WO2019142866A1 - 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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Publication number
WO2019142866A1
WO2019142866A1 PCT/JP2019/001296 JP2019001296W WO2019142866A1 WO 2019142866 A1 WO2019142866 A1 WO 2019142866A1 JP 2019001296 W JP2019001296 W JP 2019001296W WO 2019142866 A1 WO2019142866 A1 WO 2019142866A1
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Prior art keywords
resin composition
polyimide film
polyimide
polyimide precursor
film
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PCT/JP2019/001296
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English (en)
French (fr)
Japanese (ja)
Inventor
昌樹 米谷
直志 篠原
慶太 小川
隆行 金田
敏章 奥田
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旭化成株式会社
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Priority to KR1020207009549A priority Critical patent/KR102417292B1/ko
Priority to CN201980006444.7A priority patent/CN111479854B/zh
Priority to JP2019566503A priority patent/JP7564621B2/ja
Priority to KR1020227022370A priority patent/KR102650759B1/ko
Publication of WO2019142866A1 publication Critical patent/WO2019142866A1/ja
Priority to JP2022128316A priority patent/JP7536836B2/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
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • G09F9/301—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 flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
    • 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
    • G09F9/302—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 characterised by the form or geometrical disposition of the individual elements
    • 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 resin composition containing a polyimide precursor, and a polyimide film.
  • the invention further relates to flexible devices (e.g. flexible displays) and laminates and methods of making them.
  • Polyimide resins are insoluble and infusible super heat-resistant resins, and have excellent heat resistance properties (for example, heat oxidation resistance), radiation resistance, low temperature resistance, chemical resistance, and the like. For this reason, polyimide resins are used in a wide range of fields including electronic materials. Examples of application of the polyimide resin in the field of electronic materials include, for example, an insulating coating material, an insulating film, a semiconductor, an electrode protective film of a thin film transistor liquid crystal display (TFT-LCD), and the like. Recently, in place of the glass substrate conventionally used in the field of display materials, adoption of a flexible substrate utilizing its lightness and flexibility has been considered.
  • TFT-LCD thin film transistor liquid crystal display
  • Patent Document 1 discloses a resin precursor (weight-average molecular weight 30,000 to 90,000) which is polymerized from bis (diaminodiphenyl) sulfone (hereinafter also referred to as DAS) and has a siloxane unit, and the precursor is cured
  • DAS bis (diaminodiphenyl) sulfone
  • Patent Document 2 describes a resin composition comprising a polyimide precursor of a specific absorbance and an alkoxysilane compound of a specific absorbance, which is obtained by curing the resin composition. It is described that the resin to be prepared has both sufficient adhesiveness with the support and releasability by laser exfoliation and the like.
  • a resin composition containing a polyimide precursor is coated on a substrate such as glass to form a coating, which is then dried by heating, and further a polyimide precursor Is imidized to form a polyimide film, and if necessary, a device is formed on the film, and then the film is peeled off from a glass substrate as a support to obtain the desired product.
  • a slit coater when a composition containing a polyimide precursor is applied to a substrate such as glass, a slit coater may be used.
  • a coater gap (a set value for defining the distance between a glass substrate and a slit nozzle) is provided as a parameter that affects the coating film. If the size is small, the nozzle may come in contact with the substrate when the flatness of the glass substrate is poor, and the slit nozzle may be broken.
  • an object of the present invention is to provide a polyimide precursor-containing resin composition which is excellent in coating properties of slit coat and also in mechanical properties and optical properties required for applications such as flexible substrates. .
  • the present inventors have found that using a polyimide precursor having a specific structure leads to the realization of good coating properties in slit coat and good mechanical and optical properties. . That is, the present invention includes the following aspects.
  • the following formula (1) In the formula, when there are a plurality of R 1 's each independently represent a divalent organic group, and when there are a plurality of R 2' s each represent a tetravalent organic group independently, n is a positive integer.
  • a resin composition comprising a polyimide precursor having a structure represented by The weight average molecular weight of the polyimide precursor is 110,000 to 250,000, A resin composition, wherein the solid content of the resin composition is 10 to 25% by mass.
  • the shear rate dependency (TI) represented by the following formula is 0.9 to 1.1 when the viscosity of the resin composition is measured at 23 ° C. with a temperature controlled viscometer
  • the resin composition according to the above aspect 1 or 2 wherein the resin composition is a resin composition for slit coat.
  • At least one of R 1 in the formula (1) is a group represented by the following formula (2):
  • the polyimide precursor has the following formula (3): [Wherein, each of R 3 and R 4 independently represents a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms, when there are a plurality of each. , And m is an integer of 1 to 200.
  • the resin composition according to any one of the above aspects 1 to 4 which has a structure represented by [6]
  • the polyimide precursor is a copolymer of tetracarboxylic acid dianhydride containing 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride and diamine
  • the polyimide precursor is a copolymer of tetracarboxylic dianhydride and diamine, and the tetracarboxylic dianhydride is pyromellitic dianhydride and 3,3 ′, 4,4 ′.
  • -Biphenyltetracarboxylic acid dianhydride at a molar ratio of 20:80 to 80:20 of the pyromellitic acid dianhydride and the 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride,
  • the resin composition according to any one of the above embodiments 1 to 7.
  • the polyimide precursor is tetracarboxylic acid dianhydride, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 2,2′-bis (trifluoromethyl) benzidine and 9, 9.
  • the resin composition according to any one of the above embodiments which is a resin composition for a flexible device.
  • a flexible device comprising the polyimide film according to the above-mentioned aspect 13 or 14.
  • a flexible display comprising the polyimide film according to the above-mentioned aspect 13 or 14.
  • the flexible display according to the above-mentioned aspect 16 wherein the polyimide film is disposed at a place to be viewed when the flexible display is observed from the outside.
  • At least one of R 1 in the formula (1) is a group represented by the following formula (2):
  • the polyimide precursor is represented by the following formula (3): [Wherein, each of R 3 and R 4 independently represents a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms, when there are a plurality of each. , And m is an integer of 1 to 200. ]
  • the manufacturing method of the polyimide film of said 19 or 20 which has a structure represented by ⁇ .
  • a polyimide precursor-containing resin composition which is excellent in coating properties in slit coating and also excellent in mechanical properties and optical properties required for applications such as flexible substrates.
  • n is a positive integer.
  • the resin composition containing the polyimide precursor which has a structure represented by these is provided.
  • the resin composition comprises the polyimide precursor and a solvent.
  • At least one of R 1 in formula (1) is a group of the following formula (2): Is a group represented by
  • That at least one of R 1 in the formula (1) is a structure represented by the formula (2) contributes to good optical properties (especially Rth) and heat resistance of the polyimide which is a cured product of the polyimide precursor .
  • all of the n R 1 s in Formula (1) have a structure represented by Formula (2).
  • the ratio of the structure represented by Formula (2) to n R 1 in Formula (1) may be 0% or more, 10% or more, or 20% or more. It may be 100% or less, or 90% or less.
  • the embodiment is also a resin composition containing a polyimide precursor having a structure represented by the above formula (1), wherein the polyimide which is a cured product of the resin composition has a thickness direction retardation (Rth) 300. Also provided is a resin composition having the following and / or a yellowness (YI) of 20 or less.
  • the above low thickness direction retardation (Rth) indicates that the polyimide has low birefringence, and the above low yellowness (YI) indicates that the polyimide has a good color tone (that is, it is almost colorless) It represents that it is.
  • the resin composition of the present embodiment preferably has an excellent slit coat performance and gives a polyimide film having excellent mechanical properties and optical properties, so it is preferably for flexible devices (for example, for flexible substrates), particularly preferably It is useful for flexible displays.
