenylenediamine, diaminotoluene, 4,4'- and 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether
  • diamines (DA-1) to (DA-18) shown below are also preferable.
  • a diamine having at least two alkylene glycol units in the main chain is also a preferred example.
  • Preferred is a diamine containing two or more ethylene glycol chains or propylene glycol chains in one molecule, and more preferred is a diamine containing no aromatic ring.
  • Specific examples include Jeffermin (registered trademark) KH-511, Jeffermin (registered trademark) ED-600, Jeffermin (registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark).
  • EDR-148 Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (above trade names, manufactured by HUNTSMAN), 1- (2- (2- (2- (2- Aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, and the like, but is not limited thereto. .
  • x, y, and z are average values.
  • R 111 in the formula (2) is preferably represented by —Ar—L—Ar— from the viewpoint of the flexibility of the resulting cured film.
  • Ar is each independently an aromatic group
  • L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—. , —SO 2 — or —NHCO—, and a group consisting of a combination of two or more of the above.
  • Ar is preferably a phenylene group
  • L is an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S— or —SO 2 —.
  • the aliphatic hydrocarbon group here is preferably an alkylene group.
  • R 111 in formula (2) is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-line transmittance.
  • a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-line transmittance and availability.
  • Formula (51) In the formula (51), R 10 to R 17 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 10 to R 17 is a fluorine atom, a methyl group or a trifluoromethyl group. It is.
  • Examples of the monovalent organic group represented by R 10 to R 17 include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorine atom having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Alkyl group and the like.
  • Formula (61) In formula (61), R 18 and R 19 are each independently a fluorine atom or a trifluoromethyl group.
  • Diamine compounds that give the structure of formula (51) or (61) include 2,2′-dimethylbenzidine, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2′- Bis (fluoro) -4,4′-diaminobiphenyl, 4,4′-diaminooctafluorobiphenyl and the like can be mentioned. One of these may be used, or two or more may be used in combination.
  • R 115 in the formula (2) represents a tetravalent organic group.
  • a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
  • R 112 represents a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO.
  • the group is selected from —S— and —SO 2 —, and —CH 2 —, —C (CF 3 ) 2 —, —C (CH 3 ) 2 —, —O—, —CO More preferred is a divalent group selected from the group consisting of —, —S— and —SO 2 —.
  • R 115 in formula (2) include a tetracarboxylic acid residue remaining after removal of the anhydride group from tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
  • the tetracarboxylic dianhydride is preferably represented by the following formula (O).
  • Formula (O) Wherein (O) R 115 represents a tetravalent organic group.
  • a preferred range of R 115 has the same meaning as R 115 in formula (2), and preferred ranges are also the same.
  • tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl sulfide tetracarboxylic acid Acid dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4 '-Diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 2,3, 3 ', 4'-benzophenone tetracarboxylic dianhydride, 4,4'--benz
  • tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also preferable examples.
  • R 111 and R 115 in the formula (2) has a hydroxy group. More specifically, examples of R 111 include a residue of a bisaminophenol derivative.
  • R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group.
  • at least one of R 113 and R 114 preferably contains a polymerizable group, and both preferably contain a polymerizable group.
  • a polymerizable group is a group that can undergo a crosslinking reaction by the action of heat, radicals, and the like.
  • a radical photopolymerizable group is preferable.
  • the polymerizable group examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, a methylol group, and an amino group.
  • a radically polymerizable group which a polyimide precursor has group which has an ethylenically unsaturated bond is preferable.
  • the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III), and the like.
  • R 200 represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
  • R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH (OH) CH 2 — or a polyoxyalkylene group having 4 to 30 carbon atoms.
  • suitable R 201 are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group.
  • R 200 is a methyl group and R 201 is an ethylene group.
  • R 113 or R 114 in the formula (2) may be a monovalent organic group other than the polymerizable group.
  • R 113 or R 114 in Formula (2) is preferably a monovalent organic group.
  • the monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group.
  • Examples of the monovalent organic group include an aromatic group having 1, 2 or 3 (preferably 1) acidic group bonded to carbon constituting the aryl group, and a carbon constituting the aryl group.
  • Aralkyl groups having 1, 2 or 3 (preferably 1) acidic groups are particularly preferred.
  • Specific examples include an aromatic group having 6 to 20 carbon atoms having an acidic group and an aralkyl group having 7 to 25 carbon atoms having an acidic group. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned.
  • the acidic group is preferably a hydroxy group. It is more particularly preferred that R 113 or R 114 is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.
  • the number of carbon atoms of the alkyl group represented by R 113 or R 114 in Formula (2) is preferably 1-30.
  • Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, and an octadecyl group.
  • the cyclic alkyl group represented by R 113 or R 114 in Formula (2) may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group.
  • Examples of the monocyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • Examples of the polycyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group, and a pinenyl group. Is mentioned. Among these, a cyclohexyl group is most preferable from the viewpoint of achieving high sensitivity. Moreover, as an alkyl group substituted by the aromatic group, the linear alkyl group substituted by the aromatic group mentioned later is preferable.
  • aromatic group represented by R 113 or R 114 in the formula (2) include a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene.
  • the polyimide precursor forms a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. You may do it.
  • tertiary amine compounds having an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.
  • the polyimide precursor preferably has a fluorine atom in the structural unit.
  • the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.
  • an aliphatic group having a siloxane structure may be copolymerized with the polyimide precursor.
  • the diamine component for introducing an aliphatic group having a siloxane structure include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.
  • the repeating unit represented by the formula (2) is preferably a repeating unit represented by the following formula (2-A). That is, at least one of the polyimide precursors is preferably a precursor having a repeating unit represented by the formula (2-A). By adopting such a structure, it becomes possible to further widen the width of the exposure latitude.
  • a 1 , A 2 , R 111 , R 113 and R 114 in formula (2-A) are each independently synonymous with A 1 , A 2 , R 111 , R 113 and R 114 in formula (2).
  • the preferable range is also the same.
  • R 112 in formula (2-A) has the same meaning as R 112 in formula (5), and the preferred range is also the same.
  • the repeating unit represented by the formula (2) may be one type, but may be two or more types. Moreover, the polyimide precursor may contain the structural isomer of the repeating unit represented by Formula (2). The polyimide precursor may also contain other types of repeating units in addition to the repeating unit represented by the above formula (2).
  • a polyimide precursor in which 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of all repeating units is a repeating unit represented by the formula (2).
  • the polyimide precursor is preferably obtained by reacting dicarboxylic acid or a dicarboxylic acid derivative with diamine. More preferably, the dicarboxylic acid or dicarboxylic acid derivative is obtained by halogenating with a halogenating agent and then reacting with a diamine.
  • the polyimide precursor is, for example, a method of reacting a tetracarboxylic dianhydride and a diamine compound (partially replaced with a monoamine end-capping agent) at a low temperature, or a tetracarboxylic dianhydride (partly at a low temperature).
  • a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then a diamine (partially In the presence of a condensing agent and a tetracarboxylic dianhydride and an alcohol to obtain a diester, and then the remaining dicarboxylic acid is converted to an acid chloride to give a diamine (partially)
  • a method such as a method of reacting with a terminal blocking agent that is a monoamine).
  • an organic solvent is preferably used for the reaction.
  • organic solvent may be sufficient and two or more types may be sufficient.
  • the organic solvent can be appropriately determined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
  • the polyimide precursor it is preferable to seal with a terminal sealing agent such as an acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound in order to further improve storage stability.
  • a terminal sealing agent such as an acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound
  • a monoamine Preferred examples of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7.
  • -Aminonaphthalene 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2, -Hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6- Aminonaphthalene, 2-carbo Ci-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-amino Benzenesulfonic acid, 4-amino
  • a step of depositing a solid may be included. Specifically, solid precipitation can be achieved by precipitating the polyimide precursor in the reaction solution in water and dissolving it in a solvent in which the polyimide precursor such as tetrahydrofuran is soluble. Then, a polyimide precursor can be dried and a powdery polyimide precursor can be obtained.
  • the weight average molecular weight (Mw) of the polyimide precursor is preferably 18000 to 30000, more preferably 20000 to 27000, and further preferably 22000 to 25000.
  • the number average molecular weight (Mn) is preferably 7200 to 14000, more preferably 8000 to 12000, and still more preferably 9200 to 11200.
  • the dispersion degree of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more.
  • the upper limit of the degree of dispersion of the polyimide precursor is not particularly defined, but is, for example, preferably 4.5 or less, more preferably 4.0 or less, still more preferably 3.8 or less, and still more preferably 3.2 or less, 3.1 or less is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is even more preferable.
  • the polyimide is not particularly limited as long as it is a polymer compound having an imide ring.
  • the polyimide is preferably a compound represented by the following formula (4), more preferably a compound represented by the formula (4) and a compound having a polymerizable group.
  • R 131 represents a divalent organic group
  • R 132 represents a tetravalent organic group.
  • at least one of R 131 and R 132 may have a polymerizable group, and at the end of polyimide as shown in the following formula (4-1) or formula (4-2) It may have a polymerizable group.
  • R 133 is a polymerizable group, and other groups are as defined in the formula (4).
  • Formula (4-2) In formula (4-2), at least one of R 134 and R 135 is a polymerizable group, the other is an organic group, and the other groups are as defined in formula (4).
  • the polymerizable group that the polyimide preferably has is the same as the polymerizable group mentioned as the polymerizable group that may be contained in R 113 and R 114 in the above-described polyimide precursor.
  • R 131 in the formula (4) represents a divalent organic group.
  • the divalent organic group include the same divalent organic groups as R 111 in formula (2), and the preferred range is also the same.
  • R 131 include diamine residues remaining after removal of the amino groups of the diamine.
  • the diamine include aliphatic, cycloaliphatic or aromatic diamines. Specific examples include R 111 in formula (2) of the polyimide precursor.
  • R 131 in formula (4) is preferably a diamine residue having at least two alkylene glycol units in the main chain from the viewpoint of more effectively suppressing the occurrence of warpage during firing. More preferred is a diamine residue containing at least two ethylene glycol chains or propylene glycol chains in one molecule, and even more preferred is a diamine residue containing no aromatic ring.
  • Examples of the diamine containing two or more of ethylene glycol chain and propylene glycol chain in one molecule include specific examples similar to the diamine capable of deriving R 111 in formula (2). It is not limited to these.
  • R 132 in the formula (4) represents a tetravalent organic group.
  • examples of the tetravalent organic group represented by R 132 include those similar to R 115 in formula (2), and the preferred ranges are also the same.
  • four bonds of a tetravalent organic group having the following structure exemplified as R 115 in the formula (2) are bonded to four —C ( ⁇ O) — moieties in the formula (4).
  • a condensed ring is formed.
  • R 132 in formula (4) examples include a tetracarboxylic acid residue remaining after removal of the anhydride group from tetracarboxylic dianhydride.
  • R 115 in the formula (2) of the polyimide precursor can be given.
  • R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
  • R 131 and R 132 in formula (4) has a hydroxy group. More specifically, as R 131 in formula (4), 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, the above (DA-1) to (DA-18) ) Is a preferred example.
