WO2019163860A1 - Film production method, laminate production method, semiconductor device production method, and film formation composition - Google Patents

Film production method, laminate production method, semiconductor device production method, and film formation composition Download PDF

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Publication number
WO2019163860A1
WO2019163860A1 PCT/JP2019/006428 JP2019006428W WO2019163860A1 WO 2019163860 A1 WO2019163860 A1 WO 2019163860A1 JP 2019006428 W JP2019006428 W JP 2019006428W WO 2019163860 A1 WO2019163860 A1 WO 2019163860A1
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Prior art keywords
film
group
polyimide precursor
mass
solvent
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PCT/JP2019/006428
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French (fr)
Japanese (ja)
Inventor
沢野　充
慶 福原
誠也 増田
嶋田　和人
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富士フイルム株式会社
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Priority to JP2020501015A priority Critical patent/JPWO2019163860A1/en
Priority to KR1020207023969A priority patent/KR102433579B1/en
Priority to CN201980014436.7A priority patent/CN111819306A/en
Publication of WO2019163860A1 publication Critical patent/WO2019163860A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
    • B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—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
    • G03F7/16—Coating processes; Apparatus therefor

Definitions

  • the present invention relates to a film manufacturing method, a laminate manufacturing method, a semiconductor device manufacturing method, and a film forming composition.
  • Polyimide resins are excellent in heat resistance and insulation, and thus are applied to various uses. Although the use is not particularly limited, when a semiconductor device for mounting is taken as an example, it can be used as a material for an insulating film or a sealing material, or as a protective film thereof. It is also used as a base film and coverlay for flexible substrates.
  • the above polyimide resin generally has low solubility in a solvent. Therefore, a method of dissolving in a solvent in a state of a polyimide precursor before cyclization is often used. Thereby, the excellent handleability can be realized, and when manufacturing each product as described above, it can be applied and processed in various forms on a substrate or the like. Thereafter, the polyimide precursor can be heated to form a cured product.
  • the high performance possessed by polyimide resin its industrial application development is increasingly expected from the viewpoint of excellent adaptability in manufacturing.
  • Patent Document 1 describes slit coating of a resin composition containing a surfactant.
  • Patent Document 1 a technique for forming a composition containing a polyimide precursor into a film by slit coating (slit coating) is known.
  • slit coating a technique for forming a composition containing a polyimide precursor into a film by slit coating
  • An object of the present invention is to solve the above-mentioned problems, and even when a coating film is formed on a metal surface, it is possible to achieve a good surface shape by suppressing the occurrence of “Yuzu skin”.
  • An object of the present invention is to provide a method for producing a film using a slit coat, a method for producing a laminate, a method for producing a semiconductor device, and a film forming composition suitable for use in these production methods.
  • ⁇ 1> Using a composition comprising a polyimide precursor, at least two solvents having different solubility at 23 ° C. with respect to the polyimide precursor, and at least one selected from the group consisting of a surfactant and a plasticizer, A method for producing a film, comprising a step of slit coating on a member, wherein the member contains a metal at least in part.
  • the surfactant is a compound containing a perfluoroalkyl group and having a weight average molecular weight of 5,000 or less and is soluble in water.
  • ⁇ 3> The method for producing a film according to ⁇ 1> or ⁇ 2>, including a head cleaning step of cleaning the nozzle head with a cleaning liquid after the step of performing the slit coating.
  • the step of performing the slit coating includes a head standby step, wherein the nozzle head is immersed in an immersion liquid in the head standby process, and the immersion liquid has a composition that is 90% by mass or more in common with the cleaning liquid.
  • the method for producing a film according to ⁇ 3>, wherein ⁇ 5> The method for producing a film according to ⁇ 3> or ⁇ 4>, wherein the cleaning liquid contains a solvent having the highest solubility at 23 ° C. of the polyimide precursor among the at least two kinds of solvents.
  • ⁇ 6> The film production according to any one of ⁇ 3> to ⁇ 5>, wherein the cleaning liquid contains a solvent having the lowest solubility of the polyimide precursor at 23 ° C. among the at least two solvents.
  • Method. ⁇ 7> The method for producing a film according to ⁇ 4>, wherein the immersion liquid contains a solvent having the highest solubility at 23 ° C. of the polyimide precursor among the at least two kinds of solvents.
  • ⁇ 8> The method for producing a film according to ⁇ 4> or ⁇ 7>, wherein the immersion liquid contains a solvent having the lowest solubility of the polyimide precursor at 23 ° C among the at least two solvents.
  • ⁇ 9> The method for producing a film according to any one of ⁇ 1> to ⁇ 8>, comprising an exposure step of exposing the film formed by the slit coating and a development step of developing the exposed film.
  • the method for producing a film according to any one of ⁇ 1> to ⁇ 9> further including a heating step of heating the film.
  • a method for producing a laminate wherein the method for producing a film according to any one of ⁇ 1> to ⁇ 10> is performed a plurality of times.
  • ⁇ 12> The method for producing a laminate according to ⁇ 11>, including a step of applying a metal layer to the film.
  • ⁇ 13> A method for manufacturing a semiconductor device, wherein a chip is arranged on a film manufactured by the method according to any one of ⁇ 1> to ⁇ 10>.
  • ⁇ 14> A method for producing a semiconductor device, in which a chip is arranged on a laminate produced by the method according to ⁇ 11> or ⁇ 12>.
  • ⁇ 15> A film-forming composition used in the production method according to any one of ⁇ 1> to ⁇ 10>, wherein the polyimide precursor and the polyimide precursor have different solubility at 23 ° C.
  • a film-forming composition comprising two kinds of solvents and at least one selected from the group consisting of a surfactant and a plasticizer.
  • the solvent having the highest solubility of the polyimide precursor is a sulfoxide or lactam solvent, and of the at least two solvents, the solubility of the polyimide precursor is the highest.
  • the low solvent is a solvent of ketones or lactones.
  • the solubility of the polyimide precursor is higher than the average value below, and among the at least two solvents, the solubility of the polyimide precursor is below the average value below.
  • the average value is an average value of the solubility of the solvent having the highest solubility of the polyimide precursor at 23 ° C. and the solubility of the polyimide precursor having the lowest solubility at 23 ° C.
  • ⁇ 19> The film forming composition as described in any one of ⁇ 15> to ⁇ 18>, wherein the surfactant contains a fluorine atom.
  • the surfactant is a compound having a perfluoroalkyl group and having a weight average molecular weight of 5,000 or less and is soluble in water.
  • the content of the surfactant is 0.005 to 2% by mass in the solid content.
  • the plasticizer is an epoxidized oil.
  • ⁇ 23> The film forming composition according to any one of ⁇ 15> to ⁇ 22>, wherein the content of the plasticizer is 0.005 to 2% by mass in the solid content.
  • 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.
  • 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) acryl” represents both “acryl” and “methacryl”
  • (Meth) acryloyl” represents either or both of “acryloyl” and “methacryloyl”.
  • 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.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values according to 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-8220GPC (manufactured by Tosoh Corp.), guard columns HZ-L, TSKgel Super HZM-M, TSKgel.
  • the method for producing a film of the present invention includes a polyimide precursor, at least two solvents having different solubility in a polyimide precursor at 23 ° C., and at least one selected from the group consisting of a surfactant and a plasticizer. It includes a step of performing slit coating on a member containing a metal at least in part using the composition. As a result, even when a coating film is formed on the metal surface in the slit coat, it is possible to suppress the occurrence of “yuzu skin” and achieve a good surface shape (gloss).
  • the polyimide precursor is cured by heating after forming a coating film.
  • the adhesion between the polyimide resin layer and the metal has been successfully improved.
  • a predetermined surfactant it has succeeded in obtaining excellent adhesion with copper (for example, a copper layer).
  • the present invention will be described in detail below.
  • FIG. 1 is a process explanatory diagram (1) for explaining a preferred embodiment of a slit coat applied in the present invention in a schematic side view.
  • the coating apparatus 100 of this embodiment includes a transport unit 23 that transports the substrate 30 and a support stage (not shown) that supports the substrate from below.
  • a resist (resin) 21a is discharged from the nozzle head 21 to the substrate 30 through a slit-like nozzle, and the substrate 30 is conveyed in the direction d3 (slit coating process).
  • the conveyance unit 23 can be configured by a plurality of conveyance rollers and a conveyance roller driving unit that rotates the conveyance rollers.
  • the nozzle head 21 can be lifted up and down in accordance with the timing at which the transport unit transports the substrate 30. Similarly, a support stage (not shown) can also be moved and retracted from directly below the nozzle head. At this time, it is possible to wait the nozzle head and wait for the next substrate to be sent (head waiting step).
  • the nozzle head immersion process (immersion process process) and the cleaning process (head cleaning process) described below may be performed in the head standby process during the slit coating process or after the slit coating process.
  • the nozzle head cleaner 22 is disposed immediately below the nozzle head.
  • the nozzle head is lowered (d1) along a direction perpendicular to the coating surface, and the nozzle head 21 is immersed in the immersion liquid provided in the nozzle head cleaner 22 (FIG. 2).
  • the time for immersing the nozzle head in the immersion liquid in the cleaner is, for example, preferably 0.1 minutes or more, more preferably 0.2 minutes or more, and further preferably 0.5 minutes or more.
  • the upper limit is preferably 10 minutes or less, more preferably 8 minutes or less, and even more preferably 5 minutes or less. Thereby, the tip of the nozzle head 21 can be cleaned.
  • FIG. 3 is a side view of the apparatus for explaining a head maintenance process different from those shown in FIGS. 1 and 2 and shows a mode of maintenance (cleaning) of the nozzle head.
  • the apparatus of this embodiment includes a roller 24 that rotates in the d2 direction.
  • the roller bat 25 is filled with a cleaning liquid 25a so that the lower part of the roller 24 is immersed.
  • the apparatus 100 of this embodiment is further provided with a liquid draining blade 25b.
  • the roller 24 and the roller butt 25 constitute a maintenance unit 26.
  • the maintenance unit can be moved up and down in a direction perpendicular to the substrate surface.
  • the apparatus according to the present embodiment includes such a maintenance unit, so that maintenance (cleaning) of the nozzle head 21 can also be performed by raising the maintenance unit 26 d4 without lowering the nozzle head 21 d5 in the maintenance process. Can be performed.
  • the liquid flowing from d5 is switched to the cleaning liquid.
  • the time for which the cleaning liquid flows through the nozzle head is, for example, preferably 1 minute or longer, more preferably 2 minutes or longer, and further preferably 5 minutes or longer. As an upper limit, it is preferable that it is 120 minutes or less, It is more preferable that it is 60 minutes or less, It is further more preferable that it is 30 minutes or less. Thereby, the nozzle head 21 can be cleaned.
  • the slit coating step preferably includes a head standby step.
  • the head is preferably immersed in the immersion liquid.
  • the immersion liquid is preferably a liquid having a composition that is 90% by mass or more in common with the cleaning liquid, more preferably a liquid having a composition that has 95% by mass or more in common, and even more preferably the same composition.
  • the immersion liquid and the cleaning liquid are each preferably a liquid having a composition that is 90% by mass or more in common with the solvent in the film-forming composition with respect to the type and mixing ratio of the compound, and 95% by mass or more. More preferably, it is a liquid, and it is further more preferable that it is the same composition.
  • the cleaning liquid preferably contains a solvent having the highest solubility of the polyimide precursor at 23 ° C. among at least two kinds of solvents contained in the film-forming composition. Moreover, it is preferable that a washing
  • the immersion liquid preferably also contains a solvent having the highest solubility of the polyimide precursor at 23 ° C.
  • an immersion liquid contains the solvent with the lowest solubility at 23 degreeC of a polyimide precursor among the at least 2 types of solvents contained in the composition for film formation. Furthermore, among at least two kinds of solvents contained in the film-forming composition, it contains both the solvent having the highest solubility of the polyimide precursor at 23 ° C. and the solvent having the lowest solubility of the polyimide precursor at 23 ° C. preferable.
  • JP 2009-070973 A can be referred to, and the matters described therein are incorporated in this specification.
  • ⁇ Film forming composition> ⁇ Polyimide precursor As a polyimide precursor, it is preferable that the repeating structural unit (structural unit) represented by following formula (1) is included.
  • 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 are each independently an oxygen atom or NH, preferably an oxygen atom.
  • R 111 represents a divalent organic group.
  • the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group composed of an aromatic group, a heteroaromatic group, or a combination thereof, and has 2 to 20 carbon atoms.
  • An aromatic group having 6 to 20 carbon atoms is more preferable.
  • R 111 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.
  • the diamine is a straight chain aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof.
  • a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. The following 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—, —CO—, —S—, —SO 2 —, — NHCO— and a group selected from these combinations are preferable.
  • a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S— And —SO 2 — is more preferable, and —CH 2 —, —O—, —S—, —SO 2 —, —C (CF 3 ) 2 —, and —C (CH 3) 2 - and more preferably a divalent radical selected from the group consisting of.
  • 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 preferred example is a diamine having at least two alkylene glycol units in the main chain.
  • 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 -Aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, and the like. Not.
  • x, y, and z are average values.
  • R 111 is preferably represented by -Ar 0 -L 0 -Ar 0- .
  • Ar 0 is each independently an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and L 0 is a group of the above A It is synonymous and the preferable range is also the same.
  • Ar 0 is preferably a phenylene group.
  • R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-line transmittance.
  • the divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-line transmittance and availability.
  • R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group, or A trifluoromethyl group.
  • Examples of the monovalent organic group represented by R 50 to R 57 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.
  • R 58 and R 59 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.
  • Diamine compounds that give the structure of formula (51) or (61) include dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2 Examples include '-bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, and the like. One of these may be used, or two or more may be used in combination.
  • R 115 in formula (1) 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 has the same meaning as A, and the preferred range is also the same.
  • tetravalent organic group represented by R 115 in Formula (1) include a tetracarboxylic acid residue remaining after the acid dianhydride group is removed from the tetracarboxylic dianhydride. Only one tetracarboxylic dianhydride may be used, or two or more tetracarboxylic dianhydrides may be used.
  • the tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).
  • R 115 represents a tetravalent organic group. R 115 has the same meaning as R 115 in formula (1).
  • tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4 , 4′-diphenyl sulfide tetracarboxylic 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 acid Dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic
  • tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also preferable examples.
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group. At least one of R 113 and R 114 preferably contains a radical polymerizable group, and more preferably both contain a radical polymerizable group.
  • the radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferable example includes a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl 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 (poly) oxyalkylene group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atom)
  • To 12 is preferable, 1 to 6 is more preferable, and 1 to 3 is particularly preferable; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3.
  • the (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
  • R 201 examples include 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 —, and 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.
  • Preferred embodiments of the polyimide precursor include aliphatic groups, aromatic groups, arylalkyl groups, etc. having 1, 2, or 3, preferably 1, acid groups as the monovalent organic group of R 113 or R 114 Is mentioned.
  • Specific examples include an aromatic group having 6 to 20 carbon atoms having an acid group and an arylalkyl group having 7 to 25 carbon atoms having an acid group. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned.
  • the acid group is preferably a hydroxyl group. That is, R 113 or R 114 is preferably a group having a hydroxyl group.
  • R113 or R114 As the monovalent organic group represented by R113 or R114, a substituent that improves the solubility of the developer is preferably used.
  • R 113 or R 114 is more preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl or 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.
  • R 113 or R 114 is preferably a monovalent organic group.
  • the monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.
  • the alkyl group preferably has 1 to 30 carbon atoms (3 or more in the case of a cyclic group).
  • the alkyl group may be linear, branched or cyclic.
  • linear or branched alkyl group examples include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, octadecyl group. Isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group.
  • the cyclic alkyl group 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 examples include 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.
  • the polyimide precursor preferably has a fluorine atom in the structure.
  • the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less. There is no particular upper limit, but 50% by mass or less is practical.
  • an aliphatic group having a siloxane structure may be copolymerized with the structural unit represented by the formula (1).
  • the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.
  • the structural unit represented by the formula (1) is preferably a structural unit represented by the formula (1-A).
  • a 11 and A 12 each represent an oxygen atom or NH;
  • R 111 and R 112 each independently represent a divalent organic group;
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent group.
  • An organic group is represented, and at least one of R 113 and R 114 is a group containing a radical polymerizable group, and is preferably a radical polymerizable group.
  • a 11 , A 12 , R 111 , R 113 and R 114 are each independently synonymous with A 1 , A 2 , R 111 , R 113 and R 114 in formula (1), and the preferred ranges are also the same. is there. R 112 has the same meaning as R 112 in formula (5), and the preferred range is also the same.
  • the repeating structural unit represented by the formula (1) may be one type or two or more types. Moreover, the structural isomer of the structural unit represented by Formula (1) may be included.
  • the polyimide precursor may also contain other types of structural units in addition to the structural unit of the above formula (1).
  • polyimide precursor As an embodiment of the polyimide precursor, a polyimide precursor in which 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of all the structural units is a structural unit represented by the formula (1) is exemplified.
  • the weight average molecular weight (Mw) of the polyimide precursor is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, and even more preferably from 10,000 to 50,000.
  • the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and still more preferably 4000 to 25000.
  • the molecular weight dispersion of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
  • the polyimide precursor is a condensate of dicarboxylic acid or dicarboxylic acid derivative and diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting with a diamine.
  • an organic solvent is preferably used for the reaction.
  • One or more organic solvents may be used.
  • 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.
  • 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.
  • the proportion of the polyimide precursor in the film-forming composition is preferably 60% by mass or more of the component (solid content) excluding the solvent, more preferably 70% by mass or more, and 75% by mass or more. Is more preferably 99% by mass or less, and more preferably 95% by mass or less.
  • the film forming composition may contain only one type of polyimide precursor or two or more types of polyimide precursors. When 2 or more types are included, the total amount is preferably within the above range.
  • the composition (film forming composition) used in the film production method contains at least two solvents having different solubility at 23 ° C. in the polyimide precursor as the solvent. Specifically, it is preferable to use a mixed solvent of at least a solvent A having higher solubility with respect to the polyimide precursor and a solvent B having lower solubility at 23 ° C. as the solvent.
  • the solubility is defined as the amount (g) of the polyimide precursor that is soluble in 100 g of a solvent at 23 ° C. When there are three or more solvents, the average value of the solubility of the solvent having the highest solubility and the solubility of the solvent having the lowest solubility is obtained. Are classified as Solvent B.
  • the solvent having the highest solubility is preferably solvent A
  • the solvent having the lowest solubility is preferably solvent B.
  • the difference in solubility between the solvent A and the solvent B is preferably 10 g or more, more preferably 15 g or more, and further preferably 20 g or more.
  • the upper limit is not particularly defined, but can be, for example, 50 g or less.
  • the boiling point of the solvent A is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, and further preferably 130 ° C. or higher.
  • the upper limit is preferably 230 ° C. or lower, more preferably 210 ° C. or lower, and further preferably 190 ° C. or lower. By setting it as such a structure, it exists in the tendency for the surface shape after application
  • the boiling point of the solvent B is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and further preferably 200 ° C. or higher.
  • the upper limit is preferably 250 ° C. or lower, more preferably 230 ° C. or lower, and further preferably 210 ° C. or lower.
  • the solvent A and the solvent B have a predetermined difference in boiling points.
  • the difference in boiling points is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and further preferably 20 ° C. or higher. Moreover, it is preferable that it is 80 degrees C or less.
  • the boiling point means a temperature at which boiling occurs at 1013.25 hPa.
  • the solvent is preferably an organic solvent.
  • the solvent classified as solvent A include sulfoxides, amides, and lactams, and sulfoxides are preferred.
  • the solvent classified as the solvent B include esters, ethers, lactones, ketones, aromatic hydrocarbons and the like, among which lactones and ketones are preferable, and ketones are more preferable.
  • esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and lactones ( ⁇ -Butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone), alkyl oxyacetates (eg methyl alkyloxyacetate, alkyloxyethyl acetate, butyl oxyoxyacetate (eg methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxy) Methyl acetate, ethyl ethoxyacetate, etc.), alkyl esters of 3-alkyloxypropionic acid (eg, methyl 3-alky
  • 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 and 2-oxobutanoate are mentioned as preferred.
  • 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, propylene glycol monopropyl ether acetate and the like.
  • Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.
  • Suitable examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
  • As the sulfoxides for example, dimethyl sulfoxide is preferable.
  • Preferable examples of amides include lactams (N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone), N, N-dimethylacetamide, N, N-dimethylformamide and the like.
  • the content of the solvent is preferably such that the total solid concentration of the film-forming composition is 1 to 80% by mass, more preferably 1 to 60% by mass, and 5 to 40% by mass. The amount is more preferably 5% to 35% by weight.
  • the preferred range for each solvent is as follows.
  • the solvent A (based on the total mass when there are plural types) is preferably 1 to 80% by mass in the film-forming composition, and preferably 1 to 60% by mass. More preferred is 5 to 40% by mass, still more preferred is 5 to 30% by mass.
  • Solvent B (based on the total mass when there are plural kinds) is preferably 3 to 90% by mass, more preferably 6 to 80% by mass in the film-forming composition, and 10 to 60% by mass. More preferably, it is more preferably 15 to 50% by mass.
  • the mass ratio of the solvent A and the solvent B (when there are plural types, the total mass basis) is preferably 10:90 to 45:55, more preferably 15:85 to 40:60, and 20:80 More preferably, it is ⁇
  • the film-forming composition preferably contains a surfactant.
  • the surfactant is preferably a surfactant containing a fluorine atom, preferably a nonionic or anionic surfactant containing a fluorine atom, and a nonionic or anionic surfactant containing a fluorine atom. More preferably, it is an oligomer or polymer surfactant.
  • the surfactant preferably contains a fluoroalkylene group, and more preferably contains a perfluoroalkyl group.
  • the surfactant is preferably soluble in water.
  • soluble as used herein means that the solubility at 23 ° C. is 0.05% by mass or more.
  • the surfactant is preferably dissolved in water by 0.1% by mass or more at 23 ° C., more preferably by 0.5% by mass or more, and further preferably by 1% by mass or more. As an upper limit, it is practical that it is 5 mass% or less.
  • the surfactant may contain at least one of a hydrophilic group, a lipophilic group, and an ultraviolet reactive group in the molecule. Especially, in this invention, it is preferable that it is a perfluoroalkyl group containing carboxylate (anionic type) from a viewpoint of improving moisture resistance.
  • the surfactant is preferably soluble in water or slightly soluble (for example, 0.1% by mass or more), but is insoluble in hydrocarbon solvents (for example, hexane and toluene).
  • the surface tension of a 0.1% by mass solution with respect to water is preferably 10 mN / m or more, and more preferably 15 mN / m or more.
  • the upper limit is practically 50 mN / m or less.
  • the surface tension of a 0.1% solution with respect to PGME (propylene glycol monomethyl ether) is preferably more than 25 mN / m, and more preferably 26 mN / m or more.
  • the upper limit is practically 70 mN / m or less.
  • fluorosurfactants are trade names of Florinert F-C430, Florinato F-C431 (manufactured by Sumitomo 3M Co., Ltd.); Megafac F-142D, Megafac F-171 , Megafuck F-172, Megafuck F-173, Megafuck F-177, Megafuck F-183, Megafuck F-410, Megafuck F-444, Megafuck F-470, Megafuck F-471, Mega Fuck F-478, Mega Fuck F-479, Mega Fuck F-480, Mega Fuck F-482, Mega Fuck F-484, Mega Fuck F-484, Mega Fuck F-486, Mega Fuck F-487, Mega Fuck F -489, Megafuck F-553, Megafuck F-554, Megafuck F- 56, Megafuck F-557, Megafuck F-569, Megafuck F-575, Megafuck F-780F, Megafuck F-781F, Megafuck R30 (above DIC
  • the hydrophilicity In terms of the above-mentioned DIC MegaFac series surfactant, the higher the hydrophilicity, the higher the fluorine atom content.
  • the hydrophilic order is shown in part as follows: F-410> F-444> F-430, F-510, F-511, F-569, F-553, F-477, F-556 >> The order is F-554.
  • the order of F-430> F-410, F-510, F-511> F-444 >> F-569, F-553, F-554, F-477, F-556 and Become.
  • at least one is preferably the left side (greater than) >>, and in both cases, the left side (greater than) >> is preferable.
  • Megafac F-410 and F-444 (both trade names) showed good results in the adhesion test after PCT performed in the examples described later. On the other hand, F-510 etc. were inferior. Also from this viewpoint, MegaFuck F-410 and F-444 are particularly preferable, and F-444 is more particularly preferable.
  • the weight average molecular weight of the surfactant is preferably 30,000 or less, more preferably 10,000 or less, further preferably 5,000 or less, and further preferably 4,000 or less. preferable. As a lower limit, it is practical that it is 500 or more.
  • the molecular weight of the surfactant is the same as that described in Example 1 of JP-A No. 2001-208736, specifically, Asahiklin AK-225 SEC grade 1 is used as the mobile phase, and the polymer is used as the SEC column.
  • the content of the surfactant is preferably 0.0008% by mass or more, more preferably 0.005% by mass or more, and 0.01% by mass or more in the solid content of the film-forming composition. More preferably it is.
  • the upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 2% by mass or less, and may be 1% by mass or less, and may be 0.5% by mass. % Or less, 0.1 mass% or less, or 0.01 mass% or less. It is preferable that it is 0.0001 mass% or more with respect to the whole composition, It is more preferable that it is 0.0005 mass% or more, It is further more preferable that it is 0.001 mass% or more.
  • the upper limit is preferably 5% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less.
  • the content of the surfactant with respect to 100 parts by mass of the polyimide precursor is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and 0.01 parts by mass or more. Is more preferable.
  • the upper limit is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, still more preferably 2 parts by mass or less, and 1 part by mass. Or less, more preferably 0.5 parts by mass or less, and particularly preferably 0.1 parts by mass or less.
  • Surfactant may contain only 1 type and may contain 2 or more types.
  • the total amount is preferably within the above range.
  • the surfactant By adjusting the surfactant to the above range, the surface tension of the coating film of the film-forming composition can be lowered, the formation of Benard cell or its effect can be effectively suppressed, and the surface state of the film can be improved. Therefore, it is preferable.
  • the plasticizer used in the film-forming composition according to the embodiment of the present invention is not particularly defined as to the type thereof, and a known plasticizer can be used. Specific examples include phthalic acid esters, adipic acid esters, trimellitic acid esters, polyesters, phosphoric acid esters, citric acid esters, epoxy plasticizers, sebacic acid esters, azelaic acid esters, maleic acid esters, and benzoic acid esters. Epoxy plasticizers are preferred. Examples of the epoxy plasticizer include epoxidized oil (epoxidized soybean oil, epoxidized linseed oil), epoxidized fatty acid alkyl (eg, octyl) ester, and the like.
  • epoxidized oil epoxidized soybean oil, epoxidized linseed oil
  • epoxidized fatty acid alkyl eg, octyl
  • the epoxy plasticizer preferably has an epoxy group of the following formula e1 or e2 in the molecule. That is, the one in which the formula e1 is introduced at the end or in the middle of the olefin chain or paraffin chain constituting the plasticizer, the one in which the formula e2 is introduced in the middle of the chain, or both are introduced at both the end and in the middle Can be mentioned.
  • the epoxy plasticizer is preferably a fatty acid or an oil and fat, and more preferably a carboxyl group is introduced into the olefin chain or paraffin chain. However, this carboxyl group may be partially or fully esterified with an alkyl group or the like.
  • the plasticizer preferably has 3 to 48 carbon atoms, more preferably 4 to 36, and still more preferably 6 to 24.
  • Specific examples include ADEKA Corporation, O-180A, O-130P, D-32, and D-55 (all trade names), and among them, O-180A, O-130P, and D-32 are preferable. .
  • the plasticizer preferably has a viscosity at 25 ° C. of 40 mPa ⁇ s or more, more preferably 100 mPa ⁇ s or more, and further preferably 200 mPa ⁇ s or more.
  • the upper limit is practically 800 mPa ⁇ s or less.
  • the SP value is preferably 8 or more, and more preferably 8.5 or more. There is no particular upper limit, but 9.5 or less is practical.
  • the content of the plasticizer is preferably 0.0008% by mass or more, more preferably 0.005% by mass or more, and 0.01% by mass or more in the solid content of the film-forming composition. More preferably.
  • the upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 2% by mass or less, and may be 1% by mass or less, and may be 0.5% by mass. % Or less, 0.1 mass% or less, or 0.01 mass% or less.
  • the content of the plasticizer with respect to 100 parts by mass of the polyimide precursor is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and 0.01 parts by mass or more. Further preferred.
  • the upper limit is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, still more preferably 2 parts by mass or less, and 1 part by mass. Or less, more preferably 0.5 parts by mass or less, and particularly preferably 0.1 parts by mass or less. Only one kind of plasticizer or two or more kinds of plasticizers may be contained. When 2 or more types are included, the total amount is preferably within the above range. By setting the plasticizer within the above range, it is preferable to prevent the film surface from being dried, to prevent the Benard cell from continuing, and to obtain a better surface state of the coated film.
  • the film-forming composition may contain a photopolymerization initiator.
  • the photopolymerization initiator is preferably a radical photopolymerization initiator.
  • radical photopolymerization initiator which can be used by this invention, It can select suitably from well-known radical photopolymerization initiators.
  • a radical photopolymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferable.
  • it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
  • the radical 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. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
  • a known compound can be arbitrarily used.
  • halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, etc.
  • ketone compounds 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 photoradical polymerization 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, 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 in which the absorption maximum wavelength is matched with a wavelength light source 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).
  • an oxime compound is more preferable.
  • the exposure latitude can be improved more effectively.
  • Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as a photocuring accelerator.
  • Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-080068, and compounds described in JP-A No. 2006-342166.
  • the description in paragraphs 0080 to 0083 of JP-A-2015-189883 can be referred to, and the contents thereof are incorporated in the present specification.
  • Photoradical polymerization 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.
  • radical photopolymerization initiator compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can be used.
  • the content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the film-forming composition. More preferably, the content is 0.5 to 15% by mass, and still more preferably 1.0 to 10% by mass.
  • the photoinitiator may contain only 1 type and may contain 2 or more types. When two or more photopolymerization initiators are contained, the total is preferably in the above range.
  • the film forming composition may contain a thermal radical polymerization initiator.
  • the thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates a polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polyimide precursor can be advanced together with the cyclization of the polyimide precursor, so that 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-2008-063554.
  • thermal radical polymerization initiator When the thermal radical polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the film-forming composition. More preferably, it is 5 to 15% by mass.
