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WO2018025954A1 - Composition pour former une couche antiadhésive pour un substrat transparent en résine - Google Patents

Composition pour former une couche antiadhésive pour un substrat transparent en résine Download PDF

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Publication number
WO2018025954A1
WO2018025954A1 PCT/JP2017/028210 JP2017028210W WO2018025954A1 WO 2018025954 A1 WO2018025954 A1 WO 2018025954A1 JP 2017028210 W JP2017028210 W JP 2017028210W WO 2018025954 A1 WO2018025954 A1 WO 2018025954A1
Authority
WO
WIPO (PCT)
Prior art keywords
release layer
resin substrate
tetracarboxylic dianhydride
composition
aromatic
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2017/028210
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English (en)
Japanese (ja)
Inventor
和也 進藤
江原　和也
鎭嘉 葉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
Original Assignee
Nissan Chemical Corp
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 Nissan Chemical Corp filed Critical Nissan Chemical Corp
Priority to CN201780046641.2A priority Critical patent/CN109563341B/zh
Priority to KR1020197004721A priority patent/KR102365302B1/ko
Priority to JP2018531973A priority patent/JP7131385B2/ja
Publication of WO2018025954A1 publication Critical patent/WO2018025954A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • 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
    • 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
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • 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
    • C08K5/20—Carboxylic acid amides
    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits

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.
  • the resin substrate used for the touch panel is a polyimide resin substrate, an acrylic resin substrate, a polyethylene terephthalate (PET) resin substrate, a cycloolefin resin substrate having transparency equivalent to that of glass, like a TFT display panel.
  • PET polyethylene terephthalate
  • a cycloolefin resin substrate having transparency equivalent to that of glass, like a TFT display panel.
  • Patent Documents 1, 2, and 3 after an amorphous silicon thin film layer is formed on a glass substrate and a plastic substrate is formed on the thin film layer, laser irradiation is performed from the glass surface side to crystallize amorphous silicon.
  • a method of peeling a plastic substrate from a glass substrate with hydrogen gas generated along with the above is disclosed.
  • a layer to be peeled (described as “transfer target layer” in Patent Document 4) is attached to a plastic film by using the techniques disclosed in Patent Documents 1 to 3, thereby completing a liquid crystal display device. Is disclosed.
  • JP 10-125929 A Japanese Patent Laid-Open No. 10-125931 International Publication No. 2005/050754 JP-A-10-125930
  • the present invention has been made in view of the above circumstances, and in particular, it is possible to peel without damaging the transparent resin substrate of a flexible electronic device formed using an acrylic resin, a cycloolefin polymer resin, or the like. It aims at providing the composition for peeling layer formation for transparent resin substrates which gives a layer.
  • the inventors of the present invention include a polyamic acid that is a reaction product of a diamine component and a tetracarboxylic dianhydride component, and a composition containing an organic solvent.
  • a composition for forming a release layer for a transparent resin substrate comprising a polyamic acid that is a reaction product of a diamine component and a tetracarboxylic dianhydride component, and an organic solvent
  • the diamine component includes at least one of an aromatic diamine having an ester bond and / or an ether bond, and an aromatic diamine having no ester bond and an ether bond
  • the tetracarboxylic dianhydride component is an ester bond and / or Or an aromatic tetracarboxylic dianhydride having an ether bond, and an aromatic tetracarboxylic dianhydride having no ester bond and an ether bond, and the diamine component and the tetracarboxylic dianhydride component.
  • the manufacturing method of a flexible electronic device provided with the transparent resin substrate characterized by using 8 peeling layers is provided.
  • the composition for forming a release layer for a transparent resin substrate By using the composition for forming a release layer for a transparent resin substrate according to the present invention, a film having excellent adhesion to the substrate and appropriate adhesion to the transparent resin substrate and appropriate release can be obtained with good reproducibility. be able to.
  • the composition of the present invention in the manufacturing process of the flexible electronic device, the resin substrate formed on the substrate and the circuit provided on the substrate are not damaged, and the resin substrate together with the circuit etc. 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.
  • the composition for forming a release layer for a transparent resin substrate of the present invention comprises a polyamic acid that is a reaction product of a diamine component and a tetracarboxylic dianhydride component, and an organic solvent, and the diamine component is an ester.
  • a polyamic acid that is a reaction product of a diamine component and a tetracarboxylic dianhydride component, and an organic solvent
  • the diamine component is an ester.
