WO2021193568A1 - Film de polyimide et stratifié - Google Patents

Film de polyimide et stratifié Download PDF

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Publication number
WO2021193568A1
WO2021193568A1 PCT/JP2021/011794 JP2021011794W WO2021193568A1 WO 2021193568 A1 WO2021193568 A1 WO 2021193568A1 JP 2021011794 W JP2021011794 W JP 2021011794W WO 2021193568 A1 WO2021193568 A1 WO 2021193568A1
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WIPO (PCT)
Prior art keywords
polyimide film
film
structural unit
polyimide
substrate
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PCT/JP2021/011794
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English (en)
Japanese (ja)
Inventor
孝博 村谷
舜 星野
葵 大東
三田寺　淳
Original Assignee
三菱瓦斯化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 三菱瓦斯化学株式会社 filed Critical 三菱瓦斯化学株式会社
Priority to JP2022510504A priority Critical patent/JPWO2021193568A1/ja
Priority to KR1020227032883A priority patent/KR20220158718A/ko
Priority to CN202180023081.5A priority patent/CN115348987A/zh
Publication of WO2021193568A1 publication Critical patent/WO2021193568A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/40—OLEDs integrated with touch screens
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a polyimide film and a laminate.
  • a target electronic circuit is created on the substrate through various processes such as a polysilicon film, a metal oxide film such as an indium tin oxide (ITO) film, and a sputtering process and an etching process for producing a semiconductor film. Be done. Therefore, the plastic substrate is required to have heat resistance.
  • a polyimide film suitable as such a plastic substrate is underway, and a laminate using the polyimide film as an electronic circuit board is also being developed.
  • Patent Document 1 describes a polyimide film layer containing a polyimide containing aminophenylaminobenzoate as a constituent, and a polyimide film layer, for the purpose of obtaining a flexible display capable of supporting substrate warpage, lighting test, cloudiness test, and heat cycle test.
  • a flexible display including a low temperature polysilicon TFT layer formed on a film layer is disclosed.
  • Patent Document 2 includes a step of forming a polyimide layer on a support while transporting a long support for the purpose of obtaining a polyimide laminate in which warpage is suppressed.
  • a method for producing a polyimide laminate in which the tensile elastic modulus of the support, the thickness of the support, and the fracture toughness value of the support are specific values is disclosed.
  • the present invention has been made in view of such a situation, and an object of the present invention is to provide a polyimide film having less warp and curl during a process and a laminate having less warp.
  • the present inventors have found that the above problems can be solved by using polyimide having a specific radius of curvature.
  • the present invention has been completed based on such findings.
  • C (Pa ⁇ m 2 ) is a constant obtained by the following formula (2), S (Pa) is the stress of the polyimide film, and t (m) is the thickness of the polyimide film.
  • E represents the Young's modulus (Pa) of the silicon (100) which is the substrate, ⁇ represents the Poisson's ratio of the silicon (100) which is the substrate, and h represents the thickness (m) of the silicon substrate.
  • ⁇ 2> A laminate in which the polyimide film according to ⁇ 1> above is laminated on a glass substrate or a silicon substrate.
  • ⁇ 3> The laminate according to ⁇ 2> above, wherein a metal film or a semiconductor film is further laminated on the polyimide film.
  • ⁇ 4> The laminate according to ⁇ 3> above, wherein the semiconductor film is at least one selected from the group consisting of indium tin oxide, amorphous silicon, indium gallium / zinc oxide, and low-temperature polysilicon.
  • ⁇ 5> The laminate according to any one of ⁇ 2> to ⁇ 4>, which has a sacrificial layer between the glass substrate or the silicon substrate and the polyimide film.
  • a method for producing a laminate which comprises a step of laminating the polyimide film according to ⁇ 1> or the polyimide film obtained by the production method according to ⁇ 6> on a glass substrate or a silicon substrate.
  • the polyimide film of the present invention is a polyimide film composed of a polyimide resin, and has a radius of curvature R larger than 20 m when laminated on a silicon substrate having a thickness of 520 ⁇ m represented by the following formula (1).
  • C (Pa ⁇ m 2 ) is a constant obtained by the following formula (2), S (Pa) is the stress of the polyimide film, and t (m) is the thickness of the polyimide film.)
  • E represents the Young's modulus (Pa) of the silicon (100) which is the substrate, ⁇ represents the Poisson's ratio of the silicon (100) which is the substrate, and h represents the thickness (m) of the silicon substrate.
  • the warp and curl of a polyimide film and the warp of a laminate obtained by laminating a polyimide film are often judged by the coefficient of linear thermal expansion (CTE) of the polyimide resin constituting the polyimide film, and the CTE is determined. Designing small resins was being done. However, there were cases where the CTE value did not match the actual warpage or curl phenomenon. In addition, it has been required to suppress warpage and curl during the process, which is particularly during peeling from the support. On the other hand, the present inventors have found that by satisfying the above conditions, a polyimide film having less warp and curl, and a laminate using the same, which has less warp and curl, can be obtained.
  • CTE coefficient of linear thermal expansion
  • the polyimide film of the present invention has a radius of curvature R larger than 20 m when laminated on a silicon substrate having a thickness of 520 ⁇ m represented by the following formula (1).
  • C (unit: Pa ⁇ m 2 ) is a constant obtained by the following formula (2).
  • S (unit: Pa) represents the stress of the polyimide film
  • t (unit: m) represents the thickness of the polyimide film.
  • E is the Young's modulus (unit: Pa) of the silicon (100) which is the substrate
  • ⁇ is the Poisson's ratio of the silicon (100) which is the substrate
  • h is the thickness (unit: m) of the silicon substrate.
  • E is the Young's modulus of silicon (100), which is a substrate, and is 130 GPa.
  • ⁇ is the Poisson's ratio of the substrate silicon (100), which is 0.28.
  • E / (1- ⁇ ) is the biaxial elastic modulus of the substrate, but in the case of a silicon (100) substrate, it is 1.805 ⁇ 10 11 Pa.
  • the (100) plane represents the so-called Miller index.
  • h is the thickness (unit: m) of the silicon substrate, and in the case of a silicon substrate having a thickness of 520 ⁇ m, the constant C is 8134.
  • the stress of the polyimide film corresponding to S in the formula (1) is preferably 42 MPa or less, more preferably 40 MPa or less, still more preferably 30 MPa or less.
