Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • 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
  • C08G73/1067—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
  • C08G73/18—Polybenzimidazoles
• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/20—Diluents or solvents
• • 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

Definitions

• the present invention relates to a composition for forming a release layer provided directly on a glass substrate.
• Patent Documents 1, 2, and 3 an amorphous silicon thin film layer is formed on a glass substrate, a plastic substrate is formed on the thin film layer, and then a laser is irradiated from the glass surface side to accompany crystallization of amorphous silicon.
• a method of peeling a plastic substrate from a glass substrate with generated hydrogen gas is disclosed.
• Patent Document 4 discloses a method for completing a liquid crystal display device by attaching a layer to be peeled (described as “transfer target layer” in Patent Document 4) to a plastic film using the techniques disclosed in Patent Documents 1 to 3. Is disclosed.
• Patent Documents 1 to 4 particularly the method disclosed in Patent Document 4, it is essential to use a highly light-transmitting substrate, and hydrogen contained in amorphous silicon is allowed to pass through the substrate.
• hydrogen contained in amorphous silicon is allowed to pass through the substrate.
• irradiation with a relatively large laser beam is required and the layer to be peeled is damaged.
• it takes a long time for laser treatment and it is difficult to peel off a layer to be peeled having a large area there is a problem that it is difficult to increase the productivity of device fabrication.
• JP-A-10-125929 Japanese Patent Laid-Open No. 10-125931.
• an object of the present invention is to solve the above problems. Specifically, the objective of this invention is providing the composition for forming the peeling layer for making it peel without damaging the board
• the object of the present invention is to maintain adhesion with a glass substrate on which a release layer is provided and does not cause peeling at the interface with the glass substrate.
• An object of the present invention is to provide a composition for forming a release layer, which can easily peel a layer or a group of layers formed thereon from the release layer.
• the present inventor has now found the following invention. That is, the present inventor forms a release layer using a composition containing a polyamic acid having a monomer unit having a specific structure of 50 mol% or more and a weight average molecular weight of a certain value or more, and an organic solvent. It has unexpectedly been found that the layer has suitable properties that can be peeled off without damaging the substrate applied to the flexible electronic device or the like.
• This layer is a layer or layer formed above the release layer on the side opposite to the glass substrate, while maintaining adhesion to the glass substrate on which the release layer is provided and hardly causing peeling at the interface with the glass substrate. About a group, it was able to peel easily from a peeling layer. The present invention is based on such knowledge.
• a composition for forming a release layer comprising a polyamic acid containing 50 mol% or more of a monomer unit represented by the following formula (1) and having a weight average molecular weight of 10,000 or more and an organic solvent.
• X 1 represents a tetravalent organic group
• Y 1 represents a divalent group represented by the following formula (P): (Wherein R represents F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, m represents an integer of 0 to 4, and r represents an integer of 1 to 4)] .
• the Y 1 may be a divalent group represented by any of the following formulas (P1) to (P3).
• R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be the same or different and each represents F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group;
• m1, m2, m3, m4, m5 and m6 may be the same or different and each represents an integer of 0 to 4.
• the ⁇ 2> Y 1 may include at least a divalent group represented by the formula (P1).
• the polyamic acid may further include a monomer unit represented by the following formula (2).
• X 1 is as defined in ⁇ 1> above, and Y 2 represents a group represented by the following formula (P4):
• R 7 and R 8 may be the same or different and each represents F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group;
• R ′ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, l represents an integer of 0 to 4, and m is as defined in the above ⁇ 1>)].
• X 1 may be a tetravalent aromatic group.
• the tetravalent aromatic group may have at least one selected from a benzene skeleton, a naphthalene skeleton, and a biphenyl skeleton.
• the organic solvent may be a solvent represented by the following formula (A) or (B). (Wherein R a and R b may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and h represents a natural number).
• the content of the monomer unit represented by the formula (1) in the polyamic acid may be 60 mol% or more.
• the composition for forming a release layer according to the present invention is preferably for forming a release layer provided directly on a glass substrate.
• a substrate structure applied to a flexible electronic device A base substrate; A release layer that covers the base substrate in one or more regions, and is formed of the release layer forming composition according to any one of ⁇ 1> to ⁇ 9>; Including the base substrate and a flexible substrate covering the release layer; A substrate structure, wherein an adhesion force between the flexible substrate and the release layer is larger than an adhesion force between the release layer and the base substrate.
• the base substrate may include glass.
• a method for producing a release layer wherein the release layer forming composition according to any one of ⁇ 1> to ⁇ 9> is used.
