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WO2025121336A1 - Résine polyimide - Google Patents

Résine polyimide Download PDF

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Publication number
WO2025121336A1
WO2025121336A1 PCT/JP2024/042779 JP2024042779W WO2025121336A1 WO 2025121336 A1 WO2025121336 A1 WO 2025121336A1 JP 2024042779 W JP2024042779 W JP 2024042779W WO 2025121336 A1 WO2025121336 A1 WO 2025121336A1
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Prior art keywords
mol
compound represented
formula
structural unit
polyimide resin
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English (en)
Japanese (ja)
Inventor
雅也 甲山
重之 廣瀬
修也 末永
晃久 松丸
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Publication of WO2025121336A1 publication Critical patent/WO2025121336A1/fr
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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
    • 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

Definitions

  • the present invention relates to polyimide resins.
  • polyimide resins are obtained by polycondensation of aromatic tetracarboxylic anhydrides and aromatic diamines. Due to their structure, polyimide resins have molecular rigidity, resonance stabilization, and strong chemical bonds. Therefore, polyimide resins have excellent heat resistance, chemical resistance, mechanical properties, and electrical properties, and are widely used in fields such as molding materials, composite materials, electrical and electronic parts, optical materials, displays, and aerospace. In recent years, polyimides have been increasingly used as optical and electronic materials for image display devices, and properties such as colorless transparency and solvent solubility of polyimide resins are being required. However, conventional polyimides have a problem in that many of them have high haze values and yellow indexes (YI: yellowness).
  • Patent Document 1 proposes a film that includes a fluorinated polyimide layer having a total haze value of 4 or less, a yellow index of 3 or less, and a total light transmittance of 90% or more.
  • Fluorinated polyimide can improve colorlessness and transparency and improve solubility, but some compounds belonging to the group of perfluoroalkyl compounds and polyfluoroalkyl compounds (PFAS; perfluoroalkyl substances and polyfluoroalkyl substances) are restricted substances in the European REACH (Registration, Evaluation, Authorization and Restriction of Chemicals) regulations due to concerns about environmental burden and health hazards, and the regulations are expected to become stricter in the future.
  • PFAS perfluoroalkyl compounds and polyfluoroalkyl compounds
  • EEACH Registration, Evaluation, Authorization and Restriction of Chemicals
  • the use of perfluoroalkyl compounds and polyfluoroalkyl compounds in electronic components may be restricted. If it is only necessary to improve colorlessness and transparency, it is possible to improve colorlessness and transparency by using an aliphatic raw material, an alicyclic raw material, etc.
  • an object of the present invention is to provide a polyimide resin that has a high elastic modulus and high strength, is excellent in elongation, is soluble in a solvent, and is colorless and transparent.
  • an object of the present invention is to provide a polyimide resin that has the above properties without containing a perfluoroalkyl structure or a polyfluoroalkyl structure.
  • the inventors discovered that a polyimide resin containing a specific combination of structural units and a specific structure can solve the above problems, leading to the completion of the invention.
  • a method for producing a polyimide resin comprising: a step of imidizing a tetracarboxylic dianhydride containing a compound represented by the following formula (a1) and a diamine containing a compound represented by the following formula (b1) in the presence of a base catalyst and an organic solvent containing a lactone-based solvent, wherein neither the tetracarboxylic dianhydride nor the diamine contains the following structural element (c), and the amount of the base catalyst is 30 mol % or more relative to the amount of the tetracarboxylic dianhydride, or the organic solvent containing the lactone-based solvent contains an amide-based solvent.
  • a method for producing a polyimide resin comprising: a step of imidizing a tetracarboxylic dianhydride containing a compound represented by the following formula (a1) and a diamine containing a compound represented by the following formula (b1) in the presence of a base catalyst, wherein the compound represented by formula (a1) contains a compound represented by the following formula (a11): [11]
  • the present invention provides a polyimide resin that has a high elastic modulus and high strength, yet also has excellent elongation, is soluble in solvents, and is colorless and transparent.
  • a polyimide resin that has the above properties without containing a perfluoroalkyl structure or a polyfluoroalkyl structure. Therefore, the polyimide resin of the present invention is useful as an optical material or electronic material, particularly as a display material.
  • the polyimide resin of the present invention is a polyimide resin having a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, wherein the structural unit A contains a structural unit (A1) derived from a compound represented by the following formula (a1), the structural unit (A1) contains 35 mol % or more of a trans structure derived from (1R,2S,4S,5R)-cyclohexanetetracarboxylic dianhydride, and the structural unit B contains a structural unit (B1) derived from a compound represented by the following formula (b1), but does not contain the following structural element (c):
  • the polyimide resin of the present invention is colorless and has excellent transparency, has a high elastic modulus and excellent elongation, and is soluble in a solvent.
  • X is a fluorine atom, a hydrogen atom, or a carbon atom.
  • the reason why the polyimide resin of the present invention has a high elastic modulus and high strength, yet is excellent in elongation, is soluble in a solvent, and is colorless and transparent is not clear, but is thought to be as follows.
  • the polyimide resin of the present invention is considered to have excellent colorless transparency and solubility due to the inclusion of a cyclohexane structure, which is an alicyclic structure.
  • it is considered to have a high elastic modulus and high strength due to the inclusion of a rigid structure, namely a biphenyl structure having a substituent.
  • the trans structure derived from (1R,2S,4S,5R)-cyclohexanetetracarboxylic dianhydride is considered to have good packing, and it is considered that by including a certain amount or more of this structure, it is possible to achieve a high elastic modulus and high strength while maintaining the above-mentioned performance, and further, it is considered that the good packing suppresses breakage due to slippage of polymer chains and improves elongation. From the above, it is considered that the polyimide resin of the present invention has a high elastic modulus and high strength, is excellent in elongation, is soluble in a solvent, and is colorless and transparent.
  • the structural unit A is a structural unit derived from a tetracarboxylic dianhydride contained in a polyimide resin.
  • the structural unit A contains a structural unit (A1) derived from a compound represented by the following formula (a1), and the structural unit (A1) contains 35 mol % or more of a trans structure derived from (1R,2S,4S,5R)-cyclohexanetetracarboxylic dianhydride and does not contain the following structural element (c).
  • X is a fluorine atom, a hydrogen atom, or a carbon atom.
  • the structural unit A contains at least a certain amount of the structural unit (A1), particularly the trans structure, it is possible to increase the elastic modulus and strength of the polyimide resin, improve elongation, improve colorless transparency, and improve solvent solubility without containing the perfluoroalkyl structure or polyfluoroalkyl structure represented by the structural element (c).
  • the compound represented by formula (a1) is 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA).
  • HPMDA 1,2,4,5-cyclohexanetetracarboxylic dianhydride
  • the ratio of the structural unit (A1) in the structural unit A is preferably 35 mol% or more, more preferably 50 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 85 mol% or more, even more preferably 90 mol% or more, with the upper limit being 100 mol% or less.
  • the structural unit A may consist of only the structural unit (A1).
  • the structural unit (A1) contains a trans structure derived from (1R,2S,4S,5R)-cyclohexanetetracarboxylic dianhydride.
  • the trans structure derived from (1R,2S,4S,5R)-cyclohexanetetracarboxylic dianhydride refers to a structure of the following formula (1) in the skeleton of a polyimide resin. Note that the structure of the following formula (2) is a cis structure and is not included in the trans structure.
  • the raw material for obtaining the structure of formula (1) is preferably (1R,2S,4S,5R)-cyclohexanetetracarboxylic dianhydride, but is not limited to (1R,2S,4S,5R)-cyclohexanetetracarboxylic dianhydride, and may be a raw material other than (1R,2S,4S,5R)-cyclohexanetetracarboxylic dianhydride, such as (1S,2R,4S,5R)-cyclohexanetetracarboxylic dianhydride having a cis structure.
  • the structure of formula (1) is a trans structure derived from (1R,2S,4S,5R)-cyclohexanetetracarboxylic dianhydride.
  • the ratio of the trans structure derived from the (1R,2S,4S,5R)-cyclohexanetetracarboxylic dianhydride contained in the structural unit (A1) is 35 mol% or more in the structural unit (A1).
  • the ratio of the trans structure derived from the (1R,2S,4S,5R)-cyclohexanetetracarboxylic dianhydride contained in the structural unit (A1) is preferably 35 to 100 mol%, more preferably 40 to 100 mol%, even more preferably 50 to 100 mol%, still more preferably 55 to 100 mol%, even more preferably 60 to 100 mol%, even more preferably 70 to 100 mol%, even more preferably 75 to 100 mol%, and still more preferably It is preferably 80 to 100 mol%, even more preferably 85 to 100 mol%, even more preferably 90 to 100 mol%, and even more preferably 95 to 100 mol%, and the structural unit (A1) may consist only of a trans structure derived from (1R,2S,4S,5R)-cyclohexanetetracarboxylic dianhydride, and it is even more preferable that the structural unit (A1) consists only of a trans structure derived from (1R,2S,4S,
  • the transparency of the obtained polyimide resin can be improved and the elastic modulus can be increased. That is, the ratio of the structure of formula (1) contained in the structural unit (A1) is 35 mol% or more in the structural unit (A1).