  • the polyimide film is used for manufacturing a conductive film or the like described later, when setting S (stress of the polyimide film) and t (thickness of the polyimide film) in the above formula (1), it is actually manufactured. It is preferable to carry out under the same conditions as those used.
  • the film thickness of the polyimide film can be physically measured using a micrometer or the like, or optically observed using a laser microscope or the like to measure the height of the contact surface between the upper surface of the film and the substrate. You can also ask for it.
  • t is 1 ⁇ 10 -6 to 10 ⁇ 10 -6 m, more preferably 1.
  • a combination of ⁇ 10 -6 to 8 ⁇ 10 -6 m, more preferably 1 ⁇ 10 -6 to 5 ⁇ 10 -6 m is preferable.
  • t is 5 ⁇ 10 -6 to 20 ⁇ 10 -6 m, more preferably 5 ⁇ 10 -6 to 15 ⁇ 10 -6 m, and further.
  • a combination of 5 ⁇ 10 -6 to 10 ⁇ 10 -6 m is preferable.
  • the polyimide film of the present invention can be applied to a silicon substrate having a thickness of 520 ⁇ m represented by the above formula (1) from the viewpoint of reducing warpage and curl during the process and similarly reducing warpage of the laminated body.
  • the radius of curvature R when laminated is larger than 20 m (meter), but is preferably 40 m or more, and more preferably 70 m or more.
  • the upper limit is not limited, but from the viewpoint of facilitating the film formation of the polyimide film and the subsequent processing process, it is preferably 1000 m or less, more preferably 500 m or less, and further preferably 300 m or less.
  • the radius of curvature R when laminated on a silicon substrate having a thickness of 520 ⁇ m of the polyimide film is within the above range, the warp of the substrate during the process is small and the amount of warpage of the polyimide film after peeling from the substrate is also small, which is preferable.
  • Suitable physical property values of the polyimide film in the present invention are as follows.
  • the total light transmittance is preferably 88% or more, more preferably 88.5% or more, still more preferably 89% or more when the film has a thickness of 10 ⁇ m.
  • the yellow index (YI) is preferably 4.0 or less, more preferably 2.5 or less, still more preferably 2.0 or less when the film has a thickness of 10 ⁇ m. When the total light transmittance or the yellow index is in these ranges, it is suitable as a resin substrate for a flexible electronic device.
  • the haze is preferably 2.0% or less, more preferably 0.6% or less, and further preferably 0.4% or less when the film has a thickness of 10 ⁇ m. When the haze is in this range, it is suitable as a resin substrate for a flexible electronic device.
  • the polyimide film of the present invention is composed of a polyimide resin.
  • the polyimide resin constituting the polyimide film of the present invention has a structural unit A derived from tetracarboxylic acid dianhydride and a structural unit B derived from diamine.
  • a preferred example of the polyimide resin that can be used in the present invention is shown below, but the present invention is not limited thereto.
  • the structural unit A is a structural unit derived from tetracarboxylic dianhydride in the polyimide resin.
  • the structural unit A is not limited as long as it is a structural unit derived from tetracarboxylic dianhydride, but preferred structural units and combinations thereof will be described below.
  • the structural unit A is selected from the group consisting of a structural unit (A1) derived from an alicyclic tetracarboxylic dianhydride and a structural unit (A2) derived from a compound represented by the general formula (a2) described later. It preferably contains at least one structural unit, and more preferably contains the structural unit (A1). It is more preferable to include both the structural unit (A1) and the structural unit (A2).
  • the structural unit A contains a structural unit (A1) derived from an alicyclic tetracarboxylic dianhydride
  • the colorless transparency and optical isotropic property of the film can be improved.
  • the alicyclic tetracarboxylic acid dianhydride include 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, norbornan-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-.
  • 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride listed below norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5'' , 6, 6''-tetracarboxylic acid dianhydride is more preferred.
  • the structural unit (A1) is selected from the group consisting of the structural unit (A11) derived from the compound represented by the following formula (a11) and the structural unit (A12) derived from the compound represented by the following formula (a12). It is preferable to include at least one structural unit (A11) derived from the compound represented by the following formula (a11).
  • the compound represented by the formula (a11) is norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic dianhydride. It is an anhydride (CpODA). Since the constituent unit A includes the constituent unit (A11), the colorless transparency of the film is further improved.
  • the compound represented by the formula (a12) is 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA).
  • HPMDA 1,2,4,5-cyclohexanetetracarboxylic dianhydride
  • the constituent unit A may include both the constituent unit (A11) and the constituent unit (A12), but preferably includes either the constituent unit (A11) or the constituent unit (A12), and more preferably. Includes the building block (A11).
  • the structural unit (A2) is a structural unit derived from the compound represented by the following general formula (a2).
  • L is a single bond or divalent linking group.
  • the divalent linking group is preferably a substituted or unsubstituted alkylene group, more preferably -CR 1 R 2- (where R 1 and R 2 are independently hydrogen atoms or substituted or substituted or It is an unsubstituted alkyl group, or R 1 and R 2 are bonded to each other to form a ring).
  • L is one selected from the group consisting of a single bond, a group represented by the following formula (L1), a group represented by the following formula (L2), and a group represented by the following formula (L3). Is preferable.
  • * indicates a binding site with an aromatic ring.
  • the structural unit (A2) is a structural unit (A21) derived from a compound represented by the following formula (a21), a structural unit (A22) derived from a compound represented by the following formula (a22), and the following formula (a23). It is preferable that it is at least one selected from the group consisting of the structural unit (A23) derived from the compound represented by and the structural unit (A24) derived from the compound represented by the following formula (a24). More preferably, it is at least one selected from the group consisting of the structural unit (A21) derived from the compound represented by (a21) and the structural unit (A22) derived from the compound represented by the following formula (a22). , It is more preferable that the structural unit (A21) is derived from the compound represented by the following formula (a21).
  • the compound represented by the formula (a21) is biphenyltetracarboxylic dianhydride (BPDA), and specific examples thereof include 3,3', 4,4'-biphenyl represented by the following formula (a21s).
  • BPDA biphenyltetracarboxylic dianhydride
  • specific examples thereof include 3,3', 4,4'-biphenyl represented by the following formula (a21s).
  • a-BPDA 2,2,', 3,3'-biphenyltetracarboxylic dianhydride represented.
  • the compound represented by the formula (a22) is 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (BPAF).
  • the compound represented by the formula (a23) is 4,4'-(hexafluoroisopropyridene) diphthalic anhydride (6FDA).
