WO2015198970A1 - 空隙を有するポリイミドフィルム及びその製造方法 - Google Patents

空隙を有するポリイミドフィルム及びその製造方法 Download PDF

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WO2015198970A1
WO2015198970A1 PCT/JP2015/067656 JP2015067656W WO2015198970A1 WO 2015198970 A1 WO2015198970 A1 WO 2015198970A1 JP 2015067656 W JP2015067656 W JP 2015067656W WO 2015198970 A1 WO2015198970 A1 WO 2015198970A1
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group
polyimide film
film
carbon atoms
resin precursor
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PCT/JP2015/067656
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English (en)
French (fr)
Japanese (ja)
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佳季 宮本
康史 飯塚
加藤　聡
隆行 金田
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旭化成イーマテリアルズ株式会社
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Priority to KR1020207021572A priority Critical patent/KR102305617B1/ko
Priority to JP2016529524A priority patent/JP6254274B2/ja
Priority to CN201580033079.0A priority patent/CN106414575B/zh
Priority to CN202010966079.9A priority patent/CN112080026B/zh
Priority to KR1020167035080A priority patent/KR102139455B1/ko
Publication of WO2015198970A1 publication Critical patent/WO2015198970A1/ja

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    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • 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
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • 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
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to a polyimide film having voids, for example, used for a substrate for a flexible device, and a method for producing the same.
  • the polyimide film preferably has high transparency.
  • a film made of polyimide is used as a resin film.
  • a general polyimide is prepared by solution polymerization of an aromatic tetracarboxylic dianhydride and an aromatic diamine to produce a polyimide precursor (polyamic acid), followed by thermal imidization by dehydration at high temperature or using a catalyst. It is produced by chemical imidization by ring-closing dehydration.
  • Polyimide is an insoluble and infusible super heat resistant resin, and has excellent properties such as heat oxidation resistance, heat resistance, radiation resistance, low temperature resistance, and chemical resistance. For this reason, polyimide is used in a wide range of fields including electronic materials such as insulating coating agents, insulating films, etc .; semiconductor protective films; TFT-LCD electrode protective films. Recently, it has been studied to adopt a polyimide film as a flexible substrate utilizing its transparency, lightness, and flexibility in place of a glass substrate conventionally used as a substrate for display. As for the polyimide film as the flexible substrate, for example, Patent Documents 1 and 2 have been reported.
  • JP 2011-74384 A International Publication No. 2012/11820 Pamphlet
  • transparent polyimides are not sufficient for use as, for example, semiconductor insulating films, TFT-LCD insulating films, electrode protective films, ITO electrode substrates for touch panels, and heat-resistant substrates for flexible displays. .
  • a polyimide film is used as a flexible display substrate, the following steps are generally performed. First, a polyimide film is formed on a support glass by applying polyamic acid, which is a polyimide precursor, on a glass substrate as a support substrate, and then thermally curing it. Next, an inorganic film is formed on the upper surface of the polyimide film. And after forming a display element on this inorganic film, a flexible display is obtained by finally peeling the polyimide film which has a TFT element and an inorganic film from the said support glass.
  • polya polyimide film having low transparency is applied to a flexible display, color correction is required. In particular, when a film with extremely low transparency is used, correction becomes difficult.
  • the film applied to the flexible display needs to have high transparency.
  • Yellowness YI is widely used as an index of film transparency.
  • Patent Document 1 discloses a polyimide with a very low yellowness.
  • a polyimide having a low yellowness tends to have a high residual stress.
  • a polyimide with low yellowness does not have absorption in the wavelength (308 nm and 355 nm) of the laser used when peeling a film from the said support glass. Therefore, when such a polyimide film is applied to a flexible display, the energy required for laser peeling increases, or wrinkles tend to occur during peeling.
  • Patent Document 2 discloses a technique for reducing the residual stress while maintaining the glass transition temperature and Young's modulus of polyimide. This patent document aims to reduce peeling marks when the polyimide film is mechanically peeled while maintaining the adhesion between the polyimide film and the glass substrate. Patent Document 2 describes that the above object is achieved by introducing a block having a structure derived from a flexible silicon-containing diamine into a polymer chain of polyimide. Paragraphs 55 and 151 of the patent document state that the residual stress is reduced by forming a microphase-separated structure in which silicone has a uniform structure with a size of about 1 nm to 1 ⁇ m.
  • the present invention has been made in view of the above-described problems. That is, the present invention Low residual stress generated between the glass substrate and the inorganic film; Excellent adhesion to glass substrate; Preferably highly transparent; An object of the present invention is to provide a polyimide film which can be satisfactorily peeled even when the irradiation energy in the laser peeling step is low, and does not cause burning and particles, and a method for producing the same.
  • a polyimide film having a low YI and having a specific structure of voids has a high Tg, exhibits high adhesion between the glass substrate and the inorganic film, and further causes burns and particles in the laser peeling process. It has been found that the film has excellent peelability, and the present invention has been made based on this finding. That is, the present invention is as follows.
  • each R 1 independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or an aromatic having 6 to 10 carbon atoms.
  • a group; R 2 and R 3 are each independently a monovalent aliphatic hydrocarbon having 1 to 3 carbon atoms or an aromatic group having 6 to 10 carbon atoms;
  • X 1 is a tetravalent organic group having 4 to 32 carbon atoms; and
  • X 2 is a divalent organic group having 4 to 32 carbon atoms.
  • R 4 are each independently a single bond or a divalent organic group having 1 to 20 carbon atoms
  • R 5 and R 6 are each independently a monovalent organic group having 1 to 20 carbon atoms
  • R 7 is each independently a monovalent organic group having 1 to 20 carbon atoms when a plurality of R 7 are present
  • L 1 , L 2 , and L 3 are each independently an amino group, an isocyanate group, a carboxyl group
  • j is an integer from 3 to 200
  • k is an integer from 0 to 197.
