WO2020138360A1 - Copolymère d'imide-(acide amique) et son procédé de production, vernis et film de polyimide - Google Patents

Copolymère d'imide-(acide amique) et son procédé de production, vernis et film de polyimide Download PDF

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Publication number
WO2020138360A1
WO2020138360A1 PCT/JP2019/051293 JP2019051293W WO2020138360A1 WO 2020138360 A1 WO2020138360 A1 WO 2020138360A1 JP 2019051293 W JP2019051293 W JP 2019051293W WO 2020138360 A1 WO2020138360 A1 WO 2020138360A1
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structural unit
group
imide
derived
amic acid
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PCT/JP2019/051293
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English (en)
Japanese (ja)
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洋平 安孫子
葵 大東
慎司 関口
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三菱瓦斯化学株式会社
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Priority to JP2020562452A priority Critical patent/JP7392660B2/ja
Priority to CN201980085866.8A priority patent/CN113227206B/zh
Priority to KR1020217016956A priority patent/KR20210109525A/ko
Publication of WO2020138360A1 publication Critical patent/WO2020138360A1/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
    • C08G73/14—Polyamide-imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • 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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • C—CHEMISTRY; METALLURGY
    • 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

Definitions

  • the present invention relates to 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.
  • the polyimide resin has been studied in the fields of electric and electronic parts. For example, it is desired to replace a glass substrate used in an image display device such as a liquid crystal display or an OLED display with a plastic substrate for the purpose of making the device lightweight and flexible. Research is ongoing. High transparency is required for the polyimide film for such applications. Further, when a polyimide film is formed by heating and curing a varnish applied on a glass support or a silicon wafer, residual stress occurs in the polyimide film. When the residual stress of the polyimide film is large, there is a problem that the glass support and the silicon wafer are warped, so that the polyimide film is also required to reduce the residual stress. Furthermore, the polyimide film is required to have a small retardation due to birefringence and a low retardation as required properties.
  • Patent Document 1 discloses a polyimide resin synthesized by using ⁇ , ⁇ -aminopropylpolydimethylsiloxane and 4,4′-diaminodiphenyl ether as a diamine component as a polyimide resin that gives a film with low residual stress.
  • Patent Document 2 discloses, as a low residual stress polyimide film, a polyimide film formed by imidizing a polyimide resin precursor synthesized using bistrifluoromethylbenzidine as a diamine component and silicon-containing diamines. There is.
  • Patent Document 3 in order to improve solvent solubility, storage stability, and heat resistance, biphenyltetracarboxylic dianhydride or diphenylsulfonetetracarboxylic dianhydride and a specific diamine or diisocyanate are copolymerized.
  • the following polyimide polymer oligomers are disclosed.
  • Patent Documents 1 and 2 described above a polyamic acid is used as a precursor of polyimide to attempt to improve the performance, but the polyamic acid has a problem of poor storage stability.
  • the polyimide resin does not decompose like polyamic acid, but because the solubility in the solvent is low, the varnish containing the polyimide may absorb moisture in the atmosphere, or the film may be whitened during film formation.
  • the polyimide oligomer of Patent Document 3 was used, there was a problem that the yellowness (yellow index, YI) and retardation were high, and molding processability was not sufficient. Thus, it was difficult to achieve both storage stability and moldability.
  • the present invention has been made in view of such circumstances, and an object of the present invention is an imide-amic acid copolymer which is a precursor of a polyimide resin capable of achieving both storage stability and molding processability, and the same. It is intended to provide a production method, a varnish containing the copolymer, and a polyimide film.
  • the present inventors have found that a copolymer containing a specific combination of structural units can solve the above problems, and have completed the invention.
  • An imide-amic acid copolymer comprising a repeating unit represented by the following formula (1) consisting of an imide moiety (I) and an amic acid moiety (A).
  • X 1 represents a tetravalent aliphatic group having 4 to 39 carbon atoms, an alicyclic group, an aromatic group or a combination thereof, and has a bonding group of —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—.
  • X 2 is a group consisting of a tetravalent aliphatic group having 4 to 39 carbon atoms different from X 1 , an alicyclic group, an aromatic group or a combination thereof, and has —O— or —SO 2 — as a bonding group.
  • Y 1 is a group consisting of a divalent aliphatic group having 4 to 39 carbon atoms, an alicyclic group, an aromatic group or a combination thereof, and has a bonding group of —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 a plurality of Y 1's have the same composition. Have. s and t are positive integers. )