  • the compound represented by the formula (a24) is 4,4'-oxydiphthalic anhydride (ODPA).
  • the total content ratio of the constituent unit (A1) and the constituent unit (A2) in the constituent unit A is It is preferably 50 mol% or more, more preferably 55 mol% or more, further preferably 60 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more. Yes, and even more preferably 95 mol% or more.
  • the upper limit of the total content ratio of the constituent unit (A1) and the constituent unit (A2) is not particularly limited and is 100 mol% or less.
  • the structural unit A may be composed of only the structural unit (A1) and the structural unit (A2).
  • the molar ratio [(A1) / (A2)] of the constituent unit (A1) and the constituent unit (A2) is preferably from 10/90 to It is 95/5, more preferably 40/60 to 90/10, and even more preferably 50/50 to 85/15.
  • the structural unit A may include a structural unit other than the structural unit (A1) and the structural unit (A2).
  • the tetracarboxylic acid dianhydride giving such a structural unit is not particularly limited, but is pyromellitic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3.
  • the aromatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more aromatic rings
  • the alicyclic tetracarboxylic dianhydride has one alicyclic ring. It means a tetracarboxylic acid dianhydride containing the above and does not contain an aromatic ring
  • the aliphatic tetracarboxylic acid dianhydride means a tetracarboxylic acid dianhydride containing neither an aromatic ring nor an alicyclic ring.
  • the structural unit arbitrarily included in the structural unit A may be one type or two or more types.
  • the structural unit B is a structural unit derived from diamine in the polyimide resin.
  • the structural unit B is not limited as long as it is a structural unit derived from diamine, but preferable structural units and combinations thereof will be described below.
  • the structural unit B is a structural unit (B1) derived from a fluorine-containing aromatic diamine, a structural unit (B2) derived from a compound represented by the formula (b2) described later, and a compound represented by the formula (b3) described later.
  • a unit more preferably to include at least one constituent unit selected from the group consisting of the constituent unit (B1) and the constituent unit (B2), and further preferably to include the constituent unit (B1).
  • the constituent unit (B1) is included, it is preferable to include at least one constituent unit selected from the group consisting of the constituent unit (B2) and the constituent unit (B7), and it is more preferable to include the constituent unit (B7).
  • the structural unit (B1) is a structural unit (B1) derived from a fluorine-containing aromatic diamine, and is preferably a structural unit (B11) derived from a compound represented by the following general formula (b11).
  • X is a single bond or an oxygen atom.
  • the structural unit (B11) is composed of a group consisting of a structural unit (B111) derived from a compound represented by the following formula (b111) and a structural unit (B112) derived from a compound represented by the following formula (b112). It preferably contains at least one structural unit selected, and more preferably contains a structural unit (B111) derived from the compound represented by the following formula (b111).
  • the compound represented by the formula (b111) is 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA).
  • the compound represented by the formula (b112) is 2,2'-bis (trifluoromethyl) benzidine (TFMB).
  • the ratio of the constituent unit (B1) in the constituent unit B is preferably 20 mol% or more, more preferably 50 mol% or more, and further preferably 80 mol% or more.
  • the upper limit is not particularly limited, and the ratio of the constituent unit (B1) in the constituent unit B is 100 mol% or less.
  • the structural unit B When the structural unit B includes the structural unit (B1), it may be used in combination with the structural unit described later.
  • the structural unit B includes the structural unit (B111) among the structural units (B1) it is preferable to include the structural unit (B7).
  • the constituent unit B includes the constituent unit (B111) and the constituent unit (B7) the molar ratio [(B1) / (B7)] of the constituent unit (B1) and the constituent unit (B7) is preferably 90/10 or more. It is 99/1, more preferably 95/5 to 98/2.
  • the structural unit (B2) is a structural unit derived from the compound represented by the following formula (b2).
  • R is independently selected from the group consisting of a hydrogen atom, a fluorine atom, and an alkyl group having 1 to 5 carbon atoms, and is selected from the group consisting of a hydrogen atom, a fluorine atom, and a methyl group. It is preferably selected, more preferably a hydrogen atom.
  • Examples of the compound represented by the above formula (b2) include 9,9-bis (4-aminophenyl) fluorene (BAFL), 9,9-bis (3-fluoro-4-aminophenyl) fluorene, and 9,9.
  • -Bis (3-methyl-4-aminophenyl) fluorene and the like can be mentioned, and at least one selected from the group consisting of these three compounds is preferable, and 9,9-bis (4-amino) is preferable from the viewpoint of heat resistance. Phenyl) fluorene is more preferred.
  • the ratio of the constituent unit (B2) in the constituent unit B is preferably 40 mol% or more.
  • the upper limit is not particularly limited, and the ratio of the constituent unit (B2) in the constituent unit B is 100 mol% or less.
  • the constituent unit B When the constituent unit B includes the constituent unit (B2), it may be used in combination with another constituent unit.
  • the structural unit B contains a structural unit derived from 9,9-bis (4-aminophenyl) fluorene among the structural units (B2), it is preferable to include the structural unit (B112).
  • the constituent unit B contains a constituent unit derived from 9,9-bis (4-aminophenyl) fluorene and a constituent unit (B112)
  • the constituent unit (B112) is preferably contained in an amount of 60 mol% or less.
  • the structural unit (B3) is a structural unit derived from the compound represented by the following formula (b3).
  • the compound represented by the formula (b3) is bis (aminomethyl) cyclohexane (BAC), and specific examples thereof include 1,3-bis (aminomethyl) cyclohexane (1) represented by the following formula (b3a). , 3-BAC), 1,4-bis (aminomethyl) cyclohexane (1,4-BAC) represented by the following formula (b3b).
  • the cis: trans ratio of the compound represented by the formula (b3) is preferably 0: 100 to 80:20, preferably 0.1: 99.9 to 70:30, from the viewpoint of organic solvent resistance, heat resistance and the like. More preferably, 0.5: 99.5 to 60:40 is even more preferable, and 1:99 to 20:80 is even more preferable.
  • the structural unit (B4) is a structural unit derived from the compound represented by the following formula (b4).
  • Examples of the compound represented by the formula (b4) include the compound represented by the following formula (b41) (that is, 4,4′-diaminodiphenylsulfone (4,4′-DDS)) and the compound represented by the following formula (b42). (Ie, 3,3'-diaminodiphenyl sulfone (3,3'-DDS)) and the like.