  • the weight average molecular weight of the polyimide precursor is 110,000 or more and 250,000 or less.
  • the present inventor found that the weight average molecular weight of the polyimide precursor greatly affects the coating performance when using the resin composition of the present embodiment for slit coating, and has conducted intensive studies.
  • the weight average molecular weight of the polyimide precursor is 110,000 or more, the solid content of the resin composition can be adjusted to realize a good slit coat, while the weight average molecular weight is 250,000 or less
  • the polyimide precursor is found to be easy to manufacture. That is, in the present embodiment, the weight average molecular weight of the polyimide precursor is 110,000 or more in terms of coating performance, and 250,000 or less in terms of ease of manufacture.
  • the desired weight average molecular weight of the polyimide precursor may vary depending on the desired application, 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.
  • preferable examples of the lower limit of the weight average molecular weight are 111,000, 112,000, 113,000, 114,000, 115,000, 116,000, 117,000, 118,000, 119,000, 120, 90, 120. 000, 121,000, 122,000, 123,000, 124,000, 125,000, 126,000, 127,000, 128,000, 129,000, 130,000, 131,000, 132,000, 133,000, 134,000, 135,000, 136,000, 137,000, 138,000, 139,000, 140,000, 141,000, 142,000, 143,000, 144,000, 145, 000, 146,000, 147,000, 148,000, 149,00 , 150,000, 151,000, 152,000, 153,000, 154,000, 155,000, 156,000, 157,000, 158,000, 159,000, 160,000, 161,000, 162 000, 163,000, 164,000, 165,000, 166,000, 167,000, 168,000, 169,000, 170,000, 171,000, 172,000, 173,000, 174,000 , 175,000, 176,000, 177,000, 178,000, 179,000, 180,000, 181,000, 182,000, 183,000, 184,000, 185,000, 18
  • preferable examples of the upper limit of the weight average molecular weight are 249,000, 248,000, 247,000, 246,000, 245,000, 244,000, 243,000, 242,000, 241,000, 240, 240.
  • a weight average molecular weight of 120,000 or more is preferable 130,000 or more is more preferable, and 160,000 or more is particularly preferable.
  • a weight average molecular weight of the polyimide precursor is 160,000 or more and 220,000 or less.
  • Rth is 300 nm or less from the viewpoint of obtaining a low birefringence polyimide film.
  • Rth is preferably 200 nm or less, more preferably 100 nm or less, more preferably 80 nm or less, more preferably 50 nm or less, and particularly preferably 30 nm. If Rth is 300 nm or less, it is easy to capture an image correctly, and in particular, if Rth is 200 nm or less, color reproducibility of the image is good.
  • the polyimide film has a retardation in the thickness direction (Rth) of 10 ⁇ m or less in the thickness direction of 300 nm or less and / or a yellowness (YI) of 10 ⁇ m or less in the film thickness of 20 or less.
  • the polyimide film has a thickness direction retardation (Rth) in terms of a film thickness of 10 ⁇ m of 300 nm or less, and a yellowness (YI) in terms of a film thickness of 10 ⁇ m of 20 or less.
  • the yellowness of polyimide film is 20 or less in view of obtaining good optical characteristics. And preferably 18 or less, more preferably 16 or less, further preferably 14 or less, further preferably 13 or less, still more preferably 10 or less, particularly preferably 7 or less.
  • the YI at a film thickness of 10 ⁇ m of the polyimide film varies depending on the monomer skeleton of the polyimide precursor, but if the monomer skeleton is the same, the larger the weight average molecular weight of the polyimide precursor, the smaller the YI tends to be.
  • the residual stress generated between the polyimide film and the glass substrate at a film thickness of 10 ⁇ m is, for example, From the viewpoint of reducing the amount of warpage of a glass substrate with a polyimide, it is preferably 25 MPa or less, more preferably 23 MPa or less, still more preferably 20 MPa or less, still more preferably 18 MPa or less, particularly preferably 16 MPa or less.
  • the tensile elongation in film thickness of 10 micrometers of the said polyimide film is 15% or more.
  • the tensile elongation is more preferably 20% or more, still more preferably 25% or more, still more preferably 30% or more, still more preferably 35% or more, from the viewpoint of mechanical strength of the flexible display. Preferably it is 40% or more.
  • the tensile elongation of the polyimide film varies depending on the monomer skeleton of the polyimide precursor, but if it is the same monomer skeleton, the tensile elongation tends to increase as the weight average molecular weight of the polyimide precursor increases.
  • the glass transition temperature Tg of the polyimide film is preferably 360 ° C. or higher, more preferably 400 ° C. or higher, from the viewpoint of being able to raise the process temperature when forming an inorganic film such as silicon nitride on polyimide in the CVD step.
  • the polyimide film preferably has a uniform film thickness.
  • the wavelength of visible light is about 380 nm to about 700 nm, and the film thickness is particularly high from the viewpoint of obtaining good display performance and the display manufacturing process. Uniformity is required. 10 ⁇ m or less is preferable, 8 ⁇ m or less is preferable, 5 ⁇ m or less is preferable, 3 ⁇ m or less is preferable, 2 ⁇ m or less is preferable, 1 ⁇ m or less is particularly preferable, and 500 nm is uniform The following are particularly preferable, and 300 nm or less is particularly preferable.
  • the film thickness uniformity is preferably as small as possible, it may be, for example, 50 nm or more or 100 nm or more from the viewpoint of improving the yield of display production.
  • the said film thickness uniformity means the value of 3 (sigma) calculated from the film thickness of several points which are measured by the method as described in the term of [Example] of this indication, for example.
  • the shear rate dependency (TI) (hereinafter, also simply referred to as TI) of the resin composition of the present embodiment is preferably 0.9 or more and 1.1 or less.
  • TI is the viscosity ⁇ a at a measurement rotational speed a (rpm) when the viscosity of the resin composition is measured at 23 ° C.
  • Shear rate dependency is preferably 0.9 or more, or 0.95 or more, or 1.0 or more, preferably 1.1 or less, or 1.05 or less, or 1.0 or less It is.
  • the resin composition is referred to as a Newtonian fluid, which is preferable because the film thickness uniformity when slit-coating the resin composition is good.
  • a polyimide film obtained by curing a resin composition having a good film thickness uniformity has a good film thickness uniformity, and thus can be suitably used as a material of a screen of a flexible display or the like.
  • the shear rate of the resin composition is large near the injection port at the time of slit coat.
  • the shear rate of the resin composition decreases on the side opposite to the inlet (i.e., the deadlock side of the nozzle).
  • the film thickness variation in the width direction can be reduced by the small shear rate dependency (specifically, TI of 0.9 or more and 1.1 or less).
  • the small shear rate dependency specifically, TI of 0.9 or more and 1.1 or less
  • the shear rate dependency of the resin composition is considered to be correlated with the method of synthesizing the resin composition.
  • all of acid dianhydride, diamine, and silicone oil which may be acid dianhydride or diamine depending on the structure are added and heated to react, and the diamine is dissolved in a solvent
  • the acid dianhydride and the silicone oil dissolved in a solvent are dropped little by little at room temperature over time, and compared with the case where they are reacted little by little, in the former case, the monomer (ie, acid dianhydride)
  • those having higher reactivity such as those having high acidity or basicity, those having less steric hindrance, etc.
  • the polyimide precursor tends to be a block polymer.
  • the coat characteristic (slit coat characteristic) by the slit nozzle of the resin composition containing a polyimide precursor has correlation with the weight average molecular weight of a polyimide precursor, and solid content of a resin composition.