  • Preferred examples of R 132 in formula (4) include the above (DAA-1) to (DAA-5).
  • the polyimide has a fluorine atom in the structural unit.
  • the fluorine atom content in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.
  • an aliphatic group having a siloxane structure may be copolymerized with polyimide.
  • the diamine component for introducing an aliphatic group having a siloxane structure include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.
  • the main chain terminal of the polyimide is sealed with a terminal sealing agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound, etc. It is preferable to do. Of these, it is more preferable to use a monoamine.
  • a monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene and 1-hydroxy-6-aminonaphthalene.
  • the polyimide preferably has an imidization ratio of 85% or more, more preferably 90% or more.
  • the imidization ratio is 85% or more, film shrinkage due to ring closure that occurs when imidization is performed by heating is reduced, and the occurrence of warpage of the substrate can be suppressed.
  • the polyimide may contain two or more different types of repeating units of R 131 or R 132 in addition to the repeating unit of the above formula (4), all of which are one type of R 131 or R 132 .
  • the polyimide may also contain other types of repeating units in addition to the repeating unit represented by the above formula (4).
  • Polyimide may be produced by synthesizing a polyimide precursor and then cyclized by heating, or may be synthesized directly.
  • a polyimide is a method of obtaining a polyimide precursor and completely imidizing it using a known imidization reaction method, or a method of stopping an imidation reaction in the middle and introducing a part of an imide structure, By blending a completely imidized polymer and its polyimide precursor, it can be synthesized utilizing a method of partially introducing an imide structure.
  • Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by Fujifilm) and Matrimide 5218 (manufactured by HUNTSMAN).
  • the weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000.
  • the weight average molecular weight is more preferably 20,000 or more.
  • the weight average molecular weight of at least 1 type of polyimide is the said range.
  • the polybenzoxazole precursor is not particularly defined with respect to its type and the like, and preferably includes a repeating unit represented by the following formula (3).
  • R 121 represents a divalent organic group
  • R 122 represents a tetravalent organic group
  • R 123 and R 124 each independently represents a hydrogen atom or a monovalent organic group.
  • R 123 and R 124 in formula (3) have the same meaning as R 113 in formula (2), respectively, and the preferred ranges are also the same. That is, at least one of R 123 and R 124 in Formula (3) is preferably a polymerizable group.
  • R 121 in the formula (3) represents a divalent organic group.
  • the divalent organic group represented by R 121 is preferably a group containing at least one of an aliphatic group and an aromatic group.
  • As the aliphatic group a linear aliphatic group is preferable.
  • R 121 is preferably a dicarboxylic acid residue. Only one kind of dicarboxylic acid residue may be used, or two or more kinds thereof may be used.
  • dicarboxylic acid a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid containing an aromatic group are preferred, and a dicarboxylic acid containing an aromatic group is more preferred.
  • dicarboxylic acid containing an aliphatic group a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferable, and a linear or branched (preferably linear) aliphatic group and two COOHs are used. More preferred is a dicarboxylic acid.
  • the linear or branched (preferably linear) aliphatic group preferably has 2 to 30 carbon atoms, more preferably 2 to 25 carbon atoms, still more preferably 3 to 20 carbon atoms. It is particularly preferably 15 and more preferably 5 to 10.
  • the linear aliphatic group is preferably an alkylene group.
  • dicarboxylic acid containing a linear aliphatic group examples include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberin Acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexade
  • Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).
  • the dicarboxylic acid containing an aromatic group is preferably a dicarboxylic acid having the following aromatic group, more preferably a dicarboxylic acid comprising only the following aromatic group and two COOH.
  • A represents —CH 2 —, —O—, —S—, —SO 2 —, —CO—, —NHCO—, —C (CF 3 ) 2 —, and —C (CH 3) 2 - represents a divalent radical selected from the group consisting of.
  • dicarboxylic acid containing an aromatic group examples are preferably 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether and terephthalic acid.
  • R122 in Formula (3) represents a tetravalent organic group.
  • examples of the tetravalent organic group represented by R 122 include those similar to R 115 in the above formula (2), and preferred ranges thereof are also the same.
  • R 122 in formula (3) is also preferably a group derived from a bisaminophenol derivative. Examples of the group derived from a bisaminophenol derivative include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, and 3,3′-diamino-4.
  • bisaminophenol derivatives having the following aromatic groups are preferred.
  • X 1 represents —O—, —S—, —C (CF 3 ) 2 —, —CH 2 —, —SO 2 —, —NHCO—.
  • R 1 represents a hydrogen atom, alkylene, substituted alkylene, —O—, —S—, —SO 2 —, —CO—, —NHCO—, a single bond, or the following formula (A— an organic group selected from the group of sc).
  • R 2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, which may be the same or different.
  • R 3 is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, which may be the same or different.
  • R 2 is an alkyl group and R 3 is an alkyl group, which indicates high transparency to i-line and high cyclization rate when cured at low temperature. The effect can be maintained, which is preferable.
  • R 1 is more preferably alkylene or substituted alkylene.
  • Specific examples of the alkylene and substituted alkylene represented by R 1 include —CH 2 —, —CH (CH 3 ) —, —C (CH 3 ) 2 —, —CH (CH 2 CH 3 ) —, —C (CH 3 ) (CH 2 CH 3 ) —, —C (CH 2 CH 3 ) (CH 2 CH 3 ) —, —CH (CH 2 CH 2 CH 3 ) —, —C (CH 3 ) (CH 2 CH 2 CH 3 ) —, —CH (CH (CH 3 ) 2 ) —, —C (CH 3 ) (CH (CH 3 ) 2 ) —, —CH (CH 2 CH 2 CH 2 CH 3 ) —, —C (CH 3 ) (CH (CH 3 ) 2 ) —, —CH (CH 2 CH 2 CH 2 CH 3 ) —, —C (CH 3 ) (CH
  • the polybenzoxazole precursor may contain other types of repeating units in addition to the repeating unit represented by the above formula (3). It is preferable that the polybenzoxazole precursor contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that generation of warpage of the substrate accompanying ring closure of the polybenzoxazole precursor can be suppressed. .
  • SL diamine residue represented by the following formula
  • Z has an a structure and a b structure
  • R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
  • R 2s is a hydrocarbon group having 1 to 10 carbon atoms
  • R 3s , R 4s , R 5s , R 6s are aromatic groups and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different.
  • the polymerization of the a structure and the b structure may be block polymerization or random polymerization.
  • the mol% of the Z moiety is 5 to 95 mol% for the a structure, 95 to 5 mol% for the b structure, and the sum of the a and b structures is 100 mol%.
  • Z include those in which R 5s and R 6s in the b structure are phenyl groups.
  • the molecular weight of the diamine residue represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000.
  • the diamine residue represented by the formula (SL) is included as another type of repeating unit, it is also preferable that the tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic dianhydride is included as a repeating unit.
  • the tetracarboxylic acid residue, and examples of R 115 in formula (2) are examples of such tetracarboxylic acid residue, and examples of R 115 in formula (2).
  • the weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18000 to 30000, more preferably 20000 to 29000, and further preferably 22000 to 28000 when used in the composition described later.
  • the number average molecular weight (Mn) is preferably 7200 to 14000, more preferably 8000 to 12000, and still more preferably 9200 to 11200.
  • the degree of dispersion of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more.
  • the upper limit value of the degree of dispersion of the polybenzoxazole precursor is not particularly defined, but is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and more preferably 2.3 or less. Preferably, 2.2 or less is even more preferable.
  • the polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring.
  • the polybenzoxazole is preferably a compound represented by the following formula (X), more preferably a compound represented by the following formula (X) and having a polymerizable group.
  • R 133 represents a divalent organic group
  • R 134 represents a tetravalent organic group.
  • at least one of R 133 and R 134 may have a polymerizable group, and as shown in the following formula (X-1) or (X-2), polybenzoxazole You may have a polymeric group at the terminal.
  • Formula (X-1) In formula (X-1), at least one of R 135 and R 136 is a polymerizable group, the other is an organic group, and the other groups are as defined in formula (X).
  • R 137 is a polymerizable group, the other is a substituent, and the other groups are as defined in the formula (X).
  • the polymerizable group that polybenzoxazole preferably has has the same meaning as the polymerizable group described in the polymerizable group that the polyimide precursor has.
  • R 133 represents a divalent organic group.
  • the divalent organic group include an aliphatic group and an aromatic group.
  • R 134 represents a tetravalent organic group.
  • the tetravalent organic group include an example of R 122 in the formula (3) of the polybenzoxazole precursor. Preferred examples thereof are the same as those for R122 .
  • four bonds of a tetravalent organic group exemplified as R 122 are bonded to a nitrogen atom and an oxygen atom in the above formula (X) to form a condensed ring.
  • R 134 is the following organic group, the following structure is formed.
  • Polybenzoxazole preferably has an oxazolation rate of 85% or more, more preferably 90% or more.
  • the oxazolation rate is 85% or more, film shrinkage due to ring closure that occurs when oxazolation is performed by heating is reduced, and the occurrence of warpage can be more effectively suppressed.
  • the polybenzoxazole is a compound represented by the above formula (X) containing two or more different types of R 133 or R 134 in addition to the repeating unit represented by the above formula (X), all of which are one type of R 133 or R 134.
  • the repeating unit represented by these may be included.
  • Polybenzoxazole may also contain other types of repeating units in addition to the repeating unit represented by the above formula (X).
  • Polybenzoxazole is obtained, for example, by reacting a bisaminophenol derivative with a dicarboxylic acid containing R 133 and a compound selected from the dicarboxylic acid dichloride and dicarboxylic acid derivative of the above dicarboxylic acid to obtain a polybenzoxazole precursor, Can be obtained by oxazolation using a known oxazolation reaction method.
  • dicarboxylic acid an active ester dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield and the like.
  • the weight average molecular weight (Mw) of polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000.
  • the weight average molecular weight is more preferably 20,000 or more.
  • the weight average molecular weight of at least 1 type of polybenzoxazole is the said range.
  • photosensitive resins Even photosensitive resins other than those described above can be applied to the present invention.
  • photosensitive resins epoxy resins, phenol resins, and benzocyclobutene resins can be used.
  • the resin has a polymerizable group or the photosensitive resin composition contains a polymerizable compound.
  • the polymerizable compound is a compound having a polymerizable group, and a known compound that can be crosslinked by a radical, an acid, a base, or the like can be used.
  • the polymerizable group include the polymerizable groups described in the polyimide precursor.
  • One type of polymerizable compound may be included, or two or more types may be included.
  • the polymerizable compound may be in any chemical form such as a monomer, a prepolymer, an oligomer or a mixture thereof, and a multimer thereof.
  • a monomer type polymerizable compound (hereinafter also referred to as a polymerizable monomer) is a compound different from a polymer compound.
  • the polymerizable monomer is typically a low molecular compound, preferably a low molecular compound having a molecular weight of 2000 or less, more preferably a low molecular compound having a molecular weight of 1500 or less, and a low molecular compound having a molecular weight of 900 or less. More preferably it is.