  • the ratio of the structure of formula (1) contained in the structural unit (A1) is preferably 35 to 100 mol%, more preferably 40 to 100 mol%, even more preferably 50 to 100 mol%, even more preferably 55 to 100 mol%, even more preferably 60 to 100 mol%, even more preferably 70 to 100 mol%, even more preferably 75 to 100 mol%, even more preferably 80 to 100 mol%, even more preferably 85 to 100 mol%, even more preferably 90 to 100 mol%, even more preferably 95 to 100 mol%, and the structural unit (A1) may be composed only of the structure of formula (1), and it is even more preferable that the structural unit (A1) is composed only of the structure of formula (1).
  • the structural unit (A1) contains a trans structure, the transparency of the resulting polyimide resin can be improved and the elastic modulus can be increased.
  • the structural unit A may be composed only of the structural unit (A1), or may include a structural unit other than the structural unit (A1).
  • the structural unit A further includes, as a structural unit other than the structural unit (A1), a structural unit (A2) derived from a compound represented by the following formula (a2):
  • the compound represented by formula (a2) is 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA).
  • CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • the ratio of structural unit (A2) in structural unit A is preferably 0 to 27 mol%, more preferably 0.5 to 27 mol%, even more preferably 1 to 27 mol%, even more preferably 3 to 27 mol%, even more preferably 5 to 27 mol%, even more preferably 10 to 27 mol%, even more preferably 10 to 25 mol%, even more preferably 15 to 25 mol%, even more preferably 15 to 23 mol%, and even more preferably 15 to 22 mol%.
  • the ratio of the structural unit (A1) in the structural unit A is preferably 73 to 100 mol%, and when the structural unit A contains the structural unit (A2), the ratio of the structural unit (A1) in the structural unit A is preferably 99.5 mol% or less, more preferably 73 to 99.5 mol%, even more preferably 73 to 99 mol%, even more preferably 73 to 97 mol%, even more preferably 73 to 95 mol%, even more preferably 73 to 90 mol%, even more preferably 75 to 90 mol%, even more preferably 75 to 85 mol%, even more preferably 77 to 85 mol%, and even more preferably 78 to 85 mol%.
  • the molar ratio of the structural unit (A1) to the structural unit (A2) in the structural unit A [(A1)/(A2)] is preferably 73/27 to 99.5/0.5, more preferably 73/27 to 99/1, even more preferably 73/27 to 97/3, even more preferably 73/27 to 95/5, even more preferably 73/27 to 90/10, even more preferably 75/25 to 90/10, even more preferably 75/25 to 85/15, even more preferably 77/23 to 85/15, and even more preferably 78/22 to 85/15.
  • the total ratio of the structural units (A1) and (A2) in the structural unit A is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 90 mol% or more, and preferably 100 mol% or less.
  • the structural unit A may consist only of the structural units (A1) and (A2), and it is even more preferable that the structural unit A consists only of the structural units (A1) and (A2).
  • the total ratio of the structural units (A1) and (A2) in the structural unit A may be 100 mol%, and it is even more preferable that it is 100 mol%.
  • the structural unit A may contain structural units other than the structural unit (A1) and the structural unit (A2).
  • the tetracarboxylic dianhydride that gives such a structural unit is not particularly limited, but may include aromatic tetracarboxylic dianhydrides other than the above compounds, alicyclic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides.
  • ODPA 4,4'-oxydiphthalic anhydride
  • DSDA 3,3',
  • Examples of alicyclic tetracarboxylic dianhydrides include cyclohexane-1,2,3,4-tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclopentane tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyl tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, decahydro-1,4:5,8-dimethanonaphthalene-2,3,6,7-tetracarboxylic dianhydride (DNDA), 5,5'-(1,4-phenylene)-bis[hexahydro-4,7-methanoisobenzofuran-1,3-dione], 5,5'-bis-2-norborane, and the like.
  • DNDA 5,
  • aliphatic tetracarboxylic dianhydride examples include 1,2,3,4-butanetetracarboxylic dianhydride.
  • aromatic tetracarboxylic acid dianhydride refers to a tetracarboxylic acid dianhydride containing one or more aromatic rings
  • alicyclic tetracarboxylic acid dianhydride refers to a tetracarboxylic acid dianhydride containing one or more alicyclic rings but no aromatic rings
  • aliphatic tetracarboxylic acid dianhydride refers to a tetracarboxylic acid dianhydride containing neither an aromatic ring nor an alicyclic ring.
  • the structural unit optionally contained in the structural unit A may be of one type, or of two or more types.
  • the structural unit B is a structural unit derived from a diamine contained in the polyimide resin.
  • the structural unit B contains a structural unit (B1) derived from a compound represented by the following formula (b1): In addition, it does not contain the following structural element (c).
  • X is a fluorine atom, a hydrogen atom, or a carbon atom.
  • the elastic modulus can be increased while maintaining the colorless transparency and solvent solubility of the polyimide resin without containing the perfluoroalkyl structure or polyfluoroalkyl structure represented by the structural element (c).
  • the compound represented by formula (b1) is 2,2'-dimethylbenzidine (mTB).
  • the ratio of the structural unit (B1) in the structural unit B is preferably 40 to 100 mol%, more preferably 50 to 100 mol%, even more preferably 70 to 100 mol%, even more preferably 80 to 100 mol%, even more preferably 85 to 100 mol%, and even more preferably 85 to 95 mol%.
  • the ratio of the structural unit (B1) in the structural unit B may be 100 mol%, and the structural unit B may consist only of the structural unit (B1).
  • the structural unit B may consist only of the structural unit (B1), or may include a structural unit other than the structural unit (B1).
  • the structural unit B further includes, as a structural unit other than the structural unit (B1), a structural unit (B2) derived from a compound represented by the following formula (b2): (In formula (b2), each R is independently a hydrogen atom or a methyl group, Y is a divalent group containing an aromatic ring and having 12 to 30 carbon atoms, and n is 0 or 1.)
  • each R is independently a hydrogen atom or a methyl group
  • Y is a divalent group containing an aromatic ring and having 12 to 30 carbon atoms
  • n is 0 or 1.
  • Each R is independently a hydrogen atom or a methyl group, preferably a hydrogen atom, and more preferably both of the two R's are hydrogen atoms.
  • n is 0 or 1, preferably 1.
  • the compound represented by formula (b2) is 4,4'-diaminobenzanilide (DABA).
  • the structural unit B By including in the structural unit B a structural unit derived from 4,4'-diaminobenzanilide (DABA) among the structural units (B2), it is possible to improve the colorless transparency and elongation while maintaining the high elastic modulus of the polyimide resin.
  • DABA 4,4'-diaminobenzanilide
  • the compound represented by formula (b2) when n is 1, contains Y which is a divalent group having 12 to 30 carbon atoms. Y is a divalent group containing an aromatic ring and having 12 to 30 carbon atoms, and is preferably a divalent group containing an aromatic ring and having 12 to 26 carbon atoms.
  • preferred compounds when n is 1 include compounds represented by the following formula (b21), compounds represented by the following formula (b22), compounds represented by the following formula (b23), and compounds represented by the following formula (b24).
  • the compound represented by formula (b2) is preferably at least one selected from the group consisting of a compound represented by the following formula (b21), a compound represented by the following formula (b22), a compound represented by the following formula (b23), and a compound represented by the following formula (b24), more preferably at least one selected from the group consisting of a compound represented by the following formula (b21), a compound represented by the following formula (b22), and a compound represented by the following formula (b23), even more preferably at least one selected from the group consisting of a compound represented by the following formula (b21) and a compound represented by the following formula (b23), and still more preferably a compound represented by formula (b21).
  • the compound represented by formula (b21) is N,N'-(2,2'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis[4-amino-3-methylbenzamide] (AMB-mTOL).
  • AMB-mTOL N,N'-(2,2'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis[4-amino-3-methylbenzamide]
  • the structural unit B contains a structural unit derived from the compound represented by formula (b21), which is one of the structural units (B2), it is possible to improve the colorless transparency and elongation while maintaining the high elastic modulus of the polyimide resin.
  • the compound represented by formula (b22) is N,N'-[(octahydro-1,3,5,7-tetraoxobenzo[1,2-c:4,5-c']dipyrrole-2,6(1H,3H)-diyl)bis(3-methoxy-4,1-phenylene)]bis[4-amino-benzamide] (AB-MP-HPMDI).
  • the structural unit B contains a structural unit derived from the compound represented by formula (b22), which is one of the structural units (B2), it is possible to improve the colorless transparency and elongation while maintaining a high elastic modulus of the polyimide resin.
  • the compound represented by formula (b23) is N,N'-(2,2'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis[4-amino-benzamide] (AB-mTOL).
  • the structural unit B contains a structural unit derived from the compound represented by formula (b23), which is one of the structural units (B2), it is possible to improve the colorless transparency and elongation while maintaining a high elastic modulus of the polyimide resin.
  • the compound represented by formula (b24) is N,N'-(oxydi-4,1-phenylene)bis[4-amino-benzamide] (AB-44ODA).