  • Tetracarboxylic dianhydride and aromatic diamine having at least one of an ester bond and / or an aromatic tetracarboxylic dianhydride having no ether bond and having the ester bond and / or the ether bond, and the ester Aromatic tetracarboxylic dianhydrides having bonds and / or ether bonds Of those containing at least one.
  • the release layer is a layer provided immediately above a substrate (such as a glass substrate) on which a resin substrate is formed.
  • a substrate such as a glass substrate
  • the resin substrate is placed between a base and a resin substrate of a flexible electronic device formed of a transparent resin such as an acrylic resin, a polycarbonate, or a cycloolefin polymer.
  • a release layer that is provided for fixing in the process and provided so that the resin substrate can be easily peeled from the substrate after an electronic circuit or the like is formed on the resin substrate.
  • the diamine component may contain either an aliphatic diamine or an aromatic diamine, but preferably contains an aromatic diamine from the viewpoint of ensuring the strength and heat resistance of the resulting thin film.
  • the diamine component includes at least one of an aromatic diamine having an ester bond and / or an ether bond, and an aromatic diamine having no ester bond and an ether bond.
  • the aromatic diamine having an ester bond and / or an ether bond includes one or both of an ester bond and an ether bond in the molecule.
  • aromatic diamines include diamines having a structure in which a plurality of aromatic rings having 6 to 20 carbon atoms are connected by ester bonds or ether bonds.
  • Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and the like.
  • a diamine having a structure in which two or three aromatic rings are connected by an ester bond or an ether bond is preferable.
  • aromatic diamine having an ester bond and / or an ether bond include the following.
  • the aromatic diamine having no ester bond and ether bond preferably includes 1 to 5 benzene rings, and more preferably includes a benzene skeleton, a naphthyl skeleton, or a biphenyl skeleton.
  • 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.
  • the tetracarboxylic dianhydride component may contain either an aliphatic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride, but ensures the strength and heat resistance of the resulting thin film. From the viewpoint, it is preferable to include an aromatic tetracarboxylic dianhydride.
  • the tetracarboxylic dianhydride component includes an aromatic tetracarboxylic dianhydride having an ester bond and / or an ether bond, and an aromatic tetracarboxylic dianhydride having no ester bond and an ether bond. Including at least one of the objects.
  • the aromatic tetracarboxylic dianhydride having an ester bond and / or an ether bond contains either an ester bond or an ether bond in the molecule, or both of them.
  • aromatic tetracarboxylic dianhydrides include tetracarboxylic dianhydrides having a structure in which a plurality of aromatic rings having 6 to 20 carbon atoms are connected by ester bonds or ether bonds.
  • Specific examples of the aromatic ring include those similar to the above. Among these, those having a structure in which three or four aromatic rings are connected by an ester bond or an ether bond are preferable from the viewpoint of ensuring the solubility of polyamic acid in an organic solvent.
  • aromatic tetracarboxylic dianhydride having an ester bond and / or an ether bond include the following.
  • Such a tetracarboxylic dianhydride may be either an aliphatic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride, but from the viewpoint of ensuring the strength and heat resistance of the resulting thin film, an ester bond And an aromatic tetracarboxylic dianhydride having no ether bond is preferred.
  • the aromatic tetracarboxylic dianhydride having no ester bond and ether bond preferably contains 1 to 5 benzene rings, and more preferably contains a benzene skeleton, naphthyl skeleton or biphenyl skeleton.
  • 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,
  • the aromatic tetracarboxylic dianhydride having no ester bond or ether bond is preferably at least one selected from the group consisting of formulas (C1) to (C12) from the viewpoint of ensuring heat resistance. At least one selected from the group consisting of (C1) and formula (C9) is more preferable.
  • the amount of the aromatic diamine having an ester bond and / or an ether bond is such that the tetracarboxylic dianhydride component is an aromatic tetracarboxylic dianhydride having an ester bond and / or an ether bond.
  • the tetracarboxylic dianhydride component is an aromatic tetracarboxylic dianhydride having an ester bond and / or an ether bond.
  • it 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 100 mol% in the total diamine component.
  • the amount of the aromatic tetracarboxylic dianhydride having an ester bond and / or an ether bond is used when the diamine component does not contain an aromatic diamine having an ester bond and / or an ether bond.
