WO2015152121A1 - Composition for forming release layer - Google Patents

Composition for forming release layer Download PDF

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Publication number
WO2015152121A1
WO2015152121A1 PCT/JP2015/059850 JP2015059850W WO2015152121A1 WO 2015152121 A1 WO2015152121 A1 WO 2015152121A1 JP 2015059850 W JP2015059850 W JP 2015059850W WO 2015152121 A1 WO2015152121 A1 WO 2015152121A1
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WO
WIPO (PCT)
Prior art keywords
bis
release layer
composition
skeleton
aromatic polyimide
Prior art date
Application number
PCT/JP2015/059850
Other languages
French (fr)
Japanese (ja)
Inventor
江原　和也
和也 進藤
Original Assignee
日産化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to JP2016511866A priority Critical patent/JP6610534B2/en
Priority to CN201580017799.8A priority patent/CN106133062B/en
Priority to KR1020167029656A priority patent/KR102310011B1/en
Publication of WO2015152121A1 publication Critical patent/WO2015152121A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/18—Polybenzimidazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/22—Polybenzoxazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/096—Nitrogen containing compounds
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • 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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2477/00—Presence of polyamide
    • C09J2477/005—Presence of polyamide in the release coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/085—Presence of polyamine or polyimide polyimide in the release coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68318—Auxiliary support including means facilitating the separation of a device or wafer from the auxiliary support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/6835—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used as a support during build up manufacturing of active devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer
    • H01L2221/68386—Separation by peeling

Definitions

  • the present invention relates to a composition for forming a release layer provided directly on a glass substrate.
  • Patent Documents 1, 2, and 3 an amorphous silicon thin film layer is formed on a glass substrate, a plastic substrate is formed on the thin film layer, and then a laser is irradiated from the glass surface side to accompany crystallization of amorphous silicon.
  • a method of peeling a plastic substrate from a glass substrate with generated hydrogen gas is disclosed.
  • Patent Document 4 discloses a method for completing a liquid crystal display device by attaching a layer to be peeled (described as “transfer target layer” in Patent Document 4) to a plastic film using the techniques disclosed in Patent Documents 1 to 3. Is disclosed.
  • Patent Documents 1 to 4 particularly the method disclosed in Patent Document 4, it is essential to use a highly light-transmitting substrate, and hydrogen contained in amorphous silicon is allowed to pass through the substrate.
  • hydrogen contained in amorphous silicon is allowed to pass through the substrate.
  • irradiation with a relatively large laser beam is required and the layer to be peeled is damaged.
  • it takes a long time for laser treatment and it is difficult to peel off a layer to be peeled having a large area there is a problem that it is difficult to increase the productivity of device fabrication.
  • JP-A-10-125929 Japanese Patent Laid-Open No. 10-125931.
  • an object of the present invention is to solve the above problems. Specifically, the objective of this invention is providing the composition for forming the peeling layer for making it peel without damaging the board
  • a composition for forming a release layer provided directly on a glass substrate comprises (A) an aromatic polyimide and / or an aromatic polyimide precursor; and (B) an amide solvent;
  • the aromatic polyimide derived from (A) satisfies the following (1) to (4): (1) The temperature of 1% weight reduction in weight change during heating is 500 ° C. or higher; (2) A refractive index of 1.7 or more at a wavelength of 1000 nm; (3) The difference between the refractive index and the birefringence is 0.15 or more at a wavelength of 1000 nm; and (4) the surface energy is 40 dyne / cm or more.
  • the component (A) is preferably produced using at least one diamine component selected from the group consisting of p-phenylenediamine and terphenyldiamine.
  • the amount of p-phenylenediamine and / or terphenyldiamine may be 70 mol% or more in 100 mol% of all diamine components.
  • the component (A) is an aromatic diamine having at least one first skeleton selected from the group consisting of a biphenyl skeleton, an imidazole skeleton, and an oxazole skeleton. It is good to manufacture.
  • the component (A) has at least one second skeleton selected from the group consisting of a benzene skeleton, a naphthalene skeleton, and a biphenyl skeleton. It is good to manufacture using.
  • the component (B) is a solvent represented by the following formula (I) and / or (II) (wherein R 1 and R 2 are each Independently, it represents an alkyl group having 1 to 4 carbon atoms, and h represents a natural number).
  • a method for producing an object to be peeled a) a step of forming a release layer after applying the composition described in any one of ⁇ 1> to ⁇ 6> on a glass substrate; b) a step of forming an object to be peeled on the release layer; and c) a step of peeling the object to be peeled at the interface between the release layer and the object to be peeled; The said method of obtaining a to-be-separated body by having.
  • the present invention can solve the above problems. Specifically, according to the present invention, it is possible to provide a composition for forming a release layer for peeling without damaging a substrate applied to a flexible electronic device. Further, according to the present invention, in addition to the above effects or in addition to the above effects, the adhesion with the glass substrate on which the release layer is provided is maintained, and peeling at the interface with the glass substrate does not occur.
  • the composition for forming this peeling layer which can peel easily the layer or layer group formed from a peeling layer can be provided.
  • composition of the present invention comprises (A) an aromatic polyimide and / or an aromatic polyimide precursor; and (B) an amide solvent.
  • the component (A) is an aromatic polyimide and / or an aromatic polyimide precursor.
  • the “aromatic polyimide” means that both of the diamine component and the acid dianhydride component constituting the polyimide have an aromatic group, and therefore the polyimide thus obtained has mainly an aromatic group. It means having in the chain.
  • the “aromatic polyimide precursor” refers to the precursor of the above aromatic polyimide, and typically includes polyamic acid, polyamic acid ester, and polyisoimide, preferably polyamic acid. Good.
  • the aromatic polyimide can be divided into a diamine component and an acid dianhydride component constituting the polyimide, and the following can be exemplified, but the aromatic polyimide is not limited thereto.
  • the diamine component having an aromatic group include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), 1,2-diaminobenzene (o-phenylenediamine), 2, 4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine 2,6-dimethyl-p-phenylenediamine 2,4-bis (amino-t-butyl) toluene 2,4,6-trimethyl-1,3-phenylenediamine,
  • the diamine component may be at least one diamine component selected from the group consisting of p-phenylenediamine and terphenyldiamine.
  • the amount of p-phenylenediamine and / or terphenyldiamine is 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, in 100 mol% of the total diamine components.
  • the diamine component may be an aromatic diamine having at least one first skeleton selected from the group consisting of a biphenyl skeleton, an imidazole skeleton, and an oxazole skeleton.
  • acid dianhydride component having an aromatic group examples include, but are not limited to, an acid dianhydride having a benzene skeleton, an acid dianhydride having a naphthalene skeleton, and an acid dianhydride having a biphenyl skeleton.
  • the aromatic polyimide derived from (A) of the composition of the present application has the following properties (1) to (4).
  • Characteristics of (1) to (4) >> (1)
  • the temperature of 1% weight loss in weight change during heating is 500 ° C. or higher, preferably 520 ° C. or higher, more preferably 550 ° C.
  • the surface energy is 40 dyne / cm or more, preferably 45 to 70 dyne / cm, more preferably 45 ⁇ 60 dyne / cm.
  • Aromatic polyimide derived from (A)” or “Aromatic polyimide derived from (A)” means that when the component (A) consists only of “aromatic polyimide”, the “aromatic polyimide” I mean. Moreover, when (A) component consists only of “aromatic polyimide precursor”, it means this "aromatic polyimide” when all the precursors become “aromatic polyimide”. When the component (A) has “aromatic polyimide A” and “aromatic polyimide precursor B”, “aromatic polyimide B ′” and “aromatic polyimide A” formed from “aromatic polyimide precursor B” And the whole thing.
  • the release layer has good adhesion to the glass substrate, while when a release object is formed on the release layer, the release object Can be easily peeled off by cutting with a cutter or the like.
  • the composition of the present application has an amide solvent as the component (B).
  • the amide solvent means a liquid having an amide group or an alkylamide group.
  • Examples of the amide solvent include, but are not limited to, N methylpyrrolidone, N ethylpyrrolidone, DMAc, DMF, ecamide M, ecamide B (manufactured by Idemitsu Kosan Co., Ltd.), and the like.
  • a solvent represented by the following formula (I), and / or (II) (wherein R 1 and R 2 each independently represents an alkyl group having 1 to 4 carbon atoms, h is (Representing a natural number).
  • composition of the present application may have various components in addition to the components (A) and (B).
  • examples thereof include, but are not limited to, a crosslinking agent (hereinafter also referred to as a crosslinkable compound).
  • crosslinkable compound examples include a compound containing two or more epoxy groups, a melamine derivative, a benzoguanamine derivative or glycoluril having a group in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group or both.
  • a compound containing two or more epoxy groups examples include a compound containing two or more epoxy groups, a melamine derivative, a benzoguanamine derivative or glycoluril having a group in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group or both.
  • crosslinkable compound As compounds containing two or more epoxy groups, cyclohexene structures such as Epolide GT-401, Epolide GT-403, Epolide GT-301, Epolide GT-302, Celoxide 2021, Celoxide 3000 (above, manufactured by Daicel Corporation), etc.
  • Epoxy compound having: Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010, Epicoat 828 (above, manufactured by Japan Epoxy Resins Co., Ltd.
  • Cresol novolac type epoxy compound such as V8000-C7 (manufactured by DIC Corporation); naphthalene type epoxy compound such as V8000-C7 (manufactured by DIC Corporation); Denacol EX-252 (manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179, Araldite CY-182, Ara Daito CY-192, Araldite CY-184 (above, manufactured by BASF), Epicron 200, Epicron 400 (above, made by DIC Corporation), Epicoat 871, Epicoat 872 (above, made by Japan Epoxy Resins Co., Ltd.
  • benzoguanamine derivative or glycoluril having a group in which the hydrogen atom of the amino group is substituted with a methylol group, an alkoxymethyl group or both, an average of 3.7 methoxymethyl groups are substituted per triazine ring MX-750, MW-30 substituted with an average of 5.8 methoxymethyl groups per triazine ring (above, manufactured by Sanwa Chemical Co., Ltd.); Cymel 300, Cymel 301, Cymel 303, Cymel 350, Methoxymethylated melamines such as Cymel 370, Cymel 771, Cymel 325, Cymel 327, Cymel 703, Cymel 712, etc .; Butoxymethylated melamine such as Cymel 506, Cymel 508, etc .; Carboxy group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141; Methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1123; Methoxymethyl
  • a release layer provided directly on the glass substrate can be formed.
  • the release layer can be formed by applying the composition of the present invention to a glass substrate by a conventionally known technique and heating the obtained coating film at a predetermined temperature.
  • a to-be-separated body layer can be formed on a peeling layer.
  • the layer to be peeled may be a single layer or a plurality of layers. In order to fabricate various devices, it is realistic to have a plurality of layers.
  • the layer immediately above the release layer depends on the release layer to be used, but it is preferable to use a layer having good peelability with the release layer, in other words, a layer having poor adhesion to the release layer to be used. Good.
  • a method for manufacturing an object to be peeled is provided.
  • the method a) a step of forming a release layer after applying the composition of the present application on a glass substrate; b) a step of forming an object to be peeled on the release layer; and c) a step of peeling the object to be peeled at the interface between the release layer and the object to be peeled; It is possible to obtain an object to be peeled.
  • the “object to be peeled” may be a single layer or a plurality of layers.
  • the release layer has good peelability, in other words, the adhesiveness to the release layer to be used is not good. There should be.
  • BA-TME 4,4′-biphenylenebis (trimellitic acid monoester anhydride).
  • PMDA pyromellitic dianhydride.
  • IPHA isophthalaldehyde.
  • Mw weight average molecular weight
  • JASCO Corporation GPC apparatus Shodex (registered trademark) columns KF803L and KF805L
  • dimethylformamide as the elution solvent at a flow rate of 1 ml / min and column temperature. Measurements were made at 50 ° C.
  • Mw was made into the polystyrene conversion value.
  • Temperature rise ⁇ Maintain at 240 ° C. for 20 minutes ⁇ Temperature rise ⁇ Maintain at 300 ° C. for 20 minutes ⁇ Temperature rise ⁇ Maintain at 400 ° C. for 20 minutes ⁇ Temperature rise ⁇ Maintained at 450 ° C. for 60 minutes.
  • the temperature rising rate was 10 ° C./min.
  • Cure condition C maintained at 80 ° C. for 10 minutes ⁇ temperature rise ⁇ 300 ° C. for 30 minutes ⁇ temperature rise ⁇ 400 ° C. for 30 minutes.
  • the temperature rising rate was 10 ° C./min.
  • the film thickness of the obtained coating film was measured using a contact-type film thickness measuring device (Dektak 3ST manufactured by ULVAC, Inc.).
  • Table 1 shows the precursors of P1 to P7 used, the coated substrate, the curing conditions, and the film thickness of the produced release layer.
  • ⁇ Cross cut test I> For the substrates provided with the release layers of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1, the adhesion of the substrate (glass or silicon wafer) / release layer was confirmed by cross-cut test I.
  • the crosscut test I was performed as follows. (1) On the release layer, 100 1 mm squares were produced. (2) Thereafter, the above square was attached with an adhesive tape (cello tape (registered trademark)), and a peeling process was performed. (3) After the peeling step, the squares remaining on the substrate were counted.
  • the characteristics of the components constituting the release layer, ie, (1) during heating, for the substrates provided with the release layers of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1 A temperature showing 1% weight loss in weight change of (2), (2) refractive index at a wavelength of 1000 nm, (3) birefringence at a wavelength of 1000 nm, and (4) surface energy were measured. The measurement conditions for each characteristic are shown below.
  • thermogravimetric (TG) measurement was performed in a nitrogen atmosphere, and the temperature at which the weight decreased by 1% was determined.
  • the refractive index and birefringence were measured using a high-speed spectroscopic ellipsometer M-2000 (manufactured by JA Woollam Japan Co., Ltd.).
  • the refractive index was an in-plane refractive index having a value of 1000 nm
  • the birefringence was a difference between the in-plane refractive index and the out-of-plane refractive index.
  • Crosscut Test II >> About the board
  • the crosscut test II was performed in the same manner as the crosscut test I.
  • Table 2 shows (1) a temperature indicating a 1% weight decrease in weight change during heating (indicated by “(1)” in Table 2), (2) a refractive index at a wavelength of 1000 nm (in Table 2, “ (2) ”, (3) difference between the refractive index and birefringence of (2) (indicated by“ (3) ”in Table 2), (4) surface energy (in Table 2, This is indicated by “(4)” (where the unit is dyne / cm), the polyimide precursor used in the peeled layer, and the results of cross-cut tests I and II.
  • Table 2 shows the following.
  • the peeling layer of Examples 1 to 5 since the result of Test I is 5B, the peeling layer is not peeled off from the substrate, while the result of Test II is AA. It turns out that only peels.
  • the release layer formed from the composition for release layer of the present invention provides a desired release result.
  • Comparative Example 1 and Comparative Example 3 show that the release layer peels from the substrate because the result of Test I is AA.
  • Comparative Example 1 and Comparative Example 3 cannot obtain a desired peeling result.
  • Comparative Example 2 since both Test I and Test II are 5B, neither the interface between the release layer and the substrate nor the interface between the release layer and the layer to be peeled is peeled off. It can be seen that cannot be obtained.

