WO2019208587A1 - ポリイミド前駆体樹脂組成物 - Google Patents

ポリイミド前駆体樹脂組成物 Download PDF

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WO2019208587A1
WO2019208587A1 PCT/JP2019/017288 JP2019017288W WO2019208587A1 WO 2019208587 A1 WO2019208587 A1 WO 2019208587A1 JP 2019017288 W JP2019017288 W JP 2019017288W WO 2019208587 A1 WO2019208587 A1 WO 2019208587A1
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general formula
group
integer
resin composition
following general
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PCT/JP2019/017288
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English (en)
French (fr)
Japanese (ja)
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健 柏田
敏章 奥田
直志 篠原
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旭化成株式会社
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Priority to JP2019536317A priority Critical patent/JP6585329B1/ja
Priority to CN201980001427.4A priority patent/CN110637063B/zh
Priority to KR1020197023981A priority patent/KR102112483B1/ko
Publication of WO2019208587A1 publication Critical patent/WO2019208587A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
    • C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133305—Flexible substrates, e.g. plastics, organic film
    • 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 precursor resin composition and a polyimide film.
  • the present invention further relates to a method for producing a polyimide film, a display, a laminate and a flexible device.
  • Polyimide resin is an insoluble and infusible super heat resistant resin, and has excellent characteristics such as heat oxidation resistance, heat resistance, radiation resistance, low temperature resistance, and chemical resistance. For this reason, polyimide resins are used in a wide range of fields including electronic materials. Examples of application of polyimide resin in the field of electronic materials include insulating coating materials, insulating films, semiconductors, electrode protective films for thin film transistor liquid crystal displays (TFT-LCDs), and the like. Recently, using the lightness and flexibility of a polyimide film, the adoption of a flexible substrate instead of the glass substrate conventionally used in the field of display materials has been studied.
  • Patent Document 1 describes a resin precursor (weight average molecular weight 30,000 to 90,000) polymerized from bis (diaminodiphenyl) sulfone (hereinafter also referred to as DAS) and having a siloxane unit.
  • DAS bis (diaminodiphenyl) sulfone
  • Patent Document 1 discloses that polyimide obtained by curing the precursor has low residual stress generated between a support such as glass, excellent chemical resistance, and yellowness (YI due to oxygen concentration during the curing process). Value) and the influence on the total light transmittance is small.
  • Patent Document 2 describes a resin precursor polymerized from 2,2'-bis (trifluoromethyl) benzidine (hereinafter also referred to as TFMB) and having a siloxane unit.
  • Patent Document 2 describes that a polyimide film obtained by curing the precursor has a specific glass transition temperature, a low residual stress generated with an inorganic film, and excellent mechanical properties and thermal stability. is doing.
  • Patent Documents 1 and 2 use a siloxane-containing compound as a monomer for the polyimide precursor.
  • a siloxane-containing compound contains a low molecular weight cyclic siloxane (hereinafter also referred to as a low molecular cyclic siloxane). It is known that this low molecular weight cyclic siloxane is volatile and may cause a contact failure of a process manufacturing apparatus. For example, see Non-Patent Document 1.
  • Patent Documents 3 to 5 are cited as prior art documents relating to a polyimide precursor obtained by reducing this low-molecular cyclic siloxane by purification.
  • Prior art 3 describes that low molecular cyclic siloxane is removed by adding a siloxane-containing compound to acetone, then centrifuging and decanting, and the resulting polyimide is transparent and generates less outgas. ing.
  • the siloxane-containing compound is purified by stripping the siloxane-containing compound under specific conditions, or by dissolving the siloxane-containing compound in 2-butanone and reprecipitating with methanol. It is described that the adhesion of the resin is improved.
  • the present inventors synthesized a polyimide precursor using a siloxane-containing compound purified by a purification method similar to that described in Patent Documents 3 to 5, and produced a polyimide using the precursor.
  • the present invention provides a polyimide precursor resin composition that can further improve the yellowness (YI value) and reduce foreign matters generated in the polyimide manufacturing process as compared with the case of using an unpurified siloxane compound. For the purpose.
  • the low-molecular cyclic siloxane reduced in Patent Documents 3 to 5 is a methyl side chain (general formula (4) described later) and a phenyl side chain (described later). Note that this is not the general formula (3-1) or (3-2)). And it discovered that the said subject could be solved by refine
  • a polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); At least one compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2);
  • a resin composition comprising a compound represented by the following general formula (4), In the following general formula (3-1) or (3-2), the total amount of compounds in which m is an integer of 3 or more is more than 0 ppm and not more than 1,100 ppm based on the mass of the resin composition, Or The total amount of the compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2) and the compound in which n is an integer of 3 or more in the following general formula (4) is Based on the weight of the composition, it is more than 0 ppm and not more than 1,300 ppm.
  • Resin composition ⁇ Wherein P 1 represents a divalent organic group, P 2 represents a tetravalent organic group, and p represents a positive integer.
  • P 3 and P 4 are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms; An integer of 200.
  • ⁇ ⁇ Wherein m is an integer of 1 or more.
  • ⁇ ⁇ Wherein n is an integer of 2 or more.
  • a polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); At least one compound in which m is 3 or 4 in the following general formula (3-1) or (3-2);
  • a resin composition comprising a compound represented by the following general formula (4), In the following general formula (3-1) or (3-2), the total amount of compounds wherein m is 3 is greater than 0 ppm and less than or equal to 650 ppm based on the mass of the resin composition, or In the following general formula (3-1) or (3-2), the total amount of compounds in which m is 4 is greater than 0 ppm and less than or equal to 350 ppm, based on the mass of the resin composition.
  • Resin composition ⁇ Wherein P 1 represents a divalent organic group, P 2 represents a tetravalent organic group, and p represents a positive integer.
  • P 3 and P 4 are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms; An integer of 200.
  • ⁇ ⁇ Wherein m is an integer of 1 or more.
  • ⁇ ⁇ Wherein n is an integer of 2 or more.
  • a resin composition comprising a compound represented by the following general formula (4), In the following general formula (3-1) or (3-2), the total amount of compounds in which m is an integer of 3 or more is more than 0 ppm and not more than 7,500 ppm based on the solid content in the resin composition.
  • the total amount of the compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2) and the compound in which n is an integer of 3 or more in the following general formula (4) is The resin composition which is more than 0 ppm and 8,600 ppm or less on the basis of the mass of the solid content in the resin composition.
  • P 1 represents a divalent organic group
  • P 2 represents a tetravalent organic group
  • p represents a positive integer.
  • P 3 and P 4 are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms; An integer of 200.
  • ⁇ ⁇ Wherein m is an integer of 1 or more.
  • a polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); At least one compound in which m is 3 or 4 in the following general formula (3-1) or (3-2);
  • a resin composition comprising a compound represented by the following general formula (4), In the following general formula (3-1) or (3-2), whether the total amount of the compound wherein m is 3 is more than 0 ppm and not more than 4,500 ppm based on the mass of the solid content in the resin composition Or In the following general formula (3-1) or (3-2), the total amount of compounds in which m is 4 is more than 0 ppm and not more than 2,500 ppm based on the solid content in the resin composition.
  • Resin composition ⁇ Wherein P 1 represents a divalent organic group, P 2 represents a tetravalent organic group, and p represents a positive integer.
  • P 3 and P 4 are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms; An integer of 200.
  • ⁇ ⁇ Wherein m is an integer of 1 or more.
  • Item 5 The resin composition according to any one of Items 1, 2, and 4, wherein in the compound represented by the general formula (3-1) or (3-2), m is an integer of 3 to 5. [7] Item 5.
  • Item 8 The resin composition according to any one of Items 1, 2, and 4, wherein in the compound represented by the general formula (4), n is an integer of 3 to 8.
  • Item 8 The resin composition according to any one of Items 1 to 7, wherein a polyimide resin film obtained by curing the polyimide precursor is used for a flexible substrate.
  • Item 8. The resin composition according to any one of Items 1 to 7, wherein a polyimide resin film obtained by curing the polyimide precursor is used in a flexible display.
  • a polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); At least one compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2);
  • a resin composition comprising a compound represented by the following general formula (4),
  • the resin composition is as follows: A silicon-containing compound represented by the following general formula (5); In the following general formula (3-1) or (3-2), at least one compound in which m is an integer of 3 or more,
  • a raw material composition containing a compound represented by the following general formula (4) is produced by a method including polycondensation reaction with tetracarboxylic dianhydride and diamine to provide a polyimide precursor.
  • the total amount of the compounds in which m is an integer of 3 or more in the following general formula (3-1) or (3-2) contained in the raw material composition is the following general formula (3-1), (3-2) ), Greater than 0 ppm and less than or equal to 46,000 ppm, based on the total mass of the silicon-containing compounds represented by (4) and (5), or A compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2), and n in the following general formula (4) is an integer of 3 or more in the raw material composition.
  • the total amount with a certain compound is more than 0 ppm and not more than 47,000 ppm based on the total mass of the silicon-containing compounds of the above general formulas (3-1), (3-2), (4) and (5).
  • Resin composition ⁇ Wherein P 1 represents a divalent organic group, P 2 represents a tetravalent organic group, and p represents a positive integer.
  • ⁇ ⁇ Wherein P 3 and P 4 are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms; An integer of 200.
  • ⁇ ⁇ Wherein m is an integer of 1 or more.
  • ⁇ ⁇ Wherein n is an integer of 2 or more.
  • R 1 is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms
  • R 2 and R 3 are each independently a monovalent organic group having 1 to 10 carbon atoms.
  • At least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms
  • R 4 and R 5 are each independently a monovalent organic group having 1 to 10 carbon atoms
  • At least one is a monovalent aromatic group having 6 to 10 carbon atoms
  • R 6 and R 7 are each independently a monovalent organic group having 1 to 10 carbon atoms
  • at least one is an unsaturated fatty acid group.
  • L 1 and L 2 are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, Or a mercapto group, and i and j are each independently an integer of 1 to 200.
  • k is an integer of 0 to 200, is 0.05 ⁇ j / (i + j + k) ⁇ 0.50.
  • Item 11 The resin composition according to Item 10, wherein m is an integer of 3 to 5 in the compound represented by the general formula (3-1) or (3-2). [12] Item 11.