  • Tetracarboxylic dianhydride is Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 4,4′-biphenyl
  • the mass of the compound represented by the general formula (3) used when synthesizing the resin precursor is the same as that of the compound represented by the tetracarboxylic dianhydride, the diamine, and the general formula (3).
  • the resin precursor according to [9] or [10] which is 6% by mass to 25% by mass in total.
  • a resin composition comprising the resin precursor according to any one of [8] to [11] and a solvent.
  • the resin composition according to [12] is developed to form a coating film,
  • the support and the coating film are heated under conditions of an oxygen concentration of 23% by mass or less and a temperature of 250 ° C. or more to imidize the resin precursor in the coating film and form voids in the coating film.
  • the polyimide film according to any one of claims 1 to 7, which is produced by [14] The polyimide film according to [13], wherein an oxygen concentration during the heating is 2,000 ppm or less.
  • the support and the coating film are heated under an oxygen concentration of 2,000 ppm or less and a temperature of 250 ° C. or more to imidize the resin precursor in the coating film and form voids in the coating film.
  • Heating step to obtain a polyimide film having voids A peeling step of peeling the polyimide film having the voids from the support;
  • the manufacturing method of a polyimide film characterized by having.
  • a flexible display comprising the polyimide film according to any one of [1] to [7], an inorganic film, and a TFT.
  • Non-Patent Document 1 discloses a method of producing a polyimide film having voids by using a polyimide precursor in which polypropylene oxide is introduced into a main chain or a side chain.
  • a coating film of a polyimide precursor having a polypropylene oxide portion is formed, a film structure in which polypropylene oxide is microphase-separated is obtained.
  • this coating film is heat-treated, a polyimide film having voids is obtained by simultaneous imidization and thermal decomposition of polypropylene oxide.
  • the present invention provides a polyimide film that achieves the above-mentioned object and a method for producing the same by a simple method without causing deterioration of film properties.
  • the residual stress generated between the glass substrate and the inorganic film is low, the adhesiveness with the glass substrate is excellent, preferably high transparency, and the irradiation energy is low in the laser peeling process. Even in such a case, it is possible to form a polyimide film that can be peeled off and does not cause burning of the polyimide film or generation of particles.
  • Example 1 STEM image (left) and SEM image (right) of Example 1 ATR spectra of the films obtained in Examples 1 and 2 and Reference Example SEM image of Example 7
  • the polyimide film having voids is a film made of polyimide having a void structure with a size of 100 nm or less.
  • the shape of the void can be a spherical structure, a flat elliptical sphere, or the like, and is preferably a flat elliptical sphere.
  • the maximum major axis diameter is preferably 100 nm or less on average, more preferably 80 nm or less, more preferably in the range of 10 to 70 nm, and most preferably in the range of 30 to 60 nm. It is. If the gap is larger than 100 nm, haze is generated in the polyimide film. When the thickness is 1 nm or less, sufficient peelability cannot be ensured at the time of laser peeling, and the polyimide film is burnt by laser irradiation, resulting in generation of particles.
  • the porosity of the polyimide film having voids according to the present embodiment is preferably in the range of 3% by volume to 15% by volume, and more preferably in the range of 6% by volume to 12% by volume.
  • the porosity is 3% by volume or more, the easy peelability at the time of laser peeling is improved, the burning of the polyimide film is suppressed, and the generation of particles tends to be suppressed. If the volume is 15% or less, the film tends to exhibit excellent physical properties.
  • This porosity can be calculated by image analysis in scanning transmission electron microscope (STEM) or scanning electron microscope (SEM) observation.
  • the voids in the polyimide film are preferably present uniformly throughout the film.
  • a polyimide film in which voids are present uniformly is preferable because it has a high tensile elongation and a low birefringence (Rth).
  • the gap is preferably uniform in the film thickness direction of the polyimide film.
  • the uniformity in the film thickness direction of the voids can be known by image analysis in cross-sectional observation of the polyimide film performed using STEM or SEM. The details are as follows: The obtained electron microscopic image is divided into regions of 2 ⁇ m in the film thickness direction, and the porosity is obtained for each region. For these void ratios, the difference between the maximum value and the minimum value is obtained.
  • the film thickness of the void It can be evaluated that the uniformity in the direction is high, which is preferable. This value is more preferably 3% or less, still more preferably 1% or less, and particularly preferably 0.5% or less.
  • the polyimide film of the present invention preferably includes a part of a silicone structure because of excellent adhesion and adhesion between the glass substrate and the inorganic film.
  • the inorganic film include CVD films such as silicon nitride and silicon oxide, and sputtered films.
  • the content (mass ratio) of the silicone residues contained in the polyimide film is preferably in the range of 3 to 15% by mass, and more preferably 6 to 12% by mass. When the content of the silicone residue exceeds 15% by mass, sufficient peelability cannot be ensured at the time of laser peeling, and the polyimide film may be burnt by laser irradiation, resulting in generation of particles. On the other hand, if this value is 3% by mass or less, sufficient adhesion to the glass substrate cannot be secured.
  • a method for specifically producing a polyimide film having a void structure according to this embodiment will be described below.
  • each R 1 independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or an aromatic having 6 to 10 carbon atoms.
  • a group; R 2 and R 3 are each independently a monovalent aliphatic hydrocarbon having 1 to 3 carbon atoms or an aromatic group having 6 to 10 carbon atoms;
  • X 1 is a tetravalent organic group having 4 to 32 carbon atoms; and
  • X 2 is a divalent organic group having 4 to 32 carbon atoms.