  • the thermal radical polymerization initiator may contain only 1 type, and may contain 2 or more types. When two or more thermal radical polymerization initiators are contained, the total is preferably within the above range.
  • the film-forming composition preferably contains a radical polymerizable compound.
  • a radical polymerizable compound a compound having a radical polymerizable group can be used.
  • the radical polymerizable group include groups having an ethylenically unsaturated bond such as vinylphenyl group, vinyl group, (meth) acryloyl group, and allyl group.
  • the radical polymerizable group is preferably a (meth) acryloyl group.
  • the number of radical polymerizable groups contained in the radical polymerizable compound may be one or two or more.
  • the radical polymerizable compound preferably has two or more radical polymerizable groups, and preferably has three or more radical polymerizable groups. More preferred.
  • the upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.
  • the molecular weight of the radical polymerizable compound is preferably 2000 or less, more preferably 1500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the radical polymerizable compound is preferably 100 or more.
  • the film-forming composition preferably contains at least one bifunctional or higher radical polymerizable compound containing two or more polymerizable groups, and preferably contains at least one trifunctional or higher radical polymerizable compound. More preferably. Further, it may be a mixture of a bifunctional radically polymerizable compound and a trifunctional or higher functional radically polymerizable compound.
  • the number of functional groups of the radical polymerizable compound means the number of radical polymerizable groups in one molecule.
  • radical polymerizable compound examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. These are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds.
  • a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • an unsaturated carboxylic acid ester or amide having a detachable substituent such as thiol or tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
  • the radical polymerizable compound is also preferably a compound having a boiling point of 100 ° C. or higher under normal pressure.
  • examples include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
  • polyfunctional (meth) acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated bond can also be exemplified.
  • a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated bond
  • fluorene rings described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and the like, and an ethylenically unsaturated bond.
  • a compound having two or more groups having a carbonic acid or a cardo resin examples include specific unsaturated compounds described in JP-B-46-043946, JP-B-01-040337, JP-B-01-040336, and JP-A-02-024933. And vinyl phosphonic acid compounds. Further, compounds containing a perfluoroalkyl group described in JP-A-61-022048 can also be 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.
  • radical polymerizable compound examples include dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, as KAYARAD D-320; Nippon Kayaku ( A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) Acrylate (commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and their (meth) acryloyl group via an ethylene glycol residue or a propylene glycol residue
  • radical polymerizable compounds examples include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, and SR-209, manufactured by Sartomer, which is a bifunctional methacrylate having four ethyleneoxy chains. 231 and 239, DPCA-60 which is a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330 which is a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS- manufactured by Nippon Kayaku Co., Ltd.
  • radical polymerizable compound examples include urethane acrylates described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, JP-B-02-016765, and the like. Also suitable are urethane compounds having an ethylene oxide skeleton as described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418. Further, as radically polymerizable compounds, 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-01-105238 are used. It can also be used.
  • the radically polymerizable compound may be a radically polymerizable compound having an acid group such as a carboxyl group or a phosphate group.
  • the radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
  • a radically polymerizable compound having a group is more preferable.
  • the aliphatic polyhydroxy compound is pentaerythritol or dipentayl.
  • a compound that is erythritol examples include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • a preferable acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
  • a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound.
  • Monofunctional radically polymerizable compounds include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl ( (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.
  • Acrylic acid derivatives N-vinyl pyrrolidone, N-vinyl compounds such as N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc.
  • Le compounds are preferably used.
  • As the monofunctional radically polymerizable compound a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
  • the film-forming composition can further contain a polymerizable compound other than the radically polymerizable compound described above.
  • polymerizable compounds other than the above-mentioned radical polymerizable compounds include compounds having a hydroxymethyl group, alkoxymethyl group or acyloxymethyl group; epoxy compounds; oxetane compounds; benzoxazine compounds.
  • 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), (AM4) or (AM5) is preferable.
  • R 104 represents a t-valent organic group having 1 to 200 carbon atoms
  • R 105 represents a group represented by —OR 106 or —OCO—R 107
  • R 106 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms
  • R 107 represents an organic group having 1 to 10 carbon atoms.
  • R 404 represents a divalent organic group having 1 to 200 carbon atoms
  • R 405 represents a group represented by —OR 406 or —OCO—R 407
  • R 406 represents a hydrogen atom or a carbon atom.
  • R 407 represents an organic group having 1 to 10 carbon atoms.
  • R 504 represents a u-valent organic group having 1 to 200 carbon atoms
  • R 505 represents a group represented by —OR 506 or —OCO—R 507.
  • R 506 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms
  • R 507 represents an organic group having 1 to 10 carbon atoms.
  • 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.
  • NIKACALAC examples include 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, and the like. It is done.
  • 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.).
  • Epoxy compound compound having an epoxy group
  • the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
  • the epoxy group undergoes a cross-linking reaction at 200 ° C. or less and does not cause a dehydration reaction derived from the cross-linking, so that film shrinkage hardly occurs. For this reason, containing an epoxy compound is effective for low-temperature curing of the composition and suppression of warpage of the film.
  • the epoxy compound preferably contains a polyethylene oxide group. Thereby, an elasticity modulus falls more and also curvature can be suppressed.
  • the polyethylene oxide group means that the number of structural units of ethylene oxide is 2 or more, and the number of structural units is preferably 2 to 15.
  • epoxy compound examples include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidyl Examples include, but are not limited to, epoxy group-containing silicones such as (roxypropyl) siloxane.
  • Epicron (registered trademark) 850-S Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) EXA-4710, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-859CRP, Epicron (registered trademark) EXA-1514, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Rica Resin (registered trademark) ) BEO-60E (trade name, Shin Nippon Rika ( )), EP-4003S, EP-4000S (trade names, and the
  • an epoxy resin containing a polyethylene oxide group is preferable in terms of suppressing warpage and excellent heat resistance.
  • Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4822, and Licaredin (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.
  • oxetane compound compound having oxetanyl group
  • examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, Examples include 3-ethyl-3- (2-ethylhexylmethyl) oxetane and 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester.
  • Aron Oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be preferably used. Two or more kinds may be mixed.
  • a benzoxazine compound (compound having a benzoxazolyl group))
  • a benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur at the time of curing, and thermal contraction is further reduced to suppress warpage.
  • benzoxazine compound examples include Ba type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydrobenzo An oxazine compound is mentioned. These may be used alone or in combination of two or more.
  • the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the film-forming composition.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
  • the polymerizable compound one kind may be used alone, or two or more kinds may be mixed and used. When using 2 or more types together, it is preferable that the total amount becomes said range.
  • the film forming composition preferably 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 compounds and
  • an ion trapping agent that traps anions such as halogen ions can be used.
  • Examples of other migration inhibitors include rust inhibitors described in paragraph 0094 of JP2013-015701A, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656A.
  • 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 include the following compounds.
  • the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the film forming composition. More preferably, the content is 0.05 to 2.0% by mass, and still more preferably 0.1 to 1.0% by mass. Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more migration inhibitors, the total is preferably within the above range.
  • the film-forming composition preferably contains a polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone, 4-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 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
  • a polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and compounds described in paragraphs 0031 to 0046 of WO2015 / 125469 can also be used.
  • the following compound can be used (Me is a methyl group).
  • the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the film-forming composition, 0.02 It is more preferably from 3 to 3% by mass, and further preferably from 0.05 to 2.5% by mass. Only one polymerization inhibitor may be used, or two or more polymerization inhibitors may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
  • the film-forming composition preferably contains a metal adhesion improver for improving adhesion with a metal material used for electrodes, wirings, and the like.
  • metal adhesion improvers include silane coupling agents.
  • 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 WO 2011/080992, and JP-A No. 2014-191252.
  • Et represents an ethyl group.
  • the content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 0 to 100 parts by mass of the polyimide precursor.
  • the range is from 5 to 5 parts by mass.
  • Adhesion between the film after the curing step and the metal layer is improved by setting the above lower limit value or more, and heat resistance and mechanical properties of the film after the curing step are improved by setting the upper limit value or less. 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.
  • the film forming composition may contain a curing accelerator.
  • the curing accelerator may be a heat curing accelerator or a photocuring accelerator.
  • Thermosetting accelerator is preferably one that generates a base by heating. A preferable range of the heating temperature (base generation temperature) is the same as the temperature defined in the heating step described later. Salts of tertiary amines or quaternary ammonium cations and carboxylate anions are preferred.
  • the tertiary amine and quaternary ammonium cation are preferably represented by any of the following formulas (Y1-1) to (Y1-4).
  • R Y1 represents an organic group having an n Y value (n Y is an integer of 1 to 12), and is preferably a hydrocarbon group.
  • the hydrocarbon group includes an alkane-containing group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms), and an alkene group (preferably 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), a group containing an aromatic hydrocarbon (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 and further preferably 6 to 10), or a combination thereof.
  • R Y1 is preferably an aromatic hydrocarbon group.
  • R Y1 is a substituent T (hydroxyl group, carboxyl group, amino group (NR N 2 ), alkoxyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and more preferably) as long as the effects of the present invention are not impaired. 3 is more preferable), an acyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms), an alkoxycarbonyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms).
  • R N is a group synonymous with the groups represented by hydrogen or R Y2.
  • R Y2 to R Y5 each independently represents a hydrogen atom or a hydrocarbon group (preferably having a carbon number of 1 to 36, more preferably 1 to 24, and still more preferably 1 to 12), and an alkyl group (having a carbon number of 1 to 36).
  • R Y6 represents an alkyl group (preferably having a carbon number of 1 to 36, preferably 2 to 24, more preferably 4 to 18), or an alkenyl group (preferably having a carbon number of 2 to 36, more preferably 2 to 24, and 4 to 18).
  • an alkynyl group (preferably having 2 to 36 carbon atoms, more preferably 2 to 24, more preferably 4 to 18), and an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms).
  • n Y represents an integer of 1 to 12, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.
  • n X represents an integer of 1 to 12, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.
  • the alkyl group, alkenyl group, and alkynyl group may be cyclic or chain-like, and in the case of a chain, it may be linear or branched.
  • a linking group L carbonyl group, oxygen atom, sulfur atom, NR N , alkylene group (carbon number 1 to 12 is preferable, 1 to 6 is more preferable, 1 to 3 is more preferable, an alkenylene group (2 to 12 carbon atoms is preferable, 2 to 6 is more preferable, and 2 to 3 are more preferable), an arylene group (carbon number). 6 to 22 is preferable, 6 to 18 is more preferable, and 6 to 10 is more preferable), or a linking group according to a combination thereof may be interposed. Two or more of R Y2 to R Y6 may be bonded to each other to form a ring. R Y2 to R Y6 may have a substituent T.
  • R Y7 to R Y16 are a hydrogen atom or a substituent. However, not all of R Y7 to R Y9 are hydrogen atoms.
  • the substituent is preferably an organic group (preferably having a carbon number of 1 to 36, more preferably 1 to 24, and still more preferably 1 to 12), which may intervene a linking group L and has a substituent T. It is preferably a hydrocarbon group that may be present. As the hydrocarbon group, an R Y2 group is preferred.
  • R Y7 and R Y8 are carboxyalkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms; preferably 1 to 12 carboxyl groups).
  • R Y9 is preferably an aromatic group, and is preferably an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 and even more preferably 6 to 10).
  • an alkoxycarbonyl group substituted with an aromatic group is preferred (the alkoxyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, and the aromatic group preferably has 6 to 22 carbon atoms).
  • 6 to 18 are more preferable, and 6 to 14 are more preferable.
  • R Y7 and R Y8 are alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and even more preferably 1 to 3).
  • R Y9 is preferably an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms), and is preferably an alkoxycarbonyl group having an aromatic group.
  • R Y11 and R Y13 are preferably hydrogen atoms.
  • R Y13 is preferably a hydrogen atom
  • R Y10 , R Y11 , R Y12 and R Y16 are alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms). ⁇ 3 are more preferred).
  • R Y11 and R Y16 , R Y10 and R Y12 are preferably bonded to form a ring to form a bicyclo compound. Specific examples include diazabicyclononene and diazabicycloundecene.
  • the carboxylic acid anion paired with the quaternary ammonium cation of the above formula (Y1-1), formula (Y1-3) and formula (Y1-4) is represented by the following formula (X1). It is preferable.
  • EWG represents an electron withdrawing group.
  • the electron-withdrawing group means a group in which Hammett's substituent constant ⁇ m exhibits a positive value.
  • ⁇ 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 embodiment 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 (hereinafter the same).
  • 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 or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and more preferably 1 to 3). More preferably), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and 6 to 6 carbon atoms). 10 is more preferable), and represents a hydroxyl group or a carboxyl group.
  • Ar represents an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms).
  • R x1 to R x3 are an alkyl group, an alkenyl group, or an aryl group, a ring may be formed.
  • These alkyl group, alkenyl group, aryl group, and Ar may have a substituent T as long as the effects of the present invention are not impaired.
  • Ar preferably has a carboxyl group (preferably 1 to 3). * Represents a bonding position.
  • L 1 is a group having the same meaning as the linking group L, and is preferably —CR X2 R X3 —, —Ar 1 —, or a combination thereof.
  • Ar 1 is an arylene group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms).
  • Np represents an integer of 1 to 6, preferably an integer of 1 to 3, and more preferably 1 or 2.
  • the molecular weight of the thermosetting accelerator is preferably 100 or more and less than 2000, and more preferably 200 to 1000.
  • Specific examples of the thermosetting accelerator include an acidic compound that generates a base when heated to 40 ° C. or higher described in International Publication No. 2015/199219 and an ammonium salt having an anion and an ammonium cation having a pKa1 of 0 to 4, These contents are incorporated herein.
  • the content of the thermosetting accelerator in the composition is preferably 0.01 to 50% by mass with respect to the total solid content of the composition.
  • the lower limit is more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more.
  • the upper limit is more preferably 10% by mass or less, and further preferably 5% by mass or less.
  • 1 type (s) or 2 or more types can be used for a thermosetting accelerator. When using 2 or more types, it is preferable that a total amount is the said range.
  • the composition for film formation can also be set as the structure which does not contain a thermosetting accelerator substantially. “Substantially free” means less than 0.01% by mass, more preferably less than 0.005% by mass, based on the total solid content of the composition.
  • the film forming composition may contain a photocuring accelerator.
  • the photocuring accelerator is preferably one that 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 (base It is preferable that the substance generate
  • the base component was neutralized by forming a salt, such as a transition metal compound complex, a compound having an ammonium salt structure, or an amidine moiety made latent by forming a salt with a carboxylic acid.
  • a salt such as a transition metal compound complex, a compound having an ammonium salt structure, or an amidine moiety made latent by forming a salt with a carboxylic acid.
  • examples include ionic compounds, and nonionic compounds in which a base component is made latent by urethane bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds.
  • the photocuring accelerator examples include a photocuring accelerator having a cinnamic amide structure as disclosed in JP2009-080452A and International Publication No. 2009/123122, JP2006-189591A and A photocuring accelerator having a carbamate structure as disclosed in Japanese Patent Application Laid-Open No. 2008-247747, an oxime structure and a carbamoyloxime structure as disclosed in Japanese Patent Application Laid-Open Nos. 2007-249013 and 2008-003581
  • a photocuring accelerator etc. are mentioned, it is not limited to these, In addition, the structure of a well-known photocuring accelerator can be used.
  • photocuring accelerator examples include compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-093746A, compounds described in paragraphs 0022 to 0069 of JP2013-194205A, Examples include the compounds described in paragraphs 0026 to 0074 of JP2013-204019A and the compound described in paragraph 0052 of WO2010 / 064631.
  • photocuring accelerators include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, PBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, and WPBG-082 (manufactured by Wako Pure Chemical Industries, Ltd.) can also be used.
  • the content of the photocuring accelerator in the composition is preferably 0.1 to 50% by mass with respect to the total solid content of the 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.
  • 1 type (s) or 2 or more types can be used for a photocuring accelerator. When using 2 or more types, it is preferable that a total amount is the said range.
  • the film-forming composition is within a range that does not impair the effects of the present invention, and various additives, for example, thermal acid generators, sensitizing dyes, chain transfer agents, surfactants other than those described above, A higher fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like can be blended.
  • various additives for example, thermal acid generators, sensitizing dyes, chain transfer agents, surfactants other than those described above, A higher fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like can be blended.
  • the total blending amount is preferably 3% by mass or less of the solid content of the composition.
  • the film forming composition may contain a thermal acid generator.
  • the thermal acid generator generates an acid by heating, promotes cyclization of the polyimide precursor, and further improves the mechanical properties of the film.
  • Examples of the thermal acid generator include compounds described in paragraph 0059 of JP2013-167742A.
  • the preferable range of the heating temperature (acid generation temperature) of the thermal acid generator is the same as the temperature defined in the heating step described later.
  • 0.01 mass part or more is preferable with respect to 100 mass parts of polyimide precursors, and, as for content of a thermal acid generator, 0.1 mass part or more is more preferable.
  • the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less from the viewpoint of electrical insulation of the film.
  • 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.
  • the film-forming composition 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 a thermosetting accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, and the like, and effects such as electron transfer, energy transfer, and heat generation occur.
  • a thermosetting accelerator, a thermal radical polymerization initiator, and a photo radical polymerization initiator cause a chemical change and are decomposed to generate radicals, acids, or bases. Details of the sensitizing dye can be referred to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein.
  • the content of the sensitizing dye is preferably 0.01 to 20% by mass with respect to the total solid content of the film-forming composition, preferably 0.1 to The content is more preferably 15% by mass, and further preferably 0.5 to 10% by mass.
  • a sensitizing dye may be used individually by 1 type, and may use 2 or more types together.
  • the film forming composition 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, and 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 for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.
  • the content of the chain transfer agent is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the film-forming composition, and 1 to 10 parts by mass. Part is more preferable, and 1 to 5 parts by mass is more preferable. 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 in the above range.
  • the film-forming composition is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and is unevenly distributed on the surface of the composition in the process of drying after coating. May be.
  • 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 film-forming composition. Only one higher fatty acid derivative may be used, or two or more higher fatty acid derivatives may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.
  • the water content of the film-forming composition is preferably less than 5% by weight, more preferably less than 1% by weight, and even more preferably less than 0.6% by weight from the viewpoint of the coating surface properties.
  • the metal content of the film-forming composition is preferably less than 5 ppm by weight (parts per million), more preferably less than 1 ppm by weight, and even more preferably less than 0.5 ppm by weight 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.
  • the raw material having a low metal content is selected as the raw material constituting the film-forming composition.
  • the raw material to be filtered may be filtered, or the inside of the apparatus may be lined with polytetrafluoroethylene or the like, and distillation may be performed under a condition in which contamination is suppressed as much as possible.
  • the film-forming composition preferably has a halogen atom content of less than 500 ppm by weight, more preferably less than 300 ppm by weight, and even more preferably less than 200 ppm by weight from the viewpoint of wiring corrosivity.
  • a halogen ion is less than 5 mass ppm, More preferably, it is less than 1 mass ppm, More preferably, it is less than 0.5 mass ppm.
  • the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions is preferably in the above range.
  • the container for the film forming composition a conventionally known container can be used.
  • the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resins are made into a 7 layer structure. It is also preferred to use bottles that have been used. Examples of such a container include a container described in JP-A-2015-123351.
  • the film-forming composition can be prepared by mixing the above components.
  • the mixing method is not particularly limited, and can be performed by a conventionally known method.
  • the filter pore size is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
  • 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 sizes or materials may be used in combination.
  • Various materials may be filtered a plurality of times.
  • circulation filtration may be used.
  • you may pressurize and filter.
  • the pressure applied is preferably 0.05 MPa or more and 0.3 MPa or less.
  • impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined.
  • adsorbent a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
  • the production method of the present invention preferably includes an exposure step of exposing after the film formation step and a development step of developing the exposed film. After this development, the exposed film can be further cured by heating.
  • the film forming process and heating process, the film forming process, the exposure process, and the developing process (further heating process if necessary) ) are preferably performed in the above order.
  • the production method of the present invention preferably includes a film forming step in which the film forming composition is applied to a substrate to form a film.
  • 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 films, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, plasma display panel (PDP) electrode plates, etc. are not particularly limited.
  • the substrate is a member including at least a metal (for example, a substrate provided with a metal layer).
  • a metal for example, a substrate provided with a metal layer.
  • the surface shape of the resin film described above can be improved.
  • the shape of the substrate is preferably a quadrangle, and more preferably a rectangle.
  • a slit coater as means for applying the film-forming composition to the substrate.
  • the slit width of the nozzle is preferably 20 ⁇ m or more, more preferably 50 ⁇ m or more, and further preferably 80 ⁇ m or more. As an upper limit, it is preferable that it is 250 micrometers or less, It is more preferable that it is 200 micrometers or less, It is further more preferable that it is 150 micrometers or less.
  • the slit gap is preferably 30 ⁇ m or more, more preferably 50 ⁇ m or more, and further preferably 70 ⁇ m or more.
  • the scanning speed may be 1 mm / s or more, preferably 10 mm / s or more, more preferably 20 mm / s or more, and further preferably 30 mm / s or more.
  • the coating film thickness is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and further preferably 3 ⁇ m or more. As an upper limit, it is preferable that it is 100 micrometers or less, It is more preferable that it is 80 micrometers or less, It is further more preferable that it is 50 micrometers or less.
  • a drying temperature is 50 to 150 ° C, more preferably 70 to 130 ° C, and further preferably 90 to 110 ° C.
  • Examples of the drying time include 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
  • the film thickness of the dried film can be, for example, 0.5 ⁇ m or more, and can be 1 ⁇ m or more. Moreover, as an upper limit, it can be set to 100 micrometers or less, and can also be set to 30 micrometers or less. This thickness is the same in the film thickness after the heating step described later.
  • the exposure dose in the exposure step is preferably 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.
  • the exposure wavelength is (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h.
  • the development method in the development step is not particularly limited as long as a desired pattern can be formed, and for example, development methods such as paddle, spray, immersion, and ultrasonic waves can be adopted.
  • 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.
  • the developer preferably contains an organic solvent.
  • the developer preferably contains an organic solvent having a ClogP value of ⁇ 1 to 5, more preferably an organic solvent having a ClogP value of 0 to 3.
  • the ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
  • organic solvent examples include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and ⁇ -butyrolactone.
  • esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and ⁇ -butyrolactone.
  • alkyl oxyacetate alkyl eg, methyl oxyoxyacetate, alkyl oxyacetate ethyl, alkyl oxyacetate butyl (eg methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate), alkyl esters of 3-alkyloxypropionic acid (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • a preferred example of the sulfoxide is dimethyl sulfoxide.
  • cyclopentanone and ⁇ -butyrolactone are particularly preferable, and cyclopentanone is more preferable.
  • the developer is preferably 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and even more preferably 90% by mass or more of an organic solvent. Further, 100% by mass of the developer may be an organic solvent.
  • 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.
  • rinsing can be performed using a solvent contained in the film-forming composition.
  • the rinse time is preferably 5 seconds to 1 minute.
  • the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 500 ° C, more preferably 80 to 450 ° C, still more preferably 140 to 400 ° C, and still more preferably 160 to 350 ° C. Heating is preferably performed at a rate of temperature increase of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
  • the temperature at the start of heating is preferably 20 ° C to 150 ° C, more preferably 20 ° C to 130 ° C, and further preferably 25 ° C to 120 ° C.
  • the temperature at the start of heating refers to the temperature at the start of the step of heating to the maximum heating temperature. For example, when the film-forming composition is applied onto a substrate and then dried, the temperature after this drying is performed, for example, a temperature 30 to 200 ° C.
  • the temperature is gradually raised.
  • the heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes.
  • the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between the layers of the film.
  • the reason is not certain, it is considered that the ethynyl group of the polyimide precursor between layers proceeds with a crosslinking reaction at this temperature.
  • Heating may be performed in stages. For example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min, held at 180 ° C. for 60 minutes, heated from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. You may perform the pre-processing process of these.
  • the heating temperature as the pretreatment step is preferably 100 to 200 ° C, more preferably 110 to 190 ° C, and further preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the characteristics of the film.
  • the pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes.
  • the pretreatment may be performed in two or more steps.
  • the pretreatment step 1 may be performed in the range of 100 to 150 ° C.
  • the pretreatment step 2 may be performed in the range of 150 to 200 ° C. Further, it may be cooled after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
  • the heating step is preferably performed in a low oxygen concentration atmosphere by flowing an inert gas such as nitrogen, helium, or argon in order to prevent decomposition of the polyimide precursor.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
  • Metal layer formation process You may apply and form a metal layer on the surface of the film
  • metal layer there are no particular limitations on the metal layer, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferable, and copper is more preferable. Further preferred.
  • the method for forming the 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.
  • the thickness of the metal layer is preferably 0.1 to 50 ⁇ m, more preferably 1 to 10 ⁇ m at the thickest part.
  • the laminating step may include performing the film forming step and the heating step, or the film forming step, the exposure step, and the developing step in the above order again on the surface of the film or metal layer of the film forming composition. Good.
  • the laminating step may further include the drying step and the heating step.
  • a surface activation treatment process may be further performed after the heating process, the exposure process, or the metal layer formation process.
  • An example of the surface activation treatment is plasma treatment.
  • the lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
  • the resin layer / metal layer / resin layer / metal layer / resin layer / metal layer has a resin layer structure of 3 to 7 layers, more preferably 3 to 5 layers. That is, after the metal layer is provided, the film forming step and the heating step of the film forming composition, or the film forming composition, the exposure step is performed so as to cover the metal layer. It is preferable to carry out the steps and the above-described development step (further heating step if necessary) in the above order. By alternately performing the laminating step of laminating the film (resin) of the film forming composition and the metal film forming step, the film (resin layer) and the metal layer of the film forming composition can be alternately laminated. .
  • the present invention also discloses a method for manufacturing a semiconductor device in which a chip is arranged on the film of the present invention. Furthermore, the manufacturing method of the semiconductor device which arrange
  • reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) pyridine and 90 mL N-methylpyrrolidone were added.
  • the reaction mixture was then cooled to ⁇ 10 ° C. and 16.12 g (135.5 mmol) of thionyl chloride was added over 10 minutes while maintaining the temperature at ⁇ 10 ⁇ 4 ° C.
  • the viscosity increased during the addition of thionyl chloride.
  • the reaction mixture was stirred at room temperature for 2 hours.
  • composition for film formation of each Example and a comparative example was prepared as a uniform solution by mix
  • the obtained composition was used after being filtered using a polyethylene filter having a pore size of 0.8 ⁇ m.
  • a substrate was prepared by forming a copper film having a thickness of 100 nm on the surface of a non-alkali glass substrate having a width of 150 mm, a length of 150 mm, and a thickness of 0.7 mm by sputtering.
  • the coating film of the film forming composition prepared above is used. Formed.
  • the detailed conditions of the slit coater apparatus are as shown in the table below. This was left to stand at 23 ° C.
  • the coating film thickness (after drying) was measured every 10 mm from the position of 10 mm from the end of the coating part using the F20 film thickness measurement system manufactured by Filmetrics, and the average value was taken.
  • the nozzle head was immersed in the immersion liquid in the head standby step under the conditions shown in the following table. Further, after the film formation, the nozzle head was immersed in the cleaning liquid in the head cleaning process. The temperature during immersion and washing was (normal temperature (23 ° C.)).
  • the in-plane uniformity of the film thickness after coating and drying during the slit coating was evaluated.
  • the film thickness distribution of the coating film on the surface of the substrate provided with the coating film (after drying) is 90 mm in length and 10 mm in width excluding the coating part end 10 mm by a film thickness measuring device (F20 film thickness measurement system manufactured by Filmetrics).
  • the 90 mm region was measured at 81 points every 10 mm, and the maximum and minimum difference was defined as TTV (Total thickness variation).
  • TTV Total thickness variation
  • an average value of three samples was adopted. TTV was measured in an area excluding 10 mm from the end of the coating part.
  • ⁇ 2 ⁇ m Good> 2 ⁇ m: Below standard
  • Shear tests were performed on the coating films after drying the films formed by slit coating on the various substrates described in Tables 1 to 9.
  • the measuring device XYZTEC Co., Ltd. Condor Sigma bond tester
  • a film dried after coating on the substrate was exposed with an exposure amount of 400 mJ / cm 2 using a negative photomask capable of irradiating a 100 ⁇ m square pattern, and after 30 minutes, the exposed film was developed with cyclopentanone.
  • a 100 ⁇ m square film was formed by rinsing with PGMEA, and the film was pressed at 10 ⁇ m / s from the side (with a needle set at a position of 5 ⁇ m from the ground).
  • an average value of three samples was adopted. ⁇ 10 g: below standard ⁇ 10 g, ⁇ 40 g: good ⁇ 40 g: excellent
  • the same shear test was performed on a Cu-plated substrate, an Al—Si—Cu alloy-plated substrate, a Ti sputter substrate, and a Ni sputter substrate with a coating film. . Further, in Examples 32 to 36, the same shear test was performed on the Si substrate provided with the coating film. The evaluation criteria are the same.
  • ⁇ Moisture resistance> Further, a PCT (pressure cooker test) was performed on the Cu plated substrate and the Ti sputter substrate with the coating film. A PCT test apparatus (EHS-412M, manufactured by Espec Corp.) was used. The treatment conditions for the coating film were 121 ° C., 100% relative humidity (RH), and 500 hours. About the coating film after a process, adhesive evaluation (shear test) was performed on the same conditions as the above-mentioned test of ⁇ the member adhesiveness of a coating film>. The evaluation criteria are the same.
  • E Polymerization inhibitor
  • E-1 Parabenzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • E-2 4-methoxyphenol
  • F Migration inhibitor (rust inhibitor)
  • F-2 1H-tetrazole
  • G Metal adhesion improver (silane coupling agent) G-1: manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-602 G-2: The following compound (wherein Et represents an ethyl group)
  • O-180A, O-130P and D-32 (all manufactured by ADEKA) were used as shown in each table.
  • a composition containing a polyimide precursor, a specific solvent and a surfactant or a plasticizer is applied. Even when a coating film was formed on the metal surface, a good surface state of the coating film was obtained. Further, in a preferred embodiment of the present invention, the coating property of the film-forming composition, the in-plane uniformity after coating and drying, the drying time after coating, the nozzle head contamination after cleaning the nozzle head, and the member adhesion of the coating film Good performance was obtained.
  • Example of exposure and development The film forming composition prepared in Example 1 was applied on a copper wafer (corresponding to a metal layer or a member containing metal) by slit coating to form a coating film.