  • the structural unit (B4) is at least one selected from the group consisting of the structural unit (B41) derived from the compound represented by the formula (b41) and the structural unit (B42) derived from the compound represented by the formula (b42). It is preferable that the number is one.
  • the structural unit (B4) may be only the structural unit (B41), may be only the structural unit (B42), or may be a combination of the structural unit (B41) and the structural unit (B42). ..
  • the structural unit (B5) is a structural unit derived from the compound represented by the following formula (b5).
  • the compound represented by the formula (b5) is 1,5-diaminonaphthalene (DAN).
  • the structural unit (B6) is a structural unit derived from the compound represented by the following formula (b6).
  • the compound represented by the formula (b6) is 4,4'-diaminobenzanilide.
  • the structural unit (B7) is a structural unit derived from the compound represented by the following general formula (b7).
  • the structural unit (B7) is preferably used in combination with other structural units, more preferably in combination with at least one selected from the group consisting of the structural units (B1) to (B6), and the structural unit (B1). It is more preferable to use in combination with.
  • the ratio of the constituent unit (B7) in the constituent unit B is preferably 1 to 10 mol%, more preferably 2 to 5 mol%.
  • Z 1 and Z 2 independently represent a divalent aliphatic group or a divalent aromatic group which may contain an oxygen atom, and R 1 and R 2 are independently monovalent, respectively.
  • R 3 and R 4 each independently represent a monovalent aliphatic group, and R 5 and R 6 each independently represent a monovalent aliphatic group or 1 It indicates a valent aromatic group, where m and n each independently represent an integer of 1 or more, and the sum of m and n represents an integer of 2 to 1000.
  • two or more different repeating units described in [] are repeated in any of random, alternating, and block-like forms and orders, regardless of the order of []. May be.
  • the divalent aliphatic group or divalent aromatic group in Z 1 and Z 2 may be substituted with a fluorine atom.
  • the divalent aliphatic group include a divalent saturated or unsaturated aliphatic group having 1 to 20 carbon atoms and an aliphatic group containing an oxygen atom.
  • the divalent aliphatic group preferably has 3 to 20 carbon atoms.
  • Examples of the divalent saturated aliphatic group include an alkylene group having 1 to 20 carbon atoms, for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, and the like. Examples thereof include a dodecamethylene group.
  • Examples of the divalent unsaturated aliphatic group include an alkenylene group having 2 to 20 carbon atoms, and examples thereof include a vinylene group, a propenylene group, and an alkenylene group having an unsaturated double bond at the terminal.
  • Examples of the aliphatic group containing an oxygen atom include an alkyleneoxy group and an aliphatic group having an ether bond.
  • Examples of the alkyleneoxy group include a propyleneoxy group and a trimethyleneoxy group.
  • Examples of the divalent aromatic group include an arylene group having 6 to 20 carbon atoms and an aralkylene group having 7 to 20 carbon atoms.
  • Specific examples of the arylene group having 6 to 20 carbon atoms in Z 1 and Z 2 include an o-phenylene group, an m-phenylene group, a p-phenylene group, a 4,4′-biphenylylene group, a 2,6-naphthylene group and the like. Can be mentioned.
  • Z 1 and Z 2 a trimethylene group and a p-phenylene group are particularly preferable, and a trimethylene group is more preferable.
  • the monovalent aliphatic group in R 1 to R 6 includes a monovalent saturated or unsaturated aliphatic group.
  • the monovalent saturated aliphatic group include an alkyl group having 1 to 22 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
  • the monovalent unsaturated aliphatic group include an alkenyl group having 2 to 22 carbon atoms, and examples thereof include a vinyl group and a propenyl group. These groups may be substituted with fluorine atoms.
  • the monovalent aromatic group in R 1 , R 2 , R 5 and R 6 of the formula (b7) was an aryl group having 6 to 20 carbon atoms, 7 to 30 carbon atoms, and was substituted with an alkyl group. Examples thereof include an aryl group and an aralkyl group having 7 to 30 carbon atoms.
  • an aryl group is preferable, and a phenyl group is more preferable.
  • At least one of R 1 and R 2 is preferably a monovalent aromatic group, more preferably both R 1 and R 2 are monovalent aromatic groups, and both R 1 and R 2 are phenyl groups. Is more preferable.
  • R 3 and R 4 an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is more preferable.
  • R 5 and R 6 a monovalent aliphatic group is preferable, and a methyl group is more preferable.
  • the compound represented by the following formula (b71) is preferable.
  • m indicates the number of repetitions of the siloxane unit to which at least one monovalent aromatic group is bonded
  • n in the formulas (b7) and (b71) is a monovalent aliphatic group. Indicates the number of repetitions of the siloxane unit to which is bonded.
  • M and n in the formulas (b7) and (b71) independently represent integers of 1 or more, and the sum of m and n (m + n) represents an integer of 2 to 1000.
  • the sum of m and n preferably represents an integer of 3 to 500, more preferably 3 to 100, and even more preferably an integer of 3 to 50.
  • the ratio of m / n in the formulas (b7) and (b71) is preferably 5/95 to 50/50, more preferably 10/90 to 40/60, and even more preferably 20/80 to 30/70. ..
  • the functional group equivalent (amine equivalent) of the compound represented by the formula (b7) is preferably 150 to 5,000 g / mol, more preferably 400 to 4,000 g / mol, and further preferably 500 to 3,000 g / mol. Is.
  • the functional group equivalent means the mass of the compound represented by the formula (b7) per mole of the functional group (amino group).
  • the structural unit (B7) in the structural unit B By including the structural unit (B7) in the structural unit B, the colorless transparency, optical isotropic property and flexibility of the film can be improved.
  • the structural unit B may include a structural unit other than the structural units (B1) to (B7).
  • the diamine that gives such a structural unit is not particularly limited, but is limited to 1,4-phenylenediamine, p-xylylene diamine, 2,2'-dimethylbiphenyl-4,4'-diamine, and 4,4'-diamino.
  • Diphenylmethane 2,2-bis (4-aminophenyl) hexafluoropropane, 3,4'-diaminodiphenyl ether, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H- Inden-5-amine, N, N'-bis (4-aminophenyl) terephthalamide, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1,4-bis (4-aminophenoxy) )
  • Aromatic diamines such as benzene; alicyclic diamines; and aliphatic diamines such as ethylenediamine and hexamethylenediamine.
  • the aromatic diamine means a diamine containing one or more aromatic rings
  • the alicyclic diamine means a diamine containing one or more alicyclic rings and not containing an aromatic ring, and is a fat.