  • a resin composition comprising a resin precursor (polyamic acid) having a solvent and a solvent is spread on a substrate to form a coating film, By performing a heat treatment on the support and the coating film while controlling the oxygen concentration and the heating temperature, it is possible to form a polyimide film having voids having the structure as described above.
  • the unit structure 1 shown in the general formula (1) is a structure obtained by reacting tetracarboxylic dianhydride and diamine.
  • X 1 is derived from tetracarboxylic dianhydride and
  • X 2 is derived from diamine.
  • the unit structure 2 shown in the general formula (2) is a structure derived from a silicone monomer.
  • X 2 in the general formula (1) is 2,2′-bis (trifluoromethyl) benzidine, 4,4- (diaminodiphenyl) sulfone, 3,3- ( A residue derived from (diaminodiphenyl) sulfone is preferred. It is preferable that a part of R 2 and R 3 in the general formula (2) is a phenyl group. In the resin precursor of this invention, it is preferable that the total mass of the resin structure which consists of the said unit 1 and the said unit 2 is 30 mass% or more with respect to all the resin precursors.
  • tetracarboxylic dianhydride examples include aromatic tetracarboxylic dianhydrides having 8 to 36 carbon atoms, aliphatic tetracarboxylic dianhydrides having 6 to 50 carbon atoms, and carbon numbers. Is preferably a compound selected from 6-36 alicyclic tetracarboxylic dianhydrides.
  • the number of carbons herein includes the number of carbons contained in the carboxyl group.
  • examples of the aromatic tetracarboxylic dianhydride having 8 to 36 carbon atoms include 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (hereinafter also referred to as 6FDA), 5- ( 2,5-dioxotetrahydro-3-furanyl) -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride, pyromellitic dianhydride (hereinafter also referred to as PMDA), 1,2,3,4-benzene Tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (hereinafter also referred to as BTDA), 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (hereinafter also referred to as BPDA), 3, 3,4
  • Examples of the aliphatic tetracarboxylic dianhydride having 6 to 50 carbon atoms include ethylene tetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride; Examples of the alicyclic tetracarboxylic dianhydride having 6 to 36 carbon atoms include 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter also referred to as CBDA), cyclopentanetetracarboxylic dianhydride.
  • CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • Cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride (hereinafter referred to as CHDA), 3,3 ′, 4,4 '-Bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid ) Dianhydride, 1,2-ethylene-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4′-bis (cyclohexane-1,2) Dicarboxylic acid) dianhydride, 2,2-propylidene-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride,
  • the use of one or more selected from the group consisting of BTDA, PMDA, BPDA and TAHQ can reduce CTE, improve chemical resistance, improve glass transition temperature (Tg), and improve mechanical elongation. It is preferable from the viewpoint.
  • one or more selected from the group consisting of 6FDA, ODPA and BPADA to reduce yellowness, birefringence, and mechanical elongation. It is preferable from the viewpoint of improvement.
  • BPDA is preferable from the viewpoints of reducing residual stress, reducing yellowness, reducing birefringence, improving chemical resistance, improving Tg, and improving mechanical elongation.
  • CHDA is preferable from the viewpoints of reduction of residual stress and reduction of yellowness.
  • at least one selected from the group consisting of PMDA and BPDA having a tough structure that exhibits high chemical resistance, high Tg and low CTE, and low yellowness and birefringence, from 6FDA, ODPA and CHDA It is preferable to use in combination with at least one selected from the group consisting of high chemical resistance, residual stress reduction, yellowness reduction, birefringence reduction, and total light transmittance improvement. .
  • a component derived from biphenyltetracarboxylic acid (BPDA) is contained in an amount of 20 mol% or more of the total tetracarboxylic dianhydride-derived component of the resin precursor.
  • the resin precursor in this Embodiment is good also as a polyamideimide precursor by using dicarboxylic acid in addition to the above-mentioned tetracarboxylic dianhydride in the range which does not impair the performance.
  • dicarboxylic acids 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.
  • terephthalic acid is particularly preferable from the viewpoint of reducing the YI value and improving the Tg.
  • dicarboxylic acid is used together with tetracarboxylic dianhydride, it is obtained that the dicarboxylic acid is 50 mol% or less with respect to the total number of moles of the total of dicarboxylic acid and tetracarboxylic dianhydride. It is preferable from the viewpoint of chemical resistance in the film.
  • the resin precursor according to the present embodiment is, for example, 4,4- (diaminodiphenyl) sulfone (hereinafter also referred to as 4,4-DAS), 3,4 as diamine for deriving X 2 in unit 1.
  • 4,4-DAS 4,4- (diaminodiphenyl) sulfone
  • the structure represented by the general formula (2) is derived from a silicone monomer.
  • the amount of the silicone monomer used when synthesizing the resin precursor is preferably 6% by mass to 25% by mass based on the mass of the resin precursor. It is advantageous that the amount of the silicone monomer used is 6% by mass or more from the viewpoint of sufficiently obtaining the effect of reducing the stress generated between the resulting polyimide film and the inorganic film and the effect of reducing the yellowness. This value is more preferably 8% by mass or more, and further preferably 10% by mass or more.
  • the amount of the silicone monomer used is 25% by mass or less, which is advantageous from the viewpoint of improving the transparency and obtaining good heat resistance without causing the resulting polyimide film to become cloudy.
  • This value is more preferably 22% by mass or less, and further preferably 20% by mass or less.
  • the amount of silicone monomer used is particularly preferably 10% by mass or more and 20% by mass or less. .
  • the resin precursor coating is thermally cured under control of the oxygen concentration, a part of the silicone incorporated into the resin precursor is diluted in the form of cyclic trimer, cyclic tetramer, etc.