  • the obtained coating film was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform precured film (film of a film forming composition) having a thickness of about 15 ⁇ m.
  • This was exposed using an aligner (Karl-Suss MA150 [trade name]) through a mask having a line-and-space pattern (step: 5 to 20 ⁇ m).
  • Exposure was performed with a high-pressure mercury lamp, and irradiation was performed at 500 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm.
  • the precured film after the exposure was dissolved in cyclopentanone for 75 seconds and developed with a paddle.
  • the line width of the developed part was evaluated according to the following criteria.
  • the exposed width of the underlying substrate after development was within ⁇ 10% of the mask size, and it was confirmed that good exposure and development were possible.
  • the formed resin pattern was heated at 250 ° C. for 3 hours to advance the cyclization reaction of the polyimide precursor to obtain a polyimide resin, thereby obtaining an extremely stable and strong resin pattern while being a fine pattern. .
  • the produced resin pattern is made of polyimide, it has excellent insulating properties, has good compatibility with metals as described above, and can suitably cope with fine processing. Therefore, WL-CSP ( It has been found to be particularly suitable for the production of rewiring layers of wafer level chip size packages).
  • Example 1 the polyimide precursor A-1 was changed to the polyimide precursor A-2 or A-3, and the others were performed in the same manner. The same excellent effect as in Example 1 was obtained.
  • Comparative Example 1 the polyimide precursor A-1 was changed to the polyimide precursor A-2 or A-3, and the others were performed in the same manner. Similar to Comparative Example 1, the surface condition after coating and drying was inferior.

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Abstract

This film production method includes a step for performing slit coating on a member, which at least partially contains a metal, by using a composition containing: a polyimide precursor; at least two solvents having different solubilities at 23°C for the polyimide precursor; and at least one selected from the group consisting of a surfactant and a plasticizer. The present invention further pertains to a laminate production method, a semiconductor device production method and a film formation composition that relate to said film production method.

Description

膜の製造方法、積層体の製造方法、半導体デバイスの製造方法、および膜形成用組成物Film manufacturing method, laminate manufacturing method, semiconductor device manufacturing method, and film forming composition
　本発明は膜の製造方法、積層体の製造方法、半導体デバイスの製造方法、および膜形成用組成物に関する。 The present invention relates to a film manufacturing method, a laminate manufacturing method, a semiconductor device manufacturing method, and a film forming composition.
　ポリイミド樹脂は、耐熱性および絶縁性に優れるため、様々な用途に適用されている。その用途は特に限定されないが、実装用の半導体デバイスを例に挙げると、絶縁膜や封止材の材料、あるいはその保護膜としての利用が挙げられる。また、フレキシブル基板のベースフィルムやカバーレイなどとしても用いられている。
　上記のポリイミド樹脂は、一般に、溶剤への溶解性が低い。そのため、環化前のポリイミド前駆体の状態で溶剤に溶解する方法がよく用いられる。これにより、優れた取り扱い性を実現することができ、上述のような各製品を製造する際に基板などに多様な形態で塗布して加工することができる。その後、ポリイミド前駆体を加熱し、硬化した製品を形成することができる。ポリイミド樹脂がもつ高い性能に加え、このような製造上の適応性に優れる観点から、その産業上の応用展開がますます期待されている。 Polyimide resins are excellent in heat resistance and insulation, and thus are applied to various uses. Although the use is not particularly limited, when a semiconductor device for mounting is taken as an example, it can be used as a material for an insulating film or a sealing material, or as a protective film thereof. It is also used as a base film and coverlay for flexible substrates.
The above polyimide resin generally has low solubility in a solvent. Therefore, a method of dissolving in a solvent in a state of a polyimide precursor before cyclization is often used. Thereby, the excellent handleability can be realized, and when manufacturing each product as described above, it can be applied and processed in various forms on a substrate or the like. Thereafter, the polyimide precursor can be heated to form a cured product. In addition to the high performance possessed by polyimide resin, its industrial application development is increasingly expected from the viewpoint of excellent adaptability in manufacturing.
　一方、特許文献１には、界面活性剤を含む樹脂組成物をスリット塗布することが記載されている。 On the other hand, Patent Document 1 describes slit coating of a resin composition containing a surfactant.
特開２０１３－２４３１２１号公報JP 2013-243121 A
　ここで、上記特許文献１に記載のように、スリット塗布（スリットコート）により、ポリイミド前駆体を含む組成物を膜状にする技術が知られている。しかしながら、ポリイミド前駆体組成物のスリットコート対象がその表面に金属を含む場合、膜の表面がいわゆる「ゆず肌」になる場合があることが分かった。 Here, as described in Patent Document 1, a technique for forming a composition containing a polyimide precursor into a film by slit coating (slit coating) is known. However, it has been found that when the object of slit coating of the polyimide precursor composition contains a metal on its surface, the surface of the film may become so-called “Yuzu skin”.
　本発明は、上記課題を解決することを目的とするものであって、金属表面上に塗布膜を形成した場合にも、「ゆず肌」の発生を抑えて良好な面状を達成することができるスリットコートを利用した膜の製造方法、積層体の製造方法、半導体デバイスの製造方法、およびこれらの製造方法への利用に適した膜形成用組成物の提供を目的とする。 An object of the present invention is to solve the above-mentioned problems, and even when a coating film is formed on a metal surface, it is possible to achieve a good surface shape by suppressing the occurrence of “Yuzu skin”. An object of the present invention is to provide a method for producing a film using a slit coat, a method for producing a laminate, a method for producing a semiconductor device, and a film forming composition suitable for use in these production methods.
　上記課題のもと本発明者が検討を行った結果、ポリイミド前駆体を含む組成物をスリットコート法で層状に塗布した時、乾燥中にベナードセルが発生し、表面がゆず肌状になることを見出した。そして、ポリイミド前駆体を含む組成物（膜形成用塗布液）において、溶剤として、ポリイミド前駆体に対する２３℃における溶解度が異なる少なくとも２種の溶剤を用い、かつ、上記組成物に、界面活性剤および可塑剤からなる群から選択される少なくとも１種を配合することにより、上記課題が解決されることを見出した。
　具体的には、下記手段＜１＞により、好ましくは＜２＞～＜２３＞により、上記課題は解決された。 As a result of investigation by the present inventors based on the above problems, when a composition containing a polyimide precursor is applied in a layer form by a slit coating method, Benard cells are generated during drying, and the surface becomes distorted. I found it. And in the composition containing the polyimide precursor (coating liquid for film formation), as the solvent, at least two kinds of solvents having different solubility at 23 ° C. with respect to the polyimide precursor are used. It has been found that the above problem can be solved by blending at least one selected from the group consisting of plasticizers.
Specifically, the above problem has been solved by the following means <1>, preferably <2> to <23>.
＜１＞ポリイミド前駆体と、ポリイミド前駆体に対する２３℃における溶解度が異なる少なくとも２種の溶剤と、界面活性剤および可塑剤からなる群から選択される少なくとも１種とを含む組成物を用いて、部材上にスリットコートを行う工程を含み、上記部材が少なくともその一部に金属を含む、膜の製造方法。
＜２＞上記界面活性剤が、パーフルオロアルキル基を含む重量平均分子量５，０００以下の化合物で、水に可溶である、＜１＞に記載の膜の製造方法。
＜３＞スリットコートを行なう工程の後に洗浄液でノズルヘッドを洗浄するヘッド洗浄工程を含む、＜１＞または＜２＞に記載の膜の製造方法。
＜４＞上記スリットコートを行う工程において、ヘッド待機工程を含み、上記ヘッド待機工程において上記ノズルヘッドが浸漬液中に浸漬されており、上記浸漬液は上記洗浄液と９０質量％以上が共通する組成の液である、＜３＞に記載の膜の製造方法。
＜５＞上記洗浄液が、上記少なくとも２種の溶剤のうち、上記ポリイミド前駆体の２３℃における溶解度の最も高い溶剤を含む、＜３＞または＜４＞に記載の膜の製造方法。
＜６＞上記洗浄液が、上記少なくとも２種の溶剤のうち、上記ポリイミド前駆体の２３℃における溶解度の最も低い溶剤を含む、＜３＞～＜５＞のいずれか１つに記載の膜の製造方法。
＜７＞上記浸漬液が、上記少なくとも２種の溶剤のうち、上記ポリイミド前駆体の２３℃における溶解度の最も高い溶剤を含む、＜４＞に記載の膜の製造方法。
＜８＞上記浸漬液が、上記少なくとも２種の溶剤のうち、上記ポリイミド前駆体の２３℃における溶解度の最も低い溶剤を含む、＜４＞または＜７＞に記載の膜の製造方法。
＜９＞上記スリットコートにより形成した膜を露光する露光工程と、露光した膜を現像する現像工程とを有する＜１＞～＜８＞のいずれか１つに記載の膜の製造方法。
＜１０＞さらに上記膜を加熱する加熱工程を含む＜１＞～＜９＞のいずれか１つに記載の膜の製造方法。
＜１１＞＜１＞～＜１０＞のいずれか１つに記載の膜の製造方法を複数回行なう、積層体の製造方法。
＜１２＞上記膜に金属層を適用する工程を含む＜１１＞に記載の積層体の製造方法。
＜１３＞＜１＞～＜１０＞のいずれか１つに記載の方法で製造した膜にチップを配置する半導体デバイスの製造方法。
＜１４＞＜１１＞または＜１２＞に記載の方法で製造した積層体にチップを配置する半導体デバイスの製造方法。
＜１５＞＜１＞～＜１０＞のいずれか１つに記載の製造方法に用いられる膜形成用の組成物であって、ポリイミド前駆体と、上記ポリイミド前駆体に対する２３℃における溶解度が異なる少なくとも２種の溶剤と、界面活性剤および可塑剤からなる群から選択される少なくとも１種とを含む膜形成用組成物。
＜１６＞上記ポリイミド前駆体がジカルボン酸とジアミノ化合物の縮合体である＜１５＞に記載の膜形成用組成物。
＜１７＞上記少なくとも２種の溶剤のうち、上記ポリイミド前駆体の溶解度の最も高い溶剤がスルホキシド類またはラクタム類の溶剤であり、上記少なくとも２種の溶剤のうち、上記ポリイミド前駆体の溶解度の最も低い溶剤がケトン類またはラクトン類の溶剤である＜１５＞または＜１６＞に記載の膜形成用組成物。
＜１８＞上記少なくとも２種の溶剤のうち、上記ポリイミド前駆体の溶解度が下記平均値より高い溶剤の総質量と、上記少なくとも２種の溶剤のうち、上記ポリイミド前駆体の溶解度が下記平均値より低い溶剤の総質量の比率が１０：９０～４５：５５である＜１５＞～＜１７＞のいずれか１つに記載の膜形成用組成物；
　上記平均値は、ポリイミド前駆体の２３℃における溶解度が最も高い溶剤の溶解度とポリイミド前駆体の２３℃における最も低い溶剤の溶解度との平均値である。
＜１９＞上記界面活性剤がフッ素原子を含む＜１５＞～＜１８＞のいずれか１つに記載の膜形成用組成物。
＜２０＞上記界面活性剤がパーフルオロアルキル基を含む重量平均分子量５，０００以下の化合物で、水に可溶である＜１９＞に記載の膜形成用組成物。
＜２１＞上記界面活性剤の含有量が固形分中で０．００５～２質量％である＜１５＞～＜２０＞のいずれか１つに記載の膜形成用組成物。
＜２２＞上記可塑剤がエポキシ化オイルである＜１５＞～＜２１＞のいずれか１つに記載の膜形成用組成物。
＜２３＞上記可塑剤の含有量が固形分中で０．００５～２質量％である、＜１５＞～＜２２＞のいずれか１つに記載の膜形成用組成物。 <1> Using a composition comprising a polyimide precursor, at least two solvents having different solubility at 23 ° C. with respect to the polyimide precursor, and at least one selected from the group consisting of a surfactant and a plasticizer, A method for producing a film, comprising a step of slit coating on a member, wherein the member contains a metal at least in part.
<2> The method for producing a film according to <1>, wherein the surfactant is a compound containing a perfluoroalkyl group and having a weight average molecular weight of 5,000 or less and is soluble in water.
<3> The method for producing a film according to <1> or <2>, including a head cleaning step of cleaning the nozzle head with a cleaning liquid after the step of performing the slit coating.
<4> The step of performing the slit coating includes a head standby step, wherein the nozzle head is immersed in an immersion liquid in the head standby process, and the immersion liquid has a composition that is 90% by mass or more in common with the cleaning liquid. The method for producing a film according to <3>, wherein
<5> The method for producing a film according to <3> or <4>, wherein the cleaning liquid contains a solvent having the highest solubility at 23 ° C. of the polyimide precursor among the at least two kinds of solvents.
<6> The film production according to any one of <3> to <5>, wherein the cleaning liquid contains a solvent having the lowest solubility of the polyimide precursor at 23 ° C. among the at least two solvents. Method.
<7> The method for producing a film according to <4>, wherein the immersion liquid contains a solvent having the highest solubility at 23 ° C. of the polyimide precursor among the at least two kinds of solvents.
<8> The method for producing a film according to <4> or <7>, wherein the immersion liquid contains a solvent having the lowest solubility of the polyimide precursor at 23 ° C among the at least two solvents.
<9> The method for producing a film according to any one of <1> to <8>, comprising an exposure step of exposing the film formed by the slit coating and a development step of developing the exposed film.
<10> The method for producing a film according to any one of <1> to <9>, further including a heating step of heating the film.
<11> A method for producing a laminate, wherein the method for producing a film according to any one of <1> to <10> is performed a plurality of times.
<12> The method for producing a laminate according to <11>, including a step of applying a metal layer to the film.
<13> A method for manufacturing a semiconductor device, wherein a chip is arranged on a film manufactured by the method according to any one of <1> to <10>.
<14> A method for producing a semiconductor device, in which a chip is arranged on a laminate produced by the method according to <11> or <12>.
<15> A film-forming composition used in the production method according to any one of <1> to <10>, wherein the polyimide precursor and the polyimide precursor have different solubility at 23 ° C. A film-forming composition comprising two kinds of solvents and at least one selected from the group consisting of a surfactant and a plasticizer.
<16> The film forming composition according to <15>, wherein the polyimide precursor is a condensate of a dicarboxylic acid and a diamino compound.
<17> Among the at least two solvents, the solvent having the highest solubility of the polyimide precursor is a sulfoxide or lactam solvent, and of the at least two solvents, the solubility of the polyimide precursor is the highest. The film forming composition according to <15> or <16>, wherein the low solvent is a solvent of ketones or lactones.
<18> Among the at least two solvents, the solubility of the polyimide precursor is higher than the average value below, and among the at least two solvents, the solubility of the polyimide precursor is below the average value below. The film forming composition according to any one of <15> to <17>, wherein the ratio of the total mass of the low solvent is 10:90 to 45:55;
The average value is an average value of the solubility of the solvent having the highest solubility of the polyimide precursor at 23 ° C. and the solubility of the polyimide precursor having the lowest solubility at 23 ° C.
<19> The film forming composition as described in any one of <15> to <18>, wherein the surfactant contains a fluorine atom.
<20> The film forming composition according to <19>, wherein the surfactant is a compound having a perfluoroalkyl group and having a weight average molecular weight of 5,000 or less and is soluble in water.
<21> The film-forming composition according to any one of <15> to <20>, wherein the content of the surfactant is 0.005 to 2% by mass in the solid content.
<22> The film-forming composition according to any one of <15> to <21>, wherein the plasticizer is an epoxidized oil.
<23> The film forming composition according to any one of <15> to <22>, wherein the content of the plasticizer is 0.005 to 2% by mass in the solid content.
　本発明により、スリットコートにおいて、金属表面上に樹脂の塗布膜を形成した場合にも、「ゆず肌」の発生を抑えて良好な面状を達成することができる。 According to the present invention, even when a resin coating film is formed on the metal surface in the slit coat, it is possible to suppress the occurrence of “Yuzu skin” and achieve a good surface shape.
本発明において適用されるスリットコートの好ましい実施形態を模式的な側面図で説明するための工程説明図（１）である。It is process explanatory drawing (1) for demonstrating preferable embodiment of the slit coat applied in this invention with a typical side view. 本発明において適用されるスリットコートの好ましい実施形態を模式的な側面図で説明するための工程説明図（２）である。It is process explanatory drawing (2) for demonstrating preferable embodiment of the slit coat applied in this invention with a typical side view. 本発明において適用されるスリットコートの好ましい実施形態を模式的な側面図で説明するための工程説明図（３）である。It is process explanatory drawing (3) for demonstrating preferable embodiment of the slit coat applied in this invention with a typical side view.
　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形態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形態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、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）測定に従い、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－８２２０ＧＰＣ（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およびＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ２０００（東ソー（株）製）のいずれか１つ以上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。
　図面において例示した、形状、寸法、数、配置箇所等は任意であり、限定されない。 The description of the components in the present invention described below may be made based on representative 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) acryl” represents both “acryl” and “methacryl”, or “(Meth) acryloyl” represents either or both of “acryloyl” and “methacryloyl”.
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 the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values according to 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-8220GPC (manufactured by Tosoh Corp.), guard columns HZ-L, TSKgel Super HZM-M, TSKgel. It can be determined by using any one or more of Super HZ4000, TSKgel Super HZ3000, and 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.
The shape, dimensions, number, arrangement location, and the like exemplified in the drawings are arbitrary and are not limited.
　本発明の膜の製造方法は、ポリイミド前駆体と、ポリイミド前駆体に対する２３℃における溶解度が異なる少なくとも２種の溶剤と、界面活性剤および可塑剤からなる群から選択される少なくとも１種とを含む組成物を用いて、少なくとも一部に金属を含む部材上にスリットコートを行う工程を含むことを特徴とする。これにより、スリットコートにおいて、金属表面上に塗布膜を形成した場合にも、「ゆず肌」の発生を抑えて良好な面状（光沢）を達成することができる。
　ポリイミド前駆体は塗布膜とした後に加熱して硬化する。すなわち、塗布した段階では塗布膜が流動的な液状であり、その結果、ゆず肌が生じていると推測された。そして、ゆず肌を抑制するには、その結果以下の点を考慮することが重要であることと推測された。
（１）乾燥中の早い段階で対流を抑えるために溶解度の高い溶剤に加え溶解度の低い溶剤を採用する、かつ、
（２）塗布膜の表面張力を下げるために界面活性剤を採用する、または
（３）表面が先に乾燥して内部対流が継続するのを避けるために可塑剤を添加する
　そして、上記のとおり、溶解度の異なる溶剤を２種以上用い、かつ、界面活性剤および可塑剤からなる群から選択される少なくとも１種を用いることにより、ゆず肌を抑制し、面状の改善に成功したものである。さらに、ポリイミド樹脂層と金属（例えば、金属層）の密着性の向上にも成功したものである。特に、所定の界面活性剤を用いることにより、銅（例えば、銅層）との優れた密着性の獲得にも成功した。
　以下、本発明を詳細に述べる。 The method for producing a film of the present invention includes a polyimide precursor, at least two solvents having different solubility in a polyimide precursor at 23 ° C., and at least one selected from the group consisting of a surfactant and a plasticizer. It includes a step of performing slit coating on a member containing a metal at least in part using the composition. As a result, even when a coating film is formed on the metal surface in the slit coat, it is possible to suppress the occurrence of “yuzu skin” and achieve a good surface shape (gloss).
The polyimide precursor is cured by heating after forming a coating film. That is, it was speculated that the coating film was in a fluid liquid state at the stage of application, and as a result, it had been distorted. And it was estimated that it was important to consider the following points as a result in order to suppress yuzu skin.
(1) In order to suppress convection at an early stage during drying, a solvent having a low solubility is employed in addition to a solvent having a high solubility, and
(2) Adopt a surfactant to lower the surface tension of the coating film, or (3) Add a plasticizer to avoid the surface drying first and internal convection continuing and as above By using two or more solvents having different solubilities and using at least one selected from the group consisting of a surfactant and a plasticizer, the skin was successfully suppressed and the surface condition was successfully improved. . Furthermore, the adhesion between the polyimide resin layer and the metal (for example, metal layer) has been successfully improved. In particular, by using a predetermined surfactant, it has succeeded in obtaining excellent adhesion with copper (for example, a copper layer).
The present invention will be described in detail below.
＜スリットコート＞
　図１は、本発明において適用されるスリットコートの好ましい実施形態を模式的な側面図で説明するための工程説明図（１）である。本実施形態の塗布装置１００は、基板３０を搬送する搬送部２３と、基板を下方から支持する支持ステージ（図示せず）を備える。基板３０にノズルヘッド２１から、スリット状のノズルを通してレジスト（樹脂）２１ａを吐出して、基板３０をｄ３の方向へと搬送する（スリットコート工程）。搬送部２３は、複数の搬送ローラとこれらを回転させる搬送ローラ駆動部で構成することができる。ノズルヘッド２１は、搬送部が基板３０を搬送するタイミングをみて上下方向に昇降させることができる。同様に、支持ステージ（図示せず）もノズルヘッドの直下から移動し退避させることができる。このとき、ノズルヘッドを待機させ、次の基板が送られてくるのを待つことができる（ヘッド待機工程）。このスリットコート工程の間のヘッド待機工程で、あるいはスリットコート工程の後に、以下に示すノズルヘッドの浸漬処理（浸漬処理工程）や洗浄処理（ヘッド洗浄工程）を行ってもよい。 <Slit coat>
FIG. 1 is a process explanatory diagram (1) for explaining a preferred embodiment of a slit coat applied in the present invention in a schematic side view. The coating apparatus 100 of this embodiment includes a transport unit 23 that transports the substrate 30 and a support stage (not shown) that supports the substrate from below. A resist (resin) 21a is discharged from the nozzle head 21 to the substrate 30 through a slit-like nozzle, and the substrate 30 is conveyed in the direction d3 (slit coating process). The conveyance unit 23 can be configured by a plurality of conveyance rollers and a conveyance roller driving unit that rotates the conveyance rollers. The nozzle head 21 can be lifted up and down in accordance with the timing at which the transport unit transports the substrate 30. Similarly, a support stage (not shown) can also be moved and retracted from directly below the nozzle head. At this time, it is possible to wait the nozzle head and wait for the next substrate to be sent (head waiting step). The nozzle head immersion process (immersion process process) and the cleaning process (head cleaning process) described below may be performed in the head standby process during the slit coating process or after the slit coating process.
　本実施形態の装置１００では、ノズルヘッドの直下にノズルヘッドクリーナー２２が配置されている。基板への樹脂の吐出が終了すると、ノズルヘッドを塗布面に対し垂直に沿って下降（ｄ１）させノズルヘッドクリーナー２２内に備えられた浸漬液にノズルヘッド２１を浸漬させる（図２）。ノズルヘッドをクリーナー内で浸漬液に浸す時間は、例えば、０．１分以上であることが好ましく、０．２分以上であることがより好ましく、０．５分以上であることがさらに好ましい。上限としては、１０分以下であることが好ましく、８分以下であることがより好ましく、５分以下であることがさらに好ましい。これにより、ノズルヘッド２１の先端を洗浄することができる。 In the apparatus 100 of the present embodiment, the nozzle head cleaner 22 is disposed immediately below the nozzle head. When the discharge of the resin onto the substrate is completed, the nozzle head is lowered (d1) along a direction perpendicular to the coating surface, and the nozzle head 21 is immersed in the immersion liquid provided in the nozzle head cleaner 22 (FIG. 2). The time for immersing the nozzle head in the immersion liquid in the cleaner is, for example, preferably 0.1 minutes or more, more preferably 0.2 minutes or more, and further preferably 0.5 minutes or more. The upper limit is preferably 10 minutes or less, more preferably 8 minutes or less, and even more preferably 5 minutes or less. Thereby, the tip of the nozzle head 21 can be cleaned.
　図３は、上記図１、図２とは別のヘッドメンテナンス工程を説明する装置側面図であり、ノズルヘッドのメンテナンス（洗浄）の態様を示すものである。本実施形態の装置は、ｄ２方向に回転するローラ２４を備える。ローラバット２５には洗浄液２５ａが満たされ、ローラ２４の下部を浸漬させるようにされている。本実施形態の装置１００には、さらに液切りブレード２５ｂが備えられている。上記ローラ２４とローラバット２５はメンテナンス部２６を構成している。このメンテナンス部は基板面に対し垂直な方向に昇降させることができる。本実施形態の装置は、このようなメンテナンス部を備えることにより、メンテナンス処理において、ノズルヘッド２１を下降ｄ５させずに、メンテナンス部２６を上昇ｄ４させることによっても、ノズルヘッド２１のメンテナンス（洗浄）を実行することが可能である。メンテナンス部では、ｄ５から流す液を洗浄液に切り替える。ノズルヘッドに洗浄液を流す時間は、例えば、１分以上であることが好ましく、２分以上であることがより好ましく、５分以上であることがさらに好ましい。上限としては、１２０分以下であることが好ましく、６０分以下であることがより好ましく、３０分以下であることがさらに好ましい。これにより、ノズルヘッド２１を洗浄することができる。 FIG. 3 is a side view of the apparatus for explaining a head maintenance process different from those shown in FIGS. 1 and 2 and shows a mode of maintenance (cleaning) of the nozzle head. The apparatus of this embodiment includes a roller 24 that rotates in the d2 direction. The roller bat 25 is filled with a cleaning liquid 25a so that the lower part of the roller 24 is immersed. The apparatus 100 of this embodiment is further provided with a liquid draining blade 25b. The roller 24 and the roller butt 25 constitute a maintenance unit 26. The maintenance unit can be moved up and down in a direction perpendicular to the substrate surface. The apparatus according to the present embodiment includes such a maintenance unit, so that maintenance (cleaning) of the nozzle head 21 can also be performed by raising the maintenance unit 26 d4 without lowering the nozzle head 21 d5 in the maintenance process. Can be performed. In the maintenance unit, the liquid flowing from d5 is switched to the cleaning liquid. The time for which the cleaning liquid flows through the nozzle head is, for example, preferably 1 minute or longer, more preferably 2 minutes or longer, and further preferably 5 minutes or longer. As an upper limit, it is preferable that it is 120 minutes or less, It is more preferable that it is 60 minutes or less, It is further more preferable that it is 30 minutes or less. Thereby, the nozzle head 21 can be cleaned.
　本発明においては、上記のとおり、スリットコートを行う工程において、ヘッド待機工程を含むことが好ましい。ヘッド待機工程においては、ヘッドが浸漬液中に浸漬されていることが好ましい。浸漬液は洗浄液と９０質量％以上が共通する組成の液であることが好ましく、９５質量％以上が共通する組成の液であることがより好ましく、同一の組成であることがさらに好ましい。
　浸漬液および洗浄液は、それぞれ、化合物の種類や混合比率等について、膜形成用組成物における溶剤と９０質量％以上が共通する組成の液であることが好ましく、９５質量％以上が共通する組成の液であることがより好ましく、同一の組成であることがさらに好ましい。
　洗浄液は、また、膜形成用組成物に含まれる少なくとも２種の溶剤のうち、ポリイミド前駆体の２３℃における溶解度の最も高い溶剤を含むことが好ましい。また、洗浄液は、膜形成用組成物に含まれる少なくとも２種の溶剤のうち、ポリイミド前駆体の２３℃における溶解度の最も低い溶剤を含むことが好ましい。さらに、膜形成用組成物に含まれる少なくとも２種の溶剤のうち、ポリイミド前駆体の２３℃における溶解度の最も高い溶剤とポリイミド前駆体の２３℃における溶解度の最も低い溶剤の両方を含むことがより好ましい。
　浸漬液は、また、膜形成用組成物に含まれる少なくとも２種の溶剤のうち、ポリイミド前駆体の２３℃における溶解度の最も高い溶剤を含むことが好ましい。また、浸漬液は、膜形成用組成物に含まれる少なくとも２種の溶剤のうち、ポリイミド前駆体の２３℃における溶解度の最も低い溶剤を含むことが好ましい。さらに、膜形成用組成物に含まれる少なくとも２種の溶剤のうち、ポリイミド前駆体の２３℃における溶解度の最も高い溶剤とポリイミド前駆体の２３℃における溶解度の最も低い溶剤の両方を含むことがより好ましい。 In the present invention, as described above, the slit coating step preferably includes a head standby step. In the head standby step, the head is preferably immersed in the immersion liquid. The immersion liquid is preferably a liquid having a composition that is 90% by mass or more in common with the cleaning liquid, more preferably a liquid having a composition that has 95% by mass or more in common, and even more preferably the same composition.
The immersion liquid and the cleaning liquid are each preferably a liquid having a composition that is 90% by mass or more in common with the solvent in the film-forming composition with respect to the type and mixing ratio of the compound, and 95% by mass or more. More preferably, it is a liquid, and it is further more preferable that it is the same composition.
The cleaning liquid preferably contains a solvent having the highest solubility of the polyimide precursor at 23 ° C. among at least two kinds of solvents contained in the film-forming composition. Moreover, it is preferable that a washing | cleaning liquid contains the solvent with the lowest solubility in 23 degreeC of a polyimide precursor among the at least 2 types of solvents contained in the composition for film formation. Furthermore, among at least two kinds of solvents contained in the film-forming composition, it contains both the solvent having the highest solubility of the polyimide precursor at 23 ° C. and the solvent having the lowest solubility of the polyimide precursor at 23 ° C. preferable.
The immersion liquid preferably also contains a solvent having the highest solubility of the polyimide precursor at 23 ° C. among at least two solvents contained in the film-forming composition. Moreover, it is preferable that an immersion liquid contains the solvent with the lowest solubility at 23 degreeC of a polyimide precursor among the at least 2 types of solvents contained in the composition for film formation. Furthermore, among at least two kinds of solvents contained in the film-forming composition, it contains both the solvent having the highest solubility of the polyimide precursor at 23 ° C. and the solvent having the lowest solubility of the polyimide precursor at 23 ° C. preferable.
　なお、スリットコートおよびそれに適用できる装置については、特開２００９－０７０９７３号公報を参照することができ、そこに記載の事項は本明細書に組み込まれる。 In addition, regarding the slit coat and the apparatus applicable thereto, JP 2009-070973 A can be referred to, and the matters described therein are incorporated in this specification.
＜膜形成用組成物＞
＜＜ポリイミド前駆体＞＞
　ポリイミド前駆体としては下記式（１）で表される繰り返し構成単位（構成単位）を含むことが好ましい。
Figure JPOXMLDOC01-appb-C000001
 　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。 <Film forming composition>
<< Polyimide precursor >>
As a polyimide precursor, it is preferable that the repeating structural unit (structural unit) represented by following formula (1) is included.