  • the tetracarboxylic dianhydride component it 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 100 mol%.
  • the total usage-amount is the diamine component and tetracarboxylic acid.
  • the total amount of the acid dianhydride component is preferably 35 mol% or more, more preferably 40 mol% or more, still more preferably 45 mol% or more, and even more preferably 50 mol% or more.
  • the ratio of the number of moles of aromatic diamine having an ester bond and / or ether bond to the number of moles of aromatic tetracarboxylic dianhydride having an ester bond and / or ether bond is arbitrary. is there.
  • the polyamic acid contained in the composition for forming a release layer for a transparent resin substrate according to the present invention can be obtained by reacting the diamine component and the tetracarboxylic dianhydride component described above.
  • 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-dimethylpropylamide, 3- Propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3 -Tert-butoxy-N, N-dimethylpropylamide, ⁇ -butyrolactone and the like. In addition, you may use an organic solvent individually by
  • amides represented by formula (S1), amides represented by formula (S2) and formula ( At least one selected from amides represented by S3) is preferred.
  • R 1 and R 2 each independently represent an alkyl group having 1 to 10 carbon atoms.
  • R 3 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • h represents a natural number, preferably 1 to 3, more preferably 1 or 2.
  • alkyl group having 1 to 10 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n- Examples include hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. Of these, alkyl groups having 1 to 3 carbon atoms are preferable, and alkyl groups having 1 or 2 carbon atoms are more preferable.
  • 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.
  • a target reaction solution containing polyamic acid 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.
  • a solution obtained by directly or diluting or concentrating the filtrate can be used as the composition for forming a release layer of the present invention.
  • the composition for peeling layer formation can be obtained efficiently.
  • the solvent in this case include organic solvents used in the above-described reaction.
  • the solvent used for dilution is not particularly limited, and specific examples thereof include those similar to the specific examples of the reaction solvent in the above reaction.
  • the solvent used for dilution may be used singly or in combination of two or more.
  • N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2 are used because they dissolve polyamic acid well.
  • -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, isoa
  • 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 is adjusted to adjust the amount of diamine and tetracarboxylic dianhydride used as the raw material of the polyamic acid. After the reaction solution is filtered, the filtrate is diluted or concentrated. The amount can be adjusted by, for example, adjusting the amount thereof when dissolved in a solvent.
  • the viscosity of the composition for forming the release layer is appropriately set in consideration of the thickness of the release layer to be produced, etc., but in particular, a film having a thickness of about 0.05 to 5 ⁇ m can be obtained with good reproducibility. When it is intended, 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 according to the present invention may contain a component such as a crosslinking agent in addition to the polyamic acid and the organic solvent, for example, in order to improve the film strength.
  • a component such as a crosslinking agent in addition to the polyamic acid and the organic solvent, for example, in order to improve the film strength.
  • release layer forming composition of the present invention By applying the release layer forming composition of the present invention described above to a substrate, and heating the resulting coating to thermally imidize the polyamic acid, excellent adhesion to the substrate, and a transparent resin substrate A release layer made of a polyimide film having moderate adhesion and moderate peelability can be obtained.
  • the release layer of the present invention When the release layer of the present invention is formed on a substrate, the release layer may be formed on a part of the substrate or 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 concerning 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 obtained from the composition for peeling layer formation which concerns on 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.
  • the substrate surface is constituted by two or more materials
  • a certain range of the substrate surface is constituted by a certain material
  • the other surface is constituted by another material.
  • a dot pattern is formed on the entire substrate surface.
  • a material in a pattern such as a line and space pattern is present in other materials.
  • the coating method is not particularly limited.
  • a cast coating method for example, a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, an ink jet method, a printing method (a relief plate, an intaglio plate, a planographic plate). , Screen printing, etc.).
  • the heating temperature for imidization is usually appropriately determined within the range of 50 to 550 ° C., but is preferably 200 ° C. or higher, and preferably 500 ° C. or lower. 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 raised stepwise as it is, and finally from 375 ° C. to 450 ° C. for 30 minutes to 4 hours.
  • the method of heating is mentioned.
  • Examples of equipment 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, more preferably about 0.05 to 5 ⁇ m from the viewpoint of productivity. To achieve the desired thickness.
  • 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.
  • an acrylic polymer solution, a polycarbonate, and a cycloolefin polymer solution for forming a transparent resin substrate of a flexible electronic device are applied, and this coating film is heated to pass through the release layer according to the present invention.
