WO2017209176A1 - Laminate production method, semiconductor element production method, and laminate - Google Patents

Laminate production method, semiconductor element production method, and laminate 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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French (fr)
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/en
Priority to KR1020187034311A priority patent/KR102147108B1/en
Priority to JP2018520955A priority patent/JP6845848B2/en
Publication of WO2017209176A1 publication Critical patent/WO2017209176A1/en

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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.

Abstract

A laminate production method which can suppress delamination of a laminate comprising a substrate, a cured layer and a metal layer; a semiconductor element production method; and a laminate are provided. This laminate production method involves, in order: a photosensitive resin composition layer forming step for applying a photosensitive resin composition to the substrate and forming into a layer shape; an exposure step for exposing the photosensitive resin composition layer applied to the substrate; a development processing step for performing development processing on the exposed photosensitive resin composition layer; a curing step for curing the photosensitive resin composition layer after developing; and a metal layer forming step for forming a metal layer, with gas phase film formation, on the surface of the photosensitive resin composition layer after the curing step, wherein the temperature of the photosensitive resin composition layer after the curing step when forming the metal layer is less than the glass transition temperature of the photosensitive resin composition layer after the curing step.

Description

積層体の製造方法、半導体素子の製造方法および積層体LAMINATE MANUFACTURING METHOD, SEMICONDUCTOR ELEMENT MANUFACTURING METHOD, AND LAMINATE
　本発明は積層体の製造方法、半導体素子の製造方法および積層体に関する。 The present invention relates to a laminate manufacturing method, a semiconductor element manufacturing method, and a laminate.
　ポリイミド樹脂やポリベンゾオキサゾール樹脂などの樹脂は、耐熱性および絶縁性に優れるため、半導体素子の絶縁層などに用いられている。 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.
国際公開ＷＯ２０１１／０３４０９２号公報International Publication WO2011 / 034092
　半導体素子の再配線層用層間絶縁膜としてポリイミド樹脂やポリベンゾオキサゾール樹脂などの耐熱性および絶縁性に優れる樹脂の硬化膜を用い、この硬化膜と金属層を積層して、半導体素子の再配線層を製造することが行われている。
　本発明者らが、ポリイミド樹脂やポリベンゾオキサゾール樹脂などの耐熱性および絶縁性に優れる樹脂の硬化膜と金属層を積層することを検討したところ、硬化膜と金属層の密着性が不十分であり、硬化膜と金属層の間で層間剥離が起こることが分かった。 As the interlayer insulation film for the rewiring layer of the semiconductor element, a cured film of a resin having excellent heat resistance and insulation, such as polyimide resin or polybenzoxazole resin, is used, and the cured film and the metal layer are laminated to rewiring the semiconductor element. Making the layer is done.
When 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.
　ここで、一般に、半導体素子の製作に用いられる成膜方法においては、基板と銅（Ｃｕ）等からなる配線層との間にバリアメタル膜を設けることによって、配線層を構成する材料が基板に拡散して起こる配線の劣化を防止することが知られている（特許文献１参照）。
　特許文献１には、表面に微細な孔又は溝が形成された基板を準備し、基板の温度が１５０℃以上、５００℃以下の範囲に設定された状態で、基板に対してチタン又はチタン化合物からなるバリアメタル膜を形成するバリアメタル膜の形成方法が記載されている。特許文献１によれば、上記構成のバリアメタル膜の形成方法を用いることで、高アスペクト比のパターン等に対して、開口部におけるオーバーハング（底部よりも開口部の径が小さくなること）の発生を低減できると記載されている。
　しかしながら、特許文献１は、基板としてシリコンウェハの表面にシリコン酸化物膜を形成した場合しか注目していなかった。すなわち、特許文献１は、ポリイミド樹脂やポリベンゾオキサゾール樹脂などの耐熱性および絶縁性に優れる樹脂の硬化膜と金属層を積層した場合の層間剥離については注目していなかった。 Here, in general, in a film forming method used for manufacturing a semiconductor element, 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).
In 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. According to 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.
However, 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.
　本発明が解決しようとする課題は、基板と硬化膜と金属層を積層した場合の層間剥離を抑制できる積層体の製造方法を提供することである。また、本発明が解決しようとする課題は、積層体の製造方法を含む、半導体素子の製造方法を提供することである。また、本発明が解決しようとする課題は、基板と硬化膜と金属層を積層した場合の層間剥離を抑制できる積層体を提供することである。 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 | stacking a board | substrate, a cured film, and a metal layer.
　上記課題のもと、本発明者が検討を行った結果、ポリイミド樹脂やポリベンゾオキサゾール樹脂などの耐熱性および絶縁性に優れる樹脂の硬化膜のガラス転移温度未満でスパッタ法等の気相成膜を用いて金属層を形成することにより、上記課題を解決しうることを見出した。
　上記課題を解決するための手段である本発明および本発明の好ましい態様は以下のとおりである。
［１］　感光性樹脂組成物を基板に適用して層状にする、感光性樹脂組成物層形成工程と、
　基板に適用された感光性樹脂組成物層を露光する露光工程と、
　露光された感光性樹脂組成物層に対して、現像処理を行う現像処理工程と、
　現像後の感光性樹脂組成物層を硬化する硬化工程と、
　硬化工程後の感光性樹脂組成物層の表面に気相成膜により金属層を形成する金属層形成工程とを、上記順に行うことを含み、
　金属層を形成する際の硬化工程後の感光性樹脂組成物層の温度が、硬化工程後の感光性樹脂組成物層のガラス転移温度未満である、積層体の製造方法。
［２］　さらに、再度、感光性樹脂組成物層形成工程、露光工程、現像処理工程、硬化工程、および、金属層形成工程を、上記順に行うことを含む、［１］に記載の積層体の製造方法。
［３］　感光性樹脂組成物が、露光により架橋構造が構築されて有機溶剤への溶解度が低下する、［１］または［２］に記載の積層体の製造方法。
［４］　感光性樹脂組成物が、ポリイミド前駆体、ポリイミド、ポリベンゾオキサゾール前駆体およびポリベンゾオキサゾールから選択される少なくとも１種類の樹脂を含む、［１］～［３］のいずれか１つに記載の積層体の製造方法。
［５］　さらに、金属層の表面に第２の金属層を形成する第２の金属層形成工程を含む、［１］～［４］のいずれか１つに記載の積層体の製造方法。
［６］　第２の金属層が、銅を含む、［５］に記載の積層体の製造方法。
［７］　金属層が、チタン、タンタルおよび銅ならびにこれらのうち少なくとも１種類を含む化合物のうち少なくとも１種類を含む、［１］～［６］のいずれか１つに記載の積層体の製造方法。
［８］　金属層形成工程で形成される金属層の厚さが、５０～２０００ｎｍである、［１］～［７］のいずれか１つに記載の積層体の製造方法。
［９］　硬化工程後の感光性樹脂組成物のレーザー計測法に従って測定した残留応力が３５ＭＰａ未満である、［１］～［８］のいずれか１つに記載の積層体の製造方法。
［１０］　感光性樹脂組成物が、ネガ型現像用である、［１］～［９］のいずれか１つに記載の積層体の製造方法。
［１１］　硬化工程が、感光性樹脂組成物層を昇温する昇温工程と、昇温工程の最終到達温度と等しい保持温度で保持する保持工程とを含み、
　保持工程における保持温度が２５０℃以下である、［１］～［１０］のいずれか１つに記載の積層体の製造方法。
［１２］　金属層を形成する際の感光性樹脂組成物層の温度が感光性樹脂組成物層のガラス転移温度より３０℃以上低い、［１］～［１１］のいずれか１つに記載の積層体の製造方法。
［１３］　［１］～［１２］のいずれか１つに記載の積層体の製造方法を含む、半導体素子の製造方法。
［１４］　基板と、パターン硬化膜と、パターン硬化膜の表面に位置する金属層とを有し、
　パターン硬化膜は、ポリイミドまたはポリベンゾオキサゾールを含み、
　パターン硬化膜の表面に位置する金属層を構成する金属のパターン硬化膜への侵入長がパターン硬化膜の表面から１３０ｎｍ以下である、積層体。 As a result of examination by the present inventors based on the above problems, 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.
[1] 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.
[2] The layered product according to [1], further including performing the photosensitive resin composition layer forming step, the exposure step, the development processing step, the curing step, and the metal layer forming step in the above order again. 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.
[4] In any one of [1] to [3], the photosensitive resin composition includes at least one resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole. The manufacturing method of the laminated body of description.
[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.
[7] The method for producing a laminate according to any one of [1] to [6], wherein the metal layer includes at least one of titanium, tantalum, copper, and a compound including at least one of these. .
[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.
[9] The method for producing a laminate according to any one of [1] to [8], wherein the residual stress measured according to the laser measurement method of the photosensitive resin composition after the curing step is less than 35 MPa.
[10] The method for producing a laminate according to any one of [1] to [9], wherein the photosensitive resin composition is for negative development.
[11] 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 method for producing a laminate according to any one of [1] to [10], wherein a holding temperature in the holding step is 250 ° C. or lower.
[12] 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.
[13] A method for manufacturing a semiconductor element, including the method for manufacturing a laminated body according to any one of [1] to [12].
[14] 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 laminated body whose penetration | 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］　［１］～［１２］のいずれか１つに記載の積層体の製造方法で製造された積層体。
［１６］　［１３］に記載の半導体素子の製造方法で製造された半導体素子。 [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].
　本発明によれば、基板と硬化膜と金属層を積層した場合の層間剥離を抑制できる積層体の製造方法を提供することができる。また、本発明によれば、本発明の積層体の製造方法を含む、半導体素子の製造方法を提供することができる。また、本発明によれば、基板と硬化膜と金属層を積層した場合の層間剥離を抑制できる積層体を提供することができる。 According to 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 | stacking a board | substrate, a cured film, and a metal layer can be provided.
半導体素子の一実施形態の構成を示す概略図である。It is the schematic which shows the structure of one Embodiment of a semiconductor element. 本発明の積層体の製造方法で得られる積層体の一実施形態の構成を示す概略図である。It is the schematic which shows the structure of one Embodiment of the laminated body obtained with the manufacturing method of the laminated body of this invention.
　以下に記載する本発明における構成要素の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。
　本明細書における基（原子団）の表記に於いて、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、一般的に、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等の活性光線または放射線が挙げられる。
　本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
　本明細書において、「（メタ）アクリレート」は、「アクリレート」および「メタクリレート」の双方、または、いずれかを表し、「（メタ）アリル」は、「アリル」および「メタリル」の双方、または、いずれかを表し、「（メタ）アクリル」は、「アクリル」および「メタクリル」の双方、または、いずれかを表し、「（メタ）アクリロイル」は、「アクリロイル」および「メタクリロイル」の双方、または、いずれかを表す。
　本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
　本明細書において、固形分濃度とは、組成物の総質量に対する、溶剤を除く他の成分の質量百分率である。また、固形分濃度は、特に述べない限り２５℃における濃度をいう。
　本明細書において、重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、特に述べない限り、ゲル浸透クロマトグラフィー（ＧＰＣ測定）によるポリスチレン換算値として定義される。本明細書において、重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、例えば、ＨＬＣ－８２２０（東ソー（株）製）を用い、カラムとしてガードカラムＨＺ－Ｌ、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺＭ－Ｍ、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ４０００、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ３０００、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ２０００（東ソー（株）製）を用いることによって求めることができる。溶離液は特に述べない限り、ＴＨＦ（テトラヒドロフラン）を用いて測定したものとする。また、検出は特に述べない限り、ＵＶ線（紫外線）の波長２５４ｎｍ検出器を使用したものとする。 The description of the components in the present invention described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the description of the group (atomic group) in this specification, 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. For example, 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).
In this specification, unless otherwise specified, “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.
In the present specification, 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.
In the present specification, “(meth) acrylate” represents both and / or “acrylate” and “methacrylate”, and “(meth) allyl” means both “allyl” and “methallyl”, or “(Meth) acryl” represents either “acryl” and “methacryl” or any one, and “(meth) acryloyl” represents both “acryloyl” and “methacryloyl”, or Represents either.
In this specification, 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. .
In this specification, solid content concentration is the mass percentage of the other component except a solvent with respect to the gross mass of a composition. Moreover, solid content concentration says the density | concentration in 25 degreeC unless there is particular mention.
In the present specification, 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. In this specification, 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). Unless otherwise stated, the eluent is measured using THF (tetrahydrofuran). Unless otherwise specified, detection is performed using a UV ray (ultraviolet) wavelength 254 nm detector.
　［積層体の製造方法］
　本発明の積層体の製造方法は、感光性樹脂組成物を基板に適用して層状にする、感光性樹脂組成物層形成工程と、
　基板に適用された感光性樹脂組成物層を露光する露光工程と、
　露光された感光性樹脂組成物層に対して、現像処理を行う現像処理工程と、
　現像後の感光性樹脂組成物層を硬化する硬化工程と、
　硬化工程後の感光性樹脂組成物層の表面に気相成膜により金属層を形成する金属層形成工程とを、上記順に行うことを含み、
　金属層を形成する際の硬化工程後の感光性樹脂組成物層の温度が、硬化工程後の感光性樹脂組成物層のガラス転移温度未満である。
　上記構成により、基板と硬化膜と金属層を積層した場合の層間剥離を抑制できる。
　基板上の硬化膜（硬化膜とは、硬化工程後の感光性樹脂組成物層のことを言う）の表面にスパッタ法等の気相成膜により金属層を形成する場合、通常は、金属層の膜質をコントロールするために基板（および硬化膜）を加熱する。従来、高い温度でスパッタ法を用いて金属層を形成すると、硬化膜に金属原子を打ち込むことができ、その結果として層間剥離の発生を抑制できると推定されていた。
　実際、本発明者らが硬化膜の表面にスパッタ法を用いて金属層を形成した積層体の断面を透過型電子顕微鏡（Ｔｒａｎｓｍｉｓｓｉｏｎ　Ｅｌｅｃｔｒｏｎ　Ｍｉｃｒｏｓｃｏｐｅ；ＴＥＭ）等を用いて解析した結果、高い温度でスパッタ法を用いて金属層を形成すると、硬化膜の表面に金属が入り込む現象（ｐｅｎｅｔｒａｔｉｏｎ）が生じることがわかった。しかしながら、高い温度でスパッタ法を用いて金属層を形成すると、基板と硬化膜と金属層を積層した場合の層間剥離が発生することがわかった。
　一方、硬化工程後の感光性樹脂組成物層の温度（硬化膜の表面の温度）がガラス転移温度未満に抑えられるようにスパッタ法等の気相成膜により金属層を形成することで、硬化膜の表面に金属が入り込む現象（ｐｅｎｅｔｒａｔｉｏｎ）が無くなり、さらに基板と硬化膜と金属層を積層した場合の層間剥離も発生しなくなることがわかった。ガラス転移温度のことを、以下Ｔｇ（ｇｌａｓｓ　ｔｒａｎｓｉｔｉｏｎ　ｔｅｍｐｅｒａｔｕｒｅ）とも言う。
　以下、本発明の好ましい態様の詳細を説明する。 [Manufacturing method of laminate]
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.
With the above configuration, delamination when the substrate, the cured film, and the metal layer are stacked can be suppressed.
When 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. Conventionally, when 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.
Actually, as a result of analyzing the cross section of the laminate in which the metal layer is formed on the surface of the cured film using a sputtering method using a transmission electron microscope (TEM) or the like, 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.
On the other hand, it is cured by forming a metal layer by vapor deposition such as sputtering so that the temperature of the photosensitive resin composition layer after the curing step (the temperature of the surface of the cured film) is kept below the glass transition temperature. It has been found that the phenomenon of metal penetration into the surface of the film is eliminated and delamination does not occur when the substrate, the cured film and the metal layer are laminated. The glass transition temperature is hereinafter also referred to as Tg (glass transition temperature).
Hereinafter, details of preferred embodiments of the present invention will be described.
＜濾過工程＞
　本発明の積層体の製造方法は、感光性樹脂組成物を基板に適用する前に、感光性樹脂組成物を濾過する工程を含んでいてもよい。濾過は、フィルターを用いて行うことが好ましい。フィルター孔径としては、１μｍ以下が好ましく、０．５μｍ以下がより好ましく、０．１μｍ以下がさらに好ましい。フィルターの材質としては、ポリテトラフロロエチレン製、ポリエチレン製、ナイロン製のフィルターが好ましい。フィルターは、有機溶剤であらかじめ洗浄したものを用いてもよい。フィルター濾過工程では、複数種類のフィルターを直列または並列に接続して用いてもよい。複数種類のフィルターを使用する場合は、孔径および／または材質が異なるフィルターを組み合わせて使用してもよい。また、各種類の材料を用いて複数回濾過してもよく、複数回濾過する工程が循環濾過工程であってもよい。また、加圧濾過を行ってもよく、加圧濾過の場合に加える圧力は０．０５ＭＰａ以上０．３ＭＰａ以下が好ましい。
　フィルターを用いた濾過の他、吸着材を用いた濾過を行って不純物の除去を行ってもよく、フィルター濾過と吸着材を組み合わせて使用して濾過を行ってもよい。吸着材としては、公知の吸着材を用いることができ、例えば、シリカゲル、ゼオライトなどの無機系吸着材、活性炭などの有機系吸着材を使用することができる。 <Filtering process>
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 | substrate. Filtration is preferably performed using a filter. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. As a material of the filter, 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. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, 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.
In addition to filtration using a filter, impurities may be removed by filtration using an adsorbent, or filtration may be performed using a combination of filter filtration and adsorbent. As the 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.
＜感光性樹脂組成物層形成工程＞
　本発明の積層体の製造方法は、感光性樹脂組成物を基板に適用して層状にする、感光性樹脂組成物層形成工程を含む。
　感光性樹脂組成物を基板に適用する手段としては、塗布が好ましい。
　具体的には、適用する手段としては、ディップコート法、エアーナイフコート法、カーテンコート法、ワイヤーバーコート法、グラビアコート法、エクストルージョンコート法、スプレーコート法、スピンコート法、スリットコート法、およびインクジェット法などが例示される。感光性樹脂組成物層の厚さの均一性の観点から、スピンコート法、スリットコート法、スプレーコート法、インクジェット法がより好ましい。適用する手段に応じて適切な固形分濃度や塗布条件を調整することで、所望の感光性樹脂組成物層を得ることができる。また、基板の形状によっても塗布方法を適宜選択でき、ウェハ等の円形基板であればスピンコート法やスプレーコート法、インクジェット法等が好ましく、矩形基板であればスリットコート法やスプレーコート法、インクジェット法等が好ましい。スピンコート法の場合は、例えば、５００～２０００ｒｐｍ（ｒｅｖｏｌｕｔｉｏｎｓ　ｐｅｒ　ｍｉｎｕｔｅ）の回転数で、１０秒間～１分間程度で適用することができる。
　感光性樹脂組成物層（硬化工程の後は硬化膜）の厚さは、露光後で、０．１～１００μｍとなるように塗布することが好ましく、１～５０μｍとなるように塗布することがより好ましい。また、図２に示すように、形成される感光性樹脂組成物層の厚さは、必ずしも均一である必要はない。特に、凹凸のある表面上に感光性樹脂組成物層が設けられる場合、図２に示すように、厚さの異なる硬化膜が得られるであろう。特に硬化膜を複数層積層した場合、凹部として、深さの深い凹部も形成されうるが、本発明はこのような構成に対し、層間の剥離をより効果的に抑制できる点で技術的価値が高い。積層体が厚さの異なる硬化膜を有する場合、最も薄い部分の硬化膜の厚さが上記厚さであることが好ましい。 <Photosensitive resin composition layer forming step>
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 | substrate, and makes it layered.
As a means for applying the photosensitive resin composition to the substrate, coating is preferable.
Specifically, as a means to apply, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slit coating method, And an inkjet method. From the viewpoint of uniformity of the thickness of the photosensitive resin composition layer, 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. Also, 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. In the case of 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 μm after exposure, and is preferably applied to be 1 to 50 μm. 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.
＜＜基板＞＞
　基板の種類は、用途に応じて適宜定めることができるが、シリコン、窒化シリコン、ポリシリコン、酸化シリコン、アモルファスシリコンなどの半導体作製基板、石英、ガラス、光学フィルム、セラミック材料、蒸着膜、磁性膜、反射膜、Ｎｉ、Ｃｕ、Ｃｒ、Ｆｅなどの金属基板、紙、ＳＯＧ（Ｓｐｉｎ　Ｏｎ　Ｇｌａｓｓ）、ＴＦＴ（ｔｈｉｎ　ｆｉｌｍ　ｔｒａｎｓｉｓｔｏｒ；薄膜トランジスタ）アレイ基板、プラズマディスプレイパネル（ＰＤＰ）の電極板など特に制約されない。本発明では、特に、半導体作製基板が好ましく、シリコンがより好ましい。
　また、硬化膜の表面や金属層の表面に感光性樹脂組成物層を形成する場合は、硬化膜または金属層が基板として用いられてもよい。 << Board >>
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. In the present invention, a semiconductor manufacturing substrate is particularly preferable, and silicon is more preferable.
Moreover, when forming the photosensitive resin composition layer in the surface of a cured film or the surface of a metal layer, a cured film or a metal layer may be used as a board | substrate.
＜＜感光性樹脂組成物＞＞
　以下、本発明で用いる感光性樹脂組成物の詳細について説明する。
　本発明の積層体の製造方法では、感光性樹脂組成物が露光により架橋構造を形成する化合物を含むことが好ましく、ネガ型現像用であることがより好ましく、露光により架橋構造が構築されて有機溶剤への溶解度が低下することが特に好ましく、有機溶剤で現像するネガ型感光性樹脂であることが最も好ましい。
　まず、本発明で用いる感光性樹脂組成物が含んでもよい成分について説明する。感光性樹脂組成物はこれら以外の成分を含んでいてもよく、また、これらの成分を必須とするわけではない。 << Photosensitive resin composition >>
Hereinafter, the detail of the photosensitive resin composition used by this invention is demonstrated.
In the method for producing a laminate of the present invention, 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.
First, components that may be contained in the photosensitive resin composition used in the present invention will be described. The photosensitive resin composition may contain components other than these, and these components are not essential.
＜＜＜樹脂＞＞＞
　本発明で用いる感光性樹脂組成物は、樹脂を含む。
　本発明で用いる感光性樹脂組成物では、樹脂は特に制限は無く、公知の樹脂を用いることができる。樹脂は高耐熱性樹脂であることが好ましい。 <<< Resin >>>
The photosensitive resin composition used in the present invention contains a resin.
In the photosensitive resin composition used in the present invention, the resin is not particularly limited, and a known resin can be used. The resin is preferably a high heat resistant resin.
　本発明で用いる感光性樹脂組成物は、ポリイミド前駆体、ポリイミド、ポリベンゾオキサゾール前駆体およびポリベンゾオキサゾールから選択される少なくとも１種類の樹脂を含むことが好ましい。本発明の積層体の製造方法では、感光性樹脂組成物が、ポリイミド前駆体またはポリベンゾオキサゾール前駆体を含むことがより好ましく、ポリイミド前駆体を含むことがさらに好ましい。 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. In the manufacturing method of the laminated body of this invention, it is more preferable that the photosensitive resin composition contains a polyimide precursor or a polybenzoxazole precursor, and it is further more preferable that a polyimide precursor is included.
　本発明で用いる感光性樹脂組成物はポリイミド前駆体、ポリイミド、ポリベンゾオキサゾール前駆体およびポリベンゾオキサゾールのうち、１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。また、ポリイミド前駆体を２種類等、同じ種類の樹脂であって、構造の異なる樹脂を２種類以上含んでいてもよい。
　本発明で用いる感光性樹脂組成物における、樹脂の含有量は、感光性樹脂組成物の全固形分の１０～９９質量％が好ましく、５０～９８質量％がより好ましく、７０～９６質量％がさらに好ましい。 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.
　さらに、樹脂は重合性基を含むことが好ましい。
　また、感光性樹脂組成物が重合性化合物を含むことが好ましい。このような構成とすることにより、露光部に３次元ネットワークが形成され、強固な架橋膜となり、後述の表面活性化処理により感光性樹脂組成物層（硬化膜）がダメージを受けず、表面活性化処理により、硬化膜と金属層の密着性または硬化膜同士の密着性がより効果的に向上する。
　さらにまた、樹脂が、－Ａｒ－Ｌ－Ａｒ－で表される部分構造を含むことが好ましい。但し、Ａｒは、それぞれ独立に、芳香族基であり、Ｌは、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ2－または－ＮＨＣＯ－、ならびに、上記の２つ以上の組み合わせからなる基である。このような構成とすることにより、感光性樹脂組成物層（硬化膜）が柔軟な構造となり、層間剥離の発生を抑制する効果がより効果的に発揮される。Ａｒは、フェニレン基が好ましく、Ｌは、フッ素原子で置換されていてもよい炭素数１または２の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－または－ＳＯ2－がさらに好ましい。ここでの脂肪族炭化水素基は、アルキレン基が好ましい。 Further, the resin preferably contains a polymerizable group.
Moreover, it is preferable that the photosensitive resin composition contains a polymerizable compound. By adopting such a configuration, 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.
Furthermore, it is preferable that the resin includes a partial structure represented by —Ar—L—Ar—. However, Ar is each independently an aromatic group, and 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. By setting it as such a structure, the photosensitive resin composition layer (cured film) becomes a flexible structure, and the effect which suppresses generation | occurrence | production of delamination is exhibited more effectively. Ar is preferably a phenylene group, and 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 —. preferable. The aliphatic hydrocarbon group here is preferably an alkylene group.
（ポリイミド前駆体）
　ポリイミド前駆体は、その種類等について特に定めるものではなく、下記式（２）で表される繰り返し単位を含むことが好ましい。
式（２）
Figure JPOXMLDOC01-appb-C000001
 　式（２）中、Ａ1およびＡ2は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ111は、２価の有機基を表し、Ｒ115は、４価の有機基を表し、Ｒ113およびＲ114は、それぞれ独立に、水素原子または１価の有機基を表す。 (Polyimide precursor)
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).
Formula (2)
Figure JPOXMLDOC01-appb-C000001
 In 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.
　式（２）におけるＡ1およびＡ2は、酸素原子またはＮＨが好ましく、酸素原子がより好ましい。
　式（２）におけるＲ111は、２価の有機基を表す。２価の有機基としては、直鎖または分岐の脂肪族基、環状の脂肪族基および芳香族基を含む基が例示され、炭素数２～２０の直鎖または分岐の脂肪族基、炭素数６～２０の環状の脂肪族基、炭素数６～２０の芳香族基、または、これらの組み合わせからなる基が好ましく、炭素数６～２０の芳香族基を含む基がより好ましい。特に好ましい実施形態として、式（２）におけるＲ111が－Ａｒ－Ｌ－Ａｒ－で表される基であることが例示される。但し、Ａｒは、それぞれ独立に、芳香族基であり、Ｌは、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ2－または－ＮＨＣＯ－、ならびに、上記の２つ以上の組み合わせからなる基である。これらの好ましい範囲は、上述のとおりである。 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. Examples of 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. As a particularly preferred embodiment, R 111 in the formula (2) is exemplified by a group represented by —Ar—L—Ar—. However, Ar is each independently an aromatic group, and 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. These preferable ranges are as described above.
　式（２）におけるＲ111は、ジアミンから誘導されることが好ましい。ポリイミド前駆体の製造に用いられるジアミンとしては、直鎖または分岐の脂肪族、環状の脂肪族または芳香族ジアミンなどが挙げられる。ジアミンは、１種類のみ用いてもよいし、２種類以上用いてもよい。
　具体的には、炭素数２～２０の直鎖または分岐の脂肪族基、炭素数６～２０の環状の脂肪族基、炭素数６～２０の芳香族基、または、これらの組み合わせからなる基を含むジアミンであることが好ましく、炭素数６～２０の芳香族基からなる基を含むジアミンであることがより好ましい。芳香族基の例としては、下記の芳香族基が挙げられる。 R 111 in formula (2) is preferably derived from a diamine. Examples of 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.
Specifically, 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.
Figure JPOXMLDOC01-appb-C000002
 　上記芳香族基中、Ａは、単結合、または、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、－Ｓ（＝Ｏ）2－、－ＮＨＣＯ－ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１～３のアルキレン基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、－ＳＯ2－から選択される基であることがより好ましく、－ＣＨ2－、－Ｏ－、－Ｓ－、－ＳＯ2－、－Ｃ（ＣＦ3）2－、および、－Ｃ（ＣＨ3）2－からなる群から選択される２価の基であることがさらに好ましい。
Figure JPOXMLDOC01-appb-C000002
 In the 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 —.