  • a polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); At least one compound in which m is 3 or 4 in the following general formula (3-1) or (3-2);
  • a resin composition comprising a compound represented by the following general formula (4),
  • the resin composition is as follows: A silicon-containing compound represented by the following general formula (5); In the following general formula (3-1) or (3-2), at least one compound in which m is 3 or 4,
  • a raw material composition containing a compound represented by the following general formula (4) is produced by a method including polycondensation reaction with tetracarboxylic dianhydride and diamine to provide a polyimide precursor.
  • the total amount of compounds in which m is 3 in the following general formula (3-1) or (3-2) contained in the raw material composition is the following general formula (3-1), (3-2), ( 4) and greater than 0 ppm and less than or equal to 25,000 ppm, based on the total mass of the silicon-containing compounds of (5), or
  • the total amount of compounds in which m is 4 in the following general formula (3-1) or (3-2) contained in the raw material composition is the following general formula (3-1), (3-2), ( 4) and greater than 0 ppm and less than or equal to 15,000 ppm, based on the total mass of the silicon-containing compounds of (5), Resin composition.
  • ⁇ wherein P 1 represents a divalent organic group, P 2 represents a tetravalent organic group, and p represents a positive integer.
  • ⁇ ⁇ Wherein P 3 and P 4 are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms; An integer of 200.
  • ⁇ ⁇ Wherein m is an integer of 1 or more.
  • ⁇ ⁇ Wherein n is an integer of 2 or more.
  • R 1 is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms
  • R 2 and R 3 are each independently a monovalent organic group having 1 to 10 carbon atoms.
  • At least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms
  • R 4 and R 5 are each independently a monovalent organic group having 1 to 10 carbon atoms
  • At least one is a monovalent aromatic group having 6 to 10 carbon atoms
  • R 6 and R 7 are each independently a monovalent organic group having 1 to 10 carbon atoms
  • at least one is an unsaturated fatty acid group.
  • L 1 and L 2 are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, Or a mercapto group
  • i and j are each independently an integer of 1 to 200.
  • k is an integer of 0 to 200, is 0.05 ⁇ j / (i + j + k) ⁇ 0.50.
  • k is an integer of 0 to 200, is 0.05 ⁇ j / (i + j + k) ⁇ 0.50.
  • [15] 15 The resin composition according to any one of items 10 to 14, wherein L 1 and L 2 of the silicon-containing compound represented by the general formula (5) are amino groups.
  • Item 16 The resin according to any one of Items 10 to 15, wherein the compound represented by the general formula (3-1) or (3-2) is a compound represented by the general formula (3-1). Composition.
  • the tetracarboxylic dianhydride is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride, cyclohexanetetracarboxylic dianhydride and the resin composition according to any one of Items 10 to 16, which is at least one selected from the group consisting of cyclobutanetetracarboxylic dianhydrides.
  • the diamine is 4,4′-diaminodiphenylsulfone, m-tolidine, p-phenylenediamine, 2,2′-bis (trifluoromethyl) benzidine, and 2,2′-bis [4- (4-aminophenoxy).
  • the resin composition according to any one of Items 10 to 17, which is at least one selected from the group consisting of phenyl] propane.
  • a resin composition comprising a polycondensation reaction of a raw material composition containing a compound represented by the following general formula (4) with a tetracarboxylic dianhydride and a diamine to provide a polyimide precursor
  • a manufacturing method of The total amount of the compounds in which m is an integer of 3 or more in the following general formula (3-1) or (3-2) contained in the raw material composition is the following general formula (3-1), (3-2) ), Greater than 0 ppm and less than or equal to 46,000 ppm, based on the total mass of the silicon-containing compounds represented by (4) and (5), or
  • the total amount with a certain compound is more than 0 ppm and not more than 47,000 ppm based on the total mass of the silicon-containing compounds of the above general formulas (3-1), (3-2), (4) and (5).
  • a method for producing a resin composition ⁇ Wherein m is an integer of 1 or more. ⁇ ⁇ Wherein n is an integer of 2 or more. ⁇ ⁇ Wherein, R 1 is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, and R 2 and R 3 are each independently a monovalent organic group having 1 to 10 carbon atoms.
  • At least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms
  • R 4 and R 5 are each independently a monovalent organic group having 1 to 10 carbon atoms
  • At least one is a monovalent aromatic group having 6 to 10 carbon atoms
  • R 6 and R 7 are each independently a monovalent organic group having 1 to 10 carbon atoms
  • at least one is an unsaturated fatty acid group.
  • L 1 and L 2 are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, Or a mercapto group
  • i and j are each independently an integer of 1 to 200.
  • k is an integer of 0 to 200, is 0.05 ⁇ j / (i + j + k) ⁇ 0.50. ⁇
  • Item 20 The method according to Item 19, wherein in the compound represented by the general formula (3-1) or (3-2), m is an integer of 3 to 5.
  • Item 20 The method according to Item 19, wherein in the compound represented by the general formula (4), n is an integer of 3 to 8.
  • a resin composition comprising a polycondensation reaction of a raw material composition containing a compound represented by the following general formula (4) with a tetracarboxylic dianhydride and a diamine to provide a polyimide precursor
  • a manufacturing method of The total amount of compounds in which m is 3 in the following general formula (3-1) or (3-2) contained in the raw material composition is the following general formula (3-1), (3-2), ( 4) and greater than 0 ppm and less than or equal to 25,000 ppm, based on the total mass of the silicon-containing compounds of (5), or
  • the total amount of compounds in which m is 4 in the following general formula (3-1) or (3-2) contained in the raw material composition is the following general formula (3-1), (3-2), ( 4) and greater than 0 ppm and less than or equal to 15,000 ppm, based on
  • R 1 is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms
  • R 2 and R 3 are each independently a monovalent organic group having 1 to 10 carbon atoms.
  • At least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms
  • R 4 and R 5 are each independently a monovalent organic group having 1 to 10 carbon atoms
  • At least one is a monovalent aromatic group having 6 to 10 carbon atoms
  • R 6 and R 7 are each independently a monovalent organic group having 1 to 10 carbon atoms
  • at least one is an unsaturated fatty acid group.
  • L 1 and L 2 are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, Or a mercapto group, and i and j are each independently an integer of 1 to 200.
  • k is an integer of 0 to 200, is 0.05 ⁇ j / (i + j + k) ⁇ 0.50.
  • Any of items 19 to 22, wherein L 1 and L 2 of the silicon-containing compound represented by the general formula (5) are each independently selected from the group consisting of an amino group, an acid anhydride group, and an epoxy group. The method according to claim 1. [24] 24.
  • the tetracarboxylic dianhydride is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride, cyclohexanetetracarboxylic dianhydride And the method according to any one of items 19 to 25, wherein the method is at least one selected from the group consisting of cyclobutanetetracarboxylic dianhydride.
  • the diamine is 4,4′-diaminodiphenylsulfone, m-tolidine, p-phenylenediamine, 2,2′-bis (trifluoromethyl) benzidine, and 2,2′-bis [4- (4-aminophenoxy).
  • 33. A method for producing a flexible device, comprising producing a laminate by the method according to item 31 or 32.
  • a polyimide precursor resin composition that can further improve the yellowness (YI value) and reduce foreign matters generated in the polyimide manufacturing process as compared with the case of using an unpurified siloxane compound. can do.
  • FIG. 1 is a schematic diagram showing a structure above a polyimide substrate of a top emission type flexible organic EL display as an example of the display of this embodiment.
  • present embodiments exemplary embodiments of the present invention
  • present embodiments will be described in detail.
  • the present invention is not limited to this embodiment, and can be implemented with various modifications within the scope of the gist thereof.
  • the upper limit value and the lower limit value of each numerical range can be arbitrarily combined.
  • the resin composition of this embodiment contains the polyimide precursor containing the structural unit represented by the following general formula (1).
  • P 1 represents a divalent organic group
  • P 2 represents a tetravalent organic group
  • p represents a positive integer
  • the polyimide precursor having the structure represented by the general formula (1) is preferably a copolymer of an acid dianhydride having a P 2 group and a diamine having a P 1 group.
  • Acid dianhydrides containing P 2 groups include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3 ′. -Biphenyltetracarboxylic dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-cyclohexene-1,2 Dicarboxylic anhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone Tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, methylene-4
  • An acid dianhydride may be used individually by 1 type, and may be used in combination of 2 or more type.
  • pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA) are optical properties such as mechanical properties of polyimide film, low thickness direction retardation (Rth) and low yellowness (YI value). It is preferable from the viewpoint of characteristics and a high glass transition temperature.
  • the polyimide precursor having the structure represented by the general formula (1) is a copolymer of tetracarboxylic dianhydride and diamine, and the tetracarboxylic dianhydride is pyromellitic dianhydride (PMDA). ) Is more preferable.
  • the total content of pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA) in the total acid dianhydride is the viewpoint of the low Rth and YI values of the polyimide film and the high glass transition temperature. Therefore, it is preferably 60 mol% or more, more preferably 80 mol% or more, and still more preferably 100 mol%.
  • the content of pyromellitic dianhydride (PMDA) in the total acid dianhydride is preferably 0 mol% or more, preferably 10 mol% or more, and 20 mol%.
  • the above is preferable, 100 mol% or less is preferable, and 90 mol% or less is preferable.
  • the content of biphenyltetracarboxylic dianhydride (BPDA) in the total acid dianhydride is preferably 0 mol% or more, preferably 10 mol% or more, from the viewpoint of the low Rth and YI values of the polyimide film. More than mol% is preferable, 100 mol% or less is preferable and 90 mol% or less is preferable.
  • BPDA biphenyltetracarboxylic dianhydride
  • the content ratio of pyromellitic dianhydride (PMDA): biphenyltetracarboxylic dianhydride (BPDA) in the acid dianhydride is low Rth and YI value of polyimide film, high glass transition temperature, elongation, etc. Is preferably 20:80 to 80:20, and more preferably 30:70 to 70:30.
  • diaminodiphenyl sulfone such as 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone
  • p-phenylenediamine m- phenylenediamine
  • the diamine containing the P 1 group in the formula (1) preferably contains diaminodiphenyl sulfone, such as 4,4′-diaminodiphenyl sulfone and / or 3,3′-diaminodiphenyl sulfone.
