Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
  • 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
  • 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

Definitions

• the present invention relates to a release layer forming composition and a release layer.
• 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.
• the direct method is mainly known as a method for producing a flexible display (Non-Patent Document 1).
• a direct method a prefabricated resin substrate is attached to a glass substrate through an adhesive layer, and a pixel circuit including a TFT and an organic EL are directly formed on the substrate, or a resin substrate is formed on the glass substrate. And a pixel circuit including a TFT and an organic EL are directly formed on the substrate.
• a resin substrate on which a pixel circuit or the like is formed on a glass substrate is peeled off by various methods to be described later to be used for manufacturing a target electronic device such as a display panel.
• 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 laser irradiation is performed from the glass substrate side to crystallize amorphous silicon.
• a method of peeling a plastic substrate from a glass substrate by hydrogen gas generated along with the crystallization is disclosed.
• Patent Document 4 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, and a liquid crystal display device is formed. A method of completion is disclosed.
• a current glass substrate is used as a substrate (hereinafter referred to as a glass substrate), and a release layer is formed on the glass substrate using a polymer such as a cyclic olefin copolymer.
• a heat-resistant resin film such as a polyimide film
• ITO transparent electrodes, TFTs, etc. are formed and sealed on the film by a vacuum process, and finally the glass substrate is peeled off.
• the manufacturing process to remove is employ
• a slit coating method using a slit coater or the like is generally advantageous.
• the slit coating method is a coating method using a slit nozzle, and since it does not need to rotate the substrate like the conventional spin coating method, it is widely adopted from the viewpoint of reducing the amount of resin composition used and process safety. Yes.
• speeding up of the coating process is desired from the viewpoint of improving productivity.
• Patent Documents 6 and 7 disclose compositions using so-called low-viscosity solvents such as propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether as photoresist compositions suitable for the slit coating method.
• a resin or a precursor thereof
• a slit coating method should be adopted for forming the release layer. It was difficult.
• JP 10-125929 A Japanese Patent Laid-Open No. 10-125931 International Publication No. 2005/050754 JP-A-10-125930 JP 2010-1111853 A International Publication No. 2011/030744 JP 2008-70480 A
• the present invention has been made in view of the above circumstances, is soluble in so-called low-viscosity solvents such as propylene glycol monomethyl ether, can be easily applied to a slit coating method, and flexible electronics formed thereon
• a release layer forming composition that provides a release layer that can be peeled without damaging a resin substrate of a device, particularly a film substrate formed of polyimide resin, acrylic resin, cycloolefin polymer resin, or the like.
• the present inventors have found that a polyamic acid having a specific structure can be easily dissolved in a low-viscosity solvent, and the polyamic acid and an organic solvent.
• the composition containing the resin substrate has excellent adhesion to a substrate such as a glass substrate, and moderate adhesion to a resin substrate used for flexible electronic devices, particularly a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm;
• the present invention was completed by finding that a release layer having an appropriate release property can be provided.
• a release layer forming composition comprising a polyamic acid represented by the following formula (1) and an organic solvent.
• X represents an aromatic group represented by the following formula (2a) or (2b)
• Y represents a divalent aromatic group having a fluorine atom
• Z represents the formula (2a )
• X is an aromatic group represented by the formula (2b)
• m represents a natural number.
• the aromatic group represented by the above formula (2a) is an aromatic group represented by the following formula (7a) or (8a), and the above Z, independently of each other,
• the aromatic group represented by the above formula (2b) is an aromatic group represented by the following formula (7b) or (8b), and the above Z, independently of each other,
• the organic solvent is at least one selected from those having structures represented by the following formulas (S1) to (S7): Composition.
• the release layer forming composition of the present invention By using the release layer forming composition of the present invention, it is possible to obtain a release layer having excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate release with good reproducibility.
• the polyamic acid used in the present invention is excellent in solubility in a low-viscosity solvent, it is possible to easily prepare a composition that can be applied to a slit coating method by using a low-viscosity solvent. It becomes easy to apply uniformly.
