WO2022220286A1 - イミド－アミド酸共重合体及びその製造方法、ワニス、並びにポリイミドフィルム - Google Patents

イミド－アミド酸共重合体及びその製造方法、ワニス、並びにポリイミドフィルム Download PDF

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WO2022220286A1
WO2022220286A1 PCT/JP2022/017842 JP2022017842W WO2022220286A1 WO 2022220286 A1 WO2022220286 A1 WO 2022220286A1 JP 2022017842 W JP2022017842 W JP 2022017842W WO 2022220286 A1 WO2022220286 A1 WO 2022220286A1
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structural unit
imide
formula
represented
group
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PCT/JP2022/017842
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English (en)
French (fr)
Japanese (ja)
Inventor
舜 星野
孝博 村谷
琢朗 畠山
洋平 安孫子
紘二 鈴木
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三菱瓦斯化学株式会社
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Priority to JP2023514681A priority Critical patent/JPWO2022220286A1/ja
Priority to CN202280027338.9A priority patent/CN117120514A/zh
Priority to KR1020237034794A priority patent/KR20230170677A/ko
Publication of WO2022220286A1 publication Critical patent/WO2022220286A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/14—Polyamide-imides
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to an imide-amic acid copolymer that is a precursor of a polyimide resin, a method for producing the same, a varnish containing the copolymer, and a polyimide film.
  • polyimide resin Various uses of polyimide resin are being considered in fields such as electrical and electronic components. For example, it is desired to replace glass substrates used in image display devices such as liquid crystal displays and OLED displays with plastic substrates for the purpose of reducing the weight and increasing the flexibility of devices. Research is ongoing. Polyimide films for such applications are required to have transparency and low yellowness.
  • Patent Document 1 discloses two specific amic acid structural units for the purpose of obtaining a polyimide film having low residual stress, low warpage, low yellowness, and high elongation.
  • a polyimide precursor is disclosed which is characterized by containing a specific ratio of
  • Patent Document 1 discloses a technique for reducing residual stress and reducing yellowness, but it is still insufficient, especially while maintaining transparency and low yellowness, polyimide film excellent in heat resistance etc. was not able to obtain
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a polyimide having a low linear expansion coefficient, excellent heat resistance, and a small change in yellowness even after heat treatment at 400 ° C. or higher.
  • An object of the present invention is to provide an imide-amic acid copolymer which is a precursor of a polyimide resin, a method for producing the same, a varnish containing the copolymer, and a polyimide film from which a film can be obtained.
  • the present inventors have found that a copolymer containing a combination of specific structural units can solve the above problems, and have completed the invention.
  • the present invention relates to the following [1] to [16].
  • [1] A repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), wherein the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2)
  • a 1 is a tetravalent aromatic group having 4 to 39 carbon atoms or an aliphatic group having a norbornane skeleton, and the bonding groups are —O—, —SO 2 —, —CO—, It may have at least one selected from the group consisting of —CH 2 —, —C(CH 3 ) 2 —, —C 2 H 4 O— and —S—, and B 1 is represented by the general formula (3
  • a 2 is a tetravalent aromatic group having 4 to 39 carbon atoms, and the bonding groups are —O—, —SO 2 —, —CO—, at least one selected from the group consisting of -CH 2 -, -C(CH 3 ) 2 -, -C 2 H 4 O-, -OCO-, -COO-, -NHCO-, -CONH- and -S- B 2 is a group represented by the general formula (3), and X 1 and
  • Y 1 and Y 2 each independently represent a group represented by --COO-- or a group represented by --OCO--.
  • R 1 , R 2 and R 3 each independently represents an organic group having 1 to 20 carbon atoms, and h, i, j and k are integers of 0 to 4.
  • a 1 is a group represented by the following formula (4), a group represented by the following formula (5), a group represented by the following formula (6), and a group represented by the following formula (7)
  • the imide-amic acid copolymer according to [1] or [2] above which is at least one selected from the group consisting of: [4] The imide-amic acid copolymer according to any one of [1] to [3], wherein A 2 is a group represented by the following formula (8).
  • the imide repeating structural unit has a structural unit B1B derived from a structural unit A1A and a diamine derived from a tetracarboxylic dianhydride
  • Amic acid repeating structural units have a structural unit A2A derived from a tetracarboxylic dianhydride and a structural unit B2B derived from a diamine
  • the structural unit A1A contains a structural unit derived from an aromatic tetracarboxylic dianhydride or a structural unit derived from an aliphatic tetracarboxylic dianhydride having a norbornane skeleton
  • the structural unit A2A contains a structural unit derived from an aromatic tetracarboxylic dianhydride
  • the imide-amic acid copolymer according to any one of the above [1] to [4], wherein the structural units B1B and B2B contain a structural unit (B11
  • the structural unit A2A contains a structural unit (A21) derived from an aromatic tetracarboxylic dianhydride (a21),
  • the structural unit (A21) is a structural unit (A211) derived from a compound represented by the following formula (a211), a structural unit (A212) derived from a compound represented by the following formula (a212), or the following formula (a213).
  • Structural unit A1A is selected from the group consisting of a structural unit (A11) derived from a compound represented by the following formula (a11) and a structural unit (A12) derived from a compound represented by the following formula (a12)
  • ⁇ YI YI1 ⁇ YI0 ⁇ 20 (8)
  • a laminate comprising the polyimide film according to any one of [9] to [11] and at least one inorganic layer. [13] The laminate according to [12] above, wherein the yellowness YI1 after two 1-hour heat treatments at 430° C. and the yellowness YI0 before the heat treatment satisfy the following formula (8).
  • ⁇ YI YI1 ⁇ YI0 ⁇ 20
  • Step 1 A step of reacting a tetracarboxylic acid component constituting an imide moiety with a diamine component to obtain an imide oligomer
  • Step 2 The imide oligomer obtained in Step 1, a tetracarboxylic acid component constituting an amide acid moiety, and Step [15] Step of obtaining an imide-amic acid copolymer containing a repeating unit consisting of an imide moiety and an amic acid moiety by reacting a diamine component [15]
  • the imide oligomer obtained in Step 1 has amino acids at both ends of the main chain of the molecular chain.
  • An amic acid copolymer, a method for producing the same, a varnish containing the copolymer, and a polyimide film can be provided.
  • the imide-amic acid copolymer of the present invention comprises a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and a repeating unit represented by the formula (1). It is an imide-amic acid copolymer in which the molar ratio [(1)/(2)] of repeating units represented by formula (2) is from 5/95 to 60/40.
  • a 1 is a tetravalent aromatic group having 4 to 39 carbon atoms or an aliphatic group having a norbornane skeleton, and the bonding groups are —O—, —SO 2 —, —CO—, --CH 2 --, --C(CH 3 ) 2 --, --C 2 H 4 O-- and --S--
  • B 1 is represented by the general formula (3 ) is a group represented by
  • a 2 is a tetravalent aromatic group having 4 to 39 carbon atoms, and -O-, -SO 2 -, -CO-, -CH 2 -, -C(CH 3 ) 2 -, -C 2 H 4 O-, -OCO-, -COO-, -NHCO-, -CONH-, and -S-, optionally having at least one selected from the group consisting of B 2 is a group represented by the general formula (3), and X 1 and X 2 are each independently a hydrogen
  • Y 1 and Y 2 each independently represent a group represented by --COO-- or a group represented by --OCO--.
  • R 1 , R 2 and R 3 each independently represent an organic group having 1 to 20 carbon atoms.
  • h, i, j, and k are integers from 0 to 4; )
  • the imide-amic acid copolymer of the present invention is excellent as a raw material for a polyimide film, and the obtained polyimide film has a low linear expansion coefficient, excellent heat resistance, and does not change in yellowness even after heat treatment at 400 ° C. or higher.