  • the introduction amount of the silicone monomer at the time of the resin precursor so that the mass ratio of the silicone remaining after the diffusion is in the range of 4 to 18% by mass with respect to the mass of the total polyimide film.
  • Examples of the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms in the general formula (2) include an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms; Examples of the aromatic group having 6 to 10 carbon atoms include an aryl group.
  • the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms from the viewpoint of heat resistance and residual stress.
  • a methyl group, an ethyl group, a propyl group, an isopropyl group examples thereof include a butyl group, an isobutyl group, a t-butyl group, a pentyl group, and a hexyl group.
  • the cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms from the above viewpoint, and specific examples thereof include a cyclopentyl group and a cyclohexyl group.
  • Specific examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, and a naphthyl group from the above viewpoint.
  • a plurality of R 4 are each independently a single bond or a divalent organic group having 1 to 20 carbon atoms;
  • R 5 and R 6 are each independently a monovalent organic group having 1 to 20 carbon atoms;
  • R 7 is each independently a monovalent organic group having 1 to 20 carbon atoms when a plurality of R 7 are present;
  • L 1 , L 2 , and L 3 are each independently an amino group, isocyanate group, carboxyl group, acid anhydride group, acid ester group, acid halide group, hydroxy group, epoxy group, or mercapto group;
  • j is an integer from 3 to 200, and
  • k is an integer from 0 to 197.
  • ⁇ Is preferably used.
  • Examples of the divalent organic group having 1 to 20 carbon atoms in R 4 include a methylene group, an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, and an arylene group having 6 to 20 carbon atoms. Can be mentioned.
  • the alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 2 to 10 carbon atoms from the viewpoint of heat resistance, residual stress and cost, and specifically, for example, dimethylene group, trimethylene group, tetramethylene group, pentamethylene group. Group, hexamethylene group and the like.
  • the cycloalkylene group having 3 to 20 carbon atoms is preferably a cycloalkylene group having 3 to 10 carbon atoms from the above viewpoint.
  • Specific examples include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and the like.
  • divalent aliphatic hydrocarbons having 3 to 20 carbon atoms are preferred from the above viewpoint.
  • the arylene group having 6 to 20 carbon atoms is preferably an aromatic group having 3 to 20 carbon atoms from the above viewpoint, and specific examples thereof include a phenylene group and a naphthylene group.
  • R 5 and R 6 have the same meanings as R 2 and R 3 in the general formula (2), and a preferred embodiment is as described above for the general formula (2).
  • the preferred embodiment of R 7 is the same as R 2 and R 3 .
  • j is an integer of 3 to 200, preferably an integer of 10 to 200, more preferably an integer of 20 to 150, still more preferably an integer of 30 to 100, particularly preferably 35 to 80. Is an integer.
  • k is an integer of 0 to 197, preferably 0 to 100, more preferably 0 to 50, and particularly preferably 0 to 25. When k exceeds 197, when a resin composition containing a resin precursor and a solvent is prepared, problems such as clouding of the composition may occur. When k is 0, it is preferable from the viewpoint of improving the molecular weight of the resin precursor and the heat resistance of the resulting polyimide. When k is 0, it is advantageous that j is 3 to 200 from the viewpoint of improving the molecular weight of the resin precursor and the heat resistance of the resulting polyimide.
  • L 1 , L 2 and L 3 are each independently an amino group, an isocyanate group, a carboxyl group, an acid anhydride group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, Or a mercapto group.
  • the amino group may be substituted.
  • Examples of the substituted amino group include a bis (trialkylsilyl) amino group.
  • Specific examples of the compound in which L 1 , L 2 , and L 3 in the general formula (3) are amino groups include amino end-modified methylphenyl silicone (for example, X22-1660B-3 (number average, manufactured by Shin-Etsu Chemical Co., Ltd.) Molecular weight 4,400) and X22-9409 (number average molecular weight 1,300)); both-end amino-modified dimethyl silicone (for example, X22-161A (number average molecular weight 1,600), X22-161B (number manufactured by Shin-Etsu Chemical Co., Ltd.)) Average molecular weight 3,000) and KF8012 (number average molecular weight 4,400); BY16-835U (number average molecular weight 900) manufactured by Toray Dow Corning; and Silaplane FM3311 (number average molecular weight 1000 manufactured by Chi
  • L 1 , L 2 , and L 3 are carboxyl groups
  • X22-162C number average molecular weight 4,600
  • BY16-880 number average manufactured by Toray Dow Corning
  • L 1 , L 2 and L 3 are acid anhydride groups
  • L 1 , L 2 and L 3 are acid anhydride groups
  • L 1 , L 2 , and L 3 are acid anhydride groups
  • X22-168AS manufactured by Shin-Etsu Chemical, number average molecular weight 1,000
  • X22-168A manufactured by Shin-Etsu Chemical, number average.
  • Molecular weight 2,000 Molecular weight 2,000
  • X22-168B manufactured by Shin-Etsu Chemical, number average molecular weight 3,200
  • X22-168-P5-8 manufactured by Shin-Etsu Chemical, number average molecular weight 4,200
  • DMS-Z21 manufactured by Gerest, Number average molecular weight 600 to 800.
  • Specific examples of the compound in which L 1 , L 2 , and L 3 are acid ester groups include a reaction of the compound in which L 1 , L 2 , and L 3 are carboxyl groups or acid anhydride groups with an alcohol. And the like.
  • L 1 , L 2 and L 3 are acid halide groups include carboxylic acid chlorides, carboxylic acid fluorides, carboxylic acid bromides, carboxylic acid iodides and the like.