Abstract

The present invention provides a composition for forming a release layer that maintains adhesion to a glass substrate provided with the release layer and prevents release at the interface between the release layer and the glass substrate, while making it possible to easily release a layer or group of layers formed above the release layer from the release layer. The present invention provides a composition for forming a release layer that is provided directly above a glass substrate, said composition having (A) an aromatic polyimide and/or aromatic polyimide precursor, and (B) an amide solvent, wherein the aromatic polyimide of (A) satisfies the belowmentioned (1)-(4): (1) the temperature for a 1% weight reduction during weight change that occurs during heating is 500 °C or more; (2) the refractive index at a wavelength of 1000 nm is 1.7 or more; (3) the difference between the refractive index and birefringence at a wavelength of 1000 nm is 0.15 or more; and (4) the surface energy is 40 dyne/cm or more.

Description

剥離層形成用組成物Release layer forming composition
　本発明は、ガラス基板直上に設ける剥離層を形成するための組成物に関する。 The present invention relates to a composition for forming a release layer provided directly on a glass substrate.
　近年、電子デバイスには曲げるという機能付与や薄型化および軽量化といった性能が求められている。このことから、従来の重く脆弱で曲げることができないガラス基板に代わって、軽量なフレキシブルプラスチック基板を用いることが求められる。また、新世代ディスプレイでは、軽量なフレキシブルプラスチック基板を用いる、アクティブフルカラー（active full-color）ＴＦＴディスプレイパネルの開発が求められている。
　そこで、樹脂フィルムを基板とした電子デバイスの製造方法が各種検討され始めており、新世代ディスプレイでは、既存のＴＦＴ設備を転用可能なプロセスで製造検討が進められている。 In recent years, electronic devices have been required to have the functions of bending, thinning and lightening. For this reason, it is required to use a lightweight flexible plastic substrate in place of the conventional glass substrate that is fragile and cannot be bent. In the new generation display, development of an active full-color TFT display panel using a lightweight flexible plastic substrate is required.
Therefore, various methods for manufacturing electronic devices using a resin film as a substrate are being studied, and in the new generation display, manufacturing studies are being carried out in a process that can divert existing TFT equipment.
　特許文献１、２及び３は、ガラス基板上にアモルファスシリコン薄膜層を形成し、その薄膜層上にプラスチック基板を形成した後に、ガラス面側からレーザーを照射して、アモルファスシリコンの結晶化に伴い発生する水素ガスによりプラスチック基板をガラス基板から剥離する方法を開示する。
　また、特許文献４は、特許文献１～３開示の技術を用いて被剥離層（特許文献４において「被転写層」と記載される）をプラスチックフィルムに貼りつけて液晶表示装置を完成させる方法を開示する。 In Patent Documents 1, 2, and 3, an amorphous silicon thin film layer is formed on a glass substrate, a plastic substrate is formed on the thin film layer, and then a laser is irradiated from the glass surface side to accompany crystallization of amorphous silicon. A method of peeling a plastic substrate from a glass substrate with generated hydrogen gas is disclosed.
Patent Document 4 discloses a method for completing a liquid crystal display device by attaching a layer to be peeled (described as “transfer target layer” in Patent Document 4) to a plastic film using the techniques disclosed in Patent Documents 1 to 3. Is disclosed.
　しかし、特許文献１～４開示の方法、特に特許文献４開示の方法は、透光性の高い基板を使用することが必須であり、基板を通過させ、さらに非晶質シリコンに含まれる水素を放出させるのに十分なエネルギーを与えるため、比較的大きなレーザー光の照射が必要とされ、被剥離層に損傷を与えてしまうという問題がある。また、レーザー処理に長時間を要し、大きな面積を有する被剥離層を剥離するのは困難であるため、デバイス作製の生産性を挙げることは難しい、という問題もある。 However, in the methods disclosed in Patent Documents 1 to 4, particularly the method disclosed in Patent Document 4, it is essential to use a highly light-transmitting substrate, and hydrogen contained in amorphous silicon is allowed to pass through the substrate. In order to give energy sufficient to emit, there is a problem that irradiation with a relatively large laser beam is required and the layer to be peeled is damaged. In addition, since it takes a long time for laser treatment and it is difficult to peel off a layer to be peeled having a large area, there is a problem that it is difficult to increase the productivity of device fabrication.
特開平１０－１２５９２９号公報。JP-A-10-125929. 特開平１０－１２５９３１号公報。Japanese Patent Laid-Open No. 10-125931. ＷＯ２００５／０５０７５４号パンフレット。WO2005 / 050754 pamphlet. 特開平１０－１２５９３０号公報。Japanese Patent Laid-Open No. 10-125930.
　そこで、本発明の目的は、上記課題を解決することにある。
　具体的には、本発明の目的は、フレキシブル電子デバイスに適用される基板に損傷を与えることなく剥離させるための剥離層を形成するための組成物を提供することにある。
　また、本発明の目的は、上記目的に加えて、又は上記目的以外に、剥離層が設けられるガラス基板との密着性が維持されガラス基板との界面での剥離が生じない一方、剥離層より上部に形成される層又は層群を剥離層から簡易に剥離することができる、該剥離層を形成するための組成物を提供することにある。 Therefore, an object of the present invention is to solve the above problems.
Specifically, the objective of this invention is providing the composition for forming the peeling layer for making it peel without damaging the board | substrate applied to a flexible electronic device.
Further, in addition to the above object or other than the above object, the object of the present invention is to maintain adhesion with a glass substrate on which a release layer is provided and does not cause peeling at the interface with the glass substrate. An object of the present invention is to provide a composition for forming a release layer, which can easily peel a layer or a group of layers formed thereon from the release layer.
　本発明者は、以下の発明を見出した。
　＜１＞　ガラス基板直上に設ける剥離層を形成するための組成物であって、
　該組成物が
　（Ａ）芳香族ポリイミド及び／又は芳香族ポリイミド前駆体；及び
　（Ｂ）アミド系溶媒；
を有し、
（Ａ）由来の芳香族ポリイミドは、下記（１）～（４）を満たす、上記組成物。
　（１）加熱時の重量変化における１％重量減少の温度が５００℃以上；
　（２）波長１０００ｎｍで屈折率が１．７以上；
　（３）波長１０００ｎｍで屈折率と複屈折の差が０．１５以上；及び
　（４）表面エネルギーが４０ｄｙｎｅ／ｃｍ以上。 The inventor has found the following invention.
<1> A composition for forming a release layer provided directly on a glass substrate,
The composition comprises (A) an aromatic polyimide and / or an aromatic polyimide precursor; and (B) an amide solvent;
Have
The aromatic polyimide derived from (A) satisfies the following (1) to (4):
(1) The temperature of 1% weight reduction in weight change during heating is 500 ° C. or higher;
(2) A refractive index of 1.7 or more at a wavelength of 1000 nm;
(3) The difference between the refractive index and the birefringence is 0.15 or more at a wavelength of 1000 nm; and (4) the surface energy is 40 dyne / cm or more.
　＜２＞　上記＜１＞において、（Ａ）成分が、ｐ－フェニレンジアミン及びターフェニルジアミンからなる群から選ばれる少なくとも１種のジアミン成分を用いて製造されるのがよい。
　＜３＞　上記＜２＞において、ｐ－フェニレンジアミン及び／又はターフェニルジアミンの量が、全ジアミン成分１００モル％中、７０モル％以上であるのがよい。
　＜４＞　上記＜１＞～＜３＞のいずれかにおいて、（Ａ）成分が、ビフェニル骨格、イミダゾール骨格及びオキサゾール骨格からなる群から選ばれる少なくとも１種の第１の骨格を有する芳香族ジアミンを用いて製造されるのがよい。 <2> In the above item <1>, the component (A) is preferably produced using at least one diamine component selected from the group consisting of p-phenylenediamine and terphenyldiamine.
<3> In the above item <2>, the amount of p-phenylenediamine and / or terphenyldiamine may be 70 mol% or more in 100 mol% of all diamine components.
<4> In any one of the above items <1> to <3>, the component (A) is an aromatic diamine having at least one first skeleton selected from the group consisting of a biphenyl skeleton, an imidazole skeleton, and an oxazole skeleton. It is good to manufacture.
　＜５＞　上記＜１＞～＜４＞のいずれかにおいて、（Ａ）成分が、ベンゼン骨格、ナフタレン骨格及びビフェニル骨格からなる群から選ばれる少なくとも１種の第２の骨格を有する酸二無水物を用いて製造されるのがよい。
　＜６＞　上記＜１＞～＜３＞のいずれかにおいて、（Ｂ）成分が、下記式（Ｉ）で表される溶媒、及び／又は（ＩＩ）（式中、Ｒ１及びＲ２は各々独立に、炭素原子数１～４のアルキル基を表し、ｈは自然数を表す）で表される溶媒であるのがよい。 <5> In any one of the above items <1> to <4>, the component (A) has at least one second skeleton selected from the group consisting of a benzene skeleton, a naphthalene skeleton, and a biphenyl skeleton. It is good to manufacture using.
<6> In any one of the above items <1> to <3>, the component (B) is a solvent represented by the following formula (I) and / or (II) (wherein R 1 and R 2 are each Independently, it represents an alkyl group having 1 to 4 carbon atoms, and h represents a natural number).
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　＜７＞　上記＜１＞～＜６＞のいずれかに記載される組成物を用いて形成される、ガラス基板直上に設けられる剥離層。
　＜８＞　被剥離体の製造方法であって、
　ａ）上記＜１＞～＜６＞のいずれかに記載される組成物をガラス基板上に塗布した後、剥離層を形成する工程；
　ｂ）該剥離層上に、被剥離体を形成する工程；及び
　ｃ）剥離層と被剥離体との界面において、被剥離体を剥離する工程；
を有することにより、被剥離体を得る上記方法。 <7> A release layer formed using the composition described in any one of <1> to <6> above and provided immediately above the glass substrate.
<8> A method for producing an object to be peeled,
a) a step of forming a release layer after applying the composition described in any one of <1> to <6> on a glass substrate;
b) a step of forming an object to be peeled on the release layer; and c) a step of peeling the object to be peeled at the interface between the release layer and the object to be peeled;
The said method of obtaining a to-be-separated body by having.
　本発明により、上記課題を解決することができる。
　具体的には、本発明により、フレキシブル電子デバイスに適用される基板に損傷を与えることなく剥離させるための剥離層を形成するための組成物を提供することができる。
　また、本発明により、上記効果に加えて、又は上記効果以外に、剥離層が設けられるガラス基板との密着性が維持されガラス基板との界面での剥離が生じない一方、剥離層より上部に形成される層又は層群を剥離層から簡易に剥離することができる、該剥離層を形成するための組成物を提供することができる。 The present invention can solve the above problems.
Specifically, according to the present invention, it is possible to provide a composition for forming a release layer for peeling without damaging a substrate applied to a flexible electronic device.
Further, according to the present invention, in addition to the above effects or in addition to the above effects, the adhesion with the glass substrate on which the release layer is provided is maintained, and peeling at the interface with the glass substrate does not occur. The composition for forming this peeling layer which can peel easily the layer or layer group formed from a peeling layer can be provided.
　本願は、ガラス基板直上に設ける剥離層を形成するための組成物を提供する。
　以下、該組成物について詳述する。
＜組成物＞
　本発明の組成物は、（Ａ）芳香族ポリイミド及び／又は芳香族ポリイミド前駆体；及び（Ｂ）アミド系溶媒；を有する。 The present application provides a composition for forming a release layer provided directly on a glass substrate.
Hereinafter, the composition will be described in detail.