  • the structural unit B contains a structural unit derived from the compound represented by formula (b24), which is one of the structural units (B2), it is possible to improve the colorless transparency and elongation while maintaining a high elastic modulus of the polyimide resin.
  • the structural unit (B2) in the structural unit B, it is possible to improve the colorless transparency and elongation while maintaining a high elastic modulus of the polyimide resin.
  • the proportion of the structural unit (B2) in the structural unit B is preferably 1 to 60 mol%, more preferably 1 to 50 mol%, even more preferably 1 to 40 mol%, still more preferably 1 to 30 mol%, even more preferably 3 to 25 mol%, even more preferably 3 to 20 mol%, even more preferably 5 to 20 mol%, and even more preferably 5 to 15 mol%.
  • the molar ratio of the structural unit (B1) to the structural unit (B2) in the structural unit B [(B1)/(B2)] is preferably 40/60 to 99/1, more preferably 50/50 to 99/1, even more preferably 60/40 to 99/1, even more preferably 70/30 to 99/1, even more preferably 75/25 to 97/3, even more preferably 80/20 to 97/3, even more preferably 80/20 to 95/5, and even more preferably 85/15 to 95/5.
  • the total ratio of the structural unit (B1) and the structural unit (B2) in the structural unit B is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and preferably 100 mol% or less.
  • the structural units contained in the structural unit B may be only the structural unit (B1) and the structural unit (B2).
  • the structural unit B may contain structural units other than the structural unit (B1) and the structural unit (B2).
  • Diamines that provide such structural units are not particularly limited, but include aromatic diamines, alicyclic diamines, and aliphatic diamines, excluding the compound represented by formula (b1) and excluding the compound represented by formula (b2).
  • Aromatic diamines other than the above compounds include 4,4'-diaminodiphenyl sulfone (4,4'-DDS), 3,3'-diaminodiphenyl sulfone (3,3'-DDS), octafluorobenzidine (8FBZ), 2,3,5,6-tetrafluorobenzene-1,4-diamine, 2,4,5,6-tetrafluorobenzene-1,3-diamine, bis(4-aminophenyl)terephthalate (APTP), 1,4-bis(4-aminobenzoyloxy)benzene, 4,4'-diaminodiphenyl ether (4,4'-ODA), 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane (DDM), 9, 9-bis(4-aminophenyl)fluorene (BAFL), 4,4'-diaminobiphenyl (
  • alicyclic diamine examples include 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), 1,4-bis(aminomethyl)cyclohexane, 1,3-cyclohexyldiamine, 1,4-cyclohexyldiamine, isophoronediamine, bis(aminomethyl)norbornane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyl ether, and 2,2-bis(4-aminocyclohexyl)propane.
  • Aliphatic diamines include ethylenediamine and hexamethylenediamine.
  • an aromatic diamine means a diamine containing one or more aromatic rings
  • an alicyclic diamine means a diamine containing one or more alicyclic rings but no aromatic rings
  • an aliphatic diamine means a diamine containing neither an aromatic ring nor an alicyclic ring.
  • the structural unit optionally contained in the structural unit B may be of one type, or of two or more types.
  • the polyimide resin of the present invention does not contain the following structural element (c).
  • X is a fluorine atom, a hydrogen atom, or a carbon atom.
  • the structural element (c) in the present invention will be described in detail below. Note that the structural element (c) in the polyimide resin, its production method, polyimide varnish, and polyimide film of the present invention all have the same meaning.
  • the carbon atom bonded to the CF2 group other than X in formula (c) is a secondary carbon, a tertiary carbon, or a quaternary carbon, and may be a carbon atom constituting an aromatic ring, and may be substituted with an atom other than a hydrogen atom and a carbon atom. Examples of the atom other than a hydrogen atom and a carbon atom include a halogen atom, a nitrogen atom, and an oxygen atom.
  • the carbon atom X is a primary carbon, a secondary carbon, a tertiary carbon, or a quaternary carbon, and may be a carbon atom constituting an aromatic ring, and may be substituted with an atom other than a hydrogen atom and a carbon atom.
  • the atom other than a hydrogen atom and a carbon atom include a halogen atom, a nitrogen atom, and an oxygen atom.
  • the structural element (c) is a perfluoroalkyl structure or a polyfluoroalkyl structure.
  • polyimide resins containing the above structural elements include polyimide resins having a structural unit derived from the following tetracarboxylic dianhydride and a structural unit derived from the following diamine.
  • the polyimide resin of the present invention does not have any of the structural units derived from the following tetracarboxylic dianhydride and the structural units derived from the following diamine.
  • tetracarboxylic dianhydride examples include 9,9-bis(trifluoromethyl)-9H-xanthene-2,3,6,7-tetracarboxylic dianhydride (6FCDA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA).
  • the diamines include 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA), 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (2,2'-TFMB), 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-5,5'-diaminobiphenyl, 2,2-bis(4-aminophenyl)hexafluoropropane (HFDA), 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), and the like.
  • 6FODA 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether
  • the number average molecular weight of the polyimide resin is preferably 5,000 to 300,000 from the viewpoint of the mechanical strength of the resulting polyimide film.
  • the number average molecular weight of the polyimide resin can be determined, for example, from a standard polymethyl methacrylate (PMMA) equivalent value measured by gel filtration chromatography.
  • the polyimide resin may contain a structure other than the polyimide chain (a structure formed by imide bonding between the structural unit A and the structural unit B).
  • structures other than the polyimide chain that may be contained in the polyimide resin include structures containing amide bonds.
  • the structures other than the polyimide chain do not contain the structural element (c).
  • the polyimide resin preferably contains a polyimide chain (a structure formed by imide bonding of structural unit A and structural unit B) as a main structure. Therefore, the ratio of the polyimide chain in the polyimide resin is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, and even more preferably 99% by mass or more. Also, it is preferably 100% by mass or less. Even more preferably, it is 100% by mass, and the polyimide resin may be composed of only polyimide chains.
  • the structural unit A derived from a tetracarboxylic dianhydride contains a structural unit (A1) derived from a compound represented by formula (a1), and the structural unit (A1) contains 35 mol % or more of a trans structure derived from (1R,2S,4S,5R)-cyclohexanetetracarboxylic dianhydride. Therefore, it is necessary to produce the polyimide resin under conditions that result in the trans structure. According to the production method of the present invention, a polyimide resin having the trans structure can be obtained.
  • a first production method which is a first embodiment includes a step of imidizing a tetracarboxylic dianhydride containing a compound represented by the following formula (a1) and a diamine containing a compound represented by the following formula (b1) in the presence of a base catalyst and an organic solvent containing a lactone-based solvent, in which the ratio of the compound represented by formula (a1) in the tetracarboxylic dianhydride is 35 mol % or more, neither the tetracarboxylic dianhydride nor the diamine contains the following structural element (c), and the amount of the base catalyst is 30 mol % or more relative to the amount of the tetracarboxylic dianhydride, or the organic solvent containing a lactone-based solvent includes an amide-based solvent.
  • the first production method further includes a method in which the amount of the base catalyst is 30 mol % or more based on the amount of the tetracarboxylic dianhydride, and a method in which the organic solvent containing a lactone solvent contains an amide solvent.
  • the method in which the amount of the base catalyst is 30 mol % or more based on the amount of the tetracarboxylic dianhydride (The method in which the amount of the base catalyst is 30 mol % or more based on the amount of the tetracarboxylic dianhydride)
  • the polyimide resin having the trans structure can be obtained. It is believed that when the amount of the base catalyst is equal to or greater than a certain amount, the imidization reaction is promoted and at the same time the isomerization reaction from cis type to trans type easily proceeds, making it possible to obtain a polyimide resin having a trans type structure.
  • the base catalyst and organic solvent used in this method are described below.
  • the base catalyst examples include organic base catalysts such as pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine (TEA), tripropylamine, tributylamine, triethylenediamine, imidazole, N,N-dimethylaniline, and N,N-diethylaniline; and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate, and sodium hydrogencarbonate.
  • organic base catalysts such as pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine (TEA), tripropylamine, tributylamine, triethylenediamine, imidazole, N,N-dimethylaniline, and N,N-dieth
  • an organic base catalyst is more preferred, at least one selected from the group consisting of triethylamine and triethylenediamine is even more preferred, and both triethylamine and triethylenediamine are even more preferred. Therefore, it is even more preferred that the base catalyst contains both triethylamine and triethylenediamine.
  • the amount of base catalyst used in this method is 30 mol% or more, preferably 100 mol% or less, more preferably 30 to 100 mol%, even more preferably 30 to 60 mol%, and even more preferably 40 to 60 mol%, relative to the amount of the tetracarboxylic dianhydride.
  • the amount of triethylamine used in this step is preferably 20 mol% or more, preferably 100 mol% or less, more preferably 20 to 90 mol%, even more preferably 20 to 60 mol%, even more preferably 20 to 55 mol%, even more preferably 30 to 55 mol%, and even more preferably 40 to 55 mol%, relative to the amount of the tetracarboxylic dianhydride.
