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WO2025225424A1 - Composition de précurseur de polyimide et film de polyimide - Google Patents

Composition de précurseur de polyimide et film de polyimide

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Publication number
WO2025225424A1
WO2025225424A1 PCT/JP2025/014532 JP2025014532W WO2025225424A1 WO 2025225424 A1 WO2025225424 A1 WO 2025225424A1 JP 2025014532 W JP2025014532 W JP 2025014532W WO 2025225424 A1 WO2025225424 A1 WO 2025225424A1
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WO
WIPO (PCT)
Prior art keywords
solvent
polyimide
polyimide precursor
precursor composition
polyimide film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/014532
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English (en)
Japanese (ja)
Inventor
卓也 岡
雄基 根本
昇平 小橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ube Corp
Original Assignee
Ube Corp
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Filing date
Publication date
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Publication of WO2025225424A1 publication Critical patent/WO2025225424A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/21—Urea; Derivatives thereof, e.g. biuret
    • 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
    • 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 precursor composition and a polyimide film with excellent heat resistance that are suitable for use in electronic devices, such as substrates for flexible devices.
  • polyimide film Due to its excellent heat resistance, chemical resistance, mechanical strength, electrical properties, and dimensional stability, polyimide film has been widely used in fields such as electrical and electronic devices and semiconductors. Meanwhile, with the advent of an advanced information society in recent years, there has been progress in the development of optical materials such as optical fibers and optical waveguides in the optical communications field, and liquid crystal alignment films and protective films for color filters in the display device field. In particular, in the display device field, there has been active research into lightweight, highly flexible plastic substrates as an alternative to glass substrates, as well as the development of displays that can be bent or rolled.
  • Displays such as LCDs and OLEDs use semiconductor elements such as TFTs to drive each pixel.
  • Polyimide film has excellent heat resistance, chemical resistance, mechanical strength, electrical properties, and dimensional stability, making it a promising substrate for display applications.
  • NMP N-methyl-2-pyrrolidone
  • DMAc N,N-dimethylacetamide
  • Patent Document 5 discloses that certain organic solvents are superior to NMP.
  • aromatic polyimides Compared to the (semi)alicyclic polyimides described in Patent Documents 1 to 4, aromatic polyimides have issues with coloration, but because they generally have excellent heat resistance, they may be usable as substrates for displays if coloration is reduced as much as possible.
  • improvements have been made to TFT (thin film transistor) film formation methods, and film formation temperatures have been reduced compared to previous methods.
  • certain processes still require high-temperature processing, and the larger the process margin, the better the yield. Therefore, even aromatic polyimides, which generally have excellent heat resistance, could have the advantage of being adaptable to a variety of processes if their heat resistance were further improved.
  • the present invention aims to provide a polyimide precursor composition for producing a polyimide film that has improved optical transparency and heat resistance, and preferably both, while maintaining the advantages of aromatic polyimide films, such as heat resistance and linear thermal expansion coefficient.
  • a further aim of the present invention is to provide polyimide films and polyimide film/substrate laminates obtained from this polyimide precursor for flexible electronic device applications, particularly flexible display substrate applications.
  • a polyimide precursor composition comprising:
  • X1 is a tetravalent aliphatic group or aromatic group
  • Y1 is a divalent aliphatic group or aromatic group
  • R1 and R2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms;
  • 50 mol % or more of X1 are aromatic groups and/or 50 mol % or more of Y1 are aromatic groups.
  • solvent A and solvent B are selected from the following combinations (a) to (g):
  • Solvent A contains 1,3-dimethyl-2-imidazolidinone, and solvent B contains N,N-dimethylpropionamide, tetramethylurea, or N,N-dimethylisobutyramide.
  • Solvent A contains 1-butyl-2-pyrrolidone, and solvent B contains N,N-dimethylpropionamide, tetramethylurea, or N,N-dimethylisobutyramide.
  • Solvent A contains 3-methoxy-N,N-dimethylpropanamide, and solvent B contains N,N-dimethylpropionamide, tetramethylurea, or N,N-dimethylisobutyramide.
  • Solvent A contains 1-phenyl-2-pyrrolidone, and solvent B contains N,N-dimethylpropionamide, tetramethylurea, or N,N-dimethylisobutyramide.
  • Solvent A contains N,N-diphenylformamide, and solvent B contains N,N-dimethylpropionamide, tetramethylurea, or N,N-dimethylisobutyramide.
  • Solvent A contains benzanilide and solvent B contains N,N-dimethylpropionamide, tetramethylurea or N,N-dimethylisobutyramide
  • a method for producing a polyimide film/substrate laminate comprising: (a) applying the polyimide precursor composition according to any one of the preceding paragraphs onto a supporting substrate; and (b) heat-treating the polyimide precursor on the supporting substrate, and laminating a polyimide film on the supporting substrate.
  • the present invention provides a polyimide precursor composition for producing a polyimide film that retains the advantages of aromatic polyimide films, such as heat resistance and linear thermal expansion coefficient, while improving at least one of, and preferably both, optical transparency and heat resistance. Furthermore, the present invention provides a polyimide film and a polyimide film/substrate laminate obtained from this polyimide precursor.
  • a polyimide film and a polyimide film/substrate laminate obtained using the polyimide precursor composition there are provided a method for producing a flexible electronic device using the polyimide precursor composition, and a flexible electronic device.
  • the term "flexible (electronic) device” refers to a device that is flexible, and is typically completed by forming a semiconductor layer (such as transistors or diodes) on a substrate.
  • a “flexible (electronic) device” is distinguished from devices such as COF (chip-on-film), in which a "rigid” semiconductor element such as an IC chip is mounted on a conventional FPC (flexible printed circuit board).
  • COF chip-on-film
  • FPC flexible printed circuit board
  • Suitable flexible (electronic) devices include display devices such as liquid crystal displays, organic EL displays, and electronic paper, as well as solar cells and light-receiving devices such as CMOS.
  • the polyimide precursor composition for forming a polyimide film contains a polyimide precursor and at least two solvents, in which the polyimide precursor is dissolved.
  • the polyimide precursor has the following general formula (I):
  • X1 is a tetravalent aliphatic or aromatic group
  • Y1 is a divalent aliphatic or aromatic group
  • R1 and R2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
  • Particularly preferred is a polyamic acid in which R 1 and R 2 are hydrogen atoms.
  • X1 preferably comprises 50 mol% or more (preferably more than 50 mol%), more preferably 70 mol% or more, and even more preferably 80 mol% or more, 90 mol% or more, and 95 mol% or more in that order.
  • the phrase "the latter range” will be omitted.
  • Y1 preferably comprises 50 mol% or more (preferably more than 50 mol%), more preferably 70 mol% or more, and even more preferably 80 mol% or more, 90 mol% or more, and 95 mol% or more in that order.