<Composition>
The composition of the present invention comprises (A) an aromatic polyimide and / or an aromatic polyimide precursor; and (B) an amide solvent.
＜＜（Ａ）成分＞＞
　（Ａ）成分は、芳香族ポリイミド及び／又は芳香族ポリイミド前駆体である。
　ここで、「芳香族ポリイミド」とは、ポリイミドを構成するジアミン成分及び酸二無水物成分のうち双方が芳香族基を有し、それゆえそれにより得られたポリイミドが、専ら芳香族基を主鎖に有することを意味する。
　また、「芳香族ポリイミド前駆体」とは、上記の芳香族ポリイミドの前駆体をいい、典型的には、ポリアミック酸、ポリアミック酸エステル、ポリイソイミドを挙げることができ、好ましくはポリアミック酸であるのがよい。 << (A) component >>
The component (A) is an aromatic polyimide and / or an aromatic polyimide precursor.
Here, the “aromatic polyimide” means that both of the diamine component and the acid dianhydride component constituting the polyimide have an aromatic group, and therefore the polyimide thus obtained has mainly an aromatic group. It means having in the chain.
The “aromatic polyimide precursor” refers to the precursor of the above aromatic polyimide, and typically includes polyamic acid, polyamic acid ester, and polyisoimide, preferably polyamic acid. Good.
　具体的には、芳香族ポリイミドとして、該ポリイミドを構成するジアミン成分及び酸二無水物成分に分けて、次のものを挙げることができるがこれらに限定されない。
＜ジアミン成分＞
　芳香族基を有するジアミン成分として、１，４－ジアミノベンゼン（ｐ－フェニレンジアミン）、１，３－ジアミノベンゼン（ｍ－フェニレンジアミン）、１，２－ジアミノベンゼン（ｏ－フェニレンジアミン）、２，４－ジアミノトルエン、２，５－ジアミノトルエン、２，６－ジアミノトルエン、４，６－ジメチル－ｍ－フェニレンジアミン、２，５－ジメチル－ｐ－フェニレンジアミン２、６－ジメチル－ｐ－フェニレンジアミン２，４－ビス（アミノ－ｔ－ブチル）トルエン２，４，６－トリメチル－１，３-フェニレンジアミン、２，３，５，６－テトラメチル－ｐ－フェニレンジアミン、ｍ－キシリレンジアミン、ｐ－キシリレンジアミン、５－トリフルオロメチルベンゼン－１，３－ジアミン、５－トリフルオロメチルベンゼン－１，２－ジアミン、３，５－ビス（トリフルオロメチル）ベンゼン－１，２－ジアミンなどのベンゼン核１つのジアミン、４，４’－ジアミノジフェニルエーテル、３，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルメタン、３，３’－ジメチル－４，４’－ジアミノビフェニル、２，２’－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、３，３’－ジメチル－４，４’－ジアミノジフェニルメタン、３，３’－ジカルボキシ－４，４’－ジアミノジフェニルメタン、３，３’，５，５’－テトラメチル－４，４’－ジアミノジフェニルメタン、ビス（４－アミノフェニル）スルフィド、４，４’－ジアミノベンズアニリド、３，３’－ジクロロベンジジン、３，３’－ジメチルベンジジン、２，２’－ジメチルベンジジン、３，３’－ジメトキシベンジジン、２，２’－ジメトキシベンジジン、３，３’－ジアミノジフェニルエーテル、３，４’－ジアミノジフェニルエーテル、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スルフィド、３，４’－ジアミノジフェニルスルフィド、４，４’－ジアミノジフェニルスルフィド、３，３’－ジアミノジフェニルスルホン、３，４’－ジアミノジフェニルスルホン、４，４’－ジアミノジフェニルスルホン、３，３’－ジアミノベンゾフェノン、３，３’－ジアミノ－４，４’－ジクロロベンゾフェノン、３，３’－ジアミノ－４，４’－ジメトキシベンゾフェノン、３，３’－ジアミノジフェニルメタン、３，４’－ジアミノジフェニルメタン、４，４’－ジアミノジフェニルメタン、２，２－ビス（３－アミノフェニル）プロパン、２，２－ビス（４－アミノフェニル）プロパン、２，２－ビス（３－アミノフェニル）－１，１，１，３，３，３－ヘキサフルオロプロパン、２，２－ビス（４－アミノフェニル）－１，１，１，３，３，３－ヘキサフルオロプロパン、３，３’－ジアミノジフェニルスルホキシド、３，４’－ジアミノジフェニルスルホキシド、４，４’－ジアミノジフェニルスルホキシド、２，２’－ビス（トリフルオロメチル）ビフェニル‐４，４’‐ジアミン、３，３’－ビス（トリフルオロメチル）ビフェニル‐４，４’‐ジアミン、３，３’，５，５’‐テトラフルオロビフェニル‐４，４’‐ジアミン、４，４'－ジアミノオクタフルオロビフェニルなどのベンゼン核２つのジアミン、１，３－ビス（３－アミノフェニル）ベンゼン、１，３－ビス（４－アミノフェニル）ベンゼン、１，４－ビス（３－アミノフェニル）ベンゼン、１，４－ビス（４－アミノフェニル）ベンゼン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，４－ビス（３－アミノフェノキシ）ベンゼン、１，４－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）－４－トリフルオロメチルベンゼン、３，３’－ジアミノ－４－（４－フェニル）フェノキシベンゾフェノン、３，３’－ジアミノ－４，４’－ジ（４－フェニルフェノキシ）ベンゾフェノン、１，３－ビス（３－アミノフェニルスルフィド）ベンゼン、１，３－ビス（４－アミノフェニルスルフィド）ベンゼン、１，４－ビス（４－アミノフェニルスルフィド）ベンゼン、１，３－ビス（３－アミノフェニルスルホン）ベンゼン、１，３－ビス（４－アミノフェニルスルホン）ベンゼン、１，４－ビス（４－アミノフェニルスルホン）ベンゼン、１，３－ビス〔２－（４－アミノフェニル）イソプロピル〕ベンゼン、１，４－ビス〔２－（３－アミノフェニル）イソプロピル〕ベンゼン、１，４－ビス〔２－（４－アミノフェニル）イソプロピル〕ベンゼンなどのベンゼン核３つのジアミン、３，３’－ビス（３－アミノフェノキシ）ビフェニル、３，３’－ビス（４－アミノフェノキシ）ビフェニル、４，４’－ビス（３－アミノフェノキシ）ビフェニル、４，’－ビス（４－アミノフェノキシ）ビフェニル、ビス〔３－（３－アミノフェノキシ）フェニル〕エーテル、ビス〔３－（４－アミノフェノキシ）フェニル〕エーテル、ビス〔４－（３－アミノフェノキシ）フェニル〕エーテル、ビス〔４－（４－アミノフェノキシ）フェニル〕エーテル、ビス〔３－（３－アミノフェノキシ）フェニル〕ケトン、ビス〔３－（４－アミノフェノキシ）フェニル〕ケトン、ビス〔４－（３－アミノフェノキシ）フェニル〕ケトン、ビス〔４－（４－アミノフェノキシ）フェニル〕ケトン（ビス（４－アミノフェノキシ）ベンゾフェノン）、ビス〔３－（３－アミノフェノキシ）フェニル〕スルフィド、ビス〔３－（４－アミノフェノキシ）フェニル〕スルフィド、ビス〔４－（３－アミノフェノキシ）フェニル〕スルフィド、ビス〔４－（４－アミノフェノキシ）フェニル〕スルフィド、ビス〔３－（３－アミノフェノキシ）フェニル〕スルホン、ビス〔３－（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－（４－アミノフェノキシ）フェニル〕スルホン、ビス〔３－（３－アミノフェノキシ）フェニル〕メタン、ビス〔３－（４－アミノフェノキシ）フェニル〕メタン、ビス〔４－（３－アミノフェノキシ）フェニル〕メタン、ビス〔４－（４－アミノフェノキシ）フェニル〕メタン、２，２－ビス〔３－（３－アミノフェノキシ）フェニル〕プロパン、２，２－ビス〔３－（４－アミノフェノキシ）フェニル〕プロパン、２，２－ビス〔４－（３－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〕プロパン、２，２－ビス〔３－（３－アミノフェノキシ）フェニル〕－１，１，１，３，３，３－ヘキサフルオロプロパン、２，２－ビス〔３－（４－アミノフェノキシ）フェニル〕－１，１，１，３，３，３－ヘキサフルオロプロパン、２，２－ビス〔４－（３－アミノフェノキシ）フェニル〕－１，１，１，３，３，３－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）フェニル〕－１，１，１，３，３，３－ヘキサフルオロプロパン、９，９－ビス（４－アミノフェニル）フルオレン、９，９－ビス（４－アミノフェニル）フルオレン、９，９'－ビス（４－アミノフェノキシフェニル）フルオレンなどのベンゼン核４つ以上のジアミン、５－アミノ－２－（ｐ－アミノフェニル）ベンゾオキサゾール、５－アミノ－２－（ｍ－アミノフェニル）ベンゾオキサゾール、６－アミノ－２－（ｐ－アミノフェニル）ベンゾオキサゾール、６－アミノ－２－（ｍ－アミノフェニル）ベンゾオキサゾール、２，２’－ｐ－フェニレンビス（５－アミノベンゾオキサゾール）、２，２’－ｐ－フェニレンビス（６－アミノベンゾオキサゾール）、１－（５－アミノベンゾオキサゾロ）－４－（６－アミノベンゾオキサゾロ）ベンゼン、２，６－（４，４’－ジアミノジフェニル）ベンゾ〔１，２－ｄ：５，４－ｄ’〕ビスオキサゾール、２，６－（４，４’－ジアミノジフェニル）ベンゾ〔１，２－ｄ：４，５－ｄ’〕ビスオキサゾール、２，６－（３，４’－ジアミノジフェニル）ベンゾ〔１，２－ｄ：５，４－ｄ’〕ビスオキサゾール、２，６－（３，４’－ジアミノジフェニル）ベンゾ〔１，２－ｄ：４，５－ｄ’〕ビスオキサゾール、２，６－（３，３’－ジアミノジフェニル）ベンゾ〔１，２－ｄ：５，４－ｄ’〕ビスオキサゾール、２，６－（３，３’－ジアミノジフェニル）ベンゾ〔１，２－ｄ：４，５－ｄ’〕ビスオキサゾール、２，４－ジアミノピリジン、２，６－ジアミノピリジン、２，５－ジアミノピリジンなどのベンゾオキサゾール構造を有するジアミンなどが挙げられるがこれらに限定されない。これらは単独でも、２種以上を混合して用いることもできる。 Specifically, the aromatic polyimide can be divided into a diamine component and an acid dianhydride component constituting the polyimide, and the following can be exemplified, but the aromatic polyimide is not limited thereto.
<Diamine component>
Examples of the diamine component having an aromatic group include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), 1,2-diaminobenzene (o-phenylenediamine), 2, 4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine 2,6-dimethyl-p-phenylenediamine 2,4-bis (amino-t-butyl) toluene 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 5-trifluoromethylbenzene-1,3-diamine, 5-trifluoromethylbenzene A benzene nucleus such as 1,2-diamine, 3,5-bis (trifluoromethyl) benzene-1,2-diamine, one diamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4, 4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4, 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl- 4,4'-diaminodiphenylmethane, bis (4-aminophenyl) sulfide, 4,4'-diaminobenzanilide, 3,3'-dichlorobenzidine, 3,3'-di Methylbenzidine, 2,2'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 2,2'-dimethoxybenzidine, 3,3'-diaminodiphenylether, 3,4'-diaminodiphenylether, 4,4'-diaminodiphenylether 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4 ' -Diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 3,3'-diamino-4,4'-dichlorobenzophenone, 3,3'-diamino-4,4'-dimethoxybenzophenone, 3,3'-diaminodiphenylmethane 3,4'-diaminodiphenylmethane, 4,4'-diamy Diphenylmethane, 2,2-bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) -1,1,1,3,3 3-hexafluoropropane, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl Sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 2,2'-bis (trifluoromethyl) biphenyl-4,4'-diamine, 3,3'-bis (trifluoromethyl) biphenyl-4,4'-diamine Two benzene nucleus diamines such as 3,3 ′, 5,5′-tetrafluorobiphenyl-4,4′-diamine, 4,4′-diaminooctafluorobiphenyl, -Bis (3-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (3-aminophenyl) benzene, 1,4-bis (4-aminophenyl) benzene, 1 , 3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy)- 4-trifluoromethylbenzene, 3,3′-diamino-4- (4-phenyl) phenoxybenzophenone, 3,3′-diamino-4,4′-di (4-phenylphenoxy) benzophenone, 1,3-bis (3-aminophenyl sulfide) benzene, 1,3-bis (4-aminophenyl sulfide) benzene, 1,4-bis (4-aminophenyl sulfide) Benzene, 1,3-bis (3-aminophenylsulfone) benzene, 1,3-bis (4-aminophenylsulfone) benzene, 1,4-bis (4-aminophenylsulfone) benzene, 1,3-bis [ Benzene such as 2- (4-aminophenyl) isopropyl] benzene, 1,4-bis [2- (3-aminophenyl) isopropyl] benzene, 1,4-bis [2- (4-aminophenyl) isopropyl] benzene Three core diamines, 3,3′-bis (3-aminophenoxy) biphenyl, 3,3′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 4, ′ -Bis (4-aminophenoxy) biphenyl, bis [3- (3-aminophenoxy) phenyl] ether, bis [3- (4-aminophenoxy) ) Phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, bis [3- (3-aminophenoxy) phenyl] ketone, bis [3 -(4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone (bis (4-aminophenoxy) benzophenone), bis [3- (3-aminophenoxy) phenyl] sulfide, bis [3- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) ) Phenyl] sulfide, bis [3- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [3- (3-aminophenoxy) ) Phenyl] methane, bis [3- (4-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 2,2 -Bis [3- (3-aminophenoxy) phenyl] propane, 2,2-bis [3- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] 1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2 , 2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1 , 1,1,3,3,3-hexafluoropropane, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-aminophenyl) fluorene, 9,9′-bis (4- 4 or more benzene nucleus diamines such as aminophenoxyphenyl) fluorene, 5-amino-2- (p-aminophenyl) benzoxazole, 5-amino-2- (m-aminophenyl) benzoxazole, 6-amino- -(P-aminophenyl) benzoxazole, 6-amino-2- (m-aminophenyl) benzoxazole, 2,2'-p-phenylenebis (5-aminobenzoxazole), 2,2'-p-phenylene Bis (6-aminobenzoxazole), 1- (5-aminobenzoxazolo) -4- (6-aminobenzoxazolo) benzene, 2,6- (4,4′-diaminodiphenyl) benzo [1,2 -D: 5,4-d '] bisoxazole, 2,6- (4,4'-diaminodiphenyl) benzo [1,2-d: 4,5-d'] bisoxazole, 2,6- (3 , 4′-diaminodiphenyl) benzo [1,2-d: 5,4-d ′] bisoxazole, 2,6- (3,4′-diaminodiphenyl) benzo [1,2-d: 4,5- d ′] bisoxazole, 2, -(3,3'-diaminodiphenyl) benzo [1,2-d: 5,4-d '] bisoxazole, 2,6- (3,3'-diaminodiphenyl) benzo [1,2-d: 4 , 5-d ′] bisoxazole, 2,4-diaminopyridine, 2,6-diaminopyridine, diamines having a benzoxazole structure such as 2,5-diaminopyridine, and the like, but are not limited thereto. These may be used alone or in combination of two or more.
　ジアミン成分は、ある面において、ｐ－フェニレンジアミン及びターフェニルジアミンからなる群から選ばれる少なくとも１種のジアミン成分を用いるのがよい。
　この場合、ｐ－フェニレンジアミン及び／又はターフェニルジアミンの量が、全ジアミン成分１００モル％中、７０モル％以上、好ましくは８０モル％以上、より好ましくは９０モル％以上であるのがよい。 In a certain aspect, the diamine component may be at least one diamine component selected from the group consisting of p-phenylenediamine and terphenyldiamine.