  • a transparent resin substrate fixed to the glass substrate is formed.
  • the transparent resin substrate is formed with a larger area than the area of the release layer so as to cover the entire release layer.
  • the method for forming the resin substrate may follow a conventional method.
  • examples of the highly transparent resin substrate include resin substrates formed of acrylic resin, polycarbonate, and cycloolefin polymer resin, and those having a light transmittance of 80% or more at a wavelength of 400 nm are particularly preferable.
  • a desired circuit is formed on the resin substrate fixed to the base via the release layer according to the present invention, and then, for example, the resin substrate is cut along the release layer. Is peeled from the release layer to separate the resin substrate and the substrate. At this time, a part of the substrate may be cut together with the release layer.
  • the polymer substrate can be suitably peeled from the glass carrier using the laser lift-off method (LLO method) that has been used in the manufacture of high-brightness LEDs, three-dimensional semiconductor packages, and the like.
  • LLO method laser lift-off method
  • JP 2013-147599 A In manufacturing a flexible display, a polymer substrate made of polyimide or the like is provided on a glass carrier, and then a circuit or the like including an electrode or the like is formed on the substrate. Finally, the substrate is peeled off from the glass carrier together with the circuit or the like. There is a need.
  • the LLO method is adopted, that is, when a glass carrier is irradiated with a light beam having a wavelength of 308 nm from the surface opposite to the surface on which a circuit or the like is formed, the light beam with the wavelength passes through the glass carrier, Only the nearby polymer (polyimide resin) absorbs this light and evaporates (sublimates). As a result, it has been reported that peeling of the substrate from the glass carrier can be performed selectively without affecting the circuit or the like provided on the substrate, which determines the performance of the display.
  • the composition for forming a release layer of the present invention has a feature of sufficiently absorbing light having a specific wavelength (for example, 308 nm) that can be applied by the LLO method, and thus can be used as a sacrificial layer for the LLO method.
  • Mw weight average molecular weight
  • Mw molecular weight distribution of a polymer
  • GPC apparatus manufactured by JASCO Corporation (column: KD801 and KD805 manufactured by Shodex; eluent: 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).
  • resin substrate forming composition A resin substrate forming composition was prepared by the following method.
  • composition for forming release layer [Example 1-1] BCS and NMP were added to the reaction solution obtained in Synthesis Example L1, and diluted such that the polymer concentration was 5% by mass and BCS was 20% by mass to obtain a release layer forming composition L1.
  • Examples 1-2 to 1-7 Except for using the reaction solutions obtained in Synthesis Examples L2 to L7, respectively, instead of the reaction solution obtained in Synthesis Example L1, the release layer forming compositions L2 to L were prepared in the same manner as in Example 1-1. L7 was obtained.
  • Example 2-1 Production of release layer and resin substrate [Example 2-1] Using a spin coater (condition: about 3,000 rpm for about 30 seconds), the release layer forming composition L1 obtained in Example 1-1 was applied to a 100 mm ⁇ 100 mm glass substrate (hereinafter the same). It was applied on top.
  • the obtained coating film was heated at 80 ° C. for 10 minutes using a hot plate, and then heated at 300 ° C. for 30 minutes using an oven, and the heating temperature was raised to 400 ° C. (10 ° C./min. And then heated at 400 ° C. for 30 minutes to form a release layer having a thickness of about 0.1 ⁇ m on the glass substrate, thereby obtaining a glass substrate with a release layer.
  • the glass substrate was not removed from the oven, but heated in the oven.
  • the composition F1 for resin substrate formation was apply
  • the obtained coating film is heated at 80 ° C. for 10 minutes using a hot plate, and then heated at 230 ° C. for 30 minutes using a hot plate to form a resin substrate having a thickness of about 5 ⁇ m on the release layer.
  • a glass substrate with a resin substrate and a release layer was obtained. Thereafter, the light transmittance was measured using an ultraviolet-visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation). As a result, the resin substrate showed a transmittance of 80% or more at 400 nm.
  • Example 2-2 to 2-7 Example except that the release layer forming compositions L2 to L7 obtained in Examples 1-2 to 1-7 were used in place of the release layer forming composition L1 obtained in Example 1-1.
  • a release layer and a resin substrate were formed in the same manner as in 2-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer were obtained.