  • L 1 , L 2 , and L 3 are hydroxy groups
  • KF-6000 manufactured by Shin-Etsu Chemical, number average molecular weight 900
  • KF-6001 manufactured by Shin-Etsu Chemical, number average molecular weight 1,800
  • KF-6002 manufactured by Shin-Etsu Chemical, number average molecular weight 3,200
  • KF-6003 manufactured by Shin-Etsu Chemical, number average molecular weight 5,000
  • a compound having a hydroxy group is considered to react with a compound having a carboxyl group or an acid anhydride group.
  • L 1 , L 2 , and L 3 are epoxy groups
  • X22-163 manufactured by Shin-Etsu Chemical, number average molecular weight 400
  • KF-105 manufactured by Shin-Etsu Chemical, Number average molecular weight 980
  • X22-163A manufactured by Shin-Etsu Chemical, number average molecular weight 2,000
  • X22-163B manufactured by Shin-Etsu Chemical, number average molecular weight 3,500
  • X22-163C manufactured by Shin-Etsu Chemical, number average molecular weight 5)
  • both end alicyclic epoxy type X22-169AS (manufactured by Shin-Etsu Chemical, number average molecular weight 1,000), X22-169B (manufactured by Shin-Etsu Chemical, number average molecular weight 3,400); X22-9002 (manufactured by Shin-E
  • L 1 , L 2 , and L 3 are mercapto groups
  • L 1 , L 2 , and L 3 are mercapto groups
  • X22-167B manufactured by Shin-Etsu Chemical, number average molecular weight 3,400
  • X22-167C manufactured by Shin-Etsu Chemical, number average molecular weight 4
  • 600 A compound having a mercapto group is considered to react with a compound having a carboxyl group or an acid anhydride group.
  • L 1 , L 2 , and L 3 are each independently preferably an amino group or an acid anhydride group from the viewpoint of improving the molecular weight of the resin precursor or the heat resistance of the resulting polyimide. From the viewpoint of avoiding white turbidity of the resin composition containing the precursor and the solvent, and from the viewpoint of cost, It is preferable that all of L 1 , L 2 and L 3 are amino groups; or L 1 and L 2 are each independently an amino group or an acid anhydride group, and k is 0. . In the latter case, it is more preferable that both L 1 and L 2 are amino groups.
  • the number average molecular weight of the resin precursor according to the present embodiment is preferably 3,000 to 1,000,000, more preferably 5,000 to 500,000, still more preferably 7,000 to 300,000. 000, particularly preferably 10,000 to 250,000.
  • the molecular weight is preferably 3,000 or more from the viewpoint of obtaining good heat resistance and strength (for example, high elongation), and is 1,000,000 or less to obtain good solubility in a solvent. From the viewpoint, it is preferable from the viewpoint that coating can be performed without bleeding at a desired film thickness at the time of processing such as coating. From the viewpoint of obtaining a high mechanical elongation, the molecular weight is preferably 50,000 or more.
  • the number average molecular weight is a value determined by standard polystyrene conversion using gel permeation chromatography.
  • the resin precursor according to the present embodiment may be partially imidized.
  • the imidation of the resin precursor can be performed by known chemical amidation or thermal amidation. Of these, thermal imidization is preferred.
  • the imidization rate can be controlled by controlling the heating temperature and the heating time.
  • the range of the imidization rate is preferably 5% to 70% from the viewpoint of solubility in a solution and storage stability.
  • N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal or the like may be added to the above resin precursor and heated to esterify a part or all of the carboxylic acid.
  • the viscosity stability at the time of storage at room temperature of a resin composition can be improved.
  • the resin precursor according to the present embodiment as described above is preferably used as a resin composition (varnish) obtained by dissolving it in a solvent. With this configuration, a transparent polyimide film can be produced without requiring a special solvent combination.
  • the resin composition according to the present embodiment is an aspect of a resin precursor obtained by reacting tetracarboxylic dianhydride, diamine, and silicone monomer by dissolving them in a solvent, for example, an organic solvent. It can be produced as a polyamic acid solution containing a polyamic acid and a solvent.
  • the conditions at the time of reaction are not particularly limited, and examples thereof include a reaction temperature of ⁇ 20 to 150 ° C. and a reaction time of 2 to 48 hours. In order to sufficiently proceed the reaction with the silicone monomer, it is preferable to perform heating for about 30 minutes or more at a temperature of 120 ° C. or higher during the synthesis reaction.
  • the reaction is preferably performed in an inert atmosphere such as argon or nitrogen.
  • the solvent is not particularly limited as long as it is a solvent that dissolves polyamic acid.
  • reaction solvents include dimethylene glycol dimethyl ether (DMDG), m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone,
  • DMDG dimethylene glycol dimethyl ether
  • NMP N-methyl-2-pyrrolidone
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • DMSO dimethyl sulfoxide
  • One or more polar solvents selected from diethyl acetate, ecamide M100 (trade name: manufactured by Idemitsu Kosan Co., Ltd.), and ecamide B100 (trade name: manufactured by Idemitsu Kosan Co., Ltd.) are useful.
  • a low-boiling solution such as tetrahydrofuran (THF) or chloroform, or a low-absorbing solvent such as ⁇ -butyrolactone may be used together with or in place of the above solvent.
  • THF tetrahydrofuran
  • a low-absorbing solvent such as ⁇ -butyrolactone
  • an alkoxysilane compound is added to 100% by mass of the resin precursor in order to give the obtained polyimide film sufficient adhesion to the support. It may contain.
  • the content of the alkoxysilane compound is 0.01% by mass or more with respect to 100% by mass of the resin precursor, good adhesion to the support can be obtained, and the content of the alkoxysilane compound is It is preferable that it is 2 mass% or less from a viewpoint of the storage stability of a resin composition.