　ジアミンとしては、具体的には、１，２－ジアミノエタン、１，２－ジアミノプロパン、１，３－ジアミノプロパン、１，４－ジアミノブタンおよび１，６－ジアミノヘキサン；１，２－または１，３－ジアミノシクロペンタン、１，２－、１，３－または１，４－ジアミノシクロヘキサン、１，２－、１，３－または１，４－ビス（アミノメチル）シクロヘキサン、ビス－（４－アミノシクロヘキシル）メタン、ビス－（３－アミノシクロヘキシル）メタン、４，４’－ジアミノ－３，３’－ジメチルシクロヘキシルメタンおよびイソホロンジアミン；メタおよびパラフェニレンジアミン、ジアミノトルエン、４，４’－および３，３’－ジアミノビフェニル、４，４’－ジアミノジフェニルエーテル、３，３－ジアミノジフェニルエーテル、４，４’－および３，３’－ジアミノジフェニルメタン、４，４’－および３，３’－ジアミノジフェニルスルホン、４，４’－および３，３’－ジアミノジフェニルスルフィド、４，４’－および３，３’－ジアミノベンゾフェノン、３，３’－ジメチル－４，４’－ジアミノビフェニル、２，２’－ジメチル－４，４’－ジアミノビフェニル、３，３’－ジメトキシ－４，４’－ジアミノビフェニル、２，２－ビス（４－アミノフェニル）プロパン、２，２－ビス（４－アミノフェニル）ヘキサフルオロプロパン、２，２－ビス（３－ヒドロキシ－４－アミノフェニル）プロパン、２，２－ビス（３－ヒドロキシ－４－アミノフェニル）ヘキサフルオロプロパン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）プロパン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン、ビス（３－アミノ－４－ヒドロキシフェニル）スルホン、ビス（４－アミノ－３－ヒドロキシフェニル）スルホン、４，４’－ジアミノパラテルフェニル、４，４’－ビス（４－アミノフェノキシ）ビフェニル、ビス［４－（４－アミノフェノキシ）フェニル］スルホン、ビス［４－（３－アミノフェノキシ）フェニル］スルホン、ビス［４－（２－アミノフェノキシ）フェニル］スルホン、１，４－ビス（４－アミノフェノキシ）ベンゼン、９，１０－ビス（４－アミノフェニル）アントラセン、３，３’－ジメチル－４，４’－ジアミノジフェニルスルホン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，３－ビス（３－アミノフェノキシ）ベンゼン、１，３－ビス（４－アミノフェニル）ベンゼン、３，３’－ジエチル－４，４’－ジアミノジフェニルメタン、３，３’－ジメチル－４，４’－ジアミノジフェニルメタン、４，４’－ジアミノオクタフルオロビフェニル、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、９，９－ビス（４－アミノフェニル）－１０－ヒドロアントラセン、３，３’，４，４’－テトラアミノビフェニル、３，３’，４，４’－テトラアミノジフェニルエーテル、１，４－ジアミノアントラキノン、１，５－ジアミノアントラキノン、３，３－ジヒドロキシ－４，４’－ジアミノビフェニル、９，９’－ビス（４－アミノフェニル）フルオレン、４，４’－ジメチル－３，３’－ジアミノジフェニルスルホン、３，３’，５，５’－テトラメチル－４，４’－ジアミノジフェニルメタン、２，４－および２，５－ジアミノクメン、２，５－ジメチル－パラフェニレンジアミン、アセトグアナミン、２，３，５，６－テトラメチル－パラフェニレンジアミン、２，４，６－トリメチル－メタフェニレンジアミン、ビス（３－アミノプロピル）テトラメチルジシロキサン、２，７－ジアミノフルオレン、２，５－ジアミノピリジン、１，２－ビス（４－アミノフェニル）エタン、ジアミノベンズアニリド、ジアミノ安息香酸のエステル、１，５－ジアミノナフタレン、ジアミノベンゾトリフルオライド、１，３－ビス（４－アミノフェニル）ヘキサフルオロプロパン、１，４－ビス（４－アミノフェニル）オクタフルオロブタン、１，５－ビス（４－アミノフェニル）デカフルオロペンタン、１，７－ビス（４－アミノフェニル）テトラデカフルオロヘプタン、２，２－ビス［４－（３－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２－ビス［４－（２－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２－ビス［４－（４－アミノフェノキシ）－３，５－ジメチルフェニル］ヘキサフルオロプロパン、２，２－ビス［４－（４－アミノフェノキシ）－３，５－ビス（トリフルオロメチル）フェニル］ヘキサフルオロプロパン、パラビス（４－アミノ－２－トリフルオロメチルフェノキシ）ベンゼン、４，４’－ビス（４－アミノ－２－トリフルオロメチルフェノキシ）ビフェニル、４，４’－ビス（４－アミノ－３－トリフルオロメチルフェノキシ）ビフェニル、４，４’－ビス（４－アミノ－２－トリフルオロメチルフェノキシ）ジフェニルスルホン、４，４’－ビス（３－アミノ－５－トリフルオロメチルフェノキシ）ジフェニルスルホン、２，２－ビス［４－（４－アミノ－３－トリフルオロメチルフェノキシ）フェニル］ヘキサフルオロプロパン、３，３’，５，５’－テトラメチル－４，４’－ジアミノビフェニル、４，４’－ジアミノ－２，２’－ビス（トリフルオロメチル）ビフェニル、２，２’，５，５’，６，６’－ヘキサフルオロトリジンおよび４，４’’’－ジアミノクアテルフェニルから選ばれる少なくとも１種類のジアミンが挙げられる。 Specific examples of the diamine 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, 3,3-diaminodiphenyl ether 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4 ' -And 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4 '-Diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 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-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4,4'-diamino Paraterphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3′-dimethyl-4,4′-diaminodiphenyl Sulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene 1,3-bis (4-aminophenyl) benzene, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 4,4′- Diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4 -Aminophenyl) -10-hydroanthracene, 3,3 ', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diamino Anthraquinone, 3,3-dihydroxy-4,4′-diaminobiphenyl, 9,9′-bis (4-aminophenyl) fluorene, 4 4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5 -Dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2 , 7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1, 3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-amino Phenyl) octafluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) ) Phenyl] hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexa Fluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, parabis (4-amino-2-trifluoromethylphenoxy) benzene, 4 , 4′-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4′-bis (4 -Amino-3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenyl sulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) ) Diphenylsulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminobiphenyl 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,2 ′, 5,5 ′, 6,6′-hexafluorotolidine and 4,4 ′ ″-diaminoquater Examples include at least one diamine selected from phenyl.
　また、下記に示すジアミン（ＤＡ－１）～（ＤＡ－１８）も好ましい。 Further, diamines (DA-1) to (DA-18) shown below are also preferable.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　また、少なくとも２つ以上のアルキレングリコール単位を主鎖にもつジアミンも好ましい例として挙げられる。好ましくは、エチレングリコール鎖、プロピレングリコール鎖のいずれかまたは両方を１分子中にあわせて２つ以上含むジアミン、より好ましくは芳香環を含まないジアミンである。具体例としては、ジェファーミン（登録商標）ＫＨ－５１１、ジェファーミン（登録商標）ＥＤ－６００、ジェファーミン（登録商標）ＥＤ－９００、ジェファーミン（登録商標）ＥＤ－２００３、ジェファーミン（登録商標）ＥＤＲ－１４８、ジェファーミン（登録商標）ＥＤＲ－１７６、Ｄ－２００、Ｄ－４００、Ｄ－２０００、Ｄ－４０００（以上商品名、ＨＵＮＴＳＭＡＮ製）、１－（２－（２－（２－アミノプロポキシ）エトキシ）プロポキシ）プロパン－２－アミン、１－（１－（１－（２－アミノプロポキシ）プロパン－２－イル）オキシ）プロパン－２－アミンなどが挙げられるが、これらに限定されない。
　ジェファーミン（登録商標）ＫＨ－５１１、ジェファーミン（登録商標）ＥＤ－６００、ジェファーミン（登録商標）ＥＤ－９００、ジェファーミン（登録商標）ＥＤ－２００３、ジェファーミン（登録商標）ＥＤＲ－１４８、ジェファーミン（登録商標）ＥＤＲ－１７６の構造を以下に示す。 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. .
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, The structure of Jeffamine (registered trademark) EDR-176 is shown below.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　上記において、ｘ、ｙ、ｚは平均値である。 In the above, x, y, and z are average values.
　式（２）におけるＲ111は、得られる硬化膜の柔軟性の観点から、－Ａｒ－Ｌ－Ａｒ－で表されることが好ましい。但し、Ａｒは、それぞれ独立に、芳香族基であり、Ｌは、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ2－または－ＮＨＣＯ－、ならびに、上記の２つ以上の組み合わせからなる基である。Ａｒは、フェニレン基が好ましく、Ｌは、フッ素原子で置換されていてもよい炭素数１または２の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－または－ＳＯ2－がさらに好ましい。ここでの脂肪族炭化水素基は、アルキレン基が好ましい。 R 111 in the formula (2) is preferably represented by —Ar—L—Ar— from the viewpoint of the flexibility of the resulting cured film. However, Ar is each independently an aromatic group, and 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, and 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 —. preferable. The aliphatic hydrocarbon group here is preferably an alkylene group.
　式（２）におけるＲ111は、ｉ線透過率の観点から下記式（５１）または式（６１）で表わされる２価の有機基であることが好ましい。特に、ｉ線透過率、入手のし易さの観点から式（６１）で表わされる２価の有機基であることがより好ましい。
　式（５１）
Figure JPOXMLDOC01-appb-C000006
 　式（５１）中、Ｒ10～Ｒ17は、それぞれ独立に水素原子、フッ素原子または１価の有機基であり、Ｒ10～Ｒ17の少なくとも１つはフッ素原子、メチル基またはトリフルオロメチル基である。
　Ｒ10～Ｒ17の１価の有機基として、炭素数１～１０（好ましくは炭素数１～６）の無置換のアルキル基、炭素数１～１０（好ましくは炭素数１～６）のフッ化アルキル基等が挙げられる。
　式（６１）
Figure JPOXMLDOC01-appb-C000007
 　式（６１）中、Ｒ18およびＲ19は、それぞれ独立にフッ素原子またはトリフルオロメチル基である。
　式（５１）または（６１）の構造を与えるジアミン化合物としては、２，２’－ジメチルベンジジン、２，２’－ビス（トリフルオロメチル）－４，４’－ジアミノビフェニル、２，２’－ビス（フルオロ）－４，４’－ジアミノビフェニル、４，４’－ジアミノオクタフルオロビフェニル等が挙げられる。これらは１種類を用いるか、または２種類以上を組み合わせて用いてもよい。 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. In particular, a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-line transmittance and availability.
Formula (51)
Figure JPOXMLDOC01-appb-C000006
 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)
Figure JPOXMLDOC01-appb-C000007
 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.
　式（２）におけるＲ115は、４価の有機基を表す。４価の有機基としては、芳香環を含む４価の有機基が好ましく、下記式（５）または式（６）で表される基がより好ましい。
式（５）
Figure JPOXMLDOC01-appb-C000008
 　式（５）中、Ｒ112は、単結合、または、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ2－、－ＮＨＣＯ－ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１～３のアルキレン基、－Ｏ－、－ＣＯ－、－Ｓ－および－ＳＯ2－から選択される基であることがより好ましく、－ＣＨ2－、－Ｃ（ＣＦ3）2－、－Ｃ（ＣＨ3）2－、－Ｏ－、－ＣＯ－、－Ｓ－および－ＳＯ2－からなる群から選択される２価の基がさらに好ましい。 R 115 in the formula (2) represents a tetravalent organic group. As the 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.
Formula (5)
Figure JPOXMLDOC01-appb-C000008
 In the formula (5), 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. 2 -, - NHCO- and is preferably a group selected from these combinations, a single bond, an alkylene group which ~ 1 carbon atoms which may be 3-substituted by fluorine atoms, -O -, - CO- More preferably, 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 —.
式（６）
Figure JPOXMLDOC01-appb-C000009
 Formula (6)
Figure JPOXMLDOC01-appb-C000009
　式（２）におけるＲ115は、具体的には、テトラカルボン酸二無水物から無水物基の除去後に残存するテトラカルボン酸残基などが挙げられる。テトラカルボン酸二無水物は、１種類のみ用いても良いし、２種類以上用いても良い。
　テトラカルボン酸二無水物は、下記式（Ｏ）で表されることが好ましい。
式（Ｏ）
Figure JPOXMLDOC01-appb-C000010
 　式（Ｏ）中、Ｒ115は、４価の有機基を表す。Ｒ115の好ましい範囲は式（２）におけるＲ115と同義であり、好ましい範囲も同様である。 Specific examples of 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)
Figure JPOXMLDOC01-appb-C000010
 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.
　テトラカルボン酸二無水物の具体例としては、ピロメリト酸二無水物、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルスルフィドテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルメタンテトラカルボン酸二無水物、２，２’，３，３’－ジフェニルメタンテトラカルボン酸二無水物、２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、２，３，３’，４’－ベンゾフェノンテトラカルボン酸二無水物、４，４’－オキシジフタル酸二無水物、２，３，６，７－ナフタレンテトラカルボン酸二無水物、１，４，５，７－ナフタレンテトラカルボン酸二無水物、２，２－ビス（３，４－ジカルボキシフェニル）プロパン二無水物、２，２－ビス（２，３－ジカルボキシフェニル）プロパン二無水物、２，２－ビス（３，４－ジカルボキシフェニル）ヘキサフルオロプロパン二無水物、１，３－ジフェニルヘキサフルオロプロパン－３，３，４，４－テトラカルボン酸二無水物、１，４，５，６－ナフタレンテトラカルボン酸二無水物、２，２’，３，３’－ジフェニルテトラカルボン酸二無水物、３，４，９，１０－ペリレンテトラカルボン酸二無水物、１，２，４，５－ナフタレンテトラカルボン酸二無水物、１，４，５，８－ナフタレンテトラカルボン酸二無水物、１，８，９，１０－フェナントレンテトラカルボン酸二無水物、１，１－ビス（２，３－ジカルボキシフェニル）エタン二無水物、１，１－ビス（３，４－ジカルボキシフェニル）エタン二無水物、１，２，３，４－ベンゼンテトラカルボン酸二無水物、ならびに、これらの炭素数１～６のアルキルおよび／または炭素数１～６のアルコキシ誘導体から選ばれる少なくとも１種類が例示される。 Specific examples of 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'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene Tracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetra Carboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetra Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxyl Enyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and those having 1 to Examples thereof include at least one selected from 6 alkyl and / or alkoxy derivatives having 1 to 6 carbon atoms.
　また、下記に示すテトラカルボン酸二無水物（ＤＡＡ－１）～（ＤＡＡ－５）も好ましい例として挙げられる。
Figure JPOXMLDOC01-appb-C000011
 Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also preferable examples.
Figure JPOXMLDOC01-appb-C000011
　式（２）におけるＲ111とＲ115の少なくとも一方にヒドロキシ基を有することも好ましい。より具体的には、Ｒ111として、ビスアミノフェノール誘導体の残基が挙げられる。 It is also preferable that at least one of 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.
　式（２）におけるＲ113およびＲ114は、それぞれ独立に、水素原子または１価の有機基を表す。
　式（２）におけるＲ113およびＲ114の少なくとも一方が重合性基を含むことが好ましく、両方が重合性基を含むことが好ましい。重合性基とは、熱、ラジカル等の作用により、架橋反応することが可能な基である。重合性基としては、光ラジカル重合性基が好ましい。重合性基の具体例として、エチレン性不飽和結合を有する基、アルコキシメチル基、ヒドロキシメチル基、アシルオキシメチル基、エポキシ基、オキセタニル基、ベンゾオキサゾリル基、ブロックイソシアネート基、メチロール基、アミノ基が挙げられる。ポリイミド前駆体が有するラジカル重合性基としては、エチレン性不飽和結合を有する基が好ましい。
　エチレン性不飽和結合を有する基としては、ビニル基、（メタ）アリル基、下記式（ＩＩＩ）で表される基などが挙げられる。 R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group.
In Formula (2), 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. As the polymerizable group, a radical photopolymerizable group is preferable. Specific examples of the polymerizable group 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. Is mentioned. As a radically polymerizable group which a polyimide precursor has, group which has an ethylenically unsaturated bond is preferable.
Examples of 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.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　式（ＩＩＩ）において、Ｒ200は、水素原子またはメチル基を表し、メチル基がより好ましい。
　式（ＩＩＩ）において、Ｒ201は、炭素数２～１２のアルキレン基、－ＣＨ2ＣＨ（ＯＨ）ＣＨ2－または炭素数４～３０のポリオキシアルキレン基を表す。
　好適なＲ201の例は、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基、１，２－ブタンジイル基、１，３－ブタンジイル基、ペンタメチレン基、ヘキサメチレン基、オクタメチレン基、ドデカメチレン基、－ＣＨ2ＣＨ（ＯＨ）ＣＨ2－が挙げられ、エチレン基、プロピレン基、トリメチレン基、－ＣＨ2ＣＨ（ＯＨ）ＣＨ2－がより好ましい。
　特に好ましくは、Ｒ200がメチル基で、Ｒ201がエチレン基である。 In the formula (III), R 200 represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
In the formula (III), 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.
Examples of 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. , —CH 2 CH (OH) CH 2 —, ethylene group, propylene group, trimethylene group, and —CH 2 CH (OH) CH 2 — are more preferable.
Particularly preferably, R 200 is a methyl group and R 201 is an ethylene group.
　式（２）におけるＲ113またはＲ114は重合性基以外の１価の有機基であってもよい。
　有機溶剤への溶解度の観点からは、式（２）におけるＲ113またはＲ114は、１価の有機基であることが好ましい。１価の有機基としては、直鎖または分岐のアルキル基、環状アルキル基、あるいは、芳香族基を含むことが好ましい。１価の有機基としては、アリール基を構成する炭素に結合している１、２または３つ（好ましくは１つ）の酸性基を有する芳香族基、およびアリール基を構成する炭素に結合している１、２または３つ（好ましくは１つ）の酸性基を有するアラルキル基が特に好ましい。具体的には、酸性基を有する炭素数６～２０の芳香族基、酸性基を有する炭素数７～２５のアラルキル基が挙げられる。より具体的には、酸性基を有するフェニル基および酸性基を有するベンジル基が挙げられる。酸性基は、ヒドロキシ基が好ましい。
　Ｒ113またはＲ114が、水素原子、２－ヒドロキシベンジル、３－ヒドロキシベンジルおよび４－ヒドロキシベンジルであることが、より特に好ましい。 R 113 or R 114 in the formula (2) may be a monovalent organic group other than the polymerizable group.
From the viewpoint of solubility in an organic solvent, 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.
　式（２）におけるＲ113またはＲ114が表すアルキル基の炭素数は１～３０が好ましい。直鎖または分岐のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、テトラデシル基、オクタデシル基、イソプロピル基、イソブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基、１－エチルペンチル基、および２－エチルヘキシル基が挙げられる。
　式（２）におけるＲ113またはＲ114が表す環状のアルキル基は、単環の環状のアルキル基であってもよく、多環の環状のアルキル基であってもよい。単環の環状のアルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基およびシクロオクチル基が挙げられる。多環の環状のアルキル基としては、例えば、アダマンチル基、ノルボルニル基、ボルニル基、カンフェニル基、デカヒドロナフチル基、トリシクロデカニル基、テトラシクロデカニル基、カンホロイル基、ジシクロヘキシル基およびピネニル基が挙げられる。中でも、高感度化との両立の観点から、シクロヘキシル基が最も好ましい。また、芳香族基で置換されたアルキル基としては、後述する芳香族基で置換された直鎖アルキル基が好ましい。
　式（２）におけるＲ113またはＲ114が表す芳香族基としては、具体的には、置換または無置換のベンゼン環、ナフタレン環、ペンタレン環、インデン環、アズレン環、ヘプタレン環、インダセン環、ペリレン環、ペンタセン環、アセナフテン環、フェナントレン環、アントラセン環、ナフタセン環、クリセン環、トリフェニレン環、フルオレン環、ビフェニル環、ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、インドリジン環、インドール環、ベンゾフラン環、ベンゾチオフェン環、イソベンゾフラン環、キノリジン環、キノリン環、フタラジン環、ナフチリジン環、キノキサリン環、キノキサゾリン環、イソキノリン環、カルバゾール環、フェナントリジン環、アクリジン環、フェナントロリン環、チアントレン環、クロメン環、キサンテン環、フェノキサチイン環、フェノチアジン環またはフェナジン環である。ベンゼン環が最も好ましい。 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. Isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl 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.
Specific examples of the 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. Ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, Pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring Phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring or a phenazine ring. A benzene ring is most preferred.
　式（２）におけるＲ113が水素原子である場合、または、式（２）におけるＲ114が水素原子である場合、ポリイミド前駆体はエチレン性不飽和結合を有する３級アミン化合物と対塩を形成していてもよい。このようなエチレン性不飽和結合を有する３級アミン化合物の例としては、Ｎ，Ｎ－ジメチルアミノプロピルメタクリレートが挙げられる。 When R 113 in Formula (2) is a hydrogen atom, or when R 114 in Formula (2) is a hydrogen atom, the polyimide precursor forms a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. You may do it. Examples of such tertiary amine compounds having an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.
　また、ポリイミド前駆体は、構造単位中にフッ素原子を有することも好ましい。ポリイミド前駆体中のフッ素原子含有量は１０質量％以上が好ましく、また、２０質量％以下が好ましい。 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.
　また、基板との密着性を向上させる目的で、ポリイミド前駆体にシロキサン構造を有する脂肪族基を共重合してもよい。具体的には、シロキサン構造を有する脂肪族基を導入するためのジアミン成分として、ビス（３－アミノプロピル）テトラメチルジシロキサン、ビス（パラアミノフェニル）オクタメチルペンタシロキサンなどが挙げられる。 Further, for the purpose of improving the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the polyimide precursor. Specific examples of the diamine component for introducing an aliphatic group having a siloxane structure include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.
　式（２）で表される繰り返し単位は、下記式（２－Ａ）で表される繰り返し単位であることが好ましい。すなわち、ポリイミド前駆体の少なくとも１種類が、式（２－Ａ）で表される繰り返し単位を有する前駆体であることが好ましい。このような構造とすることにより、露光ラチチュードの幅をより広げることが可能になる。
式（２－Ａ）
Figure JPOXMLDOC01-appb-C000013
 　式（２－Ａ）中、Ａ1およびＡ2は、酸素原子を表し、Ｒ111およびＲ112は、それぞれ独立に、２価の有機基を表し、Ｒ113およびＲ114は、それぞれ独立に、水素原子または１価の有機基を表し、Ｒ113およびＲ114の少なくとも一方は、重合性基を含む基であり、重合性基であることが好ましい。 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.
Formula (2-A)
Figure JPOXMLDOC01-appb-C000013
 In formula (2-A), A 1 and A 2 each represent an oxygen atom, R 111 and R 112 each independently represent a divalent organic group, and R 113 and R 114 each independently represent It represents a hydrogen atom or a monovalent organic group, and at least one of R 113 and R 114 is a group containing a polymerizable group, and is preferably a polymerizable group.
　式（２－Ａ）におけるＡ1、Ａ2、Ｒ111、Ｒ113およびＲ114は、それぞれ独立に、式（２）におけるＡ1、Ａ2、Ｒ111、Ｒ113およびＲ114と同義であり、好ましい範囲も同様である。
　式（２－Ａ）におけるＲ112は、式（５）におけるＲ112と同義であり、好ましい範囲も同様である。 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.
　ポリイミド前駆体においては、式（２）で表される繰り返し単位が１種類であってもよいが、２種類以上であってもよい。また、ポリイミド前駆体は、式（２）で表される繰り返し単位の構造異性体を含んでいてもよい。また、ポリイミド前駆体は、上記の式（２）で表される繰り返し単位のほかに、他の種類の繰り返し単位も含んでよい。 In the polyimide precursor, 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).
　本発明におけるポリイミド前駆体の一実施形態として、全繰り返し単位の５０モル％以上、さらには７０モル％以上、特には９０モル％以上が式（２）で表される繰り返し単位であるポリイミド前駆体が例示される。 As one embodiment of the polyimide precursor in the present invention, 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). Is exemplified.
　ポリイミド前駆体は、ジカルボン酸またはジカルボン酸誘導体とジアミンを反応させて得られることが好ましい。ジカルボン酸またはジカルボン酸誘導体を、ハロゲン化剤を用いてハロゲン化させた後、ジアミンと反応させて得られることがより好ましい。ポリイミド前駆体は、例えば、低温中でテトラカルボン酸二無水物とジアミン化合物（一部をモノアミンである末端封止剤に置換）を反応させる方法、低温中でテトラカルボン酸二無水物（一部を酸無水物またはモノ酸クロリド化合物またはモノ活性エステル化合物である末端封止剤に置換）とジアミン化合物を反応させる方法、テトラカルボン酸二無水物とアルコールとによりジエステルを得、その後ジアミン（一部をモノアミンである末端封止剤に置換）と縮合剤の存在下で反応させる方法、テトラカルボン酸二無水物とアルコールとによりジエステルを得、その後残りのジカルボン酸を酸クロリド化し、ジアミン（一部をモノアミンである末端封止剤に置換）と反応させる方法などの方法を利用して、得られる。
　ポリイミド前駆体の製造方法では、反応に際し、有機溶剤を用いることが好ましい。有機溶剤は１種類でもよいし、２種類以上でもよい。
　有機溶剤としては、原料に応じて適宜定めることができるが、ピリジン、ジエチレングリコールジメチルエーテル（ジグリム）、Ｎ－メチルピロリドンおよびＮ－エチルピロリドンが例示される。 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). Is substituted with a terminal blocker which is an acid anhydride, a monoacid chloride compound or a monoactive ester compound) and a diamine compound, 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) Can be obtained by using a method such as a method of reacting with a terminal blocking agent that is a monoamine).
In the method for producing a polyimide precursor, an organic solvent is preferably used for the reaction. One type of 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.
　ポリイミド前駆体の製造に際し、保存安定性をより向上させるため、酸無水物、モノカルボン酸、モノ酸クロリド化合物、モノ活性エステル化合物などの末端封止剤で封止することが好ましい。これらのうち、モノアミンを用いることがより好ましく、モノアミンの好ましい化合物としては、アニリン、２－エチニルアニリン、３－エチニルアニリン、４－エチニルアニリン、５－アミノ－８－ヒドロキシキノリン、１－ヒドロキシ－７－アミノナフタレン、１－ヒドロキシ－６－アミノナフタレン、１－ヒドロキシ－５－アミノナフタレン、１－ヒドロキシ－４－アミノナフタレン、２－ヒドロキシ－７－アミノナフタレン、２－ヒドロキシ－６－アミノナフタレン、２－ヒドロキシ－５－アミノナフタレン、１－カルボキシ－７－アミノナフタレン、１－カルボキシ－６－アミノナフタレン、１－カルボキシ－５－アミノナフタレン、２－カルボキシ－７－アミノナフタレン、２－カルボキシ－６－アミノナフタレン、２－カルボキシ－５－アミノナフタレン、２－アミノ安息香酸、３－アミノ安息香酸、４－アミノ安息香酸、４－アミノサリチル酸、５－アミノサリチル酸、６－アミノサリチル酸、２－アミノベンゼンスルホン酸、３－アミノベンゼンスルホン酸、４－アミノベンゼンスルホン酸、３－アミノ－４，６－ジヒドロキシピリミジン、２－アミノフェノール、３－アミノフェノール、４－アミノフェノール、２－アミノチオフェノール、３－アミノチオフェノール、４－アミノチオフェノールなどが挙げられる。これらを２種類以上用いてもよく、複数の末端封止剤を反応させることにより、複数の異なる末端基を導入してもよい。 In the production of 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. Of these, it is more preferable to use 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-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4 -Aminothiophenol and the like. Two or more of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end capping agents.
　ポリイミド前駆体の製造に際し、固体を析出する工程を含んでいても良い。具体的には、反応液中のポリイミド前駆体を、水中に沈殿させ、テトラヒドロフラン等のポリイミド前駆体が可溶な溶剤に溶解させることによって、固体析出することができる。
　その後、ポリイミド前駆体を乾燥して、粉末状のポリイミド前駆体を得ることができる。 When manufacturing the polyimide precursor, 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.
　ポリイミド前駆体の重量平均分子量（Ｍｗ）は、好ましくは１８０００～３００００であり、より好ましくは２００００～２７０００であり、さらに好ましくは２２０００～２５０００である。また、数平均分子量（Ｍｎ）は、好ましくは７２００～１４０００であり、より好ましくは８０００～１２０００であり、さらに好ましくは９２００～１１２００である。
　上記ポリイミド前駆体の分散度は、２．５以上が好ましく、２．７以上がより好ましく、２．８以上であることがさらに好ましい。ポリイミド前駆体の分散度の上限値は特に定めるものではないが、例えば、４．５以下が好ましく、４．０以下がより好ましく、３．８以下がさらに好ましく、３．２以下が一層好ましく、３．１以下がより一層好ましく、３．０以下がさらに一層好ましく、２．９５以下が特に一層好ましい。 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.
（ポリイミド）
　ポリイミドとしては、イミド環を有する高分子化合物であれば、特に限定はない。ポリイミドは、下記式（４）で表される化合物であることが好ましく、式（４）で表される化合物であって、重合性基を有する化合物であることがより好ましい。
式（４）
Figure JPOXMLDOC01-appb-C000014
 　式（４）中、Ｒ131は、２価の有機基を表し、Ｒ132は、４価の有機基を表す。
　重合性基を有する場合、Ｒ131およびＲ132の少なくとも一方に重合性基を有していてもよいし、下記式（４－１）または式（４－２）に示すようにポリイミドの末端に重合性基を有していてもよい。 (Polyimide)
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.
Formula (4)
Figure JPOXMLDOC01-appb-C000014
 In formula (4), R 131 represents a divalent organic group, and R 132 represents a tetravalent organic group.
In the case of having a polymerizable 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.
式（４－１）
Figure JPOXMLDOC01-appb-C000015
 式（４－１）中、Ｒ133は重合性基であり、他の基は式（４）と同義である。 Formula (4-1)
Figure JPOXMLDOC01-appb-C000015
 In the formula (4-1), R 133 is a polymerizable group, and other groups are as defined in the formula (4).
式（４－２）
Figure JPOXMLDOC01-appb-C000016
 　式（４－２）中、Ｒ134およびＲ135の少なくとも一方は重合性基であり、他方は有機基であり、他の基は式（４）と同義である。 Formula (4-2)
Figure JPOXMLDOC01-appb-C000016
 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).
　ポリイミドが有することが好ましい重合性基は、上記のポリイミド前駆体において、式（２）におけるＲ113およびＲ114が含んでいてもよい重合性基として挙げた重合性基と同様である。 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.
　式（４）におけるＲ131は、２価の有機基を表す。２価の有機基としては、式（２）におけるＲ111と同様の２価の有機基が例示され、好ましい範囲も同様である。
　また、Ｒ131としては、ジアミンのアミノ基の除去後に残存するジアミン残基が挙げられる。ジアミンとしては、脂肪族、環式脂肪族または芳香族ジアミンなどが挙げられる。具体的な例としては、ポリイミド前駆体の式（２）中のＲ111の例が挙げられる。 R 131 in the formula (4) represents a divalent organic group. Examples of the divalent organic group include the same divalent organic groups as R 111 in formula (2), and the preferred range is also the same.
As the R 131, include diamine residues remaining after removal of the amino groups of the diamine. Examples of the diamine include aliphatic, cycloaliphatic or aromatic diamines. Specific examples include R 111 in formula (2) of the polyimide precursor.
　式（４）におけるＲ131は、少なくとも２つ以上のアルキレングリコール単位を主鎖にもつジアミン残基であることが、焼成時における反りの発生をより効果的に抑制する点で好ましい。より好ましくは、エチレングリコール鎖、プロピレングリコール鎖のいずれかまたは両方を１分子中にあわせて２つ以上含むジアミン残基であり、さらに好ましくは芳香環を含まないジアミン残基である。 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.
　エチレングリコール鎖、プロピレングリコール鎖のいずれか一方または両方を１分子中にあわせて２つ以上含むジアミンとしては、式（２）におけるＲ111を誘導できるジアミンと同様の具体例などが挙げられるが、これらに限定されない。 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.
　式（４）におけるＲ132は、４価の有機基を表す。Ｒ132が表す４価の有機基としては、式（２）におけるＲ115と同様のものが例示され、好ましい範囲も同様である。
　例えば、式（２）におけるＲ115として例示される下記構造の４価の有機基の４つの結合子が、上記式（４）中の４つの－Ｃ（＝Ｏ）－の部分と結合して縮合環を形成する。
Figure JPOXMLDOC01-appb-C000017
 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.
For example, 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.