  • X 1 is preferably a structure represented by the following formula (II-1) and/or formula (II-2), and Y 1 is preferably a structure represented by the following formula (III).
  • X 1 preferably 50 mol % or more (preferably more than 50 mol %), more preferably 70 mol % or more are structures represented by formula (II-1) and/or formula (II-2), and even more preferably 80 mol % or more, 90 mol % or more, and 95 mol % or more are further preferred in this order.
  • X 1 other than those of formula (II) is also preferably an aromatic group.
  • Y1 preferably 50 mol% or more (preferably more than 50 mol%), more preferably 70 mol% or more are the structure represented by formula (III), and further more preferably 80 mol% or more, 90 mol% or more, and 95 mol% or more are further preferred in this order.
  • Y1 other than formula (III) is also preferably an aromatic group.
  • the polyimide precursor composition of the present invention contains at least two solvents, with solvent A being at least one selected from the group consisting of 1,3-dimethyl-2-imidazolidinone (DMI), 3-methoxy-N,N-dimethylpropanamide (MPA), 1-butyl-2-pyrrolidone (NBP), N,N-diphenylformamide, N,N-diethylbenzamide, benzanilide, and 1-phenyl-2-pyrrolidone, and solvent B being at least one selected from the group consisting of N,N-dimethylpropionamide (DMPA), N,N-diethylformamide (DEF), N,N-diethylacetamide (DEAc), N,N-dimethylisobutyramide (DMIB), N,N-diethylpropionamide (DEPA), and tetramethylurea (TMU).
  • solvent A being at least one selected from the group consisting of 1,3-dimethyl-2-imidazolidinone
  • the polyimide precursor will be explained in terms of the monomers (tetracarboxylic acid component, diamine component, other components) that provide X1 and Y1 in general formula (I), and then the production method will be explained.
  • the tetracarboxylic acid component includes tetracarboxylic acids, tetracarboxylic acid dianhydrides, and other tetracarboxylic acid derivatives such as tetracarboxylic acid silyl esters, tetracarboxylic acid esters, and tetracarboxylic acid chlorides, which are used as raw materials for producing polyimides.
  • tetracarboxylic acid dianhydrides it is convenient to use tetracarboxylic acid dianhydrides in production, and the following description will discuss an example in which tetracarboxylic acid dianhydrides are used as the tetracarboxylic acid component.
  • the diamine component is a diamine compound having two amino groups (—NH 2 ), which is used as a raw material for producing polyimides.
  • polyimide film refers to both the film formed on a supporting (carrier) substrate and present in a laminate, and the film remaining after the substrate has been peeled off.
  • the material that constitutes the polyimide film i.e., the material obtained by heat-treating (imidizing) a polyimide precursor composition, may also be referred to as the "polyimide material.”
  • X1 preferably contains an aromatic group, and more preferably 50 mol % or more of the aromatic group is an aromatic group having four bonds directly bonded to the aromatic ring, and in terms of raw material, a tetracarboxylic acid dianhydride having four -COOH groups directly bonded to the aromatic ring is preferred.
  • X 1 is a tetravalent aromatic group, it is preferably a tetravalent group having an aromatic ring with 6 to 40 carbon atoms.
  • tetravalent groups having an aromatic ring include the following:
  • Z2 is a divalent organic group
  • Z3 and Z4 are each independently an amide bond, an ester bond, or a carbonyl bond
  • Z5 is an organic group containing an aromatic ring.
  • Z2 include aliphatic hydrocarbon groups having 2 to 24 carbon atoms and aromatic hydrocarbon groups having 6 to 24 carbon atoms.
  • Z5 include aromatic hydrocarbon groups having 6 to 24 carbon atoms.
  • the following are particularly preferred tetravalent groups having an aromatic ring, as they allow the resulting polyimide film to have both high heat resistance and high light transmittance.
  • Z1 is more preferably a direct bond, since this allows the resulting polyimide film to have high heat resistance, high light transmittance, and a low coefficient of linear thermal expansion.
  • preferred groups include those in which Z 1 in the above formula (9) is the following formula (3A):
  • Z 11 and Z 12 are each independently, preferably the same, a single bond or a divalent organic group.
  • Z 11 and Z 12 are preferably an organic group containing an aromatic ring, and examples thereof include compounds represented by the formula (3A1):
  • Z 13 and Z 14 are each independently a single bond, —COO—, —OCO— or —O—, and when Z 14 is bonded to a fluorenyl group, a structure in which Z 13 is —COO—, —OCO— or —O— and Z 14 is a single bond is preferred;
  • R 91 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, preferably methyl; and n is an integer of 0 to 4, preferably 1.
  • aromatic groups include, for example, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, pyromellitic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 4,4'-oxydiphthalic acid, bis(3,4-dicarboxyphenyl)sulfone, m-terphenyl-3,4,3',4'-tetracarboxylic acid, p-terphenyl-3,4,3',4'-tetracarboxylic acid, biscarboxyphenyld
  • tetracarboxylic acid components that provide repeating units of general formula (I) in which X1 is a tetravalent group having an aromatic ring containing a fluorine atom include 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane and derivatives thereof such as tetracarboxylic acid dianhydrides, tetracarboxylic acid silyl esters, tetracarboxylic acid esters, and tetracarboxylic acid chlorides.
  • Another preferred compound is (9H-fluorene-9,9-diyl)bis(2-methyl-4,1-phenylene)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate).
  • the tetracarboxylic acid components may be used alone or in combination.
  • tetracarboxylic acid components particularly preferred compounds are 3,3',4,4'-biphenyltetracarboxylic acid (and its derivatives, particularly s-BPDA dianhydride) and oxydiphthalic acid (and its derivatives, particularly ODPA dianhydride), which give structures represented by formula (II-1) and formula (II-2).
  • a tetracarboxylic acid component containing s-BPDA and/or ODPA in the ratios described for formula (II-1) and/or formula (II-2).
  • the other tetracarboxylic acid components can be selected from the compounds described above.
  • 3,3',4,4'-biphenyltetracarboxylic acid (and its derivatives, particularly the dianhydride s-BPDA) can be omitted, and the tetracarboxylic acid component can be selected from the above-mentioned tetracarboxylic acid components.
  • a group having an alicyclic structure is preferred.
  • the tetravalent group having an alicyclic structure is preferably a tetravalent group having an alicyclic structure having 4 to 40 carbon atoms, and more preferably has at least one aliphatic 4- to 12-membered ring, more preferably a 4-membered or 6-membered aliphatic ring.
  • Preferred tetravalent groups having an aliphatic 4-membered or 6-membered ring include the following:
  • R 31 to R 38 each independently represent a direct bond or a divalent organic group.
