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
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
  • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
  • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
  • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
  • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
• • 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
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
• • 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
• • 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
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/02—Details
  • H05B33/04—Sealing arrangements, e.g. against humidity
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2457/00—Electrical equipment

Definitions

• the present invention relates to a laminate, in particular, a laminate comprising a polyimide layer (coating) having excellent heat resistance and dimensional stability and a glass substrate, a method for producing and using the same, and a polyimide precursor solution for laminating glass substrates.
• the present invention relates to a polyimide precursor solution for forming a polyimide coating.
• FPD flat panel displays
• LCD liquid crystal display
• PDP plasma display panel
• OLED organic EL display
• electronic paper electronic elements are mainly formed on a glass substrate.
• the glass substrate is rigid and lacks flexibility, there is a problem that it is difficult to be flexible.
• Patent Documents 1 to 3 propose that a polyimide film having a low coefficient of thermal expansion (CTE) is formed on a glass substrate and laminated and used as a substrate for forming an electronic device.
• the CTE of polyimide is one of the indices indicating the dimensional stability of the polyimide, and is a glass substrate having a low CTE (for example, an alkali-free CTE of 4 ppm / ° C. or less as described in Patent Document 3).
• the closer to the CTE of the glass substrate the smaller the distortion of the polyimide generated at the interface of the laminate during the high-temperature treatment process in the electronic element forming process, and the dimensional stability of the polyimide coating is improved.
• Examples of the low thermal expansion coefficient (CTE) polyimide include aromatic tetracarboxylic acids such as 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and aromatics such as p-phenylenediamine (PDA). It is known that a polyimide obtained from a group diamine has a relatively low CTE and excellent heat resistance.
• aromatic tetracarboxylic acids such as 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and aromatics such as p-phenylenediamine (PDA).
• BPDA 4,4′-biphenyltetracarboxylic dianhydride
• PDA p-phenylenediamine
• a glass substrate on which such a polyimide coating is laminated when a glass substrate is used as a substrate for a carrier, an electronic element is formed on the surface of the polyimide coating, and finally the polyimide coating is peeled off from the glass substrate. It can be set as a flexible substrate.
• the present invention solves the above-mentioned problems, and in a laminate composed of a polyimide coating and a glass substrate, the polyimide coating has good peeling characteristics and is peeled off when peeling the polyimide coating from the glass substrate.
• Another object of the present invention is to provide a laminated body in which the polyimide coating is difficult to curl, a method for producing and using the same, and a polyimide precursor solution for laminating a glass substrate capable of forming such a polyimide coating.
• the inventors of the present invention have made the structure of the polyimide coating specific in the laminate including the glass substrate and the polyimide coating. The present inventors have found that the above problems can be solved and have completed the present invention.
• the present invention has the following purpose.
• a laminate comprising a glass substrate and a polyimide film including a filler-containing polyimide layer formed on the glass substrate, wherein the filler has a thermal expansion coefficient of 10 ppm / ° C. or less.
• Laminated body (2) The laminate according to (1), wherein the polyimide coating includes the filler-containing polyimide layer and a filler-free polyimide layer formed on the filler-containing polyimide layer.
• the filler is one or more fillers selected from the group consisting of carbon particles, ceramic particles, and silicon particles.
• the polyimide film of the laminate of the present invention has a sufficiently low CTE of the polyimide film in contact with the glass substrate, and is difficult to curl. Even if curled, the radius of curvature of the curl is sufficiently large. Moreover, since the polyimide film has favorable peelability, the laminated body of this invention can be used suitably as a laminated body at the time of manufacturing electronic devices, such as a flat panel display and a flexible device.
• the laminate of the present invention comprises a glass substrate and a polyimide coating.
• a glass substrate for example, a substrate made of soda lime glass, borosilicate glass, non-alkali glass or the like can be used, and among these, an alkali-free glass substrate can be preferably used.
• These glass substrates may be subjected to a known surface treatment such as a silane coupling agent treatment.
• the thickness of the glass substrate is preferably 0.3 to 5.0 mm. If the thickness is less than 0.3 mm, the handling property of the substrate may be lowered. Moreover, productivity may fall when thickness is thicker than 5.0 mm.