  • the content of the alkoxysilane compound is more preferably 0.02 to 2% by mass, still more preferably 0.05 to 1% by mass, and more preferably 0.05 to 0.5% with respect to the resin precursor. It is particularly preferable that the content is 1% by mass, and particularly preferable is 0.1 to 0.5% by mass.
  • alkoxysilane compounds include 3-ureidopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, phenyltrimethoxysilane, and ⁇ -aminopropyl.
  • the polyimide resin film having a void structure forms the coating film by developing the above resin composition on the surface of the support, It can be produced by heating the support and the coating film under conditions of an oxygen concentration of 23% by mass or less and a temperature of 250 ° C. or more.
  • the unit “mass%” relating to the oxygen concentration is a percentage based on volume
  • the unit “ppm” relating to the oxygen concentration which will be described later is a percentage based on volume.
  • the support is an inorganic substrate such as a glass substrate such as a non-alkali glass substrate, but is not particularly limited.
  • the method for spreading the polyimide precursor on the substrate include known coating methods such as spin coating, slit coating, and blade coating.
  • the solvent is evaporated by heating to 80 ° C. to 200 ° C. using a hot plate, oven, or the like, and a coating film (pre-baked film) is produced.
  • the silicone portion and the polyimide portion of the resin precursor form a film forming a microphase separation structure.
  • the support and the coating film are put into an oven having an oxygen concentration of 23% by mass or less, and heated to 250 ° C. or more to dehydrate and imidize the resin precursor, and at the same time, the silicone part that is microphase-separated.
  • a polyimide film according to the present embodiment can be created by disassembling and removing a part to form a void. By heating at 250 ° C. or higher, it is considered that the silicone portion in the resin precursor is thermally decomposed to form a cyclic trimer and / or a cyclic tetramer and is evaporated and removed.
  • the coated support may be put into an oven with controlled oxygen concentration as it is and heated to 250 ° C. or higher.
  • the size and porosity of the voids can be controlled, for example, by setting the silicone content in the polymer, the curing temperature, the curing time, the oxygen concentration, etc. within appropriate ranges. Specifically, for example, when the introduction amount of the silicone moiety represented by the general formula (2) in the resin precursor is increased, the silicone domain size in the pre-baked film increases.
  • the size of the silicone domain structure is one factor that controls the void structure. If the silicone part is completely pyrolyzed, the domain size in the prebaked film will be the maximum size of the voids in the resulting polyimide film. Therefore, by controlling the silicone domain size in the pre-baked film, the void size (major axis average) in the resulting polyimide film can be controlled.
  • the mass ratio of the silicone portion represented by the general formula (2) in the resin precursor may be 25% by mass or less of the entire resin precursor.
  • the size relationship between the size of the void in the polyimide film and the domain size of the silicone in the pre-baked film is It can be adjusted to any degree.
  • the oxygen concentration during heating in the present embodiment is preferably 2,000 ppm or less.
  • the oxygen concentration at the time of heating is within this range, uniform voids tend to occur in the film. Therefore, the tensile elongation of the film is high and the birefringence (Rth) tends to be low, which is preferable.
  • the uniformity of the voids in the film thickness direction tends to be slightly impaired. This phenomenon is presumed to be caused by the fact that the thermal decomposition reaction of the silicone portion of the resin precursor hardly occurs when the oxygen concentration is 2,000 ppm or more.
  • the present inventors under conditions where a significant amount of oxygen exists, the organic group on the silicon atom of the silicone is oxidized by oxygen, for example, formaldehyde, formic acid, hydrogen, carbon dioxide, etc., It is presumed that this is because it is converted into a highly crosslinked gel-like heat-resistant polymer.
  • oxygen for example, formaldehyde, formic acid, hydrogen, carbon dioxide, etc.
  • the heating temperature is preferably in the range of 250 ° C. to 480 ° C., and more preferably in the range of 280 ° C. to 450 ° C.
  • the oxygen concentration is controlled to 100 ppm or less, and the heating temperature is controlled in the range of 280 ° C. to 450 ° C.
  • the inert gas used when controlling the oxygen concentration include nitrogen gas and Ar gas. Nitrogen gas is preferable from the economical viewpoint. In order to control the oxygen concentration, heating may be performed under reduced pressure using a vacuum oven or the like.
  • the thickness of the polyimide film according to the present embodiment is not particularly limited, and is preferably in the range of 1 to 200 ⁇ m, more preferably 5 to 50 ⁇ m. Furthermore, the polyimide film according to the present embodiment preferably has a residual stress at a thickness of 10 ⁇ m of 25 MPa or less.
  • the polyimide film according to this embodiment preferably has a yellowness (YI) at a film thickness of 20 ⁇ m of 7 or less.
  • YI value of the polyimide film at a film thickness of 20 ⁇ m is more preferably 6 or less, and particularly preferably 5 or less.
  • the yellowness degree in thickness 20 micrometers can be known by performing thickness conversion with respect to the measured value of this film.
  • the present invention also provides a laminate comprising a support and a polyimide film formed on the support.
  • the laminate is formed by spreading the above resin composition on the surface of the support to form a coating film, It can be obtained by heating the support and the coating film under conditions of an oxygen concentration of 23% by mass or less and a temperature of 250 ° C. or more.
  • This laminated body is used for manufacturing a flexible device, for example. More specifically, a semiconductor device is formed on a polyimide film having a relative relationship, and then the support is peeled off to obtain a flexible device composed of the polyimide film and the semiconductor device formed thereon.
  • the polyimide film according to the present embodiment has a specific void structure, so that the residual stress generated between the glass substrate or the inorganic film is low and the adhesiveness to the glass substrate is excellent. Moreover, even when the irradiation energy is low in the laser peeling process, good peeling is possible, and no burning and particles are generated. Therefore, the polyimide film according to the present embodiment is extremely suitable for application as a substrate of a flexible display.