• the method for producing the release layer includes a step of applying the release layer forming resin composition to a substrate and heating the substrate.
• a method for producing a substrate structure applied to a flexible electronic device Preparing a base substrate, Producing a release layer that covers the base substrate in one or more regions using the release layer forming composition according to any one of ⁇ 1> to ⁇ 9>; Forming a flexible substrate on the base substrate and the release layer;
• the manufacturing method characterized by the adhesive force of the said flexible substrate and the said peeling layer being larger than the adhesive force of the said peeling layer and the said base base
• the present invention can solve the above problems. Specifically, according to the present invention, it is possible to provide a composition for forming a release layer for peeling without damaging a substrate applied to a flexible electronic device. Further, according to the present invention, in addition to the above effects or in addition to the above effects, the adhesion with the glass substrate on which the release layer is provided is maintained, and peeling at the interface with the glass substrate does not occur. It is providing the composition for forming this peeling layer which can peel the layer or layer group formed easily from a peeling layer.
• the release layer forming composition of the present invention is a polyamic acid containing 50 mol% or more of the monomer unit represented by the formula (1), and its weight average molecular weight is 10 , 1,000 or more polyamic acid and an organic solvent.
• X 1 represents a tetravalent organic group
• Y 1 represents a divalent group represented by the following formula (P).
• R represents F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, and preferably represents F or Cl.
• m represents an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1, and particularly preferably 0.
• r represents an integer of 1 to 3.
• the alkyl group having 1 to 3 carbon atoms includes methyl, ethyl, n-propyl, and i-propyl.
• the alkyl group having 1 to 3 carbon atoms is methyl, and more preferably, Methyl.
• the weight average molecular weight of the polyamic acid having the monomer unit represented by the formula (1) used in the present invention needs to be 10,000 or more, preferably 15,000 or more, more preferably 20,000 or more, more More preferably, it is 30,000 or more.
• the upper limit value of the weight average molecular weight of the polyamic acid used in the present invention is usually 2,000,000 or less, but it is possible to suppress the viscosity of the resin composition from becoming excessively high or to have a highly flexible resin thin film. In view of obtaining a good reproducibility, etc., it is preferably 1,000,000 or less, more preferably 200,000 or less.
• the monomer unit represented by the formula (1) is 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, Preferably it contains 90 mol% or more.
• the polyamic acid contained in the composition for forming a release layer of the present invention is a polymer composed only of the monomer unit represented by the formula (1), that is, the monomer represented by the formula (1). It is a polymer containing 100 mol% of units.
• the monomer unit in such a polyamic acid may be only one specific type or two or more types as long as it is represented by the formula (1).
• the number of monomer units of the formula (1) contained in the polyamic acid is preferably 2 to 4, more preferably 2 to 3.
• the group represented by the formula (P) preferably includes a divalent group represented by any one of the formulas (P1) to (P3), more preferably the formula (P1) or (P3 ), And more preferably a divalent group represented by the formula (P3).
• R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be the same or different, and F, Cl represents an alkyl group having 1 to 3 carbon atoms, or a phenyl group, and preferably represents F or Cl.
• m1, m2, m3, m4, m5 and m6 may be the same or different and each represents an integer of 0 to 4, preferably 0 to 2, more preferably 0. Represents ⁇ 1, particularly preferably 0.
• the polyamic acid used in the present invention may contain other monomer units in addition to the monomer unit represented by the formula (1).
• the content of such other monomer units needs to be less than 50 mol%, preferably less than 40 mol%, more preferably less than 30 mol%, and less than 20 mol%. Is more preferable, and it is further more preferable that it is less than 10 mol%.
• Examples of such other monomer units include a monomer unit of the formula (2).
• X 1 represents a tetravalent organic group
• Y 2 represents a group represented by the above-described formula (P4).
• R 7 and R 8 may be the same or different and each represents F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group.
• R 7 preferably represents F or Cl.
• R 8 preferably represents F or Cl.
• R ′ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
• l and m may be the same or different and each represents an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1, and particularly preferably 0.
• Examples of such other monomer units include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-methyl-1,4-phenylenediamine, and other monomer units of the formula (2).
• X 1 is a tetravalent organic group, preferably a tetravalent aromatic group.
• Tetravalent aromatic group X 1 can be taken, when creating a polyamic acid used in the present invention, it is possible to create by using an aromatic tetracarboxylic dianhydride as follows. That is, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1, 2,5,6-naphthalenetetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride
• the aromatic tetracarboxylic dianhydride desired here is selected from the following group of compounds.