  • the molecular weight of the polymerizable monomer is usually 100 or more.
  • the oligomer type polymerizable compound is typically a polymer having a relatively low molecular weight, and is preferably a polymer in which 10 to 100 polymerizable monomers are bonded.
  • the weight average molecular weight of the oligomer type polymerizable compound is preferably 2000 to 20000, more preferably 2000 to 15000, and most preferably 2000 to 10,000.
  • the number of functional groups of the polymerizable compound means the number of polymerizable groups in one molecule.
  • the photosensitive resin composition preferably contains at least one bifunctional or higher functional polymerizable compound containing two or more polymerizable groups, and preferably contains at least one trifunctional or higher functional polymerizable compound. Is more preferable. It is preferable that the photosensitive resin composition contains at least one trifunctional or higher functional polymerizable compound from the viewpoint that it can form a three-dimensional cross-linked structure to improve heat resistance. Also, a mixture of a bifunctional or lower polymerizable compound and a trifunctional or higher functional polymerizable compound may be used.
  • a compound containing a group having an ethylenically unsaturated bond; a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; an epoxy compound; an oxetane compound; and a benzoxazine compound are preferable.
  • the compound containing a group having an ethylenically unsaturated bond include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters thereof for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters thereof for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters thereof for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters thereof for
  • reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxy group, amino group, mercapto group, monofunctional or polyfunctional are also preferably used.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
  • esters of polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate.
  • Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [para (3-methacryloxy-2 -Hydroxy group Epoxy) phenyl] dimethyl methane, bis - is
  • Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
  • crotonic acid esters examples include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
  • isocrotonic acid esters examples include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
  • maleic acid esters examples include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.
  • esters examples include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59-5240. No. 1, JP-A-59-5241, JP-A-2-226149, those having an aromatic skeleton, those having an amino group described in JP-A-1-165613, etc. are preferably used. It is done.
  • amide monomers of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylic.
  • examples include amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.
  • Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.
  • urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in JP 17654, JP-B 62-39417, and JP-B 62-39418 are also suitable.
  • the compound which has a boiling point of 100 degreeC or more under a normal pressure is also preferable.
  • monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (meta ) Acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) ) Acrylate, tri
  • JP-B-46-43946 examples include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493.
  • vinyl phosphonic acid compounds examples include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493.
  • vinyl phosphonic acid compounds In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used.
  • Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photopolymerizable monomers and oligomers, can also be used.
  • n is an integer from 0 to 14, and m is an integer from 0 to 8.
  • a plurality of R and T present in the molecule may be the same or different.
  • at least one of a plurality of R is —OC ( ⁇ O) CH ⁇ CH 2 or —OC
  • a group represented by ( ⁇ O) C (CH 3 ) ⁇ CH 2 is represented.
  • Specific examples of the compound containing a group having an ethylenically unsaturated bond represented by the above formulas (MO-1) to (MO-5) are described in paragraph numbers 0248 to 0251 of JP-A-2007-2699779.
  • the compound which has been used can also be suitably used in the present invention.
  • Examples of the compound containing a group having an ethylenically unsaturated bond include dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D).
  • oligomer types can also be used.
  • preferred examples include pentaerythritol derivatives and / or dipentaerythritol derivatives of the above formulas (MO-1) and (MO-2).
  • Examples of commercially available polymerizable compounds include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, and SR-209, a bifunctional methacrylate having four ethyleneoxy chains, DPCA-60, a 6-functional acrylate having 6 pentyleneoxy chains, TPA-330, a 3-functional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10, UAB-140 manufactured by Nippon Kayaku Co., Ltd.
  • NK ester M-40G (Manufactured by Sanyo Kokusaku Pulp Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical), DPHA-40H (Nippon Kayaku Co., Ltd.) )), UA-306H, UA-306T, UA-306I, AH-600, T- 00 (manufactured by Kyoeisha Chemical Co., Ltd.), AI-600, Brenmer PME400 (manufactured by NOF Co., Ltd.), and the like.
  • Examples of the compound containing a group having an ethylenically unsaturated bond are described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765.
  • Urethane acrylates such as those described above, and urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable.
  • polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are described as polymerizable compounds. Monomers can also be used.
  • the compound containing a group having an ethylenically unsaturated bond may be a polyfunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group.
  • the polyfunctional monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. More preferred is a polyfunctional monomer having.
  • the aliphatic polyhydroxy compound in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, is pentaerythritol and / or diester. It is a pentaerythritol.
  • examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • the polyfunctional monomer having an acid group one kind may be used alone, or two or more kinds may be mixed and used.
  • a preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
  • the acid value of the polyfunctional monomer is in the above range, the production and handling properties are excellent, and further, the developability is excellent. Also, the polymerizability is good.
  • the content of the compound containing a group having an ethylenically unsaturated bond is preferably 1 to 50% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of good polymerizability and heat resistance.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 30% by mass or less.
  • the compound containing a group having an ethylenically unsaturated bond one kind may be used alone, or two or more kinds may be mixed and used.
  • the mass ratio of the resin to the compound containing a group having an ethylenically unsaturated bond is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, 90 / 10 to 50/50 is most preferable.
  • a cured film that is superior in polymerizability and heat resistance can be formed.
  • AM1 (Wherein t represents an integer of 1 to 20, R 4 represents a t-valent organic group having 1 to 200 carbon atoms, and R 5 represents a group represented by the following formula (AM2) or the following formula (AM3)). Is shown.)
  • the compound represented by the formula (AM1) is 5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the resin. More preferably, it is 10 to 35 mass parts. Further, in the total polymerizable compound, the compound represented by the following formula (AM4) is contained in an amount of 10% by mass or more and 90% by mass or less, and the compound represented by the following formula (AM5) is contained in the total thermal crosslinking agent by 10% by mass or more. It is also preferable to contain 90 mass% or less.
  • AM4 (Wherein R 4 represents a divalent organic group having 1 to 200 carbon atoms, and R 5 represents a group represented by the following formula (AM2) or the following formula (AM3)).
  • Formula (AM5) (Wherein u represents an integer of 3 to 8, R 4 represents a u-valent organic group having 1 to 200 carbon atoms, and R 5 represents a group represented by the following formula (AM2) or the following formula (AM3)). .)
  • the photosensitive resin composition layer is formed on an uneven substrate. It has excellent pattern processability and can have high heat resistance such that the 5% mass reduction temperature is 350 ° C. or higher, more preferably 380 ° C. or higher.
  • Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML.
  • Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.).
  • the photosensitive resin composition may contain a photopolymerization initiator.
  • the photosensitive resin composition contains a photo radical polymerization initiator
  • the photosensitive resin composition is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, and then irradiated with light. Curing due to radicals occurs, and the solubility in the light irradiation part can be reduced. Therefore, for example, by exposing the photosensitive resin composition layer through a photomask having a pattern in which only the electrode portion is masked, there is an advantage that regions having different solubility can be easily produced according to the electrode pattern. is there.
  • the photopolymerization initiator is not particularly limited as long as it has the ability to initiate a polymerization reaction (crosslinking reaction) of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to light in the ultraviolet region to the visible region are preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
  • the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of the compound can be measured using a known method. Specifically, for example, it is preferable to measure with a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
  • a UV-visible spectrophotometer Cary-5
  • halogenated hydrocarbon derivatives for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group
  • Acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo series
  • examples thereof include compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, and the like.
  • halogenated hydrocarbon compounds having a triazine skeleton examples include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3333724, F.I. C. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US patents Examples thereof include compounds described in the specification of No. 42122976.
  • Examples of the compounds described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloro Methyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 (2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl)- 1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) 1,3,4-oxadiazole, 2-trichloromethyl-5-
  • ketone compound examples include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein.
  • Kaya Cure DETX manufactured by Nippon Kayaku Co., Ltd.
  • Nippon Kayaku Co., Ltd. is also preferably used.
  • hydroxyacetophenone compounds As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
  • hydroxyacetophenone-based initiator IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator compounds described in JP-A-2009-191179 having a maximum absorption wavelength matched to a wavelength of 365 nm or 405 nm can also be used.
  • the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • IRGACURE-819 and IRGACURE-TPO which are commercially available products can be used.
  • the metallocene compound include IRGACURE-784 (manufactured by BASF).
  • More preferred examples of the photopolymerization initiator include oxime compounds.
  • the exposure latitude can be improved more effectively.
  • Oxime ester compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as a thermal base generator.
  • Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
  • Preferred oxime compounds include, for example, the following compounds, 3-benzooxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane- 3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2 -Ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.
  • oxime compounds include J.M. C. S. Perkin II (1979) p. 1653-1660, J.A. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995), pp. 156-162. 202-232 compounds, compounds described in JP-A-2000-66385, JP-A-2000-80068, JP-T 2004-534797, JP-A-2006-342166, international publication WO2015 Compound described in each publication of No. / 036910.
  • IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), Adekaoptomer N-1919 (manufactured by ADEKA Corporation, light described in JP2012-14052A) A polymerization initiator 2) is also preferably used.
  • TR-PBG-304 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
  • Adeka Arkles NCI-831 and Adeka Arkles NCI-930 made by ADEKA
  • DFI-091 manufactured by Daitokemix Co., Ltd.
  • JP-A-2009-221114 which have an absorption maximum at 405 nm and have good sensitivity to a g-ray light source, may be used.
  • the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 can also be suitably used.
  • cyclic oxime compounds in particular, cyclic oxime compounds fused to carbazole dyes described in JP2010-32985A and JP2010-185072A have high light absorptivity and high sensitivity. preferable.
  • a compound described in JP-A-2009-242469 which is a compound having an unsaturated bond at a specific site of the oxime compound, can also be suitably used.
  • an oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 2013.
  • Specific examples include the following compounds.
  • the most preferred oxime compound includes an oxime compound having a specific substituent described in JP-A-2007-2699779, an oxime compound having a thioaryl group disclosed in JP-A-2009-191061, and the like.
  • Photopolymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryls from the viewpoint of exposure sensitivity.
  • Selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds. are preferred.
  • More preferred photopolymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, At least one compound selected from the group consisting of a trihalomethyltriazine compound, an ⁇ -aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, and a metallocene compound or an oxime compound is more preferable, and an oxime compound. Is even more preferred.
  • Photopolymerization initiators include N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-, such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), etc.
  • Aromatic ketones such as 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, alkyl anthraquinones, etc.
  • benzoin ether compounds such as benzoin alkyl ether
  • benzoin compounds such as benzoin and alkylbenzoin
  • benzyl derivatives such as benzyldimethyl ketal.
  • a compound represented by the following formula (I) can also be used.
  • R 50 represents an alkyl group having 1 to 20 carbon atoms; an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms; an alkoxy group having 1 to 12 carbon atoms; a phenyl group; An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 1 to 12 carbon atoms, and 2 to 2 carbon atoms interrupted by one or more oxygen atoms A phenyl group substituted with at least one of 18 alkyl groups and an alkyl group having 1 to 4 carbon atoms; or biphenylyl, and R 51 is a group represented by the formula (II) or the same as R 50 R 52 to R 54 are each independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or halogen.
