WO2016140238A1 - Peeling layer forming composition - Google Patents

Peeling layer forming composition Download PDF

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Publication number
WO2016140238A1
WO2016140238A1 PCT/JP2016/056347 JP2016056347W WO2016140238A1 WO 2016140238 A1 WO2016140238 A1 WO 2016140238A1 JP 2016056347 W JP2016056347 W JP 2016056347W WO 2016140238 A1 WO2016140238 A1 WO 2016140238A1
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WO
WIPO (PCT)
Prior art keywords
release layer
substrate
composition
tetracarboxylic dianhydride
forming
Prior art date
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PCT/JP2016/056347
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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
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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 CN201680017216.6A priority Critical patent/CN107406674A/en
Priority to JP2017503670A priority patent/JP6620805B2/en
Priority to KR1020177027213A priority patent/KR102483075B1/en
Publication of WO2016140238A1 publication Critical patent/WO2016140238A1/en

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Classifications

    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • 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
    • 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
    • C08G73/1067—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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • 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
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133305—Flexible substrates, e.g. plastics, organic film
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon

Definitions

  • the present invention relates to a release layer forming composition, and more particularly, to a release layer forming composition for forming a release layer provided on a 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 substrate with high translucency, 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.
  • laser treatment takes a long time and it is difficult to peel off a layer to be peeled, there is a problem that it is difficult to increase the productivity of device fabrication.
  • JP 10-125929 A Japanese Patent Laid-Open No. 10-125931 International Publication No. 2005/050754 JP-A-10-125930
  • This invention is made
  • the present inventors have used a composition containing polyamic acid, a carbon-based filler, and an organic solvent for excellent adhesion to a substrate and a flexible electronic device.
  • the present invention has been completed by finding that a release layer having appropriate adhesion to a resin substrate to be obtained and appropriate release properties can be formed.
  • a composition for forming a release layer comprising a polyamic acid, a carbon-based filler, and an organic solvent; 2.
  • a method for producing a flexible electronic device comprising a resin substrate, characterized in that a release layer of 6 is used, 8).
  • the manufacturing method according to 7 is characterized in that the resin substrate is a substrate made of polyimide.
  • the composition for forming a release layer of the present invention By using the composition for forming a release layer of the present invention, it is possible to obtain a film having excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate peelability with good reproducibility.
  • the composition for forming a release layer of the present invention can contribute to simplification of the production process of a flexible electronic device including a resin substrate, improvement of its yield, and the like.
  • the composition for forming a release layer of the present invention contains a polyamic acid, a carbon-based filler, and an organic solvent.
  • the release layer in the present invention is a layer provided immediately above a glass substrate for a predetermined purpose.
  • a flexible electronic made of a substrate and a resin such as polyimide is used.
  • the resin substrate can be easily peeled from the substrate.
  • a release layer may be used.
  • the polyamic acid used in the present invention is not particularly limited and can be obtained by reacting diamine with tetracarboxylic dianhydride, but improves the functionality of the resulting film as a release layer.
  • the polyamic acid obtained by making an aromatic diamine and aromatic tetracarboxylic dianhydride react is preferable from the viewpoint of making it.
  • the aromatic diamine is not particularly limited as long as it has two amino groups in the molecule and has an aromatic ring, but an aromatic diamine containing 1 to 5 benzene nuclei is preferable.
  • 1,4-diaminobenzene p-phenylenediamine
  • 1,3-diaminobenzene m-phenylenediamine
  • 1,2-diaminobenzene o-phenylenediamine
  • 2,4-diamino 1,4-diaminobenzene (p-phenylenediamine)
  • 1,3-diaminobenzene m-phenylenediamine
  • 1,2-diaminobenzene o-phenylenediamine
  • 2,4-diamino 2,4-diamino.
  • Aromatic diamines are preferred. Specifically, p-phenylenediamine, m-phenylenediamine, 2- (3-aminophenyl) -5-aminobenzimidazole, 2- (4-aminophenyl) -5-aminobenzooxol, 4,4 ′ '-Diamino-p-terphenyl and the like are preferred.
  • the amount of aromatic diamine used is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and most preferably in all diamines. Is 100 mol%.
  • aromatic tetracarboxylic dianhydride is not particularly limited as long as it has two dicarboxylic anhydride sites in the molecule and has an aromatic ring, but an aromatic tetracarboxylic dianhydride contains 1 to 5 benzene nuclei.
  • aromatic tetracarboxylic dianhydrides are preferred.
  • pyromellitic dianhydride benzene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1 , 2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, naphthalene-1,2,7,8-tetracarboxylic dianhydride, naphthalene- 2,3,5,6-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, biphenyl -2,2 ', 3,3'-tetracarboxylic dianhydride, biphenyl-2,3,3', 4'-tetracarboxylic dianhydride,
  • aromatic carboxylic dianhydrides having one or two benzene nuclei are preferred from the viewpoint of improving the functionality of the resulting film as a release layer.
  • an aromatic tetracarboxylic dianhydride represented by any one of formulas (C1) to (C12) is preferred, and any one of formulas (C1) to (C7) and (C9) to (C11)
  • the aromatic tetracarboxylic dianhydride shown is more preferred.
  • the amount of aromatic tetracarboxylic dianhydride used is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, in the total tetracarboxylic dianhydride. More preferably, it is 95 mol% or more, and most preferably 100 mol%.
  • the polyamic acid contained in the composition for forming a release layer of the present invention can be obtained.
  • the weight average molecular weight of the polyamic acid is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and even more preferably 15,000 to 200,000 from the viewpoint of handling properties.
  • the weight average molecular weight is an average molecular weight obtained in terms of standard polystyrene by gel permeation chromatography (GPC) analysis.
  • the organic solvent used in such a reaction is not particularly limited as long as it does not adversely affect the reaction.
  • Specific examples thereof include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N— Ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropyl Amides, 3-propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethyl Propylamide, 3-tert-butoxy-N, N-dimethylpropylamide, ⁇ -butyrolactone, etc. That.
  • the reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent used, and is usually about 0 to 100 ° C., but it prevents imidization in the solution of the resulting polyamic acid and contains a high content of polyamic acid units. In order to maintain the amount, it is preferably about 0 to 70 ° C, more preferably about 0 to 60 ° C, and still more preferably about 0 to 50 ° C.
  • the reaction time depends on the reaction temperature and the reactivity of the raw material, and cannot be specified unconditionally, but is usually about 1 to 100 hours.
  • the carbon filler used in the present invention is not particularly limited as long as it contains carbon atoms as a main component, but is preferably a fibrous carbon material, a layered carbon material, or a particulate carbon material. These carbon-based fillers can be used alone or in combination of two or more.
  • the fibrous carbon material include carbon nanotubes (CNT) and carbon nanofibers (CNF), and CNTs are preferable from the viewpoints of dispersibility and availability.
  • CNTs are generally produced by arc discharge, chemical vapor deposition (CVD), laser ablation, etc., but the CNTs used in the present invention may be obtained by any method.
  • a single-layer CNT hereinafter also abbreviated as SWCNT
  • SWCNT a single-layer CNT in which a single carbon film (graphene sheet) is wound in a cylindrical shape and two layers in which two graphene sheets are wound in a concentric shape.
  • DWCNT single-layer CNT
  • MWCNT multi-layer CNT
  • the layered carbon material include graphite and graphene.
  • the graphite is not particularly limited, and various commercially available graphites can be used.
  • Graphene is a sheet of sp2-bonded carbon atoms with a thickness of 1 atom, and has a hexagonal lattice structure like a honeycomb made of carbon atoms and their bonds, and its thickness is about 0.38 nm. It is said.
  • graphene oxide obtained by processing graphite by the Hummers method may be used.
  • the particulate carbon material include carbon black such as furnace black, channel black, acetylene black, and thermal black.
  • the carbon black is not particularly limited, and various commercially available carbon blacks can be used, and the particle diameter is preferably 5 to 500 nm.
  • the ratio of the polyamic acid to the carbon-based filler in the composition for forming a release layer of the present invention is about 0.001 to 0.1 carbon-based filler with respect to polyamic acid 1 in terms of mass ratio, preferably 0. It is about 0.005 to 0.05, more preferably about 0.01 to 0.02.
  • the release layer forming composition of the present invention contains an organic solvent.
  • this organic solvent the same thing as the specific example of the reaction solvent of the said reaction is mentioned.
  • 2-Imidazolidinone, N-ethyl-2-pyrrolidone, and ⁇ -butyrolactone are preferred, and N-methyl-2-pyrrolidone is more preferred.
  • ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy -2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxy Propoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate and other solvents
  • the method for preparing the composition for forming a release layer of the present invention is arbitrary.
  • a preferable example of the preparation method is a method of filtering the reaction solution containing the target polyamic acid obtained by the above-described method, and adding a carbon-based filler to the obtained filtrate to perform a dispersion treatment.
  • the filtrate may be diluted or concentrated if necessary for the purpose of adjusting the concentration.
  • Dispersion treatment includes mechanical treatment, wet treatment using a ball mill, bead mill, jet mill, or the like, and ultrasonic treatment using a bath type or probe type sonicator.
  • the time for the dispersion treatment is arbitrary, but is preferably about 1 minute to 10 hours, and more preferably about 5 minutes to 5 hours. In the dispersion treatment, heat treatment may be performed as necessary.
  • the solvent used for dilution is not particularly limited, and specific examples thereof include the same examples as the specific examples of the reaction solvent for the above reaction. The solvent used for dilution may be used singly or in combination of two or more.
  • the concentration of the polyamic acid in the composition for forming a release layer of the present invention is appropriately set in consideration of the thickness of the release layer to be produced, the viscosity of the composition, etc., but is usually about 1 to 30% by mass, preferably It is about 1 to 20% by mass. By setting such a concentration, a release layer having a thickness of about 0.05 to 5 ⁇ m can be obtained with good reproducibility.