  • the amount of triethylenediamine is preferably 50 mol% or less, more preferably 1 to 50 mol%, even more preferably 1 to 20 mol%, even more preferably 1 to 10 mol%, even more preferably 1 to 7 mol%, even more preferably 1 to 6 mol%, even more preferably 2 to 6 mol%, and even more preferably 3 to 6 mol%, based on the amount of the tetracarboxylic dianhydride.
  • the organic solvent used in the present method includes a lactone solvent.
  • lactone solvents include ⁇ -butyrolactone (GBL) and ⁇ -valerolactone, with ⁇ -butyrolactone (GBL) being preferred.
  • the ratio of the lactone solvent contained in the organic solvent is preferably 10 to 100 mass%, more preferably 30 to 100 mass%, even more preferably 50 to 100 mass%, still more preferably 70 to 100 mass%, still more preferably 90 to 100 mass%, still more preferably 95 to 100 mass%, and still more preferably 99 to 100 mass%, relative to the total amount of the organic solvent, and the organic solvent may consist of only the lactone solvent.
  • the organic solvent may include an organic solvent other than a lactone-based solvent.
  • organic solvents include, but are not limited to, aprotic solvents other than lactone-based solvents, phenol-based solvents, etc.
  • Examples of aprotic solvents other than lactone-based solvents include amide-based solvents, glycol-based solvents, phosphorus-containing amide-based solvents, sulfur-containing solvents, ketone-based solvents, amine-based solvents, ester-based solvents, ether-based solvents, and carbonate-based solvents.
  • Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylcaprolactam, 1,3-dimethylimidazolidinone, tetramethylurea, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide.
  • glycol solvent examples include diethylene glycol dimethyl ether, triethylene glycol, and triethylene glycol dimethyl ether.
  • examples of phosphorus-containing amide solvents include hexamethylphosphoric amide and hexamethylphosphine triamide.
  • Examples of the sulfur-containing solvent include dimethyl sulfone, dimethyl sulfoxide, and sulfolane.
  • Examples of the ketone solvent include acetone, cyclopentanone, cyclohexanone, and methylcyclohexanone.
  • the amine solvent examples include picoline and pyridine.
  • Examples of the ester solvent include 2-methoxy-1-methylethyl acetate.
  • ether solvent examples include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, and 1,4-dioxane.
  • carbonate solvent examples include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, and propylene carbonate.
  • phenol-based solvent examples include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol.
  • organic solvents other than the lactone solvents aprotic solvents are preferred, and amide solvents are more preferred.
  • the organic solvents may be used alone or in combination of two or more.
  • the base catalyst examples include organic base catalysts such as pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine (TEA), tripropylamine, tributylamine, triethylenediamine, imidazole, N,N-dimethylaniline, and N,N-diethylaniline; and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate, and sodium hydrogencarbonate.
  • organic base catalysts such as pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine (TEA), tripropylamine, tributylamine, triethylenediamine, imidazole, N,N-dimethylaniline, and N,N-dieth
  • an organic base catalyst is more preferred, at least one selected from the group consisting of triethylamine and triethylenediamine is even more preferred, and it is even more preferred to use both triethylamine and triethylenediamine.
  • the amount of base catalyst used in this step is preferably 100 mol% or less, more preferably 1 to 100 mol%, even more preferably 1 to 60 mol%, even more preferably 5 to 60 mol%, even more preferably 10 to 60 mol%, even more preferably 30 to 60 mol%, and even more preferably 40 to 60 mol%, based on the amount of tetracarboxylic dianhydride.
  • the amount of triethylamine used in this step is preferably 100 mol% or less, more preferably 1 to 90 mol%, even more preferably 1 to 60 mol%, even more preferably 5 to 60 mol%, even more preferably 10 to 60 mol%, even more preferably 10 to 55 mol%, even more preferably 30 to 55 mol%, and even more preferably 40 to 55 mol%, relative to the amount of the tetracarboxylic dianhydride.
  • the amount of triethylenediamine is preferably 50 mol% or less, more preferably 1 to 50 mol%, even more preferably 1 to 20 mol%, even more preferably 1 to 10 mol%, even more preferably 1 to 7 mol%, even more preferably 1 to 6 mol%, even more preferably 2 to 6 mol%, and even more preferably 3 to 6 mol%, based on the amount of the tetracarboxylic dianhydride.
  • the amount of the base catalyst used in this step relative to the amount of the diamine is preferably the same as the amount relative to the amount of the tetracarboxylic dianhydride. Therefore, the amount of the base catalyst used in this step is preferably 100 mol % or less, more preferably 1 to 100 mol %, even more preferably 1 to 60 mol %, still more preferably 5 to 60 mol %, still more preferably 10 to 60 mol %, still more preferably 30 to 60 mol %, and still more preferably 40 to 60 mol %, based on the amount of the tetracarboxylic dianhydride and the diamine.
  • the amount of triethylamine used in this step is preferably 100 mol% or less, more preferably 1 to 90 mol%, even more preferably 1 to 60 mol%, even more preferably 5 to 60 mol%, even more preferably 10 to 60 mol%, even more preferably 10 to 55 mol%, even more preferably 30 to 55 mol%, and even more preferably 40 to 55 mol%, based on the amount of the tetracarboxylic dianhydride and the diamine.
  • the amount of triethylenediamine is preferably 50 mol % or less, more preferably 1 to 50 mol %, even more preferably 1 to 20 mol %, still more preferably 1 to 10 mol %, still more preferably 1 to 7 mol %, still more preferably 1 to 6 mol %, still more preferably 2 to 6 mol %, and still more preferably 3 to 6 mol %, based on the amounts of the tetracarboxylic dianhydride and the diamine.
  • "with respect to the amount of the tetracarboxylic dianhydride and the diamine” means “with respect to the amount of the tetracarboxylic dianhydride and similarly with respect to the amount of the diamine.”
  • the organic solvents used in the present method include lactone-based solvents and amide-based solvents.
  • lactone solvents include ⁇ -butyrolactone (GBL) and ⁇ -valerolactone, with ⁇ -butyrolactone (GBL) being preferred.
  • amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylcaprolactam, 1,3-dimethylimidazolidinone, tetramethylurea, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide, and N,N-dimethylacetamide is preferred.
  • the mass ratio of the lactone solvent to the amide solvent in the organic solvent [lactone solvent/amide solvent] is preferably 50/50 to 99/1, more preferably 60/40 to 99/1, even more preferably 60/40 to 97/3, even more preferably 70/30 to 95/5, even more preferably 70/30 to 90/10, even more preferably 70/30 to 85/15, and even more preferably 75/25 to 85/15.
  • the total ratio of the lactone solvent and the amide solvent contained in the organic solvent is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, even more preferably 50 to 100% by mass, even more preferably 70 to 100% by mass, even more preferably 90 to 100% by mass, even more preferably 95 to 100% by mass, and even more preferably 99 to 100% by mass, and the organic solvent may consist only of a lactone solvent and an amide solvent, and preferably consists only of a lactone solvent and an amide solvent.
  • the organic solvent may include organic solvents other than lactone solvents and amide solvents. Such organic solvents are not particularly limited, but include aprotic solvents other than lactone solvents and amide solvents, phenol solvents, etc.
  • Examples of aprotic solvents other than lactone solvents and amide solvents include glycol solvents, phosphorus-containing amide solvents, sulfur-containing solvents, ketone solvents, amine solvents, ester solvents, ether solvents, and carbonate solvents.
  • Examples of the glycol solvent include diethylene glycol dimethyl ether, triethylene glycol, and triethylene glycol dimethyl ether.
  • Examples of phosphorus-containing amide solvents include hexamethylphosphoric amide and hexamethylphosphine triamide.
  • Examples of the sulfur-containing solvent include dimethyl sulfone, dimethyl sulfoxide, and sulfolane.
  • Examples of the ketone solvent include acetone, cyclopentanone, cyclohexanone, and methylcyclohexanone.
  • Examples of the amine solvent include picoline and pyridine.
  • Examples of the ester solvent include 2-methoxy-1-methylethyl acetate.
  • Examples of the ether solvent include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, and 1,4-dioxane.
  • Examples of the carbonate solvent include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, and propylene carbonate.
  • phenol-based solvent examples include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol.
  • organic solvents other than the lactone solvents and amide solvents, aprotic solvents are preferred.
  • the organic solvents may be used alone or in combination of two or more.
  • a second production method which is a second embodiment includes a step of imidizing a tetracarboxylic dianhydride containing a compound represented by the following formula (a1) and a diamine containing a compound represented by the following formula (b1) in the presence of a base catalyst, in which the ratio of the compound represented by formula (a1) in the tetracarboxylic dianhydride is 35 mol % or more, and the compound represented by formula (a1) contains a compound represented by the following formula (a11):
  • the compound represented by formula (a1) serving as the raw material has a trans structure, a polyimide resin having the trans structure can be obtained.
  • the catalyst and organic solvent used in this method are described below.