  • R 41 to R 47 and R 71 to R 73 each independently represent one selected from the group consisting of groups represented by the formula: —CH 2 —, —CH ⁇ CH—, —CH 2 CH 2 —, —O—, and —S—.
  • R 48 is an organic group containing an aromatic ring or an alicyclic structure.
  • R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , and R 38 include a direct bond, an organic group containing an aromatic ring or an alicyclic structure, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—), a carbonyl bond, an ester bond, and an amide bond.
  • a direct bond is particularly preferred.
  • Examples of organic groups containing an aromatic ring as R 31 to R 38 or R 48 include the following.
  • W 1 is a direct bond or a divalent organic group
  • n 11 to n 13 each independently represent an integer of 0 to 4
  • R 51 , R 52 , and R 53 each independently represent an alkyl group having 1 to 6 carbon atoms, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group.
  • W 1 examples include a direct bond, a divalent group represented by the following formula (5), and a divalent group represented by the following formula (6).
  • R 61 to R 68 in formula (6) each independently represent a direct bond or a divalent group represented by formula (5).
  • a group having a bridged alicyclic structure is preferred, and the following are particularly preferred.
  • Alicyclic tetracarboxylic acid dianhydrides that provide the group having the above alicyclic structure include norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid dianhydride (abbreviated as CpODA), 2,2'-binorbornane-5,5',6,6'-tetracarboxylic acid dianhydride (abbreviated as BNBDA), monocyclic alicyclic tetracarboxylic acid dianhydrides such as 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and cyclohexane-1,2,4,5-tetracarboxylic acid dianhydride, [1,1'-bi(cyclohexane)]-3,3',4,4'-tetracarboxylic acid dianhydride, and [1,1'-bi(cyclo
  • Y 1 preferably contains an aromatic group, and more preferably 50 mol % or more (preferably more than 50 mol %) of the repeating units are aromatic groups.
  • Y 1 is a divalent group having an aromatic ring, it is preferably a divalent group having an aromatic ring having 6 to 40 carbon atoms, more preferably 6 to 20 carbon atoms.
  • divalent groups having an aromatic ring examples include the following:
  • W 1 is a direct bond or a divalent organic group
  • n 11 to n 13 each independently represent an integer of 0 to 4
  • R 51 , R 52 , and R 53 each independently represent an alkyl group having 1 to 6 carbon atoms, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group.
  • W 1 examples include a direct bond, a divalent group represented by the following formula (5), and a divalent group represented by the following formula (6).
  • W 1 is a direct bond or a divalent group selected from the group consisting of groups represented by the formula: -NHCO-, -CONH-, -COO-, and -OCO-. It is also particularly preferred that W 1 is any of the divalent groups represented by formula (6) in which R 61 to R 68 are direct bonds or a divalent group selected from the group consisting of groups represented by the formula: -NHCO-, -CONH-, -COO-, and -OCO-.
  • preferred groups include those in which W 1 in the above formula (4) is the following formula (3B):
  • Z 11 and Z 12 are each independently, preferably the same, a single bond or a divalent organic group.
  • Z 11 and Z 12 are preferably an organic group containing an aromatic ring, and examples thereof include compounds represented by the formula (3B1):
  • Z 13 and Z 14 are each independently a single bond, —COO—, —OCO— or —O—, and when Z 14 is bonded to a fluorenyl group, a structure in which Z 13 is —COO—, —OCO— or —O— and Z 14 is a single bond is preferred;
  • R 91 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, preferably phenyl; and n is an integer of 0 to 4, preferably 1.
  • W 1 in the above formula (4) is a phenylene group, that is, a terphenyldiamine compound, and particularly preferred is a compound in which all the bonds are para-bonded.
  • Another preferred group is a compound of the above formula (4) in which W 1 is the first phenyl ring of formula (6), and R 61 and R 62 are 2,2-propylidene groups.
  • Still another preferred group is a group represented by the formula (4) in which W 1 is a group represented by the following formula (3B2):
  • Examples of the compound include compounds represented by the following formula:
  • aromatic groups include, for example, p-phenylenediamine, m-phenylenediamine, benzidine, 3,3'-diamino-biphenyl, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, m-tolidine, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, N,N'-bis(4-aminophenyl)terephthalamide, N,N'-p-phenylenebis(p-aminobenzamide), 4-aminophenoxy-4-diaminobenzoate, bis(4-aminophenyl)terephthalate, biphenyl phenyl-4,4'-dicarboxylic acid bis(4-aminophenyl) ester, p-phenylenebis(p-aminobenzoate), bis(4-aminophenyl
  • Examples of diamine components that provide repeating units of general formula (I) in which Y1 is a divalent group having an aromatic ring containing a fluorine atom include 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, and 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.
  • preferred diamine compounds include 9,9-bis(4-aminophenyl)fluorene, 4,4'-(((9H-fluorene-9,9-diyl)bis([1,1'-biphenyl]-5,2-diyl))bis(oxy))diamine, [1,1':4',1"-terphenyl]-4,4"-diamine, and 4,4'-([1,1'-binaphthalene]-2,2'-diylbis(oxy))diamine.
  • the diamine components may be used alone or in combination of two or more.
  • one particularly preferred compound is p-phenylenediamine (PPD), which gives a structure represented by formula (III), and in one preferred embodiment, it is preferred to use a diamine component containing p-phenylenediamine in the ratio described for formula (III).
  • PPD p-phenylenediamine
  • the other diamine components can be selected from the compounds described above.
  • p-phenylenediamine may not be selected, and the diamine component may be selected from the diamine components listed above.
  • the divalent group having an alicyclic structure is preferably a divalent group having an alicyclic structure having 4 to 40 carbon atoms, and more preferably has at least one aliphatic 4- to 12-membered ring, more preferably aliphatic 6-membered ring.
  • divalent groups having an alicyclic structure include the following:
  • V 1 and V 2 each independently represent a direct bond or a divalent organic group
  • n 21 to n 26 each independently represent an integer of 0 to 4
  • R 81 to R 86 each independently represent an alkyl group having 1 to 6 carbon atoms, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group
  • R 91 , R 92 , and R 93 each independently represent one selected from the group consisting of groups represented by the formula: —CH 2 —, —CH ⁇ CH—, —CH 2 CH 2 —, —O—, and —S—.
  • V 1 and V 2 include a direct bond and a divalent group represented by the above formula (5).
  • the following are particularly preferred divalent groups having an alicyclic structure, as they can provide the resulting polyimide with both high heat resistance and a low linear thermal expansion coefficient.
  • divalent groups having an alicyclic structure the following are preferred.