  • R 51 is a group represented by
  • the content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1% by mass with respect to the total solid content of the photosensitive resin composition. -20% by mass, more preferably 0.1-10% by mass. Only one type of photopolymerization initiator may be used, or two or more types may be used. When there are two or more photopolymerization initiators, the total is preferably in the above range.
  • the photosensitive resin composition further contains a migration inhibitor.
  • the migration inhibitor is not particularly limited, but a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, Compounds having pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and mercapto groups, hindered phenol compounds , Salicylic acid derivative
  • an ion trapping agent that traps anions such as halogen ions can be used.
  • migration inhibitors include rust inhibitors described in paragraph 0094 of JP2013-15701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-95956A.
  • the compounds described in paragraph 0052 and the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A can be used.
  • the migration inhibitor examples include 1H-1,2,3-triazole, 1H-1,2,4-triazole and 1H-tetrazole.
  • the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the photosensitive resin composition, 0.05 to 2.0% by mass is more preferable, and 0.1 to 1.0% by mass is more preferable. Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more types of migration inhibitors, the total is preferably in the above range.
  • the photosensitive resin composition used in the present invention preferably contains a polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone, paramethoxyphenol, di-tert-butyl-paracresol, pyrogallol, para-tert-butylcatechol, parabenzoquinone, diphenyl-parabenzoquinone, 4,4′-thiobis (3-methyl).
  • a polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and compounds described in paragraphs 0031 to 0046 of international publication WO2015 / 125469 can also be used.
  • the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the photosensitive resin composition. Only one type of polymerization inhibitor may be used, or two or more types may be used. When there are two or more polymerization inhibitors, the total is preferably in the above range.
  • the photosensitive resin composition used in the present invention may contain a thermal base generator.
  • the type of the thermal base generator is not particularly defined, but it is selected from an acidic compound that generates a base when heated to 40 ° C. or higher, and an ammonium salt having an anion having an pKa1 of 0 to 4 and an ammonium cation. It is preferable to include a thermal base generator containing at least one kind.
  • pKa1 represents the logarithm ( ⁇ Log 10 Ka) of the dissociation constant (Ka) of the first proton of the acid, details of which will be described later.
  • the cyclization reaction of the polyimide precursor and the polybenzoxazole precursor can be performed at a low temperature, and the composition can be made more stable.
  • the heat base generator does not generate a base unless it is heated, cyclization of the polyimide precursor and polybenzoxazole precursor during storage is possible even if it coexists with the polyimide precursor and polybenzoxazole precursor. And is excellent in storage stability.
  • the thermal base generator contains at least one selected from an acidic compound (A1) that generates a base when heated to 40 ° C. or higher, and an ammonium salt (A2) having an anion having an pKa1 of 0 to 4 and an ammonium cation. It is preferable. Since the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, the base generated from these compounds can promote a cyclization reaction of a polyimide precursor and a polybenzoxazole precursor, Cyclization of polyimide precursors and polybenzoxazole precursors can be performed at low temperatures.
  • the solution obtained by stirring means a compound having a value measured at 20 ° C. of less than 7 using a pH (power of hydrogen) meter.
  • the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, more preferably 120 to 200 ° C.
  • the upper limit of the base generation temperature is preferably 190 ° C. or lower, more preferably 180 ° C. or lower, and further preferably 165 ° C. or lower.
  • the lower limit of the base generation temperature is preferably 130 ° C or higher, and more preferably 135 ° C or higher. If the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C. or higher, the base is unlikely to be generated during storage.
  • a photosensitive resin composition can be prepared.
  • the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200 ° C. or lower, the cyclization temperature of the polyimide precursor, polybenzoxazole precursor, and the like can be lowered.
  • the base generation temperature is measured, for example, by using differential scanning calorimetry, heating the compound to 250 ° C. at 5 ° C./min in a pressure capsule, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.
  • the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since tertiary amine has high basicity, cyclization temperature of a polyimide precursor, a polybenzoxazole precursor, etc. can be made lower. Further, the boiling point of the base generated by the thermal base generator is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and most preferably 140 ° C. or higher. The molecular weight of the generated base is preferably 80 to 2000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. The molecular weight value is a theoretical value obtained from the structural formula.
  • the acidic compound (A1) preferably contains one or more selected from an ammonium salt and a compound represented by the formula (101) or (102) described later.
  • the ammonium salt (A2) is preferably an acidic compound.
  • the ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C. or higher (preferably 120 to 200 ° C.), or 40 ° C. or higher (preferably 120 to 200 ° C.). ) May be a compound excluding an acidic compound that generates a base when heated.
  • the ammonium salt means a salt of an ammonium cation represented by the following formula (101) or formula (102) and an anion.
  • the anion may be bonded to any part of the ammonium cation via a covalent bond, and may be outside the molecule of the ammonium cation, but may be outside the molecule of the ammonium cation. preferable.
  • numerator of an ammonium cation means the case where an ammonium cation and an anion are not couple
  • the anion outside the molecule of the cation moiety is also referred to as a counter anion.
  • R 1 to R 6 each independently represents a hydrogen atom or a hydrocarbon group
  • R 7 represents a hydrocarbon group.
  • R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 5 and R 7 in Formula (101) and Formula (102) may be bonded to each other to form a ring.
  • the ammonium cation is preferably represented by any of the following formulas (Y1-1) to (Y1-5).
  • R 101 represents an n-valent organic group
  • R 1 and R 7 have the same meanings as formula (101) or formula (102).
  • Ar 101 and Ar 102 each independently represent an aryl group
  • n represents an integer of 1 or more
  • m represents an integer of 0 to 5 .
  • the ammonium salt preferably has an anion having an pKa1 of 0 to 4 and an ammonium cation.
  • the upper limit of the anion pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less.
  • the lower limit is preferably 0.5 or more, and more preferably 1.0 or more. If the pKa1 of the anion is in the above range, the polyimide precursor and the polybenzoxazole precursor can be cyclized at a low temperature, and further, the stability of the photosensitive resin composition containing the polyimide precursor and the polybenzoxazole precursor, etc. Can be improved.
  • pKa1 is 4 or less, the stability of the thermal base generator is good, the generation of a base without heating can be suppressed, and the stability of the photosensitive resin composition containing a polyimide precursor and a polybenzoxazole precursor, etc. Good properties. If pKa1 is 0 or more, the generated base is not easily neutralized, and the cyclization efficiency of the polyimide precursor and polybenzoxazole precursor is good.
  • the kind of anion is preferably one kind selected from a carboxylic acid anion, a phenol anion, a phosphate anion and a sulfate anion, and a carboxylic acid anion is more preferred because both the stability of the salt and the thermal decomposability can be achieved.
  • the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
  • the carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion.
  • it can be set as the thermal base generator which can improve more stability, sclerosis
  • an anion of a divalent carboxylic acid the stability, curability and developability of the photosensitive resin composition containing a polyimide precursor and a polybenzoxazole precursor can be further improved.
  • the carboxylic acid anion is preferably a carboxylic acid anion having a pKa1 of 4 or less.
  • pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less. According to this aspect, the stability of the photosensitive resin composition containing a polyimide precursor and a polybenzoxazole precursor can be further improved.
  • pKa1 represents the logarithm of the reciprocal of the dissociation constant of the first proton of the acid, and the determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, D.H., Hafliger Ed .: Braude, EA, Nachod, FC; Academic Press, New York, 1955), and Data for Biochemical Research (author: Dawson, R. M.). al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs) are used.
  • the carboxylate anion is preferably represented by the following formula (X1).
  • EWG represents an electron withdrawing group.
  • the electron withdrawing group means a group having a positive Hammett's substituent constant ⁇ m.
  • ⁇ m is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) p. 631-642.
  • the electron withdrawing group in this invention is not limited to the substituent described in the said literature.
  • Me represents a methyl group
  • Ac represents an acetyl group
  • Ph represents a phenyl group.
  • EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
  • R x1 to R x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group or a carboxyl group, and Ar represents an aromatic group Represents.
  • the carboxylate anion is preferably represented by the following formula (XA).
  • Formula (XA) In the formula (XA), L 10 represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an aromatic group, —NR X —, and a combination thereof, and R X represents a hydrogen atom Represents an alkyl group, an alkenyl group or an aryl group.
  • carboxylate anion examples include a maleate anion, a phthalate anion, an N-phenyliminodiacetic acid anion, and an oxalate anion. These can be preferably used.
  • thermal base generator examples include the following compounds.
  • the content of the thermal base generator in the photosensitive resin composition is preferably 0.1 to 50% by mass with respect to the total solid content of the photosensitive resin composition.
  • the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
  • One type or two or more types of thermal base generators can be used. When using 2 or more types, it is preferable that a total amount is the said range.
  • the photosensitive resin composition used in the present invention preferably contains a metal adhesion improver for improving the adhesion with a metal material used for electrodes, wirings and the like.
  • the metal adhesion improver include sulfide compounds described in paragraphs 0046 to 0049 of JP2014-186186A and paragraphs 0032 to 0043 of JP2013-072935A.
  • the metal adhesion improver also include the following compounds (N- [3- (triethoxysilyl) propyl] maleic acid monoamide and the like).
  • the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the resin.
  • Adhesiveness between the cured film and the metal layer after the curing step becomes good by setting it to 0.1 parts by mass or more, and heat resistance and mechanical properties of the cured film after the curing process are good by setting it to 30 parts by mass or less.
  • Solvent When making the photosensitive resin composition used by this invention into a layer form by application
  • esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone, and ⁇ -caprolactone , ⁇ -valerolactone, alkyl oxyacetate alkyl (eg, methyl oxyacetate, alkyl oxyacetate ethyl, alkyl oxyacetate butyl (eg methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc.) )), 3-alkyloxypropionic acid alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl
  • ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Preferred examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
  • ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like.
  • aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
  • Preferred examples of the sulfoxides include dimethyl sulfoxide.
  • the solvent is preferably in the form of a mixture of two or more types from the viewpoint of improving the coated surface.
  • a mixed solution composed of two or more selected from dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable.
  • the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
  • the content of the solvent is preferably such that the total solid concentration of the photosensitive resin composition is 5 to 80% by mass from the viewpoint of applicability. 70 mass% is more preferable, and 10 to 60 mass% is particularly preferable.
  • the content of the solvent may be adjusted according to the desired thickness and coating method. For example, if the coating method is spin coating or slit coating, the content of the solvent having a solid content concentration in the above range is preferable. In the case of spray coating, the amount is preferably 0.1% by mass to 50% by mass, and more preferably 1.0% by mass to 25% by mass.
  • a photosensitive resin composition layer having a desired thickness can be uniformly formed by adjusting the content of the solvent according to the coating method.
  • One type of solvent may be sufficient and two or more types may be sufficient. When there are two or more solvents, the total is preferably in the above range.
  • the contents of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide are determined based on the total mass of the photosensitive resin composition from the viewpoint of film strength. Is less than 5% by weight, more preferably less than 1% by weight, particularly preferably less than 0.5% by weight, and particularly preferably less than 0.1% by weight.