  • the concentration of the polyamic acid should be adjusted by adjusting the amount of diamine and tetracarboxylic dianhydride used as the raw material for the polyamic acid, adjusting the amount when the isolated polyamic acid is dissolved in the solvent, etc. Can do.
  • the viscosity of the composition for forming a release layer of the present invention is appropriately set in consideration of the thickness of the release layer to be produced, etc., but a film having a thickness of about 0.05 to 5 ⁇ m is particularly reproducible. When it is intended to obtain, it is usually about 10 to 10,000 mPa ⁇ s, preferably about 20 to 5,000 mPa ⁇ s at 25 ° C.
  • the viscosity can be measured using a commercially available liquid viscosity measurement viscometer, for example, with reference to the procedure described in JIS K7117-2 at a temperature of the composition of 25 ° C. .
  • a conical plate type (cone plate type) rotational viscometer is used as the viscometer, and preferably the composition temperature is 25 ° C. using 1 ° 34 ′ ⁇ R24 as a standard cone rotor. It can be measured under the condition of ° C.
  • An example of such a rotational viscometer is TVE-25L manufactured by Toki Sangyo Co., Ltd.
  • composition for forming a release layer of the present invention may contain a crosslinking agent or the like in order to improve the film strength, for example, in addition to the polyamic acid and the organic solvent.
  • release layer forming composition of the present invention is applied to a substrate, and the resulting coating film is heated to thermally imidize the polyamic acid.
  • a release layer made of a polyimide film having adhesion and moderate peelability can be obtained.
  • the release layer When such a release layer of the present invention is formed on a substrate, the release layer may be formed on a partial surface of the substrate, or may be formed on the entire surface.
  • a release layer As an aspect of forming a release layer on a part of the surface of the substrate, an embodiment in which the release layer is formed only within a predetermined range of the substrate surface, a release layer is formed in a pattern such as a dot pattern or a line and space pattern on the entire surface of the substrate.
  • substrate means what is used for manufacture of a flexible electronic device etc. by which the composition for peeling layer formation of this invention is applied to the surface.
  • the substrate examples include glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal (silicon wafer, etc.), Although wood, paper, slate, etc. are mentioned, since the peeling layer of this invention has sufficient adhesiveness with respect to it, glass is preferable.
  • substrate surface may be comprised with the single material and may be comprised with two or more materials. As an aspect in which the substrate surface is composed of two or more materials, a certain range of the substrate surface is composed of a certain material, and the other surface is composed of other materials. A dot pattern is formed on the entire surface of the substrate. There is a mode in which a material in a pattern such as a line and space pattern is present in other materials.
  • the coating method is not particularly limited, but for example, cast coating method, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, die coating method, ink jet method, printing method (letter plate) , Intaglio, lithographic, screen printing, etc.).
  • the heating temperature for imidization is usually appropriately determined within the range of 50 to 550 ° C., but is preferably more than 150 ° C. to 510 ° C. By setting the heating temperature in this way, it is possible to sufficiently advance the imidization reaction while preventing the obtained film from being weakened.
  • the heating time varies depending on the heating temperature, and cannot be generally defined, but is usually 5 minutes to 5 hours.
  • the imidization rate may be in the range of 50 to 100%.
  • the heating temperature is gradually increased as it is, and finally from 150 ° C. to 510 ° C. for 30 minutes to 4 hours.
  • the method of heating is mentioned.
  • Heating at 30 ° C. for 30 minutes to 4 hours is preferable.
  • Examples of the appliance used for heating include a hot plate and an oven.
  • the heating atmosphere may be under air or under an inert gas, and may be under normal pressure or under reduced pressure.
  • the thickness of the release layer is usually about 0.01 to 50 ⁇ m, and preferably about 0.05 to 20 ⁇ m from the viewpoint of productivity.
  • desired thickness is implement
  • the release layer described above has excellent adhesion to a substrate, particularly a glass substrate, moderate adhesion to a resin substrate, and moderate release. Therefore, the release layer according to the present invention, in the manufacturing process of the flexible electronic device, without damaging the resin substrate of the device, the resin substrate together with the circuit and the like formed on the resin substrate from the substrate. It can be suitably used for peeling.
  • a release layer is formed on a glass substrate by the method described above.
  • a resin solution for forming a resin substrate is applied on the release layer, and this coating film is heated to form a resin substrate fixed to the glass substrate via the release layer of the present invention.
  • the substrate is formed with a larger area than the area of the release layer so as to cover the entire release layer.
  • the resin substrate include a resin substrate made of polyimide, which is a typical resin substrate for flexible electronic devices, and examples of the resin solution for forming the resin substrate include a polyimide solution and a polyamic acid solution.
  • the method for forming the resin substrate may follow a conventional method.
  • a desired circuit is formed on the resin substrate fixed to the base via the release layer of the present invention, and then the resin substrate is cut along the release layer, for example.
  • the resin substrate and the substrate are separated by peeling from the release layer. At this time, a part of the substrate may be cut together with the release layer.
  • the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer were measured using a GPC apparatus manufactured by JASCO Corporation (column: OHpak SB803-HQ and OHpak SB804-HQ manufactured by Showa Denko KK); : Dimethylformamide / LiBr.H 2 O (29.6 mM) / H 3 PO 4 (29.6 mM) / THF (0.1% by mass); flow rate: 1.0 mL / min; column temperature: 40 ° C .; Mw: (Standard polystyrene equivalent value) was used (same in the following examples and comparative examples).
  • Examples 1-2 to 1-4> A release layer was formed in the same manner as in Example 1-1 except that the release layer-forming composition obtained in Preparation Example 3-1 was used.
  • a resin substrate having a thickness of about 10 ⁇ m on the glass substrate.
  • the temperature increase rate from room temperature to 300 ° C., 300 to 400 ° C., and 400 to 500 ° C. was 10 ° C./min.
  • a resin substrate was produced on the release layer obtained in Examples 1-2 to 1-4. Then, by performing cross-cutting of the resin substrate / peeling layer (cutting 1 mm in length and width, the same applies hereinafter), 100 mass cuts are performed, adhesive tape is applied to the 100 mass cut portions, and the tape is peeled off. The degree of peeling was evaluated based on (5B to 0B, B, A, AA).

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
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Abstract

A peeling layer forming composition is provided which contains polyamic acid, a carbon-based filler, and an organic solvent.

Description

剥離層形成用組成物Release layer forming composition
　本発明は、剥離層形成用組成物に関し、詳述すれば、基体上に設ける剥離層を形成するための剥離層形成用組成物に関する。 The present invention relates to a release layer forming composition, and more particularly, to a release layer forming composition for forming a release layer provided on a 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及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 functions such as bending, thinning and weight reduction. 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、更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 substrate with high translucency, 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 laser treatment takes a long time and it is difficult to peel off a layer to be peeled, there is a problem that it is difficult to increase the productivity of device fabrication.
特開平１０－１２５９２９号公報JP 10-125929 A 特開平１０－１２５９３１号公報Japanese Patent Laid-Open No. 10-125931 国際公開第２００５／０５０７５４号International Publication No. 2005/050754 特開平１０－１２５９３０号公報JP-A-10-125930
　本発明は、上記事情に鑑みてなされたものであり、フレキシブル電子デバイスの樹脂基板に損傷を与えることなく剥離することができる剥離層形成用組成物を提供することを目的とする。 This invention is made | formed in view of the said situation, and it aims at providing the composition for peeling layer formation which can peel without damaging the resin substrate of a flexible electronic device.
　本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、ポリアミック酸と、炭素系フィラーと、有機溶媒とを含む組成物から、基体との優れた密着性及びフレキシブル電子デバイスに用いられる樹脂基板との適度な密着性と適度な剥離性を有する剥離層を形成できることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have used a composition containing polyamic acid, a carbon-based filler, and an organic solvent for excellent adhesion to a substrate and a flexible electronic device. The present invention has been completed by finding that a release layer having appropriate adhesion to a resin substrate to be obtained and appropriate release properties can be formed.
　すなわち、本発明は、
１．　ポリアミック酸と、炭素系フィラーと、有機溶媒とを含む剥離層形成用組成物、
２．　前記ポリアミック酸が、芳香族ジアミンと芳香族テトラカルボン酸二無水物とを反応させて得られたポリアミック酸である１の剥離層形成用組成物、
３．　前記芳香族ジアミンが、ベンゼン核を１～５つ含む芳香族ジアミンであることを特徴とする２の剥離層形成用組成物、
４．　前記芳香族テトラカルボン酸二無水物が、ベンゼン核を１～５つ含む芳香族テトラカルボン酸二無水物であることを特徴とする２又は３の剥離層形成用組成物、
５．　前記炭素系フィラーが、カーボンナノチューブ又はグラフェンである１～４のいずれかの剥離層形成用組成物、
６．　１～５のいずれかの剥離層形成用組成物を用いて形成される剥離層、
７．　６の剥離層を用いることを特徴とする、樹脂基板を備えるフレキシブル電子デバイスの製造方法、
８．　前記樹脂基板が、ポリイミドからなる基板であることを特徴とする７の製造方法
を提供する。 That is, the present invention
1. A composition for forming a release layer comprising a polyamic acid, a carbon-based filler, and an organic solvent;
2. 1. A composition for forming a release layer, wherein the polyamic acid is a polyamic acid obtained by reacting an aromatic diamine with an aromatic tetracarboxylic dianhydride,
3. 2. The composition for forming a release layer according to 2, wherein the aromatic diamine is an aromatic diamine containing 1 to 5 benzene nuclei,
4). 2 or 3 composition for forming a release layer, wherein the aromatic tetracarboxylic dianhydride is an aromatic tetracarboxylic dianhydride containing 1 to 5 benzene nuclei,
5. The release layer forming composition according to any one of 1 to 4, wherein the carbon-based filler is a carbon nanotube or graphene,
6). A release layer formed using the release layer forming composition according to any one of 1 to 5,
7). A method for producing a flexible electronic device comprising a resin substrate, characterized in that a release layer of 6 is used,
8). The manufacturing method according to 7 is characterized in that the resin substrate is a substrate made of polyimide.