  • Examples of diamine components that provide repeating units of general formula (I) in which Y 1 is a divalent group having an alicyclic structure include 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, 1,4-diamino-2-n-propylcyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1,4-diamino-2-isobutylcyclohexane, 1,4-diamino-2-sec-butylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane, 1,2-diaminocyclohexane, 1,3-diaminocyclobutane, 1, Examples of the
  • any non-alicyclic aliphatic tetracarboxylic acids (particularly dianhydrides) and/or aliphatic diamines can be used as the tetracarboxylic acid component and diamine component that provide the repeating unit represented by general formula (I), but the content is preferably less than 30 mol%, with less than 20 mol%, less than 10 mol%, less than 5 mol%, and less than 2 mol% (including 0%) being more preferred in that order, relative to 100 mol% of the total of the tetracarboxylic acid component and diamine component.
  • Polyimides derived from monomers primarily composed of s-BPDA and PPD are known for their excellent heat resistance, mechanical strength, and thermal properties, and are highly trusted by users. Therefore, if the polyimide precursor composition of the present invention can improve these properties even slightly, or if it can alleviate the weak point of coloration even slightly, it will have a significant practical effect in flexible device applications.
  • the solvents contained in the polyimide precursor composition of the present invention include solvent A and solvent B.
  • Solvent A is at least one selected from the group consisting of 1,3-dimethyl-2-imidazolidinone (DMI), 3-methoxy-N,N-dimethylpropanamide (MPA), 1-butyl-2-pyrrolidone (NBP), N,N-diphenylformamide, N,N-diethylbenzamide, benzanilide, and 1-phenyl-2-pyrrolidone
  • solvent B is at least one selected from the group consisting of N,N-dimethylpropionamide (DMPA), N,N-diethylformamide (DEF), N,N-diethylacetamide (DEAc), N,N-dimethylisobutyramide (DMIB), N,N-diethylpropionamide (DEPA), and tetramethylurea (TMU).
  • Solvent A has a higher boiling point than solvent B. It should be noted that even a compound that is solid at room temperature (e.g., 25°C), such as 1-phenyl-2-pyrrolidone, can be used by mixing it with another solvent. For example, when solvent A is a solid compound and solvent B is a liquid, the method of mixing the solvents is not particularly limited. Solvent A may be added as a solid to solvent B and dissolved therein, or solvent A may be heated to a temperature above its melting point to become a liquid, and then mixed with solvent B.
  • room temperature e.g. 25°C
  • solvent A is a solid compound and solvent B is a liquid
  • solvent A may be added as a solid to solvent B and dissolved therein, or solvent A may be heated to a temperature above its melting point to become a liquid, and then mixed with solvent B.
  • the mass ratio of solvent A to solvent B is sufficient as long as both are included, and the mass of solvent A relative to the total mass of solvent A and solvent B is more than 0%, preferably more than 1%, preferably 1.5% or more, more preferably 2% or more, further preferably 3% or more, 5% or more, and may also be 8% or more, 10% or more, 20% or more, 25% or more, or 30% or more.
  • the upper limit of the mass of solvent A relative to the total mass of solvent A and solvent B is less than 100%, preferably 90% or less, and may be 80% or less, 75% or less, or 70% or less.
  • the mass of solvent A may be 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, or 8% or less of the total mass of solvent A and solvent B.
  • the ratio is preferably 10/90 to 90/10, more preferably 20/80 to 80/20, more preferably 25/75 to 75/25, and even more preferably 30/70 to 70/30.
  • the number of moles of solvent A may be 0.5 moles or more, preferably 1 mole or more, per mole of repeating units of the polyimide precursor. The upper limit can be determined from the concentration of the polyimide precursor and the range of the mass ratio of solvent A to solvent B.
  • the total amount of solvent A and solvent B is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and most preferably 95% by mass or more, and is even preferably 100% by mass, based on the total amount of solvent.
  • solvent A and solvent B are not particularly limited, but examples of the combination include: (a) Solvent A comprises DMI and solvent B comprises DMPA, TMU or DMIB; (b) solvent A comprises NBP and solvent B comprises DMPA, TMU or DMIB; (c) solvent A comprises MPA and solvent B comprises DMPA, TMU or DMIB; (d) solvent A comprises 1-phenyl-2-pyrrolidone and solvent B comprises DMPA, TMU, or DMIB; (e) solvent A comprises N,N-diphenylformamide and solvent B comprises DMPA, TMU, or DMIB; (f) solvent A comprises N,N-diethylbenzamide and solvent B comprises DMPA, TMU, or DMIB; (g) solvent A comprises benzanilide and solvent B comprises DMPA, TMU or DMIB; Combinations such as the above can be mentioned.
  • solvent A and solvent B is (a') Solvent A contains DMI and solvent B contains DMPA; (b') solvent A comprises NBP and solvent B comprises DMPA, TMU or DMIB; (c') Solvent A contains MPA and solvent B contains DMPA; (d') solvent A comprises 1-phenyl-2-pyrrolidone and solvent B comprises DMPA, TMU or DMIB; (e') Solvent A comprises N,N-diphenylformamide and solvent B comprises DMPA; (f') solvent A contains N,N-diethylbenzamide and solvent B contains DMPA; (g') Solvent A comprises benzanilide and solvent B comprises DMPA, TMU or DMIB; A combination is preferred.
  • another solvent A may be used in addition to the specified solvent A.
  • the mass of the specified solvent A is, for example, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100% of the total mass of solvent A.
  • another solvent B may be used in addition to the specified solvent B.
  • the mass of the specified solvent B is, for example, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100% of the total mass of solvent B.
  • solvent A contains 1,3-dimethyl-2-imidazolidinone (DMI), preferably at 50% by weight or more (preferably greater than 50% by weight), and may even contain 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more.
  • DMI 1,3-dimethyl-2-imidazolidinone
  • Solvent A may contain only DMI.
  • solvent B contains N,N-dimethylpropionamide (DMPA), preferably at 50% by weight or more (preferably greater than 50% by weight), and may even contain 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more.
  • Solvent B may contain only DMPA.
  • solvent A contains 1,3-dimethyl-2-imidazolidinone
  • solvent B contains N,N-dimethylpropionamide
  • the total mass of the solvents preferably contains 80% by mass or more of 1,3-dimethyl-2-imidazolidinone and N,N-dimethylpropionamide, more preferably 90% by mass or more, or even 100% by mass.
  • the mass ratio of 1,3-dimethyl-2-imidazolidinone to N,N-dimethylpropionamide can be within the range of solvent A and solvent B described above, but may also be in the range of 20/80 to 80/20, for example.
  • Solvents other than solvent A and solvent B may be contained as the residue, but those with a lower boiling point than solvent A are preferred. They may also have a lower boiling point than solvent B.