  • the polyimide precursor has a low molecular weight and / or the resin composition has a low solid content, liquid leakage from the nozzle is likely to occur, while when the polyimide precursor has a high molecular weight, And / or when the resin composition has a high solid content, clogging of the varnish tends to occur at the nozzle tip. Therefore, it is preferable to control the weight average molecular weight of the polyimide precursor in such a range that the desired slit coat characteristics can be obtained by controlling the solid content.
  • the solid content of the resin composition is 10% by mass to 25% by mass.
  • the settable coat gap i.e., the gap between the tip of the slit coat nozzle and the substrate
  • the coat gap is preferably large. For example, when the coat gap is 50 ⁇ m or more, the collision between the slit nozzle and the substrate can be avoided even when the substrate size is relatively large.
  • the intended coating gap can be realized by selecting the type and molecular weight of the polyimide precursor.
  • the preferred solids content of the resin composition may vary depending on the desired application, the type and molecular weight of the polyimide precursor, the type of solvent that the resin composition may comprise, and the like.
  • Preferred examples of the lower limit of the solid content are 11 mass%, 12 mass%, 13 mass%, 14 mass%, 15 mass%, 16 mass%, 17 mass%, 18 mass%, 19 mass%, 20 mass% , 21% by mass, 22% by mass, 23% by mass or 24% by mass.
  • Preferred examples of the upper limit of the solid content are 24 mass%, 23 mass%, 22 mass%, 21 mass%, 20 mass%, 19 mass%, 18 mass%, 17 mass%, 16 mass%, 15 mass% , 14% by mass, 13% by mass, 12% by mass or 11% by mass.
  • the solid concentration is 10 to 20% by mass, and more preferably 10 to 15% by mass.
  • the polyimide precursor has the formula (3): [Wherein, each of R 3 and R 4 independently represents a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms, when there are a plurality of each. , And m is an integer of 1 to 200. ⁇ Has a structure represented by The fact that R 3 and R 4 each is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms is due to the residual stress and Rth generated with the support.
  • m is 1 to 200, preferably 1 or more, or 3 or more, or 5 or more, preferably 200 or less, from the viewpoint of obtaining a polyimide capable of reducing the residual stress and Rth generated with the support. Or 180 or less, or 160 or less.
  • the polyimide precursor may have the structure of the formula (3) at any site in the molecule, but the structure of the formula (3) is preferably derived from the diamine component from the viewpoint of the type of siloxane monomer and cost. .
  • the ratio of the structural portion represented by the formula (3) to the total mass of the polyimide precursor is preferably 5% by mass or more, more preferably from the viewpoint of reducing the residual stress and Rth generated with the support. It is 6% by mass or more, more preferably 7% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less from the viewpoint of transparency of the cured product (for example, polyimide film) and heat resistance. More preferably, it is 25 mass% or less.
  • the polyimide precursor of the structure represented by the said Formula (1) is a polymer of the diamine component containing R 1 group, and the acid dianhydride component containing R 2 group.
  • the polyimide precursor having a structure represented by Formula (1) is a copolymer of tetracarboxylic acid dianhydride and diamine.
  • the polyimide precursor is a copolymer of tetracarboxylic acid dianhydride with pyromellitic dianhydride (PMDA) and a diamine.
  • the polyimide precursor is a copolymer of tetracarboxylic acid dianhydride containing 3,3 ', 4,4'-biphenyl tetracarboxylic acid dianhydride and a diamine.
  • the total content of pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic acid dianhydride (BPDA) in total acid dianhydrides has good slit coat performance and cured products (
  • Rth thickness direction retardation
  • YI yellowness
  • Tg glass transition temperature
  • elongation of a polyimide film it is preferably 60 mol% or more, more preferably 80 mol% or more, particularly preferably Is 100 mol%.
  • the content of pyromellitic dianhydride (PMDA) in total acid dianhydride has good slit coat performance, as well as good glass transition temperature Tg of the cured product (eg polyimide film) From the viewpoint of obtaining, 0 mol% or more is preferable, 10 mol% or more is preferable, 20 mol% or more is preferable, 100 mol% or less is preferable, and 90 mol% or less is preferable.
  • the content of biphenyltetracarboxylic acid dianhydride (BPDA) in the total acid dianhydride has good slit coat performance as well as good thickness direction retardation of the cured product (eg polyimide film)
  • BPDA biphenyltetracarboxylic acid dianhydride
  • YI yellowness
  • elongation 0 mol% or more is preferable, 10 mol% or more is preferable, 20 mol% or more is preferable, 100 mol% or less is preferable, 90 mol% or less Is preferred.
  • the content ratio of pyromellitic dianhydride (PMDA): biphenyltetracarboxylic dianhydride (BPDA) in the acid dianhydride is a good thickness direction retardation of a cured product (eg polyimide film)
  • a cured product eg polyimide film
  • the polyimide precursor is a copolymer of tetracarboxylic acid dianhydride and a diamine, said tetracarboxylic acid dianhydride being pyromellitic dianhydride and 3,3 ', 4,4.
  • the molar ratio of pyromellitic dianhydride to 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride is preferably 20:80 to 80:20, more preferably 30. : 70 to 70:30 inclusive.
  • diamine containing an R 1 group in the formula (1) examples include diaminodiphenyl sulfone (eg, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone), p-phenylenediamine, m-phenylenediamine, 4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4 4,4'-Diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphen
  • a diamine used to form a polyimide precursor having a structure represented by the formula (1) is diaminodiphenyl sulfone (eg, 4,4′-diaminodiphenyl sulfone and / or 3,3′-diaminodiphenyl sulfone) It is preferable to include.
  • the content of diaminodiphenyl sulfone in all diamines is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and may be 95 mol% or more.
  • YI yellowness
  • the diaminodiphenyl sulfone 4,4'-diaminodiphenyl sulfone is particularly preferable from the viewpoint of low yellowness (YI).
  • the diamine to be copolymerized with diaminodiphenyl sulfone is preferably diamidobiphenyls, more preferably diaminobis (triol) from the viewpoint of heat resistance of the cured product (eg polyimide film) and yellowness (YI). Fluoromethyl) biphenyl (TFMB) is included.
  • 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 degree of yellowness (YI) of the cured product (for example, polyimide film) From the viewpoint of enabling the diamine to contain other advantageous components such as diaminodiphenyl sulfone, it is preferably at most 80 mol%, more preferably at most 70 mol%.
  • the diamine comprises a silicon containing diamine.
  • the diamine comprises a silicon-containing diamine comprising a structure represented by Formula (3) above.
  • the silicon-containing diamine for example, the following formula (3a): ⁇ Wherein R 5 represents a divalent hydrocarbon group, which may be the same or different, and each of a plurality of R 3 and R 4 is the same as defined in the formula (3), and l represents an integer of 1 to 200.
  • the diamino (poly) siloxane represented by ⁇ can be used suitably.
  • R 5 in the general formula (3a) a methylene group, an ethylene group, a propylene group, a butylene group, a phenylene group, and the like.
  • R ⁇ 3 > and R ⁇ 4 > in Formula (3a) a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group etc. are mentioned.
  • the number average molecular weight of the compound represented by the above formula (3a) is preferably 500 or more, more preferably from the viewpoint of reduction of residual stress generated between a cured product (for example, a polyimide film) to be obtained and a support. Is preferably 1,000 or more, more preferably 2,000 or more, and preferably 12,000 or less, more preferably 10,000, from the viewpoint of the transparency (particularly low haze) of the resulting cured product (eg, polyimide film). The following is more preferably 8,000 or less.