In this case, the amount of p-phenylenediamine and / or terphenyldiamine is 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, in 100 mol% of the total diamine components.
　ジアミン成分は、他の面において、ビフェニル骨格、イミダゾール骨格及びオキサゾール骨格からなる群から選ばれる少なくとも１種の第１の骨格を有する芳香族ジアミンであるのがよい。 In another aspect, the diamine component may be an aromatic diamine having at least one first skeleton selected from the group consisting of a biphenyl skeleton, an imidazole skeleton, and an oxazole skeleton.
＜酸二無水物成分＞
　芳香族基を有する酸二無水物成分として、ベンゼン骨格を有する酸二無水物、ナフタレン骨格を有する酸二無水物、ビフェニル骨格を有する酸二無水物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、ピロメリット酸二無水物、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、２，２’，３，３’－ビフェニル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オキシジフタル酸二無水物、ジフェニルスルホン－３，４，３’，４’－テトラカルボン酸二無水物、ビス（３，４－ジカルボキシフェニル）スルフィド二無水物、２，２－ビス（３，４－ジカルボキシフェニル）－１，１，１，３，３，３－ヘキサフルオロプロパン二無水物、２，３，３’，４’－ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、ビス（３，４－ジカルボキシフェニル）メタン二無水物、２，２－ビス（３，４－ジカルボキシフェニル）プロパン二無水物、ｐ－フェニレンビス（トリメリット酸モノエステル酸無水物）、ｐ－メチルフェニレンビス（トリメリット酸モノエステル酸無水物）、ｐ－（２，３－ジメチルフェニレン）ビス（トリメリット酸モノエステル酸無水物）、４，４’－ビフェニレンビス（トリメリット酸モノエステル酸無水物）、１，４－ナフタレンビス（トリメリット酸モノエステル酸無水物）、２，６－ナフタレンビス（トリメリット酸モノエステル酸無水物）２，２－ビス（４-ヒドロキシフェニル）プロパンジベンゾエート－３，３’，４，４’－テトラカルボン酸二無水物、ｍ－ターフェニル－３，４，３’，４’－テトラカルボン酸二無水物、ｐ－ターフェニル－３，４，３’，４’－テトラカルボン酸二無水物、１，３－ビス（３，４－ジカルボキシフェノキシ）ベンゼン二無水物、１，４－ビス（３，４－ジカルボキシフェノキシ）ベンゼン二無水物、１，４－ビス（３，４－ジカルボキシフェノキシ）ビフェニル二無水物、２，２－ビス〔（３，４－ジカルボキシフェノキシ）フェニル〕プロパン二無水物、２，３，６，７－ナフタレンテトラカルボン酸二無水物、１，４，５，８－ナフタレンテトラカルボン酸二無水物、４，４’－（２，２－ヘキサフルオロイソプロピリデン）ジフタル酸二無水物、Ｎ，Ｎ’－（２，２’－ビス｛トリフルオロメチル｝－[１,１’－ビフェニル] －４,４’－ジイル）ビス（１,３－ジオキソ－１,３－ジヒドロキシベンゾフラン－５－カルボキシアミド）などが挙げられるが、これらに限定されない。これらは単独でも、２種以上を混合して用いることもできる。 <Acid dianhydride component>
Examples of the acid dianhydride component having an aromatic group include, but are not limited to, an acid dianhydride having a benzene skeleton, an acid dianhydride having a naphthalene skeleton, and an acid dianhydride having a biphenyl skeleton.
Specifically, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2, 3,3 ′, 4′-biphenyltetracarboxylic dianhydride oxydiphthalic dianhydride, diphenylsulfone-3,4,3 ′, 4′-tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ) Sulfide dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,3 ′, 4′- Benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4 -Dicarboxyphenyl) propane dianhydride , P-phenylenebis (trimellitic acid monoester acid anhydride), p-methylphenylenebis (trimellitic acid monoester acid anhydride), p- (2,3-dimethylphenylene) bis (trimellitic acid monoester acid) Anhydride), 4,4'-biphenylenebis (trimellitic acid monoester acid anhydride), 1,4-naphthalene bis (trimellitic acid monoester acid anhydride), 2,6-naphthalene bis (trimellitic acid mono) Ester anhydride) 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, m-terphenyl-3,4,3 ′, 4 '-Tetracarboxylic dianhydride, p-terphenyl-3,4,3', 4'-tetracarboxylic dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) ben Zendianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 2,2-bis [( 3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4 '-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, N, N'-(2,2'-bis {trifluoromethyl}-[1,1'-biphenyl] -4,4'- Diyl) bis (1,3-dioxo-1,3-dihydroxybenzofuran-5-carboxamide) and the like. These may be used alone or in combination of two or more.
＜（Ａ）由来の芳香族ポリイミドの特性＞
　本願の組成物の（Ａ）に由来する芳香族ポリイミドは、次の（１）～（４）の特性を有する。
＜＜（１）～（４）の特性＞＞　
　（１）加熱時の重量変化における１％重量減少の温度が５００℃以上、好ましくは５２０℃以上、より好ましくは５５０℃以上；
　（２）波長１０００ｎｍで屈折率が１．７以上；
　（３）波長１０００ｎｍで屈折率と複屈折の差が０．１５以上、好ましくは０．１６以上；及び
　（４）表面エネルギーが４０ｄｙｎｅ／ｃｍ以上、好ましくは４５～７０ｄｙｎｅ／ｃｍ、より好ましくは４５～６０ｄｙｎｅ／ｃｍ。 <Characteristics of (A) -derived aromatic polyimide>
The aromatic polyimide derived from (A) of the composition of the present application has the following properties (1) to (4).
<< Characteristics of (1) to (4) >>
(1) The temperature of 1% weight loss in weight change during heating is 500 ° C. or higher, preferably 520 ° C. or higher, more preferably 550 ° C. or higher;
(2) A refractive index of 1.7 or more at a wavelength of 1000 nm;
(3) The difference in refractive index and birefringence at a wavelength of 1000 nm is 0.15 or more, preferably 0.16 or more; and (4) The surface energy is 40 dyne / cm or more, preferably 45 to 70 dyne / cm, more preferably 45 ~ 60 dyne / cm.
　なお、「（Ａ）に由来する芳香族ポリイミド」又は「（Ａ）由来の芳香族ポリイミド」とは、（Ａ）成分が「芳香族ポリイミド」のみからなる場合には、該「芳香族ポリイミド」のことをいう。また、（Ａ）成分が「芳香族ポリイミド前駆体」のみからなる場合、該前駆体がすべて「芳香族ポリイミド」となった場合の該「芳香族ポリイミド」のことをいう。（Ａ）成分が「芳香族ポリイミドＡ」及び「芳香族ポリイミド前駆体Ｂ」を有する場合、「芳香族ポリイミド前駆体Ｂ」から形成される「芳香族ポリイミドＢ’」と「芳香族ポリイミドＡ」との全体をいう。 "Aromatic polyimide derived from (A)" or "Aromatic polyimide derived from (A)" means that when the component (A) consists only of "aromatic polyimide", the "aromatic polyimide" I mean. Moreover, when (A) component consists only of "aromatic polyimide precursor", it means this "aromatic polyimide" when all the precursors become "aromatic polyimide". When the component (A) has “aromatic polyimide A” and “aromatic polyimide precursor B”, “aromatic polyimide B ′” and “aromatic polyimide A” formed from “aromatic polyimide precursor B” And the whole thing.
　これらの特性を有することにより、組成物から剥離層を形成した場合、該剥離層はガラス基板との密着性が良好となる一方、剥離層上に被剥離体を形成した場合、該被剥離体はカッター等で切り込みを入れることで容易に剥離することができる。 By having these characteristics, when a release layer is formed from the composition, the release layer has good adhesion to the glass substrate, while when a release object is formed on the release layer, the release object Can be easily peeled off by cutting with a cutter or the like.
＜（Ｂ）成分＞
　本願の組成物は、（Ｂ）成分として、アミド系溶媒を有する。
　アミド系溶媒とは、アミド基、アルキルアミド基を有する液体を意味する。
　アミド系溶媒として、例えばＮメチルピロリドン、Ｎエチルピロリドン、ＤＭＡｃ、ＤＭＦ、エクアミドＭ、エクアミドＢ（出光興産（株）製）などを挙げることができるがこれらに限定されない。
　アミド系溶媒として、下記式（Ｉ）で表される溶媒、及び／又は（ＩＩ）（式中、Ｒ１及びＲ２は各々独立に、炭素原子数１～４のアルキル基を表し、ｈは自然数を表す）で表される溶媒であるのがよい。 <(B) component>
The composition of the present application has an amide solvent as the component (B).
The amide solvent means a liquid having an amide group or an alkylamide group.
Examples of the amide solvent include, but are not limited to, N methylpyrrolidone, N ethylpyrrolidone, DMAc, DMF, ecamide M, ecamide B (manufactured by Idemitsu Kosan Co., Ltd.), and the like.
As the amide-based solvent, a solvent represented by the following formula (I), and / or (II) (wherein R 1 and R 2 each independently represents an alkyl group having 1 to 4 carbon atoms, h is (Representing a natural number).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　本願の組成物は、上記（Ａ）成分及び（Ｂ）成分の他に、種々の成分を有してもよい。例えば、架橋剤（以下、架橋性化合物ともいう。）を挙げることができるがこれらに限定されない。 The composition of the present application may have various components in addition to the components (A) and (B). Examples thereof include, but are not limited to, a crosslinking agent (hereinafter also referred to as a crosslinkable compound).
　該架橋性化合物として、例えばエポキシ基を２個以上含有する化合物、アミノ基の水素原子がメチロール基、アルコキシメチル基又はその両方で置換された基を有する、メラミン誘導体、ベンゾグアナミン誘導体又はグリコールウリルなどが挙げられるが、これらに限定されない。 Examples of the crosslinkable compound include a compound containing two or more epoxy groups, a melamine derivative, a benzoguanamine derivative or glycoluril having a group in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group or both. For example, but not limited to.
　以下に、架橋性化合物の具体例を挙げるが、これに限定されない。
　エポキシ基を２個以上含有する化合物として、エポリードＧＴ－４０１、エポリードＧＴ－４０３、エポリードＧＴ－３０１、エポリードＧＴ－３０２、セロキサイド２０２１、セロキサイド３０００（以上、（株）ダイセル製）等のシクロヘキセン構造を有するエポキシ化合物；エピコート１００１、エピコート１００２、エピコート１００３、エピコート１００４、エピコート１００７、エピコート１００９、エピコート１０１０、エピコート８２８（以上、ジャパンエポキシレジン（株）製（現：三菱化学（株）製、ｊＥＲ（登録商標）シリーズ））等のビスフェノールＡ型エポキシ化合物；エピコート８０７（ジャパンエポキシレジン（株）製）等のビスフェノールＦ型エポキシ化合物；エピコート１５２、エピコート１５４（以上、ジャパンエポキシレジン（株）製（現：三菱化学（株）製、ｊＥＲ（登録商標）シリーズ））、ＥＰＰＮ２０１、ＥＰＰＮ２０２（以上、日本化薬（株）製）等のフェノールノボラック型エポキシ化合物；ＥＣＯＮ－１０２、ＥＣＯＮ－１０３Ｓ、ＥＣＯＮ－１０４Ｓ、ＥＣＯＮ－１０２０、ＥＣＯＮ－１０２５、ＥＣＯＮ－１０２７（以上、日本化薬（株）製）、エピコート１８０Ｓ７５（ジャパンエポキシレジン（株）（現：三菱化学（株）製、ｊＥＲ（登録商標）シリーズ）製）等のクレゾールノボラック型エポキシ化合物；Ｖ８０００－Ｃ７（ＤＩＣ（株）製）等のナフタレン型エポキシ化合物；デナコールＥＸ－２５２（ナガセケムテックス（株）製）、ＣＹ１７５、ＣＹ１７７、ＣＹ１７９、アラルダイトＣＹ－１８２、アラルダイトＣＹ－１９２、アラルダイトＣＹ－１８４（以上、ＢＡＳＦ社製）、エピクロン２００、エピクロン４００（以上、ＤＩＣ（株）製）、エピコート８７１、エピコート８７２（以上、ジャパンエポキシレジン（株）製（現：三菱化学（株）製、ｊＥＲ（登録商標）シリーズ））、ＥＤ－５６６１、ＥＤ－５６６２（以上、セラニーズコーティング（株）製）等の脂環式エポキシ化合物；デナコールＥＸ－６１１、デナコールＥＸ－６１２、デナコールＥＸ－６１４、デナコールＥＸ－６２２、デナコールＥＸ－４１１、デナコールＥＸ－５１２、デナコールＥＸ－５２２、デナコールＥＸ－４２１、デナコールＥＸ－３１３、デナコールＥＸ－３１４、デナコールＥＸ－３１２（以上、ナガセケムテックス（株）製）等の脂肪族ポリグリシジルエーテル化合物などを挙げることができる。 Although the specific example of a crosslinkable compound is given to the following, it is not limited to this.
As compounds containing two or more epoxy groups, cyclohexene structures such as Epolide GT-401, Epolide GT-403, Epolide GT-301, Epolide GT-302, Celoxide 2021, Celoxide 3000 (above, manufactured by Daicel Corporation), etc. Epoxy compound having: Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010, Epicoat 828 (above, manufactured by Japan Epoxy Resins Co., Ltd. (currently: Mitsubishi Chemical Corporation, jER) (Trademark) series)), etc .; Bisphenol F type epoxy compounds such as Epicoat 807 (Japan Epoxy Resin Co., Ltd.); Epicoat 152, Epicoat 154 (or more) Phenol novolac type epoxy compounds such as Japan Epoxy Resin Co., Ltd. (currently Mitsubishi Chemical Co., Ltd., jER (registered trademark) series), EPPN201, EPPN202 (Nippon Kayaku Co., Ltd.); ECON- 102, ECON-103S, ECON-104S, ECON-1020, ECON-1025, ECON-1027 (above, Nippon Kayaku Co., Ltd.), Epicoat 180S75 (Japan Epoxy Resin Co., Ltd. (currently Mitsubishi Chemical Corporation) Cresol novolac type epoxy compound such as V8000-C7 (manufactured by DIC Corporation); naphthalene type epoxy compound such as V8000-C7 (manufactured by DIC Corporation); Denacol EX-252 (manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179, Araldite CY-182, Ara Daito CY-192, Araldite CY-184 (above, manufactured by BASF), Epicron 200, Epicron 400 (above, made by DIC Corporation), Epicoat 871, Epicoat 872 (above, made by Japan Epoxy Resins Co., Ltd. (current: Alicyclic epoxy compounds such as Mitsubishi Chemical Corporation, jER (registered trademark)), ED-5661, ED-5661 (above, Celanese Coating Co., Ltd.); Denacol EX-611, Denacol EX- 612, Denacol EX-614, Denacol EX-622, Denacol EX-411, Denacol EX-512, Denacol EX-522, Denacol EX-421, Denacol EX-313, Denacol EX-314, Denacol EX-312 (above, Nagase Aliphatic polygs such as Chemtex Co., Ltd. A lysidyl ether compound etc. can be mentioned.