  • the content of diaminodiphenyl sulfone in the total diamine may be 50 mol% or more, or 70 mol% or more, or 90 mol% or more, or 95 mol% or more.
  • a larger amount of diaminodiphenylsulfone is preferred because the YI value of the polyimide film is reduced and a high glass transition temperature is obtained.
  • 4,4′-diaminodiphenyl sulfone is particularly preferable from the viewpoint of reducing the YI value.
  • Diamines may be used alone or in combination of two or more. It is preferable to copolymerize diaminodiphenyl sulfone and another diamine.
  • Other diamines to be copolymerized with diaminodiphenyl sulfone are preferably diamidobiphenyls, more preferably diaminobis (trifluoromethyl) biphenyl (TFMB), from the viewpoint of high heat resistance of the polyimide film and low YI value. .
  • the content of diaminobis (trifluoromethyl) biphenyl (TFMB) in all diamines is preferably 20 mol% or more, more preferably 30 mol% or more, from the viewpoint of the low YI value of the polyimide film. From the design point of view that allows the diamine to contain other advantageous diamines such as diaminodiphenylsulfone, the content of TFMB is preferably 80 mol% or less, more preferably 70 mol% or less.
  • the polyimide precursor in the resin composition of the present embodiment further includes a structural unit represented by the following general formula (2).
  • P 3 and P 4 are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms; An integer of 200. ⁇
  • the lower limit of the ratio of the structural part represented by the general formula (2) is preferably 5% by mass from the viewpoint of reducing the residual stress of the polyimide film generated between the substrate and the support. As mentioned above, More preferably, it is 6 mass% or more, More preferably, it is 7 mass% or more.
  • the upper limit of the ratio of the structural portion represented by the general formula (2) is preferably 40% by mass or less, more preferably 30 from the viewpoints of transparency and heat resistance of the polyimide film. It is at most 25% by mass, more preferably at most 25% by mass.
  • q is an integer of 1 to 200, and an integer of 3 to 200 is preferable from the viewpoint of heat resistance of the resulting polyimide.
  • the polyimide precursor may have the structure of the general formula (2) in any part of the molecule, but from the viewpoint of the type of siloxane monomer, the cost, and the molecular weight of the resulting polyimide precursor, the general formula
  • the structure of (2) is preferably derived from a silicon-containing compound such as a silicon-containing diamine.
  • a silicon-containing diamine for example, diamino (poly) siloxane represented by the following formula (6) is preferable.
  • each P 5 independently represents a divalent hydrocarbon group, which may be the same or different, and P 3 and P 4 are the same as those defined in the general formula (2); l represents an integer of 1 to 200.
  • Preferable structures of P 5 in the general formula (2) include a methylene group, an ethylene group, a propylene group, a butylene group, a phenylene group, and the like.
  • Preferable structures of P 3 and P 4 include a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group.
  • l is an integer of 1 to 200, and an integer of 3 to 200 is preferable from the viewpoint of the heat resistance of the polyimide used in (6).
  • the number average molecular weight of the compound represented by the general formula (6) is preferably 500 or more, more preferably 1,000 or more, from the viewpoint of reducing the residual stress generated between the obtained polyimide film and the support. More preferably, it is 2,000 or more. From the viewpoint of transparency (particularly low HAZE) of the obtained polyimide film, the number average molecular weight is preferably 12,000 or less, more preferably 10,000 or less, and still more preferably 8,000 or less.
  • Specific examples of the compound represented by the general formula (6) include both-end amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400), X22-9409 (number average).
  • the copolymerization ratio of the silicon-containing diamine is preferably 0.5 to 30% by mass, more preferably 1.0% to 25% by mass, and still more preferably 1.5% by mass with respect to the total mass of the polyimide precursor. ⁇ 20% by weight.
  • the silicon-containing diamine is 0.5% by mass or more, the residual stress generated between the silicon-containing diamine and the support can be effectively reduced.
  • the silicon-containing diamine is 30% by mass or less, the obtained polyimide film has good transparency (particularly low HAZE), which is preferable from the viewpoint of realizing a high total light transmittance and a high glass transition temperature.
  • Dicarboxylic acid As an acid component for forming the polyimide precursor in the present embodiment, in addition to acid dianhydride (for example, tetracarboxylic dianhydride exemplified above), dicarboxylic acid is used as long as its performance is not impaired.
  • An acid may be used. That is, the polyimide precursor of the present disclosure may be a polyamideimide precursor. A film obtained from such a polyimide precursor may have various properties such as mechanical elongation, glass transition temperature Tg, YI value and the like.
  • Examples of the dicarboxylic acid used include dicarboxylic acids having an aromatic ring and alicyclic dicarboxylic acids.
  • it is preferably at least one compound selected from the group consisting of aromatic dicarboxylic acids having 8 to 36 carbon atoms and alicyclic dicarboxylic acids having 6 to 34 carbon atoms.
  • the number of carbons herein includes the number of carbons contained in the carboxyl group. Of these, dicarboxylic acids having an aromatic ring are preferred.
  • dicarboxylic acid having an aromatic ring examples include isophthalic acid, terephthalic acid, 4,4′-biphenyldicarboxylic acid, 3,4′-biphenyldicarboxylic acid, 3,3′-biphenyldicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-sulfonylbisbenzoic acid, 3,4′-sulfonylbisbenzoic acid, 3,3′-sulfonylbisbenzoic acid, 4,4′-oxybisbenzoic acid, 3,4′-oxybisbenzoic acid, 3,3′-oxybisbenzoic acid, 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (3-carboxyphenyl) propane, 2,2′-dimethyl-4,4′-biphen
  • the polyimide precursor in the resin composition is a monomer unit comprising a silicon-containing compound represented by the following general formula (5), a tetracarboxylic dianhydride, and a diamine. It can also be described as a copolymer comprising
  • R 1 is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms
  • R 2 and R 3 are each independently a monovalent organic group having 1 to 10 carbon atoms.
  • At least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms
  • R 4 and R 5 are each independently a monovalent organic group having 1 to 10 carbon atoms
  • At least one is a monovalent aromatic group having 6 to 10 carbon atoms
  • R 6 and R 7 are each independently a monovalent organic group having 1 to 10 carbon atoms
  • at least one is an unsaturated fatty acid group.
  • L 1 and L 2 are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, Or a mercapto group, and i and j are each independently an integer of 1 to 200.
  • k is an integer of 0 to 200, is 0.05 ⁇ j / (i + j + k) ⁇ 0.50.
  • L 1 and L 2 of the silicon-containing compound represented by the general formula (5) are not limited, but are each independently an amino group or an acid anhydride group from the viewpoint of the molecular weight of the obtained polyimide precursor. Of these, an amino group is more preferable.
  • each R 1 is independently a single bond or a divalent organic group having 1 to 10 carbon atoms.
  • the divalent organic group having 1 to 10 carbon atoms may be linear, cyclic or branched, and may be saturated or unsaturated.
  • Examples of the divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms include methylene, ethylene, n-propylene, i-propylene, n-butylene, s-butylene, t-butylene, n-pentylene, neopentylene, n Linear or branched alkylene groups such as hexylene, n-heptylene, n-octylene, n-nonylene, and n-decylene; and cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, and cyclooctylene And cycloalkylene groups such as groups.
  • the divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferably at least one selected from the group consisting of ethylene, n-propylene, and i-propylene.
  • R 2 and R 3 are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms. It is.
  • the monovalent organic group having 1 to 10 carbon atoms may be linear, cyclic or branched, and may be saturated or unsaturated.
  • monovalent organic groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, linear or branched alkyl groups such as n-heptyl, n-octyl, n-nonyl, and n-decyl groups; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; Aromatic groups such as phenyl, tolyl, xylyl, ⁇ -naphthyl, and ⁇ -naphthyl groups.
  • the monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear, cyclic or branched, and may be saturated or unsaturated.
  • monovalent aliphatic hydrocarbon groups having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, and neopentyl groups.
  • Straight chain or branched chain alkyl groups such as cyclopropyl, cyclobutyl, and cyclopentyl groups.
  • the monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably at least one selected from the group consisting of methyl, ethyl, and n-propyl.
  • R 4 and R 5 are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is a monovalent aromatic group having 6 to 10 carbon atoms. .
  • the monovalent organic group having 1 to 10 carbon atoms may be linear, cyclic or branched, and may be saturated or unsaturated.
  • monovalent organic groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, linear or branched alkyl groups such as n-heptyl, n-octyl, n-nonyl, and n-decyl groups; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; Aromatic groups such as phenyl, tolyl, xylyl, ⁇ -naphthyl, and ⁇ -naphthyl groups.
  • Examples of the monovalent aromatic group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, ⁇ -naphthyl, and ⁇ -naphthyl groups, and is preferably phenyl, tolyl, or xylyl.
  • R 6 and R 7 are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an organic group having an unsaturated aliphatic hydrocarbon group.
  • the monovalent organic group having 1 to 10 carbon atoms may be linear, cyclic or branched, and examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, linear or branched alkyl groups such as t-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups; and cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl Cycloalkyl groups such as cycloheptyl and cyclooctyl groups, and aromatic groups such as phen
  • the monovalent organic group having 1 to 10 carbon atoms is preferably at least one selected from the group consisting of methyl, ethyl, and phenyl.
  • the organic group having an unsaturated aliphatic hydrocarbon group may be an unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms, and may be linear, cyclic, or branched.
  • Examples of the unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms include vinyl, allyl, propenyl, 3-butenyl, 2-butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, octenyl, nonenyl, decenyl, Examples include ethynyl, propynyl, butynyl, pentynyl, and hexynyl groups.
  • the unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms is preferably at least one selected from the group consisting of vinyl, allyl, and 3-butenyl.
  • R 1 to R 7 may be substituted with a substituent such as a halogen atom such as F, Cl, Br, or may be unsubstituted. .
  • I and j are each independently an integer of 1 to 200, preferably an integer of 2 to 100, more preferably an integer of 4 to 80, and still more preferably an integer of 8 to 40.
  • k is an integer of 0 to 200, preferably an integer of 0 to 50, more preferably an integer of 0 to 20, and still more preferably an integer of 0 to 50.