Figure JPOXMLDOC01-appb-C000017
　式（４）におけるＲ132の例としては、テトラカルボン酸二無水物から無水物基の除去後に残存するテトラカルボン酸残基などが挙げられる。具体的な例としては、ポリイミド前駆体の式（２）中のＲ115の例が挙げられる。硬化膜の強度の観点から、Ｒ132は１～４つの芳香環を有する芳香族ジアミン残基であることが好ましい。 Examples of R 132 in formula (4) include a tetracarboxylic acid residue remaining after removal of the anhydride group from tetracarboxylic dianhydride. As a specific example, an example of R 115 in the formula (2) of the polyimide precursor can be given. From the viewpoint of the strength of the cured film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
　式（４）におけるＲ131とＲ132の少なくとも一方がヒドロキシ基を有することも好ましい。より具体的には、式（４）におけるＲ131として、２，２－ビス（３－ヒドロキシ－４－アミノフェニル）プロパン、２，２－ビス（３－ヒドロキシ－４－アミノフェニル）ヘキサフルオロプロパン、２，２－ビスー（３－アミノ－４－ヒドロキシフェニル）プロパン、２，２－ビス－（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン、上記の（ＤＡ－１）～（ＤＡ－１８）が好ましい例として挙げられる。式（４）におけるＲ132として、上記の（ＤＡＡ－１）～（ＤＡＡ－５）が好ましい例として挙げられる。 It is also preferred that at least one of 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).
　また、ポリイミドは、構造単位中にフッ素原子を有することも好ましい。ポリイミド中のフッ素原子含有量は１０質量％以上が好ましく、また、２０質量％以下が好ましい。 Also, it is preferable that 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.
　また、基板との密着性を向上させる目的で、ポリイミドにシロキサン構造を有する脂肪族の基を共重合してもよい。具体的には、シロキサン構造を有する脂肪族基を導入するためのジアミン成分として、ビス（３－アミノプロピル）テトラメチルジシロキサン、ビス（パラアミノフェニル）オクタメチルペンタシロキサンなどが挙げられる。 Further, for the purpose of improving the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with polyimide. Specific examples of the diamine component for introducing an aliphatic group having a siloxane structure include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.
　また、感光性樹脂組成物の保存安定性を向上させるため、ポリイミドの主鎖末端をモノアミン、酸無水物、モノカルボン酸、モノ酸クロリド化合物、モノ活性エステル化合物などの末端封止剤で封止することが好ましい。これらのうち、モノアミンを用いることがより好ましい。モノアミンの好ましい例としては、アニリン、２－エチニルアニリン、３－エチニルアニリン、４－エチニルアニリン、５－アミノ－８－ヒドロキシキノリン、１－ヒドロキシ－７－アミノナフタレン、１－ヒドロキシ－６－アミノナフタレン、１－ヒドロキシ－５－アミノナフタレン、１－ヒドロキシ－４－アミノナフタレン、２－ヒドロキシ－７－アミノナフタレン、２－ヒドロキシ－６－アミノナフタレン、２－ヒドロキシ－５－アミノナフタレン、１－カルボキシ－７－アミノナフタレン、１－カルボキシ－６－アミノナフタレン、１－カルボキシ－５－アミノナフタレン、２－カルボキシ－７－アミノナフタレン、２－カルボキシ－６－アミノナフタレン、２－カルボキシ－５－アミノナフタレン、２－アミノ安息香酸、３－アミノ安息香酸、４－アミノ安息香酸、４－アミノサリチル酸、５－アミノサリチル酸、６－アミノサリチル酸、２－アミノベンゼンスルホン酸、３－アミノベンゼンスルホン酸、４－アミノベンゼンスルホン酸、３－アミノ－４，６－ジヒドロキシピリミジン、２－アミノフェノール、３－アミノフェノール、４－アミノフェノール、２－アミノチオフェノール、３－アミノチオフェノール、４－アミノチオフェノールなどが挙げられる。これらを２種類以上用いてもよく、複数の末端封止剤を反応させることにより、複数の異なる末端基を導入してもよい。 In addition, in order to improve the storage stability of the photosensitive resin composition, 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. Preferred examples of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene and 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-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-amino Benzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4 , 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, and the like. Two or more of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end capping agents.
　ポリイミドはイミド化率が８５％以上であることが好ましく、９０％以上であることがより好ましい。イミド化率が８５％以上であることにより、加熱によりイミド化される場合に起こる閉環に起因する膜収縮が小さくなり、基板の反りの発生を抑制することができる。 The polyimide preferably has an imidization ratio of 85% or more, more preferably 90% or more. When 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.
　ポリイミドは、すべてが１種類のＲ131またはＲ132である上記式（４）で表される繰り返し単位に加え、２つ以上の異なる種類のＲ131またはＲ132である繰り返し単位を含んでもよい。また、ポリイミドは、上記式（４）で表される繰り返し単位のほかに、他の種類の繰り返し単位も含んでよい。 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).
　ポリイミドは、ポリイミド前駆体を合成してから、加熱して環化させて製造してもよいし、直接に、ポリイミドを合成してもよい。
　ポリイミドは、ポリイミド前駆体を得、これを、既知のイミド化反応法を用いて完全イミド化させる方法、または、途中でイミド化反応を停止し、一部イミド構造を導入する方法、さらには、完全イミド化したポリマーと、そのポリイミド前駆体をブレンドする事によって、一部イミド構造を導入する方法を利用して合成することができる。 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.
　ポリイミドの市販品としては、Ｄｕｒｉｍｉｄｅ（登録商標）２８４（富士フイルム社製）、Ｍａｔｒｉｍｉｄｅ５２１８（ＨＵＮＴＳＭＡＮ製）が例示される。 Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by Fujifilm) and Matrimide 5218 (manufactured by HUNTSMAN).
　ポリイミドの重量平均分子量（Ｍｗ）は、５，０００～７０，０００が好ましく、８，０００～５０，０００がより好ましく、１０，０００～３０，０００が特に好ましい。重量平均分子量を５，０００以上とすることにより、硬化後の膜の耐折れ性を向上させることができる。機械特性に優れた硬化膜を得るため、重量平均分子量は、２０，０００以上がより好ましい。また、ポリイミドを２種類以上含有する場合、少なくとも１種類のポリイミドの重量平均分子量が上記範囲であることが好ましい。 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. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain a cured film having excellent mechanical properties, the weight average molecular weight is more preferably 20,000 or more. Moreover, when it contains two or more types of polyimide, it is preferable that the weight average molecular weight of at least 1 type of polyimide is the said range.
（ポリベンゾオキサゾール前駆体）
　ポリベンゾオキサゾール前駆体は、その種類等について特に定めるものではなく、下記式（３）で表される繰り返し単位を含むことが好ましい。
式（３）
Figure JPOXMLDOC01-appb-C000018
 　式（３）中、Ｒ121は、２価の有機基を表し、Ｒ122は、４価の有機基を表し、Ｒ123およびＲ124は、それぞれ独立に、水素原子または１価の有機基を表す。 (Polybenzoxazole precursor)
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).
Formula (3)
Figure JPOXMLDOC01-appb-C000018
 In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 each independently represents a hydrogen atom or a monovalent organic group. To express.
　式（３）におけるＲ123およびＲ124は、それぞれ、式（２）におけるＲ113と同義であり、好ましい範囲も同様である。すなわち、式（３）におけるＲ123およびＲ124の少なくとも一方は、重合性基であることが好ましい。 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.
　式（３）におけるＲ121は、２価の有機基を表す。Ｒ121が表す２価の有機基としては、脂肪族基および芳香族基の少なくとも一方を含む基が好ましい。脂肪族基としては、直鎖の脂肪族基が好ましい。Ｒ121は、ジカルボン酸残基が好ましい。ジカルボン酸残基は、１種類のみ用いても良いし、２種類以上用いても良い。 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.
　ジカルボン酸としては、脂肪族基を含むジカルボン酸および芳香族基を含むジカルボン酸が好ましく、芳香族基を含むジカルボン酸がより好ましい。
　脂肪族基を含むジカルボン酸としては、直鎖または分岐（好ましくは直鎖）の脂肪族基を含むジカルボン酸が好ましく、直鎖または分岐（好ましくは直鎖）の脂肪族基と２つのＣＯＯＨからなるジカルボン酸がより好ましい。直鎖または分岐（好ましくは直鎖）の脂肪族基の炭素数は、２～３０であることが好ましく、２～２５であることがより好ましく、３～２０であることがさらに好ましく、４～１５であることが特に好ましく、５～１０であることが一層好ましい。直鎖の脂肪族基はアルキレン基であることが好ましい。
　直鎖の脂肪族基を含むジカルボン酸としては、マロン酸、ジメチルマロン酸、エチルマロン酸、イソプロピルマロン酸、ジ－ｎ－ブチルマロン酸、スクシン酸、テトラフルオロスクシン酸、メチルスクシン酸、２，２－ジメチルスクシン酸、２，３－ジメチルスクシン酸、ジメチルメチルスクシン酸、グルタル酸、ヘキサフルオログルタル酸、２－メチルグルタル酸、３－メチルグルタル酸、２，２－ジメチルグルタル酸、３，３－ジメチルグルタル酸、３－エチル－３－メチルグルタル酸、アジピン酸、オクタフルオロアジピン酸、３－メチルアジピン酸、ピメリン酸、２，２，６，６－テトラメチルピメリン酸、スベリン酸、ドデカフルオロスベリン酸、アゼライン酸、セバシン酸、ヘキサデカフルオロセバシン酸、１，９－ノナン二酸、ドデカン二酸、トリデカン二酸、テトラデカン二酸、ペンタデカン二酸、ヘキサデカン二酸、ヘプタデカン二酸、オクタデカン二酸、ノナデカン二酸、エイコサン二酸、ヘンエイコサン二酸、ドコサン二酸、トリコサン二酸、テトラコサン二酸、ペンタコサン二酸、ヘキサコサン二酸、ヘプタコサン二酸、オクタコサン二酸、ノナコサン二酸、トリアコンタン二酸、ヘントリアコンタン二酸、ドトリアコンタン二酸、ジグリコール酸、さらに下記式で表されるジカルボン酸等が挙げられる。 As the 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.
As the 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.
Examples of the dicarboxylic acid containing a linear aliphatic group 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, hexadecafluorosebacic acid, 1,9-nonanedioic acid Dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosandioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosane diacid Acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosandioic acid, triacontanedioic acid, hentriacontandioic acid, dotriacontanedioic acid, diglycolic acid, and the following formula And dicarboxylic acid.
Figure JPOXMLDOC01-appb-C000019
 （式中、Ｚは炭素数１～６の炭化水素基であり、ｎは１～６の整数である。）
Figure JPOXMLDOC01-appb-C000019
 (In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).
　芳香族基を含むジカルボン酸としては、以下の芳香族基を有するジカルボン酸が好ましく、以下の芳香族基と２つのＣＯＯＨのみからなるジカルボン酸がより好ましい。 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.
Figure JPOXMLDOC01-appb-C000020
 　上記の芳香族基中、Ａは－ＣＨ2－、－Ｏ－、－Ｓ－、－ＳＯ2－、－ＣＯ－、－ＮＨＣＯ－、－Ｃ（ＣＦ3）2－、および、－Ｃ（ＣＨ3）2－からなる群から選択される２価の基を表す。
Figure JPOXMLDOC01-appb-C000020
 In the above aromatic group, 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.
　芳香族基を含むジカルボン酸の具体例としては、４，４’－カルボニル二安息香酸、４，４’－ジカルボキシジフェニルエーテルおよびテレフタル酸が好ましい。 Specific examples of the dicarboxylic acid containing an aromatic group are preferably 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether and terephthalic acid.
　式（３）におけるＲ122は、４価の有機基を表す。Ｒ122が表す４価の有機基としては、上記式（２）におけるＲ115と同様のものが例示され、好ましい範囲も同様である。
　式（３）におけるＲ122は、また、ビスアミノフェノール誘導体由来の基であることが好ましい。ビスアミノフェノール誘導体由来の基としては、例えば、３，３’－ジアミノ－４，４’－ジヒドロキシビフェニル、４，４’－ジアミノ－３，３’－ジヒドロキシビフェニル、３，３’－ジアミノ－４，４’－ジヒドロキシジフェニルスルホン、４，４’－ジアミノ－３，３’－ジヒドロキシジフェニルスルホン、ビス－（３－アミノ－４－ヒドロキシフェニル）メタン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）プロパン、２，２－ビス－（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン、２，２－ビス－（４－アミノ－３－ヒドロキシフェニル）ヘキサフルオロプロパン、ビス－（４－アミノ－３－ヒドロキシフェニル）メタン、２，２－ビス－（４－アミノ－３－ヒドロキシフェニル）プロパン、４，４’－ジアミノ－３，３’－ジヒドロキシベンゾフェノン、３，３’－ジアミノ－４，４’－ジヒドロキシベンゾフェノン、４，４’－ジアミノ－３，３’－ジヒドロキシジフェニルエーテル、３，３’－ジアミノ－４，４’－ジヒドロキシジフェニルエーテル、１，４－ジアミノ－２，５－ジヒドロキシベンゼン、１，３－ジアミノ－２，４－ジヒドロキシベンゼン、１，３－ジアミノ－４，６－ジヒドロキシベンゼンなどが挙げられる。これらのビスアミノフェノールは単独にて、あるいは混合して使用してもよい。 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. , 4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2-bis (3-amino-4- Hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4- Amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4'-diamy −3,3′-dihydroxybenzophenone, 3,3′-diamino-4,4′-dihydroxybenzophenone, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 3,3′-diamino-4,4 ′ -Dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene and the like. These bisaminophenols may be used alone or in combination.
　ビスアミノフェノール誘導体のうち、下記芳香族基を有するビスアミノフェノール誘導体が好ましい。 Of the bisaminophenol derivatives, bisaminophenol derivatives having the following aromatic groups are preferred.
Figure JPOXMLDOC01-appb-C000021
 　上記式中、Ｘ1は－Ｏ－、－Ｓ－、－Ｃ（ＣＦ3）2－、－ＣＨ2－、－ＳＯ2－、－ＮＨＣＯ－を表す。
Figure JPOXMLDOC01-appb-C000021
 In the above formula, X 1 represents —O—, —S—, —C (CF 3 ) 2 —, —CH 2 —, —SO 2 —, —NHCO—.
式（Ａ－ｓ）
Figure JPOXMLDOC01-appb-C000022
 Formula (As)
Figure JPOXMLDOC01-appb-C000022
　式（Ａ－ｓ）中、Ｒ1は、水素原子、アルキレン、置換アルキレン、－Ｏ－、－Ｓ－、－ＳＯ2－、－ＣＯ－、－ＮＨＣＯ－、単結合、または下記式（Ａ－ｓｃ）の群から選ばれる有機基である。
　式（Ａ－ｓ）中、Ｒ2は水素原子、アルキル基、アルコキシ基、アシルオキシ基、環状のアルキル基のいずれかであり、同一でも異なっても良い。
　式（Ａ－ｓ）中、Ｒ3は水素原子、直鎖または分岐のアルキル基、アルコキシ基、アシルオキシ基、環状のアルキル基のいずれかであり、同一でも異なっても良い。 In the formula (As), 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).
In the formula (As), 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.
In the formula (As), 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.
式（Ａ－ｓｃ）
Figure JPOXMLDOC01-appb-C000023
 （式（Ａ－ｓｃ）中、＊は上記式（Ａ－ｓ）で示されるビスアミノフェノール誘導体のアミノフェノール基の芳香環に結合することを示す。） Formula (A-sc)
Figure JPOXMLDOC01-appb-C000023
 (In the formula (A-sc), * indicates binding to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)
　上記式（Ａ－ｓ）中、フェノール性ヒドロキシ基のオルソ位、すなわち、Ｒ3にも置換基を有することが、アミド結合のカルボニル炭素とヒドロキシ基の距離をより接近させると考えられ、低温で硬化した際に高環化率になる効果がさらに高まる点で、特に好ましい。 In the above formula (As), it is considered that the ortho-position of the phenolic hydroxy group, that is, that R 3 also has a substituent brings the distance between the carbonyl carbon of the amide bond and the hydroxy group closer. This is particularly preferable in that the effect of achieving a high cyclization rate upon curing is further enhanced.
　また、上記式（Ａ－ｓ）中、Ｒ2がアルキル基であり、且つＲ3がアルキル基であることが、ｉ線に対する高透明性と低温で硬化した際に高環化率であるという効果を維持することができ好ましい。 Further, in the above formula (As), 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.
　また、上記式（Ａ－ｓ）中、Ｒ1がアルキレンまたは置換アルキレンであることが、さらに好ましい。Ｒ1が表すアルキレンおよび置換アルキレンの具体的な例としては、－ＣＨ2－、－ＣＨ（ＣＨ3）－、－Ｃ（ＣＨ3）2－、－ＣＨ（ＣＨ2ＣＨ3）－、－Ｃ（ＣＨ3）（ＣＨ2ＣＨ3）－、－Ｃ（ＣＨ2ＣＨ3）（ＣＨ2ＣＨ3）－、－ＣＨ（ＣＨ2ＣＨ2ＣＨ3）－、－Ｃ（ＣＨ3）（ＣＨ2ＣＨ2ＣＨ3）－、－ＣＨ（ＣＨ（ＣＨ3）2）－、－Ｃ（ＣＨ3）（ＣＨ（ＣＨ3）2）－、－ＣＨ（ＣＨ2ＣＨ2ＣＨ2ＣＨ3）－、－Ｃ（ＣＨ3）（ＣＨ2ＣＨ2ＣＨ2ＣＨ3）－、－ＣＨ（ＣＨ2ＣＨ（ＣＨ3）2）－、－Ｃ（ＣＨ3）（ＣＨ2ＣＨ（ＣＨ3）2）－、－ＣＨ（ＣＨ2ＣＨ2ＣＨ2ＣＨ2ＣＨ3）－、－Ｃ（ＣＨ3）（ＣＨ2ＣＨ2ＣＨ2ＣＨ2ＣＨ3）－、－ＣＨ（ＣＨ2ＣＨ2ＣＨ2ＣＨ2ＣＨ2ＣＨ3）－、－Ｃ（ＣＨ3）（ＣＨ2ＣＨ2ＣＨ2ＣＨ2ＣＨ2ＣＨ3）－等が挙げられるが、その中でも－ＣＨ2－、－ＣＨ（ＣＨ3）－、－Ｃ（ＣＨ3）2－が、ｉ線に対する高透明性と低温で硬化した際の高環化率であるという効果を維持しながら、溶剤に対して十分な溶解性を持つ、バランスに優れるポリベンゾオキサゾール前駆体を得ることができる点で、より好ましい。 In the above formula (As), 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 2 CH 2 CH 2 CH 3 ) —, —CH (CH 2 CH (CH 3 ) 2 ) —, —C (CH 3 ) (CH 2 CH (CH 3 ) 2 ) —, —CH (CH 2 CH 2 CH 2 CH 2 CH 3 ) —, —C (CH 3 ) (CH 2 CH 2 CH 2 CH 2 CH 3 ) —, —CH (CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) -,- (CH 3) (CH 2 CH 2 CH 2 CH 2 CH 2 CH 3) - and others as mentioned, -CH 2 Among them -, - CH (CH 3) -, - C (CH 3) 2 - is, While maintaining the effect of high transparency to i-line and high cyclization rate when cured at low temperature, it is possible to obtain a polybenzoxazole precursor with excellent solubility and sufficient balance in a solvent. This is more preferable.
　上記式（Ａ－ｓ）で示されるビスアミノフェノール誘導体の製造方法としては、例えば、特開２０１３－２５６５０６号公報の段落００８５～００９４および実施例１（段落０１８９～０１９０）を参考にすることができ、これらの内容は本明細書に組み込まれる。 As a method for producing the bisaminophenol derivative represented by the above formula (As), for example, refer to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP2013-256506A. The contents of which are incorporated herein.
　上記式（Ａ－ｓ）で示されるビスアミノフェノール誘導体の構造の具体例としては、特開２０１３－２５６５０６号公報の段落００７０～００８０に記載のものが挙げられ、これらの内容は本明細書に組み込まれる。もちろん、これらに限定されるものではない。 Specific examples of the structure of the bisaminophenol derivative represented by the above formula (As) include those described in paragraphs 0070 to 0080 of JP2013-256506A, the contents of which are described in this specification. Incorporated. Of course, it is not limited to these.
　ポリベンゾオキサゾール前駆体は上記式（３）で表される繰り返し単位のほかに、他の種類の繰り返し単位も含んでよい。
　ポリベンゾオキサゾール前駆体の閉環に伴う基板の反りの発生を抑制できる点で、ポリベンゾオキサゾール前駆体は下記式（ＳＬ）で表されるジアミン残基を他の種類の繰り返し単位として含むことが好ましい。 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. .
Figure JPOXMLDOC01-appb-C000024
 　式（ＳＬ）中、Ｚは、ａ構造とｂ構造を有し、Ｒ1sは水素原子または炭素数１～１０の炭化水素基であり、Ｒ2sは炭素数１～１０の炭化水素基であり、Ｒ3s、Ｒ4s、Ｒ5s、Ｒ6sのうち少なくとも１つは芳香族基で、残りは水素原子または炭素数１～３０の有機基で、それぞれ同一でも異なっていてもよい。ａ構造およびｂ構造の重合は、ブロック重合でもランダム重合でもよい。Ｚ部分のモル％は、ａ構造は５～９５モル％、ｂ構造は９５～５モル％であり、ａ構造およびｂ構造の和は１００モル％である。
Figure JPOXMLDOC01-appb-C000024
 In formula (SL), 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, and 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%.
　式（ＳＬ）において、好ましいＺとしては、ｂ構造中のＲ5sおよびＲ6sがフェニル基であるものが挙げられる。
　また、式（ＳＬ）で表されるジアミン残基の分子量は、４００～４，０００であることが好ましく、５００～３，０００がより好ましい。式（ＳＬ）で表されるジアミン残基の分子量を上記範囲とすることで、より効果的に、ポリベンゾオキサゾール前駆体の脱水閉環後の弾性率を下げ、基板の反りを抑制できる効果と溶剤溶解性を向上させる効果を両立することができる。 In the formula (SL), preferable examples of 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. By adjusting the molecular weight of the diamine residue represented by the formula (SL) to the above range, the solvent and the effect that the elastic modulus after dehydration and ring closure of the polybenzoxazole precursor can be reduced more effectively and the warpage of the substrate can be suppressed. The effect of improving the solubility can be achieved at the same time.
　他の種類の繰り返し単位として式（ＳＬ）で表されるジアミン残基を含む場合、テトラカルボン酸二無水物から無水物基の除去後に残存するテトラカルボン酸残基を繰り返し単位として含むことも好ましい。このようなテトラカルボン酸残基の例としては、式（２）中のＲ115の例が挙げられる。 When 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. . Examples of such tetracarboxylic acid residue, and examples of R 115 in formula (2).
　ポリベンゾオキサゾール前駆体の重量平均分子量（Ｍｗ）は、例えば、後述する組成物に用いる場合、好ましくは１８０００～３００００であり、より好ましくは２００００～２９０００であり、さらに好ましくは２２０００～２８０００である。また、数平均分子量（Ｍｎ）は、好ましくは７２００～１４０００であり、より好ましくは８０００～１２０００であり、さらに好ましくは９２００～１１２００である。
　上記ポリベンゾオキサゾール前駆体の分散度は、１．４以上であることが好ましく、１．５以上がより好ましく、１．６以上であることがさらに好ましい。ポリベンゾオキサゾール前駆体の分散度の上限値は特に定めるものではないが、例えば、２．６以下が好ましく、２．５以下がより好ましく、２．４以下がさらに好ましく、２．３以下が一層好ましく、２．２以下がより一層好ましい。 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.
（ポリベンゾオキサゾール）
　ポリベンゾオキサゾールとしては、ベンゾオキサゾール環を有する高分子化合物であれば、特に限定はない。ポリベンゾオキサゾールは、下記式（Ｘ）で表される化合物であることが好ましく、下記式（Ｘ）で表される化合物であって、重合性基を有する化合物であることがより好ましい。
Figure JPOXMLDOC01-appb-C000025
 　式（Ｘ）中、Ｒ133は、２価の有機基を表し、Ｒ134は、４価の有機基を表す。
　重合性基を有する場合、Ｒ133およびＲ134の少なくとも一方に重合性基を有していてもよいし、下記式（Ｘ－１）または式（Ｘ－２）に示すようにポリベンゾオキサゾールの末端に重合性基を有していてもよい。 (Polybenzoxazole)
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.
Figure JPOXMLDOC01-appb-C000025
 Wherein (X), R 133 represents a divalent organic group, R 134 represents a tetravalent organic group.
In the case of having a polymerizable 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.
式（Ｘ－１）
Figure JPOXMLDOC01-appb-C000026
 　式（Ｘ－１）中、Ｒ135およびＲ136の少なくとも一方は重合性基であり、他方は有機基であり、他の基は式（Ｘ）と同義である。 Formula (X-1)
Figure JPOXMLDOC01-appb-C000026
 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).
式（Ｘ－２）
Figure JPOXMLDOC01-appb-C000027
 　式（Ｘ－２）中、Ｒ137は重合性基であり、他は置換基であり、他の基は式（Ｘ）と同義である。 Formula (X-2)
Figure JPOXMLDOC01-appb-C000027
 In the formula (X-2), R 137 is a polymerizable group, the other is a substituent, and the other groups are as defined in the formula (X).
　ポリベンゾオキサゾールが有することが好ましい重合性基は、上記のポリイミド前駆体が有している重合性基で述べた重合性基と同義である。 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.
　Ｒ133は、２価の有機基を表す。２価の有機基としては、脂肪族基または芳香族基が挙げられる。具体的な例としては、ポリベンゾオキサゾール前駆体の式（３）中のＲ121の例が挙げられる。また、その好ましい例はＲ121と同様である。 R 133 represents a divalent organic group. Examples of the divalent organic group include an aliphatic group and an aromatic group. Specific examples, examples of R 121 in formula (3) of the polybenzoxazole precursor thereof. Preferred examples thereof are the same as those for R 121 .
　Ｒ134は、４価の有機基を表す。４価の有機基としては、ポリベンゾオキサゾール前駆体の式（３）中のＲ122の例が挙げられる。また、その好ましい例はＲ122と同様である。
　例えば、Ｒ122として例示される４価の有機基の４つの結合子が、上記式（Ｘ）中の窒素原子、酸素原子と結合して縮合環を形成する。例えば、Ｒ134が、下記有機基である場合、下記構造を形成する。
Figure JPOXMLDOC01-appb-C000028
 R 134 represents a tetravalent organic group. Examples of 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 .
For example, 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. For example, when R 134 is the following organic group, the following structure is formed.
Figure JPOXMLDOC01-appb-C000028
　ポリベンゾオキサゾールはオキサゾール化率が８５％以上であることが好ましく、９０％以上であることがより好ましい。オキサゾール化率が８５％以上であることにより、加熱によりオキサゾール化される場合に起こる閉環に起因する膜収縮が小さくなり、反りの発生をより効果的に抑えることができる。 Polybenzoxazole preferably has an oxazolation rate of 85% or more, more preferably 90% or more. When 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.
　ポリベンゾオキサゾールは、すべてが１種類のＲ133またはＲ134である上記式（Ｘ）で表される繰り返し単位に加え、２つ以上の異なる種類のＲ133またはＲ134を含む上記式（Ｘ）で表される繰り返し単位を含んでもよい。また、ポリベンゾオキサゾールは、上記の式（Ｘ）で表される繰り返し単位のほかに、他の種類の繰り返し単位も含んでよい。 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).
　ポリベンゾオキサゾールは、例えば、ビスアミノフェノール誘導体と、Ｒ133を含むジカルボン酸並びに上記ジカルボン酸のジカルボン酸ジクロライドおよびジカルボン酸誘導体等から選ばれる化合物とを反応させてポリベンゾオキサゾール前駆体を得、これを既知のオキサゾール化反応法を用いてオキサゾール化させることで得られる。
　なお、ジカルボン酸の場合には反応収率等を高めるため、１－ヒドロキシ－１，２，３－ベンゾトリアゾール等を予め反応させた活性エステル型のジカルボン酸誘導体を用いてもよい。 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.
In the case of 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.
　ポリベンゾオキサゾールの重量平均分子量（Ｍｗ）は、５，０００～７０，０００が好ましく、８，０００～５０，０００がより好ましく、１０，０００～３０，０００が特に好ましい。重量平均分子量を５，０００以上とすることにより、硬化後の膜の耐折れ性を向上させることができる。機械特性に優れた硬化膜を得るため、重量平均分子量は、２０，０００以上がより好ましい。また、ポリベンゾオキサゾールを２種類以上含有する場合、少なくとも１種類のポリベンゾオキサゾールの重量平均分子量が上記範囲であることが好ましい。 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. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain a cured film having excellent mechanical properties, the weight average molecular weight is more preferably 20,000 or more. Moreover, when it contains two or more types of polybenzoxazole, it is preferable that the weight average molecular weight of at least 1 type of polybenzoxazole is the said range.
（その他の感光性樹脂）
　上記以外の感光性樹脂であっても本発明に適用することが可能である。その他の感光性樹脂としては、エポキシ樹脂、フェノール樹脂、ベンゾシクロブテン系樹脂が使用可能である。 (Other photosensitive resins)
Even photosensitive resins other than those described above can be applied to the present invention. As other photosensitive resins, epoxy resins, phenol resins, and benzocyclobutene resins can be used.
＜＜＜重合性化合物＞＞＞
　樹脂が重合性基を有するか、感光性樹脂組成物が重合性化合物を含むことが好ましい。このような構成とすることにより、より耐熱性に優れた硬化膜を形成することができる。
　重合性化合物は、重合性基を有する化合物であって、ラジカル、酸、塩基などにより架橋反応が可能な公知の化合物を用いることができる。重合性基としては、上記ポリイミド前駆体で述べた重合性基などが例示される。重合性化合物は１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。
　重合性化合物は、例えば、モノマー、プレポリマー、オリゴマーまたはそれらの混合物並びにそれらの多量体などの化学的形態のいずれであってもよい。 <<< polymerizable compound >>>
It is preferable that the resin has a polymerizable group or the photosensitive resin composition contains a polymerizable compound. By setting it as such a structure, the cured film excellent in heat resistance can be formed.
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. Examples of 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.
　本発明において、モノマータイプの重合性化合物（以下、重合性モノマーともいう）は、高分子化合物とは異なる化合物である。重合性モノマーは、典型的には、低分子化合物であり、分子量２０００以下の低分子化合物であることが好ましく、１５００以下の低分子化合物であることがより好ましく、分子量９００以下の低分子化合物であることがさらに好ましい。なお、重合性モノマーの分子量は、通常、１００以上である。
　また、オリゴマータイプの重合性化合物は、典型的には比較的低い分子量の重合体であり、１０個から１００個の重合性モノマーが結合した重合体であることが好ましい。オリゴマータイプの重合性化合物の重量平均分子量は、２０００～２００００であることが好ましく、２０００～１５０００がより好ましく、２０００～１００００であることが最も好ましい。 In the present invention, 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.