Figure JPOXMLDOC01-appb-C000001
 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, and R 113 and R 114 each independently Represents a hydrogen atom or a monovalent organic group.
　Ａ１およびＡ２は、それぞれ独立に、酸素原子またはＮＨであり、酸素原子が好ましい。 A 1 and A 2 are each independently an oxygen atom or NH, preferably an oxygen atom.
＜＜＜Ｒ１１１＞＞＞
　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、複素芳香族基、またはこれらの組み合わせからなる基が例示され、炭素数２～２０の直鎖の脂肪族基、炭素数３～２０の分岐の脂肪族基、炭素数３～２０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の芳香族基がより好ましい。
　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種のみ用いてもよいし、２種以上用いてもよい。
　具体的には、ジアミンは、炭素数２～２０の直鎖脂肪族基、炭素数３～２０の分岐または環状の脂肪族基、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ものであることが好ましく、炭素数６～２０の芳香族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、下記が挙げられる。 <<< R 111 >>>
R 111 represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group composed of an aromatic group, a heteroaromatic group, or a combination thereof, and has 2 to 20 carbon atoms. A linear aliphatic group, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof. An aromatic group having 6 to 20 carbon atoms is more preferable.
R 111 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, the diamine is a straight chain aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof. And a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. The following are mentioned as an example of an aromatic group.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　式中、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－、－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－、－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。 In the formula, 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—, —CO—, —S—, —SO 2 —, — NHCO— and a group selected from these combinations are preferable. A single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S— And —SO 2 — is more preferable, and —CH 2 —, —O—, —S—, —SO 2 —, —C (CF 3 ) 2 —, and —C (CH 3) 2 - and more preferably a divalent radical selected from the group consisting of.
　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－（３’，５’－ジアミノベンゾイルオキシ）エチルメタクリレート、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- (3', 5'-diaminobenzoyloxy) ethyl methacrylate 2,4- and 2,5-diaminocumene, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-meta Phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, diaminobenzoic acid Ester, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis ( -Aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetra Decafluoroheptane, 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] hexafluoropropane, 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) diphenylsulfone 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 And at least one diamine selected from 4,6′-hexafluorotolidine and 4,4′-diaminoquaterphenyl.
　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
　また、少なくとも２つ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一方または両方を一分子中にあわせて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社製）、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 preferred example is a diamine having at least two alkylene glycol units in the main chain. 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 -Aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, and the like. Not.
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-C000004
Figure JPOXMLDOC01-appb-C000004
　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.
　Ｒ１１１は、－Ａｒ０－Ｌ０－Ａｒ０－で表されることが好ましい。但し、Ａｒ０は、それぞれ独立に、芳香族炭化水素基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が特に好ましい）であり、Ｌ０は、上記Ａの基と同義であり、好ましい範囲も同じである。Ａｒ０は、フェニレン基が好ましい。 R 111 is preferably represented by -Ar 0 -L 0 -Ar 0- . However, Ar 0 is each independently an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and L 0 is a group of the above A It is synonymous and the preferable range is also the same. Ar 0 is preferably a phenylene group.
　Ｒ１１１は、ｉ線透過率の観点から下記式（５１）または式（６１）で表される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）で表される２価の有機基であることがより好ましい。
Figure JPOXMLDOC01-appb-C000005
 　　　　
　Ｒ５０～Ｒ５７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、Ｒ５０～Ｒ５７の少なくとも１つはフッ素原子、メチル基、フルオロメチル基、ジフルオロメチル基、または、トリフルオロメチル基である。
　Ｒ５０～Ｒ５７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。
Figure JPOXMLDOC01-appb-C000006
 　　　
　Ｒ５８およびＲ５９は、それぞれ独立にフッ素原子、フルオロメチル基、ジフルオロメチル基、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、ジメチル－４,４’－ジアミノビフェニル、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。これらの１種を用いるか、２種以上を組み合わせて用いてもよい。 R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-line transmittance. In particular, the divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-line transmittance and availability.
Figure JPOXMLDOC01-appb-C000005
R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group, or A trifluoromethyl group.
Examples of the monovalent organic group represented by R 50 to R 57 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.
Figure JPOXMLDOC01-appb-C000006
R 58 and R 59 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.
Diamine compounds that give the structure of formula (51) or (61) include dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2 Examples include '-bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, and the like. One of these may be used, or two or more may be used in combination.
＜＜＜Ｒ１１５＞＞＞
　式（１）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。
Figure JPOXMLDOC01-appb-C000007
 　　　
　Ｒ１１２は、Ａと同義であり、好ましい範囲も同じである。 <<< R 115 >>>
R 115 in formula (1) 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.
Figure JPOXMLDOC01-appb-C000007
R 112 has the same meaning as A, and the preferred range is also the same.
　式（１）におけるＲ１１５が表す４価の有機基は、具体的には、テトラカルボン酸二無水物から酸二無水物基を除去した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種のみ用いてもよいし、２種以上用いてもよい。テトラカルボン酸二無水物は、下記式（７）で表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000008
 　Ｒ１１５は、４価の有機基を表す。Ｒ１１５は式（１）のＲ１１５と同義である。 Specific examples of the tetravalent organic group represented by R 115 in Formula (1) include a tetracarboxylic acid residue remaining after the acid dianhydride group is removed from the tetracarboxylic dianhydride. Only one tetracarboxylic dianhydride may be used, or two or more tetracarboxylic dianhydrides may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).
Figure JPOXMLDOC01-appb-C000008
 R 115 represents a tetravalent organic group. R 115 has the same meaning as R 115 in formula (1).
　テトラカルボン酸二無水物の具体例としては、ピロメリット酸、ピロメリット酸二無水物（ＰＭＤＡ）、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のアルキル誘導体および炭素数１～６のアルコキシ誘導体から選ばれる少なくとも１種が例示される。 Specific examples of tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4 , 4′-diphenyl sulfide tetracarboxylic 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 acid Dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride 1,4,5,7-naphthalenetetracarboxylic 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-naphthalenetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1, -Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride And at least one selected from alkyl derivatives having 1 to 6 carbon atoms and 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-C000009
 Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also preferable examples.
Figure JPOXMLDOC01-appb-C000009
＜＜＜Ｒ１１３およびＲ１１４＞＞＞
　式（１）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。Ｒ１１３およびＲ１１４の少なくとも一方がラジカル重合性基を含むことが好ましく、両方がラジカル重合性基を含むことがより好ましい。ラジカル重合性基としては、ラジカルの作用により、架橋反応することが可能な基であって、好ましい例として、エチレン性不飽和結合を有する基が挙げられる。
　エチレン性不飽和結合を有する基としては、ビニル基、アリル基、（メタ）アクリロイル基、下記式（ＩＩＩ）で表される基などが挙げられる。 <<< R 113 and R 114 >>>
R 113 and R 114 in Formula (1) each independently represent a hydrogen atom or a monovalent organic group. At least one of R 113 and R 114 preferably contains a radical polymerizable group, and more preferably both contain a radical polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferable example includes a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, a group represented by the following formula (III), and the like.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　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（アルキレン基としては炭素数１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい；繰り返し数は１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい）を表す。なお、（ポリ）オキシアルキレン基とは、オキシアルキレン基またはポリオキシアルキレン基を意味する。
　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 (poly) oxyalkylene group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atom) To 12 is preferable, 1 to 6 is more preferable, and 1 to 3 is particularly preferable; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. The (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
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 —, and 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.
　ポリイミド前駆体の好ましい実施形態として、Ｒ１１３またはＲ１１４の１価の有機基として、１、２または３つの、好ましくは１つの酸基を有する、脂肪族基、芳香族基およびアリールアルキル基などが挙げられる。具体的には、酸基を有する炭素数６～２０の芳香族基、酸基を有する炭素数７～２５のアリールアルキル基が挙げられる。より具体的には、酸基を有するフェニル基および酸基を有するベンジル基が挙げられる。酸基は、ヒドロキシル基が好ましい。すなわち、Ｒ１１３またはＲ１１４はヒドロキシル基を有する基であることが好ましい。
　Ｒ１１３またはＲ１１４が表す１価の有機基としては、現像液の溶解度を向上させる置換基が好ましく用いられる。
　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、水性現像液に対する溶解性の点からは、より好ましい。 Preferred embodiments of the polyimide precursor include aliphatic groups, aromatic groups, arylalkyl groups, etc. having 1, 2, or 3, preferably 1, acid groups as the monovalent organic group of R 113 or R 114 Is mentioned. Specific examples include an aromatic group having 6 to 20 carbon atoms having an acid group and an arylalkyl group having 7 to 25 carbon atoms having an acid group. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned. The acid group is preferably a hydroxyl group. That is, R 113 or R 114 is preferably a group having a hydroxyl group.
As the monovalent organic group represented by R113 or R114, a substituent that improves the solubility of the developer is preferably used.
R 113 or R 114 is more preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl or 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.
　有機溶剤への溶解度の観点からは、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、芳香族基を含むことが好ましく、芳香族基で置換されたアルキル基がより好ましい。
　アルキル基の炭素数は１～３０が好ましい（環状の場合は３以上）。アルキル基は直鎖、分岐、環状のいずれであってもよい。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。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。
　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。 From the viewpoint of solubility in an organic solvent, R 113 or R 114 is preferably a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.
The alkyl group preferably has 1 to 30 carbon atoms (3 or more in the case of a cyclic group). The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, octadecyl group. Isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group. The cyclic alkyl group 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 include 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, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, fluorine Nantororin ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring or a phenazine ring. A benzene ring is most preferred.
　また、ポリイミド前駆体は、構造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、２０質量％以下が好ましい。上限は特にないが５０質量％以下が実際的である。 The polyimide precursor preferably has a fluorine atom in the structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less. There is no particular upper limit, but 50% by mass or less is practical.
　また、基板との密着性を向上させる目的で、シロキサン構造を有する脂肪族基を式（１）で表される構成単位に共重合してもよい。具体的には、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 structural unit represented by the formula (1). Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.
　式（１）で表される構成単位は、式（１－Ａ）で表される構成単位であることが好ましい。
Figure JPOXMLDOC01-appb-C000011
 　Ａ１１およびＡ１２は、酸素原子またはＮＨ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、ラジカル重合性基を含む基であり、ラジカル重合性基であることが好ましい。 The structural unit represented by the formula (1) is preferably a structural unit represented by the formula (1-A).
Figure JPOXMLDOC01-appb-C000011
 A 11 and A 12 each represent an oxygen atom or NH; R 111 and R 112 each independently represent a divalent organic group; and R 113 and R 114 each independently represent a hydrogen atom or a monovalent group. An organic group is represented, and at least one of R 113 and R 114 is a group containing a radical polymerizable group, and is preferably a radical polymerizable group.
　Ａ１１、Ａ１２、Ｒ１１１、Ｒ１１３およびＲ１１４は、それぞれ、独立に、式（１）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。
　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 11 , A 12 , R 111 , R 113 and R 114 are each independently synonymous with A 1 , A 2 , R 111 , R 113 and R 114 in formula (1), and the preferred ranges are also the same. is there.
R 112 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、式（１）で表される繰り返し構成単位は１種であってもよいが、２種以上であってもよい。また、式（１）で表される構成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（１）の構成単位のほかに、他の種類の構成単位も含んでもよい。 In the polyimide precursor, the repeating structural unit represented by the formula (1) may be one type or two or more types. Moreover, the structural isomer of the structural unit represented by Formula (1) may be included. The polyimide precursor may also contain other types of structural units in addition to the structural unit of the above formula (1).
　ポリイミド前駆体の一実施形態として、全構成単位の５０モル％以上、さらには７０モル％以上、特には９０モル％以上が式（１）で表される構成単位であるポリイミド前駆体が例示される。上限としては１００モル％以下が実際的である。 As an embodiment of the polyimide precursor, a polyimide precursor in which 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of all the structural units is a structural unit represented by the formula (1) is exemplified. The As an upper limit, 100 mol% or less is practical.
　ポリイミド前駆体の重量平均分子量（Ｍｗ）は、好ましくは２０００～５０００００であり、より好ましくは５０００～１０００００であり、さらに好ましくは１００００～５００００である。また、数平均分子量（Ｍｎ）は、好ましくは８００～２５００００であり、より好ましくは、２０００～５００００であり、さらに好ましくは、４０００～２５０００である。
　ポリイミド前駆体の分子量の分散度は、１．５～３．５が好ましく、２～３がより好ましい。 The weight average molecular weight (Mw) of the polyimide precursor is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, and even more preferably from 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and still more preferably 4000 to 25000.
The molecular weight dispersion of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
　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の縮合体である。好ましくは、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。
　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種でもよいし、２種以上でもよい。
　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 a condensate of dicarboxylic acid or dicarboxylic acid derivative and diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting with a diamine.
In the method for producing a polyimide precursor, an organic solvent is preferably used for the reaction. One or more organic solvents may be used.
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、固体を析出する工程を含んでいることが好ましい。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。 In producing the polyimide precursor, it is preferable to include a step of depositing a solid. 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.
　膜形成用組成物におけるポリイミド前駆体の割合は、溶剤を除く成分（固形分）の６０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、７５質量％以上であることがさらに好ましく、また、９９質量％以下であることが好ましく、９５質量％以下であることがさらに好ましい。
　膜形成用組成物には、ポリイミド前駆体が１種のみ含まれていても、２種以上含まれていてもよい。２種以上含まれる場合、合計量が上記範囲となることが好ましい。 The proportion of the polyimide precursor in the film-forming composition is preferably 60% by mass or more of the component (solid content) excluding the solvent, more preferably 70% by mass or more, and 75% by mass or more. Is more preferably 99% by mass or less, and more preferably 95% by mass or less.
The film forming composition may contain only one type of polyimide precursor or two or more types of polyimide precursors. When 2 or more types are included, the total amount is preferably within the above range.
＜＜溶剤＞＞
　膜の製造方法に用いる組成物（膜形成用組成物）は、溶剤として、ポリイミド前駆体に対する２３℃における溶解度が異なる少なくとも２種の溶剤を含む。具体的には、溶剤として、少なくとも、ポリイミド前駆体に対してより高い溶解度を有する溶剤Ａと、２３℃における溶解度がより低い溶剤Ｂとの混合溶剤を用いることが好ましい。溶解度は、２３℃の溶剤１００ｇに溶けるポリイミド前駆体の量（ｇ）とする。
　溶剤が３種以上あるときには最も高い溶解度の溶剤の溶解度と最も低い溶剤の溶解度との平均値を求め、その平均値よりも高い溶解度の溶剤を溶剤Ａに分類し、上記平均値よりも低い溶解度のものを溶剤Ｂに分類する。さらに、溶剤が３種以上あるときに、最も高い溶解度の溶剤を溶剤Ａとすることが好ましく、最も低い溶解度のものを溶剤Ｂとすることが好ましい。
　溶剤Ａと溶剤Ｂの溶解度の差は、１０ｇ以上であることが好ましく、１５ｇ以上であることがより好ましく、２０ｇ以上であることがさらに好ましい。上限値としては特に定めるものではないが、例えば、５０ｇ以下とすることができる。このような構成とすることにより、塗布膜の乾燥中の早い段階での対流をより効果的に抑制できる。 << Solvent >>
The composition (film forming composition) used in the film production method contains at least two solvents having different solubility at 23 ° C. in the polyimide precursor as the solvent. Specifically, it is preferable to use a mixed solvent of at least a solvent A having higher solubility with respect to the polyimide precursor and a solvent B having lower solubility at 23 ° C. as the solvent. The solubility is defined as the amount (g) of the polyimide precursor that is soluble in 100 g of a solvent at 23 ° C.
When there are three or more solvents, the average value of the solubility of the solvent having the highest solubility and the solubility of the solvent having the lowest solubility is obtained. Are classified as Solvent B. Furthermore, when there are three or more solvents, the solvent having the highest solubility is preferably solvent A, and the solvent having the lowest solubility is preferably solvent B.
The difference in solubility between the solvent A and the solvent B is preferably 10 g or more, more preferably 15 g or more, and further preferably 20 g or more. The upper limit is not particularly defined, but can be, for example, 50 g or less. By setting it as such a structure, the convection in the early stage during drying of a coating film can be suppressed more effectively.
　溶剤Ａの沸点は１００℃以上であることが好ましく、１１０℃以上であることがより好ましく、１３０℃以上であることがさらに好ましい。上限は、２３０℃以下であることが好ましく、２１０℃以下であることがより好ましく、１９０℃以下であることがさらに好ましい。このような構成とすることにより、塗布後の面状がより均一になる傾向にある。
　溶剤Ｂの沸点は１５０℃以上であることが好ましく、１８０℃以上であることがより好ましく、２００℃以上であることがさらに好ましい。上限は、２５０℃以下であることが好ましく、２３０℃以下であることがより好ましく、２１０℃以下であることがさらに好ましい。このような構成とすることにより、塗布後の面状がより均一になる傾向にある。
　溶剤Ａと溶剤Ｂとは沸点に所定の差があることが好ましい。沸点の差は、０℃以上であることが好ましく、１０℃以上であることがより好ましく、２０℃以上であることがさらに好ましい。また８０℃以下であることが好ましい。このような構成とすることにより、溶剤Ｂにより長い時間、面状をより均一に保つことが可能になる。
　なお、本明細書において沸点は１０１３．２５ｈＰａにおけて沸騰する温度を意味する。 The boiling point of the solvent A is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, and further preferably 130 ° C. or higher. The upper limit is preferably 230 ° C. or lower, more preferably 210 ° C. or lower, and further preferably 190 ° C. or lower. By setting it as such a structure, it exists in the tendency for the surface shape after application | coating to become more uniform.
The boiling point of the solvent B is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and further preferably 200 ° C. or higher. The upper limit is preferably 250 ° C. or lower, more preferably 230 ° C. or lower, and further preferably 210 ° C. or lower. By setting it as such a structure, it exists in the tendency for the surface shape after application | coating to become more uniform.
It is preferable that the solvent A and the solvent B have a predetermined difference in boiling points. The difference in boiling points is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and further preferably 20 ° C. or higher. Moreover, it is preferable that it is 80 degrees C or less. By adopting such a configuration, it becomes possible to keep the surface shape more uniform for a longer time with the solvent B.
In the present specification, the boiling point means a temperature at which boiling occurs at 1013.25 hPa.
　溶剤は有機溶剤であることが好ましい。
　溶剤Ａに分類される溶剤として、例えば、スルホキシド類、アミド類、ラクタム類が挙げられ、なかでもスルホキシド類が好ましい。
　溶剤Ｂに分類される溶剤としては、エステル類、エーテル類、ラクトン類、ケトン類、芳香族炭化水素類などが挙げられ、なかでもラクトン類またはケトン類が好ましく、ケトン類がより好ましい。
　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、酢酸イソブチル、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、ラクトン類（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なものとして挙げられる。
　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なものとして挙げられる。
　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－ヘプタノン等が好適なものとして挙げられる。
　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、リモネン等が好適なものとして挙げられる。
　スルホキシド類として、例えば、ジメチルスルホキシドが好適なものとして挙げられる。
　アミド類として、ラクタム類（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、Ｎ，Ｎ－ジメチルホルムアミド等が好適なものとして挙げられる。 The solvent is preferably an organic solvent.
Examples of the solvent classified as solvent A include sulfoxides, amides, and lactams, and sulfoxides are preferred.
Examples of the solvent classified as the solvent B include esters, ethers, lactones, ketones, aromatic hydrocarbons and the like, among which lactones and ketones are preferable, and ketones are more preferable.
Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and lactones (γ -Butyrolactone, ε-caprolactone, δ-valerolactone), alkyl oxyacetates (eg methyl alkyloxyacetate, alkyloxyethyl acetate, butyl oxyoxyacetate (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 and 2-oxobutanoate are mentioned as preferred.
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, propylene glycol monopropyl ether acetate and the like.
Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.
Suitable examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
As the sulfoxides, for example, dimethyl sulfoxide is preferable.
Preferable examples of amides include lactams (N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone), N, N-dimethylacetamide, N, N-dimethylformamide and the like.
　溶剤の含有量は、膜形成用組成物の全固形分濃度が１～８０質量％になる量とすることが好ましく、１～６０質量％となる量にすることがより好ましく、５～４０質量％となる量にすることがさらに好ましく、５～３５質量％となるようにすることが一層好ましい。
　それぞれの溶剤について好ましい範囲を述べると、溶剤Ａ（複数種ある場合はその総質量基準）は、膜形成用組成物中、１～８０質量％であることが好ましく、１～６０質量％であることがより好ましく、５～４０質量％であることがさらに好ましく、５～３０質量％であることが一層好ましい。溶剤Ｂ（複数種ある場合はその総質量基準）は、膜形成用組成物中、３～９０質量％であることが好ましく、６～８０質量％であることがより好ましく、１０～６０質量％であることがさらに好ましく、１５～５０質量％であることが一層好ましい。
　溶剤Ａと溶剤Ｂの質量比率（複数種ある場合はその総質量基準）は１０：９０～４５：５５であることが好ましく、１５：８５～４０：６０であることがより好ましく、２０：８０～３０：７０であることがさらに好ましい。 The content of the solvent is preferably such that the total solid concentration of the film-forming composition is 1 to 80% by mass, more preferably 1 to 60% by mass, and 5 to 40% by mass. The amount is more preferably 5% to 35% by weight.
The preferred range for each solvent is as follows. The solvent A (based on the total mass when there are plural types) is preferably 1 to 80% by mass in the film-forming composition, and preferably 1 to 60% by mass. More preferred is 5 to 40% by mass, still more preferred is 5 to 30% by mass. Solvent B (based on the total mass when there are plural kinds) is preferably 3 to 90% by mass, more preferably 6 to 80% by mass in the film-forming composition, and 10 to 60% by mass. More preferably, it is more preferably 15 to 50% by mass.
The mass ratio of the solvent A and the solvent B (when there are plural types, the total mass basis) is preferably 10:90 to 45:55, more preferably 15:85 to 40:60, and 20:80 More preferably, it is ˜30: 70.
＜＜界面活性剤＞＞
　膜形成用組成物は、界面活性剤を含むことが好ましい。
　上記界面活性剤は、フッ素原子を含む界面活性剤であることが好ましく、フッ素原子を含有するノニオン系またはアニオン系の界面活性剤であることが好ましく、フッ素原子を含有するノニオン系またはアニオン系のオリゴマーまたはポリマー界面活性剤であることがより好ましい。また、界面活性剤はフルオロアルキレン基を含むことが好ましく、パーフルオロアルキル基を含むことがより好ましい。
　界面活性剤は水に可溶であることが好ましい。本明細書において可溶とは、２３℃で溶解度が０．０５質量％以上であることを意味する。さらに、界面活性剤は２３℃で水に０．１質量％以上溶解することが好ましく、０．５質量％以上溶解することがより好ましく、１質量％以上溶解することがさらに好ましい。上限としては、５質量％以下であることが実際的である。
　界面活性剤は分子内に、親水性基、親油性基、および紫外線反応性基の少なくとも１種を含んでいてよい。
　中でも、本発明においては、耐湿性が高まる観点から、パーフルオロアルキル基含有カルボン酸塩（アニオン系）であることが好ましい。界面活性剤は、水に可溶または少し溶ける（例えば、０．１質量％以上）が、炭化水素溶剤（例えば、ヘキサンやトルエン）には不溶であることが好ましい。水に対する０．１質量％溶液の表面張力は１０ｍＮ/ｍ以上であることが好ましく、１５ｍＮ/ｍ以上であることがより好ましい。上限は５０ｍＮ/ｍ以下であることが実際的である。ＰＧＭＥ（プロピレングリコールモノメチルエーテル）に対する０．１％溶液の表面張力は２５ｍＮ/ｍ超であることが好ましく、２６ｍＮ/ｍ以上であることがより好ましい。上限は７０ｍＮ/ｍ以下であることが実際的である。 << Surfactant >>
The film-forming composition preferably contains a surfactant.
The surfactant is preferably a surfactant containing a fluorine atom, preferably a nonionic or anionic surfactant containing a fluorine atom, and a nonionic or anionic surfactant containing a fluorine atom. More preferably, it is an oligomer or polymer surfactant. The surfactant preferably contains a fluoroalkylene group, and more preferably contains a perfluoroalkyl group.
The surfactant is preferably soluble in water. The term “soluble” as used herein means that the solubility at 23 ° C. is 0.05% by mass or more. Further, the surfactant is preferably dissolved in water by 0.1% by mass or more at 23 ° C., more preferably by 0.5% by mass or more, and further preferably by 1% by mass or more. As an upper limit, it is practical that it is 5 mass% or less.
The surfactant may contain at least one of a hydrophilic group, a lipophilic group, and an ultraviolet reactive group in the molecule.
Especially, in this invention, it is preferable that it is a perfluoroalkyl group containing carboxylate (anionic type) from a viewpoint of improving moisture resistance. The surfactant is preferably soluble in water or slightly soluble (for example, 0.1% by mass or more), but is insoluble in hydrocarbon solvents (for example, hexane and toluene). The surface tension of a 0.1% by mass solution with respect to water is preferably 10 mN / m or more, and more preferably 15 mN / m or more. The upper limit is practically 50 mN / m or less. The surface tension of a 0.1% solution with respect to PGME (propylene glycol monomethyl ether) is preferably more than 25 mN / m, and more preferably 26 mN / m or more. The upper limit is practically 70 mN / m or less.
　フッ素系界面活性剤としては、具体的には、いずれも商品名で、フロリナートＦ－Ｃ４３０、フロリナートＦ－Ｃ４３１（以上、住友スリーエム（株）製）；メガファックＦ－１４２Ｄ、メガファックＦ－１７１、メガファックＦ－１７２、メガファックＦ－１７３、メガファックＦ－１７７、メガファックＦ－１８３、メガファックＦ－４１０、メガファックＦ－４４４、メガファックＦ－４７０、メガファックＦ－４７１、メガファックＦ－４７８、メガファックＦ－４７９、メガファックＦ－４８０、メガファックＦ－４８２、メガファックＦ－４８３、メガファックＦ－４８４、メガファックＦ－４８６、メガファックＦ－４８７、メガファックＦ－４８９、メガファックＦ－５５３、メガファックＦ－５５４、メガファックＦ－５５６、メガファックＦ－５５７、メガファックＦ－５６９、メガファックＦ－５７５、メガファックＦ－７８０Ｆ、メガファックＦ－７８１Ｆ、メガファックＲ３０（以上、ＤＩＣ（株）製）；エフトップＥＦ３０１、エフトップＥＦ３０３、エフトップＥＦ３５１、エフトップＥＦ３５２（以上、新秋田化成（株）製）；サーフロンＳ３８１、サーフロンＳ３８２、サーフロンＳＣ１０１、サーフロンＳＣ１０５（以上、旭硝子（株）製）；Ｅ５８４４（（株）ダイキンファインケミカル研究所製）；ＢＭ－１０００、ＢＭ－１１００（ＢＭＣｈｅｍｉｅ社製）などが挙げられる。 Specific examples of the fluorosurfactants are trade names of Florinert F-C430, Florinato F-C431 (manufactured by Sumitomo 3M Co., Ltd.); Megafac F-142D, Megafac F-171 , Megafuck F-172, Megafuck F-173, Megafuck F-177, Megafuck F-183, Megafuck F-410, Megafuck F-444, Megafuck F-470, Megafuck F-471, Mega Fuck F-478, Mega Fuck F-479, Mega Fuck F-480, Mega Fuck F-482, Mega Fuck F-484, Mega Fuck F-484, Mega Fuck F-486, Mega Fuck F-487, Mega Fuck F -489, Megafuck F-553, Megafuck F-554, Megafuck F- 56, Megafuck F-557, Megafuck F-569, Megafuck F-575, Megafuck F-780F, Megafuck F-781F, Megafuck R30 (above DIC Corporation); F Top EF301, F Top EF303, Ftop EF351, Ftop EF352 (above, Shin-Akita Kasei Co., Ltd.); Surflon S381, Surflon S382, Surflon SC101, Surflon SC105 (above, Asahi Glass Co., Ltd.); E5844 (Daikin Fine Chemical Co., Ltd.) BM-1000, BM-1100 (manufactured by BMC Chemie), and the like.
　上記ＤＩＣ製のメガファックシリーズの界面活性剤でいうと、親水性が高いほど好ましく、フッ素原子含有量が多いほど好ましい。親水性の序列を一部のもので示すと、Ｆ－４１０＞Ｆ－４４４＞Ｆ－４３０，Ｆ－５１０，Ｆ－５１１，Ｆ－５６９，Ｆ－５５３，Ｆ－４７７，Ｆ－５５６＞＞Ｆ－５５４という序列となる。フッ素原子含有量については、Ｆ－４３０＞Ｆ－４１０，Ｆ－５１０，Ｆ－５１１＞Ｆ－４４４＞＞Ｆ－５６９，Ｆ－５５３，Ｆ－５５４，Ｆ－４７７，Ｆ－５５６という序列となる。親水性およびフッ素原子含有量において、少なくとも１つが　＞＞　の左側（より大きい）であることが好ましく、両者において　＞＞　の左側（より大きい）であることが好ましい。 In terms of the above-mentioned DIC MegaFac series surfactant, the higher the hydrophilicity, the higher the fluorine atom content. The hydrophilic order is shown in part as follows: F-410> F-444> F-430, F-510, F-511, F-569, F-553, F-477, F-556 >> The order is F-554. Regarding the fluorine atom content, the order of F-430> F-410, F-510, F-511> F-444 >> F-569, F-553, F-554, F-477, F-556 and Become. In the hydrophilicity and fluorine atom content, at least one is preferably the left side (greater than) >>, and in both cases, the left side (greater than) >> is preferable.
　界面活性剤は、なかでも、メガファック　Ｆ－４１０、Ｆ－４４４（いずれも商品名）が、後記実施例で行ったＰＣＴ後の密着性試験で良好な成績を示した。これに対し、Ｆ－５１０等は劣っていた。こうした観点からも、メガファック　Ｆ－４１０、Ｆ－４４４が特に好ましく、Ｆ－４４４がより特に好ましい。 Among the surfactants, Megafac F-410 and F-444 (both trade names) showed good results in the adhesion test after PCT performed in the examples described later. On the other hand, F-510 etc. were inferior. Also from this viewpoint, MegaFuck F-410 and F-444 are particularly preferable, and F-444 is more particularly preferable.