• R 3 is a divalent organic group having at least one aromatic ring, and preferably a group having a phenyl, biphenyl, or naphthalene skeleton).
• the tetravalent aromatic group that X 1 can take has any of a benzene skeleton, a naphthalene skeleton, a biphenyl skeleton, and a terphenyl skeleton, and more preferably benzene Those having any of a skeleton, a naphthalene skeleton, and a biphenyl skeleton, and more preferably those having any of a benzene skeleton and a biphenyl skeleton.
• the polyamic acid used in the present invention is a 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) (formula (4)) as an acid dianhydride.
• BPDA 4,4′-biphenyltetracarboxylic dianhydride
• P-phenylenediamine (pPDA) (formula (5)) and 4,4 ′′ -diamino-p-terphenyl (DATP) (formula (6)) as diamine
• pyromellitic acid as acid dianhydride It can be obtained by reacting dianhydride (PMDA) (formula (7)) and pPDA (formula (5)) as a diamine.
• the above reaction consists of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), p-phenylenediamine (pPDA) and 4,4 ′′ -diamino-p-terphenyl (DATP).
• BPDA 4,4′-biphenyltetracarboxylic dianhydride
• pPDA p-phenylenediamine
• DATP 4,4 ′′ -diamino-p-terphenyl
• the charge ratio (molar ratio) of diamine or pyromellitic dianhydride (PMDA) and pPDA can be appropriately set in consideration of the molecular weight of the desired polyamic acid, the proportion of monomer units, and the like.
• the acid anhydride component can be about 0.7 to 1.3, preferably about 0.8 to 1.2.
• the charge ratio of pPDA and DATP which is a diamine
• the substance amount (m 1 ) of pPDA is usually about 1.7 to 20 when the substance amount (m 2 ) of DATP is 1.
• it is preferably 2.1 to 20, more preferably 2.2 to 20, still more preferably 2.3 to 19, and still more preferably 2.3 to 18.
• the composition for forming a release layer according to the present invention contains such an organic solvent.
• Any organic solvent can be used as long as it does not adversely affect the reaction. Specific examples include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide.
• the organic solvent is a solvent represented by the formula (A) or (B).
• R a and R b may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms.
• h represents a natural number, preferably 1 to 3.
• the reaction temperature 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 imidation of the resulting polyamic acid and maintains a high content of polyamic acid units. Therefore, 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, it cannot be defined unconditionally, but is usually about 1 to 100 hours.
• a target reaction solution containing polyamic acid can be obtained.
• the filtrate is used as it is, or diluted or concentrated, and used as a release layer forming composition.
• the solvent used for dilution and concentration is not particularly limited, and examples thereof include those similar to the specific examples of the reaction solvent in the above reaction, and these may be used alone or in combination of two or more. .
• the solvents used are N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3 -Dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone and ⁇ -butyrolactone are preferred.
• the concentration of the polyamic acid with respect to the total mass of the composition for forming the release layer is appropriately set in consideration of the thickness of the thin film to be produced (release layer), the composition viscosity, etc., but is usually about 0.5 to 30% by mass. Preferably, it is about 5 to 25% by mass.
• the viscosity of the release layer forming composition is appropriately set in consideration of the thickness of the thin film to be produced, etc., but the object is to obtain a resin thin film having a thickness of about 0.05 to 5 ⁇ m with good reproducibility. In this case, it is usually about 10 to 10,000 mPa ⁇ s at 25 ° C., preferably about 20 to 1000 mPa ⁇ s, and more preferably about 20 to 200 mPa ⁇ s.
• the viscosity of the release layer forming composition is measured using a commercially available liquid viscosity measurement viscometer, for example, referring to the procedure described in JIS K7117-2, and the temperature of the release layer forming composition. It can be measured at 25 ° C.
• a conical plate type (cone plate type) rotational viscometer is used as the viscometer, and preferably 1 ° 34 ′ ⁇ R24 is used as a standard cone rotor with the same type viscometer. It can be measured under the condition that the temperature of the product is 25 ° C.
• An example of such a rotational viscometer is TVE-25H manufactured by Toki Sangyo Co., Ltd.
• composition of the present invention may have various components in addition to the polyamic acid and the organic solvent.
• examples thereof include, but are not limited to, a crosslinking agent (hereinafter also referred to as a crosslinkable compound).
• crosslinkable compound examples include a compound containing two or more epoxy groups, a melamine derivative, a benzoguanamine derivative or glycoluril having a hydrogen atom of an amino group substituted with a methylol group, an alkoxymethyl group or both. However, it is not limited to these.