  • the photosensitive resin composition used in the present invention has various types of additives, for example, a photobase generator, a thermal polymerization initiator, a thermal acid generator, and a silane, as necessary, as long as the effects of the present invention are not impaired.
  • Coupling agents, sensitizing dyes, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc. can be blended. .
  • the total blending amount is preferably 3% by mass or less of the solid content of the composition.
  • the photosensitive resin composition used in the present invention may contain a photobase generator.
  • a photobase generator generates a base upon exposure and does not exhibit activity under normal conditions of normal temperature and pressure. However, when an electromagnetic wave is irradiated and heated as an external stimulus, the base (basic substance) is generated. ) Is not particularly limited as long as it generates. Since the base generated by exposure works as a catalyst for curing the polyimide precursor, the benzoxazole precursor and the like by heating, it can be suitably used in the negative type.
  • the content of the photobase generator is not particularly limited as long as a desired pattern can be formed, and can be a general content.
  • the photobase generator is preferably in the range of 0.01 parts by weight or more and less than 30 parts by weight with respect to 100 parts by weight of the resin, more preferably in the range of 0.05 parts by weight to 25 parts by weight. Preferably, it is in the range of 0.1 to 20 parts by mass. Only one type of photobase generator may be used, or two or more types may be used. When there are two or more photobase generators, the total is preferably in the above range.
  • photobase generators can be used.
  • M.M. Shirai, and M.M. Tsunooka Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kadooka, polymer processing, 46, 2 (1997); Kutal, Coord. Chem. Rev. , 211, 353 (2001); Kaneko, A .; Sarker, and D.C. Neckers, Chem. Mater. 11, 170 (1999); Tachi, M .; Shirai, and M.M. Tsunooka, J. et al. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K.K. Graziano, J. et al. Photopolym.
  • transition metal compound complexes those having a structure such as an ammonium salt, and those formed by salt formation of an amidine moiety with a carboxylic acid
  • the photobase generator that can be used in the present invention is not particularly limited and known ones can be used.
  • the photobase generator include photobase generators having a cinnamic amide structure as disclosed in JP2009-80452A and International Publication WO2009 / 123122, JP2006-1889591 and JP Photobase generator having a carbamate structure as disclosed in Japanese Patent Application Laid-Open No. 2008-247747, light having an oxime structure and a carbamoyloxime structure as disclosed in Japanese Patent Application Laid-Open Nos. 2007-249013 and 2008-003581 Although a base generator etc.
  • photobase generators include compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-93746A, compounds described in paragraphs 0022 to 0069 of JP2013-194205, Examples thereof include the compounds described in paragraphs 0026 to 0074 of JP2013-204019A and the compounds described in paragraph 0052 of WO2010 / 064631.
  • the photosensitive resin composition used in the present invention may contain a thermal polymerization initiator (preferably a thermal radical polymerization initiator).
  • a thermal radical polymerization initiator a known thermal radical polymerization initiator can be used.
  • the thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can be advanced when the cyclization reaction of the polyimide precursor and the polybenzoxazole precursor is advanced.
  • the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.
  • the content of the thermal radical polymerization initiator is preferably from 0.1 to 50% by mass, preferably from 0.1 to 50% by weight based on the total solid content of the photosensitive resin composition. 30% by mass is more preferable, and 0.1 to 20% by mass is particularly preferable. Further, the thermal radical polymerization initiator is preferably contained in an amount of 0.1 to 50 parts by mass, and more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the polymerizable compound. According to this aspect, it is easy to form a cured film having more excellent heat resistance. Only one type of thermal radical polymerization initiator may be used, or two or more types may be used. When there are two or more thermal radical polymerization initiators, the total is preferably in the above range.
  • the photosensitive resin composition used in the present invention may contain a thermal acid generator.
  • the thermal acid generator generates an acid by heating, promotes cyclization of the polyimide precursor and the polybenzoxazole precursor, and further improves the mechanical properties of the cured film. Furthermore, the thermal acid generator has an effect of accelerating the crosslinking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound.
  • thermal acid generator examples include those described in paragraph 0055 of JP2013-072935A.
  • JP2013-167742A is also preferable as the thermal acid generator.
  • the content of the thermal acid generator is preferably 0.01 parts by mass or more and more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the polyimide precursor and the polybenzoxazole precursor.
  • the content of the thermal acid generator is preferably 0.01 parts by mass or more and more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the polyimide precursor and the polybenzoxazole precursor.
  • 0.01 part by mass or more By containing 0.01 part by mass or more, the crosslinking reaction and the cyclization of the polyimide precursor and the polybenzoxazole precursor are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved.
  • 20 mass parts or less are preferable from a viewpoint of the electrical insulation of a cured film, 15 mass parts or less are more preferable, and 10 mass parts or less are especially preferable.
  • One type of thermal acid generator may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes
  • the photosensitive resin composition used in the present invention may contain a silane coupling agent in order to improve the adhesion to the substrate.
  • a silane coupling agent examples include compounds described in paragraphs 0062 to 0073 of JP-A No. 2014-191002, compounds described in paragraphs 0063 to 0071 of international publication WO 2011 / 080992A1, and JP-A No. 2014-191252.
  • Examples thereof include compounds described in paragraphs 0060 to 0061, compounds described in paragraphs 0045 to 0052 of JP 2014-41264 A, and compounds described in paragraph 0055 of international publication WO 2014/097594.
  • the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin. When it is 0.1 part by mass or more, sufficient adhesion to the substrate can be imparted, and when it is 20 parts by mass or less, problems such as an increase in viscosity during storage at room temperature can be further suppressed. Only one type of silane coupling agent may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • the photosensitive resin composition used in the present invention may contain a sensitizing dye.
  • a sensitizing dye absorbs specific actinic radiation and enters an electronically excited state.
  • the sensitizing dye in an electronically excited state comes into contact with an amine generator, a thermal radical polymerization initiator, a photopolymerization initiator, and the like, and effects such as electron transfer, energy transfer, and heat generation occur.
  • the amine generator, the thermal radical polymerization initiator, and the photopolymerization initiator are decomposed by causing a chemical change to generate radicals, acids, or bases.
  • preferable sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in the region of 300 nm to 450 nm.
  • polynuclear aromatics for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9.10-dialkoxyanthracene
  • xanthenes for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
  • thioxanthones for example, 2,4-diethylthioxanthone
  • cyanines for example thiacarbocyanine, oxacarbocyanine
  • merocyanines for example merocyanine, carbomerocyanine
  • thiazines for example thionine, methylene blue, toluidine blue
  • acridines Eg, acridine orange, chloroflavin, acriflavine
  • anthrdines
  • the content of the sensitizing dye is preferably 0.01 to 20% by mass, and preferably 0.1 to 15% by mass with respect to the total solid content of the photosensitive resin composition. Is more preferable, and 0.5 to 10% by mass is even more preferable.
  • a sensitizing dye may be used individually by 1 type, and may use 2 or more types together.
  • the photosensitive resin composition used in the present invention may contain a chain transfer agent.
  • the chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (edited by the Polymer Society, 2005) pages 683-684.
  • As the chain transfer agent for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can generate hydrogen by donating hydrogen to a low activity radical to generate a radical, or after being oxidized and deprotonated.
  • thiol compounds for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.
  • 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc. can be preferably used.
  • the preferable content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 100 parts by mass based on the total solid content of the photosensitive resin composition. 1 to 10 parts by mass, particularly preferably 1 to 5 parts by mass. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more chain transfer agents, the total is preferably within the above range.
  • surfactant Various types of surfactants may be added to the photosensitive resin composition used in the present invention from the viewpoint of further improving applicability.
  • the surfactant various types of surfactants such as a fluorosurfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.
  • the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0, based on the total solid content of the photosensitive resin composition. 0.005 to 1.0 mass%. Only one type of surfactant may be used, or two or more types may be used. When two or more surfactants are used, the total is preferably in the above range.
  • a higher fatty acid derivative such as behenic acid or behenamide
  • the photosensitive resin composition has a higher fatty acid derivative
  • the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the photosensitive resin composition. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When two or more types of higher fatty acid derivatives are used, the total is preferably within the above range.
  • a crosslinked structure is constructed by exposure to reduce the solubility in an organic solvent.
  • the adhesion between the layers can be increased when the photosensitive resin composition layer is laminated.
  • the solubility of the photosensitive resin composition layer in the organic solvent is reduced by exposure, which is advantageous when a deep groove or a deep hole is provided when the number of stacked layers is increased.
  • the water content of the photosensitive resin composition used in the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass from the viewpoint of the coated surface.
  • the metal content of the photosensitive resin composition used in the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and particularly preferably less than 0.5 ppm by mass from the viewpoint of insulation.
  • the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are included, the total of these metals is preferably in the above range.
  • a raw material having a low metal content is selected as a raw material constituting the photosensitive resin composition.
  • the raw material to be filtered may be filtered, or the inside of the apparatus may be lined with polytetrafluoroethylene or the like to perform distillation under a condition in which contamination is suppressed as much as possible.
  • the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and particularly preferably less than 200 ppm by mass from the viewpoint of wiring corrosion.
  • a halogen ion is less than 5 mass ppm, More preferably, it is less than 1 mass ppm, Especially less than 0.5 mass ppm is preferable.
  • the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms, or chloride ions and bromide ions is preferably in the above range.
  • the manufacturing method of the laminated body of this invention may include the process of drying a solvent, after forming the photosensitive resin composition layer.
  • a preferable drying temperature is 50 to 150 ° C., more preferably 70 to 130 ° C., and further preferably 90 to 110 ° C.
  • the drying time is preferably 30 seconds to 20 minutes, more preferably 1 minute to 10 minutes, and further preferably 3 minutes to 7 minutes.
  • the manufacturing method of the laminated body of this invention includes the exposure process which exposes the photosensitive resin composition layer.
  • the conditions for exposure are not particularly defined, and the solubility of the exposed portion of the photosensitive resin composition in the developer is preferably changed, and more preferably the exposed portion of the photosensitive resin composition can be cured.
  • the photosensitive resin composition layer is preferably irradiated with 100 to 10,000 mJ / cm 2 , more preferably 200 to 8000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm.
  • the exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, and is preferably 240 to 550 nm.
  • Exposure may be performed by pattern exposure, or exposure may be performed by uniform irradiation over the entire surface.
  • the manufacturing method of the laminated body of this invention includes the image development process process which performs image development processing with respect to the exposed photosensitive resin composition layer.
  • the development processing step is preferably a negative development processing step. By performing the negative development processing, the unexposed portion (non-exposed portion) is removed.
  • the development method is not particularly limited, and it is preferable that a desired pattern can be formed. For example, development methods such as paddle, spray, immersion, and ultrasonic waves can be employed. In the present invention, it is preferable to perform the development processing step even when exposure is performed with uniform irradiation over the entire surface. Development is preferably performed using a developer. The developer can be used without particular limitation as long as the unexposed part (non-exposed part) is removed.
  • esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, alkyl oxyacetate alkyl (eg, methyl oxyacetate, alkyl oxyacetate, butyl oxyalkyl acetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxy) Methyl acetate, ethyl ethoxyacetate, etc.), alkyl esters of 3-alkyloxypropionic acid (eg, methyl 3-alkyloxypropionat
  • ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like.
  • aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
  • Preferred examples of the sulfoxides include dimethyl sulfoxide.
  • the development time is preferably 10 seconds to 5 minutes.
  • the temperature at the time of development is not particularly defined, but it can usually be carried out at 20 to 40 ° C.
  • rinsing may be further performed.
  • the rinsing is preferably performed with a solvent different from the developer. For example, it can rinse using the solvent contained in the photosensitive resin composition.
  • the rinse time is preferably 5 seconds to 1 minute.
  • the manufacturing method of the laminated body of this invention includes the hardening process which hardens the photosensitive resin composition layer after image development processing.
  • the curing step preferably includes a temperature raising step for raising the temperature of the photosensitive resin composition layer and a cooling step for cooling the photosensitive resin composition layer after the temperature raising step.
  • the curing step (particularly the temperature raising step and the holding step) is preferably performed in a low oxygen concentration atmosphere by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the resin.
  • the oxygen concentration is preferably 50 ppm by volume or less, more preferably 20 ppm by volume or less.
  • the temperature raising step is preferably a step of raising the temperature of the photosensitive resin composition layer to a temperature equal to or higher than the glass transition temperature.
  • the resins preferably polyimide precursor and polybenzoxazole precursor
  • polyimide and polybenzoxazole can form a three-dimensional network structure when heated with a crosslinking agent.
  • curing of an unreacted radically polymerizable compound can be advanced.
  • the final temperature reached in the temperature raising step is preferably the imidization temperature of the resin contained in the photosensitive resin composition layer.
  • the final temperature reached in the temperature raising step is preferably the highest heating temperature.
  • the maximum heating temperature is preferably 100 to 500 ° C., more preferably 150 to 450 ° C., and further preferably 160 to 350 ° C.
  • the final temperature reached in the heating step is particularly preferably 250 ° C. or less from the viewpoint of stress relaxation.
  • the temperature raising step is preferably performed at a temperature rising rate of 1 to 12 ° C./min from a temperature of 20 to 150 ° C. to the maximum heating temperature, more preferably 2 to 11 ° C./min, and further 3 to 10 ° C./min. preferable.
  • the temperature at the start of heating is preferably 20 to 150 ° C., more preferably 20 to 130 ° C., and further preferably 25 to 120 ° C.
  • the temperature at the start of heating refers to the heating temperature at the start of the step of heating to the maximum heating temperature.
  • the temperature is the temperature after drying, for example, gradually from the boiling point of the solvent contained in the photosensitive resin composition— (30 to 200) ° C. It is preferable to raise the temperature to
  • Heating may be performed in stages. As an example, before raising the temperature from 25 ° C. to 180 ° C. at 3 ° C./min, placing at 180 ° C. for 60 minutes, raising the temperature from 180 ° C. to 200 ° C. at 2 ° C./min, and placing at 200 ° C. for 120 minutes. Processing steps may be performed.
  • the heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and most preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating UV as described in US Pat. No. 9,159,547. Such a pretreatment step can improve the properties of the cured film.
  • the pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
  • the pretreatment process may be performed in two or more steps.
  • the pretreatment process 1 may be performed in the range of 100 to 150 ° C.
  • the pretreatment process 2 may be performed in the range of 150 to 200 ° C.
  • the temperature raising step is preferably 20 to 200 minutes, more preferably 20 to 100 minutes, and particularly preferably 20 to 60 minutes.
  • the manufacturing method of the laminated body of this invention includes the holding process hold
  • the heating is preferably performed at a holding temperature equal to the final temperature of the temperature raising step for 30 to 360 minutes, more preferably 30 to 300 minutes, more preferably 30 to 240. It is particularly preferable to perform heating for a minute, and it is particularly preferable to perform heating for 60 to 240 minutes.
  • the time required for the holding process is referred to as holding time.
  • the holding temperature in the holding step is preferably 150 to 450 ° C., more preferably 160 to 350 ° C. In the method for producing a laminate of the present invention, the holding temperature in the holding step is particularly preferably 250 ° C. or less from the viewpoint of stress relaxation.
  • the cooling step is preferably a step of cooling the photosensitive resin composition layer at a temperature lowering rate of 2 ° C./min or less after the temperature raising step.
  • the cooling rate in the cooling step is preferably 2 ° C./min or less, more preferably 1 ° C./min or less.
  • the cooling rate in the cooling step is preferably 0.1 ° C./min or more from the viewpoint of stress relaxation.
  • the cooling rate in the cooling step is preferably slower than the heating rate in the heating step from the viewpoint of stress relaxation.
  • the cooling step is preferably 30 to 600 minutes, more preferably 60 to 600 minutes, and particularly preferably 120 to 600 minutes.
  • the final temperature reached in the cooling step is preferably 30 ° C. or more lower than the glass transition temperature (Tg) of the photosensitive resin composition layer (cured film) after the curing step. If the final temperature in the cooling step is lowered to a temperature that is 30 ° C. or more lower than the Tg of the photosensitive resin composition layer, the polyimide is sufficiently cured and it is easy to suppress the occurrence of delamination.
  • the final ultimate temperature in the cooling step is more preferably 160 to 250 ° C., and particularly preferably 180 to 230 ° C. lower than the glass transition temperature of the photosensitive resin composition layer after the curing step.
  • Step of bringing to room temperature After the photosensitive resin composition layer reaches the final temperature reached in the cooling step, it is preferable to include a step of cooling the photosensitive resin composition layer at an arbitrary temperature lowering rate to room temperature. There is no restriction
  • the temperature lowering rate in the step of bringing to room temperature can be set to 5 to 10 ° C./min, for example.
  • the method for producing a laminate of the present invention includes a metal layer forming step of forming a metal layer by vapor phase film formation on the surface of the photosensitive resin composition layer after the curing step, The temperature of the photosensitive resin composition layer after the curing step when forming the metal layer is lower than the glass transition temperature of the photosensitive resin composition layer after the curing step.
  • the temperature of the photosensitive resin composition layer when forming the metal layer is preferably 30 ° C. or more lower than the glass transition temperature of the photosensitive resin composition layer, and is 30 to 200 ° C. lower. It is more preferable that the temperature is lower by 100 to 200 ° C.
  • the temperature of the photosensitive resin composition layer is preferably within the above range.
  • the temperature of the photosensitive resin composition layer after the curing step when forming the second metal layer is not particularly limited. However, when there is a portion provided directly on the photosensitive resin composition layer even if it is the second metal layer, the photosensitive resin composition layer after the curing step when forming the second metal layer The temperature is preferably within the above range. In particular, when the second metal layer is formed using vapor deposition, the temperature of the photosensitive resin composition layer after the curing step when forming the second metal layer is also in the above range. preferable.
  • the temperature of the photosensitive resin composition layer after the curing step in forming the second metal layer is generally used. Becomes less than the glass transition temperature of the photosensitive resin composition layer.
  • the metal layer formed in the metal layer forming step is not particularly limited, and an existing metal can be used.
  • the metal contained in the metal layer formed in the metal layer forming step include copper, aluminum, nickel, vanadium, titanium, tantalum, chromium, cobalt, gold and tungsten, and compounds containing at least one of these (including alloys). Is exemplified.
  • the metal layer formed in the metal layer forming step contains at least one of titanium, tantalum, and copper and at least one of these compounds. It is particularly preferable that at least one of copper and copper and a compound containing at least one of them is included, and it is more preferable that copper is included.
  • the metal layer contains at least one of titanium, tantalum and copper and a compound containing at least one of them include a metal layer made of titanium, tantalum, copper, TiN, TaN or TiW.
  • a metal layer made of titanium, tantalum, copper, TiN or TiW is preferable.
  • the metal contained in the metal layer formed in the metal layer forming step may be one type or two or more types.
  • the thickness of the metal layer formed in the metal layer forming step is preferably 50 to 2000 nm, more preferably 50 to 1000 nm, and 100 to 300 nm. Is particularly preferred.
  • the metal layer formed in the metal layer forming step may be one layer or two or more layers. When the metal layer formed in the metal layer forming step is one layer, the metal layer is preferably used as a barrier metal film. When the number of metal layers formed in the metal layer forming step is two or more, it is preferable that the thickness of the entire metal layer formed in the metal layer forming step is in the above range.
  • the metal layer formed in the metal layer forming step is preferably a laminated body of a barrier metal film and a seed layer.
  • the barrier metal film is preferably a layer that can shorten the penetration length of the metal into the cured film.
  • the metal type of the barrier metal film is preferably the metal described above as the metal included in the metal layer formed in the metal layer forming step.
  • the thickness of the barrier metal film is preferably 50 to 2000 nm, more preferably 50 to 1000 nm, and particularly preferably 100 to 300 nm.
  • the seed layer is preferably a layer for facilitating the formation of the pattern of the second metal layer formed in the second metal layer forming step.
  • the metal type of the seed layer is preferably the same type of metal as the second metal layer formed in the second metal layer forming step.
  • the thickness of the seed layer is preferably 50 to 2000 nm, more preferably 50 to 1000 nm, and particularly preferably 100 to 300 nm.
  • the formation method of the metal layer is not particularly limited, and an existing vapor deposition method can be applied.
  • a sputtering method, chemical vapor deposition (CVD), a plasma method, and a combination thereof may be considered.
  • the metal layer forming method is preferably a sputtering method from the viewpoint of film thickness control.
  • the manufacturing method of the laminated body of this invention further includes the 2nd metal layer formation process which forms a 2nd metal layer in the surface of a metal layer.
  • the second metal layer formed in the second metal layer forming step is not particularly limited, and an existing metal can be used.
  • the metal contained in the second metal layer formed in the second metal layer forming step include copper, aluminum, nickel, vanadium, titanium, tantalum, chromium, cobalt, gold, and tungsten.
  • the manufacturing method of the laminated body of this invention is preferable from a viewpoint which uses the laminated body of this invention as a rewiring layer of a semiconductor element that a 2nd metal layer contains copper.
  • the thickness of the second metal layer formed in the second metal layer forming step is, for example, 3 to 50 ⁇ m, preferably 3 to 10 ⁇ m, and preferably 5 to 10 ⁇ m. Is more preferable, and 5 to 7 ⁇ m is particularly preferable.
  • the thickness of the second metal layer formed in the second metal layer forming step is preferably 35 to 50 ⁇ m.
  • the method for forming the second metal layer is not particularly limited, and an existing method can be applied.
  • the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, and JP 2004-101850 A can be used.
  • photolithography, lift-off, chemical vapor deposition (CVD), electrolytic plating, electroless plating, etching, printing, and a combination thereof may be considered.
  • CVD chemical vapor deposition
  • electrolytic plating electroless plating
  • etching printing, and a combination thereof
  • a patterning method that combines photolithography and etching a patterning method that combines photolithography and electrolytic plating
  • a patterning method that combines photolithography, electrolytic plating, and etching may be mentioned.