　アミノ基の水素原子がメチロール基、アルコキシメチル基又はその両方で置換された基を有する、メラミン誘導体、ベンゾグアナミン誘導体又はグリコールウリルとして、トリアジン環１個当たりメトキシメチル基が平均３．７個置換されているＭＸ－７５０、トリアジン環１個当たりメトキシメチル基が平均５．８個置換されているＭＷ－３０（以上、（株）三和ケミカル製）；サイメル３００、サイメル３０１、サイメル３０３、サイメル３５０、サイメル３７０、サイメル７７１、サイメル３２５、サイメル３２７、サイメル７０３、サイメル７１２等のメトキシメチル化メラミン；サイメル２３５、サイメル２３６、サイメル２３８、サイメル２１２、サイメル２５３、サイメル２５４等のメトキシメチル化ブトキシメチル化メラミン；サイメル５０６、サイメル５０８等のブトキシメチル化メラミン；サイメル１１４１のようなカルボキシ基含有メトキシメチル化イソブトキシメチル化メラミン；サイメル１１２３のようなメトキシメチル化エトキシメチル化ベンゾグアナミン；サイメル１１２３－１０のようなメトキシメチル化ブトキシメチル化ベンゾグアナミン；サイメル１１２８のようなブトキシメチル化ベンゾグアナミン；サイメル１１２５－８０のようなカルボキシ基含有メトキシメチル化エトキシメチル化ベンゾグアナミン；サイメル１１７０のようなブトキシメチル化グリコールウリル；サイメル１１７２のようなメチロール化グリコールウリル（以上、三井サイアナミッド（株）製（現：日本サイテックインダストリーズ（株））等を挙げることができる。 As a melamine derivative, benzoguanamine derivative or glycoluril having a group in which the hydrogen atom of the amino group is substituted with a methylol group, an alkoxymethyl group or both, an average of 3.7 methoxymethyl groups are substituted per triazine ring MX-750, MW-30 substituted with an average of 5.8 methoxymethyl groups per triazine ring (above, manufactured by Sanwa Chemical Co., Ltd.); Cymel 300, Cymel 301, Cymel 303, Cymel 350, Methoxymethylated melamines such as Cymel 370, Cymel 771, Cymel 325, Cymel 327, Cymel 703, Cymel 712, etc .; Butoxymethylated melamine such as Cymel 506, Cymel 508, etc .; Carboxy group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141; Methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1123; Methoxymethylated butoxymethylated benzoguanamine; butoxymethylated benzoguanamine such as Cymel 1128; carboxymethyl-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80; butoxymethylated glycoluril such as Cymel 1170; Cymel 1172 Such as methylolated glycoluril (Mitsui Cyanamid Co., Ltd. (currently Japan Cytec Industries Co., Ltd.)) That.
　本願の組成物により、ガラス基板直上に設けられる剥離層を形成することができる。
　例えば、ガラス基板に本願の組成物を従来公知の手法により塗布し、得られた塗布膜を所定の温度で加熱することにより剥離層を形成することができる。
　また、被剥離体層は、剥離層上に形成することができる。被剥離体層は、一層であっても複数層であってもよい。種々のデバイスを作製するには、複数層であるのが現実的である。
　被剥離体層のうち剥離層直上の層は、用いる剥離層に依存するが、該剥離層との剥離性を良いもの、換言すると用いる剥離層との密着性が良くないもの、を用いるのがよい。 With the composition of the present application, a release layer provided directly on the glass substrate can be formed.
For example, the release layer can be formed by applying the composition of the present invention to a glass substrate by a conventionally known technique and heating the obtained coating film at a predetermined temperature.
Moreover, a to-be-separated body layer can be formed on a peeling layer. The layer to be peeled may be a single layer or a plurality of layers. In order to fabricate various devices, it is realistic to have a plurality of layers.
Of the layer to be peeled, the layer immediately above the release layer depends on the release layer to be used, but it is preferable to use a layer having good peelability with the release layer, in other words, a layer having poor adhesion to the release layer to be used. Good.
　本願の他の面として、被剥離体の製造方法を提供する。
　該方法は、
　ａ）本願の組成物をガラス基板上に塗布した後、剥離層を形成する工程；
　ｂ）該剥離層上に、被剥離体を形成する工程；及び
　ｃ）剥離層と被剥離体との界面において、被剥離体を剥離する工程；
を有することにより、被剥離体を得ることができる。
　ｂ）工程において、「被剥離体」は一層であっても複数層であってもよい。なお、「被剥離体」のうち剥離層直上の層は、用いる剥離層に依存するが、該剥離層との剥離性を良いもの、換言すると用いる剥離層との密着性が良くないもの、であるのがよい。
　以下、本発明を実施例に沿って説明するが、本発明は該実施例に限定されるものではない。 As another aspect of the present application, a method for manufacturing an object to be peeled is provided.
The method
a) a step of forming a release layer after applying the composition of the present application on a glass substrate;
b) a step of forming an object to be peeled on the release layer; and c) a step of peeling the object to be peeled at the interface between the release layer and the object to be peeled;
It is possible to obtain an object to be peeled.
In the step b), the “object to be peeled” may be a single layer or a plurality of layers. In addition, although the layer immediately above the release layer of the “object to be peeled” depends on the release layer to be used, the release layer has good peelability, in other words, the adhesiveness to the release layer to be used is not good. There should be.
EXAMPLES Hereinafter, although this invention is demonstrated along an Example, this invention is not limited to this Example.
　本実施例に用いる略語について、以下に列挙し、説明する。
＜溶媒＞
ＮＭＰ：Ｎ－メチルピロリドン。
＜アミン類＞
ＰＤＡ：p-フェニレンジアミン。
ＡＰＡＢ：２－（３－アミノフェニル）－５－アミノベンズイミダゾール。
ＤＡＴＰ：４，４”－ジアミノ－ｐ－ターフェニル。
６ＦＡＰ：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。 Abbreviations used in this example are listed and described below.
<Solvent>
NMP: N-methylpyrrolidone.
<Amines>
PDA: p-phenylenediamine.
APAB: 2- (3-aminophenyl) -5-aminobenzimidazole.
DATP: 4,4 "-diamino-p-terphenyl.
6FAP: 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
＜酸二無水物＞
ＢＰＤＡ：３，３’，４，４’－ビフェニルテトラカルボン酸二無水物。
ＢＡ－ＴＭＥ：４，４’-ビフェニレンビス（トリメリット酸モノエステル酸無水物）。
ＰＭＤＡ：ピロメリット酸二無水物。
＜アルデヒド＞
ＩＰＨＡ：イソフタルアルデヒド。 <Acid dianhydride>
BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride.
BA-TME: 4,4′-biphenylenebis (trimellitic acid monoester anhydride).
PMDA: pyromellitic dianhydride.
<Aldehyde>
IPHA: isophthalaldehyde.
［数平均分子量及び重量平均分子量の測定］
　ポリマーの重量平均分子量（以下「Ｍｗ」と略す）と分子量分布は、日本分光株式会社GPC装置（Shodex（登録商標）カラムKF803LおよびKF805L）を用い溶出溶媒としてジメチルホルムアミドを流量１ｍｌ／分、カラム温度５０℃の条件で測定した。なお、Ｍｗはポリスチレン換算値とした。 [Measurement of number average molecular weight and weight average molecular weight]
The weight average molecular weight (hereinafter abbreviated as “Mw”) and molecular weight distribution of the polymer were measured using a JASCO Corporation GPC apparatus (Shodex (registered trademark) columns KF803L and KF805L) with dimethylformamide as the elution solvent at a flow rate of 1 ml / min and column temperature. Measurements were made at 50 ° C. In addition, Mw was made into the polystyrene conversion value.
＜合成例＞
＜合成例１　ポリイミド前駆体Ｐ１の合成＞
　ＰＤＡ　１７．８ｇ（０．１６４モル）、ＤＡＴＰ　２．３８ｇ（０．００９モル）、およびＡＰＡＢＩ　２．０５ｇ（０．００９モル）をＮＭＰ　４２５ｇに溶解させ、ＢＰＤＡ　５２．８ｇ（０．１７９モル）を同時に添加した後、再度ＮＭＰ　７．４ｇを添加し、窒素雰囲気下中２３℃、２４時間反応させた。得られたポリイミド前駆体Ｐ１のＭｗは６３０００、分子量分布９．９であった。 <Synthesis example>
<Synthesis Example 1 Synthesis of Polyimide Precursor P1>
17.8 g (0.164 mol) of PDA, 2.38 g (0.009 mol) of DATP, and 2.05 g (0.009 mol) of APABI were dissolved in 425 g of NMP, and 52.8 g (0.179 mol) of BPDA. Was added at the same time, and 7.4 g of NMP was added again, and the mixture was reacted in a nitrogen atmosphere at 23 ° C. for 24 hours. Mw of the obtained polyimide precursor P1 was 63000 and molecular weight distribution 9.9.
＜合成例２　ポリイミド前駆体Ｐ２の合成＞
　ＤＡＴＰ　３０．８ｇ（０．１１８モル）をＮＭＰ　４２５ｇに溶解させ、ＢＰＤＡ　３４．１ｇ（０．１１６モル）を同時に添加した後、再度ＮＭＰ　１０ｇを添加し、窒素雰囲気下中２３℃、２４時間反応させた。得られたポリイミド前駆体Ｐ２のＭｗは７０７００、分子量分布９.７であった。 <Synthesis Example 2 Synthesis of Polyimide Precursor P2>
30.8 g (0.118 mol) of DATP was dissolved in 425 g of NMP, 34.1 g (0.116 mol) of BPDA was added at the same time, 10 g of NMP was added again, and the reaction was performed in a nitrogen atmosphere at 23 ° C. for 24 hours. I let you. Mw of obtained polyimide precursor P2 was 70700 and molecular weight distribution 9.7.
＜合成例３　ポリイミド前駆体Ｐ３の合成＞
　ＰＤＡ　２０．２６１ｇ（０．１８７５モル）とＴＰＤＡ　１２．２０６ｇ（０．０４６９モル）をＮＭＰ　６１７．４ｇに溶解し、１５℃に冷却後、ＰＭＤＡ　５０．１１２ｇ（０．２２９８モル）を添加し、窒素雰囲気下、５０℃で４８時間反応させた。得られたポリイミド前駆体Ｐ３のＭｗは８２，１００、分子量分布は２．７であった。 <Synthesis Example 3 Synthesis of Polyimide Precursor P3>
PDA 20.261 g (0.1875 mol) and TPDA 12.206 g (0.0469 mol) were dissolved in 617.4 g of NMP, cooled to 15 ° C., and PMDA 50.112 g (0.2298 mol) was added. The reaction was performed at 50 ° C. for 48 hours in a nitrogen atmosphere. Mw of the obtained polyimide precursor P3 was 82,100, and molecular weight distribution was 2.7.
＜合成例４　ポリイミド前駆体Ｐ４の合成＞
　ＰＤＡ　９．６６ｇ（０．０８９モル）とＡＰＡＢ　１．０５ｇ（０．００５モル）をＮＭＰ　４４０ｇに溶解し、ＢＰ－ＴＭＥ　４９．２ｇ（０．０９２モル）を添加し、窒素雰囲気下、室温で２４時間反応させた。得られたポリイミド前駆体Ｐ４のＭｗは５７０００、分子量分布は９．３であった。 <Synthesis Example 4 Synthesis of Polyimide Precursor P4>
Dissolve 9.66 g (0.089 mol) of PDA and 1.05 g (0.005 mol) of APAB in 440 g of NMP, add 49.2 g (0.092 mol) of BP-TME, and at room temperature under a nitrogen atmosphere. The reaction was performed for 24 hours. Mw of obtained polyimide precursor P4 was 57000, and molecular weight distribution was 9.3.
＜合成例５　ポリイミド前駆体Ｐ５の合成＞
　ＰＤＡ　３．１７６ｇ（０．０２９３７モル）をＮＭＰ　８８．２ｇに溶解し、ＢＰＤＡ　８．６２４ｇ（０．０２９３１モル）を添加した後、窒素雰囲気下、２３℃で２４時間反応させた。得られたポリイミド前駆体Ｐ５のＭｗは１０７，３００、分子量分布４．６であった。 <Synthesis Example 5 Synthesis of Polyimide Precursor P5>
3.176 g (0.02937 mol) of PDA was dissolved in 88.2 g of NMP, and 8.624 g (0.02931 mol) of BPDA was added, followed by reaction at 23 ° C. for 24 hours in a nitrogen atmosphere. Mw of the obtained polyimide precursor P5 was 107,300 and molecular weight distribution 4.6.
＜合成例６　ポリベンゾオキサゾール前駆体（Ｐ６）の合成＞
　６ＦＡＰ　３．１８ｇ（０．０５９モル）をＮＭＰ　７０ｇに溶解し、ＩＰＨＡ　７．９２ｇ（０．０６０モル）を添加した後、窒素雰囲気下、２３℃で２４時間反応させた。得られたポリマーのＭｗは１０７，３００、分子量分布４．６であった。 <Synthesis Example 6 Synthesis of Polybenzoxazole Precursor (P6)>
6.18 g (0.059 mol) of 6FAP was dissolved in 70 g of NMP, and 7.92 g (0.060 mol) of IPHA was added thereto, followed by reaction at 23 ° C. for 24 hours in a nitrogen atmosphere. Mw of the obtained polymer was 107,300, and the molecular weight distribution was 4.6.
＜合成例７　ポリイミド前駆体Ｐ７の合成＞
ＰＭＤＡ（９８）／／ｐ－ＰＤＡ（１００）