　重合性化合物の官能基数は、１分子中における重合性基の数を意味する。
　感光性樹脂組成物は、現像性の観点から、重合性基を２個以上含む２官能以上の重合性化合物を少なくとも１種類含むことが好ましく、３官能以上の重合性化合物を少なくとも１種類含むことがより好ましい。
　感光性樹脂組成物は、三次元架橋構造を形成して耐熱性を向上できるという点から、３官能以上の重合性化合物を少なくとも１種類含むことが好ましい。また、２官能以下の重合性化合物と３官能以上の重合性化合物との混合物であってもよい。 The number of functional groups of the polymerizable compound means the number of polymerizable groups in one molecule.
From the viewpoint of developability, 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.
　重合性化合物としては、エチレン性不飽和結合を有する基を含む化合物；ヒドロキシメチル基、アルコキシメチル基またはアシルオキシメチル基を有する化合物；エポキシ化合物；オキセタン化合物；ベンゾオキサジン化合物が好ましい。 As the polymerizable compound, 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.
（エチレン性不飽和結合を有する基を含む化合物）
　エチレン性不飽和結合を有する基としては、スチリル基、ビニル基、（メタ）アクリロイル基および（メタ）アリル基が好ましく、（メタ）アクリロイル基がより好ましい。 (Compound containing a group having an ethylenically unsaturated bond)
As a group having an ethylenically unsaturated bond, a styryl group, a vinyl group, a (meth) acryloyl group and a (meth) allyl group are preferable, and a (meth) acryloyl group is more preferable.
　エチレン性不飽和結合を有する基を含む化合物の具体例としては、不飽和カルボン酸（例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸など）やそのエステル類、アミド類、並びにこれらの多量体が挙げられ、好ましくは、不飽和カルボン酸と多価アルコール化合物とのエステル、および不飽和カルボン酸と多価アミン化合物とのアミド類、並びにこれらの多量体である。また、ヒドロキシ基やアミノ基、メルカプト基等の求核性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能イソシアネート類或いはエポキシ類との付加反応物や、単官能若しくは多官能のカルボン酸との脱水縮合反応物等も好適に使用される。また、イソシアネート基やエポキシ基等の親電子性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との付加反応物、さらに、ハロゲン基やトシルオキシ基等の脱離性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との置換反応物も好適である。また、別の例として、上記の不飽和カルボン酸の代わりに、不飽和ホスホン酸、スチレン等のビニルベンゼン誘導体、ビニルエーテル、アリルエーテル等に置き換えた化合物群を使用することも可能である。 Specific examples of 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. In addition, preferred are an ester of an unsaturated carboxylic acid and a polyhydric alcohol compound, an amide of an unsaturated carboxylic acid and a polyvalent amine compound, and a multimer thereof. In addition, addition 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. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, 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. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.
　多価アルコール化合物と不飽和カルボン酸とのエステルのモノマーの具体例としては、アクリル酸エステルとして、エチレングリコールジアクリレート、トリエチレングリコールジアクリレート、１，３－ブタンジオールジアクリレート、テトラメチレングリコールジアクリレート、プロピレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、トリメチロールエタントリアクリレート、ヘキサンジオールジアクリレート、１，４－シクロヘキサンジオールジアクリレート、テトラエチレングリコールジアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールジアクリレート、ジペンタエリスリトールヘキサアクリレート、ペンタエリスリトールテトラアクリレート、ソルビトールトリアクリレート、ソルビトールテトラアクリレート、ソルビトールペンタアクリレート、ソルビトールヘキサアクリレート、トリ（アクリロイルオキシエチル）イソシアヌレート、イソシアヌル酸エチレンオキシド変性トリアクリレート、ポリエステルアクリレートオリゴマー等がある。 Specific examples of 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. , Propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetra Ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Pentaerythritol diacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, isocyanuric acid ethylene oxide modified triacrylate, polyester acrylate There are oligomers and the like.
　メタクリル酸エステルとしては、テトラメチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ネオペンチルグリコールジメタクリレート、トリメチロールプロパントリメタクリレート、トリメチロールエタントリメタクリレート、エチレングリコールジメタクリレート、１，３－ブタンジオールジメタクリレート、ヘキサンジオールジメタクリレート、ペンタエリスリトールジメタクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラメタクリレート、ジペンタエリスリトールジメタクリレート、ジペンタエリスリトールヘキサメタクリレート、ソルビトールトリメタクリレート、ソルビトールテトラメタクリレート、ビス〔パラ（３－メタクリルオキシ－２－ヒドロキシプロポキシ）フェニル〕ジメチルメタン、ビス－〔パラ（メタクリルオキシエトキシ）フェニル〕ジメチルメタン等がある。 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 [para (methacryloxyethoxy) phenyl] dimethyl methane.
　イタコン酸エステルとしては、エチレングリコールジイタコネート、プロピレングリコールジイタコネート、１，３－ブタンジオールジイタコネート、１，４－ブタンジオールジイタコネート、テトラメチレングリコールジイタコネート、ペンタエリスリトールジイタコネート、ソルビトールテトライタコネート等がある。 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.
　クロトン酸エステルとしては、エチレングリコールジクロトネート、テトラメチレングリコールジクロトネート、ペンタエリスリトールジクロトネート、ソルビトールテトラジクロトネート等がある。 Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
　イソクロトン酸エステルとしては、エチレングリコールジイソクロトネート、ペンタエリスリトールジイソクロトネート、ソルビトールテトライソクロトネート等がある。 Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
　マレイン酸エステルとしては、エチレングリコールジマレート、トリエチレングリコールジマレート、ペンタエリスリトールジマレート、ソルビトールテトラマレート等がある。 Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.
　その他のエステルの例として、例えば、特公昭４６－２７９２６号公報、特公昭５１－４７３３４号公報、特開昭５７－１９６２３１号公報に記載の脂肪族アルコール系エステル類や、特開昭５９－５２４０号公報、特開昭５９－５２４１号公報、特開平２－２２６１４９号公報に記載の芳香族系骨格を有するもの、特開平１－１６５６１３号公報に記載のアミノ基を含むもの等も好適に用いられる。 Examples of other esters 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.
　また、多価アミン化合物と不飽和カルボン酸とのアミドのモノマーの具体例としては、メチレンビス－アクリルアミド、メチレンビス－メタクリルアミド、１，６－ヘキサメチレンビス－アクリルアミド、１，６－ヘキサメチレンビス－メタクリルアミド、ジエチレントリアミントリスアクリルアミド、キシリレンビスアクリルアミド、キシリレンビスメタクリルアミド等がある。 Specific examples of 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.
　その他の好ましいアミド系モノマーの例としては、特公昭５４－２１７２６号公報に記載のシクロへキシレン構造を有するものを挙げることができる。 Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.
　また、イソシアネートとヒドロキシ基の付加反応を用いて製造されるウレタン系付加重合性モノマーも好適であり、そのような具体例としては、例えば、特公昭４８－４１７０８号公報に記載されている１分子に２個以上のイソシアネート基を有するポリイソシアネート化合物に下記式で示されるヒドロキシ基を含むビニルモノマーを付加させた、１分子中に２個以上の重合性ビニル基を含むビニルウレタン化合物等が挙げられる。
　ＣＨ2＝Ｃ（Ｒ4）ＣＯＯＣＨ2ＣＨ（Ｒ5）ＯＨ
（ただし、Ｒ4およびＲ5は、ＨまたはＣＨ3を示す。）
　また、特開昭５１－３７１９３号公報、特公平２－３２２９３号公報、特公平２－１６７６５号公報に記載されているようなウレタンアクリレート類や、特公昭５８－４９８６０号公報、特公昭５６－１７６５４号公報、特公昭６２－３９４１７号公報、特公昭６２－３９４１８号公報に記載のエチレンオキサイド系骨格を有するウレタン化合物類も好適である。 In addition, urethane-based addition-polymerizable monomers produced by using an addition reaction between isocyanate and a hydroxy group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. And vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxy group represented by the following formula to a polyisocyanate compound having two or more isocyanate groups. .
CH 2 = C (R 4) COOCH 2 CH (R 5) OH
(However, R 4 and R 5 represent H or CH 3. )
Further, 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.
　また、エチレン性不飽和結合を有する基を含む化合物としては、特開２００９－２８８７０５号公報の段落番号００９５～０１０８に記載されている化合物を本発明においても好適に用いることができる。 As the compound containing a group having an ethylenically unsaturated bond, compounds described in paragraph numbers 0095 to 0108 of JP-A-2009-288705 can also be preferably used in the present invention.
　また、エチレン性不飽和結合を有する基を含む化合物としては、常圧下で１００℃以上の沸点を持つ化合物も好ましい。その例としては、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等の単官能のアクリレートやメタクリレート；ポリエチレングリコールジ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ヘキサンジオール（メタ）アクリレート、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、トリ（アクリロイルオキシエチル）イソシアヌレート、グリセリンやトリメチロールエタン等の多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後に（メタ）アクリレート化したもの、特公昭４８－４１７０８号、特公昭５０－６０３４号、特開昭５１－３７１９３号各公報に記載されているようなウレタン（メタ）アクリレート類、特開昭４８－６４１８３号、特公昭４９－４３１９１号、特公昭５２－３０４９０号各公報に記載されているポリエステルアクリレート類、エポキシ樹脂と（メタ）アクリル酸との反応生成物であるエポキシアクリレート類等の多官能のアクリレートやメタクリレートおよびこれらの混合物を挙げることができる。また、特開２００８－２９２９７０号公報の段落番号０２５４～０２５７に記載の化合物も好適である。また、多官能カルボン酸にグリシジル（メタ）アクリレート等の環状エーテル基とエチレン性不飽和基を有する化合物を反応させて得られる多官能（メタ）アクリレートなども挙げることができる。
　また、その他の好ましいエチレン性不飽和結合を有する基を含む化合物として、特開２０１０－１６０４１８号公報、特開２０１０－１２９８２５号公報、特許第４３６４２１６号等に記載される、フルオレン環を有し、エチレン性不飽和結合を有する基を２個以上有する化合物や、カルド樹脂も使用することが可能である。
　さらに、その他の例としては、特公昭４６－４３９４６号公報、特公平１－４０３３７号公報、特公平１－４０３３６号公報に記載の特定の不飽和化合物や、特開平２－２５４９３号公報に記載のビニルホスホン酸系化合物等もあげることができる。また、ある場合には、特開昭６１－２２０４８号公報に記載のペルフルオロアルキル基を含む構造が好適に使用される。さらに日本接着協会誌ｖｏｌ．２０、Ｎｏ．７、３００～３０８ページ（１９８４年）に光重合性モノマーおよびオリゴマーとして紹介されているものも使用することができる。 Moreover, as a compound containing the group which has an ethylenically unsaturated bond, the compound which has a boiling point of 100 degreeC or more under a normal pressure is also preferable. Examples include 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, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso Polyfunctional alcohols such as nurate, glycerin and trimethylolethane, which are added with ethylene oxide or propylene oxide and then (meth) acrylated, Japanese Patent Publication Nos. 48-41708, 50-6034, Japanese Patent Publication No. 51- Urethane (meth) acrylates as described in JP-B-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, Mention may be made, for example, of polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof. Further, the compounds described in paragraph numbers 0254 to 0257 of JP-A-2008-292970 are also suitable. Moreover, the polyfunctional (meth) acrylate etc. which are obtained by making the compound which has cyclic ether groups, such as glycidyl (meth) acrylate, and an ethylenically unsaturated group, react with polyfunctional carboxylic acid can also be mentioned.
In addition, other preferable compounds containing a group having an ethylenically unsaturated bond have a fluorene ring described in JP2010-160418A, JP2010-129825A, Japanese Patent No. 4364216, and the like. A compound having two or more groups having an ethylenically unsaturated bond, or a cardo resin can also be used.
Other examples include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493. And vinyl phosphonic acid compounds. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, 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.
　上記のほか、下記式（ＭＯ－１）～（ＭＯ－５）で表される、エチレン性不飽和結合を有する基を含む化合物も好適に用いることができる。なお、式中、Ｔがオキシアルキレン基の場合には、炭素原子側の末端がＲに結合する。 In addition to the above, compounds containing a group having an ethylenically unsaturated bond represented by the following formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　上記の各式において、ｎは０～１４の整数であり、ｍは０～８の整数である。分子内に複数存在するＲ、Ｔ、は、各々同一であっても、異なっていてもよい。
　上記式（ＭＯ－１）～（ＭＯ－５）で表される重合性化合物の各々において、複数のＲの内の少なくとも１つは、－ＯＣ（＝Ｏ）ＣＨ＝ＣＨ2、または、－ＯＣ（＝Ｏ）Ｃ（ＣＨ3）＝ＣＨ2で表される基を表す。
　上記式（ＭＯ－１）～（ＭＯ－５）で表される、エチレン性不飽和結合を有する基を含む化合物の具体例としては、特開２００７－２６９７７９号公報の段落番号０２４８～０２５１に記載されている化合物を本発明においても好適に用いることができる。 In the above formulas, 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.
In each of the polymerizable compounds represented by the above formulas (MO-1) to (MO-5), 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.
　また、特開平１０－６２９８６号公報において式（１）および（２）としてその具体例と共に記載の、多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後に（メタ）アクリレート化した化合物も、重合性化合物として用いることができる。 In addition, compounds described in JP-A-10-62986 as formulas (1) and (2) together with specific examples thereof, which are (meth) acrylated after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol are also polymerized. It can be used as a functional compound.
　さらに、特開２０１５－１８７２１１号公報の段落０１０４～０１３１に記載の化合物も採用でき、これらの内容は本明細書に組み込まれる。特に、同公報の段落０１２８～０１３０に記載の化合物が好ましい形態として例示される。 Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A No. 2015-187211 can also be employed, and the contents thereof are incorporated herein. In particular, the compounds described in paragraphs 0128 to 0130 of the publication are exemplified as preferred forms.
　エチレン性不飽和結合を有する基を含む化合物としては、ジペンタエリスリトールトリアクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬（株）製）、ジペンタエリスリトールテトラアクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬（株）製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬（株）製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としては　ＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬（株）製）、およびこれらの（メタ）アクリロイル基がエチレングリコール、プロピレングリコール残基を介して結合している構造が好ましい。これらのオリゴマータイプも使用できる。
　また、上記式（ＭＯ－１）、式（ＭＯ－２）のペンタエリスリトール誘導体および／またはジペンタエリスリトール誘導体も好ましい例として挙げられる。 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). -320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available products are KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product) And KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues. These oligomer types can also be used.
Further, preferred examples include pentaerythritol derivatives and / or dipentaerythritol derivatives of the above formulas (MO-1) and (MO-2).
　重合性化合物の市販品としては、例えばサートマー社製のエチレンオキシ鎖を４個有する４官能アクリレートであるＳＲ－４９４、エチレンオキシ鎖を４個有する２官能メタクリレートであるサートマー社製のＳＲ－２０９、日本化薬（株）製のペンチレンオキシ鎖を６個有する６官能アクリレートであるＤＰＣＡ－６０、イソブチレンオキシ鎖を３個有する３官能アクリレートであるＴＰＡ－３３０、ウレタンオリゴマーＵＡＳ－１０、ＵＡＢ－１４０（山陽国策パルプ社製）、ＮＫエステルＭ－４０Ｇ、ＮＫエステル４Ｇ、ＮＫエステルＭ－９３００、ＮＫエステルＡ－９３００、ＵＡ－７２００（新中村化学社製）、ＤＰＨＡ－４０Ｈ（日本化薬（株）製）、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＡＨ－６００、Ｔ－６００、ＡＩ－６００（共栄社化学社製）、ブレンマーＰＭＥ４００（日油（株）製）などが挙げられる。 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. (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.
　エチレン性不飽和結合を有する基を含む化合物としては、特公昭４８－４１７０８号公報、特開昭５１－３７１９３号公報、特公平２－３２２９３号公報、特公平２－１６７６５号公報に記載されているようなウレタンアクリレート類や、特公昭５８－４９８６０号公報、特公昭５６－１７６５４号公報、特公昭６２－３９４１７号公報、特公昭６２－３９４１８号公報に記載のエチレンオキサイド系骨格を有するウレタン化合物類も好適である。さらに、重合性化合物として、特開昭６３－２７７６５３号公報、特開昭６３－２６０９０９号公報、特開平１－１０５２３８号公報に記載される、分子内にアミノ構造やスルフィド構造を有する付加重合性モノマー類を用いることもできる。 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. Furthermore, addition 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.
　エチレン性不飽和結合を有する基を含む化合物は、カルボキシル基、スルホン酸基、リン酸基等の酸基を有する多官能モノマーであってもよい。酸基を有する多官能モノマーは、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルが好ましく、脂肪族ポリヒドロキシ化合物の未反応のヒドロキシ基に非芳香族カルボン酸無水物を反応させて酸基を持たせた多官能モノマーがより好ましい。特に好ましくは、脂肪族ポリヒドロキシ化合物の未反応のヒドロキシ基に非芳香族カルボン酸無水物を反応させて酸基を持たせた多官能モノマーにおいて、脂肪族ポリヒドロキシ化合物がペンタエリスリトールおよび／またはジペンタエリスリトールであるものである。市販品としては、例えば、東亞合成株式会社製の多塩基酸変性アクリルオリゴマーとして、Ｍ－５１０、Ｍ－５２０などが挙げられる。
　酸基を有する多官能モノマーは、１種類を単独で用いてもよいが、２種類以上を混合して用いてもよい。また、必要に応じて酸基を有しない多官能モノマーと酸基を有する多官能モノマーを併用してもよい。
　酸基を有する多官能モノマーの好ましい酸価としては、０．１～４０ｍｇＫＯＨ／ｇであり、特に好ましくは５～３０ｍｇＫＯＨ／ｇである。多官能モノマーの酸価が上記範囲であれば、製造や取扱性に優れ、さらには、現像性に優れる。また、重合性が良好である。 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. Particularly preferably, in a polyfunctional monomer 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, the aliphatic polyhydroxy compound 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.
As the polyfunctional monomer having an acid group, one kind may be used alone, or two or more kinds may be mixed and used. Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as needed.
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. When 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.
　エチレン性不飽和結合を有する基を含む化合物の含有量は、良好な重合性と耐熱性の観点から、感光性樹脂組成物の全固形分に対して、１～５０質量％が好ましい。下限は５質量％以上がより好ましい。上限は、３０質量％以下がより好ましい。エチレン性不飽和結合を有する基を含む化合物は１種類を単独で用いてもよいが、２種類以上を混合して用いてもよい。
　また、樹脂とエチレン性不飽和結合を有する基を含む化合物との質量割合（樹脂／重合性化合物）は、９８／２～１０／９０が好ましく、９５／５～３０／７０がより好ましく、９０／１０～５０／５０が最も好ましい。樹脂とエチレン性不飽和結合を有する基を含む化合物との質量割合が上記範囲であれば、重合性および耐熱性により優れた硬化膜を形成できる。 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. As 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 (resin / polymerizable compound) is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, 90 / 10 to 50/50 is most preferable. When the mass ratio of the resin and the compound containing a group having an ethylenically unsaturated bond is in the above range, a cured film that is superior in polymerizability and heat resistance can be formed.
（ヒドロキシメチル基、アルコキシメチル基またはアシルオキシメチル基を有する化合物）
　ヒドロキシメチル基、アルコキシメチル基またはアシルオキシメチル基を有する化合物としては、下記式（ＡＭ１）で示される化合物が好ましい。 (Compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group)
As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1) is preferable.
（ＡＭ１）
Figure JPOXMLDOC01-appb-C000031
 （式中、ｔは、１～２０の整数を示し、Ｒ4は炭素数１～２００のｔ価の有機基を示し、Ｒ5は下記式（ＡＭ２）または下記式（ＡＭ３）で示される基を示す。） (AM1)
Figure JPOXMLDOC01-appb-C000031
 (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.)
式（ＡＭ２）　　　式（ＡＭ３）
Figure JPOXMLDOC01-appb-C000032
 （式中Ｒ6は、水酸基または炭素数１～１０の有機基を示す。） Formula (AM2) Formula (AM3)
Figure JPOXMLDOC01-appb-C000032
 (Wherein R 6 represents a hydroxyl group or an organic group having 1 to 10 carbon atoms.)
　樹脂１００質量部に対して、式（ＡＭ１）で示される化合物が５質量部以上４０質量部以下であることが好ましい。さらに好ましくは、１０質量部以上３５質量部以下である。また、全重合性化合物中、下記式（ＡＭ４）で表される化合物を１０質量％以上９０質量％以下含有し、下記式（ＡＭ５）で表される化合物を全熱架橋剤中１０質量％以上９０質量％以下含有することも好ましい。 It is preferable that 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）
Figure JPOXMLDOC01-appb-C000033
 （式中、Ｒ4は炭素数１～２００の２価の有機基を示し、Ｒ5は下記式（ＡＭ２）または下記式（ＡＭ３）で示される基を示す。） (AM4)
Figure JPOXMLDOC01-appb-C000033
 (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)).
式（ＡＭ５）
Figure JPOXMLDOC01-appb-C000034
 （式中ｕは３～８の整数を示し、Ｒ4は炭素数１～２００のｕ価の有機基を示し、Ｒ5は下記式（ＡＭ２）または下記式（ＡＭ３）で示される基を示す。） Formula (AM5)
Figure JPOXMLDOC01-appb-C000034
 (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)). .)
式（ＡＭ２）　　式（ＡＭ３）
Figure JPOXMLDOC01-appb-C000035
 （式中Ｒ6は、水酸基または炭素数１～１０の有機基を示す。） Formula (AM2) Formula (AM3)
Figure JPOXMLDOC01-appb-C000035
 (Wherein R 6 represents a hydroxyl group or an organic group having 1 to 10 carbon atoms.)
　この範囲とすることで、凹凸のある基板上に感光性樹脂組成物層を形成した際に、クラックが生じることがより少なくなる。パターン加工性に優れ、５％質量減少温度が３５０℃以上、より好ましくは３８０℃以上となる高い耐熱性を有することができる。式（ＡＭ４）で示される化合物の具体例としては、４６ＤＭＯＣ、４６ＤＭＯＥＰ（以上、商品名、旭有機材工業（株）製）、ＤＭＬ－ＭＢＰＣ、ＤＭＬ－ＭＢＯＣ、ＤＭＬ－ＯＣＨＰ、ＤＭＬ－ＰＣＨＰ、ＤＭＬ－ＰＣ、ＤＭＬ－ＰＴＢＰ、ＤＭＬ－３４Ｘ、ＤＭＬ－ＥＰ、ＤＭＬ－ＰＯＰ、ｄｉｍｅｔｈｙｌｏｌＢｉｓＯＣ－Ｐ、ＤＭＬ－ＰＦＰ、ＤＭＬ－ＰＳＢＰ、ＤＭＬ－ＭＴｒｉｓＰＣ（以上、商品名、本州化学工業（株）製）、ＮＩＫＡＬＡＣ　ＭＸ－２９０（以上、商品名、（株）三和ケミカル製）、２，６－ｄｉｍｅｔｈｏｘｙｍｅｔｈｙｌ－４－ｔ－ｂｕｔｈｙｌｐｈｅｎｏｌ、２，６－ｄｉｍｅｔｈｏｘｙｍｅｔｈｙｌ－ｐ－ｃｒｅｓｏｌ、２，６－ｄｉａｃｅｔｈｏｘｙｍｅｔｈｙｌ－ｐ－ｃｒｅｓｏｌなどが挙げられる。 By setting it within this range, cracks are less likely to occur when 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. -PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKACALAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethylmethyl-4-t-butylphenol, 2,6-dimethylmethyl-p-cresol, 2,6-diacetylmethyl-p-cresol, etc. Mentioned That.
　また、式（ＡＭ５）で示される化合物の具体例としては、ＴｒｉＭＬ－Ｐ、ＴｒｉＭＬ－３５ＸＬ、ＴＭＬ－ＨＱ、ＴＭＬ－ＢＰ、ＴＭＬ－ｐｐ－ＢＰＦ、ＴＭＬ－ＢＰＡ、ＴＭＯＭ－ＢＰ、ＨＭＬ－ＴＰＰＨＢＡ、ＨＭＬ－ＴＰＨＡＰ、ＨＭＯＭ－ＴＰＰＨＢＡ、ＨＭＯＭ－ＴＰＨＡＰ（以上、商品名、本州化学工業（株）製）、ＴＭ－ＢＩＰ－Ａ（商品名、旭有機材工業（株）製）、ＮＩＫＡＬＡＣ　ＭＸ－２８０、ＮＩＫＡＬＡＣ　ＭＸ－２７０、ＮＩＫＡＬＡＣ　ＭＷ－１００ＬＭ（以上、商品名、（株）三和ケミカル製）が挙げられる。 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.).
＜＜＜光重合開始剤＞＞＞
　感光性樹脂組成物は、光重合開始剤を含有しても良い。特に、感光性樹脂組成物が光ラジカル重合開始剤を含むことにより、感光性樹脂組成物を半導体ウェハなどの基板に適用して感光性樹脂組成物層を形成した後、光を照射することで、ラジカルに起因する硬化が起こり、光照射部における溶解性を低下させることができる。このため、例えば、電極部のみをマスクしたパターンを持つフォトマスクを介して感光性樹脂組成物層を露光することで、電極のパターンにしたがって、溶解性の異なる領域を簡便に作製できるという利点がある。 <<< Photoinitiator >>>
The photosensitive resin composition may contain a photopolymerization initiator. In particular, when 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.
　光重合開始剤としては、重合性化合物の重合反応（架橋反応）を開始する能力を有する限り、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有するものが好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよい。
　光重合開始剤は、約３００～８００ｎｍ（好ましくは３３０～５００ｎｍ）の範囲内に少なくとも約５０のモル吸光係数を有する化合物を、少なくとも１種類含有していることが好ましい。化合物のモル吸光係数は、公知の方法を用いて測定することができる。具体的には、例えば、紫外可視分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５　ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチル溶剤を用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。 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.
　光重合開始剤としては、公知の化合物を制限なく使用できるが、例えば、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を有するもの、オキサジアゾール骨格を有するもの、トリハロメチル基を有するものなど）、アシルホスフィンオキサイド等のアシルホスフィン化合物、ヘキサアリールビイミダゾール、オキシム誘導体等のオキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、ケトオキシムエーテル、アミノアセトフェノン化合物、ヒドロキシアセトフェノン、アゾ系化合物、アジド化合物、メタロセン化合物、有機ホウ素化合物、鉄アレーン錯体などが挙げられる。 As the photopolymerization initiator, known compounds can be used without limitation. For example, 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.
　トリアジン骨格を有するハロゲン化炭化水素化合物としては、例えば、若林ら著、Ｂｕｌｌ．Ｃｈｅｍ．Ｓｏｃ．Ｊａｐａｎ，４２、２９２４（１９６９）記載の化合物、英国特許１３８８４９２号明細書記載の化合物、特開昭５３－１３３４２８号公報に記載の化合物、独国特許３３３７０２４号明細書記載の化合物、Ｆ．Ｃ．Ｓｃｈａｅｆｅｒなど著、Ｊ．Ｏｒｇ．Ｃｈｅｍ．；２９、１５２７（１９６４）記載の化合物、特開昭６２－５８２４１号公報に記載の化合物、特開平５－２８１７２８号公報に記載の化合物、特開平５－３４９２０号公報に記載の化合物、米国特許第４２１２９７６号明細書に記載されている化合物などが挙げられる。 Examples of halogenated hydrocarbon compounds having a triazine skeleton 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.
　米国特許第４２１２９７６号明細書に記載されている化合物としては、例えば、オキサジアゾール骨格を有する化合物（例えば、２－トリクロロメチル－５－フェニル－１，３，４－オキサジアゾール、２－トリクロロメチル－５－（４－クロロフェニル）－１，３，４－オキサジアゾール、２－トリクロロメチル－５－（１－ナフチル）－１，３，４－オキサジアゾール、２－トリクロロメチル－５－（２－ナフチル）－１，３，４－オキサジアゾール、２－トリブロモメチル－５－フェニル－１，３，４－オキサジアゾール、２－トリブロモメチル－５－（２－ナフチル）－１，３，４－オキサジアゾール；２－トリクロロメチル－５－スチリル－１，３，４－オキサジアゾール、２－トリクロロメチル－５－（４－クロロスチリル）－１，３，４－オキサジアゾール、２－トリクロロメチル－５－（４－メトキシスチリル）－１，３，４－オキサジアゾール、２－トリクロロメチル－５－（４－ｎ－ブトキシスチリル）－１，３，４－オキサジアゾール、２－トリブロモメチル－５－スチリル－１，３，４－オキサジアゾールなど）などが挙げられる。 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- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl)- 1,3,4-oxadiazole, 2-tribromomethyl-5-styryl-1,3,4-oxadiazole, etc.).
　また、上記以外の光重合開始剤として、特開２０１５－０８７６１１号公報の段落００８６に記載の化合物、特開昭５３－１３３４２８号公報、特公昭５７－１８１９号公報、同５７－６０９６号公報、および米国特許第３６１５４５５号明細書に記載された化合物などが例示され、これらの内容は本明細書に組み込まれる。 Further, as photopolymerization initiators other than the above, compounds described in paragraph 0086 of JP-A-2015-087611, JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, And compounds described in U.S. Pat. No. 3,615,455, and the like, the contents of which are incorporated herein.
　ケトン化合物としては、例えば、特開２０１５－０８７６１１号公報の段落００８７に記載の化合物が例示され、この内容は本明細書に組み込まれる。
　市販品では、カヤキュアーＤＥＴＸ（日本化薬（株）製）も好適に用いられる。 Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein.
As a commercial product, Kaya Cure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.
　光重合開始剤としては、ヒドロキシアセトフェノン化合物、アミノアセトフェノン化合物、および、アシルホスフィン化合物も好適に用いることができる。より具体的には、例えば、特開平１０－２９１９６９号公報に記載のアミノアセトフェノン系開始剤、特許第４２２５８９８号に記載のアシルホスフィンオキシド系開始剤も用いることができる。
　ヒドロキシアセトフェノン系開始剤としては、ＩＲＧＡＣＵＲＥ－１８４（ＩＲＧＡＣＵＲＥは登録商標）、ＤＡＲＯＣＵＲ－１１７３、ＩＲＧＡＣＵＲＥ－５００、ＩＲＧＡＣＵＲＥ－２９５９、ＩＲＧＡＣＵＲＥ－１２７（商品名：いずれもＢＡＳＦ社製）を用いることができる。
　アミノアセトフェノン系開始剤としては、市販品であるＩＲＧＡＣＵＲＥ－９０７、ＩＲＧＡＣＵＲＥ－３６９、および、ＩＲＧＡＣＵＲＥ－３７９（商品名：いずれもＢＡＳＦ社製）を用いることができる。
　アミノアセトフェノン系開始剤として、３６５ｎｍまたは４０５ｎｍ等の波長に極大吸収波長がマッチングされた特開２００９－１９１１７９号公報に記載の化合物も用いることができる。
　アシルホスフィン系開始剤としては、２，４，６－トリメチルベンゾイル－ジフェニル－ホスフィンオキサイドなどが挙げられる。また、市販品であるＩＲＧＡＣＵＲＥ－８１９やＩＲＧＡＣＵＲＥ－ＴＰＯ（商品名：いずれもＢＡＳＦ社製）を用いることができる。
　メタロセン化合物としては、ＩＲＧＡＣＵＲＥ－７８４（ＢＡＳＦ社製）などが例示される。 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.