  • solvents include water, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and N-ethyl-2-pyrrolidone, cyclic ester solvents such as gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, gamma-caprolactone, epsilon-caprolactone, and alpha-methyl-gamma-butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol-based solvents such as triethylene glycol, phenol-based solvents such as m-cresol, p-cresol, 3-chlorophenol, and 4-chlorophenol, acetophenone, sulfolane, and dimethyl sulfoxide.
  • amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidon
  • organic solvents include phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, turpentine, mineral spirits, and petroleum naphtha-based solvents. As other solvents, a combination of these solvents may also be used.
  • the polyimide precursor composition of the present invention can be produced by reacting the tetracarboxylic acid component and the diamine component in a solvent, specifically in a solvent containing at least one selected from solvent A and at least one selected from solvent B of the present invention.
  • the polyimide precursor used in the present invention (a polyimide precursor containing at least one repeating unit represented by formula (I)) can be produced by reacting the tetracarboxylic acid component and the diamine component in a solvent, specifically in a solvent containing at least one selected from solvent A and solvent B of the present invention, depending on the chemical structures of R1 and R2 .
  • Polyimide precursors can be easily produced for each classification by the following production methods. However, the production methods for the polyimide precursors used in the present invention are not limited to the following production methods.
  • a polyimide precursor can be suitably obtained as a polyimide precursor solution by reacting a tetracarboxylic dianhydride as a tetracarboxylic acid component with a diamine component in approximately equimolar amounts, preferably at a molar ratio of the diamine component to the tetracarboxylic acid component [number of moles of diamine component/number of moles of tetracarboxylic acid component] of 0.90 to 1.10, more preferably 0.95 to 1.05, in a solvent at a relatively low temperature, for example, 120° C. or lower, while suppressing imidization.
  • a polyimide precursor is obtained by dissolving a diamine in a solvent, gradually adding a tetracarboxylic dianhydride to the solution while stirring, and stirring for 1 to 72 hours at a temperature between 0 and 120°C, preferably between 5 and 80°C. If the reaction is carried out at 80°C or higher, the molecular weight may vary depending on the temperature history during polymerization, and imidization may progress due to heat, making it impossible to stably produce a polyimide precursor.
  • the order of addition of the diamine and tetracarboxylic dianhydride in the above production method is preferred because it makes it easier to increase the molecular weight of the polyimide precursor. It is also possible to reverse the order of addition of the diamine and tetracarboxylic dianhydride in the above production method, which is preferred because it reduces precipitation.
  • Tetracarboxylic dianhydride is reacted with any alcohol to obtain a diester dicarboxylic acid, which is then reacted with a chlorinating agent (e.g., thionyl chloride, oxalyl chloride) to obtain a diester dicarboxylic acid chloride.
  • a chlorinating agent e.g., thionyl chloride, oxalyl chloride
  • This diester dicarboxylic acid chloride and diamine are stirred in a solvent at temperatures ranging from ⁇ 20 to 120°C, preferably ⁇ 5 to 80°C, for 1 to 72 hours to obtain a polyimide precursor.
  • polyimide precursors can be easily obtained by dehydration condensation of diester dicarboxylic acid and diamine using a phosphorus-based condensing agent or a carbodiimide condensing agent.
  • a diamine and a silylating agent are reacted in advance to obtain a silylated diamine. If necessary, the silylated diamine is purified by distillation or other methods. The silylated diamine is then dissolved in a dehydrated solvent, and a tetracarboxylic dianhydride is gradually added while stirring. The mixture is stirred at a temperature ranging from 0 to 120°C, preferably from 5 to 80°C, for 1 to 72 hours to obtain a polyimide precursor. If the reaction is carried out at temperatures above 80°C, the molecular weight varies depending on the temperature history during polymerization, and imidization proceeds due to heat, potentially making it impossible to stably produce a polyimide precursor.
  • a polyimide precursor is obtained by mixing the polyamic acid solution obtained by method 1) with a silylating agent and stirring for 1 to 72 hours at a temperature ranging from 0 to 120° C., preferably from 5 to 80° C. If the reaction is carried out at a temperature higher than 80° C., the molecular weight may vary depending on the temperature history during polymerization, and imidization may proceed due to heat, which may make it impossible to stably produce the polyimide precursor.
  • chlorine-free silylating agent examples include N,O-bis(trimethylsilyl)trifluoroacetamide, N,O-bis(trimethylsilyl)acetamide, and hexamethyldisilazane. N,O-bis(trimethylsilyl)acetamide and hexamethyldisilazane are particularly preferred because they do not contain fluorine atoms and are low cost.
  • an amine catalyst such as pyridine, piperidine, or triethylamine can be used to accelerate the reaction.
  • This catalyst can be used as is as a polymerization catalyst for the polyimide precursor.
  • the monomer and solvent are charged and reacted at a concentration such that the solids concentration of the polyimide precursor (polyimide equivalent mass concentration) is, for example, 5 to 45 mass%.
  • the logarithmic viscosity of the polyimide precursor is not particularly limited, but it is preferable that the logarithmic viscosity in an N-methyl-2-pyrrolidone solution at a concentration of 0.5 g/dL at 30°C be 0.2 dL/g or more, more preferably 0.3 dL/g or more, and particularly preferably 0.4 dL/g or more.
  • the logarithmic viscosity is 0.2 dL/g or more, the molecular weight of the polyimide precursor is high, and the resulting polyimide has excellent mechanical strength and heat resistance.
  • the polyimide precursor composition contains at least one type of imidazole compound.
  • the imidazole compound is not particularly limited as long as it is a compound having an imidazole skeleton, and examples thereof include 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, imidazole, and benzimidazole. From the viewpoint of storage stability of the polyimide precursor composition, 2-phenylimidazole and benzimidazole are preferred. A plurality of imidazole compounds may be used in combination.
  • the content of the imidazole compound in the polyimide precursor composition can be selected appropriately, taking into consideration the balance between the effects of addition and the stability of the polyimide precursor composition.
  • the amount of the imidazole compound is preferably more than 0.0001 moles and less than 2 moles per mole of repeating units of the polyimide precursor. Addition of an imidazole compound is effective in improving light transmittance, linear thermal expansion coefficient, and/or mechanical properties, and within this content range, it is also effective in improving the storage stability of the polyimide precursor composition.
  • the content of the imidazole compound is more preferably 0.0005 mol or more, even more preferably 0.0008 mol or more, even more preferably 0.001 mol or more, and more preferably 1.0 mol or less, even more preferably 0.5 mol or less, even more preferably 0.1 mol or less, even more preferably 0.05 mol or less, and most preferably 0.01 mol or less, per 1 mol of repeating units.