  • Specific examples of the compound represented by the above formula (3a) include both terminal amine-modified methylphenylsilicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400), X22-9409 (number average) Molecular weight 1300)) Both terminal amino modified dimethyl silicone (Shin-Etsu Chemical Co., Ltd .: X22-161A (number average molecular weight 1600), X22-161B (number average molecular weight 3000), KF 8012 (number average molecular weight 4400), Toray Dow Corning: BY16-835U (number average molecular weight 900) manufactured by Chisso Corporation: Silaprene FM 3311 (number average molecular weight 1000) and the like.
  • a both-end amine modified methylphenyl silicone oil is preferable from the viewpoint of chemical resistance improvement and Tg improvement.
  • the copolymerization ratio of the silicon-containing diamine is preferably in the range of 0.5 to 30% by mass, more preferably 1.0% to 25% by mass, still more preferably 1.5% by mass with respect to the mass of all the polyimide precursors. It is mass% to 20 mass%.
  • the content is 0.5% by mass or more, the effect of reducing the stress generated with the support is good.
  • the content is 30% by mass or less, the transparency (particularly low haze) of the cured product (for example, a polyimide film) obtained is good, which is preferable in terms of realization of high total light transmittance and prevention of lowering of Tg.
  • a dicarboxylic acid can be added within a range that does not impair its performance. You may use it. That is, the polyimide precursor of the present disclosure may be a polyamideimide precursor. A film obtained from such a polyimide precursor can have good properties such as mechanical elongation, glass transition temperature Tg, yellowness (YI) and the like.
  • the dicarboxylic acid to be used include dicarboxylic acids having an aromatic ring and alicyclic dicarboxylic acids.
  • the number of carbons referred to herein includes the number of carbons contained in the carboxyl group.
  • dicarboxylic acids having an aromatic ring are preferred.
  • Isophthalic acid derivatives and the like can be mentioned.
  • these dicarboxylic acids When these dicarboxylic acids are actually copolymerized into a polymer, they may be used in the form of acid chlorides derived from thionyl chloride and the like, active esters and the like.
  • the polyimide precursor comprises tetracarboxylic acid dianhydride, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,2'-bis (trifluoromethyl) benzidine and 9 , 9-bis (4-aminophenyl) fluorene and copolymers with one or more diamines selected from the group consisting of
  • polyimide precursor As a particularly preferred polyimide precursor, the following may be mentioned.
  • the acid dianhydride component is pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic acid dianhydride (BPDA)
  • the diamine component is diaminodiphenyl sulfone (DAS) (more preferable Is a weight average molecular weight of 110,000 to 130,000, solid content 12 to 25 mass%)
  • DAS diaminodiphenyl sulfone
  • DAS diaminodiphenyl sulfone
  • a silicon-containing diamine (More preferably, weight average molecular weight 110,000 to 210,000, solid content 10 to 25 mass%)
  • the acid dianhydride component is pyromellitic dianhydride (PMDA) and
  • the silicon-containing diamine is preferably a diamino (poly) siloxane represented by the above-mentioned formula (3a) (preferably a number average molecular weight of 500 to 12,000). And, more preferably, both terminal amine-modified methylphenylsilicone oils.
  • the polyimide precursor of the present embodiment can be synthesized by subjecting a polycondensation component including an acid dianhydride component and a diamine component to a polycondensation reaction.
  • the polycondensation component comprises an acid dianhydride component and a diamine component.
  • the polycondensation reaction is preferably carried out in a suitable solvent. Specifically, for example, there is a method of dissolving a predetermined amount of diamine component in a solvent, adding a predetermined amount of acid dianhydride to the obtained diamine solution, and stirring.
  • the molecular weight of the polyimide precursor can be controlled by adjusting the type of acid dianhydride component and diamine component, adjusting the ratio of acid dianhydride component and diamine component, adding an end capping agent, adjusting the reaction conditions, etc. It is.
  • the polyimide precursor can be made higher in molecular weight as the ratio of the acid dianhydride component to the diamine component is closer to 1: 1 and as the amount of the end capping agent used is smaller. It is recommended to use high purity products as the acid dianhydride component and the diamine component. The purity thereof is preferably 98% by mass or more, more preferably 99% by mass or more, and still more preferably 99.5% by mass or more.
  • the component and the diamine component each have the above-mentioned purity.
  • the solvent for the reaction is not particularly limited as long as it can dissolve the acid dianhydride component and the diamine component, and the resulting polyimide precursor, and a polymer of high molecular weight can be obtained.
  • solvents include, for example, aprotic solvents, phenolic solvents, ethers and glycol solvents.
  • aprotic solvent for example, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-methyl Caprolactam, 1,3-dimethylimidazolidinone, tetramethyl urea, the following general formula (4):
  • Equamide M100 represented by R 12 methyl group (trade name: manufactured by Idemitsu Kosan Co., Ltd.)
  • Amide solvents Lactone solvents such as ⁇ -butyrolactone and ⁇ -valerolactone
  • Phosphorus containing amide solvents such as hexamethylphosphoric amide and hexamethylphosphine triamide
  • Sulfur containing solvents such as dimethylsulfone, dimethylsulfoxide and sul
  • ether and glycol solvents for example, 1,2-dimethoxyethane, bis (2- Examples thereof include methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,4-dioxane and the like.
  • 1,2-dimethoxyethane bis (2- Examples thereof include methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,4-dioxane and the like.
  • solvents may be used alone or in combination of two or more.
  • the boiling point at normal pressure of the solvent used for the synthesis of the polyimide precursor is preferably 60 to 300 ° C., more preferably 140 to 280 ° C., and particularly preferably 170 to 270 ° C.
  • the boiling point of the solvent is higher than 300 ° C., a drying step is required for a long time.
  • the boiling point of the solvent is lower than 60 ° C., the surface of the resin film may be roughened, air bubbles may be mixed into the resin film, and the like during the drying process, and a uniform film may not be obtained.
  • NMP N-methyl-2-pyrrolidone
  • GBL ⁇ -butyrolactone
  • (4) a compound represented by the above general formula (4) is preferable.
  • the water content in the solvent is preferably, for example, 3,000 ppm by mass or less from the viewpoint of the progress of a good polycondensation reaction.
  • the content of molecules having a molecular weight of less than 1,000 is preferably less than 5% by mass.
  • the presence of molecules having a molecular weight of less than 1,000 in the resin composition is considered to be due to the water content of the solvent used during synthesis and the raw materials (acid dianhydride, diamine). That is, it is considered that the acid anhydride group of some of the acid dianhydride monomers is hydrolyzed by water to be a carboxyl group, and remains in a low molecular state without high molecular weight formation.
  • the water content of the solvent is preferably 3,000 ppm by mass or less, and more preferably 1,000 ppm by mass or less.
  • the amount of water contained in the raw material is also preferably 3,000 ppm by mass or less, and more preferably 1,000 ppm by mass or less.
  • the water content of the solvent is the grade of solvent used (dehydration grade, general purpose grade, etc.), solvent container (bottle, 18 L can, canister can etc.), storage condition of solvent (presence or absence of rare gas inclusion etc.), from opening to use It may be considered that the time period of use (whether used immediately after opening or used after aging after opening etc.) is involved. In addition, it is considered that the noble gas substitution of the reactor before synthesis, the presence or absence of the rare gas circulation during synthesis, and the like are also involved. Therefore, when synthesizing the polyimide precursor, it is recommended to use a high purity product as a raw material and use a solvent with a small amount of water, and to take measures so that water from the environment does not enter the system before and during the reaction. Be done.
  • reaction temperatures at the time of polyimide precursor synthesis include 0 ° C. to 120 ° C., 40 ° C. to 100 ° C., or 60 to 100 ° C.
  • the time may be, for example, 1 to 100 hours, or 2 to 10 hours.