  • a copolymer composed of a tetracarboxylic acid-derived component composed of an aromatic group and the specific diamine component is considered to be able to achieve both a low linear expansion coefficient and high heat resistance necessary for TFT substrates and the like.
  • the imide-amic acid copolymer of the present invention part of the components derived from the alicyclic tetracarboxylic acid are imidized in advance during polymer polymerization, so that an imide-amic acid copolymer having a higher molecular weight than polyamic acid can be obtained. It is considered that the physical properties after film formation are excellent. Furthermore, the imide-amic acid copolymer of the present invention is considered to have excellent physical properties after film formation because the imide portion and the amic acid portion have specific structures.
  • the repeating unit represented by formula (1) is an imide moiety.
  • a 1 is a tetravalent aromatic group having 4 to 39 carbon atoms or an aliphatic group having a norbornane skeleton, and the bonding groups are —O—, —SO 2 —, —CO—, It may have at least one selected from the group consisting of -CH 2 -, -C(CH 3 ) 2 -, -C 2 H 4 O- and -S-.
  • a 1 is a tetracarboxylic dianhydride with two dicarboxylic anhydride moieties (four carboxy group moieties) removed, and A 1 and the four carbonyl groups bound thereto are derived from the tetracarboxylic dianhydride. It is a structural unit that
  • the tetravalent aromatic group means that all four carbons bonded to the imide group are aromatic carbons.
  • the bonding group refers to a bonding group that bonds each aromatic ring when A 1 contains two or more aromatic rings. However, the bonding group is not limited to these.
  • a 1 is an aromatic group
  • the heat resistance of the polyimide is improved, which is preferable.
  • An aliphatic group having a tetravalent norbornane skeleton means that all four carbons bonded to the imide group are aliphatic carbons and at least one has a norbornane skeleton.
  • the bonding group refers to a bonding group that bonds each ring structure when A 1 contains two or more ring structures. However, the bonding group is not limited to these.
  • a 1 is an aliphatic group having a norbornane skeleton
  • the heat resistance of the polyimide is improved, which is preferable.
  • a 1 is a tetravalent aromatic group having 4 to 39 carbon atoms or an aliphatic group having a norbornane skeleton.
  • the tetravalent aromatic group having 4 to 39 carbon atoms in A 1 is preferably a group represented by the following formula (4) and a group represented by the following formula (7).
  • a group represented by the following formula (5) and a group represented by the following formula (6) are preferable.
  • B 1 is a group represented by the following general formula (3).
  • B 1 is obtained by removing two amino group moieties from diamine, and is a structural unit derived from diamine. is at least one selected from the group consisting of groups represented by Moreover, it is preferable that B 1 in the formula (1) does not include a group represented by the following formula (3c).
  • Y 1 and Y 2 each independently represent a group represented by —COO— or a group represented by —OCO—.
  • R 1 , R 2 and R 3 are each independently represents an organic group having 1 to 20 carbon atoms, and h, i, j, and k are integers of 0 to 4.
  • the repeating unit represented by formula (2) is an amic acid moiety.
  • a 2 is a tetravalent aromatic group having 4 to 39 carbon atoms, and -O-, -SO 2 -, -CO-, -CH 2 -, -C( CH 3 ) 2 -, -C 2 H 4 O-, -OCO-, -COO-, -NHCO-, -CONH-, and -S- may have at least one selected from the group consisting of .
  • a 2 may be different from or the same as A 1 , but is preferably a tetravalent aromatic group having 4 to 39 carbon atoms different from A 1 .
  • a 2 is a tetracarboxylic dianhydride with two dicarboxylic anhydride moieties (four carboxy group moieties) removed, and A 2 and the four carbonyl groups bound to it are derived from the tetracarboxylic dianhydride.
  • the tetravalent aromatic group means that all four carbons bonded to the imide group are aromatic carbons.
  • the bonding group refers to a bonding group that bonds each aromatic ring when A 2 contains two or more aromatic rings. However, the bonding group is not limited to these.
  • a 2 is an aromatic group, the heat resistance of the polyimide is improved, which is preferable.
  • a 2 is a tetravalent aromatic group having 4 to 39 carbon atoms, preferably a group represented by the following formula (8), more preferably represented by the following formula (8a). is the base.
  • X 1 and X 2 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, preferably a hydrogen atom.
  • B 2 is a group represented by the following general formula (3).
  • B 2 is obtained by removing two amino group moieties from diamine, and is a structural unit derived from diamine. is at least one selected from the group consisting of groups represented by Moreover, it is preferable that B 2 in the above formula (1) does not include a group represented by the following formula (3c).
  • Y 1 and Y 2 each independently represent a group represented by —COO— or a group represented by —OCO—.
  • R 1 , R 2 and R 3 are each independently represents an organic group having 1 to 20 carbon atoms, and h, i, j, and k are integers of 0 to 4.
  • the molar ratio [(1)/(2)] between the repeating unit represented by formula (1) and the repeating unit represented by formula (2) is 5/95. ⁇ 60/40.
  • the molar ratio [(1)/(2)] of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) has transparency, low yellowness, high heat resistance, and a low coefficient of linear expansion. from the viewpoint of , it is 5/95 to 60/40, preferably 10/90 to 60/40, more preferably 15/85 to 60/40.
  • the total mass ratio of the repeating unit represented by formula (1) and the repeating unit represented by formula (2) to the imide-amic acid copolymer of the present invention is preferably 50% by mass or more, and more It is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 82% by mass or more, still more preferably 85% by mass or more, and still more preferably 90% by mass or more. More preferably, it is 95% by mass or more, and there is no upper limit, and it is 100% by mass or less.
  • the total molar ratio of the repeating unit represented by formula (1) and the repeating unit represented by formula (2) to the imide-amic acid copolymer of the present invention is preferably 50 mol% or more, and more It is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 82 mol% or more, still more preferably 85 mol% or more, still more preferably 90 mol% or more. More preferably, it is 95 mol% or more, and there is no upper limit, and it is 100 mol% or less.
  • the imide-amic acid copolymer of the present invention contains repeating units other than repeating units represented by formula (1) and repeating units represented by formula (2) within a range that does not impair the effects of the present invention.
  • the repeating unit other than the repeating unit represented by formula (1) and the repeating unit represented by formula (2) the repeating unit represented by formula (1) is a tetracarboxylic acid di It is preferable that the constitutional unit derived from anhydride and the constitutional unit derived from tetracarboxylic dianhydride of the repeating unit represented by formula (2) are exchanged. Specific examples include repeating units represented by the following formula (1a) and repeating units represented by the following formula (2a).
  • the repeating unit represented by formula (1a) and the repeating unit represented by formula (2a) are the repeating unit represented by formula (1) and the repeating unit represented by formula (2) in the imide-amic acid copolymer of the present invention. may be present at the connecting portion of the repeating unit represented by (In formula (1a), A 2 is the same as A 2 in formula (2), and B 1 is the same as B 1 in formula (1). In formula (2a), A 1 is the same as formula (1). and B 2 , X 1 and X 2 are respectively the same as B 2 , X 1 and X 2 in Formula ( 2 ).)
  • Repeating units other than the repeating unit represented by are derived from structural units derived from tetracarboxylic dianhydrides and diamines exemplified in the section ⁇ Each structural unit of the imide-amic acid copolymer> described later.
  • the structural unit derived from tetracarboxylic dianhydride includes the group represented by the formula (4), the group represented by the formula (5), the group represented by the formula (6) A group represented by the above formula (7), or a structural unit containing a group represented by the above formula (8) as part of a structural unit is preferable, and the imide portion is the above formula (4)
  • a group represented by (5), a group represented by (6) as a structural unit, or a structural unit containing a group represented by the above formula (7) as part of the group is more preferable
  • amide A structural unit containing a group represented by the above formula (8) as a part of the structural unit is more preferable for the acid moiety.