  • the tetracarboxylic dianhydride in the second embodiment may be the tetracarboxylic dianhydride mentioned for the general formula (1).
  • the tetracarboxylic dianhydride in the second embodiment is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride, cyclohexanetetra It is preferably at least one selected from the group consisting of carboxylic dianhydride and cyclobutane tetracarboxylic dianhydride.
  • the diamine in the second embodiment may be the diamine listed for the above general formula (1).
  • the diamine in the second embodiment is 4,4′-diaminodiphenylsulfone, m-tolidine, p-phenylenediamine, 2,2′-bis (trifluoromethyl) benzidine, and 2,2′-bis [4- ( It is preferably at least one selected from the group consisting of 4-aminophenoxy) phenyl] propane.
  • the weight average molecular weight of the polyimide precursor is preferably 50,000 or more, more preferably 60,000 or more, from the viewpoint of reducing the YI value of the polyimide film. From the viewpoint of reducing the haze of the polyimide film, the weight average molecular weight of the polyimide precursor is preferably 150,000 or less, more preferably 120,000 or less.
  • the desirable weight average molecular weight of the polyimide precursor may vary depending on the desired use, the type of polyimide precursor, the solid content of the resin composition, the type of solvent that the resin composition may contain, and the like.
  • Particularly preferred polyimide precursors in the present embodiment include the following (1) to (9).
  • PMDA pyromellitic dianhydride
  • BPDA biphenyltetracarboxylic dianhydride
  • DAS diaminodiphenyl sulfone
  • silicon-containing diamine More preferably, the weight average molecular weight is 80,000 to 100,000, and the solid content is 10 to 25% by mass.
  • the acid dianhydride component is pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA), and the diamine component is diaminobis (trifluoromethyl) biphenyl (TFMB) and a silicon-containing diamine.
  • PMDA pyromellitic dianhydride
  • BPDA biphenyltetracarboxylic dianhydride
  • TFMB diaminobis (trifluoromethyl) biphenyl
  • silicon-containing diamine silicon-containing diamine.
  • the acid dianhydride component is pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA), and the diamine component is diaminodiphenyl sulfone (DAS), diaminobis (trifluoromethyl) biphenyl (TFMB) and polycondensates which are silicon-containing diamines. More preferably, the weight average molecular weight is 95,000 to 120,000, and the solid content is 10 to 25% by mass.
  • PMDA pyromellitic dianhydride
  • BPDA biphenyltetracarboxylic dianhydride
  • DAS diaminodiphenyl sulfone
  • TFMB diaminobis (trifluoromethyl) biphenyl
  • polycondensates which are silicon-containing diamines. More preferably, the weight average molecular weight is 95,000 to 120,000, and the solid content is 10 to 25% by mass.
  • PMDA pyromellitic dianhydride
  • DAS diaminodiphenyl sulfone
  • TFMB diaminobis (trifluoromethyl) biphenyl
  • silicon-containing diamine More preferably, the weight average molecular weight is 110,000 to 120,000, and the solid content is 10 to 25% by mass.
  • BPDA biphenyltetracarboxylic dianhydride
  • DAS diaminodiphenylsulfone
  • TFMB diaminobis (trifluoromethyl) biphenyl
  • the weight average molecular weight is 90,000 to 100,000, and the solid content is 10 to 25% by mass.
  • the silicon-containing diamine is preferably a diamino (poly) siloxane represented by the general formula (6).
  • the number average molecular weight of the diamino (poly) siloxane is preferably 500 to 12,000, and more preferably, the diamino (poly) siloxane is a both-end amine-modified methylphenyl silicone oil.
  • the resin composition of the present embodiment is a low molecular cyclic siloxane represented by the following general formula (3-1) or (3-2), and at least m is an integer of 3 or more. Any one of the low-molecular cyclic siloxanes is included (simply “(3)” means "(3-1) or (3-2)”).
  • the composition of the present embodiment may or may not contain a compound in which m is 1 or 2 in the general formula (3-1) or (3-2).
  • the resin composition of the present embodiment may include only one of general formulas (3-1) or (3-2), or may include both of them.
  • the compound represented by the general formula (3-1) or (3-2) is preferably a compound represented by the general formula (3-1). That is, the resin composition of the present embodiment preferably contains at least a compound represented by the general formula (3-1).
  • ⁇ is an integer of 1 or more.
  • the total amount of compounds in which m is an integer of 3 or more in general formula (3) is preferably more than 0 ppm and 1,100 ppm or less, more preferably more than 0 ppm and 800 ppm or less, and still more preferably, based on the mass of the resin composition. Is more than 0 ppm and not more than 600 ppm, particularly preferably more than 0 ppm and not more than 300 ppm, particularly preferably more than 0 ppm and not more than 180 ppm.
  • the total amount of the compound represented by the general formula (3) is the total amount when the resin composition includes only one of the general formulas (3-1) or (3-2), and includes both of them. The case means the total amount.
  • the total amount of the compounds in which m is 3 to 5 in the general formula (3) is preferably more than 0 ppm and not more than 1,100 ppm, more preferably more than 0 ppm, based on the mass of the resin composition. 800 ppm or less, more preferably more than 0 ppm and 600 ppm or less, particularly preferably more than 0 ppm and 300 ppm or less, particularly preferably more than 0 ppm and 180 ppm or less.
  • the total amount of the compound in which m is 3 in the general formula (3) is preferably more than 0 ppm and 650 ppm or less, more preferably more than 0 ppm and 150 ppm or less, still more preferably more than 0 ppm and 80 ppm, based on the mass of the resin composition. It is as follows.
  • the total amount of compounds in which m is an integer of 3 or more in the general formula (3) is preferably more than 0 ppm and not more than 7,500 ppm, more preferably 0 ppm. More than 2,000 ppm, more preferably more than 0 ppm and not more than 1,100 ppm.
  • the total amount of compounds in which m is 3 in the general formula (3) is preferably more than 0 ppm and 4,500 ppm or less, more preferably more than 0 ppm and 1, 000 ppm or less, more preferably more than 0 ppm and 500 ppm or less.
  • the total amount of the compound in which m is 4 in the general formula (3) is preferably more than 0 ppm and 2,500 ppm or less, more preferably more than 0 ppm and 700 ppm or less. More preferably, it is more than 0 ppm and 400 ppm or less. It is preferable for the total amount of the compound represented by the general formula (3) to be within the above range since the YI value of the polyimide resin film obtained from the resin composition is further reduced.
  • the “solid content” means all components other than the solvent in the resin composition, and the liquid monomer component is also included in the mass of the solid content.
  • the polyimide precursor corresponds to the solid content.
  • the total mass of all monomers contained in the polyimide precursor corresponds to the solid mass.
  • the mass of the solid content can also be obtained by determining the mass of the solvent by gas chromatography (hereinafter also referred to as GC) analysis of the resin composition and subtracting the mass of the solvent from the mass of the resin composition.
  • the mass of the solid content can also be obtained by heating the resin composition, volatilizing and removing the solvent, obtaining the mass of the solvent, and subtracting the mass of the solvent from the mass of the resin composition.
  • the polyimide precursor of this embodiment is represented by the silicon-containing compound represented by the general formula (5), the compound represented by the general formula (3-1) or (3-2), and the general formula (4).
  • the raw material composition containing the compound to be obtained can be obtained by polycondensation reaction with tetracarboxylic dianhydride and diamine. In that case, the total amount of compounds in which m is an integer of 3 or more in the general formula (3) contained in the raw material composition is silicon represented by the general formulas (3), (4), and (5).
  • the total amount of the compounds in which m is 3 in the general formula (3) is preferably more than 0 ppm and 200 ppm.
  • the total amount of compounds in which m is 4 in general formula (3) is preferably more than 0 ppm and 80 ppm or less. More preferably, it is more than 0 ppm and 5 ppm or less, more preferably more than 0 ppm and 3 ppm or less. It is preferable for the total amount of the compound represented by the general formula (3) to be within the above range since the YI value of the polyimide resin film obtained from the resin composition is further reduced.
  • the resin composition of the present embodiment may further contain a compound represented by the following general formula (4) in addition to the compound represented by the above general formula (3).
  • n is an integer of 2 or more.
  • the total amount of compounds in which n is an integer of 3 or more is preferably more than 0 ppm and not more than 200 ppm, more preferably more than 0 ppm and not more than 100 ppm, still more preferably 0 ppm, based on the mass of the resin composition. More than 50 ppm.
  • the total amount of compounds having n of 3 to 8 is preferably more than 0 ppm and not more than 200 ppm, more preferably more than 0 ppm and not more than 100 ppm, and still more preferably from 0 ppm, based on the mass of the resin composition. At most 50 ppm.
  • the total amount of the compound in which m is an integer of 3 or more in the general formula (3) and the compound in which n is an integer of 3 or more in the general formula (4) is preferably based on the mass of the resin composition. It may be more than 0 ppm and not more than 1,300 ppm, more preferably more than 0 ppm and not more than 400 ppm, still more preferably more than 0 ppm and not more than 230 ppm.
  • the total amount of the compound in which m is an integer of 3 or more in the general formula (3) and the compound in which n is an integer of 3 or more in the general formula (4) is within the above range, and the general formula (3)
  • the total amount of compounds in which m is an integer of 3 or more is preferably more than 0 ppm and not more than 1,100 ppm, more preferably more than 0 ppm and not more than 800 ppm, still more preferably more than 0 ppm and more than 600 ppm, based on the mass of the resin composition.
  • it is particularly preferably more than 0 ppm and 300 ppm or less, particularly preferably more than 0 ppm and 180 ppm or less.
  • the total amount of the compound in which m is an integer of 3 or more in the general formula (3) and the compound in which n is an integer of 3 or more in the general formula (4) is within the above range, and the general formula (3 ),
  • the total amount of compounds having m of 3 to 5 is preferably more than 0 ppm and not more than 1,100 ppm, more preferably more than 0 ppm and not more than 800 ppm, still more preferably more than 0 ppm and more than 600 ppm, based on the mass of the resin composition.
  • it is particularly preferably more than 0 ppm and 300 ppm or less, particularly preferably more than 0 ppm and 180 ppm or less.