　本発明の剥離層形成用組成物を用いることで、基体との優れた密着性及び樹脂基板との適度な密着性と適度な剥離性とを有する膜を再現性よく得ることができる。このような組成物を用いることで、フレキシブル電子デバイスの製造プロセスにおいて、基体上に形成された樹脂基板や、更にその上に設けられる回路等に損傷を与えることなく、当該回路等とともに当該樹脂基板を、当該基体から分離することが可能となる。したがって、本発明の剥離層形成用組成物は、樹脂基板を備えるフレキシブル電子デバイスの製造プロセスの簡便化やその歩留り向上等に寄与し得る。 By using the composition for forming a release layer of the present invention, it is possible to obtain a film having excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate peelability with good reproducibility. By using such a composition, in the manufacturing process of the flexible electronic device, the resin substrate formed on the substrate, and further, the resin substrate together with the circuit, etc. without damaging the circuit provided on the substrate. Can be separated from the substrate. Therefore, the composition for forming a release layer of the present invention can contribute to simplification of the production process of a flexible electronic device including a resin substrate, improvement of its yield, and the like.
　以下、本発明について、より詳細に説明する。
　本発明の剥離層形成用組成物は、ポリアミック酸と、炭素系フィラーと、有機溶媒とを含む。ここで、本発明における剥離層とは、所定の目的でガラス基体直上に設けられる層であって、その典型例としては、フレキシブル電子デバイスの製造プロセスにおいて、基体と、ポリイミドといった樹脂からなるフレキシブル電子デバイスの樹脂基板との間に当該樹脂基板を所定のプロセス中において固定するために設けられ、且つ、当該樹脂基板上に電子回路等の形成した後において当該樹脂基板が当該基体から容易に剥離できるようにするために設けられる剥離層が挙げられる。 Hereinafter, the present invention will be described in more detail.
The composition for forming a release layer of the present invention contains a polyamic acid, a carbon-based filler, and an organic solvent. Here, the release layer in the present invention is a layer provided immediately above a glass substrate for a predetermined purpose. As a typical example, in a manufacturing process of a flexible electronic device, a flexible electronic made of a substrate and a resin such as polyimide is used. Provided between the device resin substrate and the resin substrate in a predetermined process, and after the electronic circuit or the like is formed on the resin substrate, the resin substrate can be easily peeled from the substrate. For example, a release layer may be used.
　本発明で用いるポリアミック酸は、特に限定されるものではなく、ジアミンとテトラカルボン酸二無水物とを反応させて得ることができるものであるが、得られる膜の剥離層としての機能性を向上させる観点から、芳香族ジアミンと芳香族テトラカルボン酸二無水物とを反応させて得られるポリアミック酸が好ましい。 The polyamic acid used in the present invention is not particularly limited and can be obtained by reacting diamine with tetracarboxylic dianhydride, but improves the functionality of the resulting film as a release layer. The polyamic acid obtained by making an aromatic diamine and aromatic tetracarboxylic dianhydride react is preferable from the viewpoint of making it.
　芳香族ジアミンとしては、分子内に２つのアミノ基を有し、かつ、芳香環を有する限り特に限定されるものではないが、ベンゼン核を１～５つ含む芳香族ジアミンが好ましい。 The aromatic diamine is not particularly limited as long as it has two amino groups in the molecule and has an aromatic ring, but an aromatic diamine containing 1 to 5 benzene nuclei is preferable.
　その具体例としては、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、２，４，６－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－ジアミン等のベンゼン核が１つのジアミン；１，２－ナフタレンジアミン、１，３－ナフタレンジアミン、１，４－ナフタレンジアミン、１，５－ナフタレンジアミン、１，６－ナフタレンジアミン、１，７－ナフタレンジアミン、１，８－ナフタレンジアミン、２，３－ナフタレンジアミン、２，６－ナフタレンジアミン、４，４’－ビフェニルジアミン、２，２’－ビス（トリフルオロメチル）－４，４’－ジアミノビフェニル、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、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、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、２－（３－アミノフェニル）－５－アミノベンズイミダゾール、２－（４－アミノフェニル）－５－アミノベンゾオキゾール等のベンゼン核が２つのジアミン；１，５－ジアミノアントラセン、２，６－ジアミノアントラセン、９，１０－ジアミノアントラセン、１，８－ジアミノフェナントレン、２，７－ジアミノフェナントレン、３，６－ジアミノフェナントレン、９，１０－ジアミノフェナントレン、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（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、４，４’’－ジアミノ－ｐ－ターフェニル、４，４’’－ジアミノ－ｍ－ターフェニル等のベンゼン核が３つのジアミン等を挙げることができるが、これらに限定されない。これらは単独でも、２種以上を組み合わせて用いることもできる。 Specific examples thereof include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), 1,2-diaminobenzene (o-phenylenediamine), 2,4-diamino. Toluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 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-1,2-diamine, 3,5-bis (trifluoromethyl ) A diamine having one benzene nucleus such as benzene-1,2-diamine; 1,2-naphthalenediamine, 1,3-naphthalenediamine, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 1,6-naphthalene Diamine, 1,7-naphthalenediamine, 1,8-naphthalenediamine, 2,3-naphthalenediamine, 2,6-naphthalenediamine, 4,4'-biphenyldiamine, 2,2'-bis (trifluoromethyl)- 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetra Methyl-4,4′-diaminodiphenylmethane, 4,4′-diaminobenzanilide, 3,3′-dichlorobenzidine, 3, '-Dimethylbenzidine, 2,2'-dimethylbenzidine, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 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-amino) Phenyl) -1,1,1,3,3,3-hexafluoropropane, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide, 4,4′-diaminodiphenyl sulfoxide, 3,3 ′ -Bis (trifluoromethyl) biphenyl-4,4'-diamine, 3,3 ', 5,5'-tetrafluorobiphenyl-4,4' Two benzene nuclei such as diamine, 4,4′-diaminooctafluorobiphenyl, 2- (3-aminophenyl) -5-aminobenzimidazole, 2- (4-aminophenyl) -5-aminobenzoxazole Diamine; 1,5-diaminoanthracene, 2,6-diaminoanthracene, 9,10-diaminoanthracene, 1,8-diaminophenanthrene, 2,7-diaminophenanthrene, 3,6-diaminophenanthrene, 9,10-diaminophenanthrene 1,3-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 (3-aminophenyl sulfide) benzene, 1,3-bis ( -Aminophenylsulfide) benzene, 1,4-bis (4-aminophenylsulfide) benzene, 1,3-bis (3-aminophenylsulfone) benzene, 1,3-bis (4-aminophenylsulfone) benzene, 1 , 4-bis (4-aminophenylsulfone) benzene, 1,3-bis [2- (4-aminophenyl) isopropyl] benzene, 1,4-bis [2- (3-aminophenyl) isopropyl] benzene, 1 3,4-bis [2- (4-aminophenyl) isopropyl] benzene, 4,4 ″ -diamino-p-terphenyl, 4,4 ″ -diamino-m-terphenyl, etc., have three diamine nuclei However, it is not limited to these. These can be used alone or in combination of two or more.
　中でも、得られる膜の剥離層としての機能性を向上させる観点から、芳香環及びそれに縮合する複素環上にメチル基等の置換基を有しない芳香族環及び複素芳香族環のみから構成される芳香族ジアミンが好ましい。具体的には、ｐ－フェニレンジアミン、ｍ－フェニレンジアミン、２－（３－アミノフェニル）－５－アミノベンズイミダゾール、２－（４－アミノフェニル）－５－アミノベンゾオキゾール、４，４’’－ジアミノ－ｐ－ターフェニル等が好ましい。 Among these, from the viewpoint of improving the functionality of the resulting film as a release layer, it is composed only of aromatic rings and heteroaromatic rings that do not have a substituent such as a methyl group on the aromatic ring and the heterocyclic ring condensed thereto. Aromatic diamines are preferred. Specifically, p-phenylenediamine, m-phenylenediamine, 2- (3-aminophenyl) -5-aminobenzimidazole, 2- (4-aminophenyl) -5-aminobenzooxol, 4,4 ′ '-Diamino-p-terphenyl and the like are preferred.
　本発明において、芳香族ジアミンの使用量は、全ジアミン中、好ましくは７０モル％以上、より好ましくは８０モル％以上、より一層好ましくは９０モル％以上、更に好ましくは９５モル％以上、最も好ましくは１００モル％である。このような使用量を採用することで、基体との優れた密着性及び樹脂基板との適度な密着性と適度な剥離性を有する膜を再現性よく得ることができる。 In the present invention, the amount of aromatic diamine used is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and most preferably in all diamines. Is 100 mol%. By adopting such a use amount, it is possible to obtain a film having excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate peelability with good reproducibility.
　芳香族テトラカルボン酸二無水物としては、分子内に２つのジカルボン酸無水物部位を有し、かつ、芳香環を有する限り特に限定されるものではないが、ベンゼン核を１～５つ含む芳香族テトラカルボン酸二無水物が好ましい。 The aromatic tetracarboxylic dianhydride is not particularly limited as long as it has two dicarboxylic anhydride sites in the molecule and has an aromatic ring, but an aromatic tetracarboxylic dianhydride contains 1 to 5 benzene nuclei. Group tetracarboxylic dianhydrides are preferred.