As the 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.
As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
As the 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.
Examples of the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) which are commercially available products can be used.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).
　光重合開始剤として、より好ましくはオキシム化合物が挙げられる。オキシム化合物を用いることにより、露光ラチチュードをより効果的に向上させることが可能になる。オキシムエステル系化合物は、露光ラチチュード（露光マージン）が広く、かつ、熱塩基発生剤としても働くため、特に好ましい。
　オキシム化合物の具体例としては、特開２００１－２３３８４２号公報に記載の化合物、特開２０００－８００６８号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物を用いることができる。
　好ましいオキシム化合物としては、例えば、下記化合物や、３－ベンゾオキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイルオキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、および２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オンなどが挙げられる。
Figure JPOXMLDOC01-appb-C000036
 More preferred examples of the photopolymerization initiator include oxime compounds. By using the oxime compound, 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.
Figure JPOXMLDOC01-appb-C000036
　オキシム化合物としては、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年）ｐ　ｐ．１６５３－１６６０、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年）ｐｐ．１５６－１６２、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｏｔｏｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ（１９９５年）ｐｐ．２０２－２３２の各文献に記載の化合物、特開２０００－６６３８５号公報に記載の化合物、特開２０００－８００６８号公報、特表２００４－５３４７９７号公報、特開２００６－３４２１６６号公報、国際公開ＷＯ２０１５／０３６９１０号公報の各公報に記載の化合物等が挙げられる。
　市販品ではＩＲＧＡＣＵＲＥ　ＯＸＥ　０１、ＩＲＧＡＣＵＲＥ　ＯＸＥ　０２、ＩＲＧＡＣＵＲＥ　ＯＸＥ　０３、ＩＲＧＡＣＵＲＥ　ＯＸＥ　０４（以上、ＢＡＳＦ社製）、アデカオプトマーＮ－１９１９（（株）ＡＤＥＫＡ製、特開２０１２－１４０５２号公報に記載の光重合開始剤２）も好適に用いられる。また、ＴＲ－ＰＢＧ－３０４（常州強力電子新材料有限公司製）、アデカアークルズＮＣＩ－８３１およびアデカアークルズＮＣＩ－９３０（ＡＤＥＫＡ社製）も用いることができる。また、ＤＦＩ－０９１（ダイトーケミックス株式会社製）も用いることができる。 Examples of 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.
Among the commercially available products, 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. Also, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (made by ADEKA) can be used. DFI-091 (manufactured by Daitokemix Co., Ltd.) can also be used.
　また、カルバゾール環のＮ位にオキシムが連結した特表２００９－５１９９０４号公報に記載の化合物、ベンゾフェノン部位にヘテロ置換基が導入された米国特許７６２６９５７号公報に記載の化合物、色素部位にニトロ基が導入された特開２０１０－１５０２５号公報および米国特許公開２００９－２９２０３９号公報に記載の化合物、国際公開ＷＯ２００９－１３１１８９号に記載のケトオキシム化合物、トリアジン骨格とオキシム骨格を分子内に含む米国特許７５５６９１０号公報に記載の化合物、４０５ｎｍに吸収極大を有しｇ線光源に対して良好な感度を有する特開２００９－２２１１１４号公報に記載の化合物などを用いてもよい。
　また、特開２００７－２３１０００号公報、および、特開２００７－３２２７４４号公報に記載される環状オキシム化合物も好適に用いることができる。環状オキシム化合物の中でも、特に特開２０１０－３２９８５号公報、特開２０１０－１８５０７２号公報に記載されるカルバゾール色素に縮環した環状オキシム化合物は、高い光吸収性を有し高感度化の観点から好ましい。
　また、オキシム化合物の特定部位に不飽和結合を有する化合物である、特開２００９－２４２４６９号公報に記載の化合物も好適に使用することができる。
　さらに、また、フッ素原子を有するオキシム化合物を用いることも可能である。そのようなオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報に記載されている化合物、特表２０１４－５００８５２号公報の０３４５段落に記載されている化合物２４、３６～４０、特開２０１３－１６４４７１号公報の０１０１段落に記載されている化合物（Ｃ－３）などが挙げられる。具体例としては、以下の化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000037
 　最も好ましいオキシム化合物は、特開２００７－２６９７７９号公報に示される特定置換基を有するオキシム化合物や、特開２００９－１９１０６１号公報に示されるチオアリール基を有するオキシム化合物などが挙げられる。 Further, compounds described in JP-T 2009-519904, in which an oxime is linked to the N-position of the carbazole ring, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, and nitro groups in the dye moiety Introduced compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039, ketoxime compounds described in International Publication No. WO 2009-131189, US Patent No. 7556910 containing a triazine skeleton and an oxime skeleton in the molecule The compounds described in 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.
In addition, the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 can also be suitably used. Among 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.
In addition, 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.
Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds 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. And the compound (C-3) described in paragraph 0101 of JP-A No. 164471. Specific examples include the following compounds.
Figure JPOXMLDOC01-appb-C000037
 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.
　光重合開始剤は、露光感度の観点から、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、アシルホスフィン化合物、フォスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム塩化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物およびその誘導体、シクロペンタジエン－ベンゼン－鉄錯体およびその塩、ハロメチルオキサジアゾール化合物、３－アリール置換クマリン化合物からなる群より選択される化合物が好ましい。
　さらに好ましい光重合開始剤は、トリハロメチルトリアジン化合物、α－アミノケトン化合物、アシルホスフィン化合物、フォスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム塩化合物、ベンゾフェノン化合物、アセトフェノン化合物であり、トリハロメチルトリアジン化合物、α－アミノケトン化合物、オキシム化合物、トリアリールイミダゾールダイマー、ベンゾフェノン化合物からなる群より選ばれる少なくとも１種類の化合物が一層好ましく、メタロセン化合物またはオキシム化合物を用いるのがより一層好ましく、オキシム化合物が特に一層好ましい。
　また、光重合開始剤は、ベンゾフェノン、Ｎ，Ｎ′－テトラメチル－４，４′－ジアミノベンゾフェノン（ミヒラーケトン）等のＮ，Ｎ′－テトラアルキル－４，４′－ジアミノベンゾフェノン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタノン－１、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノ－プロパノン－１等の芳香族ケトン、アルキルアントラキノン等の芳香環と縮環したキノン類、ベンゾインアルキルエーテル等のベンゾインエーテル化合物、ベンゾイン、アルキルベンゾイン等のベンゾイン化合物、ベンジルジメチルケタール等のベンジル誘導体などを用いることもできる。
　また、下記式（Ｉ）で表される化合物を用いることもできる。
Figure JPOXMLDOC01-appb-C000038
 式（Ｉ）中、Ｒ50は、炭素数１～２０のアルキル基；１個以上の酸素原子によって中断された炭素数２～２０のアルキル基；炭素数１～１２のアルコキシ基；フェニル基；炭素数１～２０のアルキル基、炭素数１～１２のアルコキシ基、ハロゲン原子、シクロペンチル基、シクロヘキシル基、炭素数１～１２のアルケニル基、１個以上の酸素原子によって中断された炭素数２～１８のアルキル基および炭素数１～４のアルキル基の少なくとも１つで置換されたフェニル基；またはビフェニリルであり、Ｒ51は、式（ＩＩ）で表される基であるか、Ｒ50と同じ基であり、Ｒ52～Ｒ54は各々独立に炭素数１～１２のアルキル、炭素数１～１２のアルコキシまたはハロゲンである。
Figure JPOXMLDOC01-appb-C000039
 式中、Ｒ55～Ｒ57は、上記式（Ｉ）のＲ52～Ｒ54と同じである。 Photopolymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-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, α-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 α-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. It is also possible to use quinones fused with an aromatic ring, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyldimethyl ketal.
A compound represented by the following formula (I) can also be used.
Figure JPOXMLDOC01-appb-C000038
 In the formula (I), 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.
Figure JPOXMLDOC01-appb-C000039
 In the formula, R 55 to R 57 are the same as R 52 to R 54 in the above formula (I).
　また、光重合開始剤は、国際公開ＷＯ２０１５／１２５４６９号の段落００４８～００５５に記載の化合物を用いることもできる。 As the photopolymerization initiator, compounds described in paragraphs 0048 to 0055 of International Publication No. WO2015 / 125469 can also be used.
　感光性樹脂組成物が光重合開始剤を含む場合、光重合開始剤の含有量は、感光性樹脂組成物の全固形分に対し０．１～３０質量％が好ましく、より好ましくは０．１～２０質量％であり、さらに好ましくは０．１～１０質量％である。
　光重合開始剤は１種類のみでもよいし、２種類以上であってもよい。光重合開始剤が２種類以上の場合は、その合計が上記範囲であることが好ましい。 When the photosensitive resin composition contains a photopolymerization initiator, 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.
＜＜＜マイグレーション抑制剤＞＞＞
　感光性樹脂組成物は、さらにマイグレーション抑制剤を含むことが好ましい。マイグレーション抑制剤を含むことにより、金属層（金属配線）由来の金属イオンが感光性樹脂組成物層内へ移動することを効果的に抑制可能となる。
　マイグレーション抑制剤としては、特に制限はないが、複素環（ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピラゾール環、イソオキサゾール環、イソチアゾール環、テトラゾール環、ピリジン環、ピリダジン環、ピリミジン環、ピラジン環、ピペリジン環、ピペラジン環、モルホリン環、２Ｈ－ピラン環および６Ｈ－ピラン環、トリアジン環）を有する化合物、チオ尿素類およびメルカプト基を有する化合物、ヒンダードフェノール系化合物、サリチル酸誘導体系化合物、ヒドラジド誘導体系化合物が挙げられる。特に、トリアゾール、ベンゾトリアゾール等のトリアゾール系化合物、テトラゾール、ベンゾテトラゾール等のテトラゾール系化合物が好ましく使用できる。 <<< Migration inhibitor >>>
It is preferable that the photosensitive resin composition further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the photosensitive resin composition layer.
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 compounds and hydrazide derivative compounds. In particular, triazole compounds such as triazole and benzotriazole, and tetrazole compounds such as tetrazole and benzotetrazole can be preferably used.
　また、ハロゲンイオンなどの陰イオンを捕捉するイオントラップ剤を使用することもできる。 Also, an ion trapping agent that traps anions such as halogen ions can be used.
　その他のマイグレーション抑制剤としては、特開２０１３－１５７０１号公報の００９４段落に記載の防錆剤、特開２００９－２８３７１１号公報の段落００７３～００７６に記載の化合物、特開２０１１－５９６５６号公報の段落００５２に記載の化合物、特開２０１２－１９４５２０号公報の段落０１１４、０１１６および０１１８に記載の化合物などを使用することができる。 Other 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.
　マイグレーション抑制剤の具体例としては、１Ｈ－１，２，３－トリアゾール、１Ｈ－１，２，４－トリアゾール、１Ｈ－テトラゾールを挙げることができる。 Specific examples of the migration inhibitor include 1H-1,2,3-triazole, 1H-1,2,4-triazole and 1H-tetrazole.
　感光性樹脂組成物がマイグレーション抑制剤を有する場合、マイグレーション抑制剤の含有量は、感光性樹脂組成物の全固形分に対して、０．０１～５．０質量％が好ましく、０．０５～２．０質量％がより好ましく、０．１～１．０質量％がさらに好ましい。
　マイグレーション抑制剤は１種類のみでもよいし、２種類以上であってもよい。マイグレーション抑制剤が２種類以上の場合は、その合計が上記範囲であることが好ましい。 When the photosensitive resin composition has a migration inhibitor, 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.
＜＜＜重合禁止剤＞＞＞
　本発明で用いる感光性樹脂組成物は、重合禁止剤を含むことが好ましい。
　重合禁止剤としては、例えば、ヒドロキノン、パラメトキシフェノール、ジ－ｔｅｒｔ－ブチル－パラクレゾール、ピロガロール、パラ－ｔｅｒｔ－ブチルカテコール、パラベンゾキノン、ジフェニル－パラベンゾキノン、４，４′－チオビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、２，２′－メチレンビス（４－メチル－６－ｔｅｒｔ－ブチルフェノール）、Ｎ－ニトロソ－Ｎ－フェニルヒドロキシアミンアルミニウム塩、フェノチアジン、Ｎ－ニトロソジフェニルアミン、Ｎ－フェニルナフチルアミン、エチレンジアミン四酢酸、１，２－シクロヘキサンジアミン四酢酸、グリコールエーテルジアミン四酢酸、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、５－ニトロソ－８－ヒドロキシキノリン、１－ニトロソ－２－ナフトール、２－ニトロソ－１－ナフトール、２－ニトロソ－５－（Ｎ－エチル－Ｎ－スルフォプロピルアミノ）フェノール、Ｎ－ニトロソ－Ｎ－（１－ナフチル）ヒドロキシアミンアンモニウム塩、ビス（４－ヒドロキシ－３，５－ｔｅｒｔ－ブチル）フェニルメタンなどが好適に用いられる。また、特開２０１５－１２７８１７号公報の段落００６０に記載の重合禁止剤、および、国際公開ＷＯ２０１５／１２５４６９号の段落００３１～００４６に記載の化合物を用いることもできる。
　組成物が重合禁止剤を有する場合、重合禁止剤の含有量は、感光性樹脂組成物の全固形分に対して、０．０１～５質量％が好ましい。
　重合禁止剤は１種類のみでもよいし、２種類以上であってもよい。重合禁止剤が２種類以上の場合は、その合計が上記範囲であることが好ましい。 <<< Polymerization inhibitor >>>
The photosensitive resin composition used in the present invention preferably contains a polymerization inhibitor.
Examples of the polymerization inhibitor include hydroquinone, paramethoxyphenol, di-tert-butyl-paracresol, pyrogallol, para-tert-butylcatechol, parabenzoquinone, diphenyl-parabenzoquinone, 4,4′-thiobis (3-methyl). -6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, Ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso 2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis ( 4-hydroxy-3,5-tert-butyl) phenylmethane and the like are preferably used. In addition, 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.
When the composition has a polymerization inhibitor, 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.
＜＜＜熱塩基発生剤＞＞＞
　本発明で用いる感光性樹脂組成物は、熱塩基発生剤を含んでいてもよい。
　熱塩基発生剤としては、その種類等は特に定めるものではないが、４０℃以上に加熱すると塩基を発生する酸性化合物、および、ｐＫａ１が０～４のアニオンとアンモニウムカチオンとを有するアンモニウム塩から選ばれる少なくとも一種類を含む熱塩基発生剤を含むことが好ましい。ここで、ｐＫａ１とは、酸の第一のプロトンの解離定数（Ｋａ）の対数（－Ｌｏｇ10Ｋａ）を表し、詳細は後述する。
　このような化合物を配合することにより、ポリイミド前駆体およびポリベンゾオキサゾール前駆体などの環化反応を低温で行うことができ、また、より安定性に優れた組成物とすることができる。また、熱塩基発生剤は、加熱しなければ塩基を発生しないので、ポリイミド前駆体およびポリベンゾオキサゾール前駆体などと共存させても、保存中におけるポリイミド前駆体およびポリベンゾオキサゾール前駆体などの環化を抑制でき、保存安定性に優れている。 <<< Heat base generator >>>
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. Here, 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.
By blending such a compound, 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. In addition, since 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.
　熱塩基発生剤は、４０℃以上に加熱すると塩基を発生する酸性化合物（Ａ１）、および、ｐＫａ１が０～４のアニオンとアンモニウムカチオンとを有するアンモニウム塩（Ａ２）から選ばれる少なくとも一種類を含むことが好ましい。
　上記酸性化合物（Ａ１）および上記アンモニウム塩（Ａ２）は、加熱すると塩基を発生するので、これらの化合物から発生した塩基により、ポリイミド前駆体およびポリベンゾオキサゾール前駆体などの環化反応を促進でき、ポリイミド前駆体およびポリベンゾオキサゾール前駆体などの環化を低温で行うことができる。また、これらの化合物は、塩基により環化して硬化するポリイミド前駆体およびポリベンゾオキサゾール前駆体などと共存させても、加熱しなければポリイミド前駆体およびポリベンゾオキサゾール前駆体などの環化が殆ど進行しないので、安定性に優れたポリイミド前駆体およびポリベンゾオキサゾール前駆体などを含む感光性樹脂組成物を調製することができる。
　なお、本明細書において、酸性化合物とは、化合物を容器に１ｇ採取し、イオン交換水とテトラヒドロフランとの混合液（質量比は水／テトラヒドロフラン＝１／４）を５０ｍＬ加えて、室温で１時間撹拌して得られた溶液を、ｐＨ（ｐｏｗｅｒ　ｏｆ　ｈｙｄｒｏｇｅｎ）メーターを用いて、２０℃にて測定した値が７未満である化合物を意味する。 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. In addition, even if these compounds coexist with a polyimide precursor and a polybenzoxazole precursor which are cured by cyclization with a base, the cyclization of the polyimide precursor and the polybenzoxazole precursor proceeds almost without heating. Therefore, a photosensitive resin composition containing a polyimide precursor and a polybenzoxazole precursor excellent in stability can be prepared.
In the present specification, an acidic compound means that 1 g of a compound is collected in a container, and 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio is water / tetrahydrofuran = 1/4) is added to the mixture at room temperature for 1 hour. 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.
　本発明において、酸性化合物（Ａ１）およびアンモニウム塩（Ａ２）の塩基発生温度は、４０℃以上が好ましく、１２０～２００℃がより好ましい。塩基発生温度の上限は、１９０℃以下が好ましく、１８０℃以下がより好ましく、１６５℃以下がさらに好ましい。塩基発生温度の下限は、１３０℃以上が好ましく、１３５℃以上がより好ましい。
　酸性化合物（Ａ１）およびアンモニウム塩（Ａ２）の塩基発生温度が１２０℃以上であれば、保存中に塩基が発生しにくいので、安定性に優れたポリイミド前駆体およびポリベンゾオキサゾール前駆体などを含む感光性樹脂組成物を調製することができる。酸性化合物（Ａ１）およびアンモニウム塩（Ａ２）の塩基発生温度が２００℃以下であれば、ポリイミド前駆体およびポリベンゾオキサゾール前駆体などの環化温度を低くできる。塩基発生温度は、例えば、示差走査熱量測定を用い、化合物を耐圧カプセル中５℃／分で２５０℃まで加熱し、最も温度が低い発熱ピークのピーク温度を読み取り、ピーク温度を塩基発生温度として測定することができる。 In the present invention, 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. If 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.
　本発明において、熱塩基発生剤により発生する塩基は、２級アミンまたは３級アミンが好ましく、３級アミンがより好ましい。３級アミンは、塩基性が高いので、ポリイミド前駆体およびポリベンゾオキサゾール前駆体などの環化温度をより低くできる。また、熱塩基発生剤により発生する塩基の沸点は、８０℃以上であることが好ましく、１００℃以上であることがより好ましく、１４０℃以上であることが最も好ましい。
　また、発生する塩基の分子量は、８０～２０００が好ましい。下限は１００以上がより好ましい。上限は５００以下がより好ましい。なお、分子量の値は、構造式から求めた理論値である。 In the present invention, 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.
　本発明において、上記酸性化合物（Ａ１）は、アンモニウム塩および後述する式（１０１）または（１０２）で表される化合物から選ばれる１種類以上を含むことが好ましい。 In the present invention, 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.
　本発明において、上記アンモニウム塩（Ａ２）は、酸性化合物であることが好ましい。なお、上記アンモニウム塩（Ａ２）は、４０℃以上（好ましくは１２０～２００℃）に加熱すると塩基を発生する酸性化合物を含む化合物であってもよいし、４０℃以上（好ましくは１２０～２００℃）に加熱すると塩基を発生する酸性化合物を除く化合物であってもよい。 In the present invention, 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.
　本発明において、アンモニウム塩とは、下記式（１０１）または式（１０２）で表されるアンモニウムカチオンと、アニオンとの塩を意味する。アニオンは、アンモニウムカチオンのいずれかの一部と共有結合を介して結合していてもよく、アンモニウムカチオンの分子外に有していてもよいが、アンモニウムカチオンの分子外に有していることが好ましい。なお、アニオンが、アンモニウムカチオンの分子外に有するとは、アンモニウムカチオンとアニオンが共有結合を介して結合していない場合をいう。以下、カチオン部の分子外のアニオンを対アニオンともいう。
式（１０１）　　　　式（１０２）
Figure JPOXMLDOC01-appb-C000040
 　式（１０１）および式（１０２）中、Ｒ1～Ｒ6は、それぞれ独立に、水素原子または炭化水素基を表し、Ｒ7は炭化水素基を表す。式（１０１）および式（１０２）におけるＲ1とＲ2、Ｒ3とＲ4、Ｒ5とＲ6、Ｒ5とＲ7はそれぞれ結合して環を形成してもよい。 In the present invention, 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. In addition, that an anion has outside the molecule | numerator of an ammonium cation means the case where an ammonium cation and an anion are not couple | bonded through a covalent bond. Hereinafter, the anion outside the molecule of the cation moiety is also referred to as a counter anion.
Formula (101) Formula (102)
Figure JPOXMLDOC01-appb-C000040
 In formula (101) and formula (102), R 1 to R 6 each independently represents a hydrogen atom or a hydrocarbon group, and 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.
　アンモニウムカチオンは、下記式（Ｙ１－１）～（Ｙ１－５）のいずれかで表されることが好ましい。
Figure JPOXMLDOC01-appb-C000041
 The ammonium cation is preferably represented by any of the following formulas (Y1-1) to (Y1-5).
Figure JPOXMLDOC01-appb-C000041
　式（Ｙ１－１）～（Ｙ１－５）において、Ｒ101は、ｎ価の有機基を表し、Ｒ1およびＲ7は、式（１０１）または式（１０２）と同義である。
　式（Ｙ１－１）～（Ｙ１－５）において、Ａｒ101およびＡｒ102は、それぞれ独立に、アリール基を表し、ｎは、１以上の整数を表し、ｍは、０～５の整数を表す。 In formulas (Y1-1) to (Y1-5), R 101 represents an n-valent organic group, and R 1 and R 7 have the same meanings as formula (101) or formula (102).
In formulas (Y1-1) to (Y1-5), Ar 101 and Ar 102 each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0 to 5 .
　本発明において、アンモニウム塩は、ｐＫａ１が０～４のアニオンとアンモニウムカチオンとを有することが好ましい。アニオンのｐＫａ１の上限は、３．５以下がより好ましく、３．２以下が一層好ましい。下限は、０．５以上が好ましく、１．０以上がより好ましい。アニオンのｐＫａ１が上記範囲であれば、ポリイミド前駆体およびポリベンゾオキサゾール前駆体などを低温で環化でき、さらには、ポリイミド前駆体およびポリベンゾオキサゾール前駆体などを含む感光性樹脂組成物の安定性を向上できる。ｐＫａ１が４以下であれば、熱塩基発生剤の安定性が良好で、加熱なしに塩基が発生することを抑制でき、ポリイミド前駆体およびポリベンゾオキサゾール前駆体などを含む感光性樹脂組成物の安定性が良好である。ｐＫａ１が０以上であれば、発生した塩基が中和されにくく、ポリイミド前駆体およびポリベンゾオキサゾール前駆体などの環化効率が良好である。
　アニオンの種類は、カルボン酸アニオン、フェノールアニオン、リン酸アニオンおよび硫酸アニオンから選ばれる１種類が好ましく、塩の安定性と熱分解性を両立させられるという理由からカルボン酸アニオンがより好ましい。すなわち、アンモニウム塩は、アンモニウムカチオンとカルボン酸アニオンとの塩がより好ましい。
　カルボン酸アニオンは、２個以上のカルボキシル基を持つ２価以上のカルボン酸のアニオンが好ましく、２価のカルボン酸のアニオンがより好ましい。この態様によれば、ポリイミド前駆体およびポリベンゾオキサゾール前駆体などを含む感光性樹脂組成物の安定性、硬化性および現像性をより向上できる熱塩基発生剤とすることができる。特に、２価のカルボン酸のアニオンを用いることで、ポリイミド前駆体およびポリベンゾオキサゾール前駆体などを含む感光性樹脂組成物の安定性、硬化性および現像性をさらに向上できる。
　本発明において、カルボン酸アニオンは、ｐＫａ１が４以下のカルボン酸のアニオンであることが好ましい。ｐＫａ１は、３．５以下がより好ましく、３．２以下が一層好ましい。この態様によれば、ポリイミド前駆体およびポリベンゾオキサゾール前駆体などを含む感光性樹脂組成物の安定性をより向上できる。
　ここでｐＫａ１とは、酸の第一のプロトンの解離定数の逆数の対数を表し、Ｄｅｔｅｒｍｉｎａｔｉｏｎ　ｏｆ　Ｏｒｇａｎｉｃ　Ｓｔｒｕｃｔｕｒｅｓ　ｂｙ　Ｐｈｙｓｉｃａｌ　Ｍｅｔｈｏｄｓ（著者：Ｂｒｏｗｎ，　Ｈ．　Ｃ．，　ＭｃＤａｎｉｅｌ，　Ｄ．　Ｈ．，　Ｈａｆｌｉｇｅｒ，　Ｏ．，　Ｎａｃｈｏｄ，　Ｆ．　Ｃ．；　編纂：Ｂｒａｕｄｅ，　Ｅ．　Ａ．，　Ｎａｃｈｏｄ，　Ｆ．　Ｃ．；　Ａｃａｄｅｍｉｃ　Ｐｒｅｓｓ，　Ｎｅｗ　Ｙｏｒｋ，　１９５５）や、Ｄａｔａ　ｆｏｒ　Ｂｉｏｃｈｅｍｉｃａｌ　Ｒｅｓｅａｒｃｈ（著者：Ｄａｗｓｏｎ，　Ｒ．Ｍ．Ｃ．ｅｔ　ａｌ；　Ｏｘｆｏｒｄ，　Ｃｌａｒｅｎｄｏｎ　Ｐｒｅｓｓ，　１９５９）に記載の値を参照することができる。これらの文献に記載の無い化合物については、ＡＣＤ／ｐＫａ（ＡＣＤ／Ｌａｂｓ製）のソフトを用いて構造式より算出した値を用いることとする。 In the present invention, 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. If 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. That is, 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. According to this aspect, it can be set as the thermal base generator which can improve more stability, sclerosis | hardenability, and developability of the photosensitive resin composition containing a polyimide precursor, a polybenzoxazole precursor, etc. In particular, by using 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.
In the present invention, 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.
Here, 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.
　カルボン酸アニオンは、下記式（Ｘ１）で表されることが好ましい。
Figure JPOXMLDOC01-appb-C000042
 　式（Ｘ１）において、ＥＷＧは、電子求引性基を表す。 The carboxylate anion is preferably represented by the following formula (X1).
Figure JPOXMLDOC01-appb-C000042
 In the formula (X1), EWG represents an electron withdrawing group.
　本発明において電子求引性基とは、ハメットの置換基定数σｍが正の値を示すものを意味する。ここでσｍは、都野雄甫総説、有機合成化学協会誌第２３巻第８号（１９６５）ｐ．６３１－６４２に詳しく説明されている。なお、本発明における電子求引性基は、上記文献に記載された置換基に限定されるものではない。
　σｍが正の値を示す置換基の例としては例えば、ＣＦ3基（σｍ＝０．４３）、ＣＦ3ＣＯ基（σｍ＝０．６３）、ＨＣ≡Ｃ基（σｍ＝０．２１）、ＣＨ2＝ＣＨ基（σｍ＝０．０６）、Ａｃ基（σｍ＝０．３８）、ＭｅＯＣＯ基（σｍ＝０．３７）、ＭｅＣＯＣＨ＝ＣＨ基（σｍ＝０．２１）、ＰｈＣＯ基（σｍ＝０．３４）、Ｈ2ＮＣＯＣＨ2基（σｍ＝０．０６）などが挙げられる。なお、Ｍｅはメチル基を表し、Ａｃはアセチル基を表し、Ｐｈはフェニル基を表す。 In the present invention, the electron withdrawing group means a group having a positive Hammett's substituent constant σm. Here, σm is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) p. 631-642. In addition, the electron withdrawing group in this invention is not limited to the substituent described in the said literature.
Examples of substituents in which σm has a positive value include, for example, CF 3 group (σm = 0.43), CF 3 CO group (σm = 0.63), HC≡C group (σm = 0.21), CH 2 ═CH group (σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH═CH group (σm = 0.21), PhCO group (σm = 0.34), H 2 NCOCH 2 group (σm = 0.06), and the like. Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.
　ＥＷＧは、下記式（ＥＷＧ－１）～（ＥＷＧ－６）で表される基であることが好ましい。
Figure JPOXMLDOC01-appb-C000043
 　式（ＥＷＧ－１）～（ＥＷＧ－６）中、Ｒx1～Ｒx3は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アリール基、ヒドロキシ基またはカルボキシル基を表し、Ａｒは芳香族基を表す。 EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
Figure JPOXMLDOC01-appb-C000043
 In the 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.
　本発明において、カルボン酸アニオンは、下記式（ＸＡ）で表されることが好ましい。
式（ＸＡ）
Figure JPOXMLDOC01-appb-C000044
 　式（ＸＡ）において、Ｌ10は、単結合、または、アルキレン基、アルケニレン基、芳香族基、－ＮＲX－およびこれらの組み合わせから選ばれる２価の連結基を表し、ＲXは、水素原子、アルキル基、アルケニル基またはアリール基を表す。 In the present invention, the carboxylate anion is preferably represented by the following formula (XA).
Formula (XA)
Figure JPOXMLDOC01-appb-C000044
 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.
　カルボン酸アニオンの具体例としては、マレイン酸アニオン、フタル酸アニオン、Ｎ－フェニルイミノ二酢酸アニオンおよびシュウ酸アニオンが挙げられる。これらを好ましく用いることができる。 Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenyliminodiacetic acid anion, and an oxalate anion. These can be preferably used.
　熱塩基発生剤の具体例としては、以下の化合物を挙げることができる。
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000046
 Specific examples of the thermal base generator include the following compounds.
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
　熱塩基発生剤を用いる場合、感光性樹脂組成物における熱塩基発生剤の含有量は、感光性樹脂組成物の全固形分に対し、０．１～５０質量％が好ましい。下限は、０．５質量％以上がより好ましく、１質量％以上がさらに好ましい。上限は、３０質量％以下がより好ましく、２０質量％以下がさらに好ましい。
　熱塩基発生剤は、１種類または２種類以上を用いることができる。２種類以上を用いる場合は、合計量が上記範囲であることが好ましい。 When a thermal base generator is used, 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.