  • the base catalyst examples include organic base catalysts such as pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine (TEA), tripropylamine, tributylamine, triethylenediamine, imidazole, N,N-dimethylaniline, and N,N-diethylaniline; and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate, and sodium hydrogencarbonate.
  • organic base catalysts such as pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine (TEA), tripropylamine, tributylamine, triethylenediamine, imidazole, N,N-dimethylaniline, and N,N-dieth
  • an organic base catalyst is more preferable, at least one selected from the group consisting of triethylamine and triethylenediamine is even more preferable, and it is even more preferable to use both triethylamine and triethylenediamine.
  • the amount of base catalyst used in this method is preferably 100 mol% or less, more preferably 1 to 100 mol%, even more preferably 1 to 60 mol%, even more preferably 5 to 60 mol%, even more preferably 10 to 60 mol%, even more preferably 30 to 60 mol%, and even more preferably 40 to 60 mol%, based on the amount of the tetracarboxylic dianhydride.
  • the amount of triethylamine used in this method is preferably 100 mol% or less, more preferably 1 to 90 mol%, even more preferably 1 to 60 mol%, even more preferably 5 to 60 mol%, even more preferably 10 to 60 mol%, even more preferably 10 to 55 mol%, even more preferably 30 to 55 mol%, and even more preferably 40 to 55 mol%, relative to the amount of the tetracarboxylic dianhydride.
  • the amount of triethylenediamine is preferably 50 mol% or less, more preferably 1 to 50 mol%, even more preferably 1 to 20 mol%, even more preferably 1 to 10 mol%, even more preferably 1 to 7 mol%, even more preferably 1 to 6 mol%, even more preferably 2 to 6 mol%, and even more preferably 3 to 6 mol%, based on the amount of the tetracarboxylic dianhydride.
  • the amount of the base catalyst used in this step relative to the amount of the diamine is preferably the same as the amount relative to the amount of the tetracarboxylic dianhydride. Therefore, the amount of the base catalyst used in the present method is preferably 100 mol % or less, more preferably 1 to 100 mol %, even more preferably 1 to 60 mol %, still more preferably 5 to 60 mol %, still more preferably 10 to 60 mol %, still more preferably 30 to 60 mol %, and still more preferably 40 to 60 mol %, based on the amount of the tetracarboxylic dianhydride and the diamine.
  • the amount of triethylamine used in this method is preferably 100 mol% or less, more preferably 1 to 90 mol%, even more preferably 1 to 60 mol%, even more preferably 5 to 60 mol%, even more preferably 10 to 60 mol%, even more preferably 10 to 55 mol%, even more preferably 30 to 55 mol%, and even more preferably 40 to 55 mol%, based on the amount of the tetracarboxylic dianhydride and the diamine.
  • the amount of triethylenediamine is preferably 50 mol % or less, more preferably 1 to 50 mol %, even more preferably 1 to 20 mol %, still more preferably 1 to 10 mol %, still more preferably 1 to 7 mol %, still more preferably 1 to 6 mol %, still more preferably 2 to 6 mol %, and still more preferably 3 to 6 mol %, based on the amounts of the tetracarboxylic dianhydride and the diamine.
  • "with respect to the amount of the tetracarboxylic dianhydride and the diamine” means “with respect to the amount of the tetracarboxylic dianhydride and similarly with respect to the amount of the diamine.”
  • the organic solvent used in this method is not limited as long as it does not inhibit the imidization reaction and can dissolve the resulting polyimide resin, but preferably contains a lactone-based solvent.
  • lactone solvents include ⁇ -butyrolactone (GBL) and ⁇ -valerolactone, with ⁇ -butyrolactone (GBL) being preferred.
  • the ratio of the lactone solvent contained in the organic solvent is preferably 10 to 100 mass%, more preferably 30 to 100 mass%, even more preferably 50 to 100 mass%, still more preferably 70 to 100 mass%, still more preferably 90 to 100 mass%, still more preferably 95 to 100 mass%, and still more preferably 99 to 100 mass%, and the organic solvent may consist of only the lactone solvent.
  • the organic solvent may include an organic solvent other than a lactone-based solvent.
  • organic solvents include, but are not limited to, aprotic solvents other than lactone-based solvents, phenol-based solvents, etc.
  • Examples of aprotic solvents other than lactone-based solvents include amide-based solvents, glycol-based solvents, phosphorus-containing amide-based solvents, sulfur-containing solvents, ketone-based solvents, amine-based solvents, ester-based solvents, ether-based solvents, and carbonate-based solvents.
  • Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylcaprolactam, 1,3-dimethylimidazolidinone, tetramethylurea, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide.
  • glycol solvent examples include diethylene glycol dimethyl ether, triethylene glycol, and triethylene glycol dimethyl ether.
  • examples of phosphorus-containing amide solvents include hexamethylphosphoric amide and hexamethylphosphine triamide.
  • Examples of the sulfur-containing solvent include dimethyl sulfone, dimethyl sulfoxide, and sulfolane.
  • Examples of the ketone solvent include acetone, cyclopentanone, cyclohexanone, and methylcyclohexanone.
  • the amine solvent examples include picoline and pyridine.
  • Examples of the ester solvent include 2-methoxy-1-methylethyl acetate.
  • ether solvent examples include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, and 1,4-dioxane.
  • carbonate solvent examples include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, and propylene carbonate.
  • phenol-based solvent examples include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol.
  • organic solvents other than the lactone solvents aprotic solvents are preferred, and amide solvents are more preferred.
  • the organic solvents may be used alone or in combination of two or more.
  • the tetracarboxylic dianhydride contains a compound represented by the following formula (a1), and the ratio of the compound represented by the following formula (a1) in the tetracarboxylic dianhydride is 35 mol % or more. In addition, it is preferable that the tetracarboxylic dianhydride does not contain the following structural element (c). In the first production method, the tetracarboxylic dianhydride does not contain the following structural element (c).
  • X is a fluorine atom, a hydrogen atom, or a carbon atom.
  • tetracarboxylic dianhydride contains a certain amount or more of the compound represented by formula (a1), the resulting polyimide resin can have improved colorless transparency, increased elastic modulus, good elongation, and improved solvent solubility, without containing the perfluoroalkyl structure or polyfluoroalkyl structure represented by the structural element (c).
  • the compound represented by formula (a1) is 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA).
  • the ratio of the compound represented by formula (a1) in the tetracarboxylic dianhydride is preferably 35 mol% or more, more preferably 50 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 85 mol% or more, even more preferably 90 mol% or more, with the upper limit being 100 mol% or less.
  • the tetracarboxylic dianhydride may consist only of the compound represented by formula (a1).
  • the ratio of the compound represented by formula (a11) contained in the compound represented by formula (a1) is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, even more preferably 60 to 100 mol%, even more preferably 70 to 100 mol%, even more preferably 80 to 100 mol%, even more preferably 90 to 100 mol%, even more preferably 95 to 100 mol%, may be 100 mol%, and even more preferably is 100 mol%.
  • the compound represented by formula (a1) may be composed only of the compound represented by formula (a11), and it is even more preferable that the compound represented by formula (a1) is composed only of the compound represented by formula (a11).
  • the tetracarboxylic dianhydride may consist only of the compound represented by formula (a1), or may contain a tetracarboxylic dianhydride other than the compound represented by formula (a1).
  • the tetracarboxylic dianhydride other than the compound represented by formula (a1) further contains a compound represented by the following formula (a2):
  • the compound represented by formula (a2) is 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA).
  • CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • the elastic modulus of the polyimide resin can be particularly increased.
  • the ratio of the compound represented by formula (a2) in the tetracarboxylic dianhydride is preferably 0 to 27 mol%, preferably 0.5 to 27 mol%, more preferably 1 to 27 mol%, even more preferably 3 to 27 mol%, even more preferably 5 to 27 mol%, even more preferably 10 to 27 mol%, even more preferably 10 to 25 mol%, even more preferably 15 to 25 mol%, even more preferably 15 to 23 mol%, and even more preferably 15 to 22 mol%.
  • the ratio of the compound represented by formula (a1) in the tetracarboxylic dianhydride is preferably 73 to 100 mol%, and the ratio of the compound represented by formula (a1) in the tetracarboxylic dianhydride in the case where the tetracarboxylic dianhydride contains a compound represented by formula (a2) is preferably 99.5 mol% or less, more preferably 73 to 99.5 mol%, even more preferably 73 to 99 mol%, even more preferably 73 to 97 mol%, even more preferably 73 to 95 mol%, even more preferably 73 to 90 mol%, even more preferably 75 to 90 mol%, even more preferably 75 to 85 mol%, even more preferably 77 to 85 mol%, and even more preferably 78 to 85 mol%.
  • the molar ratio of the compound represented by formula (a1) to the compound represented by formula (a2) in the tetracarboxylic dianhydride [(a1)/(a2)] is preferably 73/27 to 99.5/0.5, more preferably 73/27 to 99/1, even more preferably 73/27 to 97/3, even more preferably 73/27 to 95/5, even more preferably 73/27 to 90/10, even more preferably 75/25 to 90/10, even more preferably 75/25 to 85/15, even more preferably 77/23 to 85/15, and even more preferably 78/22 to 85/15.