  • the number average molecular weight of the imide-amic acid copolymer of the present invention is preferably 5,000 to 500,000 from the viewpoint of the mechanical strength of the resulting polyimide film. Further, the weight average molecular weight (Mw) of the imide-amic acid copolymer of the present invention is preferably 10,000 or more and 800,000 or less, more preferably 10,000 or more and 300,000 or less, from the same viewpoint. 000 or less, more preferably 100,000 or more and 300,000 or less.
  • the number-average molecular weight or weight-average molecular weight of the copolymer can be obtained, for example, from a standard polymethylmethacrylate (PMMA) conversion value by gel filtration chromatography measurement.
  • PMMA polymethylmethacrylate
  • the imide-amic acid copolymer of the present invention contains a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2), and a repeating unit represented by the formula (1).
  • the imide-amic acid copolymer of the present invention has an imide repeating structural unit and an amic acid repeating structural unit
  • the imide repeating structural unit has a structural unit B1B derived from a structural unit A1A and a diamine derived from a tetracarboxylic dianhydride
  • Amic acid repeating structural units have a structural unit A2A derived from a tetracarboxylic dianhydride and a structural unit B2B derived from a diamine
  • the structural unit A1A contains a structural unit derived from an aromatic tetracarboxylic dianhydride or a structural unit derived from an aliphatic tetracarboxylic dianhydride having a norbornane skeleton
  • the structural unit A2A contains a structural unit derived from an aromatic tetracarboxylic dianhydride
  • Structural units B1B and B2B preferably contain a structural unit (B11) derived from
  • Y 1 and Y 2 each independently represent a group represented by —COO— or a group represented by —OCO—.
  • R 1 , R 2 and R 3 are each independently represents an organic group having 1 to 20 carbon atoms, and h, i, j, and k are integers of 0 to 4.
  • Structural unit A1A is a structural unit derived from tetracarboxylic dianhydride occupying the imide portion corresponding to the repeating unit represented by formula (1) of the copolymer of the present invention, It contains structural units derived from anhydrides or structural units derived from aliphatic tetracarboxylic dianhydrides having a norbornane skeleton.
  • Structural unit A1A is not limited as long as it contains a structural unit derived from an aromatic tetracarboxylic dianhydride or a structural unit derived from an aliphatic tetracarboxylic dianhydride having a norbornane skeleton, but the structural unit A1A is at least one selected from the group consisting of a structural unit (A11) derived from a compound represented by the following formula (a11) and a structural unit (A12) derived from a compound represented by the following formula (a12). preferably included.
  • the compound represented by formula (a11) is 9,9′-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF). Inclusion of the structural unit (A11) derived from the compound represented by the formula (a11) is preferable because transparency, low yellowness, and high heat resistance are achieved.
  • the compound represented by formula (a12) is 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA). Inclusion of the structural unit (A12) derived from the compound represented by formula (a12) is preferable because transparency, low yellowness, and high heat resistance are achieved.
  • the content ratio of the structural unit (A11) in the structural unit A1A is preferably 50 mol% or more, more preferably 55 mol% or more, and still more preferably It is 60 mol % or more, more preferably 80 mol % or more, still more preferably 90 mol % or more, and still more preferably 95 mol % or more.
  • the upper limit of the content ratio of the structural unit (A11) is not particularly limited, and is 100 mol % or less.
  • the structural unit A1A may consist of only the structural unit (A11).
  • the content ratio of the structural unit (A12) in the structural unit A1A is preferably 50 mol% or more, more preferably 55 mol% or more, and still more preferably It is 60 mol % or more, more preferably 80 mol % or more, still more preferably 90 mol % or more, and still more preferably 95 mol % or more.
  • the upper limit of the content ratio of the structural unit (A12) is not particularly limited, and is 100 mol % or less.
  • the structural unit A1A may consist only of the structural unit (A12).
  • the total content ratio of the structural unit (A11) and the structural unit (A12) in the structural unit A1A is preferably 50 mol% or more. , More preferably 55 mol% or more, still more preferably 60 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% That's it.
  • the upper limit of the total content ratio of the structural unit (A11) and the structural unit (A12) is not particularly limited, and is 100 mol % or less.
  • the structural unit A1A may consist of only the structural unit (A11) and the structural unit (A12).
  • the structural unit A1A may contain structural units other than the structural unit (A11) and the structural unit (A12).
  • the tetracarboxylic dianhydride that provides such a structural unit is not particularly limited as long as it is an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride having a norbornane skeleton.
  • Structural units arbitrarily contained in the structural unit A1A may be of one type, or may be of two or more types.
  • the tetracarboxylic dianhydride that gives a structural unit derived from the tetracarboxylic dianhydride occupying the imide portion other than the structural unit A1A includes 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, bicyclo[2.2.2 ] alicyclic tetracarboxylic dianhydrides such as octa-7-ene-2,3,5,6-tetracarboxylic dianhydride and dicyclohexyltetracarboxylic dianhydride, and 1,2,3,4 Aliphatic tetracarboxylic dianhydrides such as -butanetetracarboxylic dianhydride.
  • aromatic tetracarboxylic dianhydride means tetracarboxylic dianhydride containing one or more aromatic rings
  • alicyclic tetracarboxylic dianhydride has one alicyclic ring.
  • aliphatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing neither an aromatic ring nor an alicyclic ring.
  • the structural unit B1B is a structural unit derived from a diamine occupying the imide moiety corresponding to the repeating unit represented by the formula (1) of the copolymer of the present invention, and is represented by the following general formula (b11): contains a structural unit (B11) derived from (In formula (b11), Y 1 and Y 2 each independently represent a group represented by —COO— or a group represented by —OCO—.
  • R 1 , R 2 and R 3 are each independently represents an organic group having 1 to 20 carbon atoms, and h, i, j, and k are integers of 0 to 4.)
  • the content ratio of the structural unit (B11) in the structural unit B1B is preferably 50 mol% or more, more preferably 55 mol% or more, and still more preferably It is 60 mol % or more, more preferably 80 mol % or more, still more preferably 90 mol % or more, and still more preferably 95 mol % or more.
  • the upper limit of the content ratio of the structural unit (B11) is not particularly limited, and is 100 mol% or less.
  • the structural unit B1B may consist only of the structural unit (B11).
  • the structural unit (B11) is a structural unit (B111) derived from a compound represented by the following formula (b111) and represented by the following formula (b112). preferably contains at least one selected from the group consisting of the structural unit (B112) derived from the compound.
  • the compound represented by formula (b111) is 4-aminophenyl-4-aminobenzoate (4-BAAB).
  • the compound represented by formula (b112) is 1,4-bis(4-aminobenzoyloxy)benzene (ABHQ).
  • the content ratio of the structural unit (B111) in the structural unit (B11) in the structural unit B1B is preferably 45 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, Particularly preferably, it is 99 mol % or more.
  • the upper limit of the content ratio is not particularly limited, and is 100 mol % or less.
  • the content ratio of the structural unit (B112) in the structural unit (B11) in the structural unit B1B is preferably 45 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, Particularly preferably, it is 99 mol % or more.
  • the upper limit of the content ratio is not particularly limited, and is 100 mol % or less.
  • the total content ratio of the structural unit (B111) and the structural unit (B112) in the structural unit (B11) is , preferably 45 mol % or more, more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably 99 mol % or more.
  • the upper limit of the ratio is not particularly limited, and is 100 mol % or less.
  • examples of the diamine that gives a structural unit derived from the diamine occupying the imide portion other than the structural unit B1B include 1,4-phenylenediamine, p-xylylenediamine, and 3,5-diamino.