  • the group diamine means a diamine that does not contain an aromatic ring or an alicyclic ring.
  • the structural unit arbitrarily included in the structural unit B may be one type or two or more types.
  • the polyimide resin of the present invention can be produced by reacting a tetracarboxylic acid component, which is a compound giving the above-mentioned structural unit A, with a diamine component, which is a compound giving the above-mentioned structural unit B.
  • Examples of the compound giving the structural unit A include the compound represented by the formula (a11), the compound represented by the formula (a12), and the compound represented by the formula (a2) described in the section of [Structural unit A].
  • the present invention is not limited to this, and the derivative may be used as long as the same structural unit is given.
  • Examples of the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by each of the above formulas and an alkyl ester of the tetracarboxylic acid.
  • the tetracarboxylic dianhydride represented by each of the above formulas is preferable.
  • the tetracarboxylic acid component may contain any compound other than the compound giving the structural unit (A1) and the compound giving the structural unit (A2).
  • Such optional compounds include the above-mentioned aromatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, and aliphatic tetracarboxylic acid dianhydrides, and derivatives thereof (tetracarboxylic acid, tetra). Alkyl ester of carboxylic acid, etc.).
  • the compound arbitrarily contained in the tetracarboxylic acid component may be one kind or two or more kinds.
  • Examples of the compound giving the structural unit B include the compound represented by the formula (b11), the compound represented by the formula (b2), and the compound represented by the formula (b3) described in the section of [Structural unit B].
  • the diamine component may contain any compound other than the compound giving the structural units (B1) to (B7).
  • Such arbitrary compounds include the above-mentioned aromatic diamines, alicyclic diamines, and aliphatic diamines, and derivatives thereof (diisocyanate and the like).
  • the compound arbitrarily contained in the diamine component may be one kind or two or more kinds.
  • the ratio of the amount of the tetracarboxylic acid component to the diamine component used in the production of the polyimide resin is preferably 0.9 to 1.1 mol of the diamine component with respect to 1 mol of the tetracarboxylic acid component.
  • an end-capping agent may be used in addition to the above-mentioned tetracarboxylic acid component and diamine component.
  • the terminal encapsulant monoamines or dicarboxylic acids are preferable.
  • the amount of the terminal encapsulant to be introduced is preferably 0.0001 to 0.1 mol, particularly preferably 0.001 to 0.06 mol, based on 1 mol of the tetracarboxylic acid component.
  • Examples of monoamine terminal sealants include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3-. Ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline and the like are recommended. Of these, benzylamine and aniline can be preferably used.
  • dicarboxylic acid terminal encapsulant dicarboxylic acids are preferable, and a part thereof may be ring-closed.
  • phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenonedicarboxylic acid, 3,4-benzophenonedicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1. , 2-Dicarboxylic acid, etc. are recommended.
  • phthalic acid and phthalic anhydride can be preferably used.
  • the method for reacting the above-mentioned tetracarboxylic acid component with the diamine component is not particularly limited, and a known method can be used.
  • Specific reaction methods include (1) charging a tetracarboxylic acid component, a diamine component, and a reaction solvent into a reactor, stirring at 10 to 110 ° C. for 0.5 to 30 hours, and then raising the temperature to imidize. Method of carrying out the reaction, (2) After charging the diamine component and the reaction solvent into the reactor and dissolving them, the tetracarboxylic acid component is charged, and if necessary, the mixture is stirred at 10 to 110 ° C. for 0.5 to 30 hours, and then.
  • Examples thereof include a method of carrying out an imidization reaction by raising the temperature to (3) a method of charging a tetracarboxylic acid component, a diamine component and a reaction solvent into a reactor and immediately raising the temperature to carry out the imidization reaction.
  • the reaction solvent used for producing the polyimide resin may be one that does not inhibit the imidization reaction and can dissolve the produced polyimide resin.
  • an aprotic solvent, a phenol solvent, an ether solvent, a carbonate solvent and the like can be mentioned.
  • aprotonic solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethylimidazolidinone, tetramethylurea and the like.
  • Amide-based solvents lactone-based solvents such as ⁇ -butyrolactone and ⁇ -valerolactone, phosphorus-containing amide-based solvents such as hexamethylphosphoric amide and hexamethylphosphintriamide, and sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide, and sulfolane.
  • Examples thereof include based solvents, ketone solvents such as acetone, cyclohexanone and methylcyclohexanone, amine solvents such as picolin and pyridine, and ester solvents such as acetic acid (2-methoxy-1-methylethyl).
  • phenolic solvent examples include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4. -Xylenol, 3,5-xylenol and the like can be mentioned.
  • ether solvent examples include 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, and bis [2- (2-methoxyethoxy) ethyl]. Examples include ether, tetrahydrofuran, 1,4-dioxane and the like.
  • the carbonate solvent examples include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate and the like.
  • an amide solvent or a lactone solvent is preferable.
  • the above-mentioned reaction solvent may be used alone or in mixture of 2 or more types.
  • the imidization reaction it is preferable to carry out the reaction while removing water generated during production using a Dean-Stark apparatus or the like. By performing such an operation, the degree of polymerization and the imidization rate can be further increased.
  • a known imidization catalyst can be used.
  • the imidization catalyst include a base catalyst and an acid catalyst.
  • Base catalysts include pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, imidazole, N, N.
  • Examples thereof include organic base catalysts such as dimethylaniline and N, N-diethylaniline, and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate and sodium hydrogencarbonate.
  • the acid catalyst examples include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, paratoluenesulfonic acid, naphthalenesulfonic acid and the like. Can be mentioned.
  • the above-mentioned imidization catalyst may be used alone or in combination of two or more.
  • a base catalyst more preferably an organic base catalyst, further preferably triethylamine and triethylenediamine, and particularly preferably triethylamine.
  • the temperature of the imidization reaction is preferably 120 to 250 ° C., more preferably 160 to 200 ° C. from the viewpoint of suppressing the reaction rate and gelation.
  • the reaction time is preferably 0.5 to 10 hours after the start of distillation of the produced water.
  • the solid content concentration during the imidization reaction is preferably 30 to 60% by mass, more preferably 35 to 58% by mass, and particularly preferably 40 to 56% by mass.
  • the solid content concentration at the time of the imidization reaction is in this range, the imidization reaction proceeds satisfactorily and the water generated at the time of the reaction can be easily removed, so that the degree of polymerization and the imidization rate can be increased.