• the resin substrate is separated from the substrate together with the circuit without damaging the resin substrate formed on the substrate or the circuit provided on the substrate. Is possible. Therefore, the composition for forming a release layer of the present invention can contribute to speeding up the production process of a flexible electronic device including a resin substrate, improving the yield, and the like.
• composition for forming a release layer of the present invention includes a polyamic acid represented by the following formula (1) and an organic solvent.
• 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 fixed between the base and the resin substrate of the flexible electronic device formed of polyimide resin, acrylic resin, or the like in a predetermined process.
• a release layer 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.
• X is an aromatic group represented by the following formula (2a) or (2b)
• Y is a divalent aromatic group having a fluorine atom
• Z is a formula in which X is a formula In the case of (2a), independently of each other, an aromatic group represented by the following formula (3a) or (4a), and in the case where X is the formula (2b), independently of each other, the following formula (3b) ) Or (4b), and m represents a natural number.
• the aromatic group represented by the formula (2a) is preferably an aromatic group represented by the following formula (7a) or (8a), and the aromatic group represented by the formula (2b) is An aromatic group represented by the following formula (7b) or (8b) is preferable.
• the aromatic group represented by the above formula (3a) or (4a) is preferably an aromatic group represented by the following formula (9a) or (10a), and the above formula (3b) or (
• the aromatic group represented by 4b) is preferably an aromatic group represented by the following formula (9b) or (10b).
• Y is preferably an aromatic group having a fluorine atom and containing 1 to 5 benzene rings, more preferably an aromatic group selected from the following formula (5), and an aromatic group selected from the following formula (6). Groups are more preferred.
• M may be a natural number, but is preferably a natural number of 100 or less, more preferably a natural number of 2 to 100.
• the polyamic acid represented by the above formula (1) is obtained by reacting a predetermined tetracarboxylic dianhydride component with a diamine component.
• a tetracarboxylic dianhydride component benzenetetracarboxylic dianhydride or biphenyltetracarboxylic dianhydride is used.
• the diamine component as long as it has a fluorine atom, any of an alicyclic chain, an alicyclic ring, an aromatic group, and an aromatic alicyclic group may be used.
• the polyamic acid obtained by reacting the benzenetetracarboxylic dianhydride or biphenyltetracarboxylic dianhydride with the diamine component containing the aromatic diamine is more preferable.
• the benzenetetracarboxylic dianhydride component, the biphenyltetracarboxylic dianhydride component, and the diamine component that can be used for the synthesis of the polyamic acid having the structure represented by the above formula (1) will be described in detail.
• the benzenetetracarboxylic dianhydride is not particularly limited as long as it has two dicarboxylic anhydride sites in the molecule and has a benzene ring. Specific examples thereof include pyromellitic dianhydride and benzene-1,2,3,4-tetracarboxylic dianhydride. In the present invention, pyromellitic dianhydride is preferable. These may be used individually by 1 type, or may be used in combination of 2 or more type.
• the biphenyltetracarboxylic dianhydride is not particularly limited as long as it has two dicarboxylic anhydride sites in the molecule and has a biphenyl group. Specific examples thereof include 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4 Examples include '-biphenyltetracarboxylic dianhydride. In the present invention, 3,3', 4,4'-biphenyltetracarboxylic dianhydride is preferable. These may be used individually by 1 type, or may be used in combination of 2 or more type.
• the aromatic diamine is not particularly limited as long as it has two amino groups having a fluorine atom and directly bonded to the aromatic ring in the molecule.
• An aromatic diamine containing 1 to 2, particularly 1 to 2, and further 2 is preferred.
• what has a fluoroalkyl group or a perfluoroalkyl group is more preferable, and a perfluoroalkyl group is still more preferable.
• the perfluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, an n-heptafluoropropyl group, and an i-heptafluoropropyl group.