　界面活性剤の重量平均分子量は、３０，０００以下であることが好ましく、１０，０００以下であることがより好ましく、５，０００以下であることがさらに好ましく、４，０００以下であることが一層好ましい。下限値としては、５００以上であることが実際的である。
　界面活性剤の分子量は、特開２００１－２０８７３６号公報の実施例の例１に記載の方法、具体的には、移動相としてアサヒクリンＡＫ－２２５ ＳＥＣグレード１を用い、ＳＥＣ用カラムとして、ポリマーラボラトリー社製のＰＬゲル５μｍ ＭＩＸＥＤ－Ｅ（内径７．５ｍｍ、長さ３０ｃｍ）を２本直列に連結したものを用い、移動相流速を毎分１．０ｍｌ、カラム温度を３７℃とし、検出器として示差屈折率（ＲＩ）検出器を用い、極性を－とした方法によって測定される。 The weight average molecular weight of the surfactant is preferably 30,000 or less, more preferably 10,000 or less, further preferably 5,000 or less, and further preferably 4,000 or less. preferable. As a lower limit, it is practical that it is 500 or more.
The molecular weight of the surfactant is the same as that described in Example 1 of JP-A No. 2001-208736, specifically, Asahiklin AK-225 SEC grade 1 is used as the mobile phase, and the polymer is used as the SEC column. Two PL gels 5μm MIXED-E (inner diameter 7.5 mm, length 30 cm) manufactured by Laboratories were connected in series, the mobile phase flow rate was 1.0 ml / min, the column temperature was 37 ° C., and the detector Is measured by a method in which a differential refractive index (RI) detector is used and the polarity is −.
　界面活性剤の含有量は、膜形成用組成物の固形分中で０．０００８質量％以上であることが好ましく、０．００５質量％以上であることがより好ましく、０．０１質量％以上であることがさらに好ましい。上限としては、５質量％以下であることが好ましく、４質量％以下であることがより好ましく、２質量％以下であることがさらに好ましく、１質量％以下であってもよく、０．５質量％以下、０．１質量％以下、０．０１質量％以下であってもよい。
　組成物全体に対しては、０．０００１質量％以上であることが好ましく、０．０００５質量％以上であることがより好ましく、０．００１質量％以上であることがさらに好ましい。上限としては、５質量％以下であることが好ましく、２質量％以下であることがより好ましく、１質量％以下であることがさらに好ましい。
　ポリイミド前駆体１００質量部に対する、界面活性剤の含有量は、０．００１質量部以上であることが好ましく、０．００５質量部以上であることがより好ましく、０．０１質量部以上であることがさらに好ましい。上限としては、１５質量部以下であることが好ましく、１０質量部以下であることがより好ましく、５質量部以下であることがさらに好ましく、２質量部以下であることが一層好ましく、１質量部以下であることがより一層好ましく、０．５質量部以下であることがさらに一層好ましく、０．１質量部以下であることが特に一層好ましい。
　界面活性剤は１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。
　界面活性剤を上記の範囲に調節することで、膜形成用組成物の塗布膜の表面張力を下げベナードセルの形成ないしその影響を効果的に抑え、膜の面状をより良好にすることができるため好ましい。 The content of the surfactant is preferably 0.0008% by mass or more, more preferably 0.005% by mass or more, and 0.01% by mass or more in the solid content of the film-forming composition. More preferably it is. The upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 2% by mass or less, and may be 1% by mass or less, and may be 0.5% by mass. % Or less, 0.1 mass% or less, or 0.01 mass% or less.
It is preferable that it is 0.0001 mass% or more with respect to the whole composition, It is more preferable that it is 0.0005 mass% or more, It is further more preferable that it is 0.001 mass% or more. The upper limit is preferably 5% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less.
The content of the surfactant with respect to 100 parts by mass of the polyimide precursor is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and 0.01 parts by mass or more. Is more preferable. The upper limit is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, still more preferably 2 parts by mass or less, and 1 part by mass. Or less, more preferably 0.5 parts by mass or less, and particularly preferably 0.1 parts by mass or less.
Surfactant may contain only 1 type and may contain 2 or more types. When 2 or more types are included, the total amount is preferably within the above range.
By adjusting the surfactant to the above range, the surface tension of the coating film of the film-forming composition can be lowered, the formation of Benard cell or its effect can be effectively suppressed, and the surface state of the film can be improved. Therefore, it is preferable.
＜＜可塑剤＞＞
　本発明の実施形態に係る膜形成用組成物に用いられる可塑剤は、その種類等特に定めるものではなく、公知の可塑剤を用いることができる。
　具体的には、フタル酸エステル、アジピン酸エステル、トリメリット酸エステル、ポリエステル、リン酸エステル、クエン酸エステル、エポキシ系可塑剤、セバシン酸エステル、アゼライン酸エステル、マレイン酸エステル、安息香酸エステルが例示され、エポキシ系可塑剤が好ましい。
　エポキシ系可塑剤としては、エポキシ化オイル（エポキシ化大豆油、エポキシ化アマニ油）、エポキシ化脂肪酸アルキル（例えばオクチル）エステル等が挙げられる。
エポキシ系の可塑剤としては、分子内に下記式ｅ１またはｅ２のエポキシ基を有することが好ましい。
Figure JPOXMLDOC01-appb-C000012
 　　　　
　すなわち、可塑剤を構成するオレフィン鎖またはパラフィン鎖の末端または途中に式ｅ１が導入されたもの、あるいは鎖の途中に式ｅ２が導入されたもの、または、末端と途中の両方に両者が導入されたものが挙げられる。エポキシ系可塑剤は脂肪酸または油脂であることが好ましく、上記オレフィン鎖またはパラフィン鎖にカルボキシル基が導入されていることがより好ましい。ただし、このカルボキシル基はアルキル基等で一部または全部がエステル化されていてもよい。可塑剤は、炭素数が、３～４８であることが好ましく、４～３６がより好ましく、６～２４がさらに好ましい。
　具体的には、（株）ＡＤＥＫＡ、Ｏ－１８０Ａ、Ｏ－１３０Ｐ、Ｄ－３２、Ｄ－５５（いずれも商品名）が挙げられ、なかでもＯ－１８０Ａ、Ｏ－１３０Ｐ、Ｄ－３２が好ましい。 << Plasticizer >>
The plasticizer used in the film-forming composition according to the embodiment of the present invention is not particularly defined as to the type thereof, and a known plasticizer can be used.
Specific examples include phthalic acid esters, adipic acid esters, trimellitic acid esters, polyesters, phosphoric acid esters, citric acid esters, epoxy plasticizers, sebacic acid esters, azelaic acid esters, maleic acid esters, and benzoic acid esters. Epoxy plasticizers are preferred.
Examples of the epoxy plasticizer include epoxidized oil (epoxidized soybean oil, epoxidized linseed oil), epoxidized fatty acid alkyl (eg, octyl) ester, and the like.
The epoxy plasticizer preferably has an epoxy group of the following formula e1 or e2 in the molecule.
Figure JPOXMLDOC01-appb-C000012
That is, the one in which the formula e1 is introduced at the end or in the middle of the olefin chain or paraffin chain constituting the plasticizer, the one in which the formula e2 is introduced in the middle of the chain, or both are introduced at both the end and in the middle Can be mentioned. The epoxy plasticizer is preferably a fatty acid or an oil and fat, and more preferably a carboxyl group is introduced into the olefin chain or paraffin chain. However, this carboxyl group may be partially or fully esterified with an alkyl group or the like. The plasticizer preferably has 3 to 48 carbon atoms, more preferably 4 to 36, and still more preferably 6 to 24.
Specific examples include ADEKA Corporation, O-180A, O-130P, D-32, and D-55 (all trade names), and among them, O-180A, O-130P, and D-32 are preferable. .
　可塑剤は２５℃での粘度が４０ｍＰａ・ｓ以上であることが好ましく、１００ｍＰａ・ｓ以上であることがより好ましく、２００ｍＰａ・ｓ以上であることがさらに好ましい。上限としては、８００ｍＰａ・ｓ以下であることが実際的である。ＳＰ値は８以上であることが好ましく、８．５以上であることがより好ましい。上限は特にないが、９．５以下が実際的である。 The plasticizer preferably has a viscosity at 25 ° C. of 40 mPa · s or more, more preferably 100 mPa · s or more, and further preferably 200 mPa · s or more. The upper limit is practically 800 mPa · s or less. The SP value is preferably 8 or more, and more preferably 8.5 or more. There is no particular upper limit, but 9.5 or less is practical.
　可塑剤の含有量は、膜形成用組成物の固形分中で０．０００８質量％以上であることが好ましく、０．００５質量％以上であることがより好ましく、０．０１質量％以上であることがさらに好ましい。上限としては、５質量％以下であることが好ましく、４質量％以下であることがより好ましく、２質量％以下であることがさらに好ましく、１質量％以下であってもよく、０．５質量％以下、０．１質量％以下、０．０１質量％以下であってもよい。
　ポリイミド前駆体１００質量部に対する、可塑剤の含有量は、０．００１質量部以上であることが好ましく、０．００５質量部以上であることがより好ましく、０．０１質量部以上であることがさらに好ましい。上限としては、１５質量部以下であることが好ましく、１０質量部以下であることがより好ましく、５質量部以下であることがさらに好ましく、２質量部以下であることが一層好ましく、１質量部以下であることがより一層好ましく、０．５質量部以下であることがさらに一層好ましく、０．１質量部以下であることが特に一層好ましい。
　可塑剤は、１種のみでも、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。
　可塑剤を上記の範囲に設定することにより、膜面の乾燥を防ぎ、ベナードセルが継続するのを避け、塗布膜のより良好な面状を得るために好ましい。 The content of the plasticizer is preferably 0.0008% by mass or more, more preferably 0.005% by mass or more, and 0.01% by mass or more in the solid content of the film-forming composition. More preferably. The upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 2% by mass or less, and may be 1% by mass or less, and may be 0.5% by mass. % Or less, 0.1 mass% or less, or 0.01 mass% or less.
The content of the plasticizer with respect to 100 parts by mass of the polyimide precursor is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and 0.01 parts by mass or more. Further preferred. The upper limit is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, still more preferably 2 parts by mass or less, and 1 part by mass. Or less, more preferably 0.5 parts by mass or less, and particularly preferably 0.1 parts by mass or less.
Only one kind of plasticizer or two or more kinds of plasticizers may be contained. When 2 or more types are included, the total amount is preferably within the above range.
By setting the plasticizer within the above range, it is preferable to prevent the film surface from being dried, to prevent the Benard cell from continuing, and to obtain a better surface state of the coated film.
＜＜光重合開始剤＞＞
　膜形成用組成物には、光重合開始剤を含有させてもよい。光重合開始剤は、光ラジカル重合開始剤であることが好ましい。
　本発明で用いることができる光ラジカル重合開始剤としては、特に制限はなく、公知の光ラジカル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光ラジカル重合開始剤が好ましい。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。
　光ラジカル重合開始剤は、約３００～８００ｎｍ（好ましくは３３０～５００ｎｍ）の範囲内で少なくとも約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。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。 << photopolymerization initiator >>
The film-forming composition may contain a photopolymerization initiator. The photopolymerization initiator is preferably a radical photopolymerization initiator.
There is no restriction | limiting in particular as radical photopolymerization initiator which can be used by this invention, It can select suitably from well-known radical photopolymerization initiators. For example, a radical photopolymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
The radical 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. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
　光ラジカル重合開始剤としては、公知の化合物を任意に使用できる。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化合物、オキサジアゾール骨格を有する化合物、トリハロメチル基を有する化合物など）、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。これらの詳細については、特開２０１６－０２７３５７号公報の段落０１６５～０１８２の記載を参酌でき、この内容は本明細書に組み込まれる。 As the photo radical polymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, etc. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, etc. Can be mentioned. With respect to these details, reference can be made to the descriptions in paragraphs 0165 to 0182 of JP-A-2016-027357, 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 ketone compounds 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.
　光ラジカル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等の波長光源に吸収極大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 photoradical polymerization 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, 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 in which the absorption maximum wavelength is matched with a wavelength light source 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).
　光ラジカル重合開始剤として、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。オキシム化合物は、露光ラチチュード（露光マージン）が広く、かつ、光硬化促進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２０００－０８００６８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、特開２０１５－１８９８８３号公報の段落００８０～００８３の記載を参酌でき、これらの内容は本明細書に組み込まれる。 As the photo radical polymerization initiator, an oxime compound is more preferable. By using the oxime compound, the exposure latitude can be improved more effectively. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as a photocuring accelerator.
Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-080068, and compounds described in JP-A No. 2006-342166.
As preferable oxime compounds, the description in paragraphs 0080 to 0083 of JP-A-2015-189883 can be referred to, and the contents thereof are incorporated in the present specification.
　光ラジカル重合開始剤は、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、ホ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。 Photoradical polymerization 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.
　また、光ラジカル重合開始剤は、国際公開第２０１５／１２５４６９号の段落００４８～００５５に記載の化合物を用いることもできる。 Further, as the radical photopolymerization initiator, compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can be used.
　光重合開始剤を含む場合、その含有量は、膜形成用組成物の全固形分に対し０．１～３０質量％であることが好ましく、より好ましくは０．１～２０質量％であり、さらに好ましくは０．５～１５質量％であり、一層好ましくは１．０～１０質量％である。光重合開始剤は１種のみ含有していてもよいし、２種以上含有していてもよい。光重合開始剤を２種以上含有する場合は、その合計が上記範囲であることが好ましい。 When it contains a photopolymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the film-forming composition. More preferably, the content is 0.5 to 15% by mass, and still more preferably 1.0 to 10% by mass. The photoinitiator may contain only 1 type and may contain 2 or more types. When two or more photopolymerization initiators are contained, the total is preferably in the above range.
＜＜熱ラジカル重合開始剤＞＞
　膜形成用組成物は、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は、熱のエネルギーによってラジカルを発生し、重合性を有する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、ポリイミド前駆体の環化と共に、ポリイミド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２００８－０６３５５４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 radical polymerization initiator >>
The film forming composition may contain a thermal radical polymerization initiator.
The thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates a polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polyimide precursor can be advanced together with the cyclization of the polyimide precursor, so that 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-2008-063554.
　熱ラジカル重合開始剤を含む場合、その含有量は、膜形成用組成物の全固形分に対し０．１～３０質量％であることが好ましく、より好ましくは０．１～２０質量％であり、さらに好ましくは５～１５質量％である。熱ラジカル重合開始剤は１種のみ含有していてもよいし、２種以上含有していてもよい。熱ラジカル重合開始剤を２種以上含有する場合は、その合計が上記範囲であることが好ましい。 When the thermal radical polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the film-forming composition. More preferably, it is 5 to 15% by mass. The thermal radical polymerization initiator may contain only 1 type, and may contain 2 or more types. When two or more thermal radical polymerization initiators are contained, the total is preferably within the above range.
＜＜重合性化合物＞＞
＜＜＜ラジカル重合性化合物＞＞＞
　膜形成用組成物はラジカル重合性化合物を含むことが好ましい。
　ラジカル重合性化合物は、ラジカル重合性基を有する化合物を用いることができる。ラジカル重合性基としては、ビニルフェニル基、ビニル基、（メタ）アクリロイル基およびアリル基などのエチレン性不飽和結合を有する基が挙げられる。ラジカル重合性基は、（メタ）アクリロイル基が好ましい。 << polymerizable compound >>
<<< Radically polymerizable compound >>>
The film-forming composition preferably contains a radical polymerizable compound.
As the radical polymerizable compound, a compound having a radical polymerizable group can be used. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as vinylphenyl group, vinyl group, (meth) acryloyl group, and allyl group. The radical polymerizable group is preferably a (meth) acryloyl group.
　ラジカル重合性化合物が有するラジカル重合性基の数は、１個でもよく、２個以上でもよいが、ラジカル重合性化合物はラジカル重合性基を２個以上有することが好ましく、３個以上有することがより好ましい。上限は、１５個以下が好ましく、１０個以下がより好ましく、８個以下がさらに好ましい。 The number of radical polymerizable groups contained in the radical polymerizable compound may be one or two or more. However, the radical polymerizable compound preferably has two or more radical polymerizable groups, and preferably has three or more radical polymerizable groups. More preferred. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.
　ラジカル重合性化合物の分子量は、２０００以下が好ましく、１５００以下がより好ましく、９００以下がさらに好ましい。ラジカル重合性化合物の分子量の下限は、１００以上が好ましい。 The molecular weight of the radical polymerizable compound is preferably 2000 or less, more preferably 1500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical polymerizable compound is preferably 100 or more.
　膜形成用組成物は、現像性の観点から、重合性基を２個以上含む２官能以上のラジカル重合性化合物を少なくとも１種含むことが好ましく、３官能以上のラジカル重合性化合物を少なくとも１種含むことがより好ましい。また、２官能のラジカル重合性化合物と３官能以上のラジカル重合性化合物との混合物であってもよい。なお、ラジカル重合性化合物の官能基数は、１分子中におけるラジカル重合性基の数を意味する。 From the standpoint of developability, the film-forming composition preferably contains at least one bifunctional or higher radical polymerizable compound containing two or more polymerizable groups, and preferably contains at least one trifunctional or higher radical polymerizable compound. More preferably. Further, it may be a mixture of a bifunctional radically polymerizable compound and a trifunctional or higher functional radically polymerizable compound. In addition, the number of functional groups of the radical polymerizable compound means the number of radical polymerizable groups in one molecule.
　ラジカル重合性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である。また、ヒドロキシル基やアミノ基、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あるいはアミド類と、単官能若しくは多官能イソシアネート類ある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あるいはアミド類と、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あるいはアミド類と、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。具体例としては、特開２０１６－０２７３５７号公報の段落０１１３～０１２２の記載を参酌でき、これらの内容は本明細書に組み込まれる。 Specific examples of the radical polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. These are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. Also, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group and the like with monofunctional or polyfunctional isocyanates or epoxies, monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, 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 further a halogen group A substituted reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as thiol or tosyloxy group with 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. As specific examples, the description in paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification.
　また、ラジカル重合性化合物は、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、（メタ）アクリレート化した化合物、特公昭４８－０４１７０８号公報、特公昭５０－００６０３４号公報、特開昭５１－０３７１９３号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４８－０６４１８３号公報、特公昭４９－０４３１９１号公報、特公昭５２－０３０４９０号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結合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、上述以外の好ましいラジカル重合性化合物として、特開２０１０－１６０４１８号公報、特開２０１０－１２９８２５号公報、特許第４３６４２１６号公報等に記載される、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４６－０４３９４６号公報、特公平０１－０４０３３７号公報、特公平０１－０４０３３６号公報に記載の特定の不飽和化合物や、特開平０２－０２５４９３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、特開昭６１－０２２０４８号公報に記載のペルフルオロアルキル基を含む化合物を用いることもできる。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。 The radical polymerizable compound is also preferably a compound having a boiling point of 100 ° C. or higher under normal pressure. Examples include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol. Many products such as penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, JP-B-48-0417 Urethane (meth) acrylates as described in JP-A-8, JP-B-50-006034, JP-A-51-037193, JP-A-48-064183, JP-B49-043191 Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid described in JP-B-52-030490, and mixtures thereof Can do. Also suitable are the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970. In addition, polyfunctional (meth) acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated bond can also be exemplified.
Further, as other preferable radical polymerizable compounds other than those described above, there are fluorene rings described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and the like, and an ethylenically unsaturated bond. It is also possible to use a compound having two or more groups having a carbonic acid or a cardo resin.
Other examples include specific unsaturated compounds described in JP-B-46-043946, JP-B-01-040337, JP-B-01-040336, and JP-A-02-024933. And vinyl phosphonic acid compounds. Further, compounds containing a perfluoroalkyl group described in JP-A-61-022048 can also be 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、特開２０１５－０３４９６４号公報の段落００４８～００５１に記載の化合物も好ましく用いることができ、これらの内容は本明細書に組み込まれる。 In addition to the above, compounds described in paragraphs 0048 to 0051 of JP-A No. 2015-034964 can also be preferably used, and the contents thereof are incorporated in the present specification.
　また、特開平１０－０６２９８６号公報において式（１）および式（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、ラジカル重合性化合物として用いることができる。 Further, compounds described in JP-A-10-062986 as formulas (1) and (2) together with specific examples thereof, which are (meth) acrylated after adding ethylene oxide or propylene oxide to a polyfunctional alcohol, It can be used as a radically polymerizable compound.
　さらに、特開２０１５－１８７２１１号公報の段落０１０４～０１３１に記載の化合物も他のラジカル重合性化合物として用いることができ、これらの内容は本明細書に組み込まれる。 Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A No. 2015-187211 can also be used as other radical polymerizable compounds, the contents of which are incorporated herein.
　ラジカル重合性化合物としては、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、Ａ－ＴＭＭＴ：新中村化学工業社製）、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、Ａ－ＤＰＨ；新中村化学工業社製）、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残基または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。 Examples of the radical polymerizable compound include dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, as KAYARAD D-320; Nippon Kayaku ( A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) Acrylate (commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and their (meth) acryloyl group via an ethylene glycol residue or a propylene glycol residue A bonded structure is preferred. These oligomer types can also be used.
　ラジカル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、２３１、２３９、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（日本製紙社製）、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（新中村化学工業社製）、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 radical polymerizable compounds include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, and SR-209, manufactured by Sartomer, which is a bifunctional methacrylate having four ethyleneoxy chains. 231 and 239, DPCA-60 which is a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330 which is a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS- manufactured by Nippon Kayaku Co., Ltd. 10, UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H ( Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306 , AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF Corporation) and the like.
　ラジカル重合性化合物としては、特公昭４８－０４１７０８号公報、特開昭５１－０３７１９３号公報、特公平０２－０３２２９３号公報、特公平０２－０１６７６５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５８－０４９８６０号公報、特公昭５６－０１７６５４号公報、特公昭６２－０３９４１７号公報、特公昭６２－０３９４１８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、ラジカル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０１－１０５２３８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化合物を用いることもできる。 Examples of the radical polymerizable compound include urethane acrylates described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, JP-B-02-016765, and the like. Also suitable are urethane compounds having an ethylene oxide skeleton as described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418. Further, as radically polymerizable compounds, 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-01-105238 are used. It can also be used.
　ラジカル重合性化合物は、カルボキシル基、リン酸基等の酸基を有するラジカル重合性化合物であってもよい。酸基を有するラジカル重合性化合物は、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ル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ラジカル重合性化合物がより好ましい。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ル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ラジカル重合性化合物において、脂肪族ポリヒドロキシ化合物がペンタエリスリトールまたはジペンタエリスリトールである化合物である。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。
　酸基を有するラジカル重合性化合物の好ましい酸価は、０．１～４０ｍｇＫＯＨ／ｇであり、特に好ましくは５～３０ｍｇＫＯＨ／ｇである。ラジカル重合性化合物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 radically polymerizable compound may be a radically polymerizable compound having an acid group such as a carboxyl group or a phosphate group. The radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A radically polymerizable compound having a group is more preferable. Particularly preferably, in the radical polymerizable compound in which a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentayl. A compound that is erythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
A preferable acid value of the radically polymerizable compound 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 radically polymerizable compound is in the above range, the production and handling properties are excellent, and further, the developability is excellent. Also, the polymerizability is good.
　ラジカル重合性化合物として、単官能ラジカル重合性化合物を好ましく用いることができる。単官能ラジカル重合性化合物としては、ｎ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、カルビトール（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、Ｎ－メチロール（メタ）アクリルアミド、グリシジル（メタ）アクリレート、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）アクリレート等の（メタ）アクリル酸誘導体、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム等のＮ－ビニル化合物類、アリルグリシジルエーテル、ジアリルフタレート、トリアリルトリメリテート等のアリル化合物類等が好ましく用いられる。単官能ラジカル重合性化合物としては、露光前の揮発を抑制するため、常圧下で１００℃以上の沸点を持つ化合物も好ましい。 A monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound. Monofunctional radically polymerizable compounds include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl ( (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. ) Acrylic acid derivatives, N-vinyl pyrrolidone, N-vinyl compounds such as N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. Le compounds are preferably used. As the monofunctional radically polymerizable compound, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
＜＜＜上述したラジカル重合性化合物以外の重合性化合物＞＞＞
　膜形成用組成物は、上述したラジカル重合性化合物以外の重合性化合物をさらに含むことができる。上述したラジカル重合性化合物以外の重合性化合物としては、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；ベンゾオキサジン化合物が挙げられる。 <<< Polymerizable compound other than the above-mentioned radical polymerizable compound >>>
The film-forming composition can further contain a polymerizable compound other than the radically polymerizable compound described above. Examples of polymerizable compounds other than the above-mentioned radical polymerizable compounds include compounds having a hydroxymethyl group, alkoxymethyl group or acyloxymethyl group; epoxy compounds; oxetane compounds; benzoxazine compounds.
（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）、（ＡＭ４）または（ＡＭ５）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), (AM4) or (AM5) is preferable.
Figure JPOXMLDOC01-appb-C000013
 （式中、ｔは、１～２０の整数を示し、Ｒ１０４は炭素数１～２００のｔ価の有機基を示し、Ｒ１０５は、－ＯＲ１０６または、－ＯＣＯ－Ｒ１０７で示される基を示し、Ｒ１０６は、水素原子または炭素数１～１０の有機基を示し、Ｒ１０７は、炭素数１～１０の有機基を示す。）
Figure JPOXMLDOC01-appb-C000013
 (Wherein t represents an integer of 1 to 20, R 104 represents a t-valent organic group having 1 to 200 carbon atoms, and R 105 represents a group represented by —OR 106 or —OCO—R 107. R 106 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R 107 represents an organic group having 1 to 10 carbon atoms.)
Figure JPOXMLDOC01-appb-C000014
 （式中、Ｒ４０４は炭素数１～２００の２価の有機基を示し、Ｒ４０５は、－ＯＲ４０６または、－ＯＣＯ－Ｒ４０７で示される基を示し、Ｒ４０６は、水素原子または炭素数１～１０の有機基を示し、Ｒ４０７は、炭素数１～１０の有機基を示す。）
Figure JPOXMLDOC01-appb-C000014
 (Wherein R 404 represents a divalent organic group having 1 to 200 carbon atoms, R 405 represents a group represented by —OR 406 or —OCO—R 407 , and R 406 represents a hydrogen atom or a carbon atom. An organic group having 1 to 10 carbon atoms, and R 407 represents an organic group having 1 to 10 carbon atoms.)
Figure JPOXMLDOC01-appb-C000015
 （式中ｕは３～８の整数を示し、Ｒ５０４は炭素数１～２００のｕ価の有機基を示し、Ｒ５０５は、－ＯＲ５０６または、－ＯＣＯ－Ｒ５０７で示される基を示し、Ｒ５０６は、水素原子または炭素数１～１０の有機基を示し、Ｒ５０７は、炭素数１～１０の有機基を示す。）
Figure JPOXMLDOC01-appb-C000015
 (Wherein u represents an integer of 3 to 8, R 504 represents a u-valent organic group having 1 to 200 carbon atoms, and R 505 represents a group represented by —OR 506 or —OCO—R 507. R 506 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R 507 represents an organic group having 1 to 10 carbon atoms.)
　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（商品名、（株）三和ケミカル製）、２，６－ｄｉｍｅｔｈｏｘｙｍｅｔｈｙｌ－４－ｔ－ｂｕｔｙｌｐｈｅｎｏｌ、２，６－ｄｉｍｅｔｈｏｘｙｍｅｔｈｙｌ－ｐ－ｃｒｅｓｏｌ、２，６－ｄｉａｃｅｔｏｘｙｍｅｔｈｙｌ－ｐ－ｃｒｅｓｏｌなどが挙げられる。 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 Examples include 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, and the like. It is done.
　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.).
（エポキシ化合物（エポキシ基を有する化合物））
　エポキシ化合物としては、一分子中にエポキシ基を２以上有する化合物であることが好ましい。エポキシ基は、２００℃以下で架橋反応し、かつ、架橋に由来する脱水反応が起こらないため膜収縮が起きにくい。このため、エポキシ化合物を含有することは、組成物の低温硬化および膜の反りの抑制に効果的である。 (Epoxy compound (compound having an epoxy group))
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200 ° C. or less and does not cause a dehydration reaction derived from the cross-linking, so that film shrinkage hardly occurs. For this reason, containing an epoxy compound is effective for low-temperature curing of the composition and suppression of warpage of the film.
　エポキシ化合物は、ポリエチレンオキサイド基を含有することが好ましい。これにより、より弾性率が低下し、また反りを抑制することができる。ポリエチレンオキサイド基は、エチレンオキサイドの構成単位数が２以上のものを意味し、構成単位数が２～１５であることが好ましい。 The epoxy compound preferably contains a polyethylene oxide group. Thereby, an elasticity modulus falls more and also curvature can be suppressed. The polyethylene oxide group means that the number of structural units of ethylene oxide is 2 or more, and the number of structural units is preferably 2 to 15.
　エポキシ化合物の例としては、ビスフェノールＡ型エポキシ樹脂；ビスフェノールＦ型エポキシ樹脂；プロピレングリコールジグリシジルエーテル等のアルキレングリコール型エポキシ樹脂；ポリプロピレングリコールジグリシジルエーテル等のポリアルキレングリコール型エポキシ樹脂；ポリメチル（グリシジロキシプロピル）シロキサン等のエポキシ基含有シリコーンなどを挙げることができるが、これらに限定されない。具体的には、エピクロン（登録商標）８５０－Ｓ、エピクロン（登録商標）ＨＰ－４０３２、エピクロン（登録商標）ＨＰ－７２００、エピクロン（登録商標）ＨＰ－８２０、エピクロン（登録商標）ＨＰ－４７００、エピクロン（登録商標）ＥＸＡ－４７１０、エピクロン（登録商標）ＨＰ－４７７０、エピクロン（登録商標）ＥＸＡ－８５９ＣＲＰ、エピクロン（登録商標）ＥＸＡ－１５１４、エピクロン（登録商標）ＥＸＡ－４８８０、エピクロン（登録商標）ＥＸＡ－４８５０－１５０、エピクロンＥＸＡ－４８５０－１０００、エピクロン（登録商標）ＥＸＡ－４８１６、エピクロン（登録商標）ＥＸＡ－４８２２（以上商品名、大日本インキ化学工業（株）製）、リカレジン（登録商標）ＢＥＯ－６０Ｅ（商品名、新日本理化（株））、ＥＰ－４００３Ｓ、ＥＰ－４０００Ｓ（以上商品名、（株）ＡＤＥＫＡ製）などが挙げられる。この中でも、ポリエチレンオキサイド基を含有するエポキシ樹脂が、反りの抑制および耐熱性に優れる点で好ましい。例えば、エピクロン（登録商標）ＥＸＡ－４８８０、エピクロン（登録商標）ＥＸＡ－４８２２、リカレジン（登録商標）ＢＥＯ－６０Ｅは、ポリエチレンオキサイド基を含有するので好ましい。 Examples of the epoxy compound include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidyl Examples include, but are not limited to, epoxy group-containing silicones such as (roxypropyl) siloxane. Specifically, Epicron (registered trademark) 850-S, Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) EXA-4710, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-859CRP, Epicron (registered trademark) EXA-1514, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Rica Resin (registered trademark) ) BEO-60E (trade name, Shin Nippon Rika ( )), EP-4003S, EP-4000S (trade names, and the like (Ltd.) ADEKA). Among these, an epoxy resin containing a polyethylene oxide group is preferable in terms of suppressing warpage and excellent heat resistance. For example, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4822, and Licaredin (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.