＜＜＜金属接着性改良剤＞＞＞
　本発明で用いる感光性樹脂組成物は、電極や配線などに用いられる金属材料との接着性を向上させるための金属接着性改良剤を含んでいることが好ましい。金属接着性改良剤の例としては、特開２０１４－１８６１８６号公報の段落００４６～００４９や、特開２０１３－０７２９３５号公報の段落００３２～００４３に記載のスルフィド系化合物が挙げられる。金属接着性改良剤としては、また、下記化合物（Ｎ－［３－（トリエトキシシリル）プロピル］マレイン酸モノアミドなど）も例示される。
Figure JPOXMLDOC01-appb-C000048
 　金属接着性改良剤は樹脂１００質量部に対して好ましくは０．１～３０質量部であり、さらに好ましくは０．５～１５質量部の範囲である。０．１質量部以上とすることで硬化工程後の硬化膜と金属層との接着性が良好となり、３０質量部以下とすることで硬化工程後の硬化膜の耐熱性、機械特性が良好となる。
　金属接着性改良剤は１種類のみでもよいし、２種類以上であってもよい。２種類以上用いる場合は、その合計が上記範囲であることが好ましい。 <<< Metal adhesion improver >>>
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. Examples of the metal adhesion improver include sulfide compounds described in paragraphs 0046 to 0049 of JP2014-186186A and paragraphs 0032 to 0043 of JP2013-072935A. Examples of the metal adhesion improver also include the following compounds (N- [3- (triethoxysilyl) propyl] maleic acid monoamide and the like).
Figure JPOXMLDOC01-appb-C000048
 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. Become.
Only one type of metal adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is the said range.
＜＜＜溶剤＞＞＞
　本発明で用いる感光性樹脂組成物を塗布によって層状にする場合、溶剤を配合することが好ましい。溶剤は、感光性樹脂組成物を層状に形成できれば、公知のものを制限なく使用できる。溶剤としては、エステル類、エーテル類、ケトン類、芳香族炭化水素類、スルホキシド類などの化合物が挙げられる。
　エステル類として、例えば、酢酸エチル、酢酸－ｎ－ブチル、酢酸イソブチル、ギ酸アミル、酢酸イソアミル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、γ－ブチロラクトン、ε－カプロラクトン、δ－バレロラクトン、アルキルオキシ酢酸アルキル（例：アルキルオキシ酢酸メチル、アルキルオキシ酢酸エチル、アルキルオキシ酢酸ブチル（例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等））、３－アルキルオキシプロピオン酸アルキルエステル類（例：３－アルキルオキシプロピオン酸メチル、３－アルキルオキシプロピオン酸エチル等（例えば、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル等））、２－アルキルオキシプロピオン酸アルキルエステル類（例：２－アルキルオキシプロピオン酸メチル、２－アルキルオキシプロピオン酸エチル、２－アルキルオキシプロピオン酸プロピル等（例えば、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル））、２－アルキルオキシ－２－メチルプロピオン酸メチルおよび２－アルキルオキシ－２－メチルプロピオン酸エチル（例えば、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル等）、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル等が好適に挙げられる。
　エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等が好適に挙げられる。
　ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、２－ヘプタノン、３－ヘプタノン、Ｎ－メチル－２－ピロリドン等が好適に挙げられる。
　芳香族炭化水素類として、例えば、トルエン、キシレン、アニソール、リモネン等が好適に挙げられる。
　スルホキシド類としてジメチルスルホキシドが好適に挙げられる。 <<< Solvent >>>
When making the photosensitive resin composition used by this invention into a layer form by application | coating, it is preferable to mix | blend a solvent. Any known solvent can be used without limitation as long as the photosensitive resin composition can be formed into a layer. Examples of the solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.
Examples of 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, γ-butyrolactone, and ε-caprolactone , Δ-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 3-alkyloxypropionate, etc. (for example, methyl 3-methoxypropionate, 3-methoxypropionic acid, etc.) , Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyloxy) Propyl oxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, pyruvin Ethyl acid, pill Phosphate propyl, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2-ethyl-oxobutanoate can be preferably used.
Examples of 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.
Preferred examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like.
Preferable examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
Preferred examples of the sulfoxides include dimethyl sulfoxide.
　溶剤は、塗布面状の改良などの観点から、２種類以上を混合する形態も好ましい。なかでも、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、シクロペンタノン、γ－ブチロラクトン、ジメチルスルホキシド、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールメチルエーテル、およびプロピレングリコールメチルエーテルアセテートから選択される２種類以上で構成される混合溶液が好ましい。ジメチルスルホキシドとγ－ブチロラクトンとの併用が特に好ましい。 The solvent is preferably in the form of a mixture of two or more types from the viewpoint of improving the coated surface. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone 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 γ-butyrolactone is particularly preferred.
　感光性樹脂組成物が溶剤を有する場合、溶剤の含有量は、塗布性の観点から、感光性樹脂組成物の全固形分濃度が５～８０質量％になる量とすることが好ましく、５～７０質量％がさらに好ましく、１０～６０質量％が特に好ましい。溶剤の含有量は、所望の厚さと塗布方法に応じて調節すればよい。例えば塗布方法がスピンコートやスリットコートであれば上記範囲の固形分濃度となる溶剤の含有量が好ましい。スプレーコートであれば０．１質量％～５０質量％になる量とすることが好ましく、１．０質量％～２５質量％とすることが好ましい。塗布方法に応じて溶剤の含有量を調節することで、所望の厚さの感光性樹脂組成物層を均一に形成することができる。
　溶剤は１種類のみでもよいし、２種類以上であってもよい。溶剤が２種類以上の場合は、その合計が上記範囲であることが好ましい。
　また、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミドおよびＮ，Ｎ－ジメチルホルムアミドの含有量は、膜強度の観点から、感光性樹脂組成物の全質量に対して５質量％未満が好ましく、１質量％未満がより好ましく、０．５質量％未満が特に好ましく、０．１質量％未満がより特に好ましい。 When the photosensitive resin composition has a solvent, 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.
＜＜＜その他の添加剤＞＞＞
　本発明で用いる感光性樹脂組成物は、本発明の効果を損なわない範囲で、必要に応じて、各種類の添加物、例えば、光塩基発生剤、熱重合開始剤、熱酸発生剤、シランカップリング剤、増感色素、連鎖移動剤、界面活性剤、高級脂肪酸誘導体、無機粒子、硬化剤、硬化触媒、充填剤、酸化防止剤、紫外線吸収剤、凝集防止剤等を配合することができる。これらの添加剤を配合する場合、その合計配合量は組成物の固形分の３質量％以下とすることが好ましい。 <<< Other additives >>>
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. . When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.
（光塩基発生剤）
　本発明で用いる感光性樹脂組成物は、光塩基発生剤を含んでいてもよい。光塩基発生剤とは、露光により塩基を発生するものであり、常温常圧の通常の条件下では活性を示さないが、外部刺激として電磁波の照射と加熱が行なわれると、塩基（塩基性物質）を発生するものであれば特に限定されるものではない。露光により発生した塩基はポリイミド前駆体およびベンゾオキサゾール前駆体などを加熱により硬化させる際の触媒として働くため、ネガ型において好適に用いることができる。 (Photobase generator)
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.
　光塩基発生剤の含有量としては、所望のパターンを形成できるものであれば特に限定されるものではなく、一般的な含有量とすることができる。光塩基発生剤が、樹脂１００質量部に対して、０．０１質量部以上３０質量部未満の範囲内であることが好ましく、０．０５質量部～２５質量部の範囲内であることがより好ましく、０．１質量部～２０質量部の範囲内であることがさらに好ましい。
　光塩基発生剤は１種類のみでもよいし、２種類以上であってもよい。光塩基発生剤が２種類以上の場合は、その合計が上記範囲であることが好ましい。 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.
　本発明においては、光塩基発生剤として公知のものを用いることができる。例えば、Ｍ．Ｓｈｉｒａｉ，　ａｎｄ　Ｍ．Ｔｓｕｎｏｏｋａ，　Ｐｒｏｇ．Ｐｏｌｙｍ．Ｓｃｉ．，２１，１（１９９６）；角岡正弘，高分子加工，４６，２（１９９７）；Ｃ．Ｋｕｔａｌ，Ｃｏｏｒｄ．Ｃｈｅｍ．Ｒｅｖ．，２１１，３５３（２００１）；Ｙ．Ｋａｎｅｋｏ，Ａ．Ｓａｒｋｅｒ，　ａｎｄ　Ｄ．Ｎｅｃｋｅｒｓ，Ｃｈｅｍ．Ｍａｔｅｒ．，１１，１７０（１９９９）；Ｈ．Ｔａｃｈｉ，Ｍ．Ｓｈｉｒａｉ，　ａｎｄ　Ｍ．Ｔｓｕｎｏｏｋａ，Ｊ．Ｐｈｏｔｏｐｏｌｙｍ．Ｓｃｉ．Ｔｅｃｈｎｏｌ．，１３，１５３（２０００）；Ｍ．Ｗｉｎｋｌｅ，　ａｎｄ　Ｋ．Ｇｒａｚｉａｎｏ，Ｊ．Ｐｈｏｔｏｐｏｌｙｍ．Ｓｃｉ．Ｔｅｃｈｎｏｌ．，３，４１９（１９９０）；Ｍ．Ｔｓｕｎｏｏｋａ，Ｈ．Ｔａｃｈｉ，　ａｎｄ　Ｓ．Ｙｏｓｈｉｔａｋａ，Ｊ．Ｐｈｏｔｏｐｏｌｙｍ．Ｓｃｉ．Ｔｅｃｈｎｏｌ．，９，１３（１９９６）；Ｋ．Ｓｕｙａｍａ，Ｈ．Ａｒａｋｉ，Ｍ．Ｓｈｉｒａｉ，Ｊ．Ｐｈｏｔｏｐｏｌｙｍ．Ｓｃｉ．Ｔｅｃｈｎｏｌ．，１９，８１（２００６）に記載されているように、遷移金属化合物錯体や、アンモニウム塩などの構造を有するものや、アミジン部分がカルボン酸と塩形成することで潜在化されたもののように、塩基成分が塩を形成することにより中和されたイオン性の化合物や、カルバメート誘導体、オキシムエステル誘導体、アシル化合物などのウレタン結合やオキシム結合などにより塩基成分が潜在化された非イオン性の化合物を挙げることができる。
　本発明に用いることができる光塩基発生剤は、特に限定されず公知のものを用いることができ、例えば、カルバメート誘導体、アミド誘導体、イミド誘導体、αコバルト錯体類、イミダゾール誘導体、桂皮酸アミド誘導体、オキシム誘導体等が挙げられる。
　光塩基発生剤としては、例えば、特開２００９－８０４５２号公報および国際公開ＷＯ２００９／１２３１２２号で開示されたような桂皮酸アミド構造を有する光塩基発生剤、特開２００６－１８９５９１号公報および特開２００８－２４７７４７号公報で開示されたようなカルバメート構造を有する光塩基発生剤、特開２００７－２４９０１３号公報および特開２００８－００３５８１号公報で開示されたようなオキシム構造、カルバモイルオキシム構造を有する光塩基発生剤等が挙げられるが、これらに限定されず、その他にも公知の光塩基発生剤を用いることができる。
　その他、光塩基発生剤としては、特開２０１２－９３７４６号公報の段落０１８５～０１８８、０１９９～０２００および０２０２に記載の化合物、特開２０１３－１９４２０５号公報の段落００２２～００６９に記載の化合物、特開２０１３－２０４０１９号公報の段落００２６～００７４に記載の化合物、ならびに国際公開ＷＯ２０１０／０６４６３１号の段落００５２に記載の化合物が例として挙げられる。 In the present invention, known photobase generators can be used. For example, 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. Sci. Technol. 3,419 (1990); Tsunooka, H .; Tachi, and S.M. Yoshitaka, J. et al. Photopolym. Sci. Technol. , 9, 13 (1996); Suyama, H .; Araki, M .; Shirai, J. et al. Photopolym. Sci. Technol. , 19, 81 (2006), as described in 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, An ionic compound neutralized by forming a salt with a base component, or a nonionic compound in which the base component is made latent by a urethane bond or oxime bond such as a carbamate derivative, an oxime ester derivative, or an acyl compound. Can be mentioned.
The photobase generator that can be used in the present invention is not particularly limited and known ones can be used. For example, carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, Examples thereof include oxime derivatives.
Examples of 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. are mentioned, it is not limited to these, In addition, a well-known photobase generator can be used.
Other 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.
（熱重合開始剤）
　本発明で用いる感光性樹脂組成物は、熱重合開始剤（好ましくは熱ラジカル重合開始剤）を含んでいてもよい。熱ラジカル重合開始剤としては、公知の熱ラジカル重合開始剤を用いることができる。
　熱ラジカル重合開始剤は、熱のエネルギーによってラジカルを発生し、重合性化合物の重合反応を開始または促進させる化合物である。熱ラジカル重合開始剤を添加することによって、ポリイミド前駆体およびポリベンゾオキサゾール前駆体の環化反応を進行させる際に、重合性化合物の重合反応を進行させることができる。また、ポリイミド前駆体およびポリベンゾオキサゾール前駆体がエチレン性不飽和結合を含む場合は、ポリイミド前駆体およびポリベンゾオキサゾール前駆体の環化と共に、ポリイミド前駆体およびポリベンゾオキサゾール前駆体の重合反応を進行させることもできるので、より高度な耐熱化が達成できることとなる。
　熱ラジカル重合開始剤として、具体的には、特開２００８－６３５５４号公報の段落００７４～０１１８に記載されている化合物が挙げられる。 (Thermal polymerization initiator)
The photosensitive resin composition used in the present invention may contain a thermal polymerization initiator (preferably a thermal radical polymerization initiator). As the 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. When the polyimide precursor and polybenzoxazole precursor contain an ethylenically unsaturated bond, the polymerization reaction of the polyimide precursor and polybenzoxazole precursor proceeds with the cyclization of the polyimide precursor and polybenzoxazole precursor. Therefore, higher heat resistance can be achieved.
Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.
　感光性樹脂組成物が熱ラジカル重合開始剤を有する場合、熱ラジカル重合開始剤の含有量は、感光性樹脂組成物の全固形分に対し０．１～５０質量％が好ましく、０．１～３０質量％がより好ましく、０．１～２０質量％が特に好ましい。また、重合性化合物１００質量部に対し、熱ラジカル重合開始剤を０．１～５０質量部含むことが好ましく、０．５～３０質量部含むことがより好ましい。この態様によれば、より耐熱性に優れた硬化膜を形成しやすい。
　熱ラジカル重合開始剤は１種類のみでもよいし、２種類以上であってもよい。熱ラジカル重合開始剤が２種類以上の場合は、その合計が上記範囲であることが好ましい。 When the photosensitive resin composition has a thermal radical polymerization initiator, 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.
（熱酸発生剤）
　本発明で用いる感光性樹脂組成物は、熱酸発生剤を含んでいてもよい。熱酸発生剤は、加熱により酸を発生し、ポリイミド前駆体およびポリベンゾオキサゾール前駆体の環化を促進し硬化膜の機械特性をより向上させる。さらに熱酸発生剤は、ヒドロキシメチル基、アルコキシメチル基またはアシルオキシメチル基を有する化合物、エポキシ化合物、オキセタン化合物およびベンゾオキサジン化合物から選ばれる少なくとも１種類の化合物の架橋反応を促進させる効果がある。 (Thermal acid generator)
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.
　熱酸発生剤の例としては、特開２０１３－０７２９３５号公報の段落００５５に記載のものが挙げられる。 Examples of the thermal acid generator include those described in paragraph 0055 of JP2013-072935A.
　また、特開２０１３－１６７７４２号公報の段落００５９に記載の化合物も熱酸発生剤として好ましい。 In addition, the compound described in paragraph 0059 of JP2013-167742A is also preferable as the thermal acid generator.
　熱酸発生剤の含有量は、ポリイミド前駆体およびポリベンゾオキサゾール前駆体１００質量部に対して０．０１質量部以上が好ましく、０．１質量部以上がより好ましい。０．０１質量部以上含有することで、架橋反応およびポリイミド前駆体およびポリベンゾオキサゾール前駆体の環化が促進されるため、硬化膜の機械特性および耐薬品性をより向上させることができる。また、硬化膜の電気絶縁性の観点から、２０質量部以下が好ましく、１５質量部以下がより好ましく、１０質量部以下が特に好ましい。
　熱酸発生剤は、１種類のみ用いても、２種類以上用いてもよい。２種類以上用いる場合は、合計量が上記範囲となることが好ましい。 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. 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. Moreover, 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 said range.
（シランカップリング剤）
　本発明で用いる感光性樹脂組成物は、基板との密着性を向上させるために、シランカップリング剤を含んでいてもよい。
　シランカップリング剤の例としては、特開２０１４－１９１００２号公報の段落００６２～００７３に記載の化合物、国際公開ＷＯ２０１１／０８０９９２Ａ１号の段落００６３～００７１に記載の化合物、特開２０１４－１９１２５２号公報の段落００６０～００６１に記載の化合物、特開２０１４－４１２６４号公報の段落００４５～００５２に記載の化合物、国際公開ＷＯ２０１４／０９７５９４号の段落００５５に記載の化合物が挙げられる。また、特開２０１１－１２８３５８号公報の段落００５０～００５８に記載のように異なる２種類以上のシランカップリング剤を用いることも好ましい。
　シランカップリング剤は樹脂１００質量部に対して好ましくは０．１～２０質量部であり、さらに好ましくは１～１０質量部の範囲である。０．１質量部以上であると、基板とのより充分な密着性を付与することができ、２０質量部以下であると室温保存時において粘度上昇等の問題をより抑制できる。
　シランカップリング剤は、１種類のみ用いても、２種類以上用いてもよい。２種類以上用いる場合は、合計量が上記範囲となることが好ましい。 (Silane coupling agent)
The photosensitive resin composition used in the present invention may contain a silane coupling agent in order to improve the adhesion to the substrate.
Examples of the silane coupling agent 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. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A.
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.
（増感色素）
　本発明で用いる感光性樹脂組成物は、増感色素を含んでいてもよい。増感色素は、特定の活性放射線を吸収して電子励起状態となる。電子励起状態となった増感色素は、アミン発生剤、熱ラジカル重合開始剤、光重合開始剤などと接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより、アミン発生剤、熱ラジカル重合開始剤、光重合開始剤は化学変化を起こして分解し、ラジカル、酸或いは塩基を生成する。 (Sensitizing dye)
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. As a result, 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.
　好ましい増感色素の例としては、以下の化合物類に属しており、かつ３００ｎｍから４５０ｎｍ領域に吸収波長を有するものを挙げることができる。例えば、多核芳香族類（例えば、フェナントレン、アントラセン、ピレン、ペリレン、トリフェニレン、９．１０－ジアルコキシアントラセン）、キサンテン類（例えば、フルオレッセイン、エオシン、エリスロシン、ローダミンＢ、ローズベンガル）、チオキサントン類（例えば、２，４－ジエチルチオキサントン）、シアニン類（例えばチアカルボシアニン、オキサカルボシアニン）、メロシアニン類（例えば、メロシアニン、カルボメロシアニン）、チアジン類（例えば、チオニン、メチレンブルー、トルイジンブルー）、アクリジン類（例えば、アクリジンオレンジ、クロロフラビン、アクリフラビン）、アントラキノン類（例えば、アントラキノン）、スクアリリウム類（例えば、スクアリリウム）、クマリン類（例えば、７－ジエチルアミノ－４－メチルクマリン）、スチリルベンゼン類、ジスチリルベンゼン類、カルバゾール類等が挙げられる。 Examples of preferable sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in the region of 300 nm to 450 nm. For example, 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), anthraquinones (eg, anthraquinone), squaryliums (eg, squarylium), coumarins (eg, 7-di-) Chiruamino 4-methylcoumarin), styryl benzenes, distyryl benzenes, carbazoles, and the like.
　感光性樹脂組成物が増感色素を含む場合、増感色素の含有量は、感光性樹脂組成物の全固形分に対し、０．０１～２０質量％が好ましく、０．１～１５質量％がより好ましく、０．５～１０質量％がさらに好ましい。増感色素は、１種類単独で用いてもよいし、２種類以上を併用してもよい。 When the photosensitive resin composition contains a sensitizing dye, 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.
（連鎖移動剤）
　本発明で用いる感光性樹脂組成物は、連鎖移動剤を含有してもよい。連鎖移動剤は、例えば高分子辞典第三版（高分子学会編、２００５年）６８３－６８４頁に定義されている。連鎖移動剤としては、例えば、分子内にＳＨ、ＰＨ、ＳｉＨ、ＧｅＨを有する化合物群が用いられる。これらは、低活性のラジカルに水素を供与して、ラジカルを生成するか、もしくは、酸化された後、脱プロトンすることによりラジカルを生成しうる。特に、チオール化合物（例えば、２－メルカプトベンズイミダゾール類、２－メルカプトベンズチアゾール類、２－メルカプトベンズオキサゾール類、３－メルカプトトリアゾール類、５－メルカプトテトラゾール類等）を好ましく用いることができる。 (Chain transfer agent)
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. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) can be preferably used.
　感光性樹脂組成物が連鎖移動剤を有する場合、連鎖移動剤の好ましい含有量は、感光性樹脂組成物の全固形分１００質量部に対し、好ましくは０．０１～２０質量部、さらに好ましくは１～１０質量部、特に好ましくは１～５質量部である。
　連鎖移動剤は１種類のみでもよいし、２種類以上であってもよい。連鎖移動剤が２種類以上の場合は、その合計が上記範囲であることが好ましい。 When the photosensitive resin composition has a chain transfer agent, 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.
（界面活性剤）
　本発明で用いる感光性樹脂組成物には、塗布性をより向上させる観点から、各種類の界面活性剤を添加してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種類の界面活性剤を使用できる。 (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. As 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.
　感光性樹脂組成物が界面活性剤を有する場合、界面活性剤の含有量は、感光性樹脂組成物の全固形分に対して、０．００１～２．０質量％が好ましく、より好ましくは０．００５～１．０質量％である。
　界面活性剤は１種類のみでもよいし、２種類以上であってもよい。界面活性剤が２種類以上の場合は、その合計が上記範囲であることが好ましい。 When the photosensitive resin composition has a surfactant, 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.
（高級脂肪酸誘導体）
　本発明で用いる感光性樹脂組成物には、酸素に起因する重合阻害を防止するために、ベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体を添加して、塗布後の乾燥の過程で組成物の表面に偏在させてもよい。
　感光性樹脂組成物が高級脂肪酸誘導体を有する場合、高級脂肪酸誘導体の含有量は、感光性樹脂組成物の全固形分に対して、０．１～１０質量％が好ましい。
　高級脂肪酸誘導体は１種類のみでもよいし、２種類以上であってもよい。高級脂肪酸誘導体が２種類以上の場合は、その合計が上記範囲であることが好ましい。 (Higher fatty acid derivatives)
In order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenamide is added to the photosensitive resin composition used in the present invention, and the composition is dried in the course of drying after coating. The surface may be unevenly distributed.
When 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.
＜＜感光性樹脂組成物の特性＞＞
　次に、本発明で用いる感光性樹脂組成物の特性について説明する。
　本発明で用いる感光性樹脂組成物が、露光により架橋構造が構築されて有機溶剤への溶解度が低下することが好ましい。架橋構造を有することにより、感光性樹脂組成物層を積層した際に、層間の密着力を高くすることができる。また、露光により感光性樹脂組成物層の有機溶剤への溶解度が低下することにより、積層数が増えた場合に深い溝や深い穴を設けるときに有利になる。
　本発明で用いる感光性樹脂組成物の水分含有量は、塗布面状の観点から、５質量％未満が好ましく、１質量％未満がさらに好ましく、０．６質量％未満が特に好ましい。 << Characteristics of Photosensitive Resin Composition >>
Next, the characteristics of the photosensitive resin composition used in the present invention will be described.
In the photosensitive resin composition used in the present invention, it is preferable that a crosslinked structure is constructed by exposure to reduce the solubility in an organic solvent. By having a crosslinked structure, the adhesion between the layers can be increased when the photosensitive resin composition layer is laminated. Further, 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.
　本発明で用いる感光性樹脂組成物の金属含有量は、絶縁性の観点から、５質量ｐｐｍ（ｐａｒｔｓ　ｐｅｒ　ｍｉｌｌｉｏｎ）未満が好ましく、１質量ｐｐｍ未満がさらに好ましく、０．５質量ｐｐｍ未満が特に好ましい。金属としては、ナトリウム、カリウム、マグネシウム、カルシウム、鉄、クロム、ニッケルなどが挙げられる。金属を複数含む場合は、これらの金属の合計が上記範囲であることが好ましい。
　また、感光性樹脂組成物に意図せずに含まれる金属不純物を低減する方法としては、感光性樹脂組成物を構成する原料として金属含有量が少ない原料を選択する、感光性樹脂組成物を構成する原料に対してフィルター濾過を行う、装置内をポリテトラフロロエチレン等でライニングしてコンタミネーションを可能な限り抑制した条件下で蒸留を行う等の方法を挙げることができる。 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. . Examples of 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.
In addition, as a method for reducing metal impurities that are unintentionally contained in the photosensitive resin composition, a raw material having a low metal content is selected as a raw material constituting the photosensitive resin composition. For example, 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.
　本発明で用いる感光性樹脂組成物は、ハロゲン原子の含有量が、配線腐食性の観点から、５００質量ｐｐｍ未満が好ましく、３００質量ｐｐｍ未満がより好ましく、２００質量ｐｐｍ未満が特に好ましい。中でも、ハロゲンイオンの状態で存在するものは、５質量ｐｐｍ未満が好ましく、１質量ｐｐｍ未満がさらに好ましく、０．５質量ｐｐｍ未満が特に好ましい。ハロゲン原子としては、塩素原子および臭素原子が挙げられる。塩素原子および臭素原子、あるいは塩化物イオンおよび臭化物イオンの合計がそれぞれ上記範囲であることが好ましい。 In the photosensitive resin composition used in the present invention, 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. Especially, what exists in the state of 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. Examples of 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.
＜乾燥工程＞
　本発明の積層体の製造方法は、感光性樹脂組成物層を形成後、溶剤を乾燥する工程を含んでいてもよい。好ましい乾燥温度は５０～１５０℃で、７０～１３０℃がより好ましく、９０～１１０℃がさらに好ましい。乾燥時間としては、３０秒間～２０分間が好ましく、１分間～１０分間がより好ましく、３分間～７分間がさらに好ましい。 <Drying process>
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.
＜露光工程＞
　本発明の積層体の製造方法は、感光性樹脂組成物層を露光する露光工程を含む。露光の条件は、特に定めるものではなく、感光性樹脂組成物の露光部の現像液に対する溶解度を変化させられることが好ましく、感光性樹脂組成物の露光部を硬化できることがより好ましい。例えば、露光は感光性樹脂組成物層に対して、波長３６５ｎｍでの露光エネルギー換算で１００～１００００ｍＪ／ｃｍ2照射することが好ましく、２００～８０００ｍＪ／ｃｍ2照射することがより好ましい。
　露光波長は、１９０～１０００ｎｍの範囲で適宜定めることができ、２４０～５５０ｎｍが好ましい。 <Exposure process>
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. For example, in the exposure, 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.
　パターン露光で露光を行ってもよく、全面均一照射で露光を行ってもよい。 Exposure may be performed by pattern exposure, or exposure may be performed by uniform irradiation over the entire surface.
＜現像処理工程＞
　本発明の積層体の製造方法は、露光された感光性樹脂組成物層に対して、現像処理を行う現像処理工程を含む。
　現像処理工程は、ネガ型現像処理工程であることが好ましい。ネガ型現像処理を行うことにより、露光されていない部分（非露光部）が除去される。現像方法は、特に制限は無く、所望のパターンを形成できることが好ましく、例えば、パドル、スプレー、浸漬、超音波等の現像方法が採用可能である。
　本発明では、全面均一照射で露光を行う場合も現像処理工程を行うことが好ましい。
　現像は現像液を用いて行うことが好ましい。現像液は、露光されていない部分（非露光部）が除去されるものであれば、特に制限なく使用できる。有機溶剤による現像が好ましく、エステル類として、例えば、酢酸エチル、酢酸－ｎ－ブチル、酢酸イソブチル、ギ酸アミル、酢酸イソアミル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、γ－ブチロラクトン、ε－カプロラクトン、δ－バレロラクトン、アルキルオキシ酢酸アルキル（例：アルキルオキシ酢酸メチル、アルキルオキシ酢酸エチル、アルキルオキシ酢酸ブチル（例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等））、３－アルキルオキシプロピオン酸アルキルエステル類（例：３－アルキルオキシプロピオン酸メチル、３－アルキルオキシプロピオン酸エチル等（例えば、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル等））、２－アルキルオキシプロピオン酸アルキルエステル類（例：２－アルキルオキシプロピオン酸メチル、２－アルキルオキシプロピオン酸エチル、２－アルキルオキシプロピオン酸プロピル等（例えば、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル））、２－アルキルオキシ－２－メチルプロピオン酸メチルおよび２－アルキルオキシ－２－メチルプロピオン酸エチル（例えば、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル等）、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル等、並びに、エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等が挙げられる。
　ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、２－ヘプタノン、３－ヘプタノン、Ｎ－メチル－２－ピロリドン等が挙げられる。
　芳香族炭化水素類として、例えば、トルエン、キシレン、アニソール、リモネン等が挙げられる。
　スルホキシド類としてジメチルスルホキシドが好適に挙げられる。
　中でも３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、シクロペンタノン、γ－ブチロラクトン、ジメチルスルホキシド、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールメチルエーテル、およびプロピレングリコールメチルエーテルアセテートが好ましく、シクロペンタノン、γ－ブチロラクトン、がより好ましい。
　現像時間は、１０秒間～５分間が好ましい。
　現像時の温度は、特に定めるものではないが、通常、２０～４０℃で行うことができる。
　現像液を用いた処理の後、さらに、リンスを行ってもよい。リンスは、現像液とは異なる溶剤で行うことが好ましい。例えば、感光性樹脂組成物に含まれる溶剤を用いてリンスすることができる。リンス時間は、５秒間～１分間が好ましい。 <Development process>
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. Development with an organic solvent is preferred. Examples of 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, γ-butyrolactone, ε-caprolactone, δ-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-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate) , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionate, 2-alkyloxypropion) Ethyl, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)) Methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.) , Pyruvic acid Chill, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and ethers such as 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 monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate The And so on.
Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like.
Examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
Preferred examples of the sulfoxides include dimethyl sulfoxide.
Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl Sulphoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate are preferable, and cyclopentanone and γ-butyrolactone are more preferable.