• aromatic diamine examples include 5-trifluoromethylbenzene-1,3-diamine, 5-trifluoromethylbenzene-1,2-diamine, 2,2′-bis (trifluoromethyl) -4, Examples thereof include, but are not limited to, 4′-diaminobiphenyl and 3,3′-bis (trifluoromethyl) biphenyl-4,4′-diamine. Of these, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl can be preferably used in the present invention. These may be used individually by 1 type, or may be used in combination of 2 or more type.
• the charging ratio of the diamine component and the tetracarboxylic dianhydride component is appropriately determined in consideration of the target molecular weight and molecular weight distribution, the kind of the diamine and tetracarboxylic dianhydride, etc.
• the molar ratio of the tetracarboxylic dianhydride component is preferably 1.05 to 2.5 mol, more preferably 1.07 to 1.5 mol, relative to 1 mol of the diamine component, and 1.1 to 1.5 mol. 1.3 mol is even more preferred.
• the polyamic acid contained in the composition for forming a release layer of the present invention can be obtained.
• the organic solvent used in the synthesis of the polyamic acid 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, ⁇ -butyrolacto , Propylene glycol monomethyl ether and propylene glyco
• the reaction temperature during the synthesis of the polyamic acid may be appropriately set in the range from the melting point to the boiling point of the solvent to be used, and is usually about 0 to 100 ° C. However, it prevents imidization of the resulting polyamic acid in the solution. From the viewpoint of maintaining a high content of polyamic acid units, the temperature can be 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, it cannot be defined unconditionally, but is usually about 1 to 100 hours.
• the weight average molecular weight of the polyamic acid thus obtained is usually about 5,000 to 500,000. From the viewpoint of improving the function of the resulting film as a release layer, preferably 10,000 to 200,000. About 000, more preferably about 10,000 to 150,000.
• a weight average molecular weight is a polystyrene conversion value by a gel permeation chromatography (GPC) measurement.
• n1 and m2 represent the number of repeating units, and the sum of m1 and m2 is the same as m above.
• n1 and m2 represent the number of repeating units, and the sum of m1 and m2 is the same as m above.
• the release layer forming composition of the present invention contains an organic solvent.
• the organic solvent those similar to the specific examples of the reaction solvent of the above reaction can be used. However, since the polyamic acid of the present invention is well dissolved and a highly uniform composition can be easily prepared, amides, An organic solvent selected from the group consisting of alcohols, esters, ethers, and ketones is preferable, and at least one type having a structure represented by the following formulas (S1) to (S7) is particularly preferable.
• R 1 to R 8 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.
• R 9 and R 10 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, or an acyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.
• b represents a natural number, preferably a natural number of 1 to 5, more preferably a natural number of 1 to 3.
• n represents a natural number, but is preferably a natural number of 1 to 5, more preferably a natural number of 1 to 3.
• alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n- Propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-di
• acyl group having 1 to 10 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, hexanoyl group, isohexanoyl group, heptanoyl group, isoheptanoyl group, octanoyl group Group, isooctanoyl group, nonanoyl group, isononanoyl group, decanoyl group, isodecanoyl group, benzoyl group and the like.
• organic solvent represented by the above formulas (S1) to (S7) include the following.
• Formula (S1) 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
• Formula (S2) 2- Pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone formula (S3): N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylpropylamide, N, N-dimethylbutane
• N-methyl-2-pyrrolidone, butyl cellosolve, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are more preferred, and propylene glycol monomethyl ether is preferred. Further preferred.
• These organic solvents may be used alone or in combination of two or more.
• the organic solvent when a so-called low-viscosity solvent such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate is used as the organic solvent, it is possible to obtain a low-viscosity release layer-forming composition that can be suitably applied to slit coating. it can.
• the proportion of the low-viscosity solvent in the entire solvent is preferably 60% by mass or more, more preferably 70% by mass or more, and 80% by mass or more. Is most preferred.
• 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.
• Especially low surfaces such as ethyl carbitol, butyl carbitol, ethyl carbitol acetate, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol
• a solvent having 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 it can be suitably used in the present invention.
• the composition for forming a release layer of the present invention can be prepared by a usual method.