• crosslinkable compound examples include cyclohexene structures such as Epolide GT-401, Epolide GT-403, Epolide GT-301, Epolide GT-302, Celoxide 2021, Celoxide 3000 (manufactured by Daicel Corporation).
• Epoxy compound having: Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010, Epicoat 828 (above, manufactured by Japan Epoxy Resin Co., Ltd.
• benzoguanamine derivative or glycoluril having a group in which the hydrogen atom of the amino group is substituted with a methylol group, an alkoxymethyl group, or both, an average of 3.7 methoxymethyl groups are substituted per triazine ring.
• MX-750 MW-30 substituted with an average of 5.8 methoxymethyl groups per triazine ring (above, manufactured by Sanwa Chemical Co., Ltd.); Cymel 300, Cymel 301, Cymel 303, Cymel 350, Methoxymethylated melamines such as Cymel 370, Cymel 771, Cymel 325, Cymel 327, Cymel 703, Cymel 712, and the like; Cymel 235, Cymel 236, Cymel 238, Cymel 212, Cymel 253, Cymel 254, and the like.
• base substrate examples include glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal (silicon wafer, etc.) Wood, paper, slate and the like.
• 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.).
• thermal imidization in which the composition coated on the substrate is heated as it is, and a catalyst is added to the composition and heated.
• a catalyst is added to the composition and heated. Examples include catalytic imidization.
• the catalyst imidation of polyamic acid is performed by adding a catalyst to the release layer forming composition of the present invention and adjusting the catalyst addition composition by stirring, and then applying and heating the resin thin film (release layer). ) Is obtained.
• the amount of the catalyst is 0.1 to 30 mol times, preferably 1 to 20 mol times of the amic acid group.
• acetic anhydride and the like can be added as a dehydrating agent to the catalyst additive composition, and the amount thereof is 1 to 50 mol times, preferably 3 to 30 mol times of the amic acid group.
• a tertiary amine is preferably used as the imidization catalyst.
• pyridine substituted pyridines, imidazole, substituted imidazoles, picoline, quinoline, isoquinoline and the like are preferable.
• the heating temperature during thermal imidization and catalyst imidation is preferably 450 ° C. or lower. If it exceeds 450 ° C., the resulting resin thin film becomes brittle, and a resin thin film suitable for the intended use may not be obtained. Also, considering the heat resistance and linear expansion coefficient characteristics of the resulting resin thin film, after heating the applied composition at 50 ° C. to 100 ° C. for 5 minutes to 2 hours, the heating temperature is increased stepwise as it is. In addition, it is desirable to heat at over 375 ° C to 450 ° C for 30 minutes to 4 hours. In particular, the applied composition is heated at 50 ° C. to 100 ° C. for 5 minutes to 2 hours, then over 100 ° C. to 200 ° C.
• 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 resin thin film is usually about 0.01 to 10 ⁇ m, preferably about 0.05 to 5 ⁇ m.
• the thickness of the coating film before heating is adjusted to a desired thickness. A resin thin film is formed.
• the thin film described above is most suitable for use as a peeling layer for peeling without damaging a substrate applied to a flexible electronic device.
• a release layer provided between the flexible substrate applied to the flexible electronic device and the base substrate can be formed.
• a base substrate what contains glass or a silicone wafer is preferable, More preferably, glass is included.
• the release layer can be formed by applying the composition of the present invention to a glass substrate by a conventionally known technique and heating the obtained coating film at a predetermined temperature.
• a to-be-separated body layer can be formed on a peeling layer.
• the layer to be peeled may be a single layer or a plurality of layers. In order to fabricate various devices, it is realistic to have a plurality of layers.
• the layer immediately above the release layer depends on the release layer to be used, but it is preferable to use a layer having good peelability with the release layer, in other words, a layer having poor adhesion to the release layer to be used. Good.
• a method for manufacturing an object to be peeled is provided.
• the method a) a step of forming a release layer after applying the composition of the present application on a glass substrate; b) a step of forming an object to be peeled on the release layer; and c) a step of peeling the object to be peeled at the interface between the release layer and the object to be peeled; It is possible to obtain an object to be peeled.
• the “object to be peeled” may be a single layer or a plurality of layers.
• the release layer has good peelability, in other words, the adhesiveness to the release layer to be used is not good. There should be.
• a substrate structure applied to a flexible electronic device A base substrate; A release layer covering the base substrate in one or more regions, the release layer formed by the release layer forming composition according to the present invention; Including the base substrate and a flexible substrate covering the release layer; A substrate structure is provided in which the adhesive force between the flexible substrate and the release layer is greater than the adhesive force between the release layer and the base substrate.