  • Benzoic acid 1,5-diaminonaphthalene, 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminodiphenylmethane, 1,4-bis[2-(4-aminophenyl)-2- propyl]benzene, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminobenzanilide, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl -1H-indene-5-amine, ⁇ , ⁇ '-bis(4-aminophenyl)-1,4-diisopropylbenzene, N,N'-bis(4-aminophenyl)terephthalamide, 2,2-bis( 3-amino-4-hydroxyphenyl)hexafluoropropane, and aromatic diamines such as 1,4-bis(4-aminophenoxy)benz
  • Structural unit A2A is a structural unit derived from tetracarboxylic dianhydride occupying the amic acid moiety corresponding to the repeating unit represented by formula (2) of the copolymer of the present invention, and is an aromatic tetracarboxylic acid It contains a structural unit derived from a dianhydride, preferably a structural unit derived from an aromatic tetracarboxylic dianhydride different from the structural unit A1A.
  • the structural unit A2A is not limited as long as it contains a structural unit derived from an aromatic tetracarboxylic dianhydride, but the structural unit A2A is a structural unit derived from an aromatic tetracarboxylic dianhydride (a21) It preferably contains the unit (A21).
  • the structural unit (A21) is a structural unit (A211) derived from a compound represented by the following formula (a211), a structural unit (A212) derived from a compound represented by the following formula (a212), A structural unit (A213) derived from a compound represented by (a213), a structural unit (A214) derived from a compound represented by formula (a214) below, and a structure derived from a compound represented by formula (a215) below It contains at least one selected from the group consisting of units (A215).
  • the compound represented by formula (a211) is biphenyltetracarboxylic dianhydride (BPDA), and specific examples thereof include 3,3′,4,4′-biphenyl represented by formula (a211s) below.
  • s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride represented by the following formula (a211s) is preferable.
  • the compound represented by formula (a212) is p-phenylenebis(trimellitate) dianhydride (TAHQ).
  • the compound represented by formula (a213) is pyromellitic anhydride (PMDA).
  • the compound represented by formula (a214) is p-biphenylene bis(trimellitate) dianhydride (BP-TME).
  • the compound represented by formula (a215) is bis(benzene-3,4-dicarboxylic anhydride) ester (BBDE).
  • the structural unit (A21) preferably contains the structural unit (A211) from the viewpoint of high heat resistance and low residual stress.
  • the structural unit A2A may contain structural units other than the structural unit (A21).
  • the tetracarboxylic dianhydride that provides such a structural unit is not particularly limited as long as it is an aromatic tetracarboxylic dianhydride.
  • Structural units arbitrarily contained in the structural unit A2A may be of one type, or may be of two or more types.
  • the tetracarboxylic dianhydride that gives a structural unit derived from the tetracarboxylic dianhydride occupying the amic acid portion other than the structural unit A2A includes 1, 2, 4 ,5-cyclohexanetetracarboxylic dianhydride, norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2′′-norbornane-5,5′′,6,6′′-tetracarboxylic acid di anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene- Alicyclic tetracarboxylic dianhydrides such as 2,3,5,6-tetracarboxylic dianhydride and dicyclohexyltetracarboxylic dian
  • the total ratio of the structural units (A211) to (A215) in the structural unit (A21) is preferably 45 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99. mol% or more.
  • the upper limit of the ratio is not particularly limited, and is 100 mol % or less.
  • the structural unit (A21) may contain at least one selected from the structural units (A211) to (A215), and consists of only one selected from the structural units (A211) to (A215). good too.
  • the ratio of each structural unit in the structural unit (A21) is not particularly limited, and any ratio can be
  • the ratio of the structural unit (A21) in the structural unit A2A is preferably 45 mol% or more, more preferably 60 mol% or more, and still more preferably 85 mol% or more.
  • the upper limit of the content ratio is not particularly limited, and is 100 mol % or less.
  • the structural unit (A1A contains the structural unit (A11) and the structural unit A2A contains the structural unit (A21)
  • the molar ratio [(A11)/(A21)] between A11) and the structural unit (A21) is preferably 5/95 to 60/ 40, more preferably 10/90 to 60/40, still more preferably 15/85 to 60/40.
  • the structural unit (A1A contains the structural unit (A12) and the structural unit A2A contains the structural unit (A21)
  • the structural unit ( The molar ratio [(A12)/(A21)] between A12) and the structural unit (A21) is preferably 5/95 to 60/ 40, more preferably 10/90 to 60/40, still more preferably 15/85 to 60/40.
  • the structural unit B2B is a structural unit derived from a diamine occupying the amic acid moiety corresponding to the repeating unit represented by the formula (2) of the copolymer of the present invention, and is represented by the following general formula (b11): It contains a structural unit (B11) derived from a diamine.
  • Y 1 and Y 2 each independently represent a group represented by —COO— or a group represented by —OCO—.
  • R 1 , R 2 and R 3 are each independently represents an organic group having 1 to 20 carbon atoms, and h, i, j, and k are integers of 0 to 4.
  • the content ratio of the structural unit (B11) in the structural unit B2B is preferably 50 mol% or more, more preferably 55 mol% or more, and still more preferably It is 60 mol % or more, more preferably 80 mol % or more, still more preferably 90 mol % or more, and still more preferably 95 mol % or more.
  • the upper limit of the content ratio of the structural unit (B11) is not particularly limited, and is 100 mol% or less.
  • the structural unit B2B may consist only of the structural unit (B11).
  • the structural unit (B11) is represented by the structural unit (B111) derived from the compound represented by the following formula (b111) and the following formula (b112) from the viewpoint of heat resistance, low residual stress and low coefficient of linear expansion. It preferably contains at least one selected from the group consisting of structural units (B112) derived from compounds.
  • the compound represented by formula (b111) is 4-aminophenyl-4-aminobenzoate (4-BAAB).
  • the compound represented by formula (b112) is 1,4-bis(4-aminobenzoyloxy)benzene (ABHQ).
  • the content ratio of the structural unit (B111) in the structural unit (B11) in the structural unit B2B is preferably 45 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, Particularly preferably, it is 99 mol % or more.
  • the upper limit of the ratio is not particularly limited, and is 100 mol % or less.
  • the content ratio of the structural unit (B112) in the structural unit (B11) in the structural unit B2B is preferably 45 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, Particularly preferably, it is 99 mol % or more.
  • the upper limit of the content ratio is not particularly limited, and is 100 mol % or less.
  • the total content ratio of the structural unit (B111) and the structural unit (B112) in the structural unit (B11) is , preferably 45 mol % or more, more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably 99 mol % or more.
  • the upper limit of the ratio is not particularly limited, and is 100 mol % or less.
  • diamines that give structural units derived from the diamine occupying the imide portion other than the structural unit B2B include 1,4-phenylenediamine, p-xylylenediamine, 3,5- diaminobenzoic acid, 1,5-diaminonaphthalene, 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminodiphenylmethane, 1 , 4-bis[2-(4-aminophenyl)-2-propyl]benzene, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminobenzanilide, 1-(4-amino Phenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, ⁇ , ⁇ '-
  • the imide-amic acid copolymer of the present invention may be produced by any method, but is preferably obtained by the following method.
  • the method for producing an imide-amic acid copolymer of the present invention comprises steps 1 and 2 below.
  • Step 1 A step of reacting a tetracarboxylic acid component constituting an imide moiety with a diamine component to obtain an imide oligomer
  • Step 2 The imide oligomer obtained in Step 1, a tetracarboxylic acid component constituting an amide acid moiety, and A step of reacting a diamine component to obtain an imide-amic acid copolymer containing repeating units consisting of an imide moiety and an amic acid moiety.
  • an imide-amic acid copolymer of the present invention it is possible to control the imide portion and the amic acid portion to a specific structure, so that conventional imide portions and amic acid portions exist randomly.
  • imido-amides can be expected to have improved heat resistance and low coefficient of linear expansion due to having a polyimide portion and a polyamic acid portion depending on the thermal imidization reactivity of each component. It is believed that acid copolymers can be obtained.