　ｐ－ＰＤＡ　１０．０７８ｇ（９３ｍｍｏｌ）をＮＭＰ　２２０．０ｇに溶解させた。得られた溶液に、ＰＭＤＡ　１９．９２２ｇ（９１ｍｍｏｌ）を加え、窒素雰囲気下、２３℃で２４時間反応させた。得られたポリマーのＭｗは５５，９００、分子量分布３．１であった。 <Synthesis Example 7 Synthesis of Polyimide Precursor P7>
PMDA (98) // p-PDA (100)
10.078 g (93 mmol) of p-PDA was dissolved in 220.0 g of NMP. PMDA 19.922g (91mmol) was added to the obtained solution, and it was made to react at 23 degreeC under nitrogen atmosphere for 24 hours. The obtained polymer had Mw of 55,900 and a molecular weight distribution of 3.1.
＜剥離層基板作製＞
　上記合成例１～７で得たＰ１～Ｐ７をＮＭＰにて４ｗｔ％に希釈し、１００ｍｍ×１００ｍｍガラス基板（ＯＡ－１０Ｇ無アルカリガラス）又はシリコンウエハ上にスピンコーターを用いて塗布した後、キュア条件Ａ～Ｃのいずれかで、オーブンで焼成し剥離層を作製した。
キュア条件Ａ：１２０℃で３０分維持→昇温→３００℃で６０分維持→昇温→４００℃で６０分維持。なお、昇温速度は１０℃／分であった。
キュア条件Ｂ：１２０℃で３０分維持→昇温→１８０℃で２０分維持→昇温→２４０℃で２０分維持→昇温→３００℃で２０分維持→昇温→４００℃で２０分維持→昇温→４５０℃で６０分維持。なお、昇温速度は１０℃／分であった。
キュア条件Ｃ：　８０℃で１０分維持→昇温→３００℃で３０分維持→昇温→４００℃で３０分維持。なお、昇温速度は１０℃／分であった。 <Production of release layer substrate>
P1 to P7 obtained in Synthesis Examples 1 to 7 were diluted to 4 wt% with NMP, applied onto a 100 mm × 100 mm glass substrate (OA-10G non-alkali glass) or silicon wafer using a spin coater, and then cured. Under any of the conditions A to C, firing in an oven produced a release layer.
Cure condition A : maintained at 120 ° C. for 30 minutes → temperature rise → 300 ° C. for 60 minutes → temperature rise → 400 ° C. for 60 minutes. The temperature rising rate was 10 ° C./min.
Cure condition B : Maintain at 120 ° C. for 30 minutes → Temperature rise → Maintenance at 180 ° C. for 20 minutes → Temperature rise → Maintain at 240 ° C. for 20 minutes → Temperature rise → Maintain at 300 ° C. for 20 minutes → Temperature rise → Maintain at 400 ° C. for 20 minutes → Temperature rise → Maintained at 450 ° C. for 60 minutes. The temperature rising rate was 10 ° C./min.
Cure condition C : maintained at 80 ° C. for 10 minutes → temperature rise → 300 ° C. for 30 minutes → temperature rise → 400 ° C. for 30 minutes. The temperature rising rate was 10 ° C./min.
　得られた塗布膜の膜厚は、接触式膜厚測定器（株式会社ULVAC製Dektak 3ST）を使用し、測定した。
　表１に、使用したＰ１～Ｐ７の前駆体、塗布基板、キュア条件、および作製した剥離層の膜厚を示す。 The film thickness of the obtained coating film was measured using a contact-type film thickness measuring device (Dektak 3ST manufactured by ULVAC, Inc.).
Table 1 shows the precursors of P1 to P7 used, the coated substrate, the curing conditions, and the film thickness of the produced release layer.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
＜クロスカット試験Ｉ＞
　表１で示す実施例１～５及び比較例１～３の、剥離層を備えた基板について、クロスカット試験Ｉで、基板（ガラス又はシリコンウエハ）／剥離層の密着力を確認した。
　クロスカット試験Ｉは、次のように行った。
　（１）剥離層上に、１ｍｍ角の正方形を１００個作製した。
　（２）その後、粘着テープ（セロテープ（登録商標））で上記の正方形をはりつけ、剥離工程を行った。
　（３）剥離工程後、基板に残存する、上記の正方形を数えた。 <Cross cut test I>
For the substrates provided with the release layers of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1, the adhesion of the substrate (glass or silicon wafer) / release layer was confirmed by cross-cut test I.
The crosscut test I was performed as follows.
(1) On the release layer, 100 1 mm squares were produced.
(2) Thereafter, the above square was attached with an adhesive tape (cello tape (registered trademark)), and a peeling process was performed.
(3) After the peeling step, the squares remaining on the substrate were counted.
＜クロスカット試験Ｉの結果の指標＞
　クロスカット試験の結果、剥離の程度を以下の指標で示す。
　５Ｂ：剥離せず。
　４Ｂ：５％以下の剥離。
　３Ｂ：５～１５％の剥離。
　２Ｂ：１５～３５％の剥離。
　１Ｂ：３５～６５％の剥離。
　０Ｂ：６５％～８０％の剥離。
　Ｂ：８０％～９５％の剥離。
　Ａ：９５％～１００％未満の剥離。
　ＡＡ：１００％の剥離。 <Index of results of crosscut test I>
As a result of the cross-cut test, the degree of peeling is indicated by the following index.
5B: Not peeled off.
4B: Peeling of 5% or less.
3B: 5-15% peeling.
2B: 15-35% peeling.
1B: 35-65% peeling.
0B: 65% to 80% peeling.
B: 80% to 95% peeling.
A: 95% to less than 100% peeling.
AA: 100% peeling.
　上記クロスカット試験Ｉとは別に、表１で示す実施例１～５及び比較例１～３の、剥離層を備えた基板について、該剥離層を構成する成分の特性、即ち（１）加熱時の重量変化における１％重量減少を示す温度、（２）波長１０００ｎｍでの屈折率、（３）波長１０００ｎｍでの複屈折、及び（４）表面エネルギー、を測定した。なお、各特性の測定条件などを以下に示す。 Apart from the cross-cut test I, the characteristics of the components constituting the release layer, ie, (1) during heating, for the substrates provided with the release layers of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1 A temperature showing 1% weight loss in weight change of (2), (2) refractive index at a wavelength of 1000 nm, (3) birefringence at a wavelength of 1000 nm, and (4) surface energy were measured. The measurement conditions for each characteristic are shown below.
＜（１）加熱時の重量変化における１％重量減少を示す温度＞
　ブルカー（株）製　ＴＤ－ＤＴＡ２０００ＳＴを用いて、窒素雰囲気下で熱重量（ＴＧ）測定を行い、重量が１％減少する温度を求めた。 <(1) Temperature showing a 1% weight reduction in weight change during heating>
Using a TD-DTA2000ST manufactured by Bruker Co., Ltd., thermogravimetric (TG) measurement was performed in a nitrogen atmosphere, and the temperature at which the weight decreased by 1% was determined.
＜（２）波長１０００ｎｍでの屈折率及び（３）複屈折率＞
　高速分光エリプソメーターＭ－２０００（ジェー・エー・ウーラム・ジャパン（株）製）を用いて、屈折率及び複屈折率を測定した。なお、屈折率は、１０００ｎｍの値の面内屈折率とし、複屈折率は、面内屈折率と面外屈折率の差とした。 <(2) Refractive index at a wavelength of 1000 nm and (3) Birefringence>
The refractive index and birefringence were measured using a high-speed spectroscopic ellipsometer M-2000 (manufactured by JA Woollam Japan Co., Ltd.). The refractive index was an in-plane refractive index having a value of 1000 nm, and the birefringence was a difference between the in-plane refractive index and the out-of-plane refractive index.
＜（４）表面エネルギー＞
　全自動接触角計 ＤＭ－７０１（共和界面科学（株）製）を用いて、上記合成例１～７で得たＰ１～Ｐ７から得られた剥離層の表面エネルギーを測定した。なお、測定に用いた溶媒は、水とヨウ化メチレンであり、これらの溶媒の接触角から算出した。 <(4) Surface energy>
Using a fully automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.), the surface energy of the release layer obtained from P1 to P7 obtained in Synthesis Examples 1 to 7 was measured. In addition, the solvent used for the measurement was water and methylene iodide, and was calculated from the contact angle of these solvents.
＜被剥離体の形成とその剥離試験（クロスカット試験ＩＩ）＞
　実施例１～５及び比較例１～３の、剥離層を備えた基板上に被剥離体を形成し、その剥離の程度をクロスカット試験ＩＩで確認した。
＜＜被剥離体層の作製＞＞
　剥離層を備えた基板の該剥離層上に、被剥離体としてポリイミド層を形成した。
　具体的には、表１に示す、実施例１～５及び比較例１～３の、剥離層を備える基板の、剥離層上に、上記合成例５又は合成例１で得られた前駆体Ｐ５又はＰ１をバーコーターで塗布した。その後、オーブンにて１２０℃で３０分維持→昇温→１８０℃で２０分維持→昇温→２４０℃／２０分維持→昇温→３００℃で２０分維持→昇温→４００℃で２０分維持→昇温→４５０℃で６０分維持（いずれの昇温においてもその速度は１０℃／分であった）でキュアを行い、ポリイミドからなる膜厚１５μｍの被剥離体層を作製した。 <Formation of object to be peeled and peel test (cross-cut test II)>
An object to be peeled was formed on the substrate having the peeling layer of Examples 1 to 5 and Comparative Examples 1 to 3, and the degree of peeling was confirmed by the cross-cut test II.
<< Preparation of layer to be peeled >>
A polyimide layer was formed as an object to be peeled on the release layer of the substrate provided with the release layer.
Specifically, the precursor P5 obtained in Synthesis Example 5 or Synthesis Example 1 is formed on the release layer of the substrate having the release layer of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1. Alternatively, P1 was applied with a bar coater. Then, maintain in an oven at 120 ° C. for 30 minutes → temperature increase → 180 ° C. for 20 minutes → temperature increase → 240 ° C./20 minute maintenance → temperature increase → 300 ° C. for 20 minutes → temperature increase → 400 ° C. for 20 minutes Maintenance → Temperature rise → Cure at 450 ° C. for 60 minutes (the speed was 10 ° C./min at any temperature rise) to produce a 15 μm-thick peeled layer made of polyimide.
＜＜クロスカット試験ＩＩ＞＞
　上記で得られた、被剥離体層及び剥離層を備える基板について、被剥離体層／剥離層間の密着力をクロスカット試験ＩＩで確認した。
　クロスカット試験ＩＩは、クロスカット試験Ｉと同様に行った。
　表２に、（１）加熱時の重量変化における１％重量減少を示す温度（表２中、「（１）」で表記する）、（２）波長１０００ｎｍでの屈折率（表２中、「（２）」で表記する）、（３）該（２）の屈折率と複屈折との差（表２中、「（３）」で表記する）、（４）表面エネルギー（表２中、「（４）」で表記する。ただし、単位はｄｙｎｅ／ｃｍである）、被剥離体層で用いたポリイミド前駆体、並びにクロスカット試験Ｉ及びＩＩの結果を示す。 << Crosscut Test II >>
About the board | substrate provided with the to-be-separated body layer and the peeling layer obtained above, the adhesive force between a to-be-separated body layer / peeling layer was confirmed by the crosscut test II.
The crosscut test II was performed in the same manner as the crosscut test I.
Table 2 shows (1) a temperature indicating a 1% weight decrease in weight change during heating (indicated by “(1)” in Table 2), (2) a refractive index at a wavelength of 1000 nm (in Table 2, “ (2) ”, (3) difference between the refractive index and birefringence of (2) (indicated by“ (3) ”in Table 2), (4) surface energy (in Table 2, This is indicated by “(4)” (where the unit is dyne / cm), the polyimide precursor used in the peeled layer, and the results of cross-cut tests I and II.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表２から次のことがわかる。実施例１～５の剥離層は、試験Ｉの結果が５Ｂであることから、基板から剥離層が剥がれることがない一方、試験ＩＩの結果がＡＡであることから、剥離層から被剥離体層のみが剥離することがわかる。要するに、本発明の剥離層用組成物から形成された剥離層は、所望の剥離結果をもたらすことがわかる。
　一方、比較例１及び比較例３は、試験Ｉの結果がＡＡであるため、剥離層が基板から剥離することがわかる。要するに、比較例１及び比較例３は、所望の剥離結果を得ることができないことがわかる。また、比較例２は、試験Ｉ及び試験ＩＩが共に５Ｂであることから、剥離層と基板との界面においても、剥離層と被剥離体層との界面においても剥離せず、所望の剥離結果を得ることができないことがわかる。 Table 2 shows the following. In the peeling layers of Examples 1 to 5, since the result of Test I is 5B, the peeling layer is not peeled off from the substrate, while the result of Test II is AA. It turns out that only peels. In short, it can be seen that the release layer formed from the composition for release layer of the present invention provides a desired release result.
On the other hand, Comparative Example 1 and Comparative Example 3 show that the release layer peels from the substrate because the result of Test I is AA. In short, it can be seen that Comparative Example 1 and Comparative Example 3 cannot obtain a desired peeling result. In Comparative Example 2, since both Test I and Test II are 5B, neither the interface between the release layer and the substrate nor the interface between the release layer and the layer to be peeled is peeled off. It can be seen that cannot be obtained.