  • the concentration of the polyimide precursor in the polyimide precursor composition is not particularly limited, but is typically 5 to 45 mass %, preferably 8 to 25 mass %, and more preferably 10 to 20 mass %, in terms of polyimide-equivalent mass concentration (hereinafter sometimes referred to as solids concentration).
  • the polyimide-equivalent mass refers to the mass assuming that all repeating units are completely imidized.
  • a tetracarboxylic acid component and a diamine component are reacted in predetermined amounts in a solvent, and the resulting polyimide precursor composition is used as is. Therefore, the solids concentration of the polyimide precursor composition is approximately equal to the amounts of the tetracarboxylic acid component and the diamine component charged. The concentration can be adjusted by dilution or concentration, as necessary.
  • polyimide precursor composition is cast onto a supporting substrate, and then imidized and desolvated by heat treatment to form a polyimide film, resulting in a laminate of the supporting substrate and polyimide film (polyimide film/substrate laminate).
  • a coating machine such as a slit coater with a narrow slit as a discharge outlet is used.
  • a coating machine such as a slit coater with a narrow slit as a discharge outlet is used.
  • the viscosity is too high, discharging becomes difficult, or the coating speed slows down, resulting in a decrease in production takt time.
  • the viscosity is too low, stable casting coating may become difficult. Therefore, polyimide precursor compositions used in industrial device manufacturing processes must have an appropriate viscosity to match the slit spacing, and the viscosity affects the cast coating film thickness.
  • the thickness of a polyimide film depends on the product of the solids concentration of the polyimide precursor composition and the cast film thickness, if the concentration is too low when the viscosity is adjusted to be suitable for coating, a polyimide film of the desired thickness cannot be produced.
  • a mixed solvent selected from “solvents A and B of the present application” it is possible to achieve the appropriate viscosity and solids concentration.
  • the polyimide precursor composition using this mixed solvent also has excellent viscosity stability.
  • a change in viscosity can cause a change in the cast coating film thickness, resulting in a change in the film thickness of the polyimide film, or can require a major change in the coating machine conditions, causing practical problems.
  • the polyimide precursor composition using this mixed solvent is more stable than a composition using only solvent A or only solvent B, and is preferably more stable than a composition using only solvent A or only solvent B. For example, if a composition containing only solvent A is more stable than a composition containing only solvent B, a composition using a mixed solvent containing both solvent A and solvent B will exhibit stability equal to or greater than that of a composition containing only solvent A.
  • the viscosity stability can be evaluated, for example, by the viscosity after 30 days based on the viscosity immediately after the production of the polyimide precursor composition.
  • the polyimide precursor composition of the present invention may optionally contain chemical imidizing agents (acid anhydrides such as acetic anhydride, or amine compounds such as pyridine or isoquinoline), antioxidants, UV absorbers, fillers (inorganic particles such as silica), dyes, pigments, coupling agents such as silane coupling agents, primers, flame retardants, antifoaming agents, leveling agents, rheology control agents (flow aids), etc.
  • chemical imidizing agents as acid anhydrides such as acetic anhydride, or amine compounds such as pyridine or isoquinoline
  • antioxidants antioxidants
  • UV absorbers fillers (inorganic particles such as silica), dyes, pigments
  • coupling agents such as silane coupling agents, primers, flame retardants, antifoaming agents, leveling agents, rheology control agents (flow aids), etc.
  • the polyimide precursor composition can be prepared by adding and mixing the imidazole compound or a solution of the imidazole compound to the polyimide precursor composition obtained after the reaction.
  • the tetracarboxylic acid component and the diamine component may be reacted in the presence of the imidazole compound.
  • the polyimide precursor composition of the present invention can be used to produce polyimides and polyimide films.
  • the production method is not particularly limited, and any known imidization method can be suitably applied.
  • Suitable forms of the obtained polyimide include films, laminates of polyimide films with other substrates, coating films, powders, beads, molded products, and foams.
  • the thickness of the polyimide film is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and even more preferably 5 ⁇ m or more, and is, for example, 250 ⁇ m or less, preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 50 ⁇ m or less.
  • the polyimide film of the present invention has excellent optical transparency, mechanical properties, thermal properties, and heat resistance (glass transition temperature, thermal decomposition resistance), with at least one of optical transparency and thermal decomposition resistance being particularly improved, and in preferred embodiments, both.
  • heat resistance can be classified into two categories: one related to phase change (indicated by glass transition temperature or melting temperature) and the other related to thermal decomposition (indicated by weight loss). Since these are different phenomena, there is no direct relationship between them.
  • the polyimide and polyimide film of the present invention have excellent glass transition temperature (Tg) and thermal decomposition resistance.
  • Known TFTs used in displays such as LCDs and OLEDs include amorphous silicon TFTs (a-Si TFTs), low-temperature polysilicon TFTs (LTPS TFTs), high-temperature polysilicon TFTs, and oxide TFTs.
  • a-Si TFTs amorphous silicon TFTs
  • LTPS TFTs low-temperature polysilicon TFTs
  • high-temperature polysilicon TFTs high-temperature polysilicon TFTs
  • oxide TFTs oxide TFTs.
  • High-temperature film formation is particularly advantageous for forming semiconductor layers with high charge mobility.
  • Amorphous silicon TFTs which can be formed at relatively low temperatures, require a film formation temperature of 300°C to 400°C, while low-temperature polysilicon TFTs require a film formation temperature of 600°C or below (for example, around 500°C).
  • thermal decomposition resistance of a polyimide film is insufficient, for example during the TFT formation process, outgassing due to polyimide decomposition can cause swelling between the polyimide film and the barrier film, and can contaminate the manufacturing equipment.
  • materials that are stable at high temperatures are preferred, i.e., films that have excellent thermal decomposition resistance at process temperatures and generate very little gas. From the perspective of process margins, films with a high thermal decomposition (onset) temperature are preferred, even if only slightly higher (for example, by a difference of around 2°C).
  • the thermal decomposition resistance of a polyimide film can be evaluated, for example, at the 0.5% weight loss temperature, 1% weight loss temperature, or 5% weight loss temperature of the polyimide film.
  • the 0.5% weight loss temperature of the example using the mixed solvent of solvent A and solvent B of the present invention is preferably 1° C. or more, more preferably 2° C. or more, and even more preferably 3° C. or more higher than the example using solvent A alone and/or (preferably "and") solvent B alone.
  • the 0.5% weight loss temperature of the example of this mixed solvent may be similar to the example using solvent A alone or solvent B alone, and even if it is about 2° C. lower, it may be acceptable.
  • the 1% weight loss temperature can be evaluated in the same manner.
  • solvent A is a solid at room temperature (e.g., 25°C)
  • the above improvement is preferably achieved over the example where solvent B is used alone.
  • the 0.5% weight loss temperature of the example in which a mixed solvent of solvent A and solvent B was used be improved by the same temperature difference as above.