  • Step 1 A compound that provides a structural unit A1A derived from a tetracarboxylic dianhydride and a compound that provides a structural unit B1B derived from a diamine are reacted to obtain an imide containing an imide repeating structural unit represented by formula (1).
  • Step 2 for obtaining an oligomer Step 2 The imide oligomer obtained in Step 1 is reacted with a compound giving a structural unit A2A derived from a tetracarboxylic dianhydride and a compound giving a structural unit B2B derived from a diamine, and the formula (1
  • a compound that provides the structural unit A2A contains an aromatic tetracarboxylic dianhydride
  • the compound that provides the structural unit B1B and the compound that provides the structural unit B2B include a diamine represented by the following general formula (b11).
  • Y 1 and Y 2 each independently represent a group represented by —COO— or a group represented by —OCO—.
  • R 1 , R 2 and R 3 are each independently represents an organic group having 1 to 20 carbon atoms, and h, i, j, and k are integers of 0 to 4.
  • a copolymer capable of forming a film having excellent transparency and heat resistance and having a low degree of yellowness can be produced by the production method including Steps 1 and 2 described above.
  • the method for producing the copolymer of the present invention is described below.
  • Step 1 is a step of reacting a tetracarboxylic acid component constituting an imide moiety containing a moiety corresponding to formula (1) with a diamine component to obtain an imide oligomer.
  • the tetracarboxylic acid component constituting the imide moiety is preferably an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride having a norbornane skeleton.
  • Step 1 is more preferably a step of reacting a compound that provides a tetracarboxylic dianhydride-derived structural unit A1A with a compound that provides a diamine-derived structural unit B1B to obtain an imide oligomer.
  • a compound that provides the structural unit A1A includes an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride having a norbornane skeleton.
  • the compound providing the structural unit B1B includes the compound providing the structural unit (B11), and the compound providing the structural unit (B11) is the compound represented by the formula (b111) from the compound represented by the formula (b112) It is preferable to include at least one selected from the group consisting of:
  • the tetracarboxylic acid component used in step 1 preferably contains at least one selected from the group consisting of a compound that provides the structural unit (A11) and a compound that provides the structural unit (A12). is preferably used, and may contain a tetracarboxylic acid component other than the compound that provides the structural unit (A11) and the compound that provides the structural unit (A12) within a range that does not impair the effects of the present invention.
  • the diamine component used in step 1 preferably contains a compound that provides the structural unit (B11), and a diamine component other than the compound that provides the structural unit (B11) is included within a range that does not impair the effects of the present invention. good too.
  • the molar ratio of the diamine component to the tetracarboxylic acid component is preferably 1.01 to 2 mol, more preferably 1.05 to 1.9 mol, More preferably 1.1 to 1.7 mol.
  • the method of reacting the tetracarboxylic acid component and the diamine component to obtain the imide oligomer in step 1 is not particularly limited, and a known method can be used.
  • a specific reaction method (1) a tetracarboxylic acid component, a diamine component, and a reaction solvent are charged into a reactor, stirred at 10 to 110° C. for 0.5 to 30 hours, and then heated to imidize. (2) After charging the diamine component and the reaction solvent into a reactor and dissolving them, charging the tetracarboxylic acid component, stirring at 10 to 110° C. for 0.5 to 30 hours as necessary, and then and (3) a method in which a tetracarboxylic acid component, a diamine component and a reaction solvent are charged into a reactor and the temperature is immediately raised to carry out the imidization reaction.
  • the imidization reaction it is preferable to carry out the reaction while removing water generated during production using a Dean-Stark apparatus or the like. By performing such an operation, the degree of polymerization and the imidization rate can be further increased.
  • a known imidization catalyst can be used in the above imidization reaction.
  • Examples of imidization catalysts include base catalysts and acid catalysts.
  • Base catalysts include pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, imidazole, N,N -dimethylaniline, N,N-diethylaniline and other organic base catalysts, and potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate, sodium hydrogencarbonate and other inorganic base catalysts.
  • Acid catalysts include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, and the like. is mentioned. You may use said imidization catalyst individually or in combination of 2 or more types. Among the above, from the viewpoint of handleability, a base catalyst is preferred, an organic base catalyst is more preferred, one or more selected from triethylamine and triethylenediamine are more preferred, and triethylamine is even more preferred.
  • the temperature of the imidization reaction is preferably 120 to 250°C, more preferably 160 to 200°C, from the viewpoints of reaction rate and inhibition of gelation.
  • the reaction time is preferably 0.5 to 10 hours after the start of distillation of the produced water.
  • the imide oligomer obtained in step 1 is formed from at least one selected from the group consisting of a compound that provides the structural unit (A11) and a compound that provides the structural unit (A12), and a compound that provides the structural unit (B11). It is preferred to have an imide repeating structural unit. Moreover, the imide oligomer obtained in step 1 preferably has amino groups at both ends of the main chain of the molecular chain. A solution containing an imide oligomer dissolved in a solvent is obtained by the above method.
  • the solution containing the imide oligomer obtained in step 1 contains at least a part of the components used as the tetracarboxylic acid component and the diamine component in step 1 as unreacted monomers within a range that does not impair the effects of the present invention.
  • the number average molecular weight (Mn) of the imide oligomer obtained in step 1 is preferably 1,000 to 100,000 from the viewpoint of heat resistance and mechanical strength of the resulting polyimide film. Also, the weight average molecular weight (Mw) is preferably 1,000 to 100,000 from the same viewpoint.
  • the number-average molecular weight or weight-average molecular weight of the copolymer can be determined, for example, by standard polymethyl methacrylate (PMMA) conversion by gel filtration chromatography or by a light scattering method.
  • step 2 of the production method of the present invention the imide oligomer obtained in step 1 is reacted with the tetracarboxylic acid component and the diamine component that constitute the amic acid moiety, thereby containing a repeating unit consisting of the imide moiety and the amic acid moiety.
  • This is the step of obtaining an imide-amic acid copolymer.
  • the tetracarboxylic acid component constituting the amic acid moiety used in step 2 is preferably an aromatic tetracarboxylic dianhydride.
  • step 2 more preferably, the imide oligomer obtained in step 1 is reacted with a compound that provides a structural unit A2A derived from tetracarboxylic dianhydride and a compound that provides a structural unit B2B derived from diamine, and the imide - It is a step to obtain an amic acid copolymer.
  • Compounds that provide building block A2A include aromatic tetracarboxylic dianhydrides.
  • the compound that provides the structural unit B2B preferably includes a compound that provides the structural unit (B11), and the compound that provides the structural unit (B11) is a compound represented by the formula (b111) and a compound represented by the formula (b112). It preferably contains at least one selected from the group consisting of the represented compounds.
  • the tetracarboxylic acid component used in step 2 preferably contains a compound that provides the structural unit (A21), and a tetracarboxylic acid component other than the compound that provides the structural unit (A21) within a range that does not impair the effects of the present invention.
  • the tetracarboxylic acid component used in step 2 preferably does not contain a compound that provides the structural unit (A11).
  • the diamine component used in step 2 preferably contains a compound that provides the structural unit (B11), and a diamine component other than the compound that provides the structural unit (B11) is included within a range that does not impair the effects of the present invention. good too.
  • the method of reacting the imide oligomer obtained in step 1 with the tetracarboxylic acid component and the diamine component to obtain the imide-amic acid copolymer in step 2 is not particularly limited, and a known method can be used. can.
  • a specific reaction method (1) the imide oligomer obtained in step 1, the tetracarboxylic acid component, the diamine component and the solvent are charged into a reactor and (2) After charging the imide oligomer and solvent obtained in step 1 into a reactor and dissolving them, a tetracarboxylic acid component and a diamine component are charged, and the temperature is 0 to 120 ° C., preferably 5 to 5. and a method of stirring at 80° C. for 1 to 72 hours.