  • the glass transition temperature (Tg) of the polyimide resin constituting the polyimide film in the present invention is preferably 230 ° C. or higher, more preferably 250 ° C. or higher, still more preferably 270 ° C. or higher. Further, when the polyimide film is used as a substrate for a TFT, it is more preferably 400 ° C. or higher, and even more preferably 430 ° C. or higher. Within this range, the heat resistance at the time of manufacturing the touch sensor substrate or the TFT is good.
  • the method for producing the polyimide film of the present invention is not particularly limited, but the obtained polyimide film is a polyimide film composed of a polyimide resin, and is formed on a silicon substrate having a thickness of 520 ⁇ m represented by the following formula (1).
  • a manufacturing method may be selected in which the radius of curvature R when laminated is larger than 20 m.
  • C (Pa ⁇ m 2 ) is a constant obtained by the following formula (2), S (Pa) is the stress of the polyimide film, and t (m) is the thickness of the polyimide film.)
  • E represents the Young's modulus (Pa) of the silicon (100) which is the substrate, ⁇ represents the Poisson's ratio of the silicon (100) which is the substrate, and h represents the thickness (m) of the silicon substrate.
  • the method for producing a polyimide film of the present invention is the stress S (Pa) of the polyimide film obtained by laminating on a silicon substrate having a thickness of 520 ⁇ m and the thickness t (m) of the polyimide film.
  • C (Pa ⁇ m 2 ) represents a constant obtained by the following equation (2).
  • E represents the Young's modulus (Pa) of the silicon (100) which is the substrate
  • ⁇ represents the Poisson's ratio of the silicon (100) which is the substrate
  • h represents the thickness (m) of the silicon substrate.
  • the stress S of the polyimide film may change depending on the manufacturing method or the like even if the composition of the polyimide resin is the same. Therefore, it is preferable to have a step of adjusting the stress S of the polyimide film obtained by laminating on a silicon substrate having a thickness of 520 ⁇ m and the thickness t of the polyimide film so as to satisfy the above formula (3). It is more preferable to manufacture and adjust the film under the same conditions as those used in actual production. Specifically, after measuring the stress of the polyimide film produced to an arbitrary thickness, the thickness of the polyimide film is adjusted, and the stress S of the polyimide film and the thickness t of the polyimide film are the above-mentioned formula (3).
  • the step is adjusted so as to satisfy the above conditions.
  • a polyimide resin whose film stress at a different thickness is known in advance is selected, and the thickness of the polyimide film is selected. It is preferable that the step is to adjust the amount within the specific range so that the stress S of the polyimide film and the thickness t of the polyimide film satisfy the above formula (3).
  • a polyimide varnish is applied onto a smooth support such as a glass plate, a metal plate, or plastic, or formed into a film, and then a reaction solvent contained in the varnish. And a method of removing an organic solvent such as a diluting solvent by heating.
  • the varnish coating method examples include known coating methods such as spin coating, slit coating, and blade coating. Above all, the slit coat is preferable from the viewpoints of controlling the orientation between molecules, improving chemical resistance, reducing interference unevenness, and workability.
  • the organic solvent is evaporated at a temperature of 150 ° C. or lower under atmospheric pressure or reduced pressure to make it tack-free, and then the temperature is equal to or higher than the boiling point of the organic solvent used. Although not particularly limited, it is preferably dried at 200 to 500 ° C.).
  • the pressure in the dry atmosphere may be reduced pressure, normal pressure, or pressurized. It is preferable to dry in an air atmosphere of normal pressure or reduced pressure or in a nitrogen atmosphere where the oxygen concentration of normal pressure or reduced pressure is 100 ppm or less, preferably 10 ppm or less.
  • the polyimide varnish used in the production of a polyimide film is made by dissolving a polyimide resin in an organic solvent. That is, the polyimide varnish contains a polyimide resin and an organic solvent, and the polyimide resin is dissolved in the organic solvent.
  • the organic solvent may be any one that dissolves the polyimide resin, and is not particularly limited, but it is preferable to use the above-mentioned compounds alone or in combination of two or more as the reaction solvent used for producing the polyimide resin.
  • the polyimide varnish may be a polyimide solution itself in which a polyimide resin obtained by a polymerization method is dissolved in a reaction solvent, or a diluting solvent may be further added to the polyimide solution.
  • the polyimide varnish preferably contains 2 to 40% by mass of the polyimide resin, and more preferably 3 to 30% by mass.
  • the viscosity of the polyimide varnish is preferably 0.1 to 200 Pa ⁇ s, more preferably 0.3 to 100 Pa ⁇ s, and even more preferably 1 to 100 Pa ⁇ s.
  • the viscosity of the polyimide varnish is a value measured at 25 ° C. using an E-type viscometer.
  • polyimide varnish is an inorganic filler, an adhesion accelerator, a release agent, a flame retardant, an ultraviolet stabilizer, a surfactant, a leveling agent, a defoaming agent, a fluorescent whitening agent, as long as the required characteristics of the polyimide film are not impaired.
  • Various additives such as a cross-linking agent, a polymerization initiator, and a photosensitizer may be contained.
  • the method for producing the polyimide varnish is not particularly limited, and a known method can be applied.
  • the polyimide film can also be produced by using a polyamic acid varnish in which the polyamic acid is dissolved in an organic solvent.
  • the polyamic acid contained in the polyamic acid varnish is preferably a precursor of a polyimide resin.
  • the polyamic acid, which is a precursor of the polyimide resin is a product of a polyaddition reaction between the above-mentioned tetracarboxylic acid component and the above-mentioned diamine component. By imidizing (dehydrating and ring-closing) these polyamic acids, a polyimide resin as a final product can be obtained.
  • a varnish of an imide-amidoic acid copolymer partially imidized by a method of adding a tetracarboxylic acid component or a diamine component stepwise and imidizing stepwise may be used.
  • a copolymer varnish it is possible to achieve both the stability of the varnish and the reactivity of the resin.
  • the organic solvent contained in the polyamic acid varnish and the varnish of the imide-amidoic acid copolymer can be used.
  • the polyamic acid varnish may be the polyamic acid solution itself obtained by subjecting the tetracarboxylic acid component and the diamine component to a heavy addition reaction in a reaction solvent, or may be further diluted with respect to the polyamic acid solution. It may be the one to which the solvent is added.
  • the method for producing a polyimide film using a polyamic acid varnish or an imide-amidoic acid copolymer varnish is not particularly limited, and a known method can be used.