　その具体例としては、ピロメリット酸二無水物、ベンゼン－１，２，３，４－テトラカルボン酸二無水物、ナフタレン－１，２，３，４－テトラカルボン酸二無水物、ナフタレン－１，２，５，６－テトラカルボン酸二無水物、ナフタレン－１，２，６，７－テトラカルボン酸二無水物、ナフタレン－１，２，７，８－テトラカルボン酸二無水物、ナフタレン－２，３，５，６－テトラカルボン酸二無水物、ナフタレン－２，３，６，７－テトラカルボン酸二無水物、ナフタレン－１，４，５，８－テトラカルボン酸二無水物、ビフェニル－２，２’，３，３’－テトラカルボン酸二無水物、ビフェニル－２，３，３’，４’－テトラカルボン酸二無水物、ビフェニル－３，３’，４，４’－テトラカルボン酸二無水物、アントラセン－１，２，３，４－テトラカルボン酸二無水物、アントラセン－１，２，５，６－テトラカルボン酸二無水物、アントラセン－１，２，６，７－テトラカルボン酸二無水物、アントラセン－１，２，７，８－テトラカルボン酸二無水物、アントラセン－２，３，６，７－テトラカルボン酸二無水物、フェナントレン－１，２，３，４－テトラカルボン酸二無水物、フェナントレン－１，２，５，６－テトラカルボン酸二無水物、フェナントレン－１，２，６，７－テトラカルボン酸二無水物、フェナントレン－１，２，７，８－テトラカルボン酸二無水物、フェナントレン－１，２，９，１０－テトラカルボン酸二無水物、フェナントラセン－２，３，５，６－テトラカルボン酸二無水物、フェナントレン－２，３，６，７－テトラカルボン酸二無水物、フェナントレン－２，３，９，１０－テトラカルボン酸二無水物、フェナントレン－３，４，５，６－テトラカルボン酸二無水物、フェナントレン－３，４，９，１０－テトラカルボン酸二無水物等を挙げることができるが、これらに限定されない。これらは単独でも、２種以上を組み合わせて用いることもできる。 Specific examples thereof include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1 , 2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, naphthalene-1,2,7,8-tetracarboxylic dianhydride, naphthalene- 2,3,5,6-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, biphenyl -2,2 ', 3,3'-tetracarboxylic dianhydride, biphenyl-2,3,3', 4'-tetracarboxylic dianhydride, biphenyl-3,3 ', 4,4'-tetra Carboxylic dianhydride, anthracene-1 2,3,4-tetracarboxylic dianhydride, anthracene-1,2,5,6-tetracarboxylic dianhydride, anthracene-1,2,6,7-tetracarboxylic dianhydride, anthracene-1 , 2,7,8-tetracarboxylic dianhydride, anthracene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,3,4-tetracarboxylic dianhydride, phenanthrene- 1,2,5,6-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene -1,2,9,10-tetracarboxylic dianhydride, phenanthracene-2,3,5,6-tetracarboxylic dianhydride, phenanthrene-2,3,6,7-tetracarboxylic dianhydride Water, phenanthrene-2,3,9,10-tetracarboxylic dianhydride, phenanthrene-3,4,5,6-tetracarboxylic dianhydride, phenanthrene-3,4,9,10-tetracarboxylic acid Although dianhydride etc. can be mentioned, it is not limited to these. These can be used alone or in combination of two or more.
　中でも、得られる膜の剥離層としての機能性を向上させる観点から、ベンゼン核が１つ又は２つの芳香族カルボン酸二無水物が好ましい。具体的には、式（Ｃ１）～（Ｃ１２）のいずれかで示される芳香族テトラカルボン酸二無水物が好ましく、式（Ｃ１）～（Ｃ７）及び（Ｃ９）～（Ｃ１１）のいずれかで示される芳香族テトラカルボン酸二無水物がより好ましい。 Of these, aromatic carboxylic dianhydrides having one or two benzene nuclei are preferred from the viewpoint of improving the functionality of the resulting film as a release layer. Specifically, an aromatic tetracarboxylic dianhydride represented by any one of formulas (C1) to (C12) is preferred, and any one of formulas (C1) to (C7) and (C9) to (C11) The aromatic tetracarboxylic dianhydride shown is more preferred.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　本発明において、芳香族テトラカルボン酸二無水物の使用量は、全テトラカルボン酸二無水物中、好ましくは７０モル％以上、より好ましくは８０モル％以上、より一層好ましくは９０モル％以上、更に好ましくは９５モル％以上、最も好ましくは１００モル％である。このような使用量を採用することで、基体との優れた密着性及び樹脂基板との適度な密着性と適度な剥離性を有する膜を再現性よく得ることができる。 In the present invention, the amount of aromatic tetracarboxylic dianhydride used is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, in the total tetracarboxylic dianhydride. More preferably, it is 95 mol% or more, and most preferably 100 mol%. By adopting such a use amount, it is possible to obtain a film having excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate peelability with good reproducibility.
　以上説明したジアミンとテトラカルボン酸二無水物とを反応させることで、本発明の剥離層形成用組成物が含むポリアミック酸を得ることができる。 By reacting the diamine and tetracarboxylic dianhydride described above, the polyamic acid contained in the composition for forming a release layer of the present invention can be obtained.
　前記ポリアミック酸の重量平均分子量は、５,０００～１,０００,０００が好ましく、１０,０００～５００,０００がより好ましく、ハンドリング性の観点から１５,０００～２００,０００がより一層好ましい。なお、本発明において重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）分析による標準ポリスチレン換算で得られる平均分子量である。 The weight average molecular weight of the polyamic acid is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and even more preferably 15,000 to 200,000 from the viewpoint of handling properties. In the present invention, the weight average molecular weight is an average molecular weight obtained in terms of standard polystyrene by gel permeation chromatography (GPC) analysis.
　このような反応に用いる有機溶媒は、反応に悪影響を及ぼさない限り特に限定されるものではないが、その具体例としては、ｍ－クレゾール、２－ピロリドン、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、Ｎ－ビニル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、３－メトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－エトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－プロポキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－イソプロポキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－ｓｅｃ－ブトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－ｔｅｒｔ－ブトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、γ－ブチロラクトン等が挙げられる。なお、有機溶媒は１種類単独で又は２種以上を組み合わせて使用してもよい。 The organic solvent used in such a reaction is not particularly limited as long as it does not adversely affect the reaction. Specific examples thereof include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N— Ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropyl Amides, 3-propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethyl Propylamide, 3-tert-butoxy-N, N-dimethylpropylamide, γ-butyrolactone, etc. That. In addition, you may use an organic solvent individually by 1 type or in combination of 2 or more types.
　反応温度は、用いる溶媒の融点から沸点までの範囲で適宜設定すればよく、通常０～１００℃程度であるが、得られるポリアミック酸の溶液中でのイミド化を防いでポリアミック酸単位の高含有量を維持するためには、好ましくは０～７０℃程度であり、より好ましくは０～６０℃程度であり、より一層好ましくは０～５０℃程度である。 The reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent used, and is usually about 0 to 100 ° C., but it prevents imidization in the solution of the resulting polyamic acid and contains a high content of polyamic acid units. In order to maintain the amount, it is preferably about 0 to 70 ° C, more preferably about 0 to 60 ° C, and still more preferably about 0 to 50 ° C.
　反応時間は、反応温度や原料物質の反応性に依存するため一概に規定できないが、通常１～１００時間程度である。 The reaction time depends on the reaction temperature and the reactivity of the raw material, and cannot be specified unconditionally, but is usually about 1 to 100 hours.
　本発明で用いる炭素系フィラーは、炭素原子を主成分としてなるものである限り特に限定されるものではないが、繊維状カーボン材料、層状カーボン材料、粒子状カーボン材料が好ましい。なお、これらの炭素系フィラーは、それぞれ単独で、又は２種以上組み合わせて用いることができる。 The carbon filler used in the present invention is not particularly limited as long as it contains carbon atoms as a main component, but is preferably a fibrous carbon material, a layered carbon material, or a particulate carbon material. These carbon-based fillers can be used alone or in combination of two or more.
　繊維状カーボン材料の具体例としては、カーボンナノチューブ（ＣＮＴ）、カーボンナノファイバー（ＣＮＦ）等が挙げられるが、分散性、入手性等の観点からＣＮＴが好ましい。ＣＮＴは、一般的に、アーク放電法、化学気相成長法（ＣＶＤ法）、レーザー・アブレーション法等によって作製されるが、本発明に使用されるＣＮＴはいずれの方法で得られたものでもよい。また、ＣＮＴには１枚の炭素膜（グラフェン・シート）が円筒状に巻かれた単層ＣＮＴ（以下、ＳＷＣＮＴとも略記する）と、２枚のグラフェン・シートが同心円状に巻かれた２層ＣＮＴ（以下、ＤＷＣＮＴとも略記する）と、複数のグラフェン・シートが同心円状に巻かれた多層ＣＮＴ（ＭＷＣＮＴ）とがあるが、本発明においては、ＳＷＣＮＴ、ＤＷＣＮＴ、ＭＷＣＮＴをそれぞれ単体で、又は複数を組み合わせて使用できる。 Specific examples of the fibrous carbon material include carbon nanotubes (CNT) and carbon nanofibers (CNF), and CNTs are preferable from the viewpoints of dispersibility and availability. CNTs are generally produced by arc discharge, chemical vapor deposition (CVD), laser ablation, etc., but the CNTs used in the present invention may be obtained by any method. . In addition, a single-layer CNT (hereinafter also abbreviated as SWCNT) in which a single carbon film (graphene sheet) is wound in a cylindrical shape and two layers in which two graphene sheets are wound in a concentric shape. There are CNT (hereinafter abbreviated as DWCNT) and multi-layer CNT (MWCNT) in which a plurality of graphene sheets are concentrically wound. Can be used in combination.