  • the molecular weight of the copolymer obtained in step 2 does not fluctuate depending on the temperature history during polymerization, and the progress of thermal imidization can be suppressed. can be stably manufactured.
  • a copolymer solution containing the imide-amic acid copolymer dissolved in the solvent is obtained.
  • the concentration of the copolymer in the obtained copolymer solution is preferably 1 to 50 mass %, more preferably 3 to 35 mass %, still more preferably 5 to 30 mass %.
  • the obtained copolymer liquid is preferably stored at 23°C for 3 to 10 days after step 2, and then stored at -20°C. preferable.
  • the number average molecular weight of the imide-amic acid copolymer obtained by the production method of the present invention is preferably 5,000 to 500,000 from the viewpoint of the mechanical strength of the resulting polyimide film.
  • the weight average molecular weight (Mw) of the imide-amic acid copolymer obtained by the production method of the present invention is preferably 10,000 or more and 800,000 or less, more preferably 10,000 or less, from the same viewpoint. 000 or more and 300,000 or less, more preferably 100,000 or more and 300,000 or less.
  • the number-average molecular weight or weight-average of the copolymer can be obtained, for example, from a standard polymethylmethacrylate (PMMA) conversion value by gel filtration chromatography measurement. Next, the raw materials and the like used in this production method will be described.
  • tetracarboxylic acid component used as a raw material for the imide-amic acid copolymer in the present production method is the above-mentioned ⁇ Each structural unit of the imide-amic acid copolymer> section (structural unit A1A) and (structural unit A2A) It is preferable to use the compounds that provide each structural unit described in the section.
  • the ratio of the compound that provides the structural unit (A11) in the tetracarboxylic acid component used in step 1 is It is preferably 50 mol% or more, more preferably 55 mol% or more, still more preferably 60 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more. , and more preferably 95 mol % or more.
  • the upper limit of the usage ratio of the compound that provides the structural unit (A11) is not particularly limited, and is 100 mol % or less.
  • the tetracarboxylic acid component used in step 1 may consist only of the compound that provides the structural unit (A11).
  • the ratio of the compound that provides the structural unit (A12) in the tetracarboxylic acid component used in step 1 is It is preferably 50 mol% or more, more preferably 55 mol% or more, still more preferably 60 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more. , and more preferably 95 mol % or more.
  • the upper limit of the usage ratio of the compound that provides the structural unit (A12) is not particularly limited, and is 100 mol % or less.
  • the tetracarboxylic acid component used in step 1 may consist only of a compound that provides the structural unit (A12).
  • the structural unit (A11 ) and the compound giving the structural unit (A12) are preferably 50 mol% or more, more preferably 55 mol% or more, still more preferably 60 mol% or more, and more More preferably 80 mol % or more, still more preferably 90 mol % or more, still more preferably 95 mol % or more.
  • the upper limit of the total usage ratio of the compound that provides the structural unit (A11) and the compound that provides the structural unit (A12) is not particularly limited, and is 100 mol % or less.
  • the tetracarboxylic acid component used in step 1 may consist only of the compound that provides the structural unit (A11) and the compound that provides the structural unit (A12).
  • the compound that provides the structural unit (A11) and the compound that provides the structural unit (A12) include, but are not limited to, the compound represented by the formula (a11) and the compound represented by the formula (a12), respectively. However, it may be a derivative thereof as long as it provides the same structural unit. Examples of the derivative include tetracarboxylic acids corresponding to the compounds represented by formula (a11) and the compounds represented by formula (a12), and alkyl esters of the tetracarboxylic acids.
  • a compound represented by formula (a11) is preferable.
  • a compound represented by the formula (a12) is preferable as the compound that provides the structural unit (A12).
  • the ratio of the compound that provides the structural unit (A21) is preferably 45 mol% or more, More preferably 60 mol % or more, still more preferably 85 mol % or more.
  • the upper limit of the usage ratio is not particularly limited, and is 100 mol % or less.
  • the compound giving the structural unit (A21) includes the compound represented by the formula (a211), the compound represented by the formula (a212), the compound represented by the formula (a213), and the compound represented by the formula (a214).
  • the molar ratio of the compound providing the structural unit (A11) and the compound providing the structural unit (A21) in the tetracarboxylic acid component used as a raw material for the imide-amic acid copolymer in the present production method is preferably 5/95 to 60/40, more preferably 10/90 to 60/40, from the viewpoint of transparency, low yellowness, high heat resistance, and low linear expansion coefficient, and further It is preferably 15/85 to 60/40.
  • the molar ratio of the compound providing the structural unit (A12) and the compound providing the structural unit (A21) in the tetracarboxylic acid component used as a raw material for the imide-amic acid copolymer in the present production method is preferably 5/95 to 60/40, more preferably 10/90 to 60/40, from the viewpoint of transparency, low yellowness, high heat resistance, and low linear expansion coefficient, and further It is preferably 15/85 to 60/40.
  • the total ratio of the compounds providing the structural units (A211) to (A215) in the compounds providing the structural unit (A21) is preferably 45 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol%. 99 mol % or more, particularly preferably 99 mol % or more. The upper limit of the ratio is not particularly limited, and is 100 mol % or less.
  • the tetracarboxylic acid component used as a raw material for the imide-amic acid copolymer includes a compound that provides the structural unit (A11), a compound that provides the structural unit (A12), a compound that provides the structural unit (A211), and a structural unit (A212). ), a compound that provides the structural unit (A213), a compound that provides the structural unit (A214), and a compound other than the compound that provides the structural unit (A215), and such compounds may be one type, Two or more types may be used.
  • the diamine component used as a raw material for the imide-amic acid copolymer in this production method is the above-mentioned ⁇ Each structural unit of the imide-amic acid copolymer> section (structural unit B1B) and section (structural unit B2B). It is preferable to use a compound that provides each structural unit described in .
  • the diamine component used in step 1 for obtaining the imide oligomer contains a compound that provides the structural unit (B11), the ratio of the compound that provides the structural unit (B11) in the diamine component used in step 1 is preferably 50 mol.
  • the upper limit of the usage ratio of the compound that provides the structural unit (B11) is not particularly limited, and is 100 mol % or less.
  • the diamine component used in step 1 may consist only of the compound that provides the structural unit (B11).
  • the use ratio of the compound that provides the structural unit (B11) in the diamine component used in step 2 is , preferably 50 mol% or more, more preferably 55 mol% or more, still more preferably 60 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more Yes, more preferably 95 mol % or more.
  • the upper limit of the usage ratio of the compound that provides the structural unit (B11) is not particularly limited, and is 100 mol % or less.
  • the diamine component used in step 2 may consist only of the compound that provides the structural unit (B11).
  • the compound that provides the structural unit (B11) at least one selected from the group consisting of the compound that provides the structural unit (B111) and the compound that provides the structural unit (B112) is preferable.
  • the use ratio of the compound providing the structural unit (B111) in the compounds providing the structural unit (B11) is preferably 45 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more. and particularly preferably 99 mol % or more.
  • the upper limit of the usage ratio is not particularly limited, and is 100 mol % or less.
  • the use ratio of the compound providing the structural unit (B112) in the compound providing the structural unit (B11) is preferably 45 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more. and particularly preferably 99 mol % or more.
  • the upper limit of the usage ratio is not particularly limited, and is 100 mol % or less.
  • the total usage ratio of the compound providing the structural unit (B111) and the compound providing the structural unit (B112) in the compound providing the structural unit (B11) is preferably 45 mol% or more, more preferably 70 mol%. more preferably 90 mol % or more, particularly preferably 99 mol % or more.
  • the upper limit of the total usage ratio is not particularly limited, and is 100 mol % or less.
  • the diamine component used as a raw material for the imide-amic acid copolymer may contain a compound other than the compound that provides the structural unit (B11), and such compounds may be of one type or two or more types. good.