  • a polyamic acid varnish or an imide-amidoic acid copolymer varnish is applied onto a smooth support such as a glass plate, a metal plate, or a plastic, or formed into a film, and a reaction solvent contained in the varnish or a reaction solvent or the like.
  • a polyimide film is produced by removing an organic solvent such as a diluting solvent by heating to obtain a polyamic acid film or an imide-amide acid copolymer film, and imidizing the polyamic acid in the polyamic acid film by heating. be able to.
  • the heating temperature at which the polyamic acid varnish or the varine of the imide-amidoic acid copolymer is dried to obtain the polyamic acid film or the varnish of the imide-amidoic acid copolymer is preferably 50 to 120 ° C.
  • the heating temperature for imidizing the polyamic acid portion by heating is preferably 200 to 400 ° C.
  • the imidization method is not limited to thermal imidization, and chemical imidization can also be applied.
  • the polyimide film is laminated on a glass substrate or a silicon substrate.
  • the polyimide film is in close contact with the glass substrate or the silicon substrate.
  • the polyimide film is in direct contact with the glass substrate or silicon substrate, or is a sacrificial layer, a release layer, or an adhesive layer between the glass substrate or silicon substrate and the polyimide film in order to facilitate peeling after the process. It is more preferable to have a sacrificial layer, and it is further preferable to have a sacrificial layer.
  • the laminate of the present invention may be produced by any method, but it is preferably produced by the following method.
  • the method for producing the laminate of the present invention is the polyimide film described in the section [polyimide film] or the polyimide film obtained by the method for producing the polyimide film described in the section [method for producing the polyimide film]. It is preferable to include a step of laminating on a glass substrate or a silicon substrate.
  • the glass substrate or silicon substrate is not particularly limited, and it is sufficient that the strength is sufficient to support the polyimide film when manufacturing an electronic device (conductive film) using the polyimide film as the substrate.
  • the type of glass is not particularly limited, and non-alkali glass (borosilicate glass), alkali glass, soda glass, non-fluorescent glass, phosphoric acid-based glass, boric acid-based glass, quartz and the like can be used.
  • the flatness of the upper surface of the glass substrate or the silicon substrate is high.
  • the surface roughness Rmax is preferably 10 ⁇ m or less, and more preferably 1 ⁇ m or less.
  • the laminate of the present invention preferably has a sacrificial layer between the glass substrate or silicon substrate and the polyimide film.
  • There is a method of peeling the polyimide film by obtaining a structure including a polyimide / support and then irradiating a laser from the support side to ablate the polyimide resin interface to peel the polyimide resin.
  • the laser include a solid (YAG) laser and a gas (UV excimer) laser, and a spectrum of 308 nm or the like is used.
  • the sacrificial layer is preferably formed of amorphous silicon, titanium film or aluminum film. Since the sacrificial layer can substantially absorb the laser light, the amorphous silicon can generate heat by the laser light irradiation, crystallize by the heat, and expand in volume. As a result, a low adhesion state in which the polyimide film is partially peeled from the sacrificial layer can be obtained, which is preferable because the peeling becomes easy.
  • the sacrificial layer may be formed of a metal film such as titanium (Ti) or aluminum (Al), or may be formed of an amorphous silicon (a-Si) film or the like.
  • the sacrificial layer is made of a metal film, it is formed to have a thickness of 100 to 500 nm by, for example, a sputtering method.
  • the sacrificial layer is composed of an a-Si film, it is preferable to form the sacrificial layer so that the thickness is 100 to 500 nm by using, for example, a CVD method or a sputtering method. This range is preferable because the polyimide film can be easily peeled off by using a laser.
  • a metal film or a semiconductor film is further laminated on the polyimide film.
  • a target electronic device such as a touch sensor or an OLED can be created on the polyimide film.
  • Preferred specific examples of the metal film include a copper mesh, a silver mesh and the like.
  • Preferred specific examples of the semiconductor film include at least one selected from the group consisting of indium tin oxide (ITO), amorphous silicon, indium gallium zinc oxide (IGZO) and low temperature polysilicon (LTPS).
  • ITO indium tin oxide
  • IGZO indium gallium zinc oxide
  • LTPS low temperature polysilicon
  • Another metal film or semiconductor film may be further laminated on these metal films or semiconductor films.
  • the thickness of the metal film or the semiconductor film is not particularly limited, but is preferably 10 to 400 nm, more preferably 20 to 200 nm, and further preferably 30 to 150 nm.
  • a conductive film can be obtained by peeling and removing a glass substrate or a silicon substrate from the laminate on which a metal film or a semiconductor film is laminated. That is, in the conductive film of the present invention, the glass substrate or the silicon substrate is peeled off and removed from the laminate or the laminate obtained by the method for producing the laminate described in the above section [Method for manufacturing laminate and laminate]. Can be obtained.
  • a conductive film may be obtained by laminating a metal film or a semiconductor film on a polyimide film to produce a conductive film, and then immediately peeling off a glass substrate or a silicon substrate to obtain a conductive film, or storing the film in a laminated state. If necessary, the glass substrate or the silicon substrate may be peeled off to obtain a conductive film. It is preferable to store the conductive film in a laminated state because the handleability of the conductive film during transportation is improved.
  • the method for peeling and removing the glass substrate or the silicon substrate from the laminate is not particularly limited, but since the laminate of the present invention can easily and stably peel the polyimide film from the glass substrate or the silicon substrate, laser irradiation is performed. It can be peeled off mechanically without any need.
  • CTE Coefficient of linear thermal expansion
  • the stress of the polyimide film was determined using a residual stress measuring device "FLX-2320" manufactured by KLA Tencor. For the measurement, a silicon wafer (silicon substrate) having a thickness of 520 ⁇ m and a diameter of 4 inches, for which a blank value has been measured in advance, is used. The varnish obtained in each production example was applied onto the silicon wafer under the conditions of each example and comparative example, and heat-treated under the conditions of each example and comparative example to prepare a silicon wafer in which a polyimide film was laminated. It was used for measurement.
  • a polyester film was used as a support to evaluate the amount of warpage of the polyimide film.
  • the upper limit of the measured value was set to 10 cm, and the value exceeding the upper limit was shown as ">10" in the table.
  • tetracarboxylic acid component and diamine component used in the production example, other components, and their abbreviations are as follows.
  • ⁇ Tetracarboxylic acid component> CpODA: Norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride (manufactured by JX Energy Co., Ltd.)