　なお、上記の方法でＳＷＣＮＴ、ＤＷＣＮＴ又はＭＷＣＮＴを作製する際には、ニッケル、鉄、コバルト、イットリウム等の触媒金属も残存することがあるため、この不純物を除去するための精製を必要とする場合がある。不純物の除去には、硝酸、硫酸等による酸処理とともに超音波処理が有効である。しかし、硝酸、硫酸等による酸処理ではＣＮＴを構成するπ共役系が破壊され、ＣＮＴ本来の特性が損なわれてしまう可能性があるため、適切な条件で精製して使用することが望ましい。 When SWCNT, DWCNT or MWCNT is produced by the above method, catalyst metals such as nickel, iron, cobalt, yttrium may remain, so that purification for removing these impurities is necessary. There is. In order to remove impurities, ultrasonic treatment is effective together with acid treatment with nitric acid, sulfuric acid and the like. However, acid treatment with nitric acid, sulfuric acid, or the like destroys the π-conjugated system constituting CNT and may impair the original characteristics of CNT. Therefore, it is desirable to purify and use under appropriate conditions.
　層状カーボン材料の具体例としては、グラファイト、グラフェン等が挙げられる。グラファイトについては、特に制限はなく、市販の各種グラファイトを用いることができる。グラフェンは、１原子の厚さのｓｐ２結合炭素原子のシートであって、炭素原子とその結合からできた蜂の巣のような六角形格子構造をとっており、その厚さは、０．３８ｎｍ程度と言われている。また、市販の酸化グラフェンの他に、グラファイトをＨｕｍｍｅｒｓ法により処理して得られる酸化グラフェンを用いてもよい。 Specific examples of the layered carbon material include graphite and graphene. The graphite is not particularly limited, and various commercially available graphites can be used. Graphene is a sheet of sp2-bonded carbon atoms with a thickness of 1 atom, and has a hexagonal lattice structure like a honeycomb made of carbon atoms and their bonds, and its thickness is about 0.38 nm. It is said. In addition to commercially available graphene oxide, graphene oxide obtained by processing graphite by the Hummers method may be used.
　粒子状カーボン材料の具体例としては、ファーネスブラック、チャンネルブラック、アセチレンブラック、サーマルブラック等のカーボンブラック等が挙げられる。カーボンブラックについては、特に制限はなく、市販の各種カーボンブラックを用いることができ、その粒子径は５～５００ｎｍが好ましい。 Specific examples of the particulate carbon material include carbon black such as furnace black, channel black, acetylene black, and thermal black. The carbon black is not particularly limited, and various commercially available carbon blacks can be used, and the particle diameter is preferably 5 to 500 nm.
　本発明の剥離層形成用組成物におけるポリアミック酸と炭素系フィラーとの比は、質量比で、ポリアミック酸１に対して、炭素系フィラー０．００１～０．１程度であるが、好ましくは０．００５～０．０５程度、より好ましくは０．０１～０．０２程度である。 The ratio of the polyamic acid to the carbon-based filler in the composition for forming a release layer of the present invention is about 0.001 to 0.1 carbon-based filler with respect to polyamic acid 1 in terms of mass ratio, preferably 0. It is about 0.005 to 0.05, more preferably about 0.01 to 0.02.
　本発明の剥離層形成用組成物は、有機溶媒を含むものである。この有機溶媒としては、上記反応の反応溶媒の具体例と同様のものが挙げられる。中でも、ポリアミック酸をよく溶解し、均一性の高い組成物が調製し易いことから、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、１，３－ジメチル－２－イミダゾリジノン、Ｎ－エチル－２－ピロリドン、γ－ブチロラクトンが好ましく、Ｎ－メチル－２－ピロリドンがより好ましい。 The release layer forming composition of the present invention contains an organic solvent. As this organic solvent, the same thing as the specific example of the reaction solvent of the said reaction is mentioned. Among them, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-, which dissolves polyamic acid well and is easy to prepare a highly uniform composition. 2-Imidazolidinone, N-ethyl-2-pyrrolidone, and γ-butyrolactone are preferred, and N-methyl-2-pyrrolidone is more preferred.
　なお、単独ではポリアミック酸を溶解させない溶媒であっても、ポリアミック酸が析出しない範囲であれば、組成物の調製に用いることができる。特に、エチルセロソルブ、ブチルセロソルブ、エチルカルビトール、ブチルカルビトール、エチルカルビトールアセテート、エチレングリコール、１－メトキシ－２－プロパノール、１－エトキシ－２－プロパノール、１－ブトキシ－２－プロパノール、１－フェノキシ－２－プロパノール、プロピレングリコールモノアセテート、プロピレングリコールジアセテート、プロピレングリコール－１－モノメチルエーテル－２－アセテート、プロピレングリコール－１－モノエチルエーテル－２－アセテート、ジプロピレングリコール、２－（２－エトキシプロポキシ）プロパノール、乳酸メチル、乳酸エチル、乳酸ｎ－プロピル、乳酸ｎ－ブチル、乳酸イソアミル等の低表面張力を有する溶媒を適度に混在させることができる。これにより、基板への塗布時に塗膜均一性が向上することが知られており、本発明においても好適に用い得る。 Even if the solvent alone does not dissolve the polyamic acid, it can be used for preparing the composition as long as the polyamic acid does not precipitate. In particular, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy -2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxy Propoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate and other solvents having a low surface tension can be mixed appropriately. Thereby, it is known that the coating film uniformity is improved at the time of application to the substrate, and can be suitably used in the present invention.
　本発明の剥離層形成用組成物の調製方法は任意である。調製方法の好ましい一例としては、上記説明した方法によって得られた目的とするポリアミック酸を含む反応溶液をろ過し、得られたろ液に炭素系フィラーを加えて分散処理を施す方法が挙げられる。この際、濃度調整等を目的として必要があればろ液を希釈又は濃縮してもよい。このような方法を採用することで、得られる組成物から製造される剥離層の密着性、剥離性等の悪化の原因となり得る不純物の混入を低減できるだけでなく、効率よく剥離層形成用組成物を得ることができる。 The method for preparing the composition for forming a release layer of the present invention is arbitrary. A preferable example of the preparation method is a method of filtering the reaction solution containing the target polyamic acid obtained by the above-described method, and adding a carbon-based filler to the obtained filtrate to perform a dispersion treatment. At this time, the filtrate may be diluted or concentrated if necessary for the purpose of adjusting the concentration. By adopting such a method, it is possible not only to reduce the contamination of impurities that can cause deterioration in the adhesion, peelability, etc. of the release layer produced from the resulting composition, but also to efficiently form a release layer forming composition. Can be obtained.
　分散処理としては、機械的処理である、ボールミル、ビーズミル、ジェットミル等を用いる湿式処理や、バス型やプローブ型のソニケータを用いる超音波処理が挙げられる。分散処理の時間は任意であるが、１分間から１０時間程度が好ましく、５分間から５時間程度がより好ましい。なお、分散処理の際、必要に応じて加熱処理を施してもよい。また、希釈に用いる溶媒としては、特に限定されるものではなく、その具体例としては、上記反応の反応溶媒の具体例と同様のものが挙げられる。希釈に用いる溶媒は、１種単独で又は２種以上を組み合わせて使用してもよい。 Dispersion treatment includes mechanical treatment, wet treatment using a ball mill, bead mill, jet mill, or the like, and ultrasonic treatment using a bath type or probe type sonicator. The time for the dispersion treatment is arbitrary, but is preferably about 1 minute to 10 hours, and more preferably about 5 minutes to 5 hours. In the dispersion treatment, heat treatment may be performed as necessary. The solvent used for dilution is not particularly limited, and specific examples thereof include the same examples as the specific examples of the reaction solvent for the above reaction. The solvent used for dilution may be used singly or in combination of two or more.
　本発明の剥離層形成用組成物におけるポリアミック酸の濃度は、作製する剥離層の厚み、組成物の粘度等を勘案して適宜設定するものではあるが、通常１～３０質量％程度、好ましくは１～２０質量％程度である。このような濃度とすることで、０．０５～５μｍ程度の厚さの剥離層を再現性よく得ることができる。ポリアミック酸の濃度は、ポリアミック酸の原料であるジアミンとテトラカルボン酸二無水物の使用量を調整する、単離したポリアミック酸を溶媒に溶解させる際にその量を調整する等して調整することができる。 The concentration of the polyamic acid in the composition for forming a release layer of the present invention is appropriately set in consideration of the thickness of the release layer to be produced, the viscosity of the composition, etc., but is usually about 1 to 30% by mass, preferably It is about 1 to 20% by mass. By setting such a concentration, a release layer having a thickness of about 0.05 to 5 μm can be obtained with good reproducibility. The concentration of the polyamic acid should be adjusted by adjusting the amount of diamine and tetracarboxylic dianhydride used as the raw material for the polyamic acid, adjusting the amount when the isolated polyamic acid is dissolved in the solvent, etc. Can do.
　また、本発明の剥離層形成用組成物の粘度は、作製する剥離層の厚み等を勘案して適宜設定するものではあるが、特に０．０５～５μｍ程度の厚さの膜を再現性よく得ること目的とする場合、通常、２５℃で１０～１０，０００ｍＰａ・ｓ程度、好ましくは２０～５，０００ｍＰａ・ｓ程度である。ここで、粘度は、市販の液体の粘度測定用粘度計を使用して、例えば、ＪＩＳ　Ｋ７１１７－２に記載の手順を参照して、組成物の温度２５℃の条件にて測定することができる。好ましくは、粘度計としては、円錐平板型（コーンプレート型）回転粘度計を使用し、好ましくは同型の粘度計で標準コーンロータとして１°３４’×Ｒ２４を使用して、組成物の温度２５℃の条件にて測定することができる。このような回転粘度計としては、例えば、東機産業株式会社製ＴＶＥ－２５Ｌが挙げられる。 The viscosity of the composition for forming a release layer of the present invention is appropriately set in consideration of the thickness of the release layer to be produced, etc., but a film having a thickness of about 0.05 to 5 μm is particularly reproducible. When it is intended to obtain, it is usually about 10 to 10,000 mPa · s, preferably about 20 to 5,000 mPa · s at 25 ° C. Here, the viscosity can be measured using a commercially available liquid viscosity measurement viscometer, for example, with reference to the procedure described in JIS K7117-2 at a temperature of the composition of 25 ° C. . Preferably, a conical plate type (cone plate type) rotational viscometer is used as the viscometer, and preferably the composition temperature is 25 ° C. using 1 ° 34 ′ × R24 as a standard cone rotor. It can be measured under the condition of ° C. An example of such a rotational viscometer is TVE-25L manufactured by Toki Sangyo Co., Ltd.