• the preparation method the reaction solution containing the target polyamic acid obtained by the method described above is filtered, and the concentration of the obtained filtrate is adjusted to a predetermined concentration using the organic solvent described above. Good.
• 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.
• Concentration of polyamic acid adjusts the amount of diamine component, tetracarboxylic dianhydride component and aromatic monoamine used as the raw material for polyamic acid. Etc. can be adjusted.
• 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 well, it is usually about 10 to 10,000 mPa ⁇ s at 25 ° C., preferably about 20 to 5,000 mPa ⁇ s. Further, when the composition for forming a release layer of the present invention is used in a slit coating method, the viscosity is preferably about 2 to 100 mPa ⁇ s, and preferably about 2 to 25 mPa ⁇ s from the viewpoint of productivity.
• 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.
• 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 part of the substrate surface or on the entire surface.
• a mode of forming a release layer on a part of the substrate surface a mode in which the release layer is formed only in a predetermined range on the substrate surface, a release layer in a pattern such as a dot pattern or a line and space pattern on the entire substrate surface.
• 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.), Examples include wood, paper, and slate.
• plastic polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.
• metal silicon wafer, etc.
• Examples include wood, paper, and slate.
• a glass substrate since the release layer has sufficient adhesion, a glass substrate can be preferably used.
• the substrate surface may be composed of a single material or may be composed of two or more materials.
• the substrate surface is composed of two or more materials
• a material in a pattern such as a dot pattern or a line and space pattern is present in other materials.
• the method for applying the release layer-forming composition of the present invention to the substrate is not particularly limited, and examples thereof include cast coating, spin coating, slit coating, blade coating, dip coating, and roll coating.
• Method bar coating method, die coating method, ink jet method, printing method (such as relief printing, intaglio printing, planographic printing, and screen printing).
• 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. In particular, it is preferable that heating is performed at 50 to 150 ° C. for 5 minutes to 2 hours, followed by heating at 150 to 350 ° C. for 5 minutes to 2 hours, and finally heating at 350 to 450 ° C. for 30 minutes to 4 hours.
• 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 of the present invention peels the resin substrate from the substrate together with the circuit formed on the resin substrate without damaging the resin substrate of the device in the manufacturing process of the flexible electronic device. Therefore, it can be suitably used.
• 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 examples include a substrate made of a polyimide resin, an acrylic resin, or a cycloolefin polymer resin typical as a resin substrate of a flexible electronic device, and a resin solution for forming it includes a polyimide solution, a polyamic acid solution, Examples thereof include an acrylic polymer solution and a cycloolefin polymer solution.
• the method for forming the resin substrate may follow a conventional method.
• a resin substrate with high transparency a resin substrate formed of an acrylic resin or a cycloolefin polymer resin can be exemplified, and in particular, a substrate having a light transmittance of 80% or more at a wavelength of 400 nm is preferable.
• 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. It peels from a peeling layer, and a resin substrate and a base
• the LLO method is characterized in that light having a specific wavelength, for example, light having a wavelength of 308 nm, is irradiated from the surface opposite to the surface on which a circuit or the like is formed from the glass substrate side. The irradiated light passes through the glass substrate, and only the polymer (polyimide resin) in the vicinity of the glass substrate absorbs this light and evaporates (sublimates). As a result, it is possible to selectively peel the resin substrate from the glass substrate without affecting the circuit or the like provided on the resin substrate, which determines the performance of the display.
• the composition for forming a release layer according to the present invention has a feature of sufficiently absorbing light having a specific wavelength (for example, 308 nm) that enables application of the LLO method, and can therefore be used as a sacrificial layer for the LLO method. Therefore, when a desired circuit is formed on a resin substrate fixed to a glass substrate through a release layer formed by using the composition according to the present invention, and then an LLO method is performed to irradiate a light beam of 308 nm. Only the release layer absorbs this light and evaporates (sublimates). Thereby, the release layer is sacrificed (acts as a sacrifice layer), and the resin substrate can be selectively peeled from the glass substrate.