  • a polyimide film as a flexible substrate is formed thereon using a glass substrate as a support, and a TFT or the like is further formed thereon.
  • the process of forming the TFT is typically performed at a wide range of temperatures from 150 to 650 ° C.
  • TFT-IGZO (InGaZnO) oxide semiconductors and TFTs are mainly formed at around 250 ° C. to 450 ° C. .
  • the glass substrate warps and breaks when it shrinks during normal temperature cooling after expansion in the high temperature TFT formation process, from the glass substrate of the flexible substrate. This causes problems such as peeling.
  • the thermal expansion coefficient of a glass substrate is smaller than that of a resin, a residual stress is generated between the flexible substrate and the resin film.
  • the residual stress generated between the polyimide film according to the present embodiment and the glass is 25 MPa or less on the basis of the film thickness of 10 ⁇ m.
  • the polyimide film according to the present embodiment has a tensile strength of 30% or more on the basis of a film thickness of 20 ⁇ m from the viewpoint of improving yield by being excellent in breaking strength when handled as a flexible substrate. It is preferable. In particular, when the tensile elongation is 33% or more, when an inorganic film on the polyimide film is provided, peeling or cracking of the film tends not to occur. Among these, 40% or more is particularly preferable.
  • the polyimide film according to this embodiment has at least one glass transition temperature in each of the ⁇ 150 ° C. to 0 ° C. region and the 150 ° C. to 380 ° C. region, and is greater than 0 ° C. and less than 150 ° C. It is preferred not to have a glass transition temperature in the region.
  • the polyimide film according to the present embodiment preferably has a glass transition temperature of 250 ° C. or higher in the high temperature region so as not to be softened at the TFT element forming temperature.
  • the polyimide film according to the present embodiment has chemical resistance that can withstand a photoresist stripping solution in a photolithography process used when manufacturing a TFT element.
  • the top emission method has a feature that it is easy to increase the aperture ratio because the TFT element does not get in the way.
  • the bottom emission method is characterized by easy alignment and easy manufacture. If the TFT element is transparent, it is possible to improve the aperture ratio even in the bottom emission method. Therefore, it is expected that a bottom emission method that is easy to manufacture will be adopted as a large organic EL flexible display. ing.
  • the resin substrate is disposed on the side to be visually recognized. Therefore, the resin substrate is required to have particularly low yellowness (YI value) and high total light transmittance from the viewpoint of improving the image quality.
  • the polyimide film and laminate according to the present embodiment can be suitably used particularly as a substrate, for example, in the production of semiconductor insulating films, TFT-LCD insulating films, electrode protective films, flexible devices, and the like.
  • the flexible device is, for example, a flexible display, a flexible solar cell, a flexible touch panel electrode substrate, flexible lighting, a flexible battery, or the like.
  • the polyimide film according to the present embodiment satisfying the above various physical properties can be used particularly for applications in which use is limited by the yellow color of existing polyimide films, particularly for colorless transparent substrates for flexible displays.
  • the polyimide film according to the present embodiment includes, for example, a protective film, a light-diffusing sheet and a coating film (for example, TFT-LCD interlayer, gate insulating film, liquid crystal alignment film, etc.) in TFT-LCD, It can be used in fields requiring colorless and transparent and low birefringence, such as ITO substrates for touch panels and cover glass substitute resin substrates for smartphones.
  • a coating film for example, TFT-LCD interlayer, gate insulating film, liquid crystal alignment film, etc.
  • the resin precursor composition obtained in each synthesis example was applied to a non-alkali glass substrate (thickness 0.7 mm) with a bar coater, leveled at room temperature for 5 to 10 minutes, and then subjected to a vertical curing oven (Koyo).
  • a polyimide film having a film thickness of 20 ⁇ m is formed on a glass substrate by heating (prebaking) at 140 ° C. for 60 minutes using a Lindberg company, model name VF-2000B), and further heating in a hot air oven under a nitrogen atmosphere for 60 minutes.
  • the oxygen concentration and the curing temperature in the hot air oven were set as shown in Table 1.
  • the oxygen concentration meter As the oxygen concentration meter, a zirconia LC-750L manufactured by Toray Engineering Co., Ltd. was used. After the cured laminate was immersed in water and allowed to stand for 24 hours, the polyimide film was peeled from the glass and subjected to the following evaluations. However, the evaluation of laser peelability and the measurement of adhesive strength were carried out in a state where they were not peeled off from the glass substrate, and the polyimide film was formed separately for evaluation of residual stress and infrared measurement.
  • the cured polyimide film was cut into a size of 5 mm ⁇ 50 mm, and was pulled at a speed of 100 mm / min using a tensile tester (manufactured by A & D Co., Ltd .: RTG-1210), and the tensile elongation was measured.
  • the glass transition temperature and linear expansion coefficient (CTE) in the region above room temperature were measured by thermomechanical analysis using a cured polyimide film cut to a size of 5 mm ⁇ 50 mm as a test piece. Using a thermomechanical analyzer (TMA-50) manufactured by Shimadzu Corporation as a measuring device, in a temperature range of 50 to 450 ° C. under conditions of a load of 5 g, a heating rate of 10 ° C./min and a nitrogen stream (flow rate of 20 ml / min). The test piece elongation was measured. The inflection point of the obtained chart was determined as the glass transition temperature, and the CTE of the polyimide film at 100 to 250 ° C. was determined.
  • TMA-50 thermomechanical analyzer manufactured by Shimadzu Corporation
  • ⁇ void ratio was used as an index of uniformity in the film thickness direction of the void. When this value is 5% or less, it can be evaluated that the uniformity of the voids in the film thickness direction is high. This value is more preferably 3% or less, still more preferably 1% or less, and particularly preferably 0.5% or less.