  • the total ratio of the compound represented by formula (a1) and the compound represented by formula (a2) in the tetracarboxylic dianhydride is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 90 mol% or more, and preferably 100 mol% or less.
  • the tetracarboxylic dianhydride may consist only of the compound represented by formula (a1) and the compound represented by formula (a2), and it is preferable that the tetracarboxylic dianhydride consists only of the compound represented by formula (a1) and the compound represented by formula (a2).
  • ODPA 4,4'-oxydiphthalic anhydride
  • DSDA 3,3',
  • Examples of alicyclic tetracarboxylic dianhydrides include cyclohexane-1,2,3,4-tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclopentane tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyl tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, decahydro-1,4:5,8-dimethanonaphthalene-2,3,6,7-tetracarboxylic dianhydride (DNDA), 5,5'-(1,4-phenylene)-bis[hexahydro-4,7-methanoisobenzofuran-1,3-dione], 5,5'-bis-2-norborane, and the like.
  • DNDA 5,
  • aliphatic tetracarboxylic dianhydride examples include 1,2,3,4-butanetetracarboxylic dianhydride.
  • aromatic tetracarboxylic acid dianhydride refers to a tetracarboxylic acid dianhydride containing one or more aromatic rings
  • alicyclic tetracarboxylic acid dianhydride refers to a tetracarboxylic acid dianhydride containing one or more alicyclic rings but no aromatic rings
  • aliphatic tetracarboxylic acid dianhydride refers to a tetracarboxylic acid dianhydride containing neither an aromatic ring nor an alicyclic ring.
  • the optionally contained tetracarboxylic dianhydride may be one type or two or more types.
  • the diamine contains a compound represented by the following formula (b1): In addition, it is preferable that the diamine does not contain the following structural element (c).
  • X is a fluorine atom, a hydrogen atom, or a carbon atom.
  • the elastic modulus can be increased while maintaining the colorless transparency and solvent solubility of the polyimide resin without containing a perfluoroalkyl structure or polyfluoroalkyl structure represented by the structural element (c).
  • the compound represented by formula (b1) is 2,2'-dimethylbenzidine (mTB).
  • the ratio of the compound represented by formula (b1) in the diamine is preferably 40 to 100 mol%, more preferably 50 to 100 mol%, even more preferably 70 to 100 mol%, even more preferably 80 to 100 mol%, even more preferably 85 to 100 mol%, and even more preferably 85 to 95 mol%.
  • the diamine may consist only of the compound represented by formula (b1).
  • the diamine may consist only of the compound represented by formula (b1), or may contain a diamine other than the compound represented by formula (b1).
  • the diamine other than the compound represented by formula (b1) further contains a compound represented by the following formula (b2): (In formula (b2), each R is independently a hydrogen atom or a methyl group, Y is a divalent group containing an aromatic ring and having 12 to 30 carbon atoms, and n is 0 or 1.)
  • each R is independently a hydrogen atom or a methyl group
  • Y is a divalent group containing an aromatic ring and having 12 to 30 carbon atoms
  • n is 0 or 1.
  • Each R is independently a hydrogen atom or a methyl group, preferably a hydrogen atom, and more preferably both of the two R's are hydrogen atoms.
  • n is 0 or 1, preferably 1.
  • the compound represented by formula (b2) is 4,4'-diaminobenzanilide (DABA).
  • the diamine contains a structural unit derived from 4,4'-diaminobenzanilide (DABA) among the compounds represented by formula (b2), it is possible to improve the colorless transparency and elongation while maintaining the high elastic modulus of the polyimide resin.
  • DABA 4,4'-diaminobenzanilide
  • the compound represented by formula (b2) when n is 1, contains Y which is a divalent group having 12 to 30 carbon atoms. Y is a divalent group containing an aromatic ring and having 12 to 30 carbon atoms, and is preferably a divalent group containing an aromatic ring and having 12 to 26 carbon atoms.
  • preferred compounds when n is 1 include compounds represented by the following formula (b21), compounds represented by the following formula (b22), compounds represented by the following formula (b23), and compounds represented by the following formula (b24).
  • the compound represented by formula (b2) is preferably at least one selected from the group consisting of a compound represented by the following formula (b21), a compound represented by the following formula (b22), a compound represented by the following formula (b23), and a compound represented by the following formula (b24), more preferably at least one selected from the group consisting of a compound represented by the following formula (b21), a compound represented by the following formula (b22), and a compound represented by the following formula (b23), even more preferably at least one selected from the group consisting of a compound represented by the following formula (b21) and a compound represented by the following formula (b23), and still more preferably a compound represented by formula (b21).
  • the compound represented by formula (b21) is N,N'-(2,2'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis[4-amino-3-methylbenzamide] (AMB-mTOL).
  • AMB-mTOL N,N'-(2,2'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis[4-amino-3-methylbenzamide]
  • the compound represented by formula (b22) is N,N'-[(octahydro-1,3,5,7-tetraoxobenzo[1,2-c:4,5-c']dipyrrole-2,6(1H,3H)-diyl)bis(3-methoxy-4,1-phenylene)]bis[4-amino-benzamide] (AB-MP-HPMDI).
  • the diamine contains the compound represented by formula (b22)
  • the colorless transparency and elongation of the polyimide resin can be improved while maintaining a high elastic modulus.
  • the compound represented by formula (b23) is N,N'-(2,2'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis[4-amino-benzamide] (AB-mTOL).
  • the compound represented by formula (b24) is N,N'-(oxydi-4,1-phenylene)bis[4-amino-benzamide] (AB-44ODA).
  • the diamine contains the compound represented by formula (b24)
  • the colorless transparency and elongation of the polyimide resin can be improved while maintaining a high elastic modulus.
  • the ratio of the compound represented by formula (b2) in the diamine is preferably 1 to 60 mol%, more preferably 1 to 50 mol%, even more preferably 1 to 40 mol%, even more preferably 1 to 30 mol%, even more preferably 3 to 25 mol%, even more preferably 3 to 20 mol%, even more preferably 5 to 20 mol%, and even more preferably 5 to 15 mol%.
  • the molar ratio of the compound represented by formula (b1) to the compound represented by formula (b2) in the diamine [(b1)/(b2)] is preferably 40/60 to 99/1, more preferably 50/50 to 99/1, even more preferably 60/40 to 99/1, still more preferably 70/30 to 99/1, still more preferably 75/25 to 97/3, still more preferably 80/20 to 97/3, still more preferably 80/20 to 95/5, and still more preferably 85/15 to 95/5.
  • the total ratio of the compound represented by formula (b1) and the compound represented by formula (b2) in the diamine is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and preferably 100 mol% or less.
  • the diamine may be composed of only the compound represented by formula (b1) and the compound represented by formula (b2).
  • the diamine may include a diamine other than the compound represented by formula (b1) and the compound represented by formula (b2).
  • diamines are not particularly limited, but include aromatic diamines, alicyclic diamines, and aliphatic diamines, excluding the compound represented by formula (b1) and the compound represented by formula (b2).
  • Aromatic diamines other than the above compounds include 4,4'-diaminodiphenyl sulfone (4,4'-DDS), 3,3'-diaminodiphenyl sulfone (3,3'-DDS), octafluorobenzidine (8FBZ), 2,3,5,6-tetrafluorobenzene-1,4-diamine, 2,4,5,6-tetrafluorobenzene-1,3-diamine, bis(4-aminophenyl)terephthalate (APTP), 1,4-bis(4-aminobenzoyloxy)benzene, 4,4'-diaminodiphenyl ether (4,4'-ODA), 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane (DDM), 9, 9-bis(4-aminophenyl)fluorene (BAFL), 4,4'-diaminobiphenyl (
  • alicyclic diamine examples include 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), 1,4-bis(aminomethyl)cyclohexane, 1,3-cyclohexyldiamine, 1,4-cyclohexyldiamine, isophoronediamine, bis(aminomethyl)norbornane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyl ether, and 2,2-bis(4-aminocyclohexyl)propane.
  • Aliphatic diamines include ethylenediamine and hexamethylenediamine.
  • an aromatic diamine means a diamine containing one or more aromatic rings
  • an alicyclic diamine means a diamine containing one or more alicyclic rings but no aromatic rings
  • an aliphatic diamine means a diamine containing neither an aromatic ring nor an alicyclic ring.
  • the optionally contained diamine may be one type or two or more types.
  • the method for producing a polyimide resin of the present invention includes a step of imidizing the tetracarboxylic dianhydride and the diamine, and it is preferable to carry out the imidization reaction under the following conditions.
  • the ratio of the amounts of tetracarboxylic dianhydride and diamine charged is preferably 0.9 to 1.1 moles of diamine per mole of tetracarboxylic dianhydride.
  • a terminal blocking agent may be used in this process.
  • Monoamines or dicarboxylic acids are preferred as terminal blocking agents.
  • the amount of terminal blocking agent introduced is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.06 mol, per 1 mol of tetracarboxylic dianhydride.
  • Examples of monoamine terminal blocking agents include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3-ethylbenzylamine, aniline, 3-methylaniline, and 4-methylaniline, with benzylamine and aniline being preferred.