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.
After treatment with a developer, 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.
＜硬化工程＞
　本発明の積層体の製造方法は、現像処理後の感光性樹脂組成物層を硬化する硬化工程を含む。
　硬化工程は、感光性樹脂組成物層を昇温する昇温工程と、昇温工程後に感光性樹脂組成物層を冷却する冷却工程とを含むことが好ましい。 <Curing process>
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.
　硬化工程（特に昇温工程および保持工程）は、窒素、ヘリウム、アルゴンなどの不活性ガスを流す等により、低酸素濃度の雰囲気で行うことが樹脂の分解を防ぐ点で好ましい。酸素濃度は、５０体積ｐｐｍ以下が好ましく、２０体積ｐｐｍ以下が好ましい。 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.
＜＜昇温工程＞＞
　昇温工程は、感光性樹脂組成物層をガラス転移温度以上の温度に昇温する工程であることが好ましい。
　昇温工程では、感光性樹脂組成物層に含まれる樹脂（好ましくはポリイミド前駆体およびポリベンゾオキサゾール前駆体）の環化反応を進行させることが好ましい。例えばポリイミドやポリベンゾオキサゾールでは、架橋剤と共に加熱する場合、３次元ネットワーク構造を形成することができる。また、未反応のラジカル重合性化合物の硬化なども進行させることができる。
　昇温工程の最終到達温度は、感光性樹脂組成物層に含まれる樹脂のイミド化温度であることが好ましい。
　昇温工程の最終到達温度は、最高加熱温度であることが好ましい。最高加熱温度としては、１００～５００℃が好ましく、１５０～４５０℃がより好ましく、１６０～３５０℃がさらに好ましい。本発明の積層体の製造方法は、昇温工程の最終到達温度が２５０℃以下であることが応力緩和の観点から特に好ましい。 << Temperature raising process >>
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.
In the temperature raising step, it is preferable to advance the cyclization reaction of the resins (preferably polyimide precursor and polybenzoxazole precursor) contained in the photosensitive resin composition layer. For example, polyimide and polybenzoxazole can form a three-dimensional network structure when heated with a crosslinking agent. Moreover, 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. In the laminate manufacturing method of the present invention, the final temperature reached in the heating step is particularly preferably 250 ° C. or less from the viewpoint of stress relaxation.
　昇温工程は、２０～１５０℃の温度から最高加熱温度まで１～１２℃／分の昇温速度で行うことが好ましく、２～１１℃／分がより好ましく、３～１０℃／分がさらに好ましい。昇温速度を１℃／分以上とすることにより、生産性を確保しつつ、アミンの過剰な揮発を防止することができ、昇温速度を１２℃／分以下とすることにより、硬化膜の残留応力を緩和することができる。
　加熱開始時の温度は、２０～１５０℃が好ましく、２０℃～１３０℃がより好ましく、２５℃～１２０℃がさらに好ましい。加熱開始時の温度は、最高加熱温度まで加熱する工程を開始する際の加熱温度のことをいう。例えば、感光性樹脂組成物を基板の上に適用した後、乾燥させる場合、この乾燥後の温度であり、例えば、感光性樹脂組成物に含まれる溶剤の沸点－（３０～２００）℃から徐々に昇温させることが好ましい。 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. By setting the heating rate to 1 ° C./min or more, it is possible to prevent excessive volatilization of the amine while ensuring productivity, and by setting the heating rate to 12 ° C./min or less, the cured film Residual stress can be relaxed.
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. For example, when the photosensitive resin composition is applied onto a substrate and then dried, 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
　加熱は段階的に行ってもよい。例として、２５℃～１８０℃まで３℃／分で昇温し、１８０℃にて６０分間置き、１８０～２００℃まで２℃／分で昇温し、２００℃にて１２０分間置く、といった前処理工程を行ってもよい。前処理工程としての加熱の温度は１００～２００℃が好ましく、１１０～１９０℃であることがより好ましく、１２０～１８５℃であることが最も好ましい。この前処理工程においては、米国特許９１５９５４７号に記載のとおりＵＶを照射しながら処理することも好ましい。このような前処理工程により硬化膜の特性を向上させることが可能である。前処理工程は１０秒間～２時間程度の短い時間で行うことが好ましく、１５秒間～３０分間がより好ましい。前処理工程は２段階以上のステップとしてもよく、例えば１００～１５０℃の範囲で前処理工程１を行い、その後に１５０～２００℃の範囲で前処理工程２を行ってもよい。 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. For example, the pretreatment process 1 may be performed in the range of 100 to 150 ° C., and then the pretreatment process 2 may be performed in the range of 150 to 200 ° C.
　昇温工程は、２０～２００分間であることが好ましく、２０～１００分間であることがより好ましく、２０～６０分間であることが特に好ましい。 The temperature raising step is preferably 20 to 200 minutes, more preferably 20 to 100 minutes, and particularly preferably 20 to 60 minutes.
＜＜保持工程＞＞
　本発明の積層体の製造方法は、昇温工程後、冷却工程前に、昇温工程の最終到達温度と等しい保持温度で保持する保持工程を含むことが好ましい。
　昇温工程の最終到達温度に到達した後、昇温工程の最終到達温度と等しい保持温度で３０～３６０分間加熱を行うことが好ましく、３０～３００分間加熱を行うことがより好ましく、３０～２４０分間加熱を行うことが特に好ましく、６０～２４０分間加熱を行うことがより特に好ましい。
　保持工程にかかる時間を、保持時間という。
　保持工程における保持温度が、１５０～４５０℃であることが好ましく、１６０～３５０℃がさらに好ましい。本発明の積層体の製造方法は、保持工程における保持温度が２５０℃以下であることが応力緩和の観点から特に好ましい。 << Holding process >>
It is preferable that the manufacturing method of the laminated body of this invention includes the holding process hold | maintained with the holding temperature equal to the final ultimate temperature of a temperature rising process after a temperature rising process and before a cooling process.
After reaching the final temperature of the temperature raising step, 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.
＜＜冷却工程＞＞
　冷却工程は、昇温工程後に感光性樹脂組成物層を２℃／分以下の降温速度で冷却する工程であることが好ましい。
　冷却工程の降温速度は２℃／分以下であることが好ましく、１℃／分以下であることがより好ましい。冷却工程の降温速度は０．１℃／分以上であることが応力緩和の観点から好ましい。
　冷却工程の降温速度は、昇温工程の昇温速度よりも遅いことが応力緩和の観点から好ましい。 << Cooling process >>
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.
　冷却工程は、３０～６００分間であることが好ましく、６０～６００分間であることがより好ましく、１２０～６００分間であることが特に好ましい。
　本発明の積層体の製造方法は、冷却工程の時間が、昇温工程の時間よりも長いことが応力緩和の観点から好ましい。 The cooling step is preferably 30 to 600 minutes, more preferably 60 to 600 minutes, and particularly preferably 120 to 600 minutes.
In the method for producing a laminate of the present invention, it is preferable from the viewpoint of stress relaxation that the time for the cooling step is longer than the time for the temperature raising step.
　冷却工程の最終到達温度が硬化工程後の感光性樹脂組成物層（硬化膜）のガラス転移温度（Ｔｇ）より３０℃以上低いことが好ましい。冷却工程の最終到達温度が感光性樹脂組成物層のＴｇより３０℃以上低い温度まで降温すれば、ポリイミドが十分に硬化し、かつ層間剥離の発生を抑制しやすい。
　冷却工程の最終到達温度が硬化工程後の感光性樹脂組成物層のガラス転移温度より１６０～２５０℃低いことがより好ましく、１８０～２３０℃低いことが特に好ましい。 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.
＜＜室温にする工程＞＞
　感光性樹脂組成物層が冷却工程の最終到達温度に到達した後は、感光性樹脂組成物層を任意の降温速度で冷却し、室温にする工程を含むことが好ましい。
　室温にする工程の降温速度は、特に制限は無く、冷却工程の降温速度より速いことが好ましい。室温にする工程の降温速度は、例えば、５～１０℃／分とすることができる。 << 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 | limiting in particular in the temperature fall rate of the process made into room temperature, It is preferable that it is quicker than the temperature fall rate of a cooling process. The temperature lowering rate in the step of bringing to room temperature can be set to 5 to 10 ° C./min, for example.
＜金属層形成工程＞
　本発明の積層体の製造方法は、硬化工程後の感光性樹脂組成物層の表面に気相成膜により金属層を形成する金属層形成工程を含み、
　金属層を形成する際の硬化工程後の感光性樹脂組成物層の温度が、硬化工程後の感光性樹脂組成物層のガラス転移温度未満である。 <Metal layer formation process>
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.
　本発明の積層体の製造方法は、金属層を形成する際の感光性樹脂組成物層の温度が感光性樹脂組成物層のガラス転移温度より３０℃以上低いことが好ましく、３０～２００℃低いことがより好ましく、１００～２００℃低いことが特に好ましい。
　金属層形成工程で形成される金属層が２層以上である場合、少なくとも硬化工程後の感光性樹脂組成物層に直接接触する金属層（好ましくはバリアメタル膜）を形成する際の硬化工程後の感光性樹脂組成物層の温度が上記範囲であることが好ましい。金属層形成工程で形成される金属層が２層以上である場合、２層目の金属層を形成する際の硬化工程後の感光性樹脂組成物層の温度は特に制限はない。ただし、２層目の金属層であっても感光性樹脂組成物層の上に直接設けられる部分がある場合、２層目の金属層を形成する際の硬化工程後の感光性樹脂組成物層の温度も上記範囲であることが好ましい。
　特に気相成膜を用いて２層目の金属層を形成するときは、２層目の金属層を形成する際の硬化工程後の感光性樹脂組成物層の温度も上記範囲であることが好ましい。なお、非気相成膜（めっき等）を用いて２層目の金属層を形成するときは、一般に２層目の金属層を形成する際の硬化工程後の感光性樹脂組成物層の温度は感光性樹脂組成物層のガラス転移温度未満となる。 In the method for producing a laminate of the present invention, 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.
When there are two or more metal layers formed in the metal layer forming step, at least after the curing step when forming a metal layer (preferably a barrier metal film) that is in direct contact with the photosensitive resin composition layer after the curing step The temperature of the photosensitive resin composition layer is preferably within the above range. When there are two or more metal layers formed in the metal layer forming step, 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. In addition, when forming the second metal layer using non-vapor phase film formation (plating or the like), 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.
　金属層形成工程で形成される金属層としては、特に限定なく、既存の金属を使用することができる。金属層形成工程で形成される金属層が含む金属としては、銅、アルミニウム、ニッケル、バナジウム、チタン、タンタル、クロム、コバルト、金およびタングステンならびにこれらのうち少なくとも１種類を含む化合物（合金を含む）が例示される。本発明の積層体の製造方法は、金属層形成工程で形成される金属層が、チタン、タンタルおよび銅ならびにこれらのうち少なくとも１種類を含む化合物のうち少なくとも１種類を含むことがより好ましく、チタンおよび銅ならびにこれらのうち少なくとも１種類を含む化合物のうち少なくとも１種類を含むことが特に好ましく、銅を含むことがより特に好ましい。金属層が、チタン、タンタルおよび銅ならびにこれらのうち少なくとも１種類を含む化合物のうち少なくとも１種類を含む場合の具体例として、チタン、タンタル、銅、ＴｉＮ、ＴａＮまたはＴｉＷからなる金属層が挙げられ、チタン、タンタル、銅、ＴｉＮまたはＴｉＷからなる金属層であることが好ましい。金属層形成工程で形成される金属層が含む金属は１種類であっても、２種類以上であってもよい。 The metal layer formed in the metal layer forming step is not particularly limited, and an existing metal can be used. Examples of 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. In the method for producing a laminate of the present invention, it is more preferable that 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. Specific examples of the case where 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.
　本発明の積層体の製造方法は、金属層形成工程で形成される金属層の厚さが、５０～２０００ｎｍであることが好ましく、５０～１０００ｎｍであることがより好ましく、１００～３００ｎｍであることが特に好ましい。
　本発明の積層体の製造方法は、金属層形成工程で形成される金属層が１層であっても、２層以上であってもよい。
　金属層形成工程で形成される金属層が１層である場合、金属層は、バリアメタル膜として用いられることが好ましい。
　金属層形成工程で形成される金属層が２層以上である場合、金属層形成工程で形成される金属層全体の厚さが上記範囲であることが好ましい。金属層形成工程で形成される金属層が２層以上である場合、金属層形成工程で形成される金属層が、バリアメタル膜とシード層の積層体であることが好ましい。
　バリアメタル膜は、金属の硬化膜への侵入長を短くできる層であることが好ましい。バリアメタル膜の金属の種類は、金属層形成工程で形成される金属層が含む金属として上述した金属であることが好ましい。バリアメタル膜の厚さが、５０～２０００ｎｍであることが好ましく、５０～１０００ｎｍであることがより好ましく、１００～３００ｎｍであることが特に好ましい。
　シード層は、第２の金属層形成工程で形成される第２の金属層のパターンを形成しやすくするための層であることが好ましい。シード層の金属の種類は、第２の金属層形成工程で形成される第２の金属層と同じ種類の金属であることが好ましい。シード層の厚さが、５０～２０００ｎｍであることが好ましく、５０～１０００ｎｍであることがより好ましく、１００～３００ｎｍであることが特に好ましい。 In the method for producing a laminate of the present invention, 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.
In the method for producing a laminate of the present invention, 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. When there are two or more metal layers formed in the metal layer forming step, 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.
　金属層の形成方法は、特に限定されず、既存の気相成膜の方法を適用することができる。例えば、スパッタ法、化学気相蒸着（ｃｈｅｍｉｃａｌ　ｖａｐｏｒ　ｄｅｐｏｓｉｔｉｏｎ；ＣＶＤ）、プラズマ法およびこれらを組み合わせた方法などが考えられる。これらの中でも、金属層の形成方法は、スパッタ法であることが膜厚制御の観点から好ましい。 The formation method of the metal layer is not particularly limited, and an existing vapor deposition method can be applied. For example, a sputtering method, chemical vapor deposition (CVD), a plasma method, and a combination thereof may be considered. Among these, the metal layer forming method is preferably a sputtering method from the viewpoint of film thickness control.
＜第２の金属層形成工程＞
　本発明の積層体の製造方法は、さらに、金属層の表面に第２の金属層を形成する第２の金属層形成工程を含むことが好ましい。 <Second metal layer forming step>
It is preferable that 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.
　第２の金属層形成工程で形成される第２の金属層としては、特に限定なく、既存の金属を使用することができる。第２の金属層形成工程で形成される第２の金属層が含む金属としては、銅、アルミニウム、ニッケル、バナジウム、チタン、タンタル、クロム、コバルト、金およびタングステンが例示される。本発明の積層体の製造方法は、第２の金属層が、銅を含むことが半導体素子の再配線層として本発明の積層体を用いる観点から好ましい。 The second metal layer formed in the second metal layer forming step is not particularly limited, and an existing metal can be used. Examples of 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.
　積層体の製造方法は、第２の金属層形成工程で形成される第２の金属層の厚さが、例えば３～５０μｍであり、３～１０μｍであることが好ましく、５～１０μｍであることがより好ましく、５～７μｍであることが特に好ましい。パワー半導体用途の積層体を製造する場合は、第２の金属層形成工程で形成される第２の金属層の厚さが３５～５０μｍであることが好ましい。 In the method for manufacturing a laminate, the thickness of the second metal layer formed in the second metal layer forming step is, for example, 3 to 50 μm, preferably 3 to 10 μm, and preferably 5 to 10 μm. Is more preferable, and 5 to 7 μm is particularly preferable. When manufacturing a laminated body for power semiconductors, the thickness of the second metal layer formed in the second metal layer forming step is preferably 35 to 50 μm.
　第２の金属層の形成方法は、特に限定されず、既存の方法を適用することができる。例えば、特開２００７－１５７８７９号公報、特表２００１－５２１２８８号公報、特開２００４－２１４５０１号公報、特開２００４－１０１８５０号公報に記載の方法を使用することができる。例えば、フォトリソグラフィ、リフトオフ、化学気相蒸着（ｃｈｅｍｉｃａｌ　ｖａｐｏｒ　ｄｅｐｏｓｉｔｉｏｎ；ＣＶＤ）、電解めっき、無電解めっき、エッチング、印刷、およびこれらを組み合わせた方法などが考えられる。より具体的には、フォトリソグラフィおよびエッチングを組み合わせたパターニング方法、フォトリソグラフィと電解めっきを組み合わせたパターニング方法、フォトリソグラフィ、電解めっきおよびエッチングを組み合わせたパターニング方法が挙げられる。
　フォトリソグラフィおよび電解めっきを組み合わせたパターニング方法としては、金属層形成工程で形成される金属層のシード層をスパッタリングで形成した後に、フォトリソグラフィでシード層のパターンを形成し、パターンを形成されたシード層の上に電解めっきを施して第２の金属層を形成する方法が好ましい。その後、さらにエッチングを行い、第２の金属層が形成されていない領域のシード層を除去してもよい。 The method for forming the second metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, and JP 2004-101850 A can be used. For example, photolithography, lift-off, chemical vapor deposition (CVD), electrolytic plating, electroless plating, etching, printing, and a combination thereof may be considered. More specifically, a patterning method that combines photolithography and etching, a patterning method that combines photolithography and electrolytic plating, and a patterning method that combines photolithography, electrolytic plating, and etching may be mentioned.
As a patterning method combining photolithography and electrolytic plating, 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.
＜表面活性化処理工程＞
　積層体の製造方法は、上記金属層および感光性樹脂組成物層の少なくとも一部を表面活性化処理する表面活性化処理工程を含んでもよい。
　表面活性化処理工程は、通常、金属層形成工程の後に行うことが好ましい。上記硬化工程の後、感光性樹脂組成物層に、表面活性化処理工程を行ってから、金属層を形成してもよい。
　表面活性化処理は、金属層の少なくとも一部のみに行ってもよいし、硬化工程後の感光性樹脂組成物層の少なくとも一部のみに行ってもよいし、金属層および硬化工程後の感光性樹脂組成物層の両方について、それぞれ、少なくとも一部に行ってもよい。表面活性化処理は、金属層の少なくとも一部について行うことが好ましく、金属層のうち、その上にさらに感光性樹脂組成物層を形成する領域の一部または全部に表面活性化処理を行うことがより好ましい。このように、金属層の表面に表面活性化処理を行うことにより、その表面に設けられる硬化膜との密着性を向上させることができる。
　また、表面活性化処理は、硬化工程後の感光性樹脂組成物層（硬化膜）の一部または全部についても行うことが好ましい。このように、感光性樹脂組成物層の表面に表面活性化処理を行うことにより、表面活性化処理した表面に設けられる金属層や硬化膜との密着性を向上させることができる。ネガ型現像をする場合、露光部が表面処理を受けることとなり、硬化などにより膜の強度が向上していることから、感光性樹脂組成物層（硬化膜）がダメージを受けない。
　表面活性化処理としては、具体的には、各種類の原料ガス（酸素、水素、アルゴン、窒素、窒素および水素混合ガス、ならびに、アルゴンおよび酸素混合ガスなど）のプラズマ処理；コロナ放電処理；ＣＦ4およびＯ2混合ガス、ＮＦ3およびＯ2混合ガス、ＳＦ6、ＮＦ3、ならびに、ＮＦ3およびＯ2混合ガスを用いるエッチング処理；紫外線（ｕｌｔｒａｖｉｏｌｅｔ；ＵＶ）オゾン法を用いる表面処理；塩酸水溶液に浸漬して酸化皮膜を除去した後にアミノ基とチオール基を少なくとも一種類有する化合物を含む有機表面処理剤への浸漬処理；ブラシを用いた機械的な粗面化処理から選択されることが好ましい。プラズマ処理がより好ましく、原料ガスに酸素を用いた酸素プラズマ処理が特に好ましい。コロナ放電処理の場合、エネルギーは、５００～２０００００Ｊ／ｍ2が好ましく、１０００～１０００００Ｊ／ｍ2がより好ましく、１００００～５００００Ｊ／ｍ2がさらに好ましい。 <Surface activation treatment process>
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. After the curing 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. In the case of negative development, 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.
Specifically, as 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 . Plasma treatment is more preferred, and oxygen plasma treatment using oxygen as the source gas is particularly preferred. For corona discharge treatment, the energy is preferably 500 ~ 200000J / m 2, more preferably 1000 ~ 100000J / m 2, more preferably 10000 ~ 50000J / m 2.
＜積層工程＞
　本発明の積層体の製造方法は、金属層形成工程の後に、さらに、再度、感光性樹脂組成物層形成工程、露光工程、現像処理工程、硬化工程、および、金属層形成工程を、上記順に行うことが好ましい。この場合、金属層形成工程が繰り返されるため、特に基板と硬化膜と金属層を積層した場合の層間剥離を抑制できる効果が大きい。
　本明細書では、金属層形成工程の後に、さらに、再度、感光性樹脂組成物層形成工程、露光工程、現像処理工程、硬化工程、および、金属層形成工程を、上記順に行う工程のことを、積層工程と言う。積層工程は、感光性樹脂組成物層形成工程、露光工程、現像処理工程、硬化工程、金属層形成工程、および第２の金属層形成工程を、上記順に行う工程であることがより好ましい。 <Lamination process>
In the method for producing a laminate of the present invention, after the metal layer forming step, 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.
In the present specification, after the metal layer forming step, the step of performing the photosensitive resin composition layer forming step, the exposure step, the development processing step, the curing step, and the metal layer forming step again in the above order. This is called a lamination process. 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.
　積層工程後、さらに積層工程を行う場合には、上記露光工程後、または、上記金属層形成工程後に、さらに、上記表面活性化処理工程を行うことができる。
　上記積層工程は、３～７回行うことが好ましく、３～５回行うことがより好ましい。
　例えば、硬化膜／金属層／硬化膜／金属層／硬化膜／金属層のような、硬化膜が３層以上７層以下の構成が好ましく、３層以上５層以下がさらに好ましい。多層構成にするほど、感光性樹脂組成物層は繰り返し現像液や金属エッチング処理、硬化工程における高温処理にさらされるため、本発明の積層体の製造方法に起因する金属層／硬化膜界面、あるいは、硬化膜／硬化膜界面における層間剥離の発生を抑制できる効果を奏する。
　このような構成とすることにより、感光性樹脂組成物層（硬化膜）と金属層を交互に積層することができ、再配線層などの半導体素子の多層配線構造として用いることができる。
　感光性樹脂組成物層（硬化膜）は、積層が上に行くほど厚さが厚くなることが好ましい。 When a lamination process is further performed after the lamination process, 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.
For example, 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. Since the photosensitive resin composition layer is repeatedly exposed to a developing solution, a metal etching treatment, and a high temperature treatment in a curing step as the multilayer structure is formed, 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.
By setting it as such a structure, the photosensitive resin composition layer (cured film) and a metal layer can be laminated | stacked alternately, and it can use as a multilayer wiring structure of semiconductor elements, such as a rewiring layer.
It is preferable that the thickness of the photosensitive resin composition layer (cured film) increases as the stack increases.
　［積層体］
　本発明の積層体は、基板と、パターン硬化膜と、パターン硬化膜の表面に位置する金属層とを有し、
　パターン硬化膜は、ポリイミドまたはポリベンゾオキサゾールを含み、
　パターン硬化膜の表面に位置する金属層を構成する金属のパターン硬化膜への侵入がパターン硬化膜の表面から１３０ｎｍ以下である。 [Laminate]
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.
＜パターン硬化膜＞
　本発明の積層体におけるパターン硬化膜は、本発明の積層体の製造方法における硬化工程後の感光性樹脂組成物層であることが好ましい。 <Pattern cured film>
It is preferable that 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.
＜＜Ｔｇ＞＞
　パターン硬化膜（硬化工程後の感光性樹脂組成物層）のガラス転移温度が１５０～３００℃であることが好ましく、１６０～２５０℃であることがより好ましく、１８０～２３０℃であることが特に好ましい。 << Tg >>
The glass transition temperature of the pattern cured film (photosensitive resin composition layer after the curing step) is preferably 150 to 300 ° C, more preferably 160 to 250 ° C, and particularly preferably 180 to 230 ° C. preferable.
＜＜残留応力＞＞
　パターン硬化膜（硬化工程後の感光性樹脂組成物層。好ましくは金属層形成工程後の感光性樹脂組成物層。より好ましくは金属層形成工程および第２の金属層形成工程後の感光性樹脂組成物層）のレーザー計測法に従って測定した残留応力が３５ＭＰａ未満であることが好ましく、２５ＭＰａ未満であることがより好ましく、１５ＭＰａ未満であることが特に好ましい。 << residual stress >>
Pattern cured film (photosensitive resin composition layer after curing step. Preferably 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.
＜金属層＞
　本発明の積層体における金属層は、本発明の積層体の製造方法における金属層形成工程で形成される金属層であることが好ましい。
　また、本発明の積層体における金属層は、本発明の積層体の製造方法における金属層形成工程で形成される金属層と、第２の金属層形成工程で形成される第２の金属層の積層体であってもよい。この場合、本発明の積層体の製造方法における金属層形成工程で形成される金属層と、第２の金属層形成工程で形成される第２の金属層が一体化して、本発明の積層体における金属層となってもよい。
　また、本発明の積層体の製造方法における金属層形成工程で形成される金属層が、例えばバリアメタル膜とシード層の２層であり、第２の金属層形成工程で形成される第２の金属層がシード層と同じ種類の金属である場合は、シード層と第２の金属層のみが一体化したいてもよい。この場合、シード層と第２の金属層のみが一体化した層と、バリアメタル膜との積層体が、本発明の積層体における金属層となってもよい。
　本発明の積層体における金属層の厚さとしては、最も厚肉の部分で、０．１～５０μｍが好ましく、１～１０μｍがより好ましい。
　本発明の積層体における金属層は、平坦な金属層であることが、金属層の膜質を安定化させる観点から好ましい。スパッタ法を用いて金属層を形成することで、平坦な金属層を形成できる。さらに、金属層を形成する際の硬化工程後の感光性樹脂組成物層の温度が、硬化工程後の感光性樹脂組成物層のガラス転移温度未満の条件でスパッタ法を用いて金属層を形成することで、より平坦な金属層を形成できる。 <Metal layer>
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.
Moreover, 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. In this case, 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.
In addition, 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. When 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. In this case, 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 μm, more preferably 1 to 10 μm 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.
＜金属のパターン硬化膜への侵入長＞
　パターン硬化膜の表面に位置する金属層を構成する金属のパターン硬化膜への侵入長は、パターン硬化膜の表面から１３０ｎｍ以下であり、５０ｎｍ以下であることが好ましく、３０ｎｍ以下であることがより好ましい。 <Intrusion length of metal pattern cured film>
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.
　［半導体素子の製造方法］
　本発明の半導体素子の製造方法は、本発明の積層体の製造方法を含む。
　上記構成により、本発明の半導体素子の製造方法は、基板と硬化膜と金属層を積層した場合の層間剥離が抑制された半導体素子を提供できる。 [Method for Manufacturing Semiconductor Device]
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.
　以下に、本発明の半導体素子の製造方法で得られた半導体素子の一実施形態について説明する。
　図１は、半導体素子の一実施形態の構成を示す概略図である。図１に示す半導体素子１００は、いわゆる３次元実装デバイスであり、複数の半導体チップ１０１ａ～１０１ｄが積層した半導体チップ１０１が、配線基板１２０の上に配置されている。
　なお、この実施形態では、半導体チップの積層数が４層である場合を中心に説明するが、半導体チップの積層数は特に限定されるものではなく、例えば、２層、８層、１６層、３２層等であってもよい。また、１層であってもよい。 Hereinafter, an embodiment of a semiconductor device obtained by the method for manufacturing a semiconductor device of the present invention will be described.
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.
In this embodiment, the case where the number of stacked semiconductor chips is four will be mainly described. However, 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.
　複数の半導体チップ１０１ａ～１０１ｄは、いずれもシリコン基板等の半導体ウェハからなる。
　最上段の半導体チップ１０１ａは、貫通電極を有さず、その一方の面に電極パッド（図示せず）が形成されている。
　半導体チップ１０１ｂ～１０１ｄは、貫通電極１０２ｂ～１０２ｄを有し、各半導体チップの両面には、貫通電極に一体に設けられた接続パッド（図示せず）が設けられている。 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.
　半導体チップ１０１は、貫通電極を有さない半導体チップ１０１ａと、貫通電極１０２ｂ～１０２ｄを有する半導体チップ１０１ｂ～１０１ｄとをフリップチップ接続した構造を有している。
　すなわち、貫通電極を有さない半導体チップ１０１ａの電極パッドと、これに隣接する貫通電極１０２ｂを有する半導体チップ１０１ｂの半導体チップ１０１ａ側の接続パッドが、半田バンプ等の金属バンプ１０３ａで接続されている。貫通電極１０２ｂを有する半導体チップ１０１ｂの他方の側の接続パッドが、それに隣接する貫通電極１０２ｃを有する半導体チップ１０１ｃの半導体チップ１０１ｂ側の接続パッドと、半田バンプ等の金属バンプ１０３ｂで接続されている。同様に、貫通電極１０２ｃを有する半導体チップ１０１ｃの他方の側の接続パッドが、それに隣接する貫通電極１０２ｄを有する半導体チップ１０１ｄの半導体チップ１０１ｃ側の接続パッドと、半田バンプ等の金属バンプ１０３ｃで接続されている。 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. . Similarly, the 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. Has been.
　各半導体チップ１０１ａ～１０１ｄの間隙には、アンダーフィル層１１０が形成されており、各半導体チップ１０１ａ～１０１ｄは、アンダーフィル層１１０を介して積層している。 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.
　半導体チップ１０１は、配線基板１２０の上に積層されている。
　配線基板１２０としては、例えば樹脂基板、セラミックス基板、ガラス基板等の絶縁基板を基材として用いた多層配線基板が使用される。樹脂基板を適用した配線基板１２０としては、多層銅張積層板（多層プリント配線板）等が挙げられる。 The semiconductor chip 101 is stacked on the wiring substrate 120.
As 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. Examples of the wiring substrate 120 to which the resin substrate is applied include a multilayer copper clad laminate (multilayer printed wiring board).
　配線基板１２０の一方の面には、表面電極１２０ａが設けられている。
　配線基板１２０と半導体チップ１０１との間には、再配線層１０５が形成された絶縁層１１５が配置されており、配線基板１２０と半導体チップ１０１とは、再配線層１０５を介して電気的に接続されている。絶縁層１１５として、本発明における硬化工程後の感光性樹脂組成物層（硬化膜）を用いることができる。再配線層１０５が形成された絶縁層１１５として、本発明の積層体の製造方法によって得られる積層体を用いることができる。
　再配線層１０５の一端は、半田バンプ等の金属バンプ１０３ｄを介して、半導体チップ１０１ｄの再配線層１０５側の面に形成された電極パッドに接続されている。また、再配線層１０５の他端は、配線基板の表面電極１２０ａと、半田バンプ等の金属バンプ１０３ｅを介して接続している。
　そして、絶縁層１１５と半導体チップ１０１との間には、アンダーフィル層１１０ａが形成されている。また、絶縁層１１５と配線基板１２０との間には、アンダーフィル層１１０ｂが形成されている。 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. As the insulating layer 115, the photosensitive resin composition layer (cured film) after the curing step in the present invention can be used. As 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. In addition, an underfill layer 110 b is formed between the insulating layer 115 and the wiring substrate 120.