  • a seed layer of a metal layer formed in the metal layer forming step is formed by sputtering, and then a pattern of the seed layer is formed by photolithography.
  • a method of forming a second metal layer by performing electrolytic plating on the layer is preferable. Thereafter, further etching may be performed to remove the seed layer in the region where the second metal layer is not formed.
  • the manufacturing method of a laminated body may also include the surface activation process process of carrying out the surface activation process of at least one part of the said metal layer and the photosensitive resin composition layer.
  • the surface activation treatment step is usually preferably performed after the metal layer formation step.
  • a metal layer may be formed after performing a surface activation treatment step on the photosensitive resin composition layer.
  • the surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the photosensitive resin composition layer after the curing step, or may be performed on the photosensitive layer after the metal layer and the curing step.
  • Each of the conductive resin composition layers may be performed at least partially.
  • the surface activation treatment is preferably performed on at least a part of the metal layer, and the surface activation treatment is performed on a part or all of a region of the metal layer on which the photosensitive resin composition layer is further formed. Is more preferable. Thus, by performing the surface activation treatment on the surface of the metal layer, it is possible to improve the adhesion with the cured film provided on the surface.
  • the surface activation treatment is also preferably performed on part or all of the photosensitive resin composition layer (cured film) after the curing step. Thus, by performing the surface activation treatment on the surface of the photosensitive resin composition layer, it is possible to improve the adhesion with a metal layer or a cured film provided on the surface subjected to the surface activation treatment.
  • the exposed portion is subjected to surface treatment, and the strength of the film is improved by curing or the like, so that the photosensitive resin composition layer (cured film) is not damaged.
  • the surface activation treatment plasma treatment of various kinds of source gases (oxygen, hydrogen, argon, nitrogen, nitrogen and hydrogen mixed gas, and argon and oxygen mixed gas); corona discharge treatment; CF Etching treatment using 4 and O 2 mixed gas, NF 3 and O 2 mixed gas, SF 6 , NF 3 , and NF 3 and O 2 mixed gas; surface treatment using ultraviolet (UV) ozone method; aqueous hydrochloric acid solution It is preferably selected from an immersion treatment in an organic surface treatment agent containing a compound having at least one amino group and a thiol group after removing the oxide film by immersion in a surface; mechanical roughening treatment using a brush .
  • source gases oxygen, hydrogen, argon, nitrogen, nitrogen and hydrogen mixed gas, and argon and oxygen mixed gas
  • corona discharge treatment corona discharge treatment
  • Plasma treatment is more preferred, and oxygen plasma treatment using oxygen as the source gas is particularly preferred.
  • the energy is preferably 500 ⁇ 200000J / m 2, more preferably 1000 ⁇ 100000J / m 2, more preferably 10000 ⁇ 50000J / m 2.
  • the photosensitive resin composition layer forming step, the exposure step, the development processing step, the curing step, and the metal layer forming step are again performed in the order described above. Preferably it is done. In this case, since the metal layer forming step is repeated, the effect of suppressing delamination particularly when the substrate, the cured film, and the metal layer are laminated is great.
  • the laminating step is more preferably a step in which the photosensitive resin composition layer forming step, the exposure step, the development processing step, the curing step, the metal layer forming step, and the second metal layer forming step are performed in the above order.
  • the surface activation treatment process can be further performed after the exposure process or after the metal layer formation process.
  • the lamination step is preferably performed 3 to 7 times, more preferably 3 to 5 times.
  • the configuration of the cured film is preferably 3 or more and 7 or less, more preferably 3 or more and 5 or less, such as cured film / metal layer / cured film / metal layer / cured film / metal layer.
  • the metal layer / cured film interface resulting from the method for producing a laminate of the present invention or And the effect of suppressing the occurrence of delamination at the cured film / cured film interface.
  • the photosensitive resin composition layer (cured film) and a metal layer can be laminated
  • the laminate of the present invention has a substrate, a pattern cured film, and a metal layer located on the surface of the pattern cured film,
  • the pattern cured film contains polyimide or polybenzoxazole,
  • the penetration of the metal constituting the metal layer located on the surface of the pattern cured film into the pattern cured film is 130 nm or less from the surface of the pattern cured film.
  • the pattern cured film in the laminated body of this invention is the photosensitive resin composition layer after the hardening process in the manufacturing method of the laminated body of this invention.
  • the glass transition temperature of the pattern cured film is preferably 150 to 300 ° C, more preferably 160 to 250 ° C, and particularly preferably 180 to 230 ° C. preferable.
  • Pattern cured film (photosensitive resin composition layer after curing step.
  • photosensitive resin composition layer after metal layer forming step More preferably, photosensitive resin after metal layer forming step and second metal layer forming step.
  • the residual stress measured according to the laser measurement method of the composition layer is preferably less than 35 MPa, more preferably less than 25 MPa, and particularly preferably less than 15 MPa.
  • the metal layer in the laminate of the present invention is preferably a metal layer formed in the metal layer forming step in the laminate production method of the present invention.
  • the metal layer in the laminated body of the present invention includes a metal layer formed in the metal layer forming step and a second metal layer formed in the second metal layer forming step in the laminate manufacturing method of the present invention.
  • a laminated body may be sufficient.
  • the metal layer formed in the metal layer forming step in the laminate manufacturing method of the present invention and the second metal layer formed in the second metal layer forming step are integrated to form the laminate of the present invention. It may be a metal layer.
  • the metal layer formed in the metal layer forming step in the laminate manufacturing method of the present invention is, for example, two layers of a barrier metal film and a seed layer, and the second metal layer is formed in the second metal layer forming step.
  • the metal layer is the same type of metal as the seed layer, only the seed layer and the second metal layer may be integrated.
  • a laminated body of a layer in which only the seed layer and the second metal layer are integrated and the barrier metal film may be a metal layer in the laminated body of the present invention.
  • the thickness of the metal layer in the laminate of the present invention is preferably 0.1 to 50 ⁇ m, more preferably 1 to 10 ⁇ m at the thickest part.
  • the metal layer in the laminate of the present invention is preferably a flat metal layer from the viewpoint of stabilizing the film quality of the metal layer.
  • a flat metal layer can be formed by forming a metal layer using a sputtering method. Further, the metal layer is formed by sputtering under the condition that the temperature of the photosensitive resin composition layer after the curing step when forming the metal layer is lower than the glass transition temperature of the photosensitive resin composition layer after the curing step. By doing so, a flatter metal layer can be formed.
  • the penetration length of the metal constituting the metal layer located on the surface of the pattern cured film into the pattern cured film is 130 nm or less from the surface of the pattern cured film, preferably 50 nm or less, and more preferably 30 nm or less. preferable.
  • the method for manufacturing a semiconductor element of the present invention includes the method for manufacturing a laminated body of the present invention. With the above configuration, the method for manufacturing a semiconductor element of the present invention can provide a semiconductor element in which delamination is suppressed when a substrate, a cured film, and a metal layer are stacked.
  • FIG. 1 is a schematic view showing a configuration of an embodiment of a semiconductor element.
  • a semiconductor element 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a semiconductor chip 101 in which a plurality of semiconductor chips 101 a to 101 d are stacked is arranged on a wiring board 120.
  • the number of stacked semiconductor chips is four will be mainly described.
  • the number of stacked semiconductor chips is not particularly limited. For example, two, eight, sixteen, It may be 32 layers. Moreover, one layer may be sufficient.
  • Each of the plurality of semiconductor chips 101a to 101d is made of a semiconductor wafer such as a silicon substrate.
  • the uppermost semiconductor chip 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof.
  • the semiconductor chips 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) provided integrally with the through electrodes are provided on both surfaces of each semiconductor chip.
  • the semiconductor chip 101 has a structure in which a semiconductor chip 101a that does not have through electrodes and semiconductor chips 101b to 101d that have through electrodes 102b to 102d are flip-chip connected. That is, the electrode pad of the semiconductor chip 101a having no through electrode and the connection pad on the semiconductor chip 101a side of the semiconductor chip 101b having the adjacent through electrode 102b are connected by the metal bump 103a such as a solder bump. .
  • the connection pad on the other side of the semiconductor chip 101b having the through electrode 102b is connected to the connection pad on the semiconductor chip 101b side of the semiconductor chip 101c having the adjacent through electrode 102c by a metal bump 103b such as a solder bump. .
  • connection pad on the other side of the semiconductor chip 101c having the through electrode 102c is connected to the connection pad on the semiconductor chip 101c side of the semiconductor chip 101d having the adjacent through electrode 102d by the metal bump 103c such as a solder bump.
  • the metal bump 103c such as a solder bump.
  • An underfill layer 110 is formed in the gap between the semiconductor chips 101a to 101d, and the semiconductor chips 101a to 101d are stacked via the underfill layer 110.
  • the semiconductor chip 101 is stacked on the wiring substrate 120.
  • the wiring substrate 120 for example, a multilayer wiring substrate using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a base material is used.
  • the wiring substrate 120 to which the resin substrate is applied include a multilayer copper clad laminate (multilayer printed wiring board).
  • a surface electrode 120 a is provided on one surface of the wiring board 120.
  • An insulating layer 115 on which a rewiring layer 105 is formed is disposed between the wiring board 120 and the semiconductor chip 101, and the wiring board 120 and the semiconductor chip 101 are electrically connected via the rewiring layer 105. It is connected.
  • the photosensitive resin composition layer (cured film) after the curing step in the present invention can be used.
  • the insulating layer 115 on which the rewiring layer 105 is formed a laminate obtained by the laminate manufacturing method of the present invention can be used.
  • One end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor chip 101d on the rewiring layer 105 side via a metal bump 103d such as a solder bump.
  • the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump.
  • An underfill layer 110 a is formed between the insulating layer 115 and the semiconductor chip 101.
  • an underfill layer 110 b is formed between the insulating layer 115 and the wiring substrate 120.
  • FIG. 2 is a schematic view showing the configuration of an embodiment of a laminate obtained by the laminate production method of the present invention. Specifically, FIG. 2 shows an example in which a laminate obtained by the method for producing a laminate of the present invention is used as a rewiring layer.
  • 200 indicates a laminate obtained by the method of the present invention
  • 201 indicates a photosensitive resin composition layer (cured film)
  • 203 indicates a metal layer.
  • the metal layer 203 is a layer indicated by oblique lines.
  • the photosensitive resin composition layer 201 is formed in a desired pattern by negative development.
  • the metal layer 203 is formed so as to cover a part of the surface of the pattern, and a photosensitive resin composition layer (cured film) 201 is further laminated on the surface of the metal layer 203.
  • the photosensitive resin composition layer (cured film) functions as an insulating layer, and the metal layer functions as a rewiring layer, and is incorporated as a rewiring layer in the semiconductor element as described above.
  • the mixture was stirred at a temperature of 60 ° C. for 18 hours to produce a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate.
  • the reaction mixture was then cooled to ⁇ 10 ° C. and 16.12 g (135.5 mmol) of SOCl 2 was added over 10 minutes while maintaining the temperature at ⁇ 10 ⁇ 4 ° C.