  • Dicarboxylic acids are preferred as dicarboxylic acid terminal blocking agents, and a portion of the dicarboxylic acid terminal blocking agent may be ring-closed.
  • Examples include phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenone dicarboxylic acid, 3,4-benzophenone dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, and 4-cyclohexene-1,2-dicarboxylic acid, with phthalic acid and phthalic anhydride being preferred.
  • the method for reacting the tetracarboxylic dianhydride with the diamine is not particularly limited, and any known method can be used. Specific reaction methods include (1) a method in which a tetracarboxylic dianhydride, a diamine, and an organic solvent are charged into a reactor, and the mixture is stirred at 0 to 80° C. for 0.5 to 30 hours, and then the temperature is raised to carry out an imidization reaction; (2) a method in which a diamine and an organic solvent are charged into a reactor and dissolved, and then a tetracarboxylic dianhydride is charged, and the mixture is stirred at 0 to 80° C.
  • the temperature of the imidization reaction is preferably 120 to 250°C, more preferably 160 to 200°C, from the viewpoint of reaction rate and suppression of gelation, etc.
  • the reaction time is preferably 0.5 to 10 hours after the start of distillation of the generated water.
  • the polyimide varnish of the present invention is obtained by dissolving the polyimide resin of the present invention in an organic solvent. That is, the polyimide varnish of the present invention contains the polyimide resin of the present invention and an organic solvent, and the polyimide resin is dissolved in the organic solvent.
  • the organic solvent is not particularly limited as long as it dissolves the polyimide resin. However, it is preferable to use the above-mentioned compounds as the organic solvent used in the production of the polyimide resin, either alone or in combination of two or more kinds.
  • the polyimide varnish of the present invention may be a solution of a polyimide resin obtained by carrying out polymerization and imidization in an organic solvent as described above, or may be a solution obtained by diluting the polyimide solution by further adding an organic solvent.
  • the polyimide varnish of the present invention preferably contains 5 to 40 mass %, more preferably 8 to 30 mass %, and even more preferably 10 to 20 mass % of the polyimide resin of the present invention.
  • the viscosity of the polyimide varnish is preferably 1 to 200 Pa ⁇ s, more preferably 1 to 100 Pa ⁇ s.
  • the viscosity of the polyimide varnish is a value measured at 25°C using an E-type viscometer.
  • the polyimide varnish of the present invention may contain various additives such as inorganic fillers, adhesion promoters, release agents, flame retardants, UV stabilizers, antioxidants, surfactants, leveling agents, defoamers, fluorescent brightening agents, crosslinking agents, polymerization initiators, and photosensitizers, as long as the additives do not impair the required properties of the polyimide resin and polyimide film.
  • additives such as inorganic fillers, adhesion promoters, release agents, flame retardants, UV stabilizers, antioxidants, surfactants, leveling agents, defoamers, fluorescent brightening agents, crosslinking agents, polymerization initiators, and photosensitizers, as long as the additives do not impair the required properties of the polyimide resin and polyimide film.
  • the method for producing the polyimide varnish of the present invention is not particularly limited, and any known method can be applied.
  • the organic solvent is not particularly limited as long as it dissolves the polyimide resin, but it is preferable to use the above-mentioned compounds as the organic solvent used in the production of the polyimide resin, either alone or in a mixture of two or more kinds. Among them, at least one selected from the group consisting of lactone solvents and amide solvents is preferable, lactone solvents are more preferable, and it is even more preferable to contain both lactone solvents and amide solvents.
  • At least one selected from the group consisting of ⁇ -butyrolactone (GBL) and N,N-dimethylacetamide is more preferable, ⁇ -butyrolactone (GBL) is more preferable, and it is even more preferable to contain both ⁇ -butyrolactone (GBL) and N,N-dimethylacetamide.
  • the organic solvent contained in the polyimide varnish may contain only ⁇ -butyrolactone, but the polyimide varnish preferably contains 20 mass % or more of ⁇ -butyrolactone, more preferably 20 to 90 mass %, even more preferably 20 to 70 mass %, even more preferably 20 to 60 mass %, even more preferably 20 to 50 mass %, even more preferably 30 to 50 mass %, and even more preferably 30 to 45 mass %, based on the total amount of the polyimide varnish.
  • the organic solvent contained in the polyimide varnish preferably contains 30% by mass or more of ⁇ -butyrolactone, based on the total amount of the organic solvent, more preferably contains 30 to 95% by mass, even more preferably contains 30 to 80% by mass, even more preferably contains 30 to 70% by mass, even more preferably contains 35 to 60% by mass, and even more preferably contains 35 to 50% by mass.
  • the polyimide varnish preferably contains an amide solvent in an amount of 1% by mass or more, more preferably 5 to 70% by mass, even more preferably 20 to 70% by mass, even more preferably 25 to 70% by mass, even more preferably 35 to 70% by mass, even more preferably 35 to 60% by mass, and even more preferably 40 to 60% by mass, based on the total amount of the polyimide varnish.
  • the organic solvent contained in the polyimide varnish preferably contains an amide solvent in an amount of 1% by mass or more, more preferably 5 to 70% by mass, even more preferably 20 to 70% by mass, even more preferably 30 to 70% by mass, even more preferably 40 to 65% by mass, and even more preferably 50 to 65% by mass, based on the total amount of the organic solvent.
  • the polyimide film of the present invention contains the polyimide resin described above. Therefore, the polyimide film of the present invention does not contain a perfluoroalkyl structure or a polyfluoroalkyl structure, and is excellent in colorless transparency, high elastic modulus, and elongation.
  • the polyimide film of the present invention preferably has the following physical properties.
  • the polyimide film of the present invention preferably has a YI of 7.5 or less, a total light transmittance of 80% or more, a haze of 1.0% or less, a tensile elongation at break of 5% or more in a tensile test performed under conditions of 23° C.
  • test piece of 50 ⁇ m ⁇ 10 mm ⁇ 120 mm, a tensile speed of 20 mm/min, and a chuck distance of 50 mm, and a tensile modulus of elasticity of 3.8 GPa or more calculated as the slope of the stress-strain curve obtained by the tensile test in the section from 0.1 mm to 0.5 mm strain by the least squares method.
  • the YI is preferably 7.5 or less, more preferably 7.2 or less, even more preferably 5.0 or less, even more preferably 4.0 or less, even more preferably 3.0 or less, and even more preferably 2.0 or less.
  • the total light transmittance is preferably 80% or more, more preferably 85% or more, even more preferably 86% or more, even more preferably 87% or more, and even more preferably 88% or more.
  • the haze is preferably 1.0% or less, more preferably 0.9% or less, even more preferably 0.6% or less, even more preferably 0.5% or less, even more preferably 0.4% or less, even more preferably 0.3% or less, and even more preferably 0.2% or less.
  • the tensile elongation at break in a tensile test performed under conditions of 23°C 50% RH, test piece 50 ⁇ m x 10mm x 120mm, tensile speed 20mm/min, and chuck distance 50mm is preferably 5% or more, more preferably 6% or more, even more preferably 7% or more, even more preferably 8% or more, even more preferably 9% or more, even more preferably 10% or more, and even more preferably 11% or more.
  • the tensile modulus calculated as the slope of the least squares method in the section from 0.1 mm to 0.5 mm in a stress-strain curve obtained by a tensile test performed under conditions of an environment of 23°C and 50% RH, a test piece of 50 ⁇ m ⁇ 10 mm ⁇ 120 mm, a tensile speed of 20 mm/min, and a chuck distance of 50 mm, is preferably 3.8 GPa or more, more preferably 3.9 GPa or more, even more preferably 4.0 GPa or more, still more preferably 4.1 GPa or more, still more preferably 4.2 GPa or more, and still more preferably 4.3 GPa or more.
  • the above-mentioned physical properties in the present invention can be specifically measured by the methods described in the Examples.
  • the polyimide film of the present invention contains the polyimide resin, does not contain a perfluoroalkyl structure or a polyfluoroalkyl structure, and is colorless and transparent, has a high elastic modulus, and is also excellent in elongation. Therefore, the polyimide film of the present invention is suitable for use as an optical material or electronic material, particularly as a display material.
  • the thickness of the polyimide film of the present invention is not particularly limited, but is preferably 1 to 250 ⁇ m, more preferably 5 to 100 ⁇ m, even more preferably 8 to 80 ⁇ m, and still more preferably 10 to 80 ⁇ m.
  • the film thickness is within the above range, it can be suitably used as an optical material or electronic material, particularly as a display material.
  • the thickness of the polyimide film can be easily controlled by adjusting the solids concentration and viscosity of the varnish.
  • the method for producing the polyimide film of the present invention is not particularly limited, and any known method can be used.
  • the polyimide film can be obtained by applying a polyimide varnish onto a support and drying it.
  • the following production method is preferred. That is, a preferred method for producing a polyimide film includes a coating step of coating the polyimide varnish on a support to obtain a coating film, a primary drying step of drying the coating film and peeling it off from the support to obtain a self-supporting film, and a secondary drying step of drying the self-supporting film at 210° C., preferably 220° C. or higher.