• the laminate of the present invention comprises a glass substrate and a polyimide film including a filler-containing polyimide layer formed on the glass substrate.
• a filler containing polyimide layer means the polyimide layer whose filler content is 5 mass% or more with respect to the total mass of a polyimide layer.
• the filler-free polyimide layer refers to a polyimide layer having a filler content of less than 5% by mass.
• the filler contained in the polyimide layer is a filler having a CTE of 10 ppm / ° C. or less (to be abbreviated as “specific filler” hereinafter). Thereby, favorable peelability can be ensured.
• the polyimide coating may consist of a single layer of a specific filler-containing polyimide layer (hereinafter sometimes abbreviated as “layer-1”), but the layer-1 and a filler-free polyimide layer (hereinafter referred to as “layer”). 2 ”), and layer-1 may be in direct contact with the glass substrate.
• the polyimide layer (Layer-1 or Layer-2) may contain a known additive (for example, a lubricant such as silicon dioxide and aluminum oxide) that is usually used in the production of a polyimide film.
• the polyimide coating (polyimide layer) is sometimes abbreviated as polyamic acid (hereinafter referred to as “PAA”), which is a polyimide precursor obtained by reacting approximately equimolar amounts of tetracarboxylic acids and diamine as raw materials in a solvent. ) A solution is applied on a glass substrate, dried and thermoset (imidized) to form a polyimide film (polyimide layer).
• PAA polyamic acid
• the polyimide obtained from this PAA is preferably a non-thermoplastic polyimide, and its glass transition temperature is preferably 250 ° C. or higher.
• the laminate of the present invention it is preferable to use a film obtained from a polyimide using aromatic tetracarboxylic acids as tetracarboxylic acids, regardless of whether the polyimide film is a single layer or a multilayer.
• examples of tetracarboxylic acids having an aromatic ring include pyromellitic acids, 3,3 ′, 4,4′-biphenyltetracarboxylic acids, 2 , 3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 4,4′-oxydiphthalic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid
• acids 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acids, p-terphenyltetracarboxylic acids, m-terphenyltetracarboxylic acids and the like, and mixtures thereof.
• BPDA 4,4'-biphenyltetracarboxylic dianhydride
• PMDA pyromellitic dianhydride
• the types of aromatic tetracarboxylic acids may be the same or different in the polyimides of layer-1 and layer-2, and are preferably the same.
• a film obtained from polyimide using an aromatic diamine as a diamine, regardless of whether the polyimide film is a single layer or a multilayer.
• aromatic diamines include p-phenylenediamine (PDA), m-phenylenediamine, 4,4′-oxydianiline (ODA), 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether (DADE).
• the type of diamine may be the same or different in the polyimides of layer-1 and layer-2, preferably the same.
• a polyimide film containing a filler having a CTE of 10 ppm / ° C. or less is used.
• Such filler is not particularly limited as long as the CTE is within a predetermined range.
• carbon particles graphite, carbon black, carbon nanotube, carbon nanosheet, graphene, etc.
• ceramic particles silicon nitride, silicon carbide) Etc.
• silicon particles 4.7 ppm / ° C.
• CTE value of Fira For the CTE value of Fira, see R. E. Taylor, CINDAS Data Series on Materials Properties, Thermal Expansion of Solids, Vol 1-4, ASM International, 1998, Welding, Brazing, SoldAld
• a CTE of a filler-free polyimide coating was compared by comparing the CTE of a polyimide-free polyimide coating having a CTE of 10 to 20 ppm / ° C. with a polyimide coating containing 30% by mass of filler relative to the coating mass.
• the filler is determined to have a CTE of 10 ppm / ° C. or less. Conversely, if the CTE of the filler-containing polyimide coating exceeds the CTE of the non-filler-containing polyimide coating, the filler is determined to have a CTE of more than 10 ppm / ° C. For example, metal particles such as copper and silver have a CTE of more than 10 ppm / ° C. and cannot be used as the filler of the laminate of the present invention.
• the average particle size range of the specific filler is preferably about 0.01 to 2 ⁇ m.
• the average particle diameter refers to a volume-based measurement value measured by a laser diffraction method.
• the particle shape of the specific filler is not limited, such as an indefinite shape, a spherical shape, a square shape, or a linear shape, but an indefinite shape is preferable.