• a specific wavelength for example, 308 nm
• 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.
• Resin substrate forming composition F5 > 0.6 g of VESTAGON B 1530 and 11.8 g of PGMEA were added to 10 g of the reaction solution obtained in Synthesis Example S3, and the mixture was stirred at 23 ° C. for 24 hours to prepare a resin substrate forming composition F5.
• ⁇ Preparation Example 7 Resin substrate forming composition F7> To an eggplant flask containing 100 g of carbon tetrachloride, 10 g of ZEONOR (registered trademark) 1060R (manufactured by Nippon Zeon Co., Ltd., cycloolefin polymer resin) was added. This solution was dissolved by stirring for 24 hours under a nitrogen atmosphere to prepare a resin substrate forming composition F7.
• ZEONOR registered trademark
• 1060R manufactured by Nippon Zeon Co., Ltd., cycloolefin polymer resin
• 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.
• Example 1-2 The reaction solution obtained in Synthesis Example L2 was directly used as the release layer forming composition.
• Example 1-3 BCS and NMP were added to the reaction solution obtained in Synthesis Example L3, and diluted such that the polymer concentration was 5% by mass and BCS was 20% by mass to obtain a release layer forming composition.
• Example 1-4 The reaction solution obtained in Synthesis Example L4 was used as the release layer forming composition as it was.
• 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 film-coated 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 was heated at 80 ° C. for 30 minutes using a hot plate, and then heated at 140 ° C. for 30 minutes using an oven, and the heating temperature was raised to 210 ° C. (2 ° C./min.
• a resin substrate having a thickness of about 20 ⁇ m was formed to obtain a glass substrate with a resin substrate and a release layer. During the temperature increase, the film-coated substrate was not removed from the oven but heated in the oven.
• Example 2-2 A release layer and a resin substrate were produced in the same manner as in Example 2-1, except that the resin substrate forming composition F2 was used instead of the resin substrate forming composition F1 used in Example 2-1. Then, a glass substrate with a release layer and a glass substrate with a resin substrate / release layer were obtained.
• Example 2-3 The same procedure as in Example 2-1 except that the release layer forming composition L2 obtained in Example 1-2 was used instead of the release layer forming composition L1 obtained in Example 1-1.
• 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 2-4 The release layer forming composition L2 obtained in Example 1-2 was used as the release layer forming composition, and the resin substrate forming composition F2 used in Example 2-2 was used as the resin substrate forming composition.
• Example 2-4 The release layer forming composition L2 obtained in Example 1-2 was used as the release layer forming composition, and the resin substrate forming composition F2 used in Example 2-2 was used as the resin substrate forming composition.
• Example 2-4 was used to prepare a release layer and a resin substrate in the same manner as in Example 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 2-5 The release layer forming composition L1 obtained in Example 1-1 was used as the release layer forming composition, and the resin substrate forming composition F4 was used as the resin substrate forming composition.
• a release layer and a resin substrate were prepared in the same manner as in Example 1 to obtain a glass substrate with a release layer and a glass substrate with a resin substrate / release layer.
• Example 2-6 The release layer forming composition L1 obtained in Example 1-1 was used as the release layer forming composition, and the resin substrate forming composition F5 was used as the resin substrate forming composition.
• a release layer and a resin substrate were prepared in the same manner as in Example 1 to obtain a glass substrate with a release layer and a glass substrate with a resin substrate / release layer.
• Example 2-7 The release layer forming composition L2 obtained in Example 1-2 was used as the release layer forming composition, and the resin substrate forming composition F5 was used as the resin substrate forming composition.
• a release layer and a resin substrate were prepared in the same manner as in Example 1 to obtain a glass substrate with a release layer and a glass substrate with a resin substrate / release layer.
• Example 2-8 Using the release layer forming composition L1 obtained in Example 1-1, a release layer was formed in the same manner as in Example 2-1, to obtain a glass substrate with a release layer. Immediately thereafter, using a spin coater (condition: about 15 seconds at 200 rpm), the resin substrate forming composition F6 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 L2 obtained in Example 1-2 was used instead of the release layer forming composition L1 obtained in Example 1-1.