（オキセタン化合物（オキセタニル基を有する化合物））
　オキセタン化合物としては、一分子中にオキセタン環を２つ以上有する化合物、３－エチル－３－ヒドロキシメチルオキセタン、１，４－ビス｛［（３－エチル－３－オキセタニル）メトキシ］メチル｝ベンゼン、３－エチル－３－（２－エチルヘキシルメチル）オキセタン、１，４－ベンゼンジカルボン酸－ビス［（３－エチル－３－オキセタニル）メチル］エステル等を挙げることができる。具体的な例としては、東亞合成株式会社製のアロンオキセタンシリーズ（例えば、ＯＸＴ－１２１、ＯＸＴ－２２１、ＯＸＴ－１９１、ＯＸＴ－２２３）が好適に使用することができ、これらは単独で、あるいは２種以上混合してもよい。 (Oxetane compound (compound having oxetanyl group))
Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, Examples include 3-ethyl-3- (2-ethylhexylmethyl) oxetane and 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester. As specific examples, Aron Oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be preferably used. Two or more kinds may be mixed.
（ベンゾオキサジン化合物（ベンゾオキサゾリル基を有する化合物））
　ベンゾオキサジン化合物は、開環付加反応に由来する架橋反応のため、硬化時に脱ガスが発生せず、さらに熱収縮を小さくして反りの発生が抑えられることから好ましい。 (Benzoxazine compound (compound having a benzoxazolyl group))
A benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur at the time of curing, and thermal contraction is further reduced to suppress warpage.
　ベンゾオキサジン化合物の好ましい例としては、Ｂ－ａ型ベンゾオキサジン、Ｂ－ｍ型ベンゾオキサジン（以上、商品名、四国化成工業社製）、ポリヒドロキシスチレン樹脂のベンゾオキサジン付加物、フェノールノボラック型ジヒドロベンゾオキサジン化合物が挙げられる。これらは単独で用いるか、あるいは２種以上混合してもよい。 Preferred examples of the benzoxazine compound include Ba type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydrobenzo An oxazine compound is mentioned. These may be used alone or in combination of two or more.
　重合性化合物を含有する場合、その含有量は、膜形成用組成物の全固形分に対して、０質量％超６０質量％以下であることが好ましい。下限は５質量％以上がより好ましい。上限は、５０質量％以下であることがより好ましく、３０質量％以下であることがさらに好ましい。
　重合性化合物は１種を単独で用いてもよいが、２種以上を混合して用いてもよい。２種以上を併用する場合にはその合計量が上記の範囲となることが好ましい。 When the polymerizable compound is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the film-forming composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
As the polymerizable compound, one kind may be used alone, or two or more kinds may be mixed and used. When using 2 or more types together, it is preferable that the total amount becomes said range.
＜＜マイグレーション抑制剤＞＞
　膜形成用組成物は、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膜形成用組成物の膜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、１，２，４－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、１Ｈ－テトラゾール、５－フェニル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 >>
The film forming composition preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress migration of metal ions derived from the metal layer (metal wiring) into the film of the film-forming composition.
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 1,2,4-triazole and benzotriazole, tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole 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２０１３－０１５７０１号公報の段落００９４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２０１１－０５９６５６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。 Examples of other migration inhibitors include rust inhibitors described in paragraph 0094 of JP2013-015701A, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656A. 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、下記化合物を挙げることができる。
Figure JPOXMLDOC01-appb-C000016
 Specific examples of the migration inhibitor include the following compounds.
Figure JPOXMLDOC01-appb-C000016
　膜形成用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、膜形成用組成物の全固形分に対して、０．０１～５．０質量％であることが好ましく、０．０５～２．０質量％であることがより好ましく、０．１～１．０質量％であることがさらに好ましい。
　マイグレーション抑制剤は１種のみでもよいし、２種以上であってもよい。マイグレーション抑制剤が２種以上の場合は、その合計が上記範囲であることが好ましい。 When the film forming 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 film forming composition. More preferably, the content is 0.05 to 2.0% by mass, and still more preferably 0.1 to 1.0% by mass.
Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more migration inhibitors, the total is preferably within the above range.
＜＜重合禁止剤＞＞
　膜形成用組成物は、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、４－メトキシフェノール、ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、ピロガロール、ｐ－ｔｅｒｔ－ブチルカテコール、１，４－ベンゾキノン、ジフェニル－ｐ－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－スルホプロピルアミノ）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、国際公開第２０１５／１２５４６９号の段落００３１～００４６に記載の化合物を用いることもできる。
　また、下記化合物を用いることができる（Ｍｅはメチル基である）。
Figure JPOXMLDOC01-appb-C000017
 　膜形成用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、膜形成用組成物の全固形分に対して、０．０１～５質量％であることが好ましく、０．０２～３質量％であることがより好ましく、０．０５～２．５質量％であることがさらに好ましい。
　重合禁止剤は１種のみでもよいし、２種以上であってもよい。重合禁止剤が２種以上の場合は、その合計が上記範囲であることが好ましい。 << Polymerization inhibitor >>
The film-forming composition preferably contains a polymerization inhibitor.
Examples of the polymerization inhibitor include hydroquinone, 4-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 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 WO2015 / 125469 can also be used.
Moreover, the following compound can be used (Me is a methyl group).
Figure JPOXMLDOC01-appb-C000017
 When the film-forming 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 film-forming composition, 0.02 It is more preferably from 3 to 3% by mass, and further preferably from 0.05 to 2.5% by mass.
Only one polymerization inhibitor may be used, or two or more polymerization inhibitors may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
＜金属接着性改良剤＞
　膜形成用組成物は、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。金属接着性改良剤としては、シランカップリング剤などが挙げられる。 <Metal adhesion improver>
The film-forming composition preferably contains a metal adhesion improver for improving adhesion with a metal material used for electrodes, wirings, and the like. Examples of metal adhesion improvers include silane coupling agents.
　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、国際公開第２０１１／０８０９９２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２０１４－０４１２６４号公報の段落００４５～００５２に記載の化合物、国際公開第２０１４／０９７５９４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種以上のシランカップリング剤を用いることも好ましい。また、シランカップリング剤は、下記化合物を用いることも好ましい。以下の式中、Ｅｔはエチル基を表す。
Figure JPOXMLDOC01-appb-C000018
 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 WO 2011/080992, and JP-A No. 2014-191252. The compounds described in paragraphs [0060] to [0061], the compounds described in paragraphs [0045] to [0052] of JP-A No. 2014-041264, and the compounds described in paragraph [0055] of WO2014 / 097594. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Moreover, it is also preferable to use the following compound for a silane coupling agent. In the following formula, Et represents an ethyl group.
Figure JPOXMLDOC01-appb-C000018
　また、金属接着性改良剤は、特開２０１４－１８６１８６号公報の段落００４６～００４９に記載の化合物、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を用いることもできる。 As the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used.
　金属接着性改良剤の含有量はポリイミド前駆体１００質量部に対して、好ましくは０．１～３０質量部であり、より好ましくは０．５～１５質量部の範囲であり、さらに好ましくは０．５～５質量部の範囲である。上記下限値以上とすることで硬化工程後の膜と金属層との接着性が良好となり、上記上限値以下とすることで硬化工程後の膜の耐熱性、機械特性が良好となる。金属接着性改良剤は１種のみでもよいし、２種以上であってもよい。２種以上用いる場合は、その合計が上記範囲であることが好ましい。 The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 0 to 100 parts by mass of the polyimide precursor. The range is from 5 to 5 parts by mass. Adhesion between the film after the curing step and the metal layer is improved by setting the above lower limit value or more, and heat resistance and mechanical properties of the film after the curing step are improved by setting the upper limit value or less. 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.
＜硬化促進剤＞
　膜形成用組成物は、硬化促進剤を含んでいてもよい。硬化促進剤は、熱硬化促進剤でも光硬化促進剤でもよい。
＜＜熱硬化促進剤＞＞
　熱硬化促進剤は、加熱により塩基を発生するものであることが好ましい。加熱温度（塩基発生温度）の好ましい範囲は後記加熱工程で規定される温度と同様である。第三級アミンまたは第四級アンモニウムカチオンとカルボン酸アニオンとの塩が好ましい。この第三級アミンと第四級アンモニウムカチオンは、下記式（Ｙ１－１）～式（Ｙ１－４）のいずれかで表されることが好ましい。
Figure JPOXMLDOC01-appb-C000019
 <Curing accelerator>
The film forming composition may contain a curing accelerator. The curing accelerator may be a heat curing accelerator or a photocuring accelerator.
<< Thermosetting accelerator >>
The thermosetting accelerator is preferably one that generates a base by heating. A preferable range of the heating temperature (base generation temperature) is the same as the temperature defined in the heating step described later. Salts of tertiary amines or quaternary ammonium cations and carboxylate anions are preferred. The tertiary amine and quaternary ammonium cation are preferably represented by any of the following formulas (Y1-1) to (Y1-4).
Figure JPOXMLDOC01-appb-C000019
　ＲＹ１は、ｎＹ価（ｎＹは、１～１２の整数）の有機基を表し、炭化水素基であることが好ましい。炭化水素基としては、アルカンを含む基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、アルケンを含む基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、芳香族炭化水素を含む基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）、またはそれらの組み合わせが挙げられる。ＲＹ１は中でも芳香族炭化水素基であることが好ましい。ＲＹ１は本発明の効果を損ねない範囲で、置換基Ｔ（ヒドロキシル基、カルボキシル基、アミノ基（ＮＲＮ ２）、アルコキシル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、アシル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、アルコキシカルボニル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、アシルオキシ基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、カルバモイル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、ＲＮは水素原子またはＲＹ２で表される基と同義の基である。）を有していてもよい。
　ＲＹ２～ＲＹ５は、それぞれ独立に、水素原子または炭化水素基（炭素数１～３６が好ましく、１～２４がより好ましく、１～１２がさらに好ましい）を表し、アルキル基（炭素数１～３６が好ましく、１～２４がより好ましく、１～２３がさらに好ましい）、アルケニル基（炭素数２～３６が好ましく、２～２４がより好ましく、２～２３がさらに好ましい）、アルキニル基（炭素数１～３６が好ましく、１～２４がより好ましく、１～２３がさらに好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）が好ましい。
　ＲＹ６はアルキル基（炭素数１～３６が好ましく、２～２４がより好ましく、４～１８がさらに好ましい）、アルケニル基（炭素数２～３６が好ましく、２～２４がより好ましく、４～１８がさらに好ましい）、アルキニル基（炭素数２～３６が好ましく、２～２４がより好ましく、４～１８がさらに好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）である。
　ｎＹは１～１２の整数を表し、１～６の整数が好ましく、１～３の整数がさらに好ましい。
　ｎＸは１～１２の整数を表し、１～６の整数が好ましく、１～３の整数がさらに好ましい。
　ＲＹ２～ＲＹ６において、アルキル基、アルケニル基、アルキニル基は環状でも鎖状でもよく、鎖状の場合は、直鎖状でも分岐状でもよい。アルキル基、アルケニル基、アルキニル基、アリール基には、基の途中に、あるいは母核との連結に、連結基Ｌ（カルボニル基、酸素原子、硫黄原子、ＮＲＮ、アルキレン基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、アルケニレン基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、アリーレン基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）、またはこれらの組合せに係る連結基）が介在していてもよい。
　ＲＹ２～ＲＹ６はそれぞれその２つ以上が互いに結合して環を形成してもよい。
　ＲＹ２～ＲＹ６は置換基Ｔを有していてもよい。 R Y1 represents an organic group having an n Y value (n Y is an integer of 1 to 12), and is preferably a hydrocarbon group. The hydrocarbon group includes an alkane-containing group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms), and an alkene group (preferably 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), a group containing an aromatic hydrocarbon (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 and further preferably 6 to 10), or a combination thereof. . R Y1 is preferably an aromatic hydrocarbon group. R Y1 is a substituent T (hydroxyl group, carboxyl group, amino group (NR N 2 ), alkoxyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and more preferably) as long as the effects of the present invention are not impaired. 3 is more preferable), an acyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms), an alkoxycarbonyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). Preferably 2 to 3), acyloxy group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms), carbamoyl group (preferably 1 to 12 carbon atoms, 1 to 6 carbon atoms). still more preferably, 1 to 3 is more preferred), R N is a group synonymous with the groups represented by hydrogen or R Y2.) may have.
R Y2 to R Y5 each independently represents a hydrogen atom or a hydrocarbon group (preferably having a carbon number of 1 to 36, more preferably 1 to 24, and still more preferably 1 to 12), and an alkyl group (having a carbon number of 1 to 36). 36 is preferred, 1 to 24 is more preferred, 1 to 23 is more preferred, an alkenyl group (preferably having 2 to 36 carbon atoms, more preferred is 2 to 24, still more preferred being 2 to 23), and an alkynyl group (having carbon numbers). 1 to 36 are preferred, 1 to 24 are more preferred, 1 to 23 are more preferred, and an aryl group (preferably having 6 to 22 carbon atoms, more preferred is 6 to 18 and even more preferred is 6 to 10).
R Y6 represents an alkyl group (preferably having a carbon number of 1 to 36, preferably 2 to 24, more preferably 4 to 18), or an alkenyl group (preferably having a carbon number of 2 to 36, more preferably 2 to 24, and 4 to 18). Is more preferable), an alkynyl group (preferably having 2 to 36 carbon atoms, more preferably 2 to 24, more preferably 4 to 18), and an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms). To 10 is more preferable).
n Y represents an integer of 1 to 12, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.
n X represents an integer of 1 to 12, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.
In R Y2 to R Y6 , the alkyl group, alkenyl group, and alkynyl group may be cyclic or chain-like, and in the case of a chain, it may be linear or branched. In the alkyl group, alkenyl group, alkynyl group, and aryl group, a linking group L (carbonyl group, oxygen atom, sulfur atom, NR N , alkylene group (carbon number 1 to 12 is preferable, 1 to 6 is more preferable, 1 to 3 is more preferable, an alkenylene group (2 to 12 carbon atoms is preferable, 2 to 6 is more preferable, and 2 to 3 are more preferable), an arylene group (carbon number). 6 to 22 is preferable, 6 to 18 is more preferable, and 6 to 10 is more preferable), or a linking group according to a combination thereof may be interposed.
Two or more of R Y2 to R Y6 may be bonded to each other to form a ring.
R Y2 to R Y6 may have a substituent T.
　ＲＹ７～ＲＹ１６は水素原子または置換基である。ただし、ＲＹ７～ＲＹ９のすべてが水素原子であることはない。置換基は有機基（炭素数１～３６が好ましく、１～２４がより好ましく、１～１２がさらに好ましい）であることが好ましく、連結基Ｌを介在することがあり、置換基Ｔを有していてもよい炭化水素基であることが好ましい。炭化水素基としてはＲＹ２の基が好ましい。
　式（Ｙ１－２）において、ＲＹ７およびＲＹ８はカルボキシアルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい；カルボキシル基の数は１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）が好ましい。ＲＹ９は芳香族基が好ましく、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）が好ましい。あるいは、芳香族基が置換したアルコキシカルボニル基が好ましい（アルコキシル基は炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい、芳香族基は炭素数６～２２が好ましく、６～１８がより好ましく、６～１４がさらに好ましい）。
　式（Ｙ１－２）の別の好ましい態様は、ＲＹ７およびＲＹ８がアルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）である。ＲＹ９は芳香族（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）を有する基が好ましく、芳香族基を有するアルコキシカルボニル基であることが好ましい。
　式（Ｙ１－３）において、ＲＹ１１およびＲＹ１３は水素原子であることが好ましい。ＲＹ１４およびＲＹ１５は２つが組み合わさって、＝Ｃ（ＮＲＮ ２）２の形の置換基になっていてもよい（　＝　は二重結合で窒素原子に結合することを意味する。）。
　式（Ｙ１－４）において、ＲＹ１３は水素原子であることが好ましく、ＲＹ１０、ＲＹ１１、ＲＹ１２、ＲＹ１６はアルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）であることが好ましい。このとき、ＲＹ１１とＲＹ１６、ＲＹ１０とＲＹ１２が結合して環を形成しビシクロ化合物となっていることが好ましい。具体的には、ジアザビシクロノネン、ジアザビシクロウンデセンが挙げられる。 R Y7 to R Y16 are a hydrogen atom or a substituent. However, not all of R Y7 to R Y9 are hydrogen atoms. The substituent is preferably an organic group (preferably having a carbon number of 1 to 36, more preferably 1 to 24, and still more preferably 1 to 12), which may intervene a linking group L and has a substituent T. It is preferably a hydrocarbon group that may be present. As the hydrocarbon group, an R Y2 group is preferred.
In the formula (Y1-2), R Y7 and R Y8 are carboxyalkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms; preferably 1 to 12 carboxyl groups). 1 to 6 are more preferable, and 1 to 3 are more preferable. R Y9 is preferably an aromatic group, and is preferably an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 and even more preferably 6 to 10). Alternatively, an alkoxycarbonyl group substituted with an aromatic group is preferred (the alkoxyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, and the aromatic group preferably has 6 to 22 carbon atoms). 6 to 18 are more preferable, and 6 to 14 are more preferable.
In another preferred embodiment of the formula (Y1-2), R Y7 and R Y8 are alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and even more preferably 1 to 3). R Y9 is preferably an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms), and is preferably an alkoxycarbonyl group having an aromatic group.
In the formula (Y1-3), R Y11 and R Y13 are preferably hydrogen atoms. R Y14 and R Y15 may be combined with each other to form a substituent of the form ═C (NR N 2 ) 2 (= means a double bond to a nitrogen atom).
In the formula (Y1-4), R Y13 is preferably a hydrogen atom, and R Y10 , R Y11 , R Y12 and R Y16 are alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms). ~ 3 are more preferred). At this time, R Y11 and R Y16 , R Y10 and R Y12 are preferably bonded to form a ring to form a bicyclo compound. Specific examples include diazabicyclononene and diazabicycloundecene.
　本実施形態において、上記式（Ｙ１－１）、式（Ｙ１－３）および式（Ｙ１－４）の第四級アンモニウムカチオンと対になる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-C000020
 　式（Ｘ１）において、ＥＷＧは、電子求引性基を表す。 In this embodiment, the carboxylic acid anion paired with the quaternary ammonium cation of the above formula (Y1-1), formula (Y1-3) and formula (Y1-4) is represented by the following formula (X1). It is preferable.
Figure JPOXMLDOC01-appb-C000020
 In the formula (X1), EWG represents an electron withdrawing group.
　本実施形態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、本実施形態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、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（以下、同じ）。 In the present embodiment, the electron-withdrawing group means a group in which Hammett's substituent constant σm exhibits a positive value. 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 embodiment is not limited to the substituent described in the said literature.
Examples of substituents in which σm has a positive value include 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 (hereinafter the same).
　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-C000021
 　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（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、アルケニル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）、ヒドロキシル基、またはカルボキシル基を表す。Ａｒは芳香族基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）を表す。Ｒｘ１～Ｒｘ３がアルキル基、アルケニル基、アリール基のとき、環を形成してもよい。これらのアルキル基、アルケニル基、アリール基、ならびに、Ａｒは、本発明の効果を損ねない範囲で、置換基Ｔを有していてもよい。なかでも、Ａｒは特にカルボキシル基（好ましくは１～３個）を有することが好ましい。＊は結合位置を表す。
　Ｌ１は連結基Ｌと同義の基であり、－ＣＲＸ２ＲＸ３－、－Ａｒ１－、これらを組み合わせた基であることが好ましい。Ａｒ１はアリーレン基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）である。
　Ｎｐは１～６の整数を表し、１～３の整数が好ましく、１または２がより好ましい。 EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
Figure JPOXMLDOC01-appb-C000021
 In formulas (EWG-1) to (EWG-6), R x1 to R x3 each independently represent a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and more preferably 1 to 3). More preferably), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and 6 to 6 carbon atoms). 10 is more preferable), and represents a hydroxyl group or a carboxyl group. Ar represents an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms). When R x1 to R x3 are an alkyl group, an alkenyl group, or an aryl group, a ring may be formed. These alkyl group, alkenyl group, aryl group, and Ar may have a substituent T as long as the effects of the present invention are not impaired. Among these, Ar preferably has a carboxyl group (preferably 1 to 3). * Represents a bonding position.
L 1 is a group having the same meaning as the linking group L, and is preferably —CR X2 R X3 —, —Ar 1 —, or a combination thereof. Ar 1 is an arylene group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms).
Np represents an integer of 1 to 6, preferably an integer of 1 to 3, and more preferably 1 or 2.
　熱硬化促進剤の分子量は、好ましくは、１００以上２０００未満であり、より好ましくは２００～１０００である。
　熱硬化促進剤の具体例として、国際公開第２０１５／１９９２１９号に記載の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を有するアンモニウム塩が例示され、これらの内容は本明細書に組み込まれる。 The molecular weight of the thermosetting accelerator is preferably 100 or more and less than 2000, and more preferably 200 to 1000.
Specific examples of the thermosetting accelerator include an acidic compound that generates a base when heated to 40 ° C. or higher described in International Publication No. 2015/199219 and an ammonium salt having an anion and an ammonium cation having a pKa1 of 0 to 4, These contents are incorporated herein.
　熱硬化促進剤を用いる場合、組成物における熱硬化促進剤の含有量は、組成物の全固形分に対し、０．０１～５０質量％であることが好ましい。下限は、０．０５質量％以上がより好ましく、０．１質量％以上がさらに好ましい。上限は、１０質量％以下がより好ましく、５質量％以下がさらに好ましい。
　熱硬化促進剤は、１種または２種以上を用いることができる。２種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。また、膜形成用組成物は、熱硬化促進剤を実質的に含まない構成とすることもできる。実質的に含まないとは、組成物の全固形分に対し、０．０１質量％未満であることをいい、０．００５質量％未満であることがより好ましい。 When the thermosetting accelerator is used, the content of the thermosetting accelerator in the composition is preferably 0.01 to 50% by mass with respect to the total solid content of the composition. The lower limit is more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more. The upper limit is more preferably 10% by mass or less, and further preferably 5% by mass or less.
1 type (s) or 2 or more types can be used for a thermosetting accelerator. When using 2 or more types, it is preferable that a total amount is the said range. Moreover, the composition for film formation can also be set as the structure which does not contain a thermosetting accelerator substantially. “Substantially free” means less than 0.01% by mass, more preferably less than 0.005% by mass, based on the total solid content of the composition.
＜＜光硬化促進剤＞＞
　膜形成用組成物は、光硬化促進剤を含んでいてもよい。光硬化促進剤は、露光により塩基を発生するものであることが好ましく、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ることが好ましい。露光により発生した塩基はポリイミド前駆体を加熱により硬化させる際の触媒として働くため、好適に用いることができる。露光の好ましい条件は後記露光工程で規定されるものと同様である。
　光硬化促進剤として公知のものを用いることができる。例えば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を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。 << Photocuring accelerator >>
The film forming composition may contain a photocuring accelerator. The photocuring accelerator is preferably one that 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 (base It is preferable that the substance generate | occur | produces an active substance). Since the base generated by exposure works as a catalyst for curing the polyimide precursor by heating, it can be suitably used. The preferable conditions for exposure are the same as those defined in the exposure step described later.
A well-known thing can be used as a photocuring accelerator. For example, the base component was neutralized by forming a salt, such as a transition metal compound complex, a compound having an ammonium salt structure, or an amidine moiety made latent by forming a salt with a carboxylic acid. Examples include ionic compounds, and nonionic compounds in which a base component is made latent by urethane bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds.
　光硬化促進剤としては、例えば、特開２００９－０８０４５２号公報および国際公開第２００９／１２３１２２号で開示されたような桂皮酸アミド構造を有する光硬化促進剤、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硬化促進剤、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硬化促進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硬化促進剤の構造を用いることができる。 Examples of the photocuring accelerator include a photocuring accelerator having a cinnamic amide structure as disclosed in JP2009-080452A and International Publication No. 2009/123122, JP2006-189591A and A photocuring accelerator having a carbamate structure as disclosed in Japanese Patent Application Laid-Open No. 2008-247747, an oxime structure and a carbamoyloxime structure as disclosed in Japanese Patent Application Laid-Open Nos. 2007-249013 and 2008-003581 Although a photocuring accelerator etc. are mentioned, it is not limited to these, In addition, the structure of a well-known photocuring accelerator can be used.
　その他、光硬化促進剤としては、特開２０１２－０９３７４６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、ならびに国際公開第２０１０／０６４６３１号の段落００５２に記載の化合物が例として挙げられる。 Other examples of the photocuring accelerator include compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-093746A, compounds described in paragraphs 0022 to 0069 of JP2013-194205A, Examples include the compounds described in paragraphs 0026 to 0074 of JP2013-204019A and the compound described in paragraph 0052 of WO2010 / 064631.
　光硬化促進剤の市販品としては、ＷＰＢＧ－２６６、ＷＰＢＧ－３００、ＷＰＧＢ－３４５、ＷＰＧＢ－１４０、ＷＰＢＧ－１６５、ＷＰＢＧ－０２７、ＰＢＧ－０１８、ＷＰＧＢ－０１５、ＷＰＢＧ－０４１、ＷＰＧＢ－１７２、ＷＰＧＢ－１７４、ＷＰＢＧ－１６６、ＷＰＧＢ－１５８、ＷＰＧＢ－０２５、ＷＰＧＢ－１６８、ＷＰＧＢ－１６７およびＷＰＢＧ－０８２（和光純薬（株）製）を用いることもできる。 Commercially available photocuring accelerators include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, PBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, and WPBG-082 (manufactured by Wako Pure Chemical Industries, Ltd.) can also be used.
　光硬化促進剤を用いる場合、組成物における光硬化促進剤の含有量は、組成物の全固形分に対し、０．１～５０質量％であることが好ましい。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。
　光硬化促進剤は、１種または２種以上を用いることができる。２種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 the photocuring accelerator is used, the content of the photocuring accelerator in the composition is preferably 0.1 to 50% by mass with respect to the total solid content of the 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.
1 type (s) or 2 or more types can be used for a photocuring accelerator. When using 2 or more types, it is preferable that a total amount is the said range.
＜その他の添加剤＞
　膜形成用組成物は、本発明の効果を損なわない範囲で、必要に応じて、各種の添加物、例えば、熱酸発生剤、増感色素、連鎖移動剤、上述した以外の界面活性剤、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 film-forming composition is within a range that does not impair the effects of the present invention, and various additives, for example, thermal acid generators, sensitizing dyes, chain transfer agents, surfactants other than those described above, A higher fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like can be blended. When blending these additives, the total blending amount is preferably 3% by mass or less of the solid content of the composition.
＜＜熱酸発生剤＞＞
　膜形成用組成物は、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、ポリイミド前駆体の環化を促進し膜の機械特性をより向上させる。熱酸発生剤は、特開２０１３－１６７７４２号公報の段落００５９に記載の化合物などが挙げられる。熱酸発生剤の加熱温度（酸発生温度）の好ましい範囲は後記加熱工程で規定される温度と同様である。 << thermal acid generator >>
The film forming composition may contain a thermal acid generator. The thermal acid generator generates an acid by heating, promotes cyclization of the polyimide precursor, and further improves the mechanical properties of the film. Examples of the thermal acid generator include compounds described in paragraph 0059 of JP2013-167742A. The preferable range of the heating temperature (acid generation temperature) of the thermal acid generator is the same as the temperature defined in the heating step described later.
　熱酸発生剤の含有量は、ポリイミド前駆体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。熱酸発生剤を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の環化が促進されるため、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、熱酸発生剤の含有量は、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質量部以下がさらに好ましい。
　熱酸発生剤は、１種のみ用いても、２種以上用いてもよい。２種以上用いる場合は、合計量が上記範囲となることが好ましい。 0.01 mass part or more is preferable with respect to 100 mass parts of polyimide precursors, and, as for content of a thermal acid generator, 0.1 mass part or more is more preferable. By containing 0.01 parts by mass or more of the thermal acid generator, the cross-linking reaction and the cyclization of the polyimide precursor are promoted, so that the mechanical properties and chemical resistance of the film can be further improved. In addition, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less from the viewpoint of electrical insulation of the film.
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.
＜＜増感色素＞＞
　膜形成用組成物は、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、熱硬化促進剤、熱ラジカル重合開始剤、光ラジカル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、熱硬化促進剤、熱ラジカル重合開始剤、光ラジカル重合開始剤は化学変化を起こして分解し、ラジカル、酸あるいは塩基を生成する。増感色素の詳細については、特開２０１６－０２７３５７号公報の段落０１６１～０１６３の記載を参酌でき、この内容は本明細書に組み込まれる。 << Sensitizing dye >>
The film-forming composition 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 a thermosetting accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, and the like, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a thermosetting accelerator, a thermal radical polymerization initiator, and a photo radical polymerization initiator cause a chemical change and are decomposed to generate radicals, acids, or bases. Details of the sensitizing dye can be referred to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein.
　膜形成用組成物が増感色素を含む場合、増感色素の含有量は、膜形成用組成物の全固形分に対し、０．０１～２０質量％であることが好ましく、０．１～１５質量％であることがより好ましく、０．５～１０質量％であることがさらに好ましい。増感色素は、１種単独で用いてもよいし、２種以上を併用してもよい。 When the film-forming composition contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass with respect to the total solid content of the film-forming composition, preferably 0.1 to The content is more preferably 15% by mass, and further preferably 0.5 to 10% by mass. A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.
＜＜連鎖移動剤＞＞
　膜形成用組成物は、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、および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 film forming composition 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, and 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.