• the content of the specific filler is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 20 to 30% by mass with respect to the total mass of the polyimide coating.
• total mass of the polyimide coating is “when the polyimide coating has a single layer structure”, “the total mass of the filler-containing polyimide layer (layer-1) constituting the single-layer polyimide coating” In the case where the polyimide coating has a multilayer structure, it means “the total mass of the filler-containing polyimide layer (layer-1) constituting the polyimide coating having the multilayer structure”.
• the thickness of the polyimide coating is preferably 1 to 50 ⁇ m when the polyimide coating has a single layer structure.
• the thickness of layer-1 is preferably 0.1-5 ⁇ m, more preferably 0.5-4 ⁇ m. preferable.
• the thickness of layer-2 is preferably about 5 to 50 ⁇ m.
• the method for producing a laminate of the present invention is characterized in that a filler-containing polyimide precursor layer (Layer-1) is formed by applying a filler-containing polyimide precursor solution onto a glass substrate, drying, and heat-treating.
• the filler-containing polyimide precursor solution is a polyimide precursor solution for laminating glass substrates containing a specific filler.
• the polyimide coating when the polyimide coating has a single-layer structure composed of only layer-1, the polyimide coating is applied to, for example, a PAA solution containing no specific filler (hereinafter sometimes abbreviated as “PAA-S”).
• PAA-S a PAA solution containing no specific filler
• PAA-F PAA solution in which a specific filler is uniformly blended is applied to a glass substrate, dried, and then thermally cured.
• This solution PAA-F corresponds to the filler-containing polyimide precursor solution.
• the drying temperature after coating is preferably 80 to 150 ° C.
• the thermosetting temperature is preferably 350 to 450 ° C., more preferably 380 to 420 ° C.
• thermosetting temperature exceeds 450 ° C., a part of the polyimide coating may be thermally decomposed.
• higher fatty acids such as stearic acid and palmitic acid, and release agents such as amides and metal salts thereof can be blended.
• stearic acid is preferred.
• the compounding amount of the release agent is preferably 0.01 to 2% by mass, more preferably 0.1 to 1% by mass with respect to the total mass of the polyimide coating.
• the specific filler into the PAA-S it may be uniformly mixed using a known method such as a planetary mixer, a sand mill, a ball mill, a jet mill, a three-roll, a stirring propeller, or the like.
• these PAA solutions may be added with known additives such as various surfactants and organic silane coupling agents as long as the effects of the present invention are not impaired.
• you may add other polymers other than PAA in the range which does not impair the effect of this invention as needed.
• PAA-S can be obtained, for example, by polymerizing a substantially equimolar amount of the above-described aromatic tetracarboxylic dianhydride and aromatic diamine in a solvent.
• the solvent is not particularly limited as long as it is a solvent that dissolves PAA.
• an amide solvent, a urea solvent, an ether solvent, and the like can be used.
• amide solvent examples include N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc) and the like.
• urea solvent examples include tetramethylurea, tetraethylurea, dimethylethyleneurea, dimethylpropyleneurea and the like.
• ether solvents include 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl.
• the reaction temperature for producing the PAA solution is preferably ⁇ 30 to 70 ° C., more preferably ⁇ 15 to 60 ° C.
• the addition order of the monomer and the solvent is not particularly limited, and may be any order.
• the solid content concentration of the polyimide precursor is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass.
• This PAA may be partially imidized.
• a commercial item can also be used for these PAA solutions.
• the polyimide coating has a multilayer structure composed of layer-1 and layer-2
• PAA-F is applied on the glass plate and dried.
• PAA-S is applied onto this coating (layer-1), dried to form layer-2, and then thermally cured all at once.
• the drying temperature after coating is preferably 80 to 150 ° C. for both layer-1 and layer-2.
• the thermosetting temperature is preferably 350 to 450 ° C., more preferably 380 to 420 ° C. It should be noted that it is preferable to apply PAA-S without applying thermosetting after applying and drying Layer-1. By doing so, the adhesive strength at the interface between layer-1 and layer-2 is improved, and a strongly integrated polyimide film can be obtained.
• a known method such as a table coater, a dip coater, a bar coater, a spin coater, a die coater, or a spray coater is used. It can be applied in batch mode.