• 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 L1 obtained in Example 1-1, a release layer was formed in the same manner as in Example 2-1, to obtain a glass substrate with a release layer. Immediately thereafter, using a spin coater (condition: about 15 seconds at 200 rpm), the resin substrate forming composition F7 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 2-10 was the same as Example 2-10 except that the release layer forming composition L2 obtained in Example 1-2 was used instead of the release layer forming composition L1 obtained in Example 1-1.
• 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 2-12 Using a spin coater (conditions: about 3,000 rpm for about 30 seconds), the release layer forming composition L3 obtained in Example 1-3 was used as a glass substrate of 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 film-coated substrate was not removed from the oven but heated in the oven.
• composition F3 for resin substrate formation was apply
• the obtained coating film was heated at 80 ° C. for 30 minutes using a hot plate, and then heated at 230 ° C. for 30 minutes using an oven to form an acrylic substrate having a thickness of about 3 ⁇ m on the release layer. .
• the film-coated substrate was not removed from the oven but heated in the oven.
• Example 2-13 A release layer and a resin substrate were prepared in the same manner as in Example 2-12, except that the resin substrate forming composition F4 was used instead of the resin substrate forming composition F3 used in Example 2-12. Then, a glass substrate with a release layer and a glass substrate with a resin substrate / release layer were obtained.
• Example 2-14 A release layer and a resin substrate were prepared in the same manner as in Example 2-12, except that the resin substrate forming composition F5 was used instead of the resin substrate forming composition F3 used in Example 2-12. Then, a glass substrate with a release layer and a glass substrate with a resin substrate / release layer were obtained.
• Example 2-15 The same procedure as in Example 2-12 except that the release layer forming composition L4 obtained in Example 1-4 was used instead of the release layer forming composition L3 obtained in Example 1-3.
• 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 2-16 The release layer forming composition L4 obtained in Example 1-4 was used as the release layer forming composition, and the resin substrate forming composition F5 used in Example 2-14 was used as the resin substrate forming composition.
• the release layer forming composition L4 obtained in Example 1-4 was used as the release layer forming composition
• the resin substrate forming composition F5 used in Example 2-14 was used as the resin substrate forming composition.
• Example 2-17 Using the release layer forming composition L3 obtained in Example 1-3, a release layer was formed in the same manner as in Example 2-12 to obtain a glass substrate with a release layer. Immediately thereafter, using a spin coater (condition: about 15 seconds at 200 rpm), the resin substrate forming composition F6 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 2-17 was the same as Example 2-17 except that the release layer forming composition L4 obtained in Example 1-4 was used instead of the release layer forming composition L3 obtained in Example 1-3.
• 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 2-19 Using the release layer forming composition L3 obtained in Example 1-3, a release layer was formed in the same manner as in Example 2-12 to obtain a glass substrate with a release layer. Immediately thereafter, using a spin coater (condition: about 15 seconds at 200 rpm), the resin substrate forming composition F7 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 2-20 The same procedure as in Example 2-19 except that the release layer forming composition L4 obtained in Example 1-4 was used instead of the release layer forming composition L3 obtained in Example 1-3.
• 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 2-5 The same procedure as in Example 2-12 except that the release layer forming composition HL1 obtained in Comparative Example 1-1 was used instead of the release layer forming composition L3 obtained in Example 1-3.
• 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. Combinations of the release layer and the resin substrate are as shown in Table 2.
• 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. Further, after a cellophane tape (Nichiban CT-24) is put on the produced strip, autograph AG-500N (manufactured by Shimadzu Corporation) is used, at 90 degrees with respect to the surface of the substrate, that is, , Peeled in the vertical direction, peel strength was measured, 100% peel (all peel), and peel strength of less than 0.1 N / 25 mm was taken as AAA.
• Tables 1 and 2 The above results are shown in Tables 1 and 2.

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