  • the total amount of compounds in which n is an integer of 3 or more in the general formula (4) is preferably more than 0 ppm and not more than 1,100 ppm, more preferably from 0 ppm. More than 700 ppm, more preferably more than 0 ppm and 400 ppm or less.
  • a compound in which m is an integer of 3 or more in general formula (3), and a compound in which n is an integer of 3 or more in general formula (4) The total amount of is preferably more than 0 ppm and not more than 8,600 ppm, more preferably more than 0 ppm and not more than 2,700 ppm, and still more preferably more than 0 ppm and not more than 1,500 ppm.
  • the total amount of the compound represented by the general formula (3) and the compound represented by the general formula (4) is within the above range, the total number of foreign matters attached in the manufacturing process of the polyimide resin film is reduced. preferable.
  • the total amount of compounds in which n is an integer of 3 or more in general formula (4) is preferably more than 0 ppm It is 200 ppm or less, More preferably, it is more than 0 ppm and 100 ppm or less, More preferably, it is more than 0 ppm and 50 ppm or less.
  • a compound in which m is an integer of 3 or more in general formula (3) When based on the total mass of the silicon-containing compounds of general formulas (3), (4) and (5), a compound in which m is an integer of 3 or more in general formula (3), and Among them, the total amount with the compound in which n is an integer of 3 or more is preferably more than 0 ppm and 4,700 ppm or less, more preferably more than 0 ppm and 1,100 ppm or less, still more preferably more than 0 ppm and 6,300 ppm or less.
  • the total amount of the compound represented by the general formula (3) and the compound represented by the general formula (4) is within the above range, the total number of foreign matters attached in the manufacturing process of the polyimide resin film is reduced. preferable.
  • the solvent is removed by the above, and the polyimide resin film is formed by imidization by heating at a higher temperature, for example, 350 ° C. for 1 hour continuously in the same oven.
  • the cyclic siloxane of the general formula (4) is more volatile than the cyclic siloxane of the general formula (3). Therefore, it is considered that when the solvent is removed, the cyclic siloxane of the general formula (4) volatilizes, and during the imidization, the cyclic siloxane of the general formula (3) volatilizes and adheres to the oven.
  • the resin composition typically includes a solvent.
  • a solvent those having good solubility of the polyimide precursor and capable of appropriately controlling the solution viscosity of the resin composition are preferable, and a reaction solvent for the polyimide precursor can be used as a solvent for the composition.
  • NMP N-methyl-2-pyrrolidone
  • GBL ⁇ -butyrolactone
  • Specific examples of the solvent composition include N-methyl-2-pyrrolidone (NMP) alone or a mixed solvent of N-methyl-2-pyrrolidone (NMP) and ⁇ -butyrolactone (GBL).
  • the resin composition of the present embodiment may further include an additional component in addition to the polyimide precursor, the low molecular cyclic siloxane, and the solvent.
  • additional component include a surfactant and an alkoxysilane compound.
  • surfactant By adding a surfactant to the resin composition of the present embodiment, the coating properties of the resin composition can be improved. Specifically, the generation of streaks in the coating film can be prevented.
  • surfactants include silicone surfactants, fluorine surfactants, and nonionic surfactants other than these.
  • silicone surfactants include organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, X-70-093 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.); SH-28PA, SH -190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (trade names, manufactured by Toray Dow Corning Silicone); SILWET L-77, L-7001, FZ-2105, FZ -2120, FZ-2154, FZ-2164, FZ-2166, L-7604 (trade name, manufactured by Nihon Unicar); DBE-814, DBE-224, DBE-621, CMS-626, CMS-222, KF- 352A, KF-354L, KF-355A, KF-6020, DBE-821, DBE-712 (Geles t), BYK-307, BYK-310, BYK-378, BYK-333 (trade name, manufactured by BYK Japan);
  • fluorine-based surfactant examples include Megafac F171, F173, R-08 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.); Fluorard FC4430, FC4432 (tradename, Sumitomo 3M Co., Ltd.) .
  • nonionic surfactants other than these include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like.
  • silicone-based surfactants and fluorine-based surfactants are preferable, and the YI value and total light transmission depending on the oxygen concentration during the curing process. From the viewpoint of reducing the influence on the rate, a silicone-based surfactant is preferable.
  • the amount thereof is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the polyimide precursor in the resin composition.
  • the resin composition is a polyimide precursor.
  • the alkoxysilane compound can be contained in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass. Good adhesiveness can be obtained between a support body and a polyimide film because content of the alkoxysilane compound with respect to 100 mass parts of polyimide precursors is 0.01 mass part or more.
  • the content of the alkoxysilane compound is preferably 0.02 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, and still more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the polyimide precursor. is there.
  • an alkoxysilane compound in addition to the above-mentioned improvement in adhesion, the coating property of the resin composition is improved (suppresses unevenness), and the influence of the oxygen concentration during curing on the YI value of the polyimide film is reduced. You can also
  • alkoxysilane compound examples include 3-ureidopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltripropoxysilane, ⁇ -aminopropyltributoxysilane, ⁇ -aminoethyltriethoxysilane, ⁇ -aminoethyltripropoxysilane, ⁇ -aminoethyltributoxysilane, ⁇ -aminobutyltriethoxysilane, ⁇ - Aminobutyltrimethoxysilane, ⁇ -aminobutyltripropoxysilane, ⁇ -aminobutyltributoxysilane, phenylsilanetriol, trimethoxyphenylsilane
  • the manufacturing method of the resin composition in this embodiment is not specifically limited, For example, it can be based on the following method.
  • the resin composition of the present embodiment can be produced by subjecting a polycondensation component including an acid dianhydride, a diamine, and a silicon-containing compound to a polycondensation reaction.
  • a polycondensation component including an acid dianhydride, a diamine, and a silicon-containing compound
  • the silicon-containing compound is purified before the polycondensation reaction, and the general formula (3) Reducing the total amount of these compounds.
  • the resin composition may be purified to reduce the total amount of the compound of general formula (3).
  • stripping may be performed while blowing an inert gas such as nitrogen gas into the silicon-containing compound in an arbitrary container.
  • the stripping temperature is preferably 200 ° C. or higher and 300 ° C. or lower, more preferably 220 ° C. or higher and 300 ° C. or lower, and further preferably 240 ° C. or higher and 300 ° C. or lower.
  • the vapor pressure of stripping is preferably as low as possible, and is 1000 Pa or less, more preferably 300 Pa or less, still more preferably 200 Pa or less, and still more preferably 133.32 Pa (1 mmHg) Pa or less.
  • the stripping time is preferably 4 hours or longer and 12 hours or shorter, more preferably 6 hours or longer and 10 hours or shorter.
  • the polyimide precursor of this embodiment can be synthesized by subjecting a polycondensation component including an acid dianhydride, a diamine, and a silicon-containing compound to a polycondensation reaction. It is preferable to use the above-mentioned purified silicon-containing compound.
  • the polycondensation component consists of an acid dianhydride, a diamine, and a silicon-containing compound.
  • the polycondensation reaction is preferably performed in a suitable solvent. Specifically, for example, after dissolving a predetermined amount of a diamine component and a silicon-containing compound in a solvent, a predetermined amount of acid dianhydride is added to the obtained diamine solution, followed by stirring.
  • acid dianhydride: diamine 100: 90.
  • the range of 0.95 to 1.05 mole part) is more preferred.
  • the molecular weight of the polyimide precursor can be controlled by adjusting the type of acid dianhydride, diamine and silicon-containing compound, adjusting the molar ratio of acid dianhydride and diamine, adding a terminal blocker, adjusting the reaction conditions, etc. Is possible.
  • a polyimide precursor can be made high molecular weight, so that the molar ratio of an acid dianhydride component and a diamine component is close to 1: 1, and the usage-amount of terminal blocker is small.
  • the purity is preferably 98% by mass or more, more preferably 99% by mass or more, and still more preferably 99.5% by mass or more. It can also be highly purified by reducing the water content in the acid dianhydride component and the diamine component.
  • the acid dianhydride component as a whole and the diamine component as a whole preferably have the above purity, and all types used It is more preferable that the acid dianhydride component and the diamine component have the above-mentioned purity.
  • the solvent for the reaction is not particularly limited as long as it can dissolve the acid dianhydride component, the diamine component, and the resulting polyimide precursor, and provide a high molecular weight polymer.
  • solvents include aprotic solvents, phenol solvents, ethers, glycol solvents, and the like.
  • aprotic solvent include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, 1,3-dimethyl.
  • phenolic solvents examples include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3, Examples include 4-xylenol and 3,5-xylenol.
  • ether and glycol solvents include 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, and bis [2- (2-methoxyethoxy) ethyl. ], Ether, tetrahydrofuran, 1,4-dioxane and the like. These solvents may be used alone or in combination of two or more.
  • the boiling point of the solvent used for the synthesis of the polyimide precursor at normal pressure is preferably 60 to 300 ° C, more preferably 140 to 280 ° C, and still more preferably 170 to 270 ° C.
  • the boiling point of the solvent is lower than 300 ° C., the drying process is shortened.
  • the boiling point of the solvent is 60 ° C. or higher, the surface of the resin film is not easily roughened during the drying step, bubbles are not easily mixed into the resin film, and a more uniform film can be obtained.
  • NMP N-methyl-2-pyrrolidone
  • GBL ⁇ -butyrolactone
  • (6) a compound represented by the general formula (6)
  • the water content in the solvent is preferably 3,000 mass ppm or less, for example, in order to allow the polycondensation reaction to proceed satisfactorily.
  • the content of molecules having a molecular weight of less than 1,000 is preferably less than 5% by mass.
  • the reason why molecules having a molecular weight of less than 1,000 are present in the resin composition is considered to be due to the water content of the solvent and raw materials (acid dianhydride and diamine) used during the synthesis. That is, it is considered that the acid anhydride group of some acid dianhydride monomers is hydrolyzed by moisture to become a carboxyl group and remains in a low molecular weight state without increasing its molecular weight.
  • the water content of the solvent is preferably 3,000 mass ppm or less, more preferably 1,000 mass ppm or less.
  • the amount of water contained in the raw material is also preferably 3,000 mass ppm or less, and more preferably 1,000 mass ppm or less.