  • the 0.5% weight loss temperature of the example in which this mixed solvent was used may be acceptable compared to the example in which NMP was used alone.
  • the decrease be limited to about 5°C, preferably 3°C, and more preferably 2°C.
  • the 1% weight loss temperature can be evaluated in the same manner.
  • the 0.5% weight loss temperature is preferably above 553°C, more preferably 554°C or higher, and even more preferably 555°C or higher.
  • the 1% weight loss temperature is preferably above 575°C, more preferably 576°C or higher, and even more preferably 577°C or higher.
  • the 450 nm light transmittance of the polyimide film when measured on a 10 ⁇ m-thick film, is improved by preferably 1% or more, more preferably 2% or more, in the example using the mixed solvent of solvent A and solvent B of the present invention, compared to the example using solvent A alone and/or (preferably "and") solvent B alone.
  • the 450 nm light transmittance of the example of this mixed solvent may be approximately the same as that of the example using solvent A alone or solvent B alone, and in some cases, a value about 2% lower may be acceptable.
  • solvent A is a solid at room temperature (e.g., 25°C)
  • the above improvement is preferably achieved over the example where solvent B is used alone.
  • the 450 nm light transmittance of a 10 ⁇ m thick film is preferably 68% or more, more preferably 69% or more, and even more preferably 70% or more.
  • the yellowness index (YI) of the polyimide film is preferably 40 or less, more preferably 35 or less, even more preferably 33 or less, and even more preferably 32 or less. Generally, a value of 0 or more is preferred.
  • the haze value of the polyimide film when measured on a 10 ⁇ m thick film, is preferably less than 1.0%, more preferably 0.8% or less, and even more preferably 0.7% or less. For example, if the haze value exceeds 1%, the film will become cloudy enough to be recognized visually, making it unsuitable for optical applications.
  • the breaking strength of the polyimide film is preferably 150 MPa or more, more preferably 200 MPa or more, even more preferably 220 MPa or more, even more preferably 250 MPa or more, and even more preferably 280 MPa or more.
  • the breaking strength can be, for example, a value obtained from a film having a thickness of approximately 5 to 100 ⁇ m.
  • a polyimide film/substrate laminate can be produced using the polyimide precursor composition of the present invention.
  • the polyimide film/substrate laminate can be produced by (a) applying the polyimide precursor composition to a supporting substrate, and (b) heat-treating the polyimide precursor on the supporting substrate to produce a laminate (polyimide film/substrate laminate) in which a polyimide film is laminated on the supporting substrate.
  • step (a) a polyimide precursor composition is cast onto a substrate, and a polyimide film is formed by imidization and desolvation through heat treatment, yielding a laminate of a supporting substrate and polyimide film (polyimide film/substrate laminate).
  • a heat-resistant material is used as the support substrate, such as a plate- or sheet-shaped substrate of a ceramic material (glass, alumina, etc.), a metal material (iron, stainless steel, copper, aluminum, etc.), a semiconductor material (silicon, compound semiconductor, etc.), or a film- or sheet-shaped substrate of a heat-resistant plastic material (polyimide, etc.).
  • a flat, smooth plate is preferred, and commonly used substrates include glass substrates such as soda-lime glass, borosilicate glass, alkali-free glass, and sapphire glass; semiconductor (including compound semiconductor) substrates such as silicon, GaAs, InP, and GaN; and metal substrates such as iron, stainless steel, copper, and aluminum.
  • the method for casting the polyimide precursor composition onto the substrate is not particularly limited, but examples include conventionally known methods such as slit coating, die coating, blade coating, spray coating, inkjet coating, nozzle coating, spin coating, screen printing, bar coating, and electrodeposition.
  • the thickness of the polyimide film is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and even more preferably 5 ⁇ m or more. If the thickness is less than 1 ⁇ m, the polyimide film will not maintain sufficient mechanical strength, and when used, for example, as a flexible electronic device substrate, it may not be able to withstand the stress and may break. Furthermore, the thickness of the polyimide film is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and even more preferably 20 ⁇ m or less. If the polyimide film is too thick, it may become difficult to thin the flexible device. To make the polyimide film thinner while maintaining sufficient durability for a flexible device, the thickness is preferably 2 to 50 ⁇ m.
  • the polyimide film/substrate laminate has little warpage. Measurement details are described in Japanese Patent No. 6798633.
  • the residual stress is preferably less than 27 MPa.
  • the polyimide film in the polyimide film/substrate laminate may have a second layer, such as a resin film or an inorganic film, on its surface. That is, a flexible electronic device substrate may be formed by forming a polyimide film on a substrate and then laminating the second layer thereon. It is preferable to have at least an inorganic film, and particularly preferable to have one that functions as a barrier layer against water vapor, oxygen (air), etc.
  • water vapor barrier layers include inorganic films containing inorganic substances selected from the group consisting of metal oxides, metal nitrides, and metal oxynitrides, such as silicon nitride (SiN x ) , silicon oxide (SiO x ), silicon oxynitride (SiO x N y ), aluminum oxide (Al 2 O 3 ), titanium oxide (TiO 2 ), and zirconium oxide (ZrO 2 ).
  • metal oxides silicon nitride (SiN x )
  • silicon oxide SiO x
  • silicon oxynitride SiO x N y
  • Al 2 O 3 aluminum oxide
  • TiO 2 titanium oxide
  • ZrO 2 zirconium oxide
  • known methods for forming these thin films include physical vapor deposition methods such as vacuum deposition, sputtering, and ion plating, and chemical vapor deposition methods (chemical vapor deposition methods) such as plasma CVD and catalytic chemical vapor deposition (Cat-CVD).
  • This second layer may also be multiple layers.
  • the second layer is multiple layers, it is also possible to combine a resin film and an inorganic film; for example, a three-layer structure of barrier layer/polyimide layer/barrier layer may be formed on the polyimide film in a polyimide film/substrate laminate.
  • step (c) the polyimide/substrate laminate obtained in step (b) is used to form at least one layer selected from a conductive layer and a semiconductor layer on a polyimide film (including polyimide film having a second layer such as an inorganic film laminated on its surface). These layers may be formed directly on the polyimide film (including polyimide film having a second layer laminated on it), or may be formed indirectly after laminating other layers required for the device.
  • a TFT liquid crystal display device for example, metal wiring, amorphous silicon or polysilicon TFTs, and transparent pixel electrodes are formed on a polyimide film, which has an inorganic film formed over its entire surface as needed.
  • the TFT includes, for example, a gate metal layer, a semiconductor layer such as an amorphous silicon film, a gate insulating layer, and wiring connected to the pixel electrodes. Further structures required for the liquid crystal display can be formed on top of this using known methods. Transparent electrodes and color filters may also be formed on the polyimide film.