  • Example 2-8 Using the release layer-forming composition L6 obtained in Example 1-6, a release layer was formed in the same manner as in Example 2-1, to obtain a glass substrate with a release layer. Then, immediately using a spin coater (condition: about 15 seconds at a rotation speed of 200 rpm), the resin substrate forming composition F2 was applied on the release layer (resin thin film) on the glass substrate. The obtained coating film was heated at 80 ° C. for 2 minutes using a hot plate, and then heated at 230 ° C. for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 ⁇ m on the release layer. A glass substrate with a resin substrate and a release layer was obtained. Thereafter, the light transmittance was measured using an ultraviolet-visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation). As a result, the resin substrate showed a transmittance of 80% or more at 400 nm.
  • UV-2600 ultraviolet-visible spectrophotometer
  • Example 2-8 was the same as Example 2-8 except that the release layer forming composition L7 obtained in Example 1-7 was used instead of the release layer forming composition L6 obtained in Example 1-6.
  • a release layer and a resin substrate were prepared, and a glass substrate with a release layer and a glass substrate with a resin substrate / release layer were obtained.
  • Example 2-10 Using the release layer-forming composition L6 obtained in Example 1-6, a release layer was formed in the same manner as in Example 2-1, to obtain a glass substrate with a release layer. Then, immediately using a spin coater (condition: about 15 seconds at a rotation speed of 200 rpm), the resin substrate forming composition F3 was applied on the release layer (resin thin film) on the glass substrate. The obtained coating film was heated at 80 ° C. for 2 minutes using a hot plate, and then heated at 230 ° C. for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 ⁇ m on the release layer. A glass substrate with a resin substrate and a release layer was obtained. Thereafter, the light transmittance was measured using an ultraviolet-visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation). As a result, the resin substrate showed a transmittance of 80% or more at 400 nm.
  • UV-2600 ultraviolet-visible spectrophotometer
  • Example 2-11 The same procedure as in Example 2-10 except that the release layer forming composition L7 obtained in Example 1-7 was used instead of the release layer forming composition L6 obtained in Example 1-6.
  • a release layer and a resin substrate were prepared, and a glass substrate with a release layer and a glass substrate with a resin substrate / release layer were obtained.
  • a peel force evaluation test was carried out using the resin substrate / glass substrate with the release layer produced in Examples 2-8 to 2-11.
  • a resin substrate / glass substrate with a release layer was cut into a 25 mm ⁇ 50 mm width rectangle so as to penetrate to the back surface of the resin substrate with a cutter knife to produce a strip.
  • cello tape registered trademark, Nichiban CT-24
  • Autograph AG-500N manufactured by Shimadzu Corporation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention porte sur une composition pour former une couche antiadhésive pour un substrat transparent en résine, ladite composition comprenant un poly(acide amique), qui est un réactif entre un constituant de type diamine et un constituant de type dianhydride tétracarboxylique, et un solvant organique : le constituant de type diamine comprenant au moins l'une parmi une diamine aromatique comprenant une liaison ester et/ou une liaison éther et une diamine aromatique ne comprenant pas de liaison ester ou de liaison éther ; le constituant de type dianhydride tétracarboxylique comprenant au moins l'un parmi un dianhydride tétracarboxylique aromatique comprenant une liaison ester et/ou une liaison éther et un dianhydride tétracarboxylique aromatique ne comprenant pas de liaison ester ou de liaison éther ; et au moins l'un parmi le constituant de type diamine et le constituant de type dianhydride tétracarboxylique comprenant un constituant comprenant une liaison ester et/ou une liaison éther.