  • the water content of the solvent includes the grade of solvent used (dehydration grade, general-purpose grade, etc.), solvent container (bottle, 18L can, canister can, etc.), solvent storage status (whether or not rare gas is sealed, etc.), from opening to use (Such as use immediately after opening or use after lapse of time after opening) and the like. It is considered that the rare gas replacement in the reactor before the synthesis, the presence or absence of the rare gas flow during the synthesis, etc. are also involved. Therefore, when synthesizing a polyimide precursor, it is recommended to use a high-purity product as a raw material, use a solvent with a small amount of water, and take measures to prevent moisture from the environment from entering the system before and during the reaction. Is done.
  • the reaction temperature during the synthesis of the polyimide precursor is preferably 0 ° C. to 120 ° C., 40 ° C. to 100 ° C., or 60 to 100 ° C. May preferably be 1 to 100 hours, or 2 to 10 hours.
  • the resin composition of this embodiment may contain other additional polyimide precursors in addition to the polyimide precursor in this embodiment.
  • the mass proportion of the additional polyimide precursor is preferably 30 mass with respect to the total amount of the polyimide precursor in the resin composition from the viewpoint of reducing the oxygen dependency of the YI value and the total light transmittance of the polyimide film. % Or less, more preferably 10% by mass or less.
  • the polyimide precursor in this embodiment may be partially imidized (partial imidization).
  • partial imidization By partially imidizing the polyimide precursor, viscosity stability when storing the resin composition can be improved.
  • the imidation ratio in this case is preferably 5% or more, more preferably 8% or more, preferably from the viewpoint of balancing the solubility of the polyimide precursor in the resin composition and the storage stability of the solution. 80% or less, more preferably 70% or less, and still more preferably 50% or less.
  • This partial imidization can be obtained by heating the polyimide precursor to perform dehydration ring closure. This heating is preferably performed at a temperature of 120 to 200 ° C., more preferably 150 to 180 ° C., preferably for 15 minutes to 20 hours, more preferably for 30 minutes to 10 hours.
  • N, N-dimethylformamide dimethyl acetal or N, N-dimethylformamide diethyl acetal is added to the polyamic acid obtained by the above reaction and heated, and a part or all of the carboxylic acid is esterified.
  • esterification viscosity stability during storage can be improved.
  • These ester-modified polyamic acids are prepared by sequentially reacting the above acid dianhydride component with one equivalent of a monohydric alcohol with respect to the acid anhydride group and a dehydrating condensing agent such as thionyl chloride or dicyclohexylcarbodiimide. It can also be obtained by a condensation reaction with a diamine component.
  • the synthesized polyimide precursor solution can be used as it is as the resin composition.
  • a resin composition is prepared by adding a further solvent and one or more additional components to the polyimide precursor at room temperature (25 ° C.) to 80 ° C. and stirring and mixing. May be. This stirring and mixing can be performed using an appropriate apparatus such as a three-one motor (manufactured by Shinto Chemical Co., Ltd.) equipped with a stirring blade, a rotation and revolution mixer, and the like. If necessary, the resin composition may be heated to 40 ° C to 100 ° C.
  • the solvent used when synthesizing the polyimide precursor is different from the solvent to be contained in the resin composition
  • the solvent in the synthesized polyimide precursor solution is appropriately changed, for example, by reprecipitation or solvent distillation.
  • the polyimide precursor may be isolated by removing by this method.
  • a resin composition is prepared by adding a desired solvent and, if necessary, additional components to the isolated polyimide precursor in a temperature range of room temperature (25 ° C.) to 80 ° C., and stirring and mixing. May be.
  • the resin composition After preparing the resin composition as described above, the resin composition is heated, for example, at 130 to 200 ° C., for example, for 5 minutes to 2 hours, so that a part of the polyimide precursor is removed to such an extent that the polymer does not precipitate.
  • Dehydration imidization may be performed (partial imidization). By controlling the heating temperature and the heating time, the imidization rate can be controlled. By partially imidizing the polyimide precursor, viscosity stability when storing the resin composition can be improved.
  • the solution viscosity of the resin composition is preferably 500 to 100,000 mPa ⁇ s, more preferably 1,000 to 50,000 mPa ⁇ s, and still more preferably 3,000 to 20,000 mPa ⁇ s in terms of slit coat performance. s. Specifically, it is preferably 500 mPa ⁇ s or more, more preferably 1,000 mPa ⁇ s or more, and still more preferably 3,000 mPa ⁇ s or more, in that liquid leakage from the slit nozzle is difficult.
  • the slit nozzle is preferably 100,000 mPa ⁇ s or less, more preferably 50,000 mPa ⁇ s or less, and still more preferably 20,000 mPa ⁇ s or less in that the slit nozzle is less likely to be clogged.
  • the solution viscosity of the resin composition at the time of synthesizing the polyimide precursor is higher than 200,000 mPa ⁇ s, there may be a problem that stirring at the time of synthesis becomes difficult. However, even if the solution becomes highly viscous during synthesis, it is possible to obtain a resin composition with good handleability by adding a solvent after the reaction and stirring.
  • the solution viscosity of the resin composition in the present embodiment is a value measured at 23 ° C. using an E-type viscometer (for example, VISCONICEHD, manufactured by Toki Sangyo).
  • the water content of the resin composition of the present embodiment is preferably 3,000 mass ppm or less, more preferably 2,500 mass ppm or less, and still more preferably 2 from the viewpoint of viscosity stability when storing the resin composition.
  • a polyimide film (hereinafter also referred to as a polyimide resin film) can be provided using the resin composition of the present embodiment.
  • the method for producing a polyimide film of the present embodiment includes a coating step of applying the resin composition of the present embodiment on the surface of a support; a film forming step of heating the resin composition to form a polyimide resin film; A peeling step of peeling the polyimide resin film from the support.
  • the resin composition of the present embodiment is coated on the surface of the support.
  • the support is not particularly limited as long as it has heat resistance to the heating temperature in the subsequent film formation step (heating step) and has good peelability in the peeling step.
  • the support include glass substrates, such as non-alkali glass substrates; silicon wafers; PET (polyethylene terephthalate), OPP (stretched polypropylene), polyethylene glycol terephthalate, polyethylene glycol naphthalate, polycarbonate, polyimide, polyamideimide, and polyetherimide.
  • resin substrates such as polyetheretherketone, polyethersulfone, polyphenylenesulfone, and polyphenylenesulfide; and metal substrates such as stainless steel, alumina, copper, and nickel.
  • a thin film-like polyimide molded body for example, a glass substrate, a silicon wafer or the like is preferable.
  • a thick film-like polyimide sheet for example, a PET (polyethylene terephthalate) is used.
  • a support made of OPP (stretched polypropylene) or the like is preferable.
  • a doctor blade knife coater As a coating method, in general, a doctor blade knife coater, an air knife coater, a roll coater, a rotary coater, a flow coater, a die coater, a bar coater or the like, a spin coat, a spray coat, a dip coat or the like; a screen printing And printing techniques represented by gravure printing and the like.
  • the resin composition of the present embodiment is preferably applied by slit coating.
  • the coating thickness should be appropriately adjusted according to the desired thickness of the resin film and the content of the polyimide precursor in the resin composition, but is preferably about 1 to 1,000 ⁇ m.
  • the temperature in the coating step may be room temperature, and the resin composition may be heated to, for example, 40 to 80 ° C. in order to reduce the viscosity and improve workability.
  • the drying process may be performed following the coating process, or the drying process may be omitted and the process may proceed directly to the next film formation process (heating process).
  • the drying step is performed for the purpose of removing the organic solvent in the resin composition.
  • appropriate apparatuses such as a hot plate, a box-type dryer, and a conveyor type dryer, can be used, for example.
  • the temperature in the drying step is preferably 80 to 200 ° C, more preferably 100 to 150 ° C.
  • the duration of the drying step is preferably 1 minute to 10 hours, more preferably 3 minutes to 1 hour.
  • a coating film containing a polyimide precursor is formed on the support.
  • the heating step is a step of obtaining a polyimide resin film by removing the organic solvent contained in the coating film and advancing the imidization reaction of the polyimide precursor in the coating film.
  • This heating process can be performed using apparatuses, such as an inert gas oven, a hot plate, a box-type dryer, and a conveyor type dryer, for example. This step may be performed simultaneously with the drying step, or both steps may be performed sequentially.
  • the heating step may be performed in an air atmosphere, but in view of safety and good transparency of the resulting polyimide film, low thickness direction retardation (Rth) and low YI value, in an inert gas atmosphere Preferably it is done.
  • the inert gas include nitrogen and argon.
  • the heating temperature may be appropriately set according to the type of polyimide precursor and the type of solvent in the resin composition, but is preferably 250 ° C. to 550 ° C., more preferably 300 to 450 ° C. If it is 250 degreeC or more, imidation will advance favorable, and if it is 550 degrees C or less, inconveniences, such as a transparency fall of the polyimide film obtained and a heat resistant deterioration, can be avoided.
  • the heating time is preferably about 0.1 to 10 hours.
  • the oxygen concentration in the ambient atmosphere in the heating step is preferably 2,000 ppm by mass or less, more preferably 100 ppm by mass or less, and still more preferably from the viewpoint of the transparency and YI value of the resulting polyimide film. Is 10 mass ppm or less.
  • the YI value of the resulting polyimide film can be made 30 or less.
  • the peeling step the polyimide resin film on the support is peeled off after being cooled to, for example, room temperature (25 ° C.) to about 50 ° C.
  • Examples of the peeling step include the following aspects (1) to (4).
  • a method of peeling a polyimide resin After producing a structure including a polyimide resin film / support by the above method, by irradiating a laser from the support side of the structure to ablate the interface between the support and the polyimide resin film, A method of peeling a polyimide resin.
  • the laser include a solid (YAG) laser and a gas (UV excimer) laser. It is preferable to use a spectrum with a wavelength of 308 nm or the like (refer to JP-T-2007-512568, JP-T2012-511173, etc.).
  • the release layer include parylene (registered trademark, manufactured by Japan Parylene Godo Kaisha) and tungsten oxide; vegetable oil-based, silicone-based, fluorine-based, alkyd-based release agents may be used (Japanese Patent Laid-Open No. 2010-069757). No., JP 2013-179306, etc.). You may use together this method (2) and the laser irradiation of the method (1).