  • the resin composition of the present embodiment may be a combination of a polyimide precursor having a structure represented by Formula (1) and another additional polyimide precursor, but the mass ratio of the additional polyimide precursor Is 30% by mass or less based on the total amount of the polyimide precursor in the resin composition from the viewpoint of reducing the degree of yellowness (YI) of the cured product (for example, polyimide film) and the oxygen dependency of the total light transmittance. Is preferable, and 10% by mass or less is more preferable.
  • a part of the polyimide precursor may be imidized.
  • the partially imidized polyimide precursor can improve the viscosity stability of the resin composition when stored at room temperature.
  • the imidation ratio in this case is preferably 5% or more, more preferably 8% or more, from the viewpoint of balancing the solubility of the polyimide precursor in the resin composition with the storage stability of the solution, and is preferably Is 80% or less, more preferably 70% or less, and still more preferably 50% or less.
  • This partial imidization is obtained by heating and dehydrating the ring closure of the polyimide precursor.
  • This heating can be carried out preferably 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 to esterify part or all of the carboxylic acid,
  • the resin composition in which the viscosity stability at the time of room temperature storage was improved can also be obtained.
  • ester-modified polyamic acids are obtained by sequentially reacting the above-mentioned acid dianhydride component with one equivalent of a monohydric alcohol with respect to an acid anhydride group, and a dehydration condensation agent such as thionyl chloride or dicyclohexylcarbodiimide. It can also be obtained by a method of condensation reaction with a diamine component.
  • the resin composition comprises a solvent.
  • the solvent one having good solubility of the polyimide precursor and capable of appropriately controlling the solution viscosity of the resin composition is preferable, and the reaction solvent of the polyimide precursor can be used as a solvent of the composition.
  • NMP N-methyl-2-pyrrolidone
  • GBL ⁇ -butyrolactone
  • a compound represented by the above general formula (4), and the like are preferable.
  • NMP N-methyl-2-pyrrolidone
  • GBL ⁇ -butyrolactone
  • the resin composition of the present embodiment may contain additional components in addition to (a) a polyimide precursor and (b) a solvent.
  • additional components include (c) surfactants, (d) alkoxysilane compounds, and the like.
  • the coatability of the resin composition can be improved by adding a surfactant to the resin composition of the present embodiment. Specifically, the generation of streaks in the coated film can be prevented.
  • surfactants include silicone surfactants, fluorine surfactants, and nonionic surfactants other than these.
  • silicone surfactants such as organosiloxane polymers KF-640, 642, 643, KP 341, X-70-092, X-70-093 (all trade names, 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 Co., Ltd.), SILWET L-77 , L-7001, FZ-2105, FZ-2120, FZ-2154, FZ-2164, FZ-2166, L-7604 (all trade names, manufactured by Nippon Unicar Co., Ltd.), DBE-814, DBE-224, DBE- 621, CMS-626, CMS-222, KF-352A, KF-354L, KF-355A, KF-6020, DB E-821, DBE-712 (Gelest), BYK-307, BYK-310, BYK-378, BY
  • fluorinated surfactants for example, Megafac F171, F173, R-08 (Dainippon Ink and Chemicals, Inc., trade name), Florard FC4430, FC4432 (Sumitomo 3M Ltd., trade name), etc .;
  • a nonionic surfactant other than, for example, polyoxyethylene uralyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether and the like can be mentioned, respectively.
  • silicone surfactants and fluorosurfactants are preferable from the viewpoint of the coating property (stripping suppression) of the resin composition, and the yellowness (YI) value due to the oxygen concentration at the curing step is preferable.
  • silicone surfactants are preferred.
  • the amount thereof is preferably 0.001 to 5 parts by mass, and 0.01 to 3 parts by mass with respect to 100 parts by mass of (a) polyimide precursor in the resin composition. Is more preferred.
  • (D) Alkoxysilane Compound When the polyimide film obtained from the resin composition according to the present embodiment is used for a flexible substrate or the like, the resin composition from the viewpoint of obtaining good adhesion between the support and the polyimide film in the manufacturing process.
  • the substance may contain 0.01 to 20 parts by mass of the alkoxysilane compound with respect to 100 parts by mass of the (a) polyimide precursor.
  • the content of the alkoxysilane compound is 0.01 parts by mass or more based on 100 parts by mass of the polyimide precursor, good adhesion can be obtained between the support and the polyimide film.
  • the content of the alkoxysilane compound is more preferably 0.02 to 15 parts by mass, still more preferably 0.05 to 10 parts by mass, with respect to 100 parts by mass of the polyimide precursor. Particularly preferred is 8 parts by mass.
  • an alkoxysilane compound as an additive of the resin composition according to the present embodiment, in addition to the improvement of the above-mentioned adhesion, the improvement of the coating property (suppression of uneven streaks) of the resin composition, and It is also possible to reduce the oxygen concentration dependence during curing of the yellowness (YI) value of the cured film.
  • 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 synthesized polyimide precursor solution can be used as it is as the resin composition.
  • one or more of (b) a solvent and one or more additional components are added to (a) a polyimide precursor in a temperature range of room temperature (25 ° C.) to 80 ° C. and stirred and mixed. And may be used as a resin composition.
  • appropriate devices such as a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) equipped with stirring blades, a rotation and revolution mixer, and the like can be used. Further, heat of 40 to 100 ° C. may be added if necessary.
  • the solvent in the synthesized polyimide precursor solution is, for example, reprecipitated, After removing by a suitable method such as evaporation of solvent and isolating (a) the polyimide precursor, (b) a solvent and, if necessary, additional components are added in a temperature range of room temperature to 80 ° C.
  • the resin composition may be prepared by stirring and mixing.
  • the composition is heated, for example, at 130 to 200 ° C., for example, for 5 minutes to 2 hours to dehydrate a portion of the polyimide precursor to such an extent that the polymer does not precipitate.
  • the imidization rate can be controlled by controlling the heating temperature and the heating time.
  • the partially imidized polyimide precursor can improve the viscosity stability of the resin composition when stored at room temperature.
  • 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 particularly preferably 3,000 to 20,000 mPa ⁇ s. preferable.
  • the viscosity 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 terms of preventing liquid leakage from the slit nozzle.
  • the solution viscosity of the resin composition is higher than 200,000 mPa ⁇ s, there may be a problem that stirring at the time of synthesis becomes difficult. However, even when the solution has a high viscosity at the time of synthesis, it is possible to obtain a resin composition having a manageable viscosity by adding a solvent and stirring after completion of the reaction.
  • the solution viscosity of the resin composition in the present disclosure is a value measured at 23 ° C. using an E-type viscometer (for example, VISCONICEHD, manufactured by Toki Sangyo Co., Ltd.).
  • the water content of the resin composition according to the present embodiment is preferably 3,000 ppm by mass or less.
  • the water content of the resin composition is preferably 2,500 mass ppm or less, preferably 2,000 mass ppm or less, and preferably 1,500 mass ppm or less from the viewpoint of viscosity stability when storing the resin composition.
  • the amount is preferably 1,000 ppm by mass or less, more preferably 500 ppm by mass or less, preferably 300 ppm by mass or less, and preferably 100 ppm by mass or less.
  • the resin composition is coated on the surface of the support.
  • the support is not particularly limited as long as it has heat resistance at the heating temperature of the subsequent film forming step (heating step), and further, if the peelability in the peeling step is good.