PCT/JP2017/028210 2016-08-03 2017-08-03 Composition pour former une couche antiadhésive pour un substrat transparent en résine Ceased WO2018025954A1 (fr)

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CN201780046641.2A CN109563341B (zh) 2016-08-03 2017-08-03 用于透明树脂基板的剥离层形成用组合物
KR1020197004721A KR102365302B1 (ko) 2016-08-03 2017-08-03 투명 수지 기판용 박리층 형성용 조성물
JP2018531973A JP7131385B2 (ja) 2016-08-03 2017-08-03 透明樹脂基板用剥離層形成用組成物

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021125308A1 (fr) * 2019-12-20 2021-06-24 日産化学株式会社 Composition formant une couche de libération

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7429519B2 (ja) * 2019-11-05 2024-02-08 株式会社カネカ 多層ポリイミドフィルム
CN112521296B (zh) * 2021-02-05 2021-05-11 武汉柔显科技股份有限公司 二胺化合物、使用其的耐热性树脂或耐热性树脂前体、感光树脂组合物、固化膜及显示装置
CN116003794A (zh) * 2022-12-29 2023-04-25 中国科学院化学研究所 一种高频高耐热可热封性聚(芳酯-酰亚胺)树脂及其制备方法与应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013153124A (ja) * 2011-10-20 2013-08-08 Nitto Denko Corp 半導体装置の製造方法
WO2014050933A1 (fr) * 2012-09-27 2014-04-03 新日鉄住金化学株式会社 Procédé de production de dispositif d'affichage
JP2016120630A (ja) * 2014-12-24 2016-07-07 株式会社カネカ 剥離層の製造方法及びポリイミド積層体
WO2016129546A1 (fr) * 2015-02-10 2016-08-18 日産化学工業株式会社 Composition pour la formation d'une couche antiadhésive

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4619462B2 (ja) 1996-08-27 2011-01-26 セイコーエプソン株式会社 薄膜素子の転写方法
JP4619461B2 (ja) 1996-08-27 2011-01-26 セイコーエプソン株式会社 薄膜デバイスの転写方法、及びデバイスの製造方法
JP3809681B2 (ja) 1996-08-27 2006-08-16 セイコーエプソン株式会社 剥離方法
GB0327093D0 (en) 2003-11-21 2003-12-24 Koninkl Philips Electronics Nv Active matrix displays and other electronic devices having plastic substrates
TW200819501A (en) * 2006-09-11 2008-05-01 Mitsui Chemicals Inc Polyimide-based resin composition, method of manufacturing thereof and metal laminate
JP2008144049A (ja) * 2006-12-11 2008-06-26 Du Pont Toray Co Ltd 成形用ポリイミドフィルム、その製造方法並びに成形品
JP2009068004A (ja) * 2007-08-20 2009-04-02 Hitachi Chem Co Ltd 接着剤組成物、フィルム状接着剤、接着剤シート及びそれを用いた半導体装置
TWI354854B (en) 2008-09-15 2011-12-21 Ind Tech Res Inst Substrate structures applied in flexible electrica
US20140249269A1 (en) * 2011-10-20 2014-09-04 Nitto Denko Corporation Thermally-detachable sheet
JP6031877B2 (ja) * 2012-08-02 2016-11-24 日立化成株式会社 接着物の製造方法、接着剤パターンの形成方法、及び接着剤
CN103755959B (zh) * 2014-01-22 2016-03-02 江苏亚宝绝缘材料股份有限公司 一种柔性透明聚酰亚胺薄膜
WO2015174472A1 (fr) * 2014-05-14 2015-11-19 宇部興産株式会社 Stratifié de polyimide et son procédé de fabrication
CN104485344B (zh) * 2014-12-08 2017-12-05 信利（惠州）智能显示有限公司 一种柔性显示器制备方法
CN104725636A (zh) * 2015-02-02 2015-06-24 上海交通大学 含醚键和叔丁基的可溶性聚酰亚胺及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013153124A (ja) * 2011-10-20 2013-08-08 Nitto Denko Corp 半導体装置の製造方法
WO2014050933A1 (fr) * 2012-09-27 2014-04-03 新日鉄住金化学株式会社 Procédé de production de dispositif d'affichage
JP2016120630A (ja) * 2014-12-24 2016-07-07 株式会社カネカ 剥離層の製造方法及びポリイミド積層体
WO2016129546A1 (fr) * 2015-02-10 2016-08-18 日産化学工業株式会社 Composition pour la formation d'une couche antiadhésive

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021125308A1 (fr) * 2019-12-20 2021-06-24 日産化学株式会社 Composition formant une couche de libération
JPWO2021125308A1 (fr) * 2019-12-20 2021-06-24
JP7740023B2 (ja) 2019-12-20 2025-09-17 日産化学株式会社 積層体

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KR20190035757A (ko) 2019-04-03
TWI817931B (zh) 2023-10-11
KR102365302B1 (ko) 2022-02-22
JPWO2018025954A1 (ja) 2019-06-13
CN109563341A (zh) 2019-04-02
JP7131385B2 (ja) 2022-09-06
TW201821540A (zh) 2018-06-16

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