  • Compounds that provide the structural unit (B11) include, but are not limited to, diamines, and derivatives thereof may be used as long as they provide the same structural unit. Such derivatives include diisocyanates corresponding to diamines.
  • a diamine is preferable as the compound that provides the structural unit (B11).
  • the charging ratio of the tetracarboxylic acid component and the diamine component used in all the steps of copolymer production including steps 1 and 2 is 0.9 for the diamine component per 1 mol of the tetracarboxylic acid component. It is preferably ⁇ 1.1 mol.
  • a terminal blocker may be used in addition to the above-described tetracarboxylic acid component and diamine component for the production of the imide-amic acid copolymer.
  • a terminal blocking agent is preferably used in step 2.
  • Monoamines or dicarboxylic acids are preferable as the terminal blocking agent.
  • the amount of the terminal blocker to be introduced is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.06 mol, per 1 mol of the tetracarboxylic acid component.
  • Monoamine terminal blockers include, for example, methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3- ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline and the like.
  • benzylamine and aniline are preferred.
  • Dicarboxylic acids are preferable as the dicarboxylic acid end blocking agent, and a part of them may be ring-closed.
  • phthalic acid for example, phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenonedicarboxylic acid, 3,4-benzophenonedicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1 , 2-dicarboxylic acid and the like.
  • phthalic acid and phthalic anhydride are preferred.
  • the solvent used in the method for producing the copolymer of the present invention is not particularly limited as long as it can dissolve the resulting imide-amic acid copolymer.
  • Examples include aprotic solvents, phenolic solvents, ether solvents, carbonate solvents and the like.
  • aprotic solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethylimidazolidinone, tetramethylurea and the like.
  • lactone solvents such as ⁇ -butyrolactone and ⁇ -valerolactone
  • phosphorus-containing amide solvents such as hexamethylphosphoricamide and hexamethylphosphinetriamide
  • sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide, and sulfolane.
  • ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and methylcyclohexanone
  • ester solvents such as acetic acid (2-methoxy-1-methylethyl).
  • phenolic solvents include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4 -xylenol, 3,5-xylenol, and the like.
  • ether solvents include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl] ether, tetrahydrofuran, 1,4-dioxane and the like.
  • carbonate solvents include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate and the like.
  • amide-based solvents or lactone-based solvents are preferred, amide-based solvents are more preferred, and N-methyl-2-pyrrolidone is even more preferred.
  • the above reaction solvents may be used alone or in combination of two or more.
  • the varnish of the present invention is obtained by dissolving the imide-amic acid copolymer of the present invention, which is a precursor of the polyimide resin, in an organic solvent. That is, the varnish of the present invention contains the imide-amic acid copolymer of the present invention and an organic solvent, and the imide-amic acid copolymer is dissolved in the organic solvent.
  • the organic solvent is not particularly limited as long as it dissolves the copolymer of the present invention, but the compounds described above as the solvent used in the production of the copolymer of the present invention may be used singly or in combination of two or more. It is preferable to use
  • the varnish of the present invention may be the above-described copolymer solution itself, or may be obtained by adding a diluent solvent to the copolymer solution.
  • the varnish of the present invention can further contain an imidization catalyst and a dehydration catalyst from the viewpoint of efficiently advancing the imidization of the amic acid sites in the copolymer of the present invention.
  • the imidization catalyst may be an imidization catalyst having a boiling point of 40° C. or higher, and an imidization catalyst having a boiling point of 40° C. or higher can avoid the possibility of volatilization before imidization sufficiently proceeds.
  • the imidization catalyst includes amine compounds such as pyridine or picoline; imidazole compounds such as imidazole, 1,2-dimethylimidazole, 1-benzylimidazole, 1-benzyl-2-methylimidazole and benzimidazole; and the like.
  • dehydration catalysts include acid anhydrides such as acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride and trifluoroacetic anhydride; and carbodiimide compounds such as dicyclohexylcarbodiimide. You may use these individually or in combination of 2 or more types.
  • the varnish of the present invention preferably contains 3 to 40% by mass of the copolymer of the present invention, more preferably 5 to 40% by mass, even more preferably 6 to 30% by mass.
  • the viscosity of the varnish is preferably 0.1 to 100 Pa ⁇ s, more preferably 0.1 to 20 Pa ⁇ s.
  • the viscosity of the varnish is a value measured at 25°C using an E-type viscometer.
  • the varnish of the present invention contains an inorganic filler, an adhesion promoter, a release agent, a flame retardant, an ultraviolet stabilizer, a surfactant, a leveling agent, an antifoaming agent, and a fluorescent brightening agent within a range that does not impair the required properties of the polyimide film.
  • Various additives such as agents, cross-linking agents, polymerization initiators, and photosensitizers may also be included.
  • the method for producing the varnish of the present invention is not particularly limited, and known methods can be applied.
  • the polyimide film of the present invention contains a polyimide resin obtained by imidizing the amic acid site in the imide-amic acid copolymer of the present invention. Therefore, the polyimide film of the present invention has excellent transparency and heat resistance, and a low degree of yellowness.
  • the polyimide film of the present invention can be produced using a varnish obtained by dissolving the aforementioned copolymer in an organic solvent.
  • the method for producing a polyimide film using the varnish of the present invention is not particularly limited, and known methods can be used.
  • a smooth support such as a glass plate, a metal plate, or a plastic, or forming it into a film
  • an organic solvent such as a reaction solvent or dilution solvent contained in the varnish is heated. to obtain a copolymer film, imidize the amic acid site of the copolymer in the copolymer film by heating (dehydration ring closure), and then peel off from the support to produce a polyimide film be able to.
  • the weight average molecular weight (Mw) of the polyimide resin contained in the polyimide film of the present invention is preferably 10,000 to 800,000, more preferably 10,000 to 300,000, from the viewpoint of mechanical strength of the film. and more preferably 100,000 to 300,000.
  • the weight average molecular weight of the polyimide resin can be determined, for example, from a standard polymethyl methacrylate (PMMA) conversion value obtained by gel filtration chromatography.
  • the heating temperature for drying the varnish of the present invention to obtain a copolymer film is preferably 50 to 150°C.
  • the heating temperature for imidizing the copolymer of the present invention is preferably 200 to 500.degree. C., more preferably 300 to 470.degree. C., still more preferably 400 to 450.degree.
  • the heating time is preferably 1 minute to 6 hours, more preferably 5 minutes to 2 hours, and still more preferably 15 minutes to 1 hour.
  • Examples of the heating atmosphere include air gas, nitrogen gas, oxygen gas, hydrogen gas, and nitrogen/hydrogen mixed gas. in a hydrogen concentration of 0.5% or less is preferred.
  • the imidization method is not limited to thermal imidization, and chemical imidization can also be applied.
  • the thickness of the polyimide film of the present invention can be appropriately selected depending on the application, etc., but is preferably 1 to 250 ⁇ m, more preferably 5 to 100 ⁇ m, and still more preferably 5 to 50 ⁇ m.
  • the thickness of the polyimide film can be easily controlled by adjusting the solid content concentration and viscosity of the varnish.
  • ⁇ Polyimide film physical properties> By using the imide-amic acid copolymer of the present invention, it is possible to form a polyimide film having a low linear expansion coefficient, excellent heat resistance, and little change in yellowness even after heat treatment.
  • Preferred physical properties of the polyimide film are as follows.
  • the coefficient of linear expansion (in the range of 100°C to 400°C) is preferably 25 ppm/°C or less, more preferably 20 ppm/°C or less, and even more preferably 15 ppm/°C or less.
  • the glass transition temperature (Tg) of the polyimide film of the present invention is preferably 430°C or higher, more preferably 450°C or higher, and even more preferably 480°C or higher.
  • the 1% weight loss temperature (Td1%) is preferably 500°C or higher, more preferably 510°C or higher, and even more preferably 520°C or higher.