　膜形成用組成物が連鎖移動剤を有する場合、連鎖移動剤の含有量は、膜形成用組成物の全固形分１００質量部に対し、０．０１～２０質量部が好ましく、１～１０質量部がより好ましく、１～５質量部がさらに好ましい。連鎖移動剤は１種のみでもよいし、２種以上であってもよい。連鎖移動剤が２種以上の場合は、その合計が上記範囲であることが好ましい。 When the film-forming composition has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the film-forming composition, and 1 to 10 parts by mass. Part is more preferable, and 1 to 5 parts by mass is more preferable. 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 in the above range.
＜＜高級脂肪酸誘導体＞＞
　膜形成用組成物は、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。
　膜形成用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、膜形成用組成物の全固形分に対して、０．１～１０質量％であることが好ましい。高級脂肪酸誘導体は１種のみでもよいし、２種以上であってもよい。高級脂肪酸誘導体が２種以上の場合は、その合計が上記範囲であることが好ましい。 << Higher fatty acid derivative >>
In order to prevent polymerization inhibition due to oxygen, the film-forming composition is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and is unevenly distributed on the surface of the composition in the process of drying after coating. May be.
When the film-forming 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 film-forming composition. Only one higher fatty acid derivative may be used, or two or more higher fatty acid derivatives may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.
＜その他の含有物質についての制限＞
　膜形成用組成物の水分含有量は、塗布面性状の観点から、５質量％未満が好ましく、１質量％未満がより好ましく、０．６質量％未満がさらに好ましい。 <Restrictions on other contained substances>
The water content of the film-forming composition is preferably less than 5% by weight, more preferably less than 1% by weight, and even more preferably less than 0.6% by weight from the viewpoint of the coating surface properties.
　膜形成用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未満がより好ましく、０．５質量ｐｐｍ未満がさらに好ましい。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、膜形成用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、膜形成用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、膜形成用組成物を構成する原料に対してフィルターろ過を行う、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 film-forming composition is preferably less than 5 ppm by weight (parts per million), more preferably less than 1 ppm by weight, and even more preferably less than 0.5 ppm by weight 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.
Further, as a method for reducing metal impurities that are unintentionally contained in the film-forming composition, the raw material having a low metal content is selected as the raw material constituting the film-forming 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, and distillation may be performed under a condition in which contamination is suppressed as much as possible.
　膜形成用組成物は、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未満がさらに好ましい。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未満がより好ましく、０．５質量ｐｐｍ未満がさらに好ましい。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、あるいは塩素イオンおよび臭素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。 The film-forming composition preferably has a halogen atom content of less than 500 ppm by weight, more preferably less than 300 ppm by weight, and even more preferably less than 200 ppm by weight from the viewpoint of wiring corrosivity. 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, More preferably, it is less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions is preferably in the above range.
　膜形成用組成物の収容容器としては従来公知の収容容器を用いることができる。また、収容容器としては、原材料や組成物中への不純物混入を抑制することを目的に、容器内壁を６種６層の樹脂で構成された多層ボトルや、６種の樹脂を７層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開２０１５－１２３３５１号公報に記載の容器が挙げられる。 As the container for the film forming composition, a conventionally known container can be used. In addition, as a container, for the purpose of suppressing contamination of raw materials and compositions, the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resins are made into a 7 layer structure. It is also preferred to use bottles that have been used. Examples of such a container include a container described in JP-A-2015-123351.
＜組成物の調製＞
　膜形成用組成物は、上記各成分を混合して調製することができる。混合方法は特に限定はなく、従来公知の方法で行うことができる。
　また、組成物中のゴミや微粒子等の異物を除去する目的で、フィルターを用いたろ過を行うことが好ましい。フィルター孔径は、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。フィルターの材質は、ポリテトラフロロエチレン、ポリエチレンまたはナイロンが好ましい。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。フィルターろ過工程では、複数種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。複数種のフィルターを使用する場合は、孔径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、各種材料を複数回ろ過してもよい。複数回ろ過する場合は、循環ろ過であってもよい。また、加圧してろ過を行ってもよい。加圧してろ過を行う場合、加圧する圧力は０．０５ＭＰａ以上０．３ＭＰａ以下が好ましい。
　フィルターを用いたろ過の他、吸着材を用いた不純物の除去処理を行ってもよい。フィルターろ過と吸着材を用いた不純物除去処理とを組み合わせてもよい。吸着材としては、公知の吸着材を用いることができる。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が挙げられる。 <Preparation of composition>
The film-forming composition can be prepared by mixing the above components. The mixing method is not particularly limited, and can be performed by a conventionally known method.
Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the composition. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. 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 using a plurality of types of filters, filters having different pore sizes or materials may be used in combination. Various materials may be filtered a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and filter. When the pressure is applied for filtration, the pressure applied is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
＜各工程＞
　本発明の製造方法は、膜の形成工程の後、露光する露光工程と、露光された膜に対して現像を行う現像工程とを有する態様とすることが好ましい。この現像の後、加熱することで露光された膜をさらに硬化させることができる。 <Each process>
The production method of the present invention preferably includes an exposure step of exposing after the film formation step and a development step of developing the exposed film. After this development, the exposed film can be further cured by heating.
　さらに積層体とするには、上記の膜の製造方法に従って、膜を形成した後、さらに、再度、膜の形成工程および加熱工程、膜形成工程、露光工程、および現像工程（必要によりさらに加熱工程）を、上記順に行うことが好ましい。特に、上記各工程を順に複数回、（好ましくは、２～５回、すなわち、合計で３～６回）行うことが好ましい。このように膜を積層することにより、所望の回数積層した積層体とすることができる。積層体とする際には、金属層を適用することも好ましい。 Further, to form a laminate, after forming the film according to the above-described film manufacturing method, the film forming process and heating process, the film forming process, the exposure process, and the developing process (further heating process if necessary) ) Are preferably performed in the above order. In particular, it is preferable to perform each of the above steps a plurality of times in order (preferably 2 to 5 times, that is, 3 to 6 times in total). By laminating the films in this way, it is possible to obtain a laminated body that is laminated a desired number of times. In forming a laminate, it is also preferable to apply a metal layer.
＜＜膜形成工程＞＞
　本発明の製造方法においては、上述したとおり、膜形成用組成物を基板に適用して膜状にする、膜形成工程を含むことが好ましい。
　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（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。ただし、本発明においては、基板は少なくとも一部に金属を含む部材（例えば、金属層が設けられた基板）である。本発明においては、スリットコートによって、金属表面に膜形成用組成物を適用することにより、上述した樹脂膜の面状を良好にすることができる。また、基板の形状は四角形であることが好ましく、矩形であることがより好ましい。 << Film formation process >>
As described above, the production method of the present invention preferably includes a film forming step in which the film forming composition is applied to a substrate to form a film.
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 films, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, plasma display panel (PDP) electrode plates, etc. are not particularly limited. However, in the present invention, the substrate is a member including at least a metal (for example, a substrate provided with a metal layer). In the present invention, by applying the film-forming composition to the metal surface by slit coating, the surface shape of the resin film described above can be improved. Further, the shape of the substrate is preferably a quadrangle, and more preferably a rectangle.
　本発明の膜の製造方法においては、膜形成用組成物を基板に適用する手段として、スリットコーターを用いることが好ましい。
　ノズルのスリット幅は２０μｍ以上であることが好ましく、５０μｍ以上であることがより好ましく、８０μｍ以上であることがさらに好ましい。上限としては、２５０μｍ以下であることが好ましく、２００μｍ以下であることがより好ましく、１５０μｍ以下であることがさらに好ましい。
　スリットギャップは、３０μｍ以上であることが好ましく、５０μｍ以上であることがより好ましく、７０μｍ以上であることがさらに好ましい。上限としては、２００μｍ以下であることが好ましく、１５０μｍ以下であることがより好ましく、１２０μｍ以下であることがさらに好ましい。
　スキャン速度は、１ｍｍ／ｓ以上であってもよく、１０ｍｍ／ｓ以上であることが好ましく、２０ｍｍ／ｓ以上であることがより好ましく、３０ｍｍ／ｓ以上であることがさらに好ましい。上限としては、５００ｍｍ／ｓ以下であることが好ましく、４００ｍｍ／ｓ以下であることがより好ましく、３００ｍｍ／ｓ以下であることがさらに好ましい。
　塗布膜厚は、１μｍ以上であることが好ましく、２μｍ以上であることがより好ましく、３μｍ以上であることがさらに好ましい。上限としては、１００μｍ以下であることが好ましく、８０μｍ以下であることがより好ましく、５０μｍ以下であることがさらに好ましい。 In the film production method of the present invention, it is preferable to use a slit coater as means for applying the film-forming composition to the substrate.
The slit width of the nozzle is preferably 20 μm or more, more preferably 50 μm or more, and further preferably 80 μm or more. As an upper limit, it is preferable that it is 250 micrometers or less, It is more preferable that it is 200 micrometers or less, It is further more preferable that it is 150 micrometers or less.
The slit gap is preferably 30 μm or more, more preferably 50 μm or more, and further preferably 70 μm or more. As an upper limit, it is preferable that it is 200 micrometers or less, It is more preferable that it is 150 micrometers or less, It is further more preferable that it is 120 micrometers or less.
The scanning speed may be 1 mm / s or more, preferably 10 mm / s or more, more preferably 20 mm / s or more, and further preferably 30 mm / s or more. As an upper limit, it is preferable that it is 500 mm / s or less, It is more preferable that it is 400 mm / s or less, It is further more preferable that it is 300 mm / s or less.
The coating film thickness is preferably 1 μm or more, more preferably 2 μm or more, and further preferably 3 μm or more. As an upper limit, it is preferable that it is 100 micrometers or less, It is more preferable that it is 80 micrometers or less, It is further more preferable that it is 50 micrometers or less.
＜＜乾燥工程＞＞
　本発明の製造方法においては、膜の形成後、溶剤を除去するために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～２０分が例示され、１分～１０分が好ましく、３分～７分がより好ましい。
　乾燥した膜の膜厚は、例えば、０．５μｍ以上とすることができ、１μｍ以上とすることができる。また、上限値としては、１００μｍ以下とすることができ、３０μｍ以下とすることもできる。この厚さは後記加熱工程の後の膜厚においても同様である。 << Drying process >>
In the manufacturing method of this invention, after forming a film | membrane, the process of drying in order to remove a solvent may be included. A preferred drying temperature is 50 to 150 ° C, more preferably 70 to 130 ° C, and further preferably 90 to 110 ° C. Examples of the drying time include 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
The film thickness of the dried film can be, for example, 0.5 μm or more, and can be 1 μm or more. Moreover, as an upper limit, it can be set to 100 micrometers or less, and can also be set to 30 micrometers or less. This thickness is the same in the film thickness after the heating step described later.
＜＜露光工程＞＞
　露光工程における露光量は、例えば、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。
　露光波長は、光源との関係でいうと、（１）半導体レーザー（波長　８３０ｎｍ、５３２ｎｍ、４８８ｎｍ、４０５ｎｍ　ｅｔｃ．）、（２）メタルハライドランプ、（３）高圧水銀灯、ｇ線（波長　４３６ｎｍ）、ｈ線（波長　４０５ｎｍ）、ｉ線（波長　３６５ｎｍ）、ブロード（ｇ，ｈ，ｉ線の３波長）、（４）エキシマレーザー、ＫｒＦエキシマレーザー（波長　２４８ｎｍ）、ＡｒＦエキシマレーザー（波長　１９３ｎｍ）、Ｆ２エキシマレーザー（波長　１５７ｎｍ）、（５）極端紫外線；ＥＵＶ（波長　１３．６ｎｍ）、（６）電子線等が挙げられる。本発明の膜形成用組成物については、特に高圧水銀灯による露光が好ましく、なかでも、ｉ線による露光が好ましい。これにより、特に高い露光感度が得られうる。 << Exposure process >>
For example, the exposure dose in the exposure step is preferably 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.
The exposure wavelength is (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h. Line (wavelength 405 nm), i line (wavelength 365 nm), broad (3 wavelengths of g, h, i line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, and the like. For the film-forming composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferable, and i-line exposure is particularly preferable. Thereby, particularly high exposure sensitivity can be obtained.
＜＜現像工程＞＞
　現像工程においける現像方法は、所望のパターンを形成できれば特に制限は無く、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。
　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）が除去されるのであれば、特に制限なく使用できる。現像液は、有機溶剤を含むことが好ましい。本発明では、現像液は、ＣｌｏｇＰ値が－１～５の有機溶剤を含むことが好ましく、ＣｌｏｇＰ値が０～３の有機溶剤を含むことがより好ましい。ＣｌｏｇＰ値は、ＣｈｅｍＢｉｏＤｒａｗにて構造式を入力して計算値として求めることができる。
　有機溶剤は、エステル類として、例えば、酢酸エチル、酢酸－ｎ－ブチル、ギ酸アミル、酢酸イソアミル、酢酸イソブチル、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、ならびに、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、ならびに、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、ならびに、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、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。
　本発明では、特にシクロペンタノン、γ－ブチロラクトンが好ましく、シクロペンタノンがより好ましい。
　現像液は、５０質量％以上が有機溶剤であることが好ましく、７０質量％以上が有機溶剤であることがより好ましく、９０質量％以上が有機溶剤であることがさらに好ましい。また、現像液は、１００質量％が有機溶剤であってもよい。 << Development process >>
The development method in the development step is not particularly limited as long as a desired pattern can be formed, and for example, development methods such as paddle, spray, immersion, and ultrasonic waves can be adopted.
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. The developer preferably contains an organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of −1 to 5, more preferably an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkyl oxyacetate alkyl (eg, methyl oxyoxyacetate, alkyl oxyacetate ethyl, alkyl oxyacetate butyl (eg methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate), alkyl esters of 3-alkyloxypropionic acid (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, 3-methoxypropyl) Ethyl pionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 -Propyl alkyloxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyl Methyl oxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate , Pyruvic acid Cyl, 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, and the like As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. A preferred example of the sulfoxide is dimethyl sulfoxide.
In the present invention, cyclopentanone and γ-butyrolactone are particularly preferable, and cyclopentanone is more preferable.
The developer is preferably 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and even more preferably 90% by mass or more of an organic solvent. Further, 100% by mass of the developer may be an organic solvent.
　現像時間としては、１０秒～５分が好ましい。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、膜形成用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～１分が好ましい。 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, rinsing can be performed using a solvent contained in the film-forming composition. The rinse time is preferably 5 seconds to 1 minute.
＜＜加熱工程＞＞
　加熱工程では、ポリイミド前駆体の環化反応が進行する。加熱工程における加熱温度（最高加熱温度）としては、５０～５００℃が好ましく、８０～４５０℃がより好ましく、１４０～４００℃がさらに好ましく、１６０～３５０℃が一層好ましい。
　加熱は、加熱開始時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、２～１０℃／分がより好ましく、３～１０℃／分がさらに好ましい。昇温速度を２℃／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、膜の残存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温度のことをいう。例えば、膜形成用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、膜形成用組成物に含まれる溶剤の沸点よりも、３０～２００℃低い温度から徐々に昇温させることが好ましい。
　加熱時間（最高加熱温度での加熱時間）は、１０～３６０分であることが好ましく、２０～３００分であることがより好ましく、３０～２４０分であることがさらに好ましい。
　特に多層の積層体を形成する場合、膜の層間の密着性の観点から、加熱温度は１８０℃～３２０℃で加熱することが好ましく、１８０℃～２６０℃で加熱することがより好ましい。その理由は定かではないが、この温度とすることで、層間のポリイミド前駆体のエチニル基同士が架橋反応を進行しているためと考えられる。 << Heating process >>
In the heating step, the cyclization reaction of the polyimide precursor proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 500 ° C, more preferably 80 to 450 ° C, still more preferably 140 to 400 ° C, and still more preferably 160 to 350 ° C.
Heating is preferably performed at a rate of temperature increase of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min. By setting the temperature increase rate to 2 ° C./min or more, it is possible to prevent excessive volatilization of the amine while securing productivity, and by setting the temperature increase rate to 12 ° C./min or less, the film remains. Stress can be relaxed.
The temperature at the start of heating is preferably 20 ° C to 150 ° C, more preferably 20 ° C to 130 ° C, and further preferably 25 ° C to 120 ° C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the maximum heating temperature. For example, when the film-forming composition is applied onto a substrate and then dried, the temperature after this drying is performed, for example, a temperature 30 to 200 ° C. lower than the boiling point of the solvent contained in the film-forming composition. It is preferable that the temperature is gradually raised.
The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes.
In particular, when a multilayer laminate is formed, the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between the layers of the film. Although the reason is not certain, it is considered that the ethynyl group of the polyimide precursor between layers proceeds with a crosslinking reaction at this temperature.
　加熱は段階的に行ってもよい。例として、２５℃から１８０℃まで３℃／分で昇温し、１８０℃にて６０分保持し、１８０℃から２００℃まで２℃／分で昇温し、２００℃にて１２０分保持する、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℃であることがさらに好ましい。この前処理工程においては、米国特許第９１５９５４７号明細書に記載のように紫外線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とよく、１５秒～３０分間がより好ましい。前処理は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。
　さらに、加熱後冷却してもよく、この場合の冷却速度としては、１～５℃／分であることが好ましい。 Heating may be performed in stages. For example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min, held at 180 ° C. for 60 minutes, heated from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. You may perform the pre-processing process of these. The heating temperature as the pretreatment step is preferably 100 to 200 ° C, more preferably 110 to 190 ° C, and further preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the characteristics of the film. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, the pretreatment step 1 may be performed in the range of 100 to 150 ° C., and then the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
Further, it may be cooled after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
　加熱工程は、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ポリイミド前駆体の分解を防ぐ点で好ましい。酸素濃度は、５０ｐｐｍ（体積比）以下が好ましく、２０ｐｐｍ（体積比）以下がより好ましい。 The heating step is preferably performed in a low oxygen concentration atmosphere by flowing an inert gas such as nitrogen, helium, or argon in order to prevent decomposition of the polyimide precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
＜＜金属層形成工程＞＞
　現像処理後の膜形成用組成物の膜の表面に金属層を適用し形成してもよい。
　金属層としては、特に限定なく、既存の金属種を使用することができ、銅、アルミニウム、ニッケル、バナジウム、チタン、クロム、コバルト、金およびタングステンが例示され、銅およびアルミニウムがより好ましく、銅がさらに好ましい。
　金属層の形成方法は、特に限定なく、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号公報に記載された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、電解メッキ、無電解メッキ、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、スパッタリング、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メッキを組み合わせたパターニング方法が挙げられる。
　金属層の厚さとしては、最も厚肉部で、０．１～５０μｍが好ましく、１～１０μｍがより好ましい。 << Metal layer formation process >>
You may apply and form a metal layer on the surface of the film | membrane of the film forming composition after image development processing.
There are no particular limitations on the metal layer, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferable, and copper is more preferable. Further preferred.
The method for forming the 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, electrolytic plating, electroless plating, etching, printing, and a combination of these can be considered. More specifically, a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating may be mentioned.
The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm at the thickest part.
＜＜積層工程＞＞
　積層工程は、膜形成用組成物の膜または金属層の表面に、再度、上記膜形成工程および加熱工程、あるいは膜形成工程、上記露光工程、および上記現像工程を、上記順に行うことを含んでもよい。積層工程には、さらに、上記乾燥工程や加熱工程等を含んでいてもよい。
　積層工程後、さらに積層工程を行う場合には、上記加熱工程後、上記露光工程後、または、上記金属層形成工程後に、さらに、表面活性化処理工程を行ってもよい。表面活性化処理としては、プラズマ処理が例示される。
　上記積層工程は、２～５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、樹脂層／金属層／樹脂層／金属層／樹脂層／金属層のような、樹脂層が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。
　すなわち、金属層を設けた後、さらに、上記金属層を覆うように、上記膜形成用組成物の膜形成工程および加熱工程、あるいは、膜形成用組成物には、上記膜形成工程、上記露光工程、および、上記現像工程（必要によりさらに加熱工程）を、上記順に行うことが好ましい。膜形成用組成物の膜（樹脂）を積層する積層工程と、金属膜形成工程を交互に行うことにより、膜形成用組成物の膜（樹脂層）と金属層を交互に積層することができる。 << Lamination process >>
The laminating step may include performing the film forming step and the heating step, or the film forming step, the exposure step, and the developing step in the above order again on the surface of the film or metal layer of the film forming composition. Good. The laminating step may further include the drying step and the heating step.
When a lamination process is further performed after the lamination process, a surface activation treatment process may be further performed after the heating process, the exposure process, or the metal layer formation process. An example of the surface activation treatment is plasma treatment.
The lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
For example, the resin layer / metal layer / resin layer / metal layer / resin layer / metal layer has a resin layer structure of 3 to 7 layers, more preferably 3 to 5 layers.
That is, after the metal layer is provided, the film forming step and the heating step of the film forming composition, or the film forming composition, the exposure step is performed so as to cover the metal layer. It is preferable to carry out the steps and the above-described development step (further heating step if necessary) in the above order. By alternately performing the laminating step of laminating the film (resin) of the film forming composition and the metal film forming step, the film (resin layer) and the metal layer of the film forming composition can be alternately laminated. .
　本発明の製造方法で得られる膜形成用組成物の膜を再配線層用層間絶縁膜の形成に用いた半導体デバイスの具体例としては、特開２０１６－０２７３５７号公報の段落０２１３～０２１８の記載および図１の記載を参酌でき、これらの内容は本明細書に組み込まれる。 Specific examples of the semiconductor device in which the film of the film forming composition obtained by the production method of the present invention is used for forming the interlayer insulating film for the rewiring layer are described in paragraphs 0213 to 0218 of JP-A-2016-027357. And the description of FIG. 1 can be referred to, the contents of which are incorporated herein.
　本発明では、また、本発明の膜にチップを配置する半導体デバイスの製造方法を開示する。さらに、本発明の積層体にチップを配置する半導体デバイスの製造方法を開示する。ここでのチップおよびチップの配置方法については、半導体の３次元実装技術、傳田 精一、ＣＱ出版社、２０１１年６月１日発行の記載を参酌でき、これらの内容は本明細書に組み込まれる。 The present invention also discloses a method for manufacturing a semiconductor device in which a chip is arranged on the film of the present invention. Furthermore, the manufacturing method of the semiconductor device which arrange | positions a chip | tip to the laminated body of this invention is disclosed. Regarding the chip and the chip arrangement method here, the description of the semiconductor three-dimensional mounting technology, Junichi Hamada, CQ Publisher, issued on June 1, 2011 can be referred to, and the contents thereof are incorporated in this specification. .
　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.
＜合成例１＞
［ピロメリット酸二無水物、４，４’－ジアミノジフェニルエーテルおよび３－ヒドロキシベンジルアルコールからのポリイミド前駆体樹脂Ａ－１の合成］
　１４．０６ｇ（６４．５ミリモル）のピロメリット酸二無水物（１４０℃で１２時間乾燥）と、１６．３３ｇ（１３１．５８ミリモル）の３－ヒドロキシベンジルアルコールとを、５０ｍＬのＮ－メチルピロリドンに懸濁させ、モレキュラーシーブで乾燥させた。懸濁液を１００℃で３時間加熱した。加熱してから数分後に透明な溶液が得られた。反応混合物を室温に冷却し、２１．４３ｇ（２７０．９ミリモル）のピリジンおよび９０ｍＬのＮ－メチルピロリドンを加えた。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）の塩化チオニルを１０分かけて加えた。塩化チオニルを加えている間、粘度が増加した。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’－ジアミノジフェニルエーテル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リットルの水の中でポリイミド前駆体樹脂を沈殿させ、水－ポリイミド前駆体樹脂混合物を５０００ｒｐｍの速度で１５分間撹拌した。ポリイミド前駆体樹脂を濾過して除き、４リットルの水の中で再度３０分間撹拌し再び濾過した。次いで、得られたポリイミド前駆体樹脂を減圧下で、４５℃で３日間乾燥した。このポリイミド前駆体は、Ｍｗ＝２２８００、Ｍｎ＝８１００であった。 <Synthesis Example 1>
[Synthesis of polyimide precursor resin A-1 from pyromellitic dianhydride, 4,4′-diaminodiphenyl ether and 3-hydroxybenzyl alcohol]
14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C. for 12 hours) and 16.33 g (131.58 mmol) of 3-hydroxybenzyl alcohol were mixed with 50 mL of N-methylpyrrolidone. And dried with molecular sieves. The suspension was heated at 100 ° C. for 3 hours. A few minutes after heating, a clear solution was obtained. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) pyridine and 90 mL N-methylpyrrolidone were added. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of thionyl chloride was added over 10 minutes while maintaining the temperature at −10 ± 4 ° C. The viscosity increased during the addition of thionyl chloride. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 11.08 g (58.7 mmol) of 4,4′-diaminodiphenyl ether 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 polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor resin was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried at 45 ° C. under reduced pressure for 3 days. This polyimide precursor had Mw = 22800 and Mn = 8100.
＜合成例２＞
［オキシジフタル酸二無水物、２－ヒドロキシエチルメタクリレートおよび４，４’－ジアミノジフェニルエーテルからのポリイミド前駆体樹脂Ａ－２の合成］
　撹拌機、コンデンサーおよび内部温度計を取りつけた平底ジョイントを備えた乾燥反応器中で水分を除去しながら、オキシジフタル酸二無水物２０．０ｇ（６４．５ミリモル）をジグリム１４０ｍＬ中に懸濁させた。２－ヒドロキシエチルメタクリレート１６．８ｇ（１２９ミリモル）、ヒドロキノン０．０５ｇおよびピリジン１０．７ｇ（１３５ミリモル）を続いて添加し、６０℃の温度で１８時間撹拌した。次いで、混合物を－２０℃まで冷却した後、塩化チオニル１６．１ｇ（１３５．５ミリモル）を９０分かけて滴下した。ピリジニウムヒドロクロリドの白色沈澱が得られた。次いで、混合物を室温まで温め、２時間撹拌した後、ピリジン９．７ｇ（１２３ミリモル）およびＮ－メチルピロリドン（ＮＭＰ）２５ｍＬを添加し、透明溶液を得た。次いで、得られた透明液体に、４，４’－ジアミノジフェニルエーテル１１．８ｇ（５８．７ミリモル）をＮＭＰ１００ｍＬ中に溶解させたものを、１時間かけて滴下により添加した。４，４’－ジアミノジフェニルエーテルを添加している間、粘度が増加した。次いで、メタノール５．６ｇ（１７．５ミリモル）と３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシトルエン０．０５ｇを加え、混合物を２時間撹拌した。次いで、４リットルの水の中でポリイミド前駆体樹脂を沈殿させ、水－ポリイミド前駆体樹脂混合物を５００ｒｐｍの速度で１５分間撹拌した。ポリイミド前駆体樹脂を濾過して除き、４リットルの水の中で再度３０分間撹拌し再び濾過した。次いで、得られたポリイミド前駆体樹脂を減圧下で、４５℃で３日間乾燥した。このポリイミド前駆体は、Ｍｗ＝２３５００、Ｍｎ＝８８００であった。 <Synthesis Example 2>
[Synthesis of polyimide precursor resin A-2 from oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
20.0 g (64.5 mmol) of oxydiphthalic dianhydride was suspended in 140 mL of diglyme while removing moisture in a dry reactor equipped with a stirrer, condenser and internal thermometer. . 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 18 hours. Next, after the mixture was cooled to −20 ° C., 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature and stirred for 2 hours, after which 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to give a clear solution. Next, a solution obtained by dissolving 11.8 g (58.7 mmol) of 4,4′-diaminodiphenyl ether in 100 mL of NMP was added dropwise to the obtained transparent liquid over 1 hour. The viscosity increased during the addition of 4,4'-diaminodiphenyl ether. Subsequently, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred for 15 minutes at a speed of 500 rpm. The polyimide precursor resin was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried at 45 ° C. under reduced pressure for 3 days. This polyimide precursor had Mw = 23500 and Mn = 8800.
＜合成例３＞
［オキシジフタル酸二無水物、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、２－ヒドロキシエチルメタクリレートおよび４，４’－ジアミノジフェニルエーテルからのポリイミド前駆体樹脂Ａ－３の合成］
　撹拌機、コンデンサーおよび内部温度計を取りつけた平底ジョイントを備えた乾燥反応器中で水分を除去しながら、オキシジフタル酸二無水物１０．０ｇ（３２．２ミリモル）と３，３’，４，４’－ビフェニルテトラカルボン酸二無水物９．４７ｇ（３２．３ミリモル）をジグリム１４０ｍＬ中に懸濁させた。２－ヒドロキシエチルメタクリレート１６．８ｇ（１２９ミリモル）、ヒドロキノン０．０５ｇおよびピリジン１０．７ｇ（１３５ミリモル）を続いて添加し、６０℃の温度で１８時間撹拌した。次いで、混合物を－２０℃まで冷却した後、塩化チオニル１６．１ｇ（１３５．５ミリモル）を９０分かけて滴下した。ピリジニウムヒドロクロリドの白色沈澱が得られた。次いで、混合物を室温まで温め、２時間撹拌した後、ピリジン９．７ｇ（１２３ミリモル）およびＮ－メチルピロリドン（ＮＭＰ）２５ｍＬを添加し、透明溶液を得た。次いで、得られた透明液体に、４，４’－ジアミノジフェニルエーテル１１．８ｇ（５８．７ミリモル）をＮＭＰ１００ｍＬ中に溶解させたのもを、１時間かけて滴下により添加した。４，４’－ジアミノジフェニルエーテルを添加している間、粘度が増加した。次いで、メタノール５．６ｇ（１７．５ミリモル）と３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシトルエン０．０５ｇを加え、混合物を２時間撹拌した。次いで、４リットルの水の中でポリイミド前駆体樹脂を沈殿させ、水－ポリイミド前駆体樹脂混合物を５００ｒｐｍの速度で１５分間撹拌した。ポリイミド前駆体樹脂を濾過して除き、４リットルの水の中で再度３０分間撹拌し再び濾過した。次いで、得られたポリイミド前駆体樹脂を減圧下で、４５℃で３日間乾燥した。このポリイミド前駆体は、Ｍｗ＝２４３００、Ｍｎ＝９５００であった。 <Synthesis Example 3>
[Synthesis of polyimide precursor resin A-3 from oxydiphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
While removing moisture in a dry reactor equipped with a flat bottom joint fitted with a stirrer, condenser and internal thermometer, 10.0 g (32.2 mmol) of oxydiphthalic dianhydride and 3,3 ′, 4,4 9.47 g (32.3 mmol) of '-biphenyltetracarboxylic dianhydride was suspended in 140 mL of diglyme. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 18 hours. Next, after the mixture was cooled to −20 ° C., 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature and stirred for 2 hours, after which 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to give a clear solution. Next, 11.8 g (58.7 mmol) of 4,4′-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise to the obtained transparent liquid over 1 hour. The viscosity increased during the addition of 4,4'-diaminodiphenyl ether. Subsequently, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred for 15 minutes at a speed of 500 rpm. The polyimide precursor resin was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried at 45 ° C. under reduced pressure for 3 days. This polyimide precursor had Mw = 24300 and Mn = 9500.