  • glass for example, alkali-free glass
  • silicon wafer for example, PET (polyethylene terephthalate), OPP (oriented polypropylene), polyethylene glycol terephthalate, polyethylene glycol naphthalate, polycarbonate, polyimide, polyamide imide, polyether imide, polyether ether Resin substrates such as ketone, polyether sulfone, polyphenylene sulfone and polyphenylene sulfide; metal substrates such as stainless steel, alumina, copper, nickel and the like are used.
  • PET polyethylene terephthalate
  • OPP oriented polypropylene
  • polyethylene glycol terephthalate polyethylene glycol naphthalate
  • polycarbonate polyimide
  • polyamide imide polyether imide
  • polyether ether Resin substrates such as ketone, polyether sulfone, polyphenylene sulfone and polyphenylene sulfide
  • metal substrates such as stainless steel, alumina,
  • a thin film polyimide molded body for example, a glass substrate, a silicon wafer or the like is preferable, and when forming a thick film polyimide molded body (for example, a thick film, a sheet etc.), for example, PET A support made of (polyethylene terephthalate), OPP (oriented polypropylene) or the like is preferred.
  • Coating methods generally include doctor blade knife coater, air knife coater, roll coater, rotary coater, flow coater, die coater, bar coater and other coating methods, spin coating, spray coating, dip coating and other coating methods; screen printing And printing techniques represented by gravure printing etc., and the resin composition of the present embodiment is particularly useful for slit coating (that is, coating with a slit coater).
  • the coating thickness should be appropriately adjusted in accordance with the desired thickness of the polyimide film and the content of the polyimide precursor in the resin composition, and is preferably about 1 to 1,000 ⁇ m.
  • the application step is sufficient at room temperature, the resin composition may be heated, for example, in the range of 40 to 80 ° C. for the purpose of lowering the viscosity to improve the workability.
  • a drying step may be performed, or the drying step may be omitted and the process may proceed directly to the next film forming step (heating step).
  • the drying step is performed for the purpose of removing the organic solvent in the resin composition.
  • appropriate devices such as a hot plate, a box dryer, a conveyor dryer and the like can be used, for example.
  • the drying step is preferably performed at 80 to 200 ° C., and more preferably 100 to 150 ° C.
  • the implementation time of the drying step is preferably 1 minute to 10 hours, and more preferably 3 minutes to 1 hour.
  • the coating film containing the polyimide precursor is formed on the support.
  • a film forming step (heating step) is performed.
  • the heating step is a step of removing the organic solvent remaining in the coating film in the above-described drying step and advancing the imidization reaction of the polyimide precursor in the coating film to obtain a polyimide film.
  • This heating step can be performed using an apparatus such as, for example, an inert gas oven, a hot plate, a box dryer, a conveyor dryer, and the like. This step may be performed simultaneously with the drying step or both steps may be performed sequentially.
  • the heating step may be carried out in an air atmosphere, but from the viewpoint of safety, good transparency of the obtained polyimide film, low thickness direction retardation (Rth) and low yellowness (YI), inert gas It is recommended to do under the atmosphere.
  • the inert gas include nitrogen, argon and the like.
  • the heating temperature may be appropriately set depending on the type of polyimide precursor and the type of solvent in the resin composition, but is preferably 250 ° C. to 550 ° C., and more preferably 300 to 450 ° C. If the temperature is 250 ° C. or higher, the imidization proceeds well, and if the temperature is 550 ° C. or lower, disadvantages such as a decrease in transparency of the obtained polyimide film and a deterioration in heat resistance can be avoided.
  • the heating time is preferably about 0.1 to 10 hours.
  • the oxygen concentration in the ambient atmosphere in the above heating step is preferably 2,000 ppm by mass or less, and 100 mass ppm or less from the viewpoint of the transparency and yellowness (YI) value of the polyimide film obtained. More preferably, 10 mass ppm or less is more preferable.
  • the yellowness (YI) value of the obtained polyimide film can be made to be 30 or less.
  • peeling step the polyimide film on the support is peeled, for example, after cooling to about room temperature to about 50 ° C.
  • this peeling step include the following embodiments (1) to (4).
  • a polyimide film / substrate comprising a polyimide film / support is produced by the above method, and then the laser is irradiated from the substrate side of the structure to ablate the interface between the substrate and the polyimide film. How to peel off the resin.
  • the type of laser includes a solid (YAG) laser, a gas (UV excimer) laser and the like. It is preferable to use a spectrum such as a wavelength of 308 nm (see, for example, JP-A-2007-512568, JP-A-2012-511173, etc.).
  • the peeling layer include a method using Parylene (registered trademark, manufactured by Japan Parylene Joint Company) and tungsten oxide; a method using a releasing agent such as vegetable oil type, silicone type, fluorine type and alkyd type (JP-A-2010) -67957, JP-A-2013-179306 etc.).
  • This method (2) may be used in combination with the laser irradiation of the above (1).
  • the metal for example, copper (as a specific example, electrolytic copper foil “DFF” manufactured by Mitsui Mining & Smelting Co., Ltd.), aluminum or the like can be used.
  • DFF electrolytic copper foil
  • ferric chloride or the like can be used for copper, and dilute hydrochloric acid or the like can be used for aluminum.
  • the method (1) or (2) is appropriate from the viewpoint of the refractive index difference between the front and back of the obtained polyimide film, the yellowness (YI) value, and the elongation. From the viewpoint of the difference in refractive index between the front and back, it is more appropriate to carry out method (1), that is, an irradiation step of irradiating the laser from the support side prior to the peeling step.
  • method (3) when copper is used as a support body, the yellowness (YI) value of the polyimide film obtained becomes large, and the tendency for elongation to become small is seen. This is considered to be the effect of copper ions.
  • the thickness of the polyimide film obtained by the above method is not particularly limited, but is preferably in the range of 1 to 200 ⁇ m, more preferably 5 to 100 ⁇ m.
  • the polyimide film obtained from the polyimide precursor according to the present embodiment can be applied as, for example, a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, etc.
  • a TFT substrate or a color filter substrate in the manufacture of flexible devices, particularly a TFT substrate or a color filter substrate And can be suitably used as a touch panel substrate.
  • a flexible device to which the polyimide film according to the present embodiment can be applied for example, a TFT device for a flexible display, a flexible solar cell, a flexible touch panel, a flexible illumination, a flexible battery, a flexible printed circuit, a flexible color filter, a smartphone Facing surface cover lens etc. can be mentioned.
  • the process of forming a TFT on a flexible substrate using a polyimide film is typically performed at a wide range of temperatures from 150 to 650.degree. 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 be able 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. Therefore, it is necessary to appropriately select a polymer structure having a glass transition temperature higher than the TFT manufacturing process maximum temperature and a thermal decomposition start temperature.
  • LTPS low temperature polysilicon
  • a process temperature of 380 ° C. to 520 ° C. is generally required, and the polyimide film of the present embodiment needs to be able to withstand that temperature. It is necessary to appropriately select a glass transition temperature higher than the TFT manufacturing process maximum temperature and a thermal decomposition start temperature.
  • the optical properties of the polyimide film tend to decrease as they are exposed to high temperature processes.
  • the polyimide obtained from the polyimide precursor of the present embodiment has good optical properties even after thermal history.
  • the present embodiment also provides a flexible device including a polyimide film which is a cured product of the resin composition of the present embodiment.
  • a preferred example of the flexible device is a flexible display.
  • the polyimide film is excellent in optical properties (eg, Rth and / or yellowness). Therefore, in a preferred embodiment, the polyimide film is disposed at a location (specifically, the screen portion of the flexible display) to be viewed when the display is observed from the outside.
  • FIG. 1 is a view showing a structure of a top emission type flexible organic EL display as an example of a display provided in one embodiment of the present invention above a polyimide substrate.