　なお、本発明の剥離層形成用組成物は、ポリアミック酸と有機溶媒の他に、例えば膜強度を向上させるために、架橋剤等を含んでいてもよい。 The composition for forming a release layer of the present invention may contain a crosslinking agent or the like in order to improve the film strength, for example, in addition to the polyamic acid and the organic solvent.
　以上説明した本発明の剥離層形成組成物を基体に塗布し、得られた塗膜を加熱してポリアミック酸を熱イミド化することで、基体との優れた密着性及び樹脂基板との適度な密着性と適度な剥離性を有する、ポリイミド膜からなる剥離層を得ることができる。 The above-described release layer forming composition of the present invention is applied to a substrate, and the resulting coating film is heated to thermally imidize the polyamic acid. A release layer made of a polyimide film having adhesion and moderate peelability can be obtained.
　このような本発明の剥離層を基体上に形成する場合、剥離層は基体の一部表面に形成されていてもよいし、全面に形成されていてもよい。基体の一部表面に剥離層を形成する態様としては、基体表面のうち所定の範囲にのみ剥離層を形成する態様、基体表面全面にドットパターン、ラインアンドスペースパターン等のパターン状に剥離層を形成する態様等がある。なお、本発明において、基体とは、その表面に本発明の剥離層形成用組成物が塗られるものであって、フレキシブル電子デバイス等の製造に用いられるものを意味する。 When such a release layer of the present invention is formed on a substrate, the release layer may be formed on a partial surface of the substrate, or may be formed on the entire surface. As an aspect of forming a release layer on a part of the surface of the substrate, an embodiment in which the release layer is formed only within a predetermined range of the substrate surface, a release layer is formed in a pattern such as a dot pattern or a line and space pattern on the entire surface of the substrate. There are forms to be formed. In addition, in this invention, a base | substrate means what is used for manufacture of a flexible electronic device etc. by which the composition for peeling layer formation of this invention is applied to the surface.
　基体（基材）としては、例えば、ガラス、プラスチック（ポリカーボネート、ポリメタクリレート、ポリスチレン、ポリエステル、ポリオレフィン、エポキシ、メラミン、トリアセチルセルロース、ＡＢＳ、ＡＳ、ノルボルネン系樹脂等）、金属(シリコンウエハ等)、木材、紙、スレート等が挙げられるが、特に、本発明の剥離層がそれに対する十分な密着性を有することから、ガラスが好ましい。なお、基体表面は、単一の材料で構成されていてもよく、２以上の材料で構成されていてもよい。２以上の材料で基体表面が構成される態様としては、基体表面のうちのある範囲はある材料で構成され、その余の表面はその他の材料で構成されている態様、基体表面全体にドットパターン、ラインアンドスペースパターン等のパターン状にある材料がその他の材料中に存在する態様等がある。 Examples of the substrate (base material) include glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal (silicon wafer, etc.), Although wood, paper, slate, etc. are mentioned, since the peeling layer of this invention has sufficient adhesiveness with respect to it, glass is preferable. In addition, the base | substrate surface may be comprised with the single material and may be comprised with two or more materials. As an aspect in which the substrate surface is composed of two or more materials, a certain range of the substrate surface is composed of a certain material, and the other surface is composed of other materials. A dot pattern is formed on the entire surface of the substrate. There is a mode in which a material in a pattern such as a line and space pattern is present in other materials.
　塗布する方法は、特に限定されるものではないが、例えば、キャストコート法、スピンコート法、ブレードコート法、ディップコート法、ロールコート法、バーコート法、ダイコート法、インクジェット法、印刷法（凸版、凹版、平版、スクリーン印刷等）等が挙げられる。 The coating method is not particularly limited, but for example, cast coating method, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, die coating method, ink jet method, printing method (letter plate) , Intaglio, lithographic, screen printing, etc.).
　イミド化するための加熱温度は、通常５０～５５０℃の範囲内で適宜決定されるものではあるが、好ましくは１５０℃超～５１０℃である。加熱温度をこのようにすることで、得られる膜の脆弱化を防ぎつつ、イミド化反応を十分に進行させることが可能となる。加熱時間は、加熱温度によって異なるため一概に規定できないが、通常５分～５時間である。また、イミド化率は、５０～１００％の範囲であればよい。 The heating temperature for imidization is usually appropriately determined within the range of 50 to 550 ° C., but is preferably more than 150 ° C. to 510 ° C. By setting the heating temperature in this way, it is possible to sufficiently advance the imidization reaction while preventing the obtained film from being weakened. The heating time varies depending on the heating temperature, and cannot be generally defined, but is usually 5 minutes to 5 hours. The imidization rate may be in the range of 50 to 100%.
　本発明における加熱態様の好ましい一例としては、５０～１５０℃で５分間～２時間加熱した後に、そのまま段階的に加熱温度を上昇させて最終的に１５０℃超～５１０℃で３０分～４時間加熱する手法が挙げられる。特に、５０～１５０℃で５分間～２時間加熱した後に、１５０℃超～３５０℃で５分間～２時間、次いで３５０℃超～４５０℃で３０分～４時間、最後に４５０℃超～５１０℃で３０分～４時間加熱することが好ましい。 As a preferred example of the heating mode in the present invention, after heating at 50 to 150 ° C. for 5 minutes to 2 hours, the heating temperature is gradually increased as it is, and finally from 150 ° C. to 510 ° C. for 30 minutes to 4 hours. The method of heating is mentioned. In particular, after heating at 50 to 150 ° C. for 5 minutes to 2 hours, above 150 ° C. to 350 ° C. for 5 minutes to 2 hours, then above 350 ° C. to 450 ° C. for 30 minutes to 4 hours, and finally above 450 ° C. to 510 ° C. Heating at 30 ° C. for 30 minutes to 4 hours is preferable.
　加熱に用いる器具は、例えばホットプレート、オーブン等が挙げられる。加熱雰囲気は、空気下であっても不活性ガス下であってもよく、また、常圧下であっても減圧下であってもよい。 Examples of the appliance used for heating include a hot plate and an oven. The heating atmosphere may be under air or under an inert gas, and may be under normal pressure or under reduced pressure.
　剥離層の厚さは、通常０．０１～５０μｍ程度、生産性の観点から、好ましくは０．０５～２０μｍ程度である。なお、所望の厚さは、加熱前の塗膜の厚さを調整することによって実現する。 The thickness of the release layer is usually about 0.01 to 50 μm, and preferably about 0.05 to 20 μm from the viewpoint of productivity. In addition, desired thickness is implement | achieved by adjusting the thickness of the coating film before a heating.
　以上説明した剥離層は、基体、特にガラスの基体との優れた密着性及び樹脂基板との適度な密着性と適度な剥離性を有する。それ故、本発明に係る剥離層は、フレキシブル電子デバイスの製造プロセスにおいて、当該デバイスの樹脂基板に損傷を与えることなく、当該樹脂基板を、その樹脂基板上に形成された回路等とともに、基体から剥離させるために好適に用いることができる。 The release layer described above has excellent adhesion to a substrate, particularly a glass substrate, moderate adhesion to a resin substrate, and moderate release. Therefore, the release layer according to the present invention, in the manufacturing process of the flexible electronic device, without damaging the resin substrate of the device, the resin substrate together with the circuit and the like formed on the resin substrate from the substrate. It can be suitably used for peeling.
　以下、本発明の剥離層を用いたフレキシブル電子デバイスの製造方法の一例について説明する。
　本発明の剥離層形成用組成物を用いて、上述の方法によって、ガラス基体上に剥離層を形成する。この剥離層の上に、樹脂基板を形成するための樹脂溶液を塗布し、この塗膜を加熱することで、本発明の剥離層を介して、ガラス基体に固定された樹脂基板を形成する。この際、剥離層を全て覆うようにして、剥離層の面積と比較して大きい面積で、基板を形成する。前記樹脂基板としては、フレキシブル電子デバイスの樹脂基板として代表的なポリイミドからなる樹脂基板が挙げられ、それを形成するための樹脂溶液としては、ポリイミド溶液やポリアミック酸溶液が挙げられる。当該樹脂基板の形成方法は、常法に従えばよい。 Hereinafter, an example of the manufacturing method of the flexible electronic device using the peeling layer of this invention is demonstrated.
Using the composition for forming a release layer of the present invention, a release layer is formed on a glass substrate by the method described above. A resin solution for forming a resin substrate is applied on the release layer, and this coating film is heated to form a resin substrate fixed to the glass substrate via the release layer of the present invention. At this time, the substrate is formed with a larger area than the area of the release layer so as to cover the entire release layer. Examples of the resin substrate include a resin substrate made of polyimide, which is a typical resin substrate for flexible electronic devices, and examples of the resin solution for forming the resin substrate include a polyimide solution and a polyamic acid solution. The method for forming the resin substrate may follow a conventional method.
　次に、本発明の剥離層を介して基体に固定された当該樹脂基板の上に、所望の回路を形成し、その後、例えば剥離層に沿って樹脂基板をカットし、この回路とともに樹脂基板を剥離層から剥離して、樹脂基板と基体とを分離する。この際、基体の一部を剥離層とともにカットしてもよい。 Next, a desired circuit is formed on the resin substrate fixed to the base via the release layer of the present invention, and then the resin substrate is cut along the release layer, for example. The resin substrate and the substrate are separated by peeling from the release layer. At this time, a part of the substrate may be cut together with the release layer.