• size of an adhesive force here can be confirmed by the crosscut test shown in the Example of this application, for example.
• BPDA 3,3′-4,4′-biphenyltetracarboxylic dianhydride.
• BA-TME 4,4-biphenylenebis (trimellitic acid monoester anhydride).
• PMDA pyromellitic dianhydride.
• IPHA isophthalaldehyde.
• Mw weight average molecular weight
• Mw molecular weight distribution of the polymer
• the temperature rising rate was 10 ° C./min.
• Cure condition C maintained at 80 ° C. for 10 minutes ⁇ temperature rise ⁇ 300 ° C. for 30 minutes ⁇ temperature rise ⁇ 400 ° C. for 30 minutes.
• the temperature rising rate was 10 ° C./min.
• the film thickness of the obtained coating film was measured using a contact-type film thickness measuring device (Dektak 3ST manufactured by ULVAC, Inc.).
• Table 1 shows the precursors of P1 to P7 used, the coated substrate, the curing conditions, and the film thickness of the produced release layer.
• ⁇ Cross cut test I> For the substrates provided with the release layers of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1, the adhesion of the substrate (glass or silicon wafer) / release layer was confirmed by cross-cut test I.
• the crosscut test I was performed as follows. (1) On the film, 100 1 mm squares were produced. (2) Thereafter, the above square was attached with an adhesive tape (cello tape (registered trademark)), and a peeling process was performed. (3) After the peeling step, the squares remaining on the substrate were counted.
• the characteristics of the components constituting the release layer, ie, (1) during heating, for the substrates provided with the release layers of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1 A temperature showing 1% weight loss in weight change of (2), (2) refractive index at a wavelength of 1000 nm, (3) birefringence at a wavelength of 1000 nm, and (4) surface energy were measured. The measurement conditions for each characteristic are shown below.
• thermogravimetric (TG) measurement was performed in a nitrogen atmosphere, and the temperature at which the weight decreased by 1% was determined.
• the refractive index and the birefringence were measured using a high-speed spectroscopic ellipsometer M-2000 (manufactured by JA Woollam Japan Co., Ltd.).
• the refractive index was an in-plane refractive index having a value of 1000 nm
• the birefringence was a difference between the in-plane refractive index and the out-of-plane refractive index.
• the surface energy of each member was measured using a fully automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.).
• the solvent used for the measurement was water and methylene iodide, and was calculated from the contact angle of these solvents.
• a polyimide layer was formed as an object to be peeled on the release layer of the substrate provided with the release layer.
• the precursor P5 obtained in Synthesis Example 5 or Synthesis Example 1 is formed on the release layer of the substrate having the release layer of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1.
• P1 was applied with a bar coater. Then, maintain in an oven at 120 ° C. for 30 minutes ⁇ temperature increase ⁇ 180 ° C. for 20 minutes ⁇ temperature increase ⁇ 240 ° C./20 minute maintenance ⁇ temperature increase ⁇ 300 ° C. for 20 minutes ⁇ temperature increase ⁇ 400 ° C. for 20 minutes Maintenance ⁇ Temperature rise ⁇ Cure at 450 ° C. for 60 minutes (the speed was 10 ° C./min at any temperature rise) to produce a 15 ⁇ m-thick peeled layer made of polyimide.
• Crosscut Test II >> About the board
• the crosscut test II was performed in the same manner as the crosscut test I.
• Table 2 shows (1) a temperature indicating a 1% weight decrease in weight change during heating (indicated by “(1)” in Table 2), (2) a refractive index at a wavelength of 1000 nm (in Table 2, “ (2) ”, (3) difference between the refractive index and birefringence of (2) (indicated by“ (3) ”in Table 2), (4) surface energy (in Table 2, This is indicated by “(4)” (where the unit is dyne / cm), the polyimide precursor used in the peeled layer, and the results of cross-cut tests I and II.
• Table 2 shows the following.
• the peeling layer of Examples 1 to 5 since the result of Test I is 5B, the peeling layer is not peeled off from the substrate, while the result of Test II is AA. It turns out that only peels.
• the release layer formed from the composition for release layer of the present invention provides a desired release result.
• Comparative Example 1 and Comparative Example 3 show that the release layer peels from the substrate because the result of Test I is AA.
• Comparative Example 1 and Comparative Example 3 cannot obtain a desired peeling result.
• Comparative Example 2 since both Test I and Test II are 5B, neither the interface between the release layer and the substrate nor the interface between the release layer and the layer to be peeled is peeled off. It can be seen that cannot be obtained.

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