  • the reaction mixture was diluted with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours.
  • polyimide precursor Aa-1 The structure of polyimide precursor Aa-1 is shown below.
  • ⁇ Preparation of photosensitive resin composition> The following components were mixed to prepare a photosensitive resin composition as a uniform solution.
  • composition of Photosensitive Resin Composition A-1 >> Resin: polyimide precursor (Aa-1) 32 parts by mass polymerizable compound B-1 6.9 parts by mass photopolymerization initiator C-1 1.0 part by mass polymerization inhibitor: parabenzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) 08 parts by mass migration inhibitor: 1H-tetrazole (manufactured by Tokyo Chemical Industry) 0.12 parts by mass Metal adhesion improver: N- [3- (triethoxysilyl) propyl] maleic acid monoamide 0.70 parts by mass Solvent: ⁇ -butyrolactone 48.00 parts by mass Solvent: dimethyl sulfoxide 12.00 parts by mass
  • composition of Photosensitive Resin Composition A-2 >> Resin: polyimide precursor (Aa-1) 32 parts by weight polymerizable compound B-1 6.9 parts by weight photopolymerization initiator C-1 1.0 part by weight polymerization inhibitor: 2,6-di-tert-butyl- 4-Methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.1 parts by mass migration inhibitor: 1H-1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.1 parts by mass Solvent: ⁇ -butyrolactone 48.00 parts by mass solvent : Dimethyl sulfoxide 12.00 parts by mass
  • B-1 NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd., trifunctional acrylate, the following structure)
  • Each photosensitive resin composition was filtered under pressure through a filter having a pore width of 0.8 ⁇ m.
  • Photosensitive resin composition layer forming step> Thereafter, each photosensitive resin composition was applied on a silicon wafer by spin coating to form a layer, thereby forming a photosensitive resin composition layer.
  • the obtained silicon wafer having the photosensitive resin composition layer was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform photosensitive resin composition layer having a thickness of 20 ⁇ m on the silicon wafer.
  • the photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C) at an exposure wavelength of 365 nm (i-line) and an exposure energy of 500 mJ / cm 2 (overall uniform irradiation).
  • a stepper Nekon NSR 2005 i9C
  • the entire surface is exposed by uniform irradiation, immersed in a developer, and a cured film is formed through a curing process.
  • a cured film having a pattern formed through a curing process may be formed by pattern exposure and immersion in a developer to remove an unexposed portion.
  • the photosensitive resin composition layer When the photosensitive resin composition layer is patterned, more interfaces are generated than when the patterning is not performed, and a portion having a small contact area is formed between the layers when the substrate, the cured film, and the metal layer are laminated. In this case, delamination is more likely to occur, and the effects of the present invention can be obtained more significantly.
  • Temperature rising process First, in a nitrogen atmosphere having an oxygen concentration of 20 vol ppm or less, a substrate having a photosensitive resin composition layer after development processing is placed on a temperature-adjustable plate, and the temperature is increased from room temperature (20 ° C.) to 10 ° C./min. The temperature was raised at a temperature rate and heated to a final temperature of 230 ° C. over 21 minutes.
  • Cooling process >> The photosensitive resin composition layer heated for 3 hours in the holding step was slowly cooled from 230 ° C. to a final temperature of 170 ° C. in the cooling step over 30 minutes at a rate of 2 ° C./min.
  • Step of bringing to room temperature >> After the photosensitive resin composition layer reached the final reached temperature of 170 ° C. in the cooling step, the photosensitive resin composition layer was cooled at a temperature lowering rate of 5 to 10 ° C./min to room temperature to obtain a cured film. .
  • ⁇ Metal layer formation process> in a sputtering apparatus (manufactured by AMAT, product name Endura), on the photosensitive resin composition layer after the curing step, on the condition that the temperature of the photosensitive resin composition layer becomes 150 ° C. using a sputtering method.
  • a first metal layer used as a barrier metal film was formed by forming a Ti film with a thickness of 100 nm, and a Cu metal film was successively formed with a thickness of 300 nm to form a second metal layer used as a seed layer.
  • the total thickness of the metal layer formed in the metal layer forming step using the sputtering method was 400 nm.
  • the temperature of the photosensitive resin composition layer is the color of the surface of the photosensitive resin composition layer with a sticker (Thermo Label, Nippon Oil Giken Co., Ltd.) that changes color depending on the temperature. Measured by looking at the change.
  • a dry film resist (trade name Photec RY-3525, manufactured by Hitachi Chemical Co., Ltd.) is pasted on the seed layer with a roll laminator, and a photo tool with a pattern formed thereon is brought into close contact, and EXM-1201 manufactured by Oak Manufacturing Co., Ltd.
  • the exposure was performed with an energy amount of 100 mJ / cm 2 using a mold exposure machine.
  • spray development was performed for 90 seconds with a 1% by mass aqueous sodium carbonate solution at 30 ° C. to open the dry film resist.
  • a copper plating layer having a thickness of 7 ⁇ m was formed on the dry film resist and on the seed layer where the dry film resist was opened by using an electrolytic copper plating method.
  • the dry film resist was stripped using a stripping solution.
  • the seed layer (300 nm Cu layer) where the dry film resist was peeled off was removed using an etching solution, and a patterned metal layer was formed on the surface of the photosensitive resin composition layer after the curing step.
  • the same photosensitive resin composition is used again to cure from the photosensitive resin composition filtration step in the same manner as described above.
  • the procedure up to the step was performed again to form a laminate having two layers of the photosensitive resin composition layer after the curing step.
  • the metal layer forming step and the second metal layer forming step were performed again on the laminate having two photosensitive resin composition layers after the curing step in the same manner as described above to form a laminate.
  • Examples 2 to 6 and Comparative Examples 1 to 3 Laminates of Examples 2 to 6 and Comparative Examples 1 to 3 were produced in the same manner as Example 1 except that the conditions shown in the following table were changed. In the same manner as in Example 1, the properties of the cured film were measured and the laminate was evaluated.
  • Comparative Examples 1 to 3 when the temperature of the photosensitive resin composition layer after the curing step when forming the metal layer is equal to or higher than the glass transition temperature of the photosensitive resin composition layer after the curing step, A laminate having a large residual stress of the film and a long metal penetration depth after the metal layer forming step using the sputtering method was obtained. In the laminates of Comparative Examples 1 to 3 in which the residual stress of the cured film was large and the metal penetration length was long, it was found that delamination occurred when the substrate, the cured film, and the metal layer were laminated.
  • Example 1 the metal layer (copper thin film) was changed to an aluminum thin film and the others were performed in the same manner. As a result, good results were obtained as in Example 1.
  • the solid content concentration of the photosensitive resin composition 1 was reduced to 1/10 without changing the composition ratio, and spray coating was performed using a spray gun (“NanoSpray” manufactured by Austrian EV Group (EVG)).
  • a laminate was formed. The same excellent effect as in Example 1 was obtained.
  • a laminate was produced in the same manner as in Example 1 except that heating (pretreatment) was performed at 100 ° C. for 10 minutes before heating at 230 ° C. for 3 hours. Characteristics were evaluated. The same excellent effect as in Example 1 was obtained.
  • Example 1 In the production of the laminated body of Example 1, a laminated body was produced in the same manner as in Example 1 except that heating (pretreatment) was performed at 150 ° C. for 10 minutes before heating at 230 ° C. for 3 hours. Characteristics were evaluated. The same excellent effect as in Example 1 was obtained. In the production of the laminate of Example 1, the same procedure as in Example 1 was performed except that heating (pretreatment) was performed at 180 ° C. for 10 minutes while irradiating UV light before heating at 230 ° C. for 3 hours. Laminates were manufactured and properties were evaluated. The same excellent effect as in Example 1 was obtained.
  • the laminate produced by the laminate production method of the present invention can suppress delamination when a substrate, a cured film and a metal layer are laminated. Furthermore, the laminate produced by the laminate production method of the present invention can suppress delamination even when two or more laminates of a substrate, a cured film and a metal layer are laminated.
  • Such a laminate can be used to manufacture an interlayer insulating layer for a rewiring layer of a semiconductor element, and can provide an interlayer insulating layer for a rewiring layer in which delamination is suppressed.
  • Such a laminate is used for manufacturing an interlayer insulating layer for power semiconductors, a copper pillar intermediate film for a three-dimensional integrated circuit (IC) or a single layer insulating layer, and an interlayer insulating layer for panels.
  • IC integrated circuit
  • a single layer insulating layer insulating layer for panels.

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  • Formation Of Insulating Films (AREA)

Abstract

La présente invention a trait à un procédé de fabrication de stratifié qui peut empêcher la délamination d'un stratifié comportant un substrat, une couche durcie et une couche métallique ; à un procédé de fabrication d'élément semi-conducteur ; et à un stratifié. Ce procédé de fabrication de stratifié comprend, dans l'ordre : une étape de formation de couche de composition de résine photosensible, qui consiste à appliquer une composition de résine photosensible sur le substrat et à lui donner une forme de couche ; une étape d'exposition qui consiste à exposer la couche de composition de résine photosensible appliquée sur le substrat ; une étape de traitement de développement qui consiste à effectuer un traitement de développement sur cette couche de composition de résine photosensible exposée ; une étape de durcissement qui consiste à faire durcir ladite couche de composition de résine photosensible après le développement ; et une étape de formation de couche métallique qui consiste à former une couche métallique, à l'aide d'une formation de film en phase gazeuse, sur la surface de la couche de composition de résine photosensible après l'étape de durcissement, la température de cette couche de composition de résine photosensible après l'étape de durcissement lors de la formation de la couche métallique étant inférieure à la température de transition vitreuse de ladite couche de composition de résine photosensible après l'étape de durcissement.
PCT/JP2017/020249 2016-06-02 2017-05-31 Procédé de fabrication de stratifié, procédé de fabrication d'élément semi-conducteur, et stratifié WO2017209176A1 (fr)

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CN113168093A (zh) * 2018-12-05 2021-07-23 富士胶片株式会社 图案形成方法、感光性树脂组合物、固化膜、层叠体及器件
CN113168093B (zh) * 2018-12-05 2024-04-30 富士胶片株式会社 图案形成方法、感光性树脂组合物、固化膜、层叠体及器件
WO2022064933A1 (fr) * 2020-09-24 2022-03-31 富士フイルム株式会社 Procédé de production de motif composite, composition de résine, procédé de production de corps multicouche et procédé de production de dispositif à semi-conducteur
WO2022244717A1 (fr) * 2021-05-17 2022-11-24 富士フイルム株式会社 Composition permettant de former une partie contenant un polyimide, procédé de fabrication de corps assemblé, corps assemblé, procédé et dispositif de fabrication de dispositif
WO2023120037A1 (fr) * 2021-12-23 2023-06-29 富士フイルム株式会社 Procédé de production de corps assemblé, corps assemblé, procédé de production de stratifié, stratifié, procédé de production de dispositif, dispositif et composition pour former une partie précurseur contenant du polyimide
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TWI736629B (zh) 2021-08-21
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