　以下、実施例を挙げて本発明を更に詳細に説明するが、本発明は、これら実施例に限定されるものではない。
［１］化合物の略語
ｐ－ＰＤＡ：ｐ－フェニレンジアミン（東京化成工業（株）製）
ＤＡＴＰ：４，４’’－ジアミノ－ｐ－ターフェニル（東京化成工業（株）製）
ＡＢＯ：２－（４－アミノフェニル）－５－アミノベンゾオキゾール（Changzhou Sunlight Pharmaceutical Co., Ltd.製）
ＰＭＤＡ：ピロメリット酸二無水物（東京化成工業（株）製）
ＣＮＴ：カーボンナノチューブ、製品名ＮＣ７０００（Ｎａｎｏｃｙｌ社製）
ＧＲＡ：グラフェン、製品名ｉＧｕｒａｆｅｎ－α（（株）アイテック製）
ＮＭＰ：Ｎ－メチル－２－ピロリドン EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these Examples.
[1] Abbreviation of compound p-PDA: p-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
DATP: 4,4 ″ -diamino-p-terphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.)
ABO: 2- (4-aminophenyl) -5-aminobenzooxol (manufactured by Changzhou Sunlight Pharmaceutical Co., Ltd.)
PMDA: pyromellitic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)
CNT: carbon nanotube, product name NC7000 (manufactured by Nanocyl)
GRA: graphene, product name iGurafen-α (manufactured by ITEC Co., Ltd.)
NMP: N-methyl-2-pyrrolidone
＜重量平均分子量及び分子量分布の測定＞
　ポリマーの重量平均分子量（Ｍｗ）及び分子量分布（Ｍｗ／Ｍｎ）の測定は、日本分光(株)製ＧＰＣ装置（カラム：昭和電工(株)製OHpak SB803-HQ、及びOHpak SB804-HQ；溶離液：ジメチルホルムアミド／ＬｉＢｒ・Ｈ2Ｏ（２９.６ｍＭ）／Ｈ3ＰＯ4（２９.６ｍＭ）／ＴＨＦ（０.１質量％）；流量：１.０ｍＬ／分；カラム温度：４０℃；Ｍｗ：標準ポリスチレン換算値）を用いて行った（以下の実施例及び比較例において、同じ）。 <Measurement of weight average molecular weight and molecular weight distribution>
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer were measured using a GPC apparatus manufactured by JASCO Corporation (column: OHpak SB803-HQ and OHpak SB804-HQ manufactured by Showa Denko KK); : Dimethylformamide / LiBr.H 2 O (29.6 mM) / H 3 PO 4 (29.6 mM) / THF (0.1% by mass); flow rate: 1.0 mL / min; column temperature: 40 ° C .; Mw: (Standard polystyrene equivalent value) was used (same in the following examples and comparative examples).
［２］樹脂基板用組成物の調製例
＜調製例１－１　ポリアミック酸の合成＞
　ｐ－ＰＤＡ　２０．３ｇ（１８８ｍｍｏｌ）とＤＡＴＰ　１２．２ｇ（４７ｍｍｏｌ）をＮＭＰ　６１７．４ｇに溶解させた。得られた溶液を１５℃に冷却し、そこへＰＭＤＡ　５０．１ｇ（２３０ｍｍｏｌ）を加え、窒素雰囲気下、５０℃まで昇温し４８時間反応させた。得られたポリマーのＭｗは８２，１００、分子量分布は２．７であった。なお、得られた反応液からポリアミック酸を単離せず、当該反応液をそのまま樹脂基板形成用組成物として用いた。 [2] Preparation Example of Resin Substrate Composition <Preparation Example 1-1 Synthesis of Polyamic Acid>
20.3 g (188 mmol) of p-PDA and 12.2 g (47 mmol) of DATP were dissolved in 617.4 g of NMP. The obtained solution was cooled to 15 ° C., PMDA 50.1 g (230 mmol) was added thereto, and the temperature was raised to 50 ° C. in a nitrogen atmosphere to react for 48 hours. Mw of the obtained polymer was 82,100, and molecular weight distribution was 2.7. In addition, the polyamic acid was not isolated from the obtained reaction liquid, but the reaction liquid was directly used as a resin substrate forming composition.
［３］フィラー分散液の調製
＜調製例２－１＞
　ｐ－ＰＤＡ　２．４９ｇ（２３．０ｍｍｏｌ）をＮＭＰ　６３ｇに溶解させた。その後、ＰＭＤＡ　４．５１ｇ（２０．７ｍｍｏｌ）を加え、窒素雰囲気下、室温で２４時間撹拌した。そして、得られた溶液にＣＮＴ　０．０７ｇを加え、室温にて更に３０分撹拌した後、得られた混合物を撹拌させながら超音波発生装置（ＵＩＰ１０００ｈｄ（Ｔｒａｎｓｄｕｃｅｒ製）、以下同様）にて５００ｗの超音波処理を１０分間行い、フィラー分散液を得た。 [3] Preparation of filler dispersion <Preparation Example 2-1>
2.49 g (23.0 mmol) of p-PDA was dissolved in 63 g of NMP. Thereafter, 4.51 g (20.7 mmol) of PMDA was added, and the mixture was stirred at room temperature for 24 hours under a nitrogen atmosphere. Then, 0.07 g of CNT was added to the obtained solution, and the mixture was further stirred at room temperature for 30 minutes. Sonication was performed for 10 minutes to obtain a filler dispersion.
＜調製例２－２＞
　ｐ－ＰＤＡ　１．７２ｇ（１５．９ｍｍｏｌ）とＤＡＴＰ１．０３ｇ（３．９７ｍｍｏｌ）をＮＭＰ　６３ｇに溶解させた。その後、ＰＭＤＡ　４．２５ｇ（１９．５ｍｍｏｌ）を加え、窒素雰囲気下、室温で２４時間撹拌した。
　そして、得られた溶液にＣＮＴ　０．０７ｇを加え、室温にて更に３０分撹拌した後、得られた混合物を撹拌させながら超音波発生装置にて５００ｗの超音波処理を１０分間行い、フィラー分散液を得た。 <Preparation Example 2-2>
1.72 g (15.9 mmol) of p-PDA and 1.03 g (3.97 mmol) of DATP were dissolved in 63 g of NMP. Thereafter, 4.25 g (19.5 mmol) of PMDA was added, and the mixture was stirred at room temperature for 24 hours under a nitrogen atmosphere.
Then, 0.07 g of CNT was added to the obtained solution, and the mixture was further stirred at room temperature for 30 minutes, and then the obtained mixture was stirred for 10 minutes with an ultrasonic generator while stirring the mixture, to disperse the filler. A liquid was obtained.
＜調製例２－３＞
　ＡＢＯ　３．５９ｇ（１５．９ｍｍｏｌ）をＮＭＰ　６３ｇに溶解させた。その後、ＰＭＤＡ　３．４０ｇ（１５．６ｍｍｏｌ）を加え、窒素雰囲気下、室温で２４時間撹拌した。そして、得られた溶液にＣＮＴ　０．０７ｇを加え、室温にて更に３０分撹拌した後、得られた混合物を撹拌させながら超音波発生装置にて５００ｗの超音波処理を１０分間行い、フィラー分散液を得た。 <Preparation Example 2-3>
3.59 g (15.9 mmol) of ABO was dissolved in 63 g of NMP. Thereafter, 3.40 g (15.6 mmol) of PMDA was added, and the mixture was stirred at room temperature for 24 hours under a nitrogen atmosphere. Then, 0.07 g of CNT was added to the obtained solution, and the mixture was further stirred at room temperature for 30 minutes, and then the obtained mixture was stirred for 10 minutes with an ultrasonic generator while stirring the mixture, to disperse the filler. A liquid was obtained.
＜調製例２－４＞
　ＡＢＯ　３．５９ｇ（１５．９ｍｍｏｌ）をＮＭＰ　６３ｇに溶解させた。得られた溶液に、ＰＭＤＡ　３．４０ｇ（１５．６ｍｍｏｌ）を加え、窒素雰囲気下、室温で２４時間撹拌した。そして、得られた溶液にＧＲＡ　０．０７ｇを加え、室温にて更に３０分撹拌した後、得られた混合物を撹拌させながら超音波発生装置にて５００ｗの超音波処理を１０分間行い、フィラー分散液を得た。 <Preparation Example 2-4>
3.59 g (15.9 mmol) of ABO was dissolved in 63 g of NMP. PMDA 3.40 g (15.6 mmol) was added to the resulting solution, and the mixture was stirred at room temperature for 24 hours under a nitrogen atmosphere. Then, 0.07 g of GRA was added to the obtained solution, and the mixture was further stirred for 30 minutes at room temperature. Then, the resulting mixture was stirred for 500 minutes with an ultrasonic generator while stirring the mixture, and the filler dispersion was performed. A liquid was obtained.
［４］剥離層形成用組成物の調製
＜調製例３－１＞
　調製例２－１で得られたフィラー分散液１０ｇと、ＮＭＰとを混合して、固形分濃度５質量％の剥離性形成用組成物を得た。なお、ここでの固形分とは、ポリアミック酸及びフィラーを合せたものを意味する。 [4] Preparation of release layer forming composition <Preparation Example 3-1>
10 g of the filler dispersion obtained in Preparation Example 2-1 and NMP were mixed to obtain a peelable forming composition having a solid content concentration of 5% by mass. In addition, solid content here means what combined polyamic acid and a filler.
＜調製例３－２～３－４＞
　調製例２－１で得られた分散液の代わりに、それぞれ調製例２－２～２－４で得られた分散液を用いた以外は、実施例３－１と同様の方法によって、固形分濃度５質量％の剥離層形成用組成物を得た。 <Preparation Examples 3-2 to 3-4>
A solid content was obtained in the same manner as in Example 3-1, except that the dispersion obtained in Preparation Examples 2-2 to 2-4 was used instead of the dispersion obtained in Preparation Example 2-1. A composition for forming a release layer having a concentration of 5% by mass was obtained.