＜膜形成用組成物の調製＞
　下表に示す割合（質量部）で配合して均一な溶液として、各実施例、比較例の膜形成用組成物を調製した。後述の例では、得られた組成物を、０．８μｍのポアサイズを有するポリエチレン製フィルターを用いてろ過して用いた。 <Preparation of film-forming composition>
The composition for film formation of each Example and a comparative example was prepared as a uniform solution by mix | blending in the ratio (mass part) shown in the following table. In the examples described later, the obtained composition was used after being filtered using a polyethylene filter having a pore size of 0.8 μm.
＜スリットコートによる膜形成＞
　基板として、横１５０ｍｍ、縦１５０ｍｍ、厚み０．７ｍｍの無アルカリガラス基板の表面上に１００ｎｍ厚さの銅膜をスパッタにて製膜した基板を準備した。この基板の表面に、スリットコーター（ＳＣＲＥＥＮファインテックソリューションズ社製、ＬＣ－Ｒ３００Ｇ、但し、スリットヘッド幅を１００ｍｍ、塗布長１００ｍｍに設定）を用いて、上記で調製した膜形成用組成物の塗布膜を形成した。スリットコーターの装置の詳細な条件は下表に示したとおりである。これを、２３℃、減圧５０Ｐａに５分間放置してから、ホットプレート１００℃で５分間放置の条件で乾燥した。塗布膜厚（乾燥後）はフィルメトリクス社製、Ｆ２０膜厚測定システムを用いて、塗布部の端部から１０ｍｍの位置から１０ｍｍおきに測定して、その平均値をとった。製膜時には、ヘッド待機工程で、ノズルヘッドを下記表に示す条件で、浸漬液に浸漬した。また、製膜後には、ヘッド洗浄工程で、ノズルヘッドを洗浄液に浸漬した。浸漬時および洗浄時の温度は（常温（２３℃））とした。 <Film formation by slit coating>
As a substrate, a substrate was prepared by forming a copper film having a thickness of 100 nm on the surface of a non-alkali glass substrate having a width of 150 mm, a length of 150 mm, and a thickness of 0.7 mm by sputtering. Using the slit coater (LC-R300G, manufactured by SCREEN Finetech Solutions Co., Ltd., where the slit head width is set to 100 mm and the coating length is set to 100 mm) on the surface of this substrate, the coating film of the film forming composition prepared above is used. Formed. The detailed conditions of the slit coater apparatus are as shown in the table below. This was left to stand at 23 ° C. and a reduced pressure of 50 Pa for 5 minutes, and then dried on the hot plate at 100 ° C. for 5 minutes. The coating film thickness (after drying) was measured every 10 mm from the position of 10 mm from the end of the coating part using the F20 film thickness measurement system manufactured by Filmetrics, and the average value was taken. At the time of film formation, the nozzle head was immersed in the immersion liquid in the head standby step under the conditions shown in the following table. Further, after the film formation, the nozzle head was immersed in the cleaning liquid in the head cleaning process. The temperature during immersion and washing was (normal temperature (23 ° C.)).
＜塗布性＞
　上記スリットコート時の塗布性について評価した。基板に製膜した塗布膜を、２３℃、減圧５０Ｐａに５分間放置してから、ホットプレート１００℃で５分間放置の条件で乾燥後、目視で観察し、はじきやスジが観察されるかを確認した。観察領域は塗布部の端面から１０ｍｍを除いた全面とした。各実施例、比較例で、３つの試料の平均値を採用した。
　はじきやスジが少ないか全くなく、均一であった：優良
　はじきやスジがやや認められるが概ね均一であった：良
　はじきやスジが多かった：標準以下 <Applicability>
The applicability during the slit coating was evaluated. The coating film formed on the substrate is left to stand at 23 ° C. and a reduced pressure of 50 Pa for 5 minutes, and then dried under the condition of standing at a hot plate at 100 ° C. for 5 minutes. confirmed. The observation area was the entire surface excluding 10 mm from the end face of the application part. In each example and comparative example, an average value of three samples was adopted.
There was little or no repelling or streaking, and it was uniform: Excellent Repelling and streaking were slightly recognized, but it was almost uniform: Good Repelling and streaking were many: Substandard
＜塗布乾燥後の面状＞
　上記スリットコート時の塗布乾燥後の面状について評価した。基板に製膜した塗布膜（乾燥後）を目視で観察し、蛍光灯の反射状態から、面状を確認した。各実施例、比較例で、３つの試料の平均値を採用した。
　塗布部全体で蛍光灯がそのままミラー反射して見える－光沢：優良
　塗布部の少なくとも一部に蛍光灯がぼやけて見える部分がある－弱ゆず肌：良
　塗布部全面で蛍光灯がぼやけて見える－ゆず肌：標準以下 <Surface shape after coating and drying>
The surface condition after coating and drying during the slit coating was evaluated. The coating film (after drying) formed on the substrate was visually observed, and the surface shape was confirmed from the reflection state of the fluorescent lamp. In each example and comparative example, an average value of three samples was adopted.
Fluorescent lamps appear to be mirror-reflected as they are throughout the application area-Gloss: Excellent. At least part of the application area appears to cause the fluorescent lamp to appear blurred.-Weak skin: Good. Fluorescent lamp appears to be blurred throughout the application area. Yuzu skin: below standard
＜塗布乾燥後の面内均一性＞
　上記スリットコート時の塗布乾燥後の膜厚の面内均一性について評価した。塗布膜（乾燥後）を付した基板の表面の塗布膜の膜厚分布を、膜厚の測定装置（フィルメトリックス社製、Ｆ２０膜厚測定システム）により塗布部端部１０ｍｍを除く縦９０ｍｍ、横９０ｍｍ領域を１０ｍｍおきに８１点測定し、その最大最小の差をＴＴＶ（Total thickness variation）とした。各実施例、比較例で、３つの試料の平均値を採用した。
　ＴＴＶは、塗布部端部から１０ｍｍを除いた領域で測定した。
　≦１μｍ：優良
　＞１μｍ、≦２μｍ：良
　＞２μｍ：標準以下 <In-plane uniformity after coating and drying>
The in-plane uniformity of the film thickness after coating and drying during the slit coating was evaluated. The film thickness distribution of the coating film on the surface of the substrate provided with the coating film (after drying) is 90 mm in length and 10 mm in width excluding the coating part end 10 mm by a film thickness measuring device (F20 film thickness measurement system manufactured by Filmetrics). The 90 mm region was measured at 81 points every 10 mm, and the maximum and minimum difference was defined as TTV (Total thickness variation). In each example and comparative example, an average value of three samples was adopted.
TTV was measured in an area excluding 10 mm from the end of the coating part.
≦ 1 μm: Excellent> 1 μm, ≦ 2 μm: Good> 2 μm: Below standard
＜塗布後乾燥時間＞
　上記の乾燥工程において、ホットプレートに載せてから乾燥にかかるまでの時間を評価した。指定時間経過時点で塗布部の表面に綿棒で触れてみて跡が残れば乾燥未了、跡が残らなければ乾燥完了とした。各実施例、比較例で、３つの試料の平均値を採用した。なお、測定は、１００℃での乾燥時間とした。
　≦３００ｓｅｃ：優良
　＞３００ｓｅｃ、≦４００：良
　＞４００ｓｅｃ：標準以下 <Drying time after application>
In the above drying process, the time from drying on the hot plate to drying was evaluated. When the surface of the coated part was touched with a cotton swab after the specified time had elapsed, if a trace remained, drying was incomplete, and if no trace remained, drying was completed. In each example and comparative example, an average value of three samples was adopted. In addition, the measurement was made into the drying time at 100 degreeC.
≦ 300 sec: excellent> 300 sec, ≦ 400: good> 400 sec: below standard
＜ノズルヘッド洗浄後ノズルヘッド汚れ＞
　上記の製膜工程において、表に示す組成の洗浄液をバットに入れ、ノズルヘッドを、２３℃で、表に示す時間、ノズルヘッドのスリットが洗浄液に浸かるように浸漬し、ノズルヘッド洗浄後のノズルヘッドの汚れを評価した。各実施例、比較例で、３回の試験で採用した。なお、測定は、１００℃での乾燥時間とした。
　３回とも汚れが確認されなかった：無し
　３回のうち１回以上汚れが確認された：有り <Nozzle head dirt after nozzle head cleaning>
In the above film forming process, the cleaning liquid having the composition shown in the table is put into a vat, and the nozzle head is immersed at 23 ° C. for the time shown in the table so that the slit of the nozzle head is immersed in the cleaning liquid. The dirt on the head was evaluated. Each example and comparative example was adopted in three tests. In addition, the measurement was made into the drying time at 100 degreeC.
Dirt was not confirmed in all three times: None Dirt was confirmed more than once in 3 times: Existence
＜塗布膜の部材密着性（シアテスト）＞
　表１～表９に記載の各種基板上で上記スリットコートによって形成された膜の乾燥後の塗布膜について、シアテストを行った。測定装置は（ＸＹＺＴＥＣ社製、Ｃｏｎｄｏｒ　Ｓｉｇｍａボンドテスター）を使用した。試験は、上記基板に塗布後乾燥した膜を１００μｍ角のパターンを照射できるネガ型フォトマスクを用いて４００ｍＪ／ｃｍ２の露光量で露光し、３０分後に露光後の膜をシクロペンタノンで現像した後、ＰＧＭＥＡでリンスすることで、１００μｍ角の膜を形成し、その膜を１０μｍ／ｓで側面から、（下地から５μｍの位置にセットした針）で、押すかたちで行った。各実施例、比較例で、３つの試料の平均値を採用した。
　＜１０ｇ：標準以下
　≧１０ｇ、＜４０ｇ：良
　≧４０ｇ：優良
　同様のシアテストを、塗布膜を付した、Ｃｕメッキ基板、Ａｌ－Ｓｉ－Ｃｕ合金メッキ基板、Ｔｉスパッタ基板、Ｎｉスパッタ基板で行った。さらに、実施例３２～３６については、同様のシアテストを、塗布膜を付したＳｉ基板でも行った。評価基準も同じである。 <Member adhesion of coating film (shear test)>
Shear tests were performed on the coating films after drying the films formed by slit coating on the various substrates described in Tables 1 to 9. The measuring device (XYZTEC Co., Ltd. Condor Sigma bond tester) was used. In the test, a film dried after coating on the substrate was exposed with an exposure amount of 400 mJ / cm 2 using a negative photomask capable of irradiating a 100 μm square pattern, and after 30 minutes, the exposed film was developed with cyclopentanone. After that, a 100 μm square film was formed by rinsing with PGMEA, and the film was pressed at 10 μm / s from the side (with a needle set at a position of 5 μm from the ground). In each example and comparative example, an average value of three samples was adopted.
<10 g: below standard ≧ 10 g, <40 g: good ≧ 40 g: excellent The same shear test was performed on a Cu-plated substrate, an Al—Si—Cu alloy-plated substrate, a Ti sputter substrate, and a Ni sputter substrate with a coating film. . Further, in Examples 32 to 36, the same shear test was performed on the Si substrate provided with the coating film. The evaluation criteria are the same.
＜耐湿性＞
　また、塗布膜を付した、Ｃｕメッキ基板、Ｔｉスパッタ基板について、ＰＣＴ（プレッシャークッカテスト）を行った。ＰＣＴの試験装置は（エスペック社製、ＥＨＳ－４１２Ｍ）を用いた。塗布膜の処理条件は、１２１℃、１００％相対湿度（ＲＨ）、５００時間とした。処理後の塗布膜について、上記＜塗布膜の部材密着性＞の試験と同じ条件で密着性の評価（シアテスト）を行った。評価基準も同じである。
 
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000030
 ｓｅｃ：秒、ｍｉｎ：分
＊１　浸漬：ヘッド待機時浸漬：塗布後３０秒浸漬、浸漬後３０秒後吐出
＊２　比較例２：※DMSO100%だと空気中の水分を吸って乾燥できない
溶解不良：固形分が溶剤に溶解できなかったため塗布できなかった
測定不能：塗布できなかったため測定できなかった
実施不能：塗布できなかったため密着テストができなかった <Moisture resistance>
Further, a PCT (pressure cooker test) was performed on the Cu plated substrate and the Ti sputter substrate with the coating film. A PCT test apparatus (EHS-412M, manufactured by Espec Corp.) was used. The treatment conditions for the coating film were 121 ° C., 100% relative humidity (RH), and 500 hours. About the coating film after a process, adhesive evaluation (shear test) was performed on the same conditions as the above-mentioned test of <the member adhesiveness of a coating film>. The evaluation criteria are the same.

Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000030
 sec: second, min: minute * 1 Immersion: Immersion during head standby: 30 seconds after application, 30 seconds after application * 2 Comparative example 2: * Dissolving failure that cannot be dried by absorbing moisture in the air when DMSO is 100% : Cannot be applied because the solid content could not be dissolved in the solvent. Cannot be measured.
ポリイミド前駆体Ａ－１、Ａ－２およびＡ－３の各溶剤に対する溶解度（質量％）［２３℃］
Figure JPOXMLDOC01-appb-I000031
Solubility (% by mass) of polyimide precursors A-1, A-2 and A-3 in each solvent [23 ° C.]
Figure JPOXMLDOC01-appb-I000031
界面活性剤（メガファック［商品名］、ＤＩＣ）
　水溶解性は、２３℃の水１００ｇに溶解した量（ｇ）を単位、質量％にて示した。分子量は重量平均分子量である。
Figure JPOXMLDOC01-appb-T000032
 Surfactant (Megafuck [trade name], DIC)
For water solubility, the amount (g) dissolved in 100 g of water at 23 ° C. was shown in units of mass%. The molecular weight is a weight average molecular weight.
Figure JPOXMLDOC01-appb-T000032
（Ｃ）光ラジカル重合開始剤
Ｃ－１：ＢＡＳＦ社製、ＩＲＧＡＣＵＲＥ　ＯＸＥ－０１
Ｃ－２：下記化合物
Figure JPOXMLDOC01-appb-C000033
 (C) Photoradical polymerization initiator C-1: IRGACURE OXE-01 manufactured by BASF
C-2: The following compound
Figure JPOXMLDOC01-appb-C000033
（Ｄ）ラジカル重合性化合物
Ｄ－１：新中村化学工業社製、ＮＫエステル　Ａ－９３００
Ｄ－２：ＳＲ－２０９（テトラエチレングリコールジメタクリレート、サートマー社製） (D) Radical polymerizable compound D-1: manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-9300
D-2: SR-209 (tetraethylene glycol dimethacrylate, manufactured by Sartomer)
（Ｅ）重合禁止剤
Ｅ－１：パラベンゾキノン（東京化成工業（株）製）
Ｅ－２：４－メトキシフェノール　　　　　　
（Ｆ）マイグレーション抑制剤（防錆剤）
Ｆ－２：１Ｈ－テトラゾール (E) Polymerization inhibitor E-1: Parabenzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)
E-2: 4-methoxyphenol
(F) Migration inhibitor (rust inhibitor)
F-2: 1H-tetrazole
（Ｇ）金属接着性改良剤（シランカップリング剤）
Ｇ－１：信越化学工業社製、品番：ＫＢＭ－６０２
Ｇ－２：下記化合物（式中、Ｅｔはエチル基を表す。）
Figure JPOXMLDOC01-appb-C000034
 (G) Metal adhesion improver (silane coupling agent)
G-1: manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-602
G-2: The following compound (wherein Et represents an ethyl group)
Figure JPOXMLDOC01-appb-C000034
（Ｈ）硬化促進剤（熱塩基発生剤）
Ｈ－１：下記化合物
Figure JPOXMLDOC01-appb-C000035
 Ｈ－２：下記化合物
Figure JPOXMLDOC01-appb-C000036
 (H) Curing accelerator (thermal base generator)
H-1: The following compound
Figure JPOXMLDOC01-appb-C000035
 H-2: The following compound
Figure JPOXMLDOC01-appb-C000036
　可塑剤としては、各表のとおり、Ｏ－１８０Ａ、Ｏ－１３０ＰおよびＤ－３２（すべてＡＤＥＫＡ社製）を使用した。 As the plasticizer, O-180A, O-130P and D-32 (all manufactured by ADEKA) were used as shown in each table.
　上記の結果から分かるとおり、本発明において、スリットコートを実施するに当たり、塗布する膜形成用組成物として、ポリイミド前駆体と特定の溶剤と界面活性剤または可塑剤とを含有させたものを適用すると、金属表面上に塗布膜を形成した際にも、良好な塗布膜の面状が得られた。また、本発明の好ましい実施形態においては、膜形成用組成物の塗布性、塗布乾燥後の面内均一性、塗布後乾燥時間、ノズルヘッド洗浄後ノズルヘッド汚れ、塗布膜の部材密着性においても良好な性能が得られた。 As can be seen from the above results, in the present invention, when carrying out slit coating, as a film-forming composition to be applied, a composition containing a polyimide precursor, a specific solvent and a surfactant or a plasticizer is applied. Even when a coating film was formed on the metal surface, a good surface state of the coating film was obtained. Further, in a preferred embodiment of the present invention, the coating property of the film-forming composition, the in-plane uniformity after coating and drying, the drying time after coating, the nozzle head contamination after cleaning the nozzle head, and the member adhesion of the coating film Good performance was obtained.
＜露光、現像を行った実施例＞
　実施例１で作製した膜形成用組成物をスリットコートで銅ウェハ（金属層、金属を含む部材に相当する）上に塗布して塗布膜を形成した。得られた塗布膜をホットプレート上で、１００℃で５分間乾燥し、約１５μｍの厚さの均一な予備硬化膜（膜形成用組成物の膜）を得た。これを、アライナー（Ｋａｒｌ－Ｓｕｓｓ　ＭＡ１５０［商品名］）を用いて、（ステップ：５～２０μｍの）ラインアンドスペースのパターンを有するマスクを介して露光した。露光は高圧水銀ランプで行い、波長３６５ｎｍでの露光エネルギー換算で５００ｍＪ／ｃｍ２照射した。
　露光後の予備硬化膜をシクロペンタノンで７５秒間溶解してパドル現像した。現像された部位の線幅を以下の基準で評価した。現像後における下地基板の露出幅がマスクサイズに対して±１０％以内であり、良好な露光現像が可能であることを確認した。
　形成された樹脂パターンを２５０℃で３時間加熱し、ポリイミド前駆体を環化反応を進行させてポリイミド樹脂とすることで、微細なパターンでありながら、きわめて安定で強度のある樹脂パターンを得た。
　作製された樹脂パターンはポリイミドで構成されているため、優れた絶縁性を有するものであり、かつ上記のとおり金属との相性がよく、微細な加工にも好適に対応できることから、ＷＬ－ＣＳＰ（ウェハレベルチップサイズパッケージ）の再配線層の製造に特に適していることが分かった。 <Example of exposure and development>
The film forming composition prepared in Example 1 was applied on a copper wafer (corresponding to a metal layer or a member containing metal) by slit coating to form a coating film. The obtained coating film was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform precured film (film of a film forming composition) having a thickness of about 15 μm. This was exposed using an aligner (Karl-Suss MA150 [trade name]) through a mask having a line-and-space pattern (step: 5 to 20 μm). Exposure was performed with a high-pressure mercury lamp, and irradiation was performed at 500 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm.
The precured film after the exposure was dissolved in cyclopentanone for 75 seconds and developed with a paddle. The line width of the developed part was evaluated according to the following criteria. The exposed width of the underlying substrate after development was within ± 10% of the mask size, and it was confirmed that good exposure and development were possible.
The formed resin pattern was heated at 250 ° C. for 3 hours to advance the cyclization reaction of the polyimide precursor to obtain a polyimide resin, thereby obtaining an extremely stable and strong resin pattern while being a fine pattern. .
Since the produced resin pattern is made of polyimide, it has excellent insulating properties, has good compatibility with metals as described above, and can suitably cope with fine processing. Therefore, WL-CSP ( It has been found to be particularly suitable for the production of rewiring layers of wafer level chip size packages).
　実施例１において、ポリイミド前駆体Ａ－１を、ポリイミド前駆体Ａ－２またはＡ－３に変更し、他は同様に行った。実施例１と同様に優れた効果が得られた。一方、比較例１において、ポリイミド前駆体Ａ－１を、ポリイミド前駆体Ａ－２またはＡ－３に変更し、他は同様に行った。比較例１と同様に、塗布乾燥後の面状が劣っていた。 In Example 1, the polyimide precursor A-1 was changed to the polyimide precursor A-2 or A-3, and the others were performed in the same manner. The same excellent effect as in Example 1 was obtained. On the other hand, in Comparative Example 1, the polyimide precursor A-1 was changed to the polyimide precursor A-2 or A-3, and the others were performed in the same manner. Similar to Comparative Example 1, the surface condition after coating and drying was inferior.
２１　ノズルヘッド
２２　ノズルヘッドクリーナー
２３　搬送部
２１ａ　樹脂
２４　ローラ
２５　ローラバット
２５ｂ　液切りブレード
２５ａ　洗浄液
２６　メンテナンス部
１００　スリットコート装置 21 Nozzle head 22 Nozzle head cleaner 23 Conveying section 21a Resin 24 Roller 25 Roller butt 25b Liquid cutting blade 25a Cleaning liquid 26 Maintenance section 100 Slit coating device

Claims (23)

  1. 　ポリイミド前駆体と、
    　前記ポリイミド前駆体に対する２３℃における溶解度が異なる少なくとも２種の溶剤と、
    　界面活性剤および可塑剤からなる群から選択される少なくとも１種と
    を含む組成物を用いて、
    部材上にスリットコートを行う工程を含み、前記部材が少なくともその一部に金属を含む、膜の製造方法。     A polyimide precursor;
    At least two solvents having different solubility at 23 ° C. in the polyimide precursor;
    Using a composition comprising at least one selected from the group consisting of a surfactant and a plasticizer,
    A method for producing a film, comprising the step of performing slit coating on a member, wherein the member contains a metal at least in part.
  2. 　前記界面活性剤が、パーフルオロアルキル基を含む重量平均分子量５，０００以下の化合物で、水に可溶である、請求項１に記載の膜の製造方法。 The method for producing a film according to claim 1, wherein the surfactant is a compound containing a perfluoroalkyl group and having a weight average molecular weight of 5,000 or less and is soluble in water.
  3. 　スリットコートを行なう工程の後に洗浄液でノズルヘッドを洗浄するヘッド洗浄工程を含む、請求項１または２に記載の膜の製造方法。 The method for producing a film according to claim 1 or 2, comprising a head cleaning step of cleaning the nozzle head with a cleaning liquid after the slit coating step.
  4. 　前記スリットコートを行う工程において、ヘッド待機工程を含み、前記ヘッド待機工程において前記ノズルヘッドが浸漬液中に浸漬されており、前記浸漬液は前記洗浄液と９０質量％以上が共通する組成の液である、請求項３に記載の膜の製造方法。 The slit coating step includes a head standby step, and the nozzle head is immersed in an immersion liquid in the head standby step, and the immersion liquid is a liquid having a composition that is 90% by mass or more in common with the cleaning liquid. The method for producing a film according to claim 3.
  5. 　前記洗浄液が、前記少なくとも２種の溶剤のうち、前記ポリイミド前駆体の２３℃における溶解度の最も高い溶剤を含む、請求項３または４に記載の膜の製造方法。 The method for producing a film according to claim 3 or 4, wherein the cleaning liquid contains a solvent having the highest solubility of the polyimide precursor at 23 ° C among the at least two kinds of solvents.
  6. 　前記洗浄液が、前記少なくとも２種の溶剤のうち、前記ポリイミド前駆体の２３℃における溶解度の最も低い溶剤を含む、請求項３～５のいずれか１項に記載の膜の製造方法。 The method for producing a film according to any one of claims 3 to 5, wherein the cleaning liquid contains a solvent having the lowest solubility of the polyimide precursor at 23 ° C among the at least two kinds of solvents.
  7. 　前記浸漬液が、前記少なくとも２種の溶剤のうち、前記ポリイミド前駆体の２３℃における溶解度の最も高い溶剤を含む、請求項４に記載の膜の製造方法。 The method for producing a film according to claim 4, wherein the immersion liquid contains a solvent having the highest solubility of the polyimide precursor at 23 ° C among the at least two kinds of solvents.
  8. 　前記浸漬液が、前記少なくとも２種の溶剤のうち、前記ポリイミド前駆体の２３℃における溶解度の最も低い溶剤を含む、請求項４または７に記載の膜の製造方法。 The method for producing a film according to claim 4 or 7, wherein the immersion liquid contains a solvent having the lowest solubility of the polyimide precursor at 23 ° C among the at least two kinds of solvents.
  9. 　前記スリットコートにより形成した膜を露光する露光工程と、露光した膜を現像する現像工程とを有する、請求項１～８のいずれか１項に記載の膜の製造方法。 The method for producing a film according to any one of claims 1 to 8, comprising an exposure step of exposing the film formed by the slit coating and a development step of developing the exposed film.
  10. 　さらに前記膜を加熱する加熱工程を含む、請求項１～９のいずれか１項に記載の膜の製造方法。 The method for producing a film according to any one of claims 1 to 9, further comprising a heating step of heating the film.
  11. 　請求項１～１０のいずれか１項に記載の膜の製造方法を複数回行なう、積層体の製造方法。 A method for producing a laminate, wherein the method for producing a film according to any one of claims 1 to 10 is performed a plurality of times.
  12. 　前記膜に金属層を適用する工程を含む、請求項１１に記載の積層体の製造方法。 The manufacturing method of the laminated body of Claim 11 including the process of applying a metal layer to the said film | membrane.
  13. 　請求項１～１０のいずれか１項に記載の方法で製造した膜にチップを配置する半導体デバイスの製造方法。 A method for manufacturing a semiconductor device, wherein a chip is arranged on a film manufactured by the method according to any one of claims 1 to 10.
  14. 　請求項１１または１２に記載の方法で製造した積層体にチップを配置する半導体デバイスの製造方法。 A method for manufacturing a semiconductor device, in which a chip is arranged on a laminate manufactured by the method according to claim 11.
  15. 　請求項１～１０のいずれか１項に記載の製造方法に用いられる膜形成用の組成物であって、ポリイミド前駆体と、前記ポリイミド前駆体に対する２３℃における溶解度が異なる少なくとも２種の溶剤と、界面活性剤および可塑剤からなる群から選択される少なくとも１種とを含む膜形成用組成物。 A film-forming composition used in the production method according to any one of claims 1 to 10, comprising a polyimide precursor and at least two solvents having different solubility at 23 ° C in the polyimide precursor. And a film-forming composition comprising at least one selected from the group consisting of a surfactant and a plasticizer.
  16. 　前記ポリイミド前駆体がジカルボン酸またはジカルボン酸誘導体とジアミンの縮合体である請求項１５に記載の膜形成用組成物。 The film forming composition according to claim 15, wherein the polyimide precursor is a condensate of dicarboxylic acid or a dicarboxylic acid derivative and a diamine.
  17. 　前記少なくとも２種の溶剤のうち、前記ポリイミド前駆体の溶解度の最も高い溶剤がスルホキシド類の溶剤であり、前記少なくとも２種の溶剤のうち、前記ポリイミド前駆体の溶解度の最も低い溶剤がケトン類またはラクトン類の溶剤である、請求項１５または１６に記載の膜形成用組成物。 Of the at least two solvents, the solvent having the highest solubility of the polyimide precursor is a sulfoxide solvent, and of the at least two solvents, the solvent having the lowest solubility of the polyimide precursor is a ketone or The composition for film formation according to claim 15 or 16, which is a solvent for lactones.
  18. 　前記少なくとも２種の溶剤のうち、前記ポリイミド前駆体の溶解度が下記平均値より高い溶剤の総質量と、前記少なくとも２種の溶剤のうち、前記ポリイミド前駆体の溶解度が下記平均値より低い溶剤の総質量の比率が１０：９０～４５：５５である、請求項１５～１７のいずれか１項に記載の膜形成用組成物；
    　前記平均値は、ポリイミド前駆体の２３℃における溶解度が最も高い溶剤の溶解度とポリイミド前駆体の２３℃における最も低い溶剤の溶解度との平均値である。     Of the at least two solvents, the total mass of the solvent having a solubility of the polyimide precursor higher than the average value below, and of the at least two solvents, the solubility of the polyimide precursor is lower than the average value below. The film-forming composition according to any one of claims 15 to 17, wherein the ratio of the total mass is 10:90 to 45:55;
    The average value is an average value of the solubility of the solvent having the highest solubility of the polyimide precursor at 23 ° C. and the solubility of the polyimide precursor having the lowest solubility at 23 ° C.
  19. 　前記界面活性剤がフッ素原子を含む、請求項１５～１８のいずれか１項に記載の膜形成用組成物。 The film forming composition according to any one of claims 15 to 18, wherein the surfactant contains a fluorine atom.
  20. 　前記界面活性剤がパーフルオロアルキル基を含む重量平均分子量５，０００以下の化合物で、水に可溶である、請求項１９に記載の膜形成用組成物。 The film-forming composition according to claim 19, wherein the surfactant is a compound containing a perfluoroalkyl group and having a weight average molecular weight of 5,000 or less and is soluble in water.
  21. 　前記界面活性剤の含有量が固形分中で０．００５～２質量％である、請求項１５～２０のいずれか１項に記載の膜形成用組成物。 The film-forming composition according to any one of claims 15 to 20, wherein the content of the surfactant is 0.005 to 2% by mass in the solid content.
  22. 　前記可塑剤がエポキシ化オイルである、請求項１５～２１のいずれか１項に記載の膜形成用組成物。 The film-forming composition according to any one of claims 15 to 21, wherein the plasticizer is an epoxidized oil.
  23. 　前記可塑剤の含有量が固形分中で０．００５～２質量％である、請求項１５～２２のいずれか１項に記載の膜形成用組成物。 The film-forming composition according to any one of claims 15 to 22, wherein the content of the plasticizer is 0.005 to 2% by mass in the solid content.
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