Claims (6)

  1. 　ガラス基板直上に設ける剥離層を形成するための組成物であって、
    　該組成物が
    　（Ａ）芳香族ポリイミド及び／又は芳香族ポリイミド前駆体；及び
    　（Ｂ）アミド系溶媒；
    を有し、
    前記（Ａ）由来の芳香族ポリイミドは、下記（１）～（４）を満たす、上記組成物：
    　（１）加熱時の重量変化における１％重量減少の温度が５００℃以上；
    　（２）波長１０００ｎｍで屈折率が１．７以上；
    　（３）波長１０００ｎｍで屈折率と複屈折の差が０．１５以上；及び
    　（４）表面エネルギーが４０ｄｙｎｅ／ｃｍ以上。     A composition for forming a release layer provided directly on a glass substrate,
    The composition comprises (A) an aromatic polyimide and / or an aromatic polyimide precursor; and (B) an amide solvent;
    Have
    The aromatic polyimide derived from (A) satisfies the following (1) to (4):
    (1) The temperature of 1% weight reduction in weight change during heating is 500 ° C. or higher;
    (2) A refractive index of 1.7 or more at a wavelength of 1000 nm;
    (3) The difference between the refractive index and the birefringence is 0.15 or more at a wavelength of 1000 nm; and (4) the surface energy is 40 dyne / cm or more.
  2. 　前記（Ａ）成分が、ｐ－フェニレンジアミン及びターフェニルジアミンからなる群から選ばれる少なくとも１種のジアミン成分を用いて製造される請求項１記載の組成物。 The composition according to claim 1, wherein the component (A) is produced using at least one diamine component selected from the group consisting of p-phenylenediamine and terphenyldiamine.
  3. 　ｐ－フェニレンジアミン及び／又はターフェニルジアミンの量が、全ジアミン成分１００モル％中、７０モル％以上である請求項２記載の組成物。 3. The composition according to claim 2, wherein the amount of p-phenylenediamine and / or terphenyldiamine is 70 mol% or more in 100 mol% of all diamine components.
  4. 　前記（Ａ）成分が、ビフェニル骨格、イミダゾール骨格及びオキサゾール骨格からなる群から選ばれる少なくとも１種の第１の骨格を有する芳香族ジアミンを用いて製造される請求項１～３のいずれか１項記載の組成物。 The component (A) is produced using an aromatic diamine having at least one first skeleton selected from the group consisting of a biphenyl skeleton, an imidazole skeleton, and an oxazole skeleton. The composition as described.
  5. 　前記（Ａ）成分が、ベンゼン骨格、ナフタレン骨格及びビフェニル骨格からなる群から選ばれる少なくとも１種の第２の骨格を有する酸二無水物を用いて製造される請求項１～４のいずれか１項記載の組成物。 The component (A) is produced using an acid dianhydride having at least one second skeleton selected from the group consisting of a benzene skeleton, a naphthalene skeleton, and a biphenyl skeleton. A composition according to item.
  6. 　前記（Ｂ）成分が、下記式（Ｉ）で表される溶媒、及び／又は（ＩＩ）（式中、Ｒ１及びＲ２は各々独立に、炭素原子数１～４のアルキル基を表し、ｈは自然数を表す）で表される溶媒である請求項１～５のいずれか１項記載の組成物。
    Figure JPOXMLDOC01-appb-C000001
         The component (B) is a solvent represented by the following formula (I), and / or (II) (wherein R 1 and R 2 each independently represents an alkyl group having 1 to 4 carbon atoms, The composition according to any one of claims 1 to 5, wherein h represents a natural number).
    Figure JPOXMLDOC01-appb-C000001
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016140238A1 (en) * 2015-03-04 2016-09-09 日産化学工業株式会社 Peeling layer forming composition
WO2016158990A1 (en) * 2015-03-31 2016-10-06 日産化学工業株式会社 Composition for forming release layer, and release layer
JPWO2014199965A1 (en) * 2013-06-10 2017-02-23 日産化学工業株式会社 Resin composition for display substrate, resin thin film for display substrate, and method for producing resin thin film for display substrate
WO2018025955A1 (en) * 2016-08-03 2018-02-08 日産化学工業株式会社 Composition for forming releasing layer
JP2022504001A (en) * 2018-11-20 2022-01-13 エルジー・ケム・リミテッド A laminate for manufacturing a flexible element and a method for manufacturing a flexible element using the same