  • SAXS small angle X-ray scattering measurement
  • the polyimide film after heating at the oxygen concentration and curing temperature shown in Table 1 was also measured in the same manner as described above, and the absorbance at 1,100 cm ⁇ 1, which is the absorption of SiO bond, was obtained.
  • the residual ratio of silicone residues was estimated by comparing the value of the pre-baked film and the value of the cured polyimide film.
  • the silicone content in the obtained polyimide film was computed from the preparation amount of the silicone monomer at the time of synthesize
  • As a measuring apparatus of ATR “Nicolet Continium” manufactured by Thermo Fisher Scientific Co., Ltd. was used. In FIG. 2, the ATR spectrum of the film obtained by Example 1, 2 and the reference example was shown.
  • the chart of FIG. 2 is a spectrum of the films obtained in Reference Example 1, Example 2, and Example 1 in order from the top.
  • the polyimide film of the laminate obtained above is cut using a cutter knife with two cuts having a width of 10 mm and a length of 100 mm, the end is peeled off and sandwiched between chucks, and the tensile speed is 100 mm / min. 180 ° peel strength was measured.
  • As a tensile tester RTG-1210 manufactured by A & D Corporation was used.
  • both-end amine-modified methylphenyl silicone oil manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4,400)
  • a silicone monomer solution obtained by dissolving in 298 g of NMP was added dropwise from a dropping funnel.
  • the oil bath was removed and the temperature was returned to room temperature to obtain an NMP solution (resin precursor composition) of a transparent resin precursor (polyamic acid). It was.
  • the number average molecular weight (Mn) of the polyamic acid obtained here was about 33,000.
  • a silicone monomer solution obtained by dissolving 113.64 g of silicone monomer X22-1660B-3 (17% by mass with respect to the whole resin precursor) in 568 g of NMP was dropped from a dropping funnel. After completion of dropping, the mixture was stirred at room temperature for 1 hour, heated to 80 ° C., stirred for 4 hours, and then returned to room temperature by removing the oil bath, thereby transparent NMP containing polyamic acid having an average molecular weight of 62,000. A solution (resin precursor composition) was obtained.
  • Synthesis Example 8 A transparent containing polyamic acid having a number average molecular weight of 58,000 was carried out in the same manner as in Synthesis Example 7 except that the amount of TFMB added was 317.02 g (0.99 mol) and no silicone monomer solution was added. NMP solution (resin precursor composition) was obtained.
  • Examples 1 to 18 and Comparative Examples 1 to 3 Using the resin precursor composition synthesized in the above synthesis example, a polyimide film was produced under the conditions of oxygen concentration and cure temperature described in Table 1 according to the above-described method, and various evaluations were performed. The evaluation results are shown in Tables 2 and 3. In FIG. 1, the STEM image (left) and SEM image (right) which image
  • Reference example 1 This reference example was carried out in order to verify that when the curing temperature was lowered, all of the silicone component remained in the film and no voids were formed.
  • a film was formed by the above-described method except that the resin precursor composition obtained in Synthesis Example 1 was used and the curing conditions were an oxygen concentration of 50 ppm and a curing temperature of 95 ° C., and ATR measurement and electron microscope observation were performed. It was. The results are shown in Table 2.
  • the difference in electron density between domain structures in the sea-island structure obtained by SAXS observation is in the examples, since the value was close to the difference in electron density between polyimide and air, voids were formed in the film; In one comparative example, since the value was close to the difference in electron density between polyimide and silicone, no voids were formed; Each was confirmed.
  • the cross-sectional STEM image of the film thickness direction of Example 1 it can confirm that an island part is white. From this, it can be determined that the island portion is a void. Similarly, from the SEM image, it can be confirmed that the island portion is recessed, so that it can be determined that the portion is a void.
  • the polyimide film obtained from the resin precursor according to the present invention has low residual stress generated between the glass substrate and the inorganic film, excellent adhesion to the glass substrate, and irradiation energy in the laser peeling process. It was confirmed that good peeling is possible even when the film thickness is low, and that no burning of the polyimide film or generation of particles occurs at the time of peeling.
  • the polyimide film of the present invention can be suitably used for, for example, semiconductor insulating films, TFT-LCD insulating films, electrode protective films, flexible display substrates, touch panel ITO electrode substrates, and the like. It is particularly useful as various substrates.

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KR20180018392A (ko) * 2016-08-10 2018-02-21 신닛테츠 수미킨 가가쿠 가부시키가이샤 폴리이미드 전구체 및 폴리이미드, 투명 폴리이미드 필름의 제조방법
JP2018028053A (ja) * 2016-08-10 2018-02-22 新日鉄住金化学株式会社 透明ポリイミドフィルムの製造方法
CN107799668A (zh) * 2016-08-31 2018-03-13 株式会社半导体能源研究所 半导体装置的制造方法
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JP2019172970A (ja) * 2018-03-26 2019-10-10 東レ株式会社 表示デバイスまたは受光デバイスの基板用樹脂組成物、並びに、それを用いた表示デバイスまたは受光デバイスの基板、表示デバイス、受光デバイス、表示デバイスまたは受光デバイスの製造方法。
WO2019188380A1 (ja) * 2018-03-30 2019-10-03 株式会社カネカ ポリアミド酸およびその製造方法、ポリアミド酸溶液、ポリイミド、ポリイミド膜、積層体およびその製造方法、ならびにフレキシブルデバイスおよびその製造方法
JPWO2019188380A1 (ja) * 2018-03-30 2021-04-01 株式会社カネカ ポリアミド酸およびその製造方法、ポリアミド酸溶液、ポリイミド、ポリイミド膜、積層体およびその製造方法、ならびにフレキシブルデバイスおよびその製造方法
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