  • s-BPDA 3,3', 4,4'-biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation)
  • BPAF 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride
  • BAFL 9,9-bis (4-aminophenyl) fluorene
  • TFMB 2,2'-bis (trifluoromethyl) benzidine
  • GBL ⁇ -Butyrolactone (manufactured by Mitsubishi Chemical Corporation)
  • TEA Triethylamine (manufactured by Kanto Chemical Co., Inc.)
  • NMP N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation)
  • Manufacturing example 2 26.227 g (0.0780 mol) of 6FODA in a 500 mL five-necked round-bottom flask equipped with a stainless steel half-moon agitator, a nitrogen inlet tube, a Dean Stark with a cooling tube, a thermometer, and a glass end cap. And 109.317 g of NMP was added, and the mixture was stirred at a system temperature of 50 ° C. and a nitrogen atmosphere at a rotation speed of 200 rpm to obtain a solution. 23.536 g (0.0800 mol) of s-BPDA and 27.329 g of NMP were collectively added to this solution, and the mixture was stirred with a mantle heater at 50 ° C. for 7 hours.
  • Heating was performed with a mantle heater, and the temperature inside the reaction system was raised to 190 ° C. over about 30 minutes. The mixture was stirred for 5 hours while collecting the components to be distilled off. Then, GBL was added so that the solid content concentration became 10% by mass, the temperature was cooled to 100 ° C., and then the mixture was stirred for about 1 hour to homogenize to obtain a polyimide varnish.
  • Example 1 The varnish obtained in Production Example 1 is applied onto a glass substrate (non-alkali glass AN100, thickness 0.7 mm) by spin coating, held on a hot plate at 80 ° C. for 20 minutes, and then hot air is used under a nitrogen atmosphere. The solvent was evaporated by heating in a dryer at 350 ° C. for 30 minutes and cured to form a polyimide film on a glass substrate. The polyimide film was peeled off and each physical property was measured. The results are shown in Table 1. The amount of film warpage of the obtained polyimide film was measured. The results are shown in Table 2. Further, a polyimide film was similarly produced using a silicon wafer instead of the glass substrate, the polyimide film was laminated on the silicon wafer, and the stress S was measured. The radius of curvature R is shown in Table 2.
  • Example 2 The varnish obtained in Production Example 2 is coated on a glass substrate (non-alkali glass AN100, thickness 0.7 mm) by spin coating, held on a hot plate at 80 ° C. for 20 minutes, and then under an air atmosphere. , The solvent was evaporated by heating in a hot air dryer at 260 ° C. for 60 minutes and cured to form a polyimide film on a glass substrate. The polyimide film was peeled off and each physical property was measured. The results are shown in Table 1. The amount of film warpage of the obtained polyimide film was measured. The results are shown in Table 2. Further, a polyimide film was similarly produced using a silicon wafer instead of the glass substrate, the polyimide film was laminated on the silicon wafer, and the stress S was measured. The radius of curvature R is shown in Table 2.
  • Comparative Example 1 The varnish obtained in Production Example 3 is coated on a glass substrate (non-alkali glass AN100, thickness 0.7 mm) by spin coating, held on a hot plate at 80 ° C. for 20 minutes, and then under a nitrogen atmosphere. , The solvent was evaporated by heating in a hot air dryer at 400 ° C. for 30 minutes and cured to form a polyimide film on a glass substrate. The polyimide film was peeled off and each physical property was measured. The results are shown in Table 1. The amount of film warpage of the obtained polyimide film was measured. The results are shown in Table 2. Further, a polyimide film was similarly produced using a silicon wafer instead of the glass substrate, the polyimide film was laminated on the silicon wafer, and the stress S was measured. The radius of curvature R is shown in Table 2.
  • Example 3 The results are shown in Table 1 for a film having a thickness of 7.4 ⁇ m (Example 3). The amount of warpage of each of the obtained laminates was measured. The results are shown in Table 3. Further, a silicon wafer is used instead of the glass substrate, and the coating amount is similarly changed in four steps to prepare a polyimide film having the same thickness as that of the above Examples and Comparative Examples, and the polyimide film is laminated on the silicon wafer. The stress S was measured. The radius of curvature R is shown in Table 3.

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Abstract

Le film de polyimide selon l'invention est formé à partir d'une résine de polyimide et présente, lorsqu'il est stratifié sur un substrat de silicium ayant une épaisseur de 520 µm, un rayon de courbure R supérieur à 20 m.
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WO2016063988A1 (fr) * 2014-10-23 2016-04-28 宇部興産株式会社 Précurseur de polyimide, polyimide, et film de polyimide
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WO2019065523A1 (fr) * 2017-09-29 2019-04-04 三菱瓦斯化学株式会社 Résine polyimide, vernis polyimide et film polyimide
WO2019116940A1 (fr) * 2017-12-15 2019-06-20 三菱瓦斯化学株式会社 Résine polyimide, vernis de polyimide et film de polyimide
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JP7099019B2 (ja) 2018-04-09 2022-07-12 大日本印刷株式会社 ポリイミド積層体の製造方法、及びポリイミドフィルムの製造方法

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JP2015223823A (ja) * 2014-05-30 2015-12-14 東レ株式会社 積層体、積層体の製造方法、及びこれを用いたフレキシブルデバイスの製造方法
WO2016063988A1 (fr) * 2014-10-23 2016-04-28 宇部興産株式会社 Précurseur de polyimide, polyimide, et film de polyimide
WO2018066522A1 (fr) * 2016-10-07 2018-04-12 Ｊｘｔｇエネルギー株式会社 Polyimide, résine de précurseur de polyimide, solution de ceux-ci, procédé de fabrication de polyimide, et film mettant en œuvre ce polyimide
WO2019065523A1 (fr) * 2017-09-29 2019-04-04 三菱瓦斯化学株式会社 Résine polyimide, vernis polyimide et film polyimide
WO2019116940A1 (fr) * 2017-12-15 2019-06-20 三菱瓦斯化学株式会社 Résine polyimide, vernis de polyimide et film de polyimide
WO2019131894A1 (fr) * 2017-12-28 2019-07-04 宇部興産株式会社 Précurseur de polyimide, polyimide, film de polyimide, vernis et substrat
WO2019211972A1 (fr) * 2018-05-01 2019-11-07 三菱瓦斯化学株式会社 Résine polyimide, vernis polyimide et film polyimide
WO2020226062A1 (fr) * 2019-05-09 2020-11-12 三菱瓦斯化学株式会社 Corps stratifié

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