  • the organic EL structure 25 shown in FIG. 1 is, for example, an organic EL element 250a emitting red light, an organic EL element 250b emitting green light, and an organic EL element 250c emitting blue light, each forming a matrix.
  • the light emitting area of each organic EL element is defined by the barrier rib (bank) 251.
  • Each organic EL element is composed of 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)
  • a plurality of interlayer insulating films 258 provided with contact holes 257 and lower electrodes 259 are provided, which are selected from metal oxide semiconductors (such as IGZO).
  • the organic EL element is sealed by a sealing substrate 2b, and a hollow portion 261 is formed between each organic EL element and the sealing substrate 2b.
  • a polyimide film is prepared on a glass substrate support, and the process of manufacturing the organic EL substrate shown in FIG. 1 above, the sealing substrate manufacturing process, and assembly of bonding both substrates
  • the process and the peeling process of peeling the organic electroluminescent display produced on the polyimide film from the glass substrate support are included.
  • a well-known manufacturing process can be applied to the organic EL substrate manufacturing process, the sealing substrate manufacturing process, and the assembling process. Although the example is given below, it is not limited to this.
  • the peeling process may be the same as the peeling process of the polyimide film mentioned above.
  • the polyimide film of the present disclosure is produced on a glass substrate support by the method described above, and silicon nitride (SiN) and silicon oxide (SiO) are formed thereon by CVD or sputtering.
  • a multi-barrier layer (lower substrate 2a in FIG. 1) having a multi-layered 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 of SiO or the like is formed thereon by the CVD method, and a TFT device (TFT 256 in FIG. 1) such as 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 a contact hole 257 is formed of a photosensitive acrylic resin or the like.
  • An ITO film is formed by sputtering or the like, and the lower electrode 259 is formed to be paired with the TFT.
  • a partition (bank) 251 is formed of 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. Further, the upper electrode (cathode) 255 is formed so as to cover the light emitting layer 254 and the partition (bank) 251.
  • an organic EL material corresponding to the organic EL element 250a emitting red light in FIG. 1 emitting red light
  • an organic EL material emitting green light (FIG. 1) Corresponding to the organic EL element 250b emitting green light
  • the organic EL material emitting blue light correspond to the organic EL element 250c emitting blue light in FIG.
  • the device above the polyimide substrate is peeled from the glass substrate support by a known peeling method such as laser peeling.
  • a top emission type flexible organic EL display is manufactured.
  • a see-through flexible organic EL display is manufactured.
  • a bottom emission type flexible organic EL display may be manufactured by a known method.
  • a flexible liquid crystal display can be manufactured using the polyimide film of the present embodiment.
  • a polyimide film according to the present invention is prepared on a glass substrate support by the above-mentioned method, and amorphous silicon, metal oxide semiconductor (IGZO etc.), or A TFT substrate made of low temperature polysilicon is manufactured.
  • a polyimide film is prepared on a glass substrate support, and a color filter glass substrate provided with a polyimide film using a color resist or the like according to a known method Create a CF substrate).
  • a sealing material composed of a thermosetting epoxy resin or the like is applied to one of a TFT substrate and a CF substrate by screen printing in a frame-like pattern lacking a liquid crystal injection port, and the other substrate is a liquid crystal layer Spray a spherical spacer of plastic or silica with a diameter corresponding to the thickness.
  • the 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 flexible device for example, flexible display
  • a glass substrate is used as the support.
  • Preferred specific procedures of the coating step and the film forming step are the same as those described above for the method for producing the polyimide film.
  • the above-described element is formed on a polyimide film as a flexible substrate, which is formed on a support. Thereafter, the polyimide film and the device may optionally be peeled off from the support in the peeling step.
  • Weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) under the following conditions.
  • NMP manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph
  • lithium bromide monohydrate of 24.8 mmol / L manufactured by Wako Pure Chemical Industries, purity 99.5%
  • 63 A 2 mmol / L phosphoric acid manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph
  • a calibration curve for calculating weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).
  • Shodex KD-806M made by Showa Denko
  • Flow rate 1.0 mL / min
  • Column temperature 40 ° C.
  • PU-2080 Plus manufactured by JASCO
  • Detector RI-2031 Plus (RI: differential refractometer, manufactured by JASCO) and UV-2075 Plus (UV-VIS: ultraviolet-visible spectrophotometer, manufactured by JASCO)
  • TI Shear rate dependency evaluation>
  • the viscosity of the resin composition to be measured using the temperature controller-equipped viscometer (TVE-35H manufactured by Toki Sangyo K. K.) at 23 ° C. It measured using a measurable rotational speed and a cone rotor, and performed shear rate dependence evaluation. Specifically, the viscosity ⁇ a (mPa ⁇ s) at the measurement rotation speed a (rpm) and the viscosity ⁇ b (mPa ⁇ s) at the measurement rotation speed b (rpm) are measured (where a * 10 b There was a) TI, which is represented by the following equation.
  • measurable rotational speeds are, for example, 0.5, 1, 2.5, 5, 10, 20, 50, and 100 rpm.
  • Specific examples of measurable cone rotors are, for example, 1 ° 34 ′ (corn rotor angle) ⁇ R 24 (corn rotor diameter), 1 ° 34 ′ ⁇ R 12, 0.8 ° ⁇ R 24, 0.8 ° ⁇ R12, 3 ° ⁇ R24, 3 ° ⁇ R12, 3 ° ⁇ R17.65, 3 ° ⁇ R14, 3 ° ⁇ R12, 3 ° ⁇ R9.7.
  • the film thickness of the resin composition (varnish) prepared in Examples and Comparative Examples is 10 ⁇ m after imidization (heating at 100 ° C. for 1 hour and heating at 400 ° C. for 30 minutes at an oxygen concentration of 10 mass ppm or less)
  • the glass substrate was coated (coating speed 100 mm / sec) so as to be The coating gap set value of the slit coater at that time was described in the table.
  • the film thickness was measured using a contact-type step gauge. From the results, the film thickness uniformity of the polyimide film (the standard deviation of the film thickness at 30 points) was calculated and evaluated according to the following criteria. Good: In-plane film thickness uniformity (3 sigma) is 1.0 ⁇ m or less Possible: In-plane film thickness uniformity (3 sigma) is more than 1.0 ⁇ m 2.0 ⁇ m or less Defect: In-plane film thickness uniformity (3 sigma) Exceeds 2.0 ⁇ m
  • ⁇ Cured film yellowness (YI)> The polyimide films according to the examples and comparative examples produced on the glass substrate in the above ⁇ coating evaluation> (coat gap) were used.
  • the yellowness (YI) value (film thickness converted to 10 ⁇ m) of the obtained sample was measured using a D65 light source by Nippon Denshoku Kogyo Co., Ltd. (Spectrophotometer: SE600). The results are listed in the table.
  • ⁇ Cured film Rth (retardation, retardation in the thickness direction)>
  • the polyimide films according to the examples and comparative examples produced on the glass substrate in the above ⁇ coating evaluation> (coat gap) were used.
  • the Rth (film thickness converted to 10 ⁇ m) of the obtained sample was measured using a retardation birefringence measurement apparatus (KOBRA-WR manufactured by Oji Scientific Instruments). The wavelength of the measurement light was 589 nm. The results are listed in the table.
  • varnish transparent polyamic acid
  • the obtained varnish was stored in a freezer (setting ⁇ 20 ° C., the same applies hereinafter), and was thawed and used for evaluation.