  • the coating step is a step of applying a polyimide varnish onto a support to obtain a coating film.
  • the support is preferably a glass plate, a metal plate, a metal drum, a metal belt, or a plastic film having a smooth surface, more preferably a glass plate or a plastic film, and even more preferably a plastic film. From the viewpoint of improving productivity, it is preferable to use an endless support such as a metal drum or a metal belt, or a long plastic film as the support, and produce the polyimide film by a roll-to-roll method.
  • the coating method include known coating methods such as spin coating, slit coating, blade coating, and die coating, and can be applied without any particular limitation.
  • a glass rod, a coater, or the like may also be used.
  • the coating thickness is preferably 1 to 250 ⁇ m, more preferably 5 to 100 ⁇ m, even more preferably 8 to 80 ⁇ m, and still more preferably 10 to 80 ⁇ m, in terms of the thickness of the polyimide film after drying. If necessary, a release agent may be applied in advance to the surface of the support.
  • the primary drying step is a step in which the coating film is dried and peeled off from the support to obtain a self-supporting film.
  • the primary drying is a step of removing a part of the organic solvent to obtain a self-supporting film, and the organic solvent is removed by heating the coating film on the support.
  • the temperature when removing the organic solvent is preferably 50 to 140°C, more preferably 50 to 120°C. In order to prevent heating for a long time, the temperature may be gradually increased.
  • the first temperature is preferably 50 to 90°C, more preferably 50 to 70°C.
  • the final temperature is preferably 80 to 140°C, more preferably 90 to 120°C.
  • the organic solvent is preferably removed under a nitrogen atmosphere.
  • the organic solvent may be removed under reduced pressure, normal pressure, or increased pressure.
  • the resulting film is peeled off from the support, and after peeling, the film has self-supporting properties.
  • the secondary drying step is a step of drying the self-supporting film at 210° C. or higher.
  • the edges of the self-supporting film obtained in the previous step are fixed and dried at 210° C. or higher.
  • the temperature of the secondary drying is preferably 210 to 300° C., more preferably 210 to 280° C., even more preferably 210 to 260° C., still more preferably 220 to 260° C., and even more preferably 220 to 240° C.
  • the secondary drying is preferably carried out under a nitrogen atmosphere, and may be carried out under any of reduced pressure, normal pressure, and increased pressure.
  • the secondary drying time may be appropriately adjusted depending on the above temperature, but is preferably 3 to 60 minutes, more preferably 5 to 60 minutes, even more preferably 5 to 30 minutes, and even more preferably 5 to 20 minutes. From the viewpoint of further improving the colorless transparency, the time is preferably from 3 to 30 minutes, more preferably from 3 to 20 minutes, even more preferably from 3 to 15 minutes, and even more preferably from 5 to 15 minutes. On the other hand, from the viewpoint of further improving the elastic modulus, the time is more preferably from 10 to 50 minutes, even more preferably from 15 to 40 minutes, and even more preferably from 17 to 28 minutes. After secondary drying, the product is cooled and may be annealed.
  • Polyimide resin structure The structures of the polyimide resins obtained in the examples and comparative examples were analyzed by the following method.
  • Ratio of trans structure derived from cyclohexanetetracarboxylic dianhydride HPMDA trans structure ratio
  • the ratio of the trans structure derived from cyclohexanetetracarboxylic dianhydride in the polyimide resin was calculated as follows by measuring the 1 H-NMR spectrum of the polyimide resin. The 1 H-NMR spectrum was measured using an NMR spectrophotometer (ASCEnd TM 500, manufactured by BRUKER CORPORATION) and a deuterated dimethyl sulfoxide solution of the polyimide resin.
  • the ratio of the trans structure derived from cyclohexanetetracarboxylic dianhydride was calculated from the integral value of the peak derived from the cyclohexanetetracarboxylic acid moiety shown below.
  • the tensile modulus, tensile strength, and tensile elongation at break were measured in accordance with JIS K7127:1999 using a tensile tester "Strograph VG-1E" manufactured by Toyo Seiki Co., Ltd.
  • the chuck distance was 50 mm
  • the test piece size was 10 mm x 120 mm
  • the test speed (tensile speed) was 20 mm/min
  • the measurement temperature was 23°C.
  • the tensile modulus was calculated as the slope of the stress-strain curve obtained by the tensile test in the section from 0.1 mm to 0.5 mm strain by the least squares method.
  • Example 2 the type and amount of diamine, tetracarboxylic dianhydride, and imidization catalyst were changed to the raw materials shown in Table 1.
  • the type of solvent was changed to the solvent shown in Table 1, and the amount of solvent at the start of the reaction was adjusted so that the concentration of the resulting polyimide resin was 30 mass%.
  • a polyimide varnish containing a polyimide resin was obtained in the same manner as in Example 1, except that the reaction temperature was changed to the temperature shown in Table 1.
  • the reaction temperature temperature at reflux
  • a polyimide film was obtained in the same manner as in Example 1. The physical properties and evaluation results of the film are shown in Table 1.
  • the polyimide resin of the present invention has the above properties even though it does not contain a perfluoroalkyl structure or a polyfluoroalkyl structure. It is also found that the polyimide resin obtained by the manufacturing method of the present invention contains 35 mol % or more of a trans structure derived from (1R,2S,4S,5R)-cyclohexanetetracarboxylic dianhydride. Therefore, it is found that the polyimide resin obtained by the manufacturing method of the present invention has a high elastic modulus and high strength, as well as excellent elongation and colorless transparency.

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Abstract

L'invention concerne une résine polyimide qui possède une unité structurale (A) dérivée d'un dianhydride tétracarboxylique, et une unité structurale (B) dérivée d'une diamine. L'unité structurale (A) contient une unité structurale (A1) dérivée d'un composé représenté par la formule (a1). L'unité structurale (A1) contient 35% en moles ou plus d'une unité structurale de type trans dérivée d'un dianhydride （１Ｒ，２Ｓ，４Ｓ，５Ｒ）－cyclohexanetétracarboxylique. L'unité structurale (B) contient une unité structurale (B1) dérivée d'un composé représenté par la formule (b1). La résine polyimide de l'invention ne contient aucun élément structurel (c). (Dans la formule (c), X représente un atome de fluor, un atome d'hydrogène ou un atome de carbone.)
PCT/JP2024/042779 2023-12-08 2024-12-04 Résine polyimide Pending WO2025121336A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013050696A (ja) * 2011-07-29 2013-03-14 Fujifilm Corp 感光性樹脂組成物、レリーフパターン形成材料、感光性膜、ポリイミド膜、硬化レリーフパターン、その製造方法、及び半導体装置
WO2016060213A1 (fr) * 2014-10-17 2016-04-21 三菱瓦斯化学株式会社 Composition de résine de polyimide, film de polyimide et stratifié
JP2016222798A (ja) * 2015-05-29 2016-12-28 三菱瓦斯化学株式会社 ポリイミド樹脂
JP2017133027A (ja) * 2016-09-13 2017-08-03 Ｊｘｔｇエネルギー株式会社 ポリイミド、ポリイミドの製造方法、ポリイミド溶液及びポリイミドフィルム
WO2017159298A1 (fr) * 2016-03-14 2017-09-21 三菱瓦斯化学株式会社 Procédé de régulation de structure de squelette de polyimide, et procédé de fabrication de polyimide
JP2017186473A (ja) * 2016-04-07 2017-10-12 株式会社カネカ フィルム
WO2017191822A1 (fr) * 2016-05-06 2017-11-09 三菱瓦斯化学株式会社 Résine de polyimide
JP2018158535A (ja) * 2017-03-23 2018-10-11 宇部興産株式会社 ポリイミドフィルムとハードコート層とを含む積層体

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013050696A (ja) * 2011-07-29 2013-03-14 Fujifilm Corp 感光性樹脂組成物、レリーフパターン形成材料、感光性膜、ポリイミド膜、硬化レリーフパターン、その製造方法、及び半導体装置
WO2016060213A1 (fr) * 2014-10-17 2016-04-21 三菱瓦斯化学株式会社 Composition de résine de polyimide, film de polyimide et stratifié
JP2016222798A (ja) * 2015-05-29 2016-12-28 三菱瓦斯化学株式会社 ポリイミド樹脂
WO2017159298A1 (fr) * 2016-03-14 2017-09-21 三菱瓦斯化学株式会社 Procédé de régulation de structure de squelette de polyimide, et procédé de fabrication de polyimide
JP2017186473A (ja) * 2016-04-07 2017-10-12 株式会社カネカ フィルム
WO2017191822A1 (fr) * 2016-05-06 2017-11-09 三菱瓦斯化学株式会社 Résine de polyimide
JP2017133027A (ja) * 2016-09-13 2017-08-03 Ｊｘｔｇエネルギー株式会社 ポリイミド、ポリイミドの製造方法、ポリイミド溶液及びポリイミドフィルム
JP2018158535A (ja) * 2017-03-23 2018-10-11 宇部興産株式会社 ポリイミドフィルムとハードコート層とを含む積層体

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