　図２は、本発明の積層体の製造方法で得られる積層体の一実施形態の構成を示す概略図である。図２は、具体的には、本発明の積層体の製造方法によって得られる積層体を再配線層として用いる一例を示したものである。図２において、２００は本発明の方法で得られる積層体を、２０１は感光性樹脂組成物層（硬化膜）を、２０３は金属層を示している。図２において、金属層２０３は斜線で示した層である。感光性樹脂組成物層２０１は、ネガ型現像によって、所望のパターンで形成されている。金属層２０３は、上記パターンの表面の一部を覆うように形成され、上記金属層２０３の表面に、さらに、感光性樹脂組成物層（硬化膜）２０１が積層される。そして、感光性樹脂組成物層（硬化膜）が絶縁層として働き、金属層が再配線層として働き、上述のような半導体素子に再配線層として組み込まれる。 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. In FIG. 2, 200 indicates a laminate obtained by the method of the present invention, 201 indicates a photosensitive resin composition layer (cured film), and 203 indicates a metal layer. In FIG. 2, 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.
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。「部」、「％」は特に述べない限り、質量基準である。 The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. “Parts” and “%” are based on mass unless otherwise specified.
　［実施例１］
＜ポリイミド前駆体の合成＞
＜＜４，４’－オキシジフタル酸二無水物、４，４’－オキシジアニリンおよび２－ヒドロキシエチルメタクリレートからのポリイミド前駆体Ａａ－１（ラジカル重合性基を有するポリイミド前駆体）の合成＞＞
　２０．０ｇ（６４．５ミリモル）の４，４’－オキシジフタル酸二無水物（４，４’－オキシジフタル酸を１４０℃で１２時間乾燥したもの）と、１８．６ｇ（１２９ミリモル）の２－ヒドロキシエチルメタクリレートと、０．０５ｇのハイドロキノンと、１０．７ｇのピリジンと、１４０ｇのダイグライム（ジエチレングリコールジメチルエーテル）と混合した。混合物を６０℃の温度で１８時間撹拌して、４，４’－オキシジフタル酸と２－ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、反応混合物を－１０℃に冷却し、温度を－１０±４℃に保ちながら１６．１２ｇ（１３５．５ミリモル）のＳＯＣｌ2を１０分かけて加えた。反応混合物を５０ｍｌのＮ－メチルピロリドンで希釈した後、反応混合物を室温で２時間撹拌した。次いで、１００ｍｌのＮ－メチルピロリドンに１１．０８ｇ（５８．７ミリモル）の４，４’－オキシジアニリンを溶解させた溶液を、２０～２３℃で２０分かけて反応混合物に滴下した。次いで、反応混合物を室温で１晩撹拌した。次いで、５リットルの水の中に反応混合物を加えて、ポリイミド前駆体を沈殿させた。水およびポリイミド前駆体の混合物を５０００ｒｐｍの速度で１５分間撹拌した。水およびポリイミド前駆体の混合物を濾過して、濾液を除き、４リットルの水の中にポリイミド前駆体を含む残渣を加えた。水およびポリイミド前駆体の混合物を再度３０分間撹拌し、再び濾過して、残渣としてポリイミド前駆体を得た。次いで、得られたポリイミド前駆体を減圧下で、４５℃で３日間乾燥し、ポリイミド前駆体Ａａ－１を得た。
　ポリイミド前駆体Ａａ－１の構造を以下に示す。
Figure JPOXMLDOC01-appb-C000049
 [Example 1]
<Synthesis of polyimide precursor>
<< Synthesis of polyimide precursor Aa-1 (polyimide precursor having a radical polymerizable group) from 4,4'-oxydiphthalic dianhydride, 4,4'-oxydianiline and 2-hydroxyethyl methacrylate >>
20.0 g (64.5 mmol) of 4,4′-oxydiphthalic dianhydride (4,4′-oxydiphthalic acid dried at 140 ° C. for 12 hours) and 18.6 g (129 mmol) of 2- Hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diglyme (diethylene glycol dimethyl ether) were mixed. 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. After the reaction mixture was diluted with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution of 11.08 g (58.7 mmol) of 4,4′-oxydianiline dissolved in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred overnight at room temperature. The reaction mixture was then added into 5 liters of water to precipitate the polyimide precursor. The mixture of water and polyimide precursor was stirred for 15 minutes at a speed of 5000 rpm. The mixture of water and polyimide precursor was filtered to remove the filtrate and the residue containing the polyimide precursor in 4 liters of water was added. The mixture of water and the polyimide precursor was again stirred for 30 minutes and filtered again to obtain a polyimide precursor as a residue. Next, the obtained polyimide precursor was dried at 45 ° C. under reduced pressure for 3 days to obtain a polyimide precursor Aa-1.
The structure of polyimide precursor Aa-1 is shown below.
Figure JPOXMLDOC01-appb-C000049
＜感光性樹脂組成物の調製＞
　下記の成分を混合し、均一な溶液として、感光性樹脂組成物を調製した。 <Preparation of photosensitive resin composition>
The following components were mixed to prepare a photosensitive resin composition as a uniform solution.
＜＜感光性樹脂組成物Ａ－１の組成＞＞
樹脂：ポリイミド前駆体（Ａａ－１）　　　　　　　　　　　３２質量部
重合性化合物Ｂ－１　　　　　　　　　　　　　　　　　　６．９質量部
光重合開始剤Ｃ－１　　　　　　　　　　　　　　　　　　１．０質量部
重合禁止剤：パラベンゾキノン（東京化成工業製）　　　０．０８質量部
マイグレーション抑制剤：１Ｈ－テトラゾール（東京化成工業製）
　　　　　　　　　　　　　　　　　　　　　　　　　　０．１２質量部
金属接着性改良剤：Ｎ－［３－（トリエトキシシリル）プロピル］マレイン酸モノアミド　　　　　　　　　　　　　　　　　　　　０．７０質量部
溶剤：γ－ブチロラクトン　　　　　　　　　　　　　４８．００質量部
溶剤：ジメチルスルホキシド　　　　　　　　　　　　１２．００質量部 << 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: γ-butyrolactone 48.00 parts by mass Solvent: dimethyl sulfoxide 12.00 parts by mass
＜＜感光性樹脂組成物Ａ－２の組成＞＞
樹脂：ポリイミド前駆体（Ａａ－１）　　　　　　　　　　　３２質量部
重合性化合物Ｂ－１　　　　　　　　　　　　　　　　　　６．９質量部
光重合開始剤Ｃ－１　　　　　　　　　　　　　　　　　　１．０質量部
重合禁止剤：２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール（東京化成工業製）　　　　　　　　　　　　　　　　　　　　　０．１質量部
マイグレーション抑制剤：１Ｈ－１，２，４－トリアゾール（東京化成工業製）　　　　　　　　　　　　　　　　　　　　　　　　　０．１質量部
溶剤：γ－ブチロラクトン　　　　　　　　　　　　　４８．００質量部
溶剤：ジメチルスルホキシド　　　　　　　　　　　　１２．００質量部 << 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: γ-butyrolactone 48.00 parts by mass solvent : Dimethyl sulfoxide 12.00 parts by mass
　各添加剤の詳細は以下のとおりである。
Ｂ－１：ＮＫエステル　Ａ－９３００（新中村化学工業（株）製、３官能アクリレート、下記構造）
Figure JPOXMLDOC01-appb-C000050
 Details of each additive are as follows.
B-1: NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd., trifunctional acrylate, the following structure)
Figure JPOXMLDOC01-appb-C000050
（Ｃ）光重合開始剤
Ｃ－１:特表２０１４－５００８５２号公報の０３４５段落に記載されている化合物２４
Figure JPOXMLDOC01-appb-C000051
 (C) Photopolymerization initiator C-1: Compound 24 described in paragraph 0345 of JP-T-2014-500852
Figure JPOXMLDOC01-appb-C000051
＜濾過工程＞
　各感光性樹脂組成物を、細孔の幅が０．８μｍのフィルターを通して加圧濾過した。 <Filtering process>
Each photosensitive resin composition was filtered under pressure through a filter having a pore width of 0.8 μm.
＜感光性樹脂組成物層形成工程＞
　その後、各感光性樹脂組成物をシリコンウェハ上にスピンコート法により適用して層状にし、感光性樹脂組成物層を形成した。 <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.
＜乾燥工程＞
　得られた感光性樹脂組成物層を有するシリコンウェハをホットプレート上で、１００℃で５分間乾燥し、シリコンウェハ上に２０μｍの厚さの均一な感光性樹脂組成物層を得た。 <Drying process>
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 μm on the silicon wafer.
＜露光工程＞
　次いで、シリコンウェハ上の感光性樹脂組成物層を、ステッパー（Ｎｉｋｏｎ　ＮＳＲ　２００５　ｉ９Ｃ）を用いて、３６５ｎｍ（ｉ線）の露光波長で、５００ｍＪ／ｃｍ2の露光エネルギーで露光した（全面均一照射）。
　本実施例では、応力の測定を容易にするために全面均一照射で露光し、現像液に浸漬し、硬化工程を経て硬化膜を形成する。ただし、パターン露光し、現像液に浸漬して未露光部を除き、硬化工程を経てパターンを形成された硬化膜を形成してもよい。
　感光性樹脂組成物層をパターン化する場合の方が、パターン化しない場合よりも多くの界面が生じ、基板と硬化膜と金属層を積層した場合の層間に接触面積が少ない箇所が生じる。この場合、より層間剥離が生じやすくなり、本発明の効果がより顕著に得られる。 <Exposure process>
Next, 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). .
In this embodiment, in order to facilitate the measurement of stress, the entire surface is exposed by uniform irradiation, immersed in a developer, and a cured film is formed through a curing process. However, 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.
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.
＜現像処理工程＞
　全面露光された感光性樹脂組成物層を、シクロペンタノンに６０秒間浸漬して、現像処理した。 <Development process>
The exposed photosensitive resin composition layer was immersed in cyclopentanone for 60 seconds and developed.
＜硬化工程＞
　次いで、現像処理後の感光性樹脂組成物層を以下の（１）～（４）の方法で硬化した。 <Curing process>
Next, the photosensitive resin composition layer after the development treatment was cured by the following methods (1) to (4).
＜＜（１）昇温工程＞＞
　まず、酸素濃度２０体積ｐｐｍ以下の窒素雰囲気下で、現像処理後の感光性樹脂組成物層を有する基板を温度調整可能なプレートの上に乗せ、室温（２０℃）から１０℃／分の昇温速度で昇温し、２１分間かけて最終到達温度２３０℃まで加熱した。 << (1) 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.
＜＜（２）保持工程＞＞
　その後、感光性樹脂組成物層を昇温工程の最終到達温度（保持温度）の２３０℃で３時間維持した。 << (2) Holding process >>
Then, the photosensitive resin composition layer was maintained for 3 hours at 230 ° C., the final temperature (holding temperature) in the temperature raising step.
＜＜（３）冷却工程＞＞
　保持工程で３時間加熱後の感光性樹脂組成物層を、２３０℃から２℃／分の降温速度で、３０分間かけて冷却工程の最終到達温度１７０℃までゆっくり冷却した。 << (3) 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.
＜＜（４）室温にする工程＞＞
　感光性樹脂組成物層が冷却工程の最終到達温度１７０℃に到達した後は、感光性樹脂組成物層を５～１０℃／分の降温速度で冷却し、室温にして、硬化膜を得た。 << (4) 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. .
＜金属層形成工程＞
　次いで、スパッタ装置（ＡＭＡＴ製、製品名Ｅｎｄｕｒａ）の中で、硬化工程後の感光性樹脂組成物層の上に、スパッタ法を用いて感光性樹脂組成物層の温度が１５０℃となる条件でＴｉを１００ｎｍ成膜してバリアメタル膜として用いる１層目の金属層を形成し、連続してＣｕを３００ｎｍ成膜し、シード層として用いる２層目の金属層を形成した。
　スパッタ法を用いる金属層形成工程で形成した金属層全体の厚さは４００ｎｍとした。
　スパッタ装置内において、感光性樹脂組成物層の温度は、感光性樹脂組成物層の表面の温度を、温度で変色するシール（サーモラベル、日油技研工業株式会社）を表面に貼って色の変化を見ることによって測定して求めた。 <Metal layer formation process>
Next, 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.
In the sputtering apparatus, 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.
＜第２の金属層形成工程＞
　次いで、シード層の上にドライフィルムレジスト（日立化成株式会社製、商品名　Ｐｈｏｔｅｃ　ＲＹ－３５２５）をロールラミネーターで貼着し、パターンを形成したフォトツールを密着させ、株式会社オーク製作所製ＥＸＭ－１２０１型露光機を使用して、１００ｍＪ／ｃｍ2のエネルギー量で露光を行った。次いで、３０℃の１質量％炭酸ナトリウム水溶液で、９０秒間スプレー現像を行い、ドライフィルムレジストを開口させた。次いで、電解銅めっき法を用いて、ドライフィルムレジスト上およびドライフィルムレジストが開口した部分のシード層上に、厚さ７μｍの銅めっき層を形成した。次いで、剥離液を用いて、ドライフィルムレジストを剥離した。次いでドライフィルムレジストが剥離された部分のシード層（３００ｎｍのＣｕ層）を、エッチング液を用いて除去し、硬化工程後の感光性樹脂組成物層の表面にパターン化された金属層を形成した。 <Second metal layer forming step>
Next, 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. Next, 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. Subsequently, a copper plating layer having a thickness of 7 μm 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. Next, the dry film resist was stripped using a stripping solution. Next, 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. .
＜硬化膜の特性＞
＜＜ガラス転移温度の測定＞＞
　硬化工程後の感光性樹脂組成物層（硬化膜）について、ガラス転移温度の測定を以下の方法で行った。
　動的粘弾性測定装置にセットし、引っ張り法、周波数１Ｈｚで、昇温速度１０℃／分で０℃から３５０℃まで昇温し、ｔａｎδのピーク温度からＴｇを求めた。
　得られた結果を下記表１に記載した。 <Characteristics of cured film>
<< Measurement of glass transition temperature >>
About the photosensitive resin composition layer (cured film) after a hardening process, the glass transition temperature was measured with the following method.
The temperature was increased from 0 ° C. to 350 ° C. at a rate of 10 ° C./min with a tension method at a frequency of 1 Hz, and Tg was determined from the peak temperature of tan δ.
The obtained results are shown in Table 1 below.
＜＜応力の測定＞＞
　金属層形成工程および第２の金属層形成工程後の感光性樹脂組成物層（硬化膜）について、応力の測定を以下の方法で行った。
　感光性樹脂組成物層の塗布前のシリコンウェハについて、薄膜応力測定装置にウェハをセットし、室温下でレーザースキャンし、ブランク数値を求めた。
　薄膜応力測定装置に金属層形成工程および第２の金属層形成工程後の感光性樹脂組成物層（硬化膜）を形成したウェハをセットし、室温下でレーザースキャン後、感光性樹脂組成物層の塗布前のブランク数値と比較し、膜厚および曲率半径から応力を測定した。
　得られた結果を下記表１に記載した。 << Measurement of stress >>
About the photosensitive resin composition layer (cured film) after a metal layer formation process and a 2nd metal layer formation process, the measurement of the stress was performed with the following method.
About the silicon wafer before application | coating of the photosensitive resin composition layer, the wafer was set to the thin film stress measuring device, the laser scan was carried out at room temperature, and the blank numerical value was calculated | required.
The wafer on which the photosensitive resin composition layer (cured film) after the metal layer forming step and the second metal layer forming step is set is set in the thin film stress measuring device, and after laser scanning at room temperature, the photosensitive resin composition layer The stress was measured from the film thickness and the radius of curvature in comparison with the blank value before coating.
The obtained results are shown in Table 1 below.
＜積層工程＞
　さらに、金属層と硬化工程後の感光性樹脂組成物層により凹凸が形成されている面に、再度、同じ感光性樹脂組成物を用いて上記と同様に感光性樹脂組成物の濾過工程から硬化工程までの手順を再度実施して、硬化工程後の感光性樹脂組成物層を２層有する積層体を形成した。
　さらに、硬化工程後の感光性樹脂組成物層を２層有する積層体に対して、上記と同様に金属層形成工程および第２の金属層形成工程を再度実施して、積層体を形成した。 <Lamination process>
Furthermore, on the surface where irregularities are formed by the metal layer and 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.
Further, 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.
＜積層体の評価＞
＜＜金属の硬化膜への侵入長の測定＞＞
　金属層形成工程および第２の金属層形成工程後の積層体について、スパッタ法を用いる金属層形成工程後の金属の硬化膜への侵入長の測定を以下の方法で行った。
　収束イオンビーム（Ｆｏｃｕｓｅｄ　Ｉｏｎ　Ｂｅａｍ；ＦＩＢ）と透過型電子顕微鏡（ＴＥＭ）により断面図の直接観察による測長を行い、高角度散乱暗視野走査透過電子顕微鏡（ｈｉｇｈ－ａｎｇｌｅ　ａｎｎｕｌａｒ　ｄａｒｋ－ｆｉｅｌｄ　ｓｃａｎｎｉｎｇ　ｔｒａｎｓｍｉｓｓｉｏｎ　ｅｌｅｃｔｒｏｎ　ｍｉｃｒｏｓｃｏｐｙ；ＨＡＡＤＦ－ＳＴＥＭ）と電子エネルギー損失分光法（Ｅｌｅｃｔｒｏｎ　Ｅｎｅｒｇｙ　Ｌｏｓｓ　Ｓｐｅｃｔｒｏｓｃｏｐｙ；ＥＥＬＳ）の併用で元素分析を行った。
　得られた結果を下記表１に記載した。 <Evaluation of laminate>
<< Measurement of penetration depth of metal into hardened film >>
About the laminated body after a metal layer formation process and a 2nd metal layer formation process, the penetration | invasion length to the cured film of the metal after the metal layer formation process using a sputtering method was measured with the following method.
The length is measured by direct observation of a cross-sectional view using a focused ion beam (FIB) and a transmission electron microscope (TEM), and a high-angle scattering dark-field scanning transmission electron microscope (high-angle scattering dark-field scanning transmission electron microscope). Elemental analysis was performed using a combination of microscopic (HAADF-STEM) and electron energy loss spectroscopy (EELS).
The obtained results are shown in Table 1 below.
＜＜サイクル試験後の剥離試験＞＞
　積層工程後の積層体について、サイクル試験後の剥離試験を以下の方法で行った。
　各積層体を、窒素中－５５℃で３０分間冷却し、その後１２５℃で３０分間加熱するサイクルを５００サイクル行った。その後、各積層体を、硬化膜の面に対し、垂直方向に幅５ｍｍとなるように、かつ、硬化膜と金属層が接している部分と、金属層と第２の金属層が接している部分を、それぞれ、切り出し、その断面を観察して、１つの切り出し片における、硬化膜と金属層の間、および金属層と第２の金属層の間での剥がれの有無を光学顕微鏡で確認した。「剥離なし」であることが好ましい。
　得られた結果を下記表１に記載した。 << Peeling test after cycle test >>
About the laminated body after a lamination process, the peeling test after a cycle test was done with the following method.
Each laminate was cooled in nitrogen at −55 ° C. for 30 minutes and then heated at 125 ° C. for 30 minutes for 500 cycles. Thereafter, each laminated body has a width of 5 mm perpendicular to the surface of the cured film, and the portion where the cured film and the metal layer are in contact with each other, and the metal layer and the second metal layer are in contact with each other. Each part was cut out and the cross section was observed, and the presence or absence of peeling between the cured film and the metal layer and between the metal layer and the second metal layer in one cut piece was confirmed with an optical microscope. . “No peeling” is preferred.
The obtained results are shown in Table 1 below.
　［実施例２～６および比較例１～３］
　下記表で示す条件に変更した以外は実施例１と同様にして、実施例２～６および比較例１～３の積層体を製造した。
　実施例１と同様にして、硬化膜の特性の測定および積層体の評価を行った。 [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.
Figure JPOXMLDOC01-appb-T000052
Figure JPOXMLDOC01-appb-T000052
　上記表１より、金属層を形成する際の硬化工程後の感光性樹脂組成物層の温度が、硬化工程後の感光性樹脂組成物層のガラス転移温度未満である場合、硬化膜の残留応力が小さく、スパッタ法を用いる金属層形成工程後の金属の侵入長が短い積層体を提供できることがわかった。硬化膜の残留応力が小さく、金属の侵入長が短い本発明の積層体では、基板と硬化膜と金属層を積層した場合の層間剥離を抑制できることがわかった。
　一方、比較例１～３より、金属層を形成する際の硬化工程後の感光性樹脂組成物層の温度が、硬化工程後の感光性樹脂組成物層のガラス転移温度以上である場合、硬化膜の残留応力が大きく、スパッタ法を用いる金属層形成工程後の金属の侵入長が長い積層体が得られた。硬化膜の残留応力が大きく、金属の侵入長が長い比較例１～３の積層体では、基板と硬化膜と金属層を積層した場合に層間剥離が発生することがわかった。 From the said Table 1, when the 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, the residual stress of a cured film It was found that a laminate having a small metal penetration length after the metal layer forming step using a sputtering method can be provided. It was found that the laminate of the present invention with a small residual stress of the cured film and a short metal penetration length can suppress delamination when the substrate, the cured film, and the metal layer are laminated.
On the other hand, from 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.
　実施例１において、金属層（銅薄膜）をアルミ薄膜に変更し、他は同様に行ったところ、実施例１と同様に良好な結果が得られた。
　実施例１において、感光性樹脂組成物１の固形分濃度を組成比を変えずに１／１０にし、スプレーガン（オーストリアＥＶグループ（ＥＶＧ）社製「ＮａｎｏＳｐｒａｙ」）を用いてスプレー塗布した以外は、実施例１と同様にして積層体を形成した。実施例１と同様の優れた効果が得られた。
　実施例１の積層体の製造において、２３０℃で３時間の加熱を行う前に１００℃で１０分間の加熱（前処理）を行った以外は実施例１と同様にして積層体を製造し、特性を評価した。実施例１と同様に優れた効果が得られた。
　実施例１の積層体の製造において、２３０℃で３時間の加熱を行う前に１５０℃で１０分間の加熱（前処理）を行った以外は実施例１と同様にして積層体を製造し、特性を評価した。実施例１と同様に優れた効果が得られた。
　実施例１の積層体の製造において、２３０℃で３時間の加熱を行う前にＵＶ光を照射しながら１８０℃で１０分間の加熱（前処理）を行った以外は実施例１と同様にして積層体を製造し、特性を評価した。実施例１と同様に優れた効果が得られた。 In 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.
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)). In the same manner as in Example 1, a laminate was formed. The same excellent effect as in Example 1 was obtained.
In the production of the laminate of Example 1, 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.
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.
　本発明の積層体の製造方法で製造された積層体は、基板と硬化膜と金属層を積層した場合の層間剥離を抑制することができる。さらに本発明の積層体の製造方法で製造された積層体は、基板と硬化膜と金属層の積層体が２組以上積層された場合も層間剥離を抑制することができる。このような積層体は、半導体素子の再配線層用層間絶縁層を製造するために利用することができ、層間剥離が抑制された再配線層用層間絶縁層を提供できる。また、このような積層体は、パワー半導体用途の層間絶縁層、三次元ＩＣ（Ｔｈｒｅｅ－Ｄｉｍｅｎｓｉｏｎａｌ　Ｉｎｔｅｇｒａｔｅｄ　Ｃｉｒｃｕｉｔ）用の銅ピラー中膜または単層絶縁層およびパネル用途の層間絶縁層を製造するために利用できる。 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. In addition, 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. Available.
１００：半導体素子
１０１、１０１ａ～１０１ｄ：半導体チップ
１０２ｂ、１０２ｃ、１０２ｄ：貫通電極
１０３ａ～１０３ｅ：金属バンプ
１０５：再配線層
１１０、１１０ａ、１１０ｂ：アンダーフィル層
１１５：絶縁層
１２０：配線基板
１２０ａ：表面電極
２００：積層体
２０１：感光性樹脂組成物層（硬化膜）
２０３：金属層 100: Semiconductor elements 101, 101a to 101d: Semiconductor chips 102b, 102c, 102d: Through electrodes 103a to 103e: Metal bumps 105: Rewiring layers 110, 110a, 110b: Underfill layers 115: Insulating layers 120: Wiring substrates 120a: Surface electrode 200: Laminate 201: Photosensitive resin composition layer (cured film)
203: Metal layer

Claims (14)

  1. 　感光性樹脂組成物を基板に適用して層状にする、感光性樹脂組成物層形成工程と、
    　前記基板に適用された感光性樹脂組成物層を露光する露光工程と、
    　前記露光された感光性樹脂組成物層に対して、現像処理を行う現像処理工程と、
    　前記現像後の感光性樹脂組成物層を硬化する硬化工程と、
    　前記硬化工程後の感光性樹脂組成物層の表面に気相成膜により金属層を形成する金属層形成工程とを、上記順に行うことを含み、
    　前記金属層を形成する際の前記硬化工程後の感光性樹脂組成物層の温度が、前記硬化工程後の感光性樹脂組成物層のガラス転移温度未満である、積層体の製造方法。     Applying a photosensitive resin composition to a substrate to form a layer, and forming a photosensitive resin composition layer; and
    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 the development;
    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 said hardening process at the time of forming the said metal layer is less than the glass transition temperature of the photosensitive resin composition layer after the said hardening process.
  2. 　さらに、再度、前記感光性樹脂組成物層形成工程、前記露光工程、前記現像処理工程、前記硬化工程、および、前記金属層形成工程を、上記順に行うことを含む、請求項１に記載の積層体の製造方法。 Furthermore, the lamination of Claim 1 including performing the said photosensitive resin composition layer formation process, the said exposure process, the said image development process, the said hardening process, and the said metal layer formation process in the said order again. Body manufacturing method.
  3. 　前記感光性樹脂組成物が、露光により架橋構造が構築されて有機溶剤への溶解度が低下する、請求項１または２に記載の積層体の製造方法。 The method for producing a laminate according to claim 1 or 2, wherein the photosensitive resin composition has a cross-linked structure built by exposure and the solubility in an organic solvent decreases.
  4. 　前記感光性樹脂組成物が、ポリイミド前駆体、ポリイミド、ポリベンゾオキサゾール前駆体およびポリベンゾオキサゾールから選択される少なくとも１種類の樹脂を含む、請求項１～３のいずれか１項に記載の積層体の製造方法。 The laminate according to any one of claims 1 to 3, wherein the photosensitive resin composition comprises at least one resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole. Manufacturing method.
  5. 　さらに、前記金属層の表面に第２の金属層を形成する第２の金属層形成工程を含む、請求項１～４のいずれか１項に記載の積層体の製造方法。 The method for producing a laminate according to any one of claims 1 to 4, further comprising a second metal layer forming step of forming a second metal layer on a surface of the metal layer.
  6. 　前記第２の金属層が、銅を含む、請求項５に記載の積層体の製造方法。 The method for manufacturing a laminated body according to claim 5, wherein the second metal layer contains copper.
  7. 　前記金属層が、チタン、タンタルおよび銅ならびにこれらのうち少なくとも１種類を含む化合物のうち少なくとも１種類を含む、請求項１～６のいずれか１項に記載の積層体の製造方法。 The method for producing a laminate according to any one of claims 1 to 6, wherein the metal layer contains at least one of titanium, tantalum, copper, and a compound containing at least one of them.
  8. 　前記金属層形成工程で形成される前記金属層の厚さが、５０～２０００ｎｍである、請求項１～７のいずれか１項に記載の積層体の製造方法。 The method for producing a laminate according to any one of claims 1 to 7, wherein the metal layer formed in the metal layer forming step has a thickness of 50 to 2000 nm.
  9. 　前記硬化工程後の前記感光性樹脂組成物のレーザー計測法に従って測定した残留応力が３５ＭＰａ未満である、請求項１～８のいずれか１項に記載の積層体の製造方法。 The method for producing a laminate according to any one of claims 1 to 8, wherein a residual stress measured according to a laser measurement method of the photosensitive resin composition after the curing step is less than 35 MPa.
  10. 　前記感光性樹脂組成物が、ネガ型現像用である、請求項１～９のいずれか１項に記載の積層体の製造方法。 The method for producing a laminate according to any one of claims 1 to 9, wherein the photosensitive resin composition is for negative development.
  11. 　前記硬化工程が、前記感光性樹脂組成物層を昇温する昇温工程と、前記昇温工程の最終到達温度と等しい保持温度で保持する保持工程とを含み、
    　前記保持工程における前記保持温度が２５０℃以下である、請求項１～１０のいずれか１項に記載の積層体の製造方法。     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 method for producing a laminate according to any one of claims 1 to 10, wherein the holding temperature in the holding step is 250 ° C or lower.
  12. 　前記金属層を形成する際の感光性樹脂組成物層の温度が前記感光性樹脂組成物層のガラス転移温度より３０℃以上低い、請求項１～１１のいずれか１項に記載の積層体の製造方法。 The laminate according to any one of claims 1 to 11, wherein the temperature of the photosensitive resin composition layer when forming the metal layer is lower by 30 ° C or more than the glass transition temperature of the photosensitive resin composition layer. Production method.
  13. 　請求項１～１２のいずれか１項に記載の積層体の製造方法を含む、半導体素子の製造方法。 A method for manufacturing a semiconductor element, including the method for manufacturing a laminate according to any one of claims 1 to 12.
  14. 　基板と、パターン硬化膜と、前記パターン硬化膜の表面に位置する金属層とを有し、
    　前記パターン硬化膜は、ポリイミドまたはポリベンゾオキサゾールを含み、
    　前記パターン硬化膜の表面に位置する金属層を構成する金属の前記パターン硬化膜への侵入長がパターン硬化膜の表面から１３０ｎｍ以下である、積層体。     A substrate, a pattern cured film, and a metal layer located on the surface of the pattern cured film,
    The pattern cured film includes polyimide or polybenzoxazole,
    The laminated body whose penetration | invasion length to the said pattern cured film of the metal which comprises the metal layer located in the surface of the said pattern cured film is 130 nm or less from the surface of a pattern cured film.
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JPWO2017209176A1 (en) 2019-05-23
KR102147108B1 (en) 2020-08-25
TWI736629B (en) 2021-08-21
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JP6845848B2 (en) 2021-03-24
CN109313397B (en) 2023-04-11

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