  • Example 1-1 In a 3 L separable flask with stir bar, while introducing nitrogen gas, as diamine, 4,4'-DAS (15.3 g) and TFMB (12.4 g), and twice the mass of the total mass of these diamines The polymerization solvent (NMP) was added. Next, the dropping funnel was set in the above separable flask, and while introducing nitrogen gas into the dropping funnel, PMDA (15.3 g) and BPDA (8.8 g) as acid dianhydride, and these acid dianhydrides were prepared. Two times the mass of polymerization solvent (NMP) was added. And it stirred with the small stirring blade at room temperature.
  • NMP polymerization solvent
  • the combinations of acid dianhydride and diamine are as shown in Tables 1 to 4, and accordingly, the amount of polymerization solvent used is changed (that is, adjusted to be twice the mass of acid dianhydride or diamine).
  • “heat to 70 ° C. and stir for 4 hours” Change the temperature to 40 ° C and stir for 12 hours.
  • Examples 1-9, 2-9, 3-9, and 4-9 add the additional solvent (NMP) to the additional solvent (NMP and GBL).
  • Example 1-1 The conditions were the same as in Example 1-1, except that the NMP / GBL after addition was adjusted to be 100/100 (w / w).
  • the solid contents shown in Tables 1 to 4 were adjusted to the values shown in the table by changing the amount of the additional solvent.
  • the weight average molecular weight was measured after "stirring for 12 hours" and further extending the reaction time. As a result, it did not become larger than after stirring for 12 hours.
  • Comparative Examples 2-1 to 2-6, 3-1 to 3-6, 4-1 to 4-7 the amount of NMP of Comparative Example 1-1 is 745 g (Comparative Example 2-1), 799 g (Comparative Example 3-1), and 850 g (Comparative Example 4-1).
  • the reaction was conducted in the same manner as in Comparative Example 1-1 except that the acid dianhydride and the diamine were blended as shown in Table 2, respectively.
  • Comparative Examples 2-2 to 2-6 are Comparative Example 2-1 and Comparative Examples 3-2 to 3-6 except that the NMP amount is changed to obtain the solid contents in Tables 2 to 4.
  • Comparative Example 3-1 and Comparative Examples 4-2 to 4-7 were respectively performed in the same manner as Comparative Example 4-1.
  • Example 5-1 In a 3 L separable flask equipped with a stir bar, while introducing nitrogen gas, 4,4′-DAS (24.3 g) as diamine and 2 times the mass of NMP of the total mass of diamine were added. Next, the dropping funnel was set in the above separable flask, and while introducing nitrogen gas into the dropping funnel, PMDA (10.9 g) and BPDA (14.7 g) as acid dianhydrides, and 2 of these acid dianhydrides Double mass of NMP was added. And it stirred with the small stirring blade at room temperature. Then, while stirring the diamine solution in the separable flask, dropping of the acid dianhydride solution was started while stirring the small stirring blade of the dropping funnel at room temperature.
  • the dropping was performed at a low speed, and was dropped over 30 minutes. After the dropwise addition, the residue was washed with a washing solvent (NMP), and the residue was dropped (molar ratio of acid dianhydride to diamine (100: 98)). Thereafter, additional solvent (NMP) was added to make the solid content in Table 5 finally. Subsequently, the mixture was stirred at room temperature for 30 minutes and then heated to 70 ° C. using an oil bath and stirred for 4 hours. Thereafter, the oil bath was removed, and the temperature was returned to room temperature to obtain a transparent polyamic acid in NMP solution (hereinafter also referred to as varnish). The obtained varnish was stored in a freezer (setting ⁇ 20 ° C., the same applies hereinafter), and was thawed and used for evaluation.
  • NMP washing solvent
  • additional solvent NMP
  • the formulations of acid dianhydride and diamine were as shown in Tables 5 to 9, and accordingly, the amount of polymerization solvent used was changed (that is, adjusted to be twice the mass of acid dianhydride or diamine). Further, for Examples 5-3 to 5-9, 6-5 to 6-9, 7-4, 8-1, and 8-2, "the temperature is raised to 70 ° C.
  • Comparative Examples 6-2 to 6-6 are performed in the same manner as Comparative Example 6-1 except that the solid content in Table 6 is changed by changing the amount of NMP, and Comparative Examples 7-2 to 7-6 are NMP.
  • the procedure of Comparative Example 7-1 was repeated except that the amount was changed to obtain the solid content in Table 7.
  • the amount of NMP was changed from 718 g to 215 g (Comparative Example 7-7) and 163 g (Comparative Example 7-8), respectively, and the composition of acid dianhydride and diamine was as shown in Table 7.
  • the same procedure as in Comparative Example 7-1 was performed except that “stirring for 4 hours” was changed to “stirring for 3 hours”.
  • varnish transparent polyamic acid
  • the obtained varnish was stored in a freezer and thawed for evaluation.
  • Comparative Examples 9-2 to 9-3 Comparative Example except that the amount of NMP was changed from 495 g to 438 g (Comparative Example 9-2) and 374 g (Comparative Example 9-3), respectively, and the composition of the acid dianhydride and the diamine was as shown in Table 9. It went in the same way as 9-1.
  • Example 9-1 In a 3 L separable flask with a stirring rod, TFMB (31.3 g) as a diamine and NMP (63 g) twice as much as the total mass of the diamine were added while introducing nitrogen gas. Next, the dropping funnel was set in the above separable flask, and while introducing nitrogen gas into the dropping funnel, BPAF (45.8 g) as acid dianhydride and NMP (92 g) twice the mass of this acid dianhydride were added. Was added. And it stirred with the small stirring blade at room temperature.
  • varnish a transparent polyamic acid in NMP solution (hereinafter also referred to as varnish).
  • the obtained varnish was stored in a freezer (setting ⁇ 20 ° C., the same applies hereinafter), and was thawed and used for evaluation.
  • Examples 9-2 and 9-3 The composition of acid dianhydride and diamine was as shown in Table 9, and the amount of polymerization solvent used was changed accordingly (ie, adjusted to be twice the mass of acid dianhydride or diamine) Others were performed in the same manner as in Example 9-1.
  • the solid content shown in Table 9 was adjusted to the values shown in the table by changing the amount of the additional solvent.
  • Example 10-1 NMP (246 g) is added to a 3 L separable flask with a stirring rod while introducing nitrogen gas, and 4,4'-DAS (14.4 g) and TFMB (12.4 g) as diamines are modified with amine-modified methyl phenyl silicone Oil (10.56 g) was added with stirring, followed by PMDA (15.3 g) and BPDA (8.8 g) as acid dianhydride (molar ratio of acid dianhydride and diamine (100: 99) ). Next, the temperature was raised to 70 ° C. using an oil bath, and after stirring for 8 hours, the oil bath was removed and the temperature was returned to room temperature to obtain an NMP solution of transparent polyamic acid. The obtained varnish was stored in a freezer (setting ⁇ 20 ° C., the same applies hereinafter), and was thawed and used for evaluation.
  • Examples 10-2 to 10-5 The amount of NMP was changed from 246 g to 225 g (Example 10-2), 242 g (Example 10-3), 185 g (Example 10-4), 201 g (Example 10-5), respectively, and acid dianhydride and The procedure of Example 10-1 was repeated except that the diamine composition was as shown in Table 10. The results of the evaluation are shown in Table 10.
  • the resin composition of the present disclosure can be suitably applied to applications such as flexible devices (for example, flexible substrates), particularly flexible displays.
  • the resin composition of the present disclosure can be suitably used to form a transparent substrate of a display device such as a liquid crystal display, an organic electroluminescence display, a field emission display, an electronic paper and the like.
  • the resin composition of the present disclosure can be used to form a thin film transistor (TFT) substrate, a color filter substrate, a transparent conductive film (ITO, Indium Thin Oxide) substrate, and the like.
  • TFT thin film transistor
  • ITO Indium Thin Oxide

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