  • the metal for example, copper (as an example, electrolytic copper foil “DFF” manufactured by Mitsui Mining & Smelting Co., Ltd.), aluminum, or the like can be used.
  • the etchant ferric chloride or the like can be used for copper, and dilute hydrochloric acid or the like can be used for aluminum.
  • the adhesive film is pasted on the surface of the polyimide resin film to separate the adhesive film / polyimide resin film from the support, and then from the adhesive film.
  • a method of separating a polyimide resin film is
  • the method (1) or (2) is preferable from the viewpoint of the refractive index difference between the front and back of the polyimide resin film to be obtained, the YI value, and the elongation. From the viewpoint of the refractive index difference between the front and back surfaces of the polyimide resin film to be obtained, it is more preferable to perform the method (1), that is, the irradiation step of irradiating the laser from the support side prior to the peeling step.
  • the method (3) when using copper as a support body, the YI value of the polyimide resin film obtained becomes large, and the tendency for elongation to become small is seen. This is considered to be an influence of copper ions.
  • the thickness of the resulting polyimide film is not limited, but is preferably 1 to 200 ⁇ m, more preferably 5 to 100 ⁇ m.
  • the YI value at a film thickness of 10 ⁇ m of the polyimide film obtained from the resin composition of the present embodiment is preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, particularly preferably, from the viewpoint of obtaining good optical properties. Is 14 or less, particularly preferably 13 or less, particularly preferably 10 or less, particularly preferably 7 or less.
  • the YI value varies depending on the monomer skeleton of the polyimide precursor, but if the monomer skeleton is the same, the YI value tends to be smaller as the weight average molecular weight of the polyimide precursor is larger.
  • the YI value is influenced by, for example, the amine value of the silicon-containing compound to be used.
  • the amine value When the amine value is high, the YI value is large, and when the amine value is small, the YI value tends to be small.
  • a polyimide precursor using a purified silicon-containing compound that is, the total amount of the compound represented by the general formula (3) is within the above range uses an unpurified silicon-containing compound having the same amine value.
  • the YI value of the resulting polyimide resin film tends to be lower than that of the polyimide precursor.
  • the non-cyclic low molecular weight diamine used for the production of the polyimide precursor remains, decomposes when the polyimide is cured, generates radicals, and increases (deteriorates) the YI value. Can be.
  • the amount of the cyclic siloxane represented by the general formula (3) not only the cyclic siloxane represented by the general formula (3) is removed during purification, but among the diamine components that increase the amine value. It is considered that low molecular weight diamine which is relatively easy to volatilize is also removed.
  • the YI value of the polyimide resin film is further improved in the polyimide precursor in which the total amount of the compound represented by the general formula (3) is reduced according to the present embodiment.
  • the difference in YI value between a polyimide precursor using a purified silicon-containing compound and a polyimide precursor using an unpurified silicon-containing compound can be obtained from the following equation.
  • (Difference in YI value) (YI value of a polyimide resin film obtained by curing a polyimide precursor obtained using an unpurified silicon compound)-(Polyimide precursor obtained using a purified silicon compound) YI value of polyimide resin film with cured body)
  • the difference in YI value is preferably 1.5 or more, more preferably 2 or more, and further preferably 2.5 or more.
  • the method of measuring the YI value refer to the column of Examples.
  • the polyimide film obtained from the resin composition of the present embodiment includes, for example, a semiconductor insulating film, a thin film transistor liquid crystal display (TFT-LCD) insulating film, an electrode protective film, a liquid crystal display, an organic electroluminescence display, a field emission display, It can be applied as a transparent substrate of a display device such as electronic paper.
  • the polyimide film obtained from the resin composition of the present embodiment is suitably used as a thin film transistor (TFT) substrate, a color filter substrate, a touch panel substrate, and a transparent conductive film (ITO, Indium Thin Oxide) substrate in the manufacture of flexible devices. Can be used.
  • a TFT device for flexible display for example, a TFT device for flexible display, a flexible solar cell, a flexible touch panel, flexible lighting, a flexible battery, a flexible printed circuit board, a flexible color filter, a surface cover lens for smartphones, etc.
  • a TFT device for flexible display for example, a TFT device for flexible display, a flexible solar cell, a flexible touch panel, flexible lighting, a flexible battery, a flexible printed circuit board, a flexible color filter, a surface cover lens for smartphones, etc.
  • the process of forming a TFT on a flexible substrate using a polyimide film is typically performed at a wide temperature range of 150 to 650 ° C. Specifically, when manufacturing a TFT device using amorphous silicon, a process temperature of 250 ° C. to 350 ° C. is generally required, and the polyimide film of this embodiment needs to withstand that temperature. Specifically, it is necessary to appropriately select a polymer structure having a glass transition temperature higher than the process temperature and a thermal decomposition start temperature.
  • a process temperature of 320 ° C. to 400 ° C. is generally required, and the polyimide film of this embodiment needs to be able to withstand that temperature. For this reason, it is necessary to appropriately select a polymer structure having a glass transition temperature and a thermal decomposition start temperature higher than the TFT fabrication process maximum temperature.
  • LTPS low-temperature polysilicon
  • a process temperature of 380 ° C. to 520 ° C. is generally required, and the polyimide film of this embodiment needs to withstand that temperature. It is necessary to appropriately select a glass transition temperature and a thermal decomposition start temperature that are equal to or higher than the TFT manufacturing process maximum temperature.
  • the optical properties (especially, light transmittance, retardation properties, and YI value) of the polyimide film tend to decrease as they are exposed to high temperature processes.
  • the polyimide obtained from the polyimide precursor of this embodiment has good optical characteristics even after undergoing a thermal history.
  • the display manufacturing method of the present embodiment includes a coating step of applying the resin composition of the present embodiment on the surface of a support; a film forming step of heating the resin composition to form a polyimide resin film; An element forming step of forming an element on the polyimide resin film; and a peeling step of peeling the polyimide resin film on which the element is formed from the support.
  • FIG. 1 is a schematic diagram showing a structure above a polyimide substrate of a top emission type flexible organic EL display as an example of the display of this embodiment.
  • the organic EL structure unit 25 in FIG. 1 will be described.
  • the organic EL element 250a that emits red light, the organic EL element 250b that emits green light, and the organic EL element 250c that emits blue light are arranged in a matrix as one unit. 251, the light emitting region of each organic EL element is defined.
  • Each organic EL element includes a lower electrode (anode) 252, a hole transport layer 253, a light emitting layer 254, and an upper electrode (cathode) 255.
  • a TFT 256 low temperature polysilicon (LTPS) or metal oxide for driving an organic EL element is formed on the lower layer 2a showing a CVD multilayer film (multi-barrier layer) made of silicon nitride (SiN) or silicon oxide (SiO).
  • a plurality of interlayer insulating films 258 provided with contact holes 257 and a lower electrode 259 are provided.
  • the organic EL element is sealed with a sealing substrate 2b, and a hollow portion 261 is formed between each organic EL element and the sealing substrate 2b.
  • the manufacturing process of the flexible organic EL display includes preparing a polyimide film on a glass substrate support, manufacturing the organic EL substrate shown in FIG. 1 above, manufacturing the sealing substrate, and both substrates.
  • the assembly process which bonds together, and the peeling process which peels the organic electroluminescent display produced on the polyimide film from the glass substrate support body are included.
  • a well-known manufacturing process can be applied to the organic EL substrate manufacturing process, the sealing substrate manufacturing process, and the assembly process.
  • One example is given below, but the present invention is not limited to this.
  • the peeling process is the same as the polyimide film peeling process described above.
  • a polyimide film is prepared on a glass substrate support by the above method, and a multilayer of silicon nitride (SiN) and silicon oxide (SiO) is formed thereon by CVD or sputtering.
  • a multi-barrier layer (lower substrate 2a in FIG. 1) having a structure is produced, and a metal wiring layer for driving the TFT is produced thereon using a photoresist or the like.
  • An active buffer layer made of SiO or the like is formed thereon by using a CVD method, and a TFT device (TFT 256 in FIG. 1) such as a metal oxide semiconductor (IGZO) or low-temperature polysilicon (LTPS) is formed thereon.
  • IGZO metal oxide semiconductor
  • LTPS low-temperature polysilicon
  • an interlayer insulating film 258 provided with contact holes 257 is formed with a photosensitive acrylic resin or the like.
  • An ITO film is formed by sputtering or the like, and a lower electrode 259 is formed so as to make a pair with the TFT.
  • a partition (bank) 251 is formed with photosensitive polyimide or the like, a hole transport layer 253 and a light emitting layer 254 are formed in each space partitioned by the partition.
  • An upper electrode (cathode) 255 is formed so as to cover the light emitting layer 254 and the partition (bank) 251.
  • an organic EL material that emits red light corresponding to the organic EL element 250a that emits red light in FIG. 1
  • an organic EL material that emits green light in FIG. 1
  • the organic EL element 250b emitting green light and the organic EL material emitting blue light corresponding to the organic EL element 250c emitting blue light in FIG.
  • an organic EL substrate is produced.
  • the organic EL substrate is sealed with a sealing film or the like (sealing substrate 2b in FIG. 1), and the device above the polyimide substrate is peeled off from the glass substrate support by a known peeling method such as laser peeling.
  • An emission-type flexible organic EL display can be produced.
  • a see-through flexible organic EL display can be produced. You may produce a bottom emission type flexible organic electroluminescent display by a well-known method.
  • a flexible liquid crystal display can be produced using the polyimide film of the present embodiment.
  • a polyimide film is produced on a glass substrate support by the above method, and using, for example, amorphous silicon, a metal oxide semiconductor (IGZO, etc.), and low-temperature polysilicon.
  • a TFT substrate is produced.
  • a polyimide film is produced on a glass substrate support according to the coating step and film forming step of the present embodiment, and a color filter glass substrate (CF substrate) provided with the polyimide film using a color resist or the like according to a known method. ).
  • CF substrate color filter glass substrate
  • One of the TFT substrate and the CF substrate is coated with a sealing material made of thermosetting epoxy resin or the like by screen printing on a frame-like pattern lacking the liquid crystal inlet, and the thickness of the liquid crystal layer is equivalent to the other substrate Sprinkle spherical spacers made of plastic or silica.