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110050013B (en) * 2016-12-08 2022-11-29 日产化学株式会社 Method for producing release layer
CN110791220A (en) * 2018-08-02 2020-02-14 达迈科技股份有限公司 Transparent polyimide composite film for flexible display and method for manufacturing the same
KR102251290B1 (en) * 2018-11-02 2021-05-11 주식회사 엘지화학 Polyimide film for flexible substrate
US20220119676A1 (en) * 2018-12-24 2022-04-21 Pi Advanced Materials Co., Ltd. Polyamic acid composition for manufacturing display substrate and method for manufacturing substrate for display by using same
KR102013535B1 (en) * 2018-12-31 2019-08-22 에스케이씨코오롱피아이 주식회사 Method for Preparing Polyimide Precursor Composition With Improved Storage Stability and Viscosity Stability, and Polyimide Precursor Composition Prepared by Using the Same

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05315630A (en) * 1992-05-13 1993-11-26 Sanyo Electric Co Ltd Manufacture of flexible thin film solar cell
JP2009021322A (en) * 2007-07-11 2009-01-29 Hitachi Displays Ltd Method of manufacturing semiconductor device
WO2010071145A1 (en) * 2008-12-19 2010-06-24 東洋紡績株式会社 Laminated body, manufacturing method thereof, and laminated circuit board
WO2011030716A1 (en) * 2009-09-08 2011-03-17 旭硝子株式会社 Glass/resin laminate, and electronic device using same
JP2012035583A (en) * 2010-08-11 2012-02-23 Kaneka Corp Method of manufacturing laminate, and flexible device
JP2012102155A (en) * 2010-11-05 2012-05-31 Kaneka Corp Polyimide film, laminate, and flexible device
JP2014022459A (en) * 2012-07-13 2014-02-03 Asahi Kasei E-Materials Corp Laminate and manufacturing method of flexible device
JP2014218056A (en) * 2013-05-10 2014-11-20 ユニチカ株式会社 Laminate for flexible device
JP2015074783A (en) * 2013-10-04 2015-04-20 財團法人工業技術研究院Ｉｎｄｕｓｔｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ Release layer, substrate structure, and method of producing flexible electronic device

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06334204A (en) * 1993-05-21 1994-12-02 Ind Technol Res Inst Preparation of flexible amorphous silicon solar cell
JP3809681B2 (en) 1996-08-27 2006-08-16 セイコーエプソン株式会社 Peeling method
JP4619462B2 (en) 1996-08-27 2011-01-26 セイコーエプソン株式会社 Thin film element transfer method
JP4619461B2 (en) 1996-08-27 2011-01-26 セイコーエプソン株式会社 Thin film device transfer method and device manufacturing method
GB0327093D0 (en) 2003-11-21 2003-12-24 Koninkl Philips Electronics Nv Active matrix displays and other electronic devices having plastic substrates
JP2006117791A (en) * 2004-10-21 2006-05-11 Nippon Steel Chem Co Ltd Method for producing polyimide film
TWI321241B (en) * 2005-09-14 2010-03-01 Ind Tech Res Inst Flexible pixel array substrate and method of fabricating the same
JP2013153124A (en) * 2011-10-20 2013-08-08 Nitto Denko Corp Method for manufacturing semiconductor device
WO2013058054A1 (en) * 2011-10-20 2013-04-25 日東電工株式会社 Thermally-detachable sheet
TW201324685A (en) * 2011-10-20 2013-06-16 Nitto Denko Corp Thermally-detachable sheet
JP5931672B2 (en) * 2012-09-24 2016-06-08 新日鉄住金化学株式会社 Polyimide laminate and method for producing the same
KR102467104B1 (en) * 2014-03-31 2022-11-14 닛산 가가쿠 가부시키가이샤 Composition for forming releasing layer

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05315630A (en) * 1992-05-13 1993-11-26 Sanyo Electric Co Ltd Manufacture of flexible thin film solar cell
JP2009021322A (en) * 2007-07-11 2009-01-29 Hitachi Displays Ltd Method of manufacturing semiconductor device
WO2010071145A1 (en) * 2008-12-19 2010-06-24 東洋紡績株式会社 Laminated body, manufacturing method thereof, and laminated circuit board
WO2011030716A1 (en) * 2009-09-08 2011-03-17 旭硝子株式会社 Glass/resin laminate, and electronic device using same
JP2012035583A (en) * 2010-08-11 2012-02-23 Kaneka Corp Method of manufacturing laminate, and flexible device
JP2012102155A (en) * 2010-11-05 2012-05-31 Kaneka Corp Polyimide film, laminate, and flexible device
JP2014022459A (en) * 2012-07-13 2014-02-03 Asahi Kasei E-Materials Corp Laminate and manufacturing method of flexible device
JP2014218056A (en) * 2013-05-10 2014-11-20 ユニチカ株式会社 Laminate for flexible device
JP2015074783A (en) * 2013-10-04 2015-04-20 財團法人工業技術研究院Ｉｎｄｕｓｔｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ Release layer, substrate structure, and method of producing flexible electronic device

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2014199965A1 (en) * 2013-06-10 2017-02-23 日産化学工業株式会社 Resin composition for display substrate, resin thin film for display substrate, and method for producing resin thin film for display substrate
WO2016140238A1 (en) * 2015-03-04 2016-09-09 日産化学工業株式会社 Peeling layer forming composition
WO2016158990A1 (en) * 2015-03-31 2016-10-06 日産化学工業株式会社 Composition for forming release layer, and release layer
WO2018025955A1 (en) * 2016-08-03 2018-02-08 日産化学工業株式会社 Composition for forming releasing layer
JPWO2018025955A1 (en) * 2016-08-03 2019-06-13 日産化学株式会社 Release layer forming composition
JP7135857B2 (en) 2016-08-03 2022-09-13 日産化学株式会社 Composition for forming release layer
JP2022504001A (en) * 2018-11-20 2022-01-13 エルジー・ケム・リミテッド A laminate for manufacturing a flexible element and a method for manufacturing a flexible element using the same
JP7311079B2 (en) 2018-11-20 2023-07-19 エルジー・ケム・リミテッド LAMINATED BODY FOR FLEXIBLE DEVICE MANUFACTURING AND METHOD FOR MANUFACTURING FLEXIBLE DEVICE USING THE SAME

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