• another polymer layer may be formed on the layer-1 when the polyimide coating has a single layer structure, and on the layer-2 when it has a multilayer structure.
• the laminate of the present invention obtained as described above is useful for manufacturing an electronic device because the polyimide coating can be easily peeled off from the glass substrate after the electronic element is formed on the surface of the polyimide coating. . Since the polyimide coating contains filler, the adhesive strength with the glass interface is weakened accordingly, and peeling can be easily performed. In addition, after peeling, the polyimide film on which the electronic element is formed is sufficiently prevented from curling.
• any electronic element conventionally used in the field of electronic devices can be used.
• the formation method of an electronic element can employ
• Examples of the electronic device include a flat panel display (FPD) such as a liquid crystal display (LCD), a plasma display panel (PDP), and an organic EL display (OLED); and a flexible device such as electronic paper.
• FPD flat panel display
• LCD liquid crystal display
• PDP plasma display panel
• OLED organic EL display
• flexible device such as electronic paper.
• PAA-S1 to PAA-S2> PAA-S1
• PDA 0.6 mol
• dehydrated DMAc polymerization solvent
• BPDA 0.6 mol
• Mw weight average molecular weight in terms of polystyrene by GPC was 62000.
• PAA-S2 A polyimide precursor solution PAA-S2 was prepared in the same manner as PAA-S1, except that “PDA (0.6 mol)” was changed to “a mixture of PDA (0.5 mol) and ODA (0.1 mol)”. Got.
• the solid content concentration of PAA-S2 was 16% by mass, and the weight average molecular weight (Mw) in terms of polystyrene by GPC was 72000.
• PAA-F2 to PAA-F6 ⁇ Preparation of filler-containing polyimide precursor solutions PAA-F2 to PAA-F6>
• PAA-F2 Silicon particles (average particle size: 0.5 ⁇ m, CTE: 4.7 ppm / ° C.) and dehydrated DMAc (diluting solvent) are added to PAA-S1, and mixed for 60 minutes using a planetary mixer to obtain a solid content.
• PAA-F3 PAA-F3 was obtained in the same manner as PAA-F2, except that the silicon particle content was 20% by mass relative to the total solid mass.
• PAA-F4 PAA-F4 was obtained in the same manner as PAA-F2, except that graphite particles (average particle size: 0.3 ⁇ m, CTE: 0.5 ppm / ° C.) were used as the filler.
• PAA-F5 PAA-, except that carbon black (channel black with an average particle size of 0.03 ⁇ m, CTE: 0.5 ppm / ° C.) was used as the filler, and the carbon black content was 23 mass% based on the total solid mass. In the same manner as F2, PAA-F5 was obtained.
• PAA-F6 Silicon particles (average particle size: 0.5 ⁇ m, CTE: 4.7 ppm / ° C.), stearic acid, and dehydrated DMAc (diluted solvent) are added to PAA-S2, and mixed for 60 minutes using a planetary mixer.
• a polyimide precursor solution PAA-F6 containing 30% by mass of silicon particles and 0.5% by mass of stearic acid with respect to the total solid content mass was obtained.
• PAA-F7 was obtained in the same manner as PAA-F2, except that copper particles (average particle size: 0.6 ⁇ m, CTE: 17 ppm / ° C.) were used as the filler.
• Example 2 A filler-containing polyimide precursor solution PAA-F2 was applied on the surface of a non-alkali glass substrate (CTE: 3.2 ppm / ° C.) having a thickness of 0.7 mm using a table coater and dried at 130 ° C. for 10 minutes to form a PAA coating. Formed. Next, after raising the temperature from 100 ° C. to 400 ° C. over 2 hours under a nitrogen gas stream, heat treatment was carried out at 400 ° C. for 2 hours, and PAA was thermoset to imidize. As a result, a laminate A-2 comprising a glass substrate and a filler-containing polyimide film having a thickness of about 15 ⁇ m was obtained.
• CTE 3.2 ppm / ° C.
• CTE of coating As a result of peeling the polyimide film from the laminate A-2 and measuring the CTE, the CTE was 6.3 ppm / ° C.