  • Td1% weight loss temperature
  • the above physical property values in the present invention can be specifically measured by the methods described in Examples.
  • the polyimide film of the present invention has excellent heat resistance.
  • the difference between the yellowness index (YI1) and the initial yellowness index (YI0) is preferably 20.0 or less. , more preferably 10.0 or less, still more preferably 8.0 or less, still more preferably 6.0 or less, and even more preferably 5.0 or less.
  • the yellowness YI1 after two 1-hour heat treatments at 430° C. and the initial yellowness YI0 satisfy the following formula (8).
  • ⁇ YI YI1 ⁇ YI0 ⁇ 20 (8)
  • the heat resistance test method can be performed by the method described in Examples.
  • the polyimide film of the present invention is suitably used as films for various members such as color filters, flexible displays, semiconductor parts, and optical members.
  • the polyimide film of the present invention is particularly suitably used as a substrate for image display devices such as liquid crystal displays and OLED displays.
  • the laminate of the present invention comprises the polyimide film and at least one inorganic layer.
  • the inorganic layer is preferably laminated on the polyimide film.
  • Inorganic layers include metal films, semiconductor films, and insulating films.
  • the semiconductor film is laminated on the polyimide film, and it is even more preferable that the insulating film and the semiconductor film are laminated on the polyimide film, More preferably, the insulating film and the semiconductor film are laminated in this order on the polyimide film.
  • the laminate of the present invention may have an insulating film between the polyimide film and the metal film or semiconductor film, and preferably has an insulating film.
  • a SiO 2 film is preferable as the insulating film, and the SiO 2 film functions as a buffer film when forming a metal film or a semiconductor film.
  • Preferred specific examples of the metal film include copper mesh and silver mesh.
  • Preferred specific examples of the semiconductor film include at least one selected from the group consisting of indium tin oxide (ITO), amorphous silicon, indium-gallium-zinc oxide (IGZO), and low-temperature polysilicon (LTPS).
  • ITO indium tin oxide
  • IGZO indium-gallium-zinc oxide
  • LTPS low-temperature polysilicon
  • Another metal film or semiconductor film may be further laminated on these metal films or semiconductor films.
  • the thickness of the metal film or semiconductor film is not particularly limited, it is preferably 1 to 400 nm, more preferably 10 to 300 nm, still more preferably 20 to 200 nm.
  • the laminate of the present invention has excellent heat resistance.
  • the difference between the yellowness index (YI1) and the initial yellowness index (YI0) is preferably 20.0. or less, more preferably 10.0 or less, still more preferably 8.0 or less, even more preferably 6.0 or less, and even more preferably 5.0 or less.
  • the yellowness YI1 after two 1-hour heat treatments at 430° C. and the initial yellowness YI0 satisfy the following formula (8).
  • ⁇ YI YI1 ⁇ YI0 ⁇ 20 (8)
  • the heat resistance test method can be performed by the method described in Examples.
  • Tg Glass transition temperature (evaluation of heat resistance) Using a thermomechanical analyzer "TMA / SS6100" manufactured by Hitachi High-Tech Science Co., Ltd., a sample size of 3 mm ⁇ 20 mm, a tensile mode, a load of 50 mN, and a heating rate of 10 ° C./min, from 40 ° C. to 550 ° C. TMA measurement was performed, and the place where the inflection point of elongation was observed was determined as the glass transition temperature.
  • CTE Coefficient of linear expansion
  • Td1% weight loss temperature (evaluation of heat resistance)
  • a simultaneous differential thermal thermogravimetric measurement device "NEXTA STA200RV” manufactured by Hitachi High-Tech Science Co., Ltd. was used. The sample was heated from 40°C to 150°C at a heating rate of 10°C/min, held at 150°C for 30 minutes to remove moisture, and then heated to 550°C. The temperature at which the weight decreased by 1% compared to the weight after holding at 150° C. for 30 minutes was taken as the 1% weight loss temperature (Td1%). The higher the weight loss temperature, the better the heat resistance.
  • NMP N-methyl-2-pyrrolidone (manufactured by Tokyo Junyaku Kogyo Co., Ltd.)
  • TEA triethylamine (manufactured by Kanto Chemical Co., Ltd.)
  • Example 1 4-BAAB 6.848 g (0.030 mol ) and 30.064 g of NMP were added, the temperature in the system was set to 70° C. under a nitrogen atmosphere, and the mixture was stirred at a rotation speed of 200 rpm to obtain a solution. After adding 9.169 g (0.020 mol) of BPAF and 10.000 g of NMP to this solution all at once, 0.101 g of TEA and 5.000 g of NMP were added as an imidization catalyst, heated with a mantle heater, The temperature in the reaction system was raised to 190°C over about 20 minutes. The temperature in the reaction system was kept at 190° C. and refluxed for 1 hour while collecting the components to be distilled off.
  • the obtained varnish was applied onto a glass plate by spin coating, held on a hot plate at 80°C for 20 minutes, and then heated in a hot air dryer at 430°C for 60 minutes in a nitrogen atmosphere to evaporate the solvent. , to obtain a polyimide film.
  • Table 1 shows the physical properties and evaluation results of the film.
  • Example 2 A polyimide varnish having a solid concentration of about 15% by mass was obtained in the same manner as in Example 1, except that 9.169 g (0.020 mol) of BPAF was changed to 8.885 g (0.020 mol) of 6FDA. A polyimide film was obtained in the same manner as in Example 1 using the obtained varnish. Table 1 shows the physical properties and evaluation results of the film.
  • Example 3 BPAF 9.169 g (0.020 mol) was changed to BPAF 13.7529 g (0.030 mol), 4-BAAB 6.848 g (0.030 mol) was changed to ABHQ 13.934 g (0.040 mol) Then, 23.538 g (0.080 mol) of s-BPDA was changed to 20.5954 g (0.070 mol) of s-BPDA, and 15.978 g (0.070 mol) of 4-BAAB was replaced with 20.902 g (0.070 mol) of ABHQ.
  • a polyimide varnish having a solid concentration of about 15% by mass was obtained in the same manner as in Example 1, except that the content was changed to 0.060 mol).
  • a polyimide film was obtained in the same manner as in Example 1 using the obtained varnish. Table 1 shows the physical properties and evaluation results of the film.
  • Example 4 Change 4-BAAB 6.848 g (0.030 mol) to ABHQ 10.451 g (0.030 mol), 4-BAAB 15.978 g (0.070 mol) ABHQ 24.385 g (0.070 mol)
  • a polyimide varnish having a solid content concentration of about 15% by mass was obtained in the same manner as in Example 1, except that it was changed to .
  • a polyimide film was obtained in the same manner as in Example 1 using the obtained varnish. Table 1 shows the physical properties and evaluation results of the film.
  • a polyimide film was obtained in the same manner as in Example 1 using the obtained varnish. Table 1 shows the physical properties and evaluation results of the film.
  • the polyimide films obtained from the imide-amic acid copolymers of Examples having specific imide repeating structural units and amic acid repeating structural units have a low coefficient of linear expansion and excellent heat resistance. It can be seen that Furthermore, the polyimide films obtained from the imide-amic acid copolymers of Examples 1 to 4 having specific imide repeating structural units and amic acid repeating structural units, and laminates of the films and inorganic films were subjected to repeated heat treatments. The heat resistance at the time was particularly excellent. On the other hand, when the polyimide film obtained from the imide-amic acid copolymer of Comparative Example 1 was heat-treated in both the heat resistance evaluation of the polyimide film and the heat resistance evaluation of the laminate, the yellowness changed significantly.
  • the raw material composition constituting the polyimide film is the same in Example 1 and Comparative Example 2, the polyimide film of Comparative Example 2 obtained from polyamic acid has a lower glass transition temperature than the polyimide film of Example 1. , the coefficient of linear expansion was large, and thus the heat resistance was poor.

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