  • a polyimide film can be formed over the entire surface with an inorganic film as needed, and then, in addition to a transparent electrode, a light-emitting layer, a hole transport layer, an electron transport layer, etc., a TFT can be formed as needed.
  • the peeling method may be a mechanical peeling method in which physical peeling is performed by applying an external force, or a so-called laser peeling method in which peeling is performed by irradiating the substrate surface with laser light.
  • the (semi-)finished product is made of polyimide film as a substrate, and the necessary structures or components for the device are then formed or incorporated to complete the device.
  • Example 1 [Preparation of Polyimide Precursor Composition] 10.8 g (0.1 mol) of PPD was placed in a reaction vessel purged with nitrogen gas, and solvents A and B were added to form a mixed solvent containing 75% by mass of 1,3-dimethyl-2-imidazolidinone (DMI) as solvent A and 25% by mass of N,N-dimethylpropionamide (DMPA) as solvent B.
  • the total mass of solvents A and B was 292.9 g, which was an amount that resulted in a total mass of charged monomers (the sum of the diamine component and the carboxylic acid component) of 12% by mass.
  • This solution was then stirred at room temperature for 3 hours. 29.1 g (0.1 mol) of s-BPDA was gradually added to this solution. This solution was stirred at room temperature for 12 hours, yielding a uniform and viscous polyimide precursor composition.
  • the initial viscosity of the resulting polyimide precursor composition (viscosity immediately after production) was measured, and then it was stored at 23°C in a sealed container filled with nitrogen gas. The viscosity after 30 days of storage was divided by the initial viscosity to determine the "viscosity retention rate (%)," which was used as an index of viscosity stability. The results are shown in Table 1.
  • a 6-inch Corning Eagle-XG (registered trademark) (500 ⁇ m thick) glass substrate was used.
  • the polyimide precursor composition was applied to the glass substrate and heated from room temperature to 430°C in a nitrogen atmosphere (oxygen concentration 200 ppm or less) on the glass substrate to thermally imidize it, yielding a polyimide film/substrate laminate.
  • the laminate was immersed in 40°C water (for example, at a temperature ranging from 20°C to 100°C) to peel the polyimide film from the glass substrate. After drying, the properties of the polyimide film were evaluated.
  • the thickness of the polyimide film was approximately 10 ⁇ m. The evaluation results are shown in Table 1.
  • Example 1 While maintaining the same varnish concentration (monomer concentration), the solvent composition was changed to that shown in Tables 1 to 7, and polyimide precursor compositions were obtained in the same manner as in Example 1. Thereafter, polyimide films were produced in the same manner as in Example 1, and the film properties were evaluated in the same manner. The results are shown in Tables 1 to 7.
  • the values listed in the acid dianhydride column in the tables represent the content of each component relative to 100 mol% of the total amount of acid dianhydride.
  • the values listed in the diamine column in the tables represent the content of each component relative to 100 mol% of the total amount of diamine.
  • the values listed in the solvent column in the tables represent the content of each solvent when the total amount of solvent is taken as 100 mass%.
  • the viscosity stability of the obtained polyimide precursor compositions was evaluated in the same manner as in Example 1 for the examples listed in Table 1.
  • Examples 39 to 58, Comparative Examples 13 to 17, and Reference Example 2 The monomer compositions and solvents used in Example 1 were changed to those shown in Tables 8 to 10, and polyimide precursor compositions were obtained in the same manner as in Example 1. Thereafter, polyimide films were produced in the same manner as in Example 1, and the film properties were evaluated in the same manner. The results are shown in Tables 8 to 10. The values in the tables represent the content of each component, as in Tables 1 to 7.
  • the present invention can be suitably applied to the manufacture of flexible electronic devices, such as display devices such as liquid crystal displays, organic EL displays, and electronic paper, as well as light-receiving devices such as solar cells and CMOS.
  • display devices such as liquid crystal displays, organic EL displays, and electronic paper
  • light-receiving devices such as solar cells and CMOS.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

La présente invention propose une composition de précurseur de polyimide pour produire un film de polyimide aromatique dans lequel la transmittance de lumière et/ou la résistance à la chaleur sont améliorées. La composition de précurseur de polyimide comprend : un précurseur de polyimide ayant une unité de répétition représentée par la formule (I) ; un solvant A choisi parmi la 1,3-diméthyl-2-imidazolidinone, le 3-méthoxy-N,N-diméthylpropanamide, la 1-butyl-2-pyrrolidone, le N,N-diphénylformamide, le N,N-diéthylbenzamide, le benzanilide et la 1-phényl-2-pyrrolidone ; et un solvant B choisi parmi le N,N-diméthylpropionamide, le N,N-diéthylformamide, le N,N-diéthylacétamide N, le N-diméthylisobutylamide, le N,N-diéthylpropionamide et la tétraméthyl urée. (Dans la formule, R1 et R2 sont chacun un atome d'hydrogène ou similaire, et pas moins de 50 % en moles de X1 est un groupe aromatique et/ou pas moins de 50 % en moles de Y1 est un groupe aromatique.)
PCT/JP2025/014532 2024-04-26 2025-04-11 Composition de précurseur de polyimide et film de polyimide Pending WO2025225424A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015155504A (ja) * 2014-02-20 2015-08-27 東京応化工業株式会社 ポリイミド樹脂の製造方法、ポリイミド膜の製造方法、ポリアミック酸溶液の製造方法、ポリイミド膜、及びポリアミック酸溶液
WO2015186782A1 (fr) * 2014-06-04 2015-12-10 宇部興産株式会社 Procédé de production d'un film de polyimide
WO2016167038A1 (fr) * 2015-04-15 2016-10-20 東レ株式会社 Composition de résine résistant à la chaleur, procédé de fabrication d'un film de résine résistant à la chaleur, procédé de fabrication d'un film d'isolation intercouche ou d'un film protecteur de surface et procédé de fabrication de composant électronique ou de composant semi-conducteur

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015155504A (ja) * 2014-02-20 2015-08-27 東京応化工業株式会社 ポリイミド樹脂の製造方法、ポリイミド膜の製造方法、ポリアミック酸溶液の製造方法、ポリイミド膜、及びポリアミック酸溶液
WO2015186782A1 (fr) * 2014-06-04 2015-12-10 宇部興産株式会社 Procédé de production d'un film de polyimide
WO2016167038A1 (fr) * 2015-04-15 2016-10-20 東レ株式会社 Composition de résine résistant à la chaleur, procédé de fabrication d'un film de résine résistant à la chaleur, procédé de fabrication d'un film d'isolation intercouche ou d'un film protecteur de surface et procédé de fabrication de composant électronique ou de composant semi-conducteur

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