• the CTE is measured using a TMA-7 manufactured by Perkin Elmer, with a 20 mm load applied in the longitudinal direction to a 13 mm ⁇ 3 mm sample, and measured at a temperature rising rate of 10 ° C./min. This was done by measuring the dimensional change at 250 ° C.
• Table 1 shows the CTE measurement results of the polyimide coating of A-2.
• the peeling property between the polyimide coating of the laminate A-2 and the glass substrate interface was evaluated as follows. That is, the adhesive strength between the polyimide coating and the glass substrate interface was measured by a 180 ° peel test based on JIS K6854, and when the adhesive strength was less than 0.1 N / cm, the peel property at the interface was determined to be “good”. . On the other hand, when the adhesive strength was 0.1 N / cm or more, the peeling property was determined to be “bad”. Table 1 shows the evaluation results of the peeling characteristics of A-2.
• the curl characteristics of the polyimide film peeled from the laminate were evaluated as follows. That is, the curvature radius of the polyimide film which was peeled from the glass substrate and cut into a 10 cm square was measured. When the radius of curvature was 50 mm or more, the curling characteristic was determined as “good”. On the contrary, when the radius of curvature is less than 50 mm, the curl characteristic is determined as “bad”. Table 1 shows the evaluation results of curl characteristics of the polyimide coating obtained from A-2.
• Example 3 A laminate A-3 comprising a filler-containing polyimide coating was obtained in the same manner as in Example 2 except that PAA-F3 was used as the filler-containing polyimide precursor solution.
• the coating CTE, peel property, and curl property of A-3 were measured or evaluated by the same method as in Example 2, and are shown in Table 1.
• Example 4 A laminate A-4 comprising a filler-containing polyimide coating was obtained in the same manner as in Example 2 except that PAA-F4 was used as the filler-containing polyimide precursor solution.
• the coating CTE, peel properties, and curl properties of A-4 were measured or evaluated by the same methods as in Example 2, and are shown in Table 1.
• Example 5 A laminate A-5 comprising a filler-containing polyimide coating was obtained in the same manner as in Example 2 except that PAA-F5 was used as the filler-containing polyimide precursor solution.
• the coating CTE, peel properties, and curl properties of A-5 were measured or evaluated by the same method as in Example 2, and are shown in Table 1.
• Example 6 PAA-F6 was coated on a surface of a non-alkali glass substrate (CTE: 3.2 ppm / ° C.) having a thickness of 0.7 mm using a table coater and dried at 130 ° C. for 10 minutes to form a PAA coating. Next, under a nitrogen gas stream, the temperature was raised from 100 ° C. to 380 ° C. over 2 hours, and then heat-treated at 380 ° C. for 2 hours to thermoset PAA and imidize. As a result, a laminate A-6 comprising a glass substrate and a filler-containing polyimide coating having a thickness of about 20 ⁇ m was obtained.
• the coating CTE, peel properties, and curl properties of A-6 were measured or evaluated by the same method as in Example 2, and are shown in Table 1.
• Example 2 Except that PAA-S1 was used as the polyimide precursor solution, the same procedure as in Example 2 was performed to obtain a laminate AR-1 composed of a polyimide coating containing no filler.
• AR-1 film CTE, peel properties and curl properties were measured or evaluated in the same manner as in Example 2, and are shown in Table 1.
• Example 3 A laminate AR-2 comprising a filler-containing polyimide coating was obtained in the same manner as in Example 2 except that PAA-S2 was used as the filler-containing polyimide precursor solution.
• the coating CTE, peel characteristics, and curl characteristics of AR-2 were measured or evaluated by the same method as in Example 2, and are shown in Table 1.
• Example 4 A laminate AR-7 comprising a filler-containing polyimide coating was obtained in the same manner as in Example 2 except that PAA-F7 was used as the filler-containing polyimide precursor solution.
• the coating CTE, peel properties, and curl properties of AR-7 were measured or evaluated by the same method as in Example 2, and are shown in Table 1.
• Example 7 PAA-F2 was coated on the surface of the alkali-free glass substrate with a table coater and dried at 130 ° C. for 10 minutes to form a PAA film. Next, the temperature was returned to room temperature (25 ° C.), and PAA-S1 was applied onto the PAA film with a table coater and dried at 130 ° C. for 10 minutes to form a second PAA film. Next, after raising the temperature from 100 ° C. to 400 ° C. over 2 hours under a nitrogen gas stream, heat treatment was carried out at 400 ° C. for 2 hours, and PAA was thermoset to imidize.