  • a liquid crystal layer is formed by injecting a liquid crystal material into the space surrounded by the TFT substrate, the CF substrate and the sealing material by a decompression method, applying a thermosetting resin to the liquid crystal injection port, and sealing the liquid crystal material by heating.
  • a flexible liquid crystal display can be manufactured by peeling the glass substrate on the CF side and the glass substrate on the TFT side at the interface between the polyimide film and the glass substrate by a laser peeling method or the like.
  • the manufacturing method of the laminated body of this embodiment comprises: a coating step of applying the resin composition of this embodiment on the surface of a support; and a film forming step of heating the resin composition to form a polyimide resin film; An element forming step of forming an element on the polyimide resin film.
  • the element in the laminate examples include those exemplified in the production of the flexible device.
  • the support for example, a glass substrate can be used.
  • Preferred specific procedures for the coating step and the film forming step are the same as those described for the method for producing the polyimide film.
  • the element forming step the element is formed on a polyimide resin film as a flexible substrate formed on the support. Then, you may peel a polyimide resin film and an element from a support body arbitrarily in a peeling process.
  • the total mass of the monomers used for the polyimide precursor can be used as the mass of the solid content contained in the resin composition.
  • the mass of solid content can be calculated
  • the GC conditions include the following conditions. Apparatus: Gas chromatograph (manufactured by Agilent, gas chromatograph 6890N type) Inlet temperature: 280 ° C Injection volume: 1 ⁇ L Oven temperature: After holding at 50 ° C. for 1 minute, the temperature is raised to 350 ° C.
  • Weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) under the following conditions.
  • GPC gel permeation chromatography
  • NMP manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph
  • 24.8 mmol / L lithium bromide monohydrate manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5%
  • 63 just before the measurement is used.
  • .2 mmol / L phosphoric acid dissolved by adding Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph was used.
  • a calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation). Column: Shodex KD-806M (manufactured by Showa Denko) Flow rate: 1.0 mL / min Column temperature: 40 ° C Pump: PU-2080Plus (manufactured by JASCO) Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO) and UV-2075Plus (UV-VIS: UV-visible light spectrometer, manufactured by JASCO)
  • GC / MS measurement was performed using the following apparatus. Pyrolyzer: Py-3030iD (Frontier Lab) GC system: 7890B (Agilent Technology) MSD: 5977A (Agilent Technology) Column: UA-1 (inner diameter 0.25 mm, length 15 m, liquid phase thickness 0.25 ⁇ m) (Frontier Lab) All GC / MS measurements were performed under the following measurement conditions. Column temperature: held at 40 ° C. for 5 minutes, heated at 20 ° C./minute, held at 320 ° C. for 11 minutes, total 30 minutes inlet temperature: 320 ° C.
  • Injection method Split method (split ratio 1/20) Interface temperature: 320 ° C Ion source temperature: 230 ° C Ionization method: Electron ionization method (EI) Measuring method: SCAN method (m / z 10-800)
  • Dm ⁇ ( ⁇ g / g) ⁇ Dm ⁇ (GC-Area) ⁇ / ⁇ Slope of D4 calibration curve ⁇ / ⁇ Weight of weighed resin composition (mg) ⁇ ⁇ 1000 M in the formula corresponds to the carbon number m in the general formula (3), and m is an integer of 3 or more.
  • Dn ( ⁇ g / g) ⁇ Dn (GC-Area) ⁇ / ⁇ D4 slope of the calibration curve ⁇ / ⁇ mass of the weighed resin composition (mg) ⁇ ⁇ 1000 N in a formula respond
  • the mass of the solid content contained in the resin composition is obtained by GC analysis of the resin composition to obtain the mass of the solvent, and the mass of the resin composition is subtracted from the mass of the solvent, or the resin composition is heated. Then, the solvent can be removed by volatilization, the mass of the solvent can be determined, and the mass of the solvent can be subtracted from the mass of the resin composition.
  • GC system 7890A (Agilent Technology)
  • Carrier gas He Injection method: Split method (split ratio 1/10)
  • the amount of the low molecular cyclic siloxane of the general formula (3) was calculated according to the following formula.
  • Dm ⁇ ( ⁇ m / g) ⁇ total amount of compounds of general formula (3) ( ⁇ g) ⁇ / ⁇ total mass of compounds of general formulas (3-1), (3-2), (4) and (5)
  • ( g) ⁇ ⁇ Dm ⁇ (GC-Area) ⁇ / ⁇ n-tetradecane (GC-Area) ⁇ GC-Area Factor ⁇ ⁇ 20 ⁇ 100 M in the formula corresponds to the carbon number m in the general formula (3), and m is an integer of 3 or more.
  • the GC-Area Factor in the formula was calculated according to the following formula.
  • GC-Area Factor molecular weight / carbon number
  • the amount of the low molecular cyclic siloxane of the general formula (4) was calculated according to the following formula.
  • Dn ( ⁇ g / g) ⁇ total amount of compound of general formula (4) ( ⁇ g) ⁇ / ⁇ total mass of compounds of general formulas (3-1), (3-2), (4) and (5)
  • ( g) ⁇ ⁇ Dn (GC-Area) ⁇ / ⁇ n-tetradecane (GC-Area) ⁇ GC-Area Factor ⁇ ⁇ 20 ⁇ 100 N in a formula respond
  • the GC-Area Factor in the formula was calculated according to the following formula.
  • GC-Area Factor molecular weight / carbon number
  • Table 2 shows the retention time (minutes) of the cyclic siloxane in the GC measurement using the apparatus used and the measurement conditions described above. The same applies to the subsequent GC measurements.
  • One of the glass substrates having a coating film of the resin composition is dried in an oven (KLO-30NH, manufactured by Koyo Thermo System) in a nitrogen atmosphere (oxygen concentration of 300 ppm or less) at 100 ° C. for 30 minutes to remove the solvent. Removed. Subsequently, a polyimide resin film was formed on the glass substrate by heating at 350 ° C. for 1 hour in a nitrogen atmosphere (oxygen concentration of 300 ppm or less). Of the obtained 200 mm square polyimide resin film, the size and number of foreign matters were counted using a microscope (VHX-6000, manufactured by Keyence) in the range of the center 50 mm square. The observation conditions are as follows.
  • the number of foreign matters having a major axis of 50 ⁇ m or more and less than 1000 ⁇ m was evaluated according to the following criteria.
  • the number of foreign matters is 10 or more and less than 50: A (good)
  • the number of foreign objects is 50 or more and less than 100: B (possible)
  • the number of foreign objects is 100 or more: C (impossible)
  • the polyimide precursor film obtained by using the purified silicon compound and the polyimide precursor film obtained by using the silicon compound that has not been refined are cured, respectively.
  • the difference was evaluated.
  • the resin compositions of Examples and Comparative Examples were applied to a 200 mm square non-alkali glass substrate (hereinafter also referred to as a glass substrate) so that the film thickness after curing was 10 ⁇ m to form a coating film.
  • the application was performed using a slit coater (TN25000, Tokyo Ohka Kogyo Co., Ltd.).
  • One of the glass substrates having a coating film of the obtained resin composition was dried in an oven (KLO-30NH, Koyo Thermo System) in a nitrogen atmosphere (oxygen concentration 300 ppm or less) at 100 ° C. for 30 minutes. The solvent was removed. Then, it heated at 400 degreeC under nitrogen atmosphere (oxygen concentration 300 ppm or less) for 1 hour, and formed the polyimide resin film on the glass substrate.
  • YI value was measured using Nippon Denshoku Industries Co., Ltd. (Spectrophotometer: SE600). A D65 light source was used as the light source. The difference in YI value was determined from the following formula.
  • (Difference in YI value) (YI value of a polyimide resin film obtained by curing a polyimide precursor obtained using an unpurified silicon compound)-(Polyimide precursor obtained using a purified silicon compound) YI value of polyimide resin film with cured body)
  • the curing of the polyimide precursor obtained using the silicon compound that has not been purified and the curing of the polyimide precursor obtained using the purified silicon compound are the same. Equipment errors were eliminated by heat treatment in an oven batch.
  • ⁇ Method for purifying silicon-containing compound The silicon-containing compounds described in Examples and Comparative Examples described later were treated by the following purification method to reduce the low molecular cyclic siloxane contained. The concentration of the low-molecular cyclic siloxane after purification was analyzed by the above method.
  • acetone was distilled off with an evaporator to obtain a purified silicon-containing compound.
  • ⁇ Purification D> According to Purification Example 1 described in JP-A-2006-028533 500 g of a silicon-containing compound was placed in a flask, and stripping was performed at a temperature of 250 ° C. and a pressure of 1330 Pa for 8 hours while blowing nitrogen gas.
  • ⁇ Purification E> According to Purification Example 2 described in JP-A-2006-028533 100 g of a silicon-containing compound was placed in 300 g of 2-butanone and uniformly dissolved. This solution was slowly poured into methanol with stirring to perform reprecipitation. The above reprecipitation was repeated a total of 3 times, and then dried to obtain a purified silicon-containing compound.
  • Example 2 to 32 and Comparative Examples 17 to 19 In Example 1, it carried out like Example 1 except having changed the kind and quantity of a solvent, acid dianhydride, diamine, and a silicon-containing compound into what was described in Table 2 and 3.
  • the types of silicon-containing compounds in Table 3 are as follows.
  • An unpurified silicon-containing compound (in the general formula (1), L 1 and L 2 are amino groups, R 1 is —CH 2 CH 2 CH 2 —, and R 2 , R 3 , R 6 , R 7) Is a methyl group, R 4 and R 5 are phenyl groups, j is 15, i + j + k is 10, and a compound having a number average molecular weight of 4400) (5.72 g) is added with stirring, followed by PMDA (acid dianhydride). 15.3 g) was added. The molar ratio of acid dianhydride to diamine was 100: 97.
  • varnish a transparent NMP solution of polyamic acid (hereinafter also referred to as varnish).
  • the obtained varnish was stored in a freezer (set at ⁇ 20 ° C., the same applies hereinafter), and thawed before evaluation.
  • Comparative Example 2 to Comparative Example 16 >> In Comparative Example 1, the same procedure as in Comparative Example 1 was performed, except that the types and amounts of the solvent, acid dianhydride, diamine, and silicon-containing compound were changed to those described in Table 3.

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