［５］剥離層の形成
＜実施例１－１＞
　スピンコータ（条件：回転数３０００ｒｐｍ×３０秒）を用いて、調製例３－１で得られた剥離用形成組成物を、１００ｍｍ×１００ｍｍの無アルカリガラス基板上に塗布し、得られた塗膜を、ホットプレートを用いて８０℃で１０分間加熱した。
　そして、得られた膜を、真空ガス置換炉（ＫＤＦ－９００ＧＬ（デンケン・ハイデンタル（株）製））の中に入れ、室温下で炉内を６０分間減圧してから窒素置換した。
　その後、室温から３００℃まで昇温し、３００℃で３０分間、４００℃で６０分間、５００℃で１０分間順次加熱し、ガラス基板上に厚さ約０．１μｍの剥離層を作製した。
　なお、室温～３００℃、３００～４００℃、４００～５００℃の昇温速度は１０℃／分とした。 [5] Formation of Release Layer <Example 1-1>
Using a spin coater (conditions: rotation speed 3000 rpm × 30 seconds), the release composition obtained in Preparation Example 3-1 was applied onto a 100 mm × 100 mm non-alkali glass substrate, and the resulting coating film was applied. The mixture was heated at 80 ° C. for 10 minutes using a hot plate.
The obtained film was placed in a vacuum gas replacement furnace (KDF-900GL (manufactured by Denken Hydental Co., Ltd.)), and the inside of the furnace was depressurized at room temperature for 60 minutes and then replaced with nitrogen.
Thereafter, the temperature was raised from room temperature to 300 ° C., and heated sequentially at 300 ° C. for 30 minutes, 400 ° C. for 60 minutes, and 500 ° C. for 10 minutes to produce a release layer having a thickness of about 0.1 μm on the glass substrate.
The temperature increase rate from room temperature to 300 ° C., 300 to 400 ° C., and 400 to 500 ° C. was 10 ° C./min.
＜実施例１－２～１－４＞
　調製例３－１で得られた剥離層形成用組成物を用いた以外は、実施例１－１と同様の方法で剥離層を形成した。 <Examples 1-2 to 1-4>
A release layer was formed in the same manner as in Example 1-1 except that the release layer-forming composition obtained in Preparation Example 3-1 was used.
［６］剥離層の評価
　作製した剥離層について、以下の手法により剥離層としての機能を評価した。
＜ガラス基板と剥離層との密着性評価＞
　ガラス基板上に形成された剥離層のクロスカット（縦横１ｍｍ間隔、以下同様）、１００マスカットを行った。すなわち、このクロスカットにより、１ｍｍ四方のマス目を１００個形成した。
　そして、この１００マスカット部分に粘着テープを張り付けて、そのテープを剥がし、以下の基準（５Ｂ～０Ｂ，Ｂ，Ａ，ＡＡ）に基づき、剥離の程度を評価した。
５Ｂ：０％剥離（剥離なし）
４Ｂ：５％未満の剥離
３Ｂ：５～１５％未満の剥離
２Ｂ：１５～３５％未満の剥離
１Ｂ：３５～６５％未満の剥離
０Ｂ：６５～８０％未満の剥離
　Ｂ：８０～９５％未満の剥離
　Ａ：９５～１００％未満の剥離
ＡＡ：１００％剥離（すべて剥離） [6] Evaluation of Release Layer For the prepared release layer, the function as the release layer was evaluated by the following method.
<Evaluation of adhesion between glass substrate and release layer>
The release layer formed on the glass substrate was cross-cut (1 mm in length and width, the same applies hereinafter) and 100 muscuts. That is, 100 crosses of 1 mm square were formed by this cross cut.
Then, an adhesive tape was attached to the 100 muscat portion, the tape was peeled off, and the degree of peeling was evaluated based on the following criteria (5B to 0B, B, A, AA).
5B: 0% peeling (no peeling)
4B: less than 5% peeling 3B: less than 5-15% peeling 2B: 15-35% peeling 1B: 35-65% peeling 0B: 65-80% peeling B: 80-95% peeling Peeling A: 95 to less than 100% peeling AA: 100% peeling (all peeling)
＜剥離層と樹脂基板との密着性評価＞
　バーコータ―（ギャップ：２５０μｍ）を用いて、実施例１－１で得られた剥離層の上に、調製例１－１で得られた樹脂基板形成用組成物を塗布した。その後、得られた塗膜を、ホットプレートを用いて８０℃で３０分間加熱した。
　そして、得られた膜を、真空ガス置換炉（ＫＤＦ－９００ＧＬ（デンケン・ハイデンタル（株）製））の中に入れ、室温下で炉内を６０分間減圧してから窒素置換した。
　その後、室温から３００℃まで昇温し、３００℃で３０分間、４００℃で３０分間、５００℃で６０分間順次加熱し、ガラス基板上に厚さ約１０μｍの樹脂基板を形成した。
　なお、室温～３００℃、３００～４００℃、４００～５００℃の昇温速度は１０℃／分とした。同様にして、実施例１－２～１－４で得られた剥離層上に樹脂基板を作製した。
　そして、樹脂基板・剥離層のクロスカットのクロスカット（縦横１ｍｍ間隔、以下同様）を行うことにより、１００マスカットを行い、この１００マスカット部分に粘着テープを張り付けて、そのテープを剥がし、上記の基準（５Ｂ～０Ｂ，Ｂ，Ａ，ＡＡ）に基づき、剥離の程度を評価した。 <Evaluation of adhesion between release layer and resin substrate>
Using the bar coater (gap: 250 μm), the resin substrate forming composition obtained in Preparation Example 1-1 was applied on the release layer obtained in Example 1-1. Thereafter, the obtained coating film was heated at 80 ° C. for 30 minutes using a hot plate.
The obtained film was placed in a vacuum gas replacement furnace (KDF-900GL (manufactured by Denken Hydental Co., Ltd.)), and the inside of the furnace was depressurized at room temperature for 60 minutes and then replaced with nitrogen.
Thereafter, the temperature was raised from room temperature to 300 ° C., and heated successively at 300 ° C. for 30 minutes, 400 ° C. for 30 minutes, and 500 ° C. for 60 minutes to form a resin substrate having a thickness of about 10 μm on the glass substrate.
The temperature increase rate from room temperature to 300 ° C., 300 to 400 ° C., and 400 to 500 ° C. was 10 ° C./min. Similarly, a resin substrate was produced on the release layer obtained in Examples 1-2 to 1-4.
Then, by performing cross-cutting of the resin substrate / peeling layer (cutting 1 mm in length and width, the same applies hereinafter), 100 mass cuts are performed, adhesive tape is applied to the 100 mass cut portions, and the tape is peeled off. The degree of peeling was evaluated based on (5B to 0B, B, A, AA).
　剥離性評価の結果を表１に示す。表１に示される通り、本発明の剥離層は、ガラス基板との密着性に優れ、かつ、樹脂基板との剥離性に優れていることがわかった。 The results of peelability evaluation are shown in Table 1. As shown in Table 1, it was found that the release layer of the present invention was excellent in adhesion to the glass substrate and excellent in peelability from the resin substrate.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

Claims (8)

  1. 　ポリアミック酸と、炭素系フィラーと、有機溶媒とを含む剥離層形成用組成物。 A composition for forming a release layer comprising polyamic acid, a carbon-based filler, and an organic solvent.
  2. 　前記ポリアミック酸が、芳香族ジアミンと芳香族テトラカルボン酸二無水物とを反応させて得られたポリアミック酸である請求項１記載の剥離層形成用組成物。 The composition for forming a release layer according to claim 1, wherein the polyamic acid is a polyamic acid obtained by reacting an aromatic diamine and an aromatic tetracarboxylic dianhydride.
  3. 　前記芳香族ジアミンが、ベンゼン核を１～５つ含む芳香族ジアミンであることを特徴とする請求項２記載の剥離層形成用組成物。 The composition for forming a release layer according to claim 2, wherein the aromatic diamine is an aromatic diamine containing 1 to 5 benzene nuclei.
  4. 　前記芳香族テトラカルボン酸二無水物が、ベンゼン核を１～５つ含む芳香族テトラカルボン酸二無水物であることを特徴とする請求項２又は３記載の剥離層形成用組成物。 The composition for forming a release layer according to claim 2 or 3, wherein the aromatic tetracarboxylic dianhydride is an aromatic tetracarboxylic dianhydride containing 1 to 5 benzene nuclei.
  5. 　前記炭素系フィラーが、カーボンナノチューブ又はグラフェンである請求項１～４のいずれか１項記載の剥離層形成用組成物。 The composition for forming a release layer according to any one of claims 1 to 4, wherein the carbon-based filler is a carbon nanotube or graphene.
  6. 　請求項１～５のいずれか１項に記載の剥離層形成用組成物を用いて形成される剥離層。 A release layer formed using the release layer forming composition according to any one of claims 1 to 5.
  7. 　請求項６に記載の剥離層を用いることを特徴とする、樹脂基板を備えるフレキシブル電子デバイスの製造方法。 A method for producing a flexible electronic device comprising a resin substrate, wherein the release layer according to claim 6 is used.
  8. 　前記樹脂基板が、ポリイミドからなる基板であることを特徴とする請求項７に記載の製造方法。 The manufacturing method according to claim 7, wherein the resin substrate is a substrate made of polyimide.
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US11927904B2 (en) * 2021-06-16 2024-03-12 Canon Kabushiki Kaisha Electrophotographic belt having a substrate containing a polyimide resin and carbon nanotubes, electrophotographic image forming apparatus, fixing device, and varnish

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JP6620805B2 (en) 2019-12-18
KR20170125362A (en) 2017-11-14

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