• a polyimide film (thickness: 23 ⁇ m) in which a glass substrate and layer-1 (filler-containing polyimide layer: thickness 3 ⁇ m) and layer-2 (filler-free polyimide layer: thickness 20 ⁇ m) are formed in this order on the glass substrate.
• layer-1 fill-containing polyimide layer: thickness 3 ⁇ m
• layer-2 fill-free polyimide layer: thickness 20 ⁇ m
• Example 8 A glass substrate and a layer-1 (filler-containing polyimide layer: thickness 3 ⁇ m) and layer-on the glass substrate in the same manner as in Example 7 except that PAA-F3 was used for forming the layer-1.
• a laminate L-3 was obtained comprising a polyimide film (thickness: 24 ⁇ m) in which 2 (filler-free polyimide layer: thickness 21 ⁇ m) was formed in this order.
• the peel characteristics and curl characteristics were evaluated by the same method as in Example 2, and are shown in Table 2.
• Example 9 A glass substrate and a layer-1 (filler-containing polyimide layer: thickness 2 ⁇ m) and layer-on the glass substrate in the same manner as in Example 7 except that PAA-F4 was used for forming the layer-1.
• a laminate L-4 comprising 2 (filler-free polyimide layer: thickness 20 ⁇ m) and a polyimide coating (thickness: 22 ⁇ m) formed in this order was obtained.
• the peel characteristics and curl characteristics were evaluated by the same method as in Example 2, and are shown in Table 2.
• Example 10 A glass substrate and a layer-1 (filler-containing polyimide layer: thickness 2 ⁇ m) and layer-on the glass substrate in the same manner as in Example 7 except that PAA-F5 was used for forming the layer-1.
• a laminate L-5 comprising 2 (film-free polyimide layer: thickness 21 ⁇ m) and a polyimide coating (thickness: 23 ⁇ m) formed in this order was obtained.
• the peel characteristics and curl characteristics were evaluated by the same method as in Example 2, and are shown in Table 2.
• Example 11 A glass substrate and a layer-1 (filler-containing polyimide layer: thickness 2 ⁇ m) and layer-on the glass substrate in the same manner as in Example 7 except that PAA-F6 was used for forming the layer-1.
• the peel characteristics and curl characteristics were evaluated by the same method as in Example 2, and are shown in Table 2.
• Example 5 A glass substrate and a layer-1 (filler-free polyimide layer: thickness) were formed on the glass substrate in the same manner as in Example 7 except that the filler-free PAA-S1 was used for forming the layer-1. 3 ⁇ m) and a laminate LR-1 composed of a polyimide coating (thickness: 23 ⁇ m) in which layer-2 (filler-free polyimide layer: thickness 20 ⁇ m) was formed in this order was obtained. The peel characteristics and curl characteristics were evaluated by the same method as in Example 2, and are shown in Table 2.
• Example 6 A glass substrate and a layer-1 (filler-containing polyimide layer: thickness 3 ⁇ m) and layer-on the glass substrate in the same manner as in Example 7 except that PAA-F7 was used for forming the layer-1.
• a laminate LR-7 consisting of a polyimide film (thickness: 23 ⁇ m) in which 2 (filler-free polyimide layer: thickness 20 ⁇ m) was formed in this order, the release characteristics and curl characteristics were the same as in Example 2. The results are shown in Table 2.
• the layer-1 in contact with the glass substrate contains a predetermined filler. For this reason, it can be seen that the peel characteristics are good, the CTE of layer-1 is low, and the curl characteristics are also good.
• the layer-1 of LR-7 shown in Comparative Example 6 contains filler, the CTE of the copper particles as the filler is high even though the peeling property is good. It can be seen that the characteristics are poor. Further, it can be seen from Comparative Example 5 that when a polyimide-free polyimide coating is used as layer-1, both the peeling characteristics and the curling characteristics are poor even if the polyimide coating is a multilayer.
• the laminate of the present invention has good releasability and the peeled polyimide coating is difficult to curl, by forming an electronic element on the surface of the polyimide coating constituting the laminate, the electronic device can be produced. Useful.

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