  • the imide-amic acid copolymer according to any one of [1] to [5] above, wherein X 2 is a tetravalent aromatic group having 4 to 39 carbon atoms.
  • the imide moiety (I) has a structural unit IA derived from tetracarboxylic dianhydride and a structural unit IB derived from a diamine,
  • the amic acid moiety (A) has a structural unit AA derived from a tetracarboxylic dianhydride and a structural unit AB derived from a diamine,
  • the structural unit IA contains a structural unit (A-1) derived from an alicyclic tetracarboxylic dianhydride (a-1),
  • the imide moiety (I) has a structural unit IA derived from tetracarboxylic dianhydride and a structural unit IB derived from a diamine
  • the amic acid moiety (A) has a structural unit AA derived from a tetracarboxylic dianhydride and a structural unit AB derived from a diamine
  • the structural unit IA contains a structural unit (A-1) derived from an alicyclic tetracarboxylic dianhydride (a-1),
  • the imide-amic acid copolymer according to any one of the above [1] to [6], wherein the structural unit IB and the structural unit AB include a structural unit derived from a fluorine-containing aromatic diamine.
  • the structural unit AA contains a structural unit (A-2) derived from the tetracarboxylic dianhydride (a-2),
  • the structural unit (A-2) is a structural unit (A-2-1) derived from a compound represented by the following formula (a-2-1), and a compound represented by the following formula (a-2-2)
  • a structural unit (A-2-2) derived from, a structural unit (A-2-3) derived from a compound represented by the following formula (a-2-3), and the following formula (a-2-4)
  • the imide-amic acid copolymer according to any one of the above [7] to [9], containing at least one selected from the group consisting of structural units (A-2-4) derived from the compound represented by Polymer.
  • Z 1 and Z 2 each independently represent a divalent aliphatic group or a divalent aromatic group
  • R 1 and R 2 each independently represent a monovalent aromatic group.
  • R 3 and R 4 each independently represent a monovalent aliphatic group
  • R 5 and R 6 each independently represent a monovalent aliphatic group or a monovalent aromatic group.
  • Group, m and n each independently represent an integer of 1 or more, and the sum of m and n represents an integer of 2 to 1000. However, at least one of R 1 and R 2 is a monovalent aromatic group. Indicates.
  • the structural unit (A-1) is a structural unit (A-1-1) derived from a compound represented by the following formula (a-1-1), and a compound represented by the following formula (a-1-2) At least one selected from the group consisting of a structural unit (A-1-2) derived from the above and a structural unit (A-1-3) derived from a compound represented by the following formula (a-1-3):
  • the imide-amic acid copolymer according to any one of [7] to [13] above.
  • the constitutional unit IB and the constitutional unit AB further include a constitutional unit (B-3) derived from a compound represented by the following formula (b-3).
  • a constitutional unit (B-3) derived from a compound represented by the following formula (b-3).
  • each R independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 5 carbon atoms.
  • Mw weight average molecular weight of the polyimide resin
  • Step 1 Step of Reacting Tetracarboxylic Acid Component Constituting Imide Moiety (I) with Diamine Component to Obtain Imide Oligomer
  • Step 2 Imide Oligomer Obtained in Step 1 and Amide Acid Moiety
  • A Reacting a tetracarboxylic acid component to obtain an imide-amic acid copolymer containing a repeating unit of the imide moiety (I) and the amic acid moiety (A) represented by the following formula (1):
  • X 1 represents a tetravalent aliphatic group having 4 to 39 carbon atoms, an alicyclic group, an aromatic group or a combination thereof, and has a bonding group of —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—.
  • X 2 is a group consisting of a tetravalent aliphatic group having 4 to 39 carbon atoms different from X 1 , an alicyclic group, an aromatic group or a combination thereof, and has —O— or —SO 2 — as a bonding group.
  • Y 1 is a group consisting of a divalent aliphatic group having 4 to 39 carbon atoms, an alicyclic group, an aromatic group or a combination thereof, and has a bonding group of —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 a plurality of Y 1's have the same composition. Have. s and t are positive integers. )
  • step 1 The method for producing an imide-amic acid copolymer according to the above [19], wherein the imide oligomer obtained in step 1 has amino groups at both ends of the main chain of the molecular chain.
  • step 1 the imide-amic acid copolymer according to [19] or [20], wherein the molar ratio of the diamine component to the tetracarboxylic acid component (diamine/tetracarboxylic acid) is 1.01 to 2. Production method.
  • the tetracarboxylic acid component constituting the imide moiety (I) used in step 1 is an alicyclic tetracarboxylic acid component, and the tetracarboxylic acid component constituting the amic acid moiety (A) used in step 2 is aromatic.
  • an imide-amic acid copolymer which is a precursor of a polyimide resin capable of achieving both storage stability and molding processability, a method for producing the same, a varnish containing the copolymer, and a polyimide film are provided.
  • a method for producing the same a varnish containing the copolymer, and a polyimide film are provided.
  • the imide-amic acid copolymer of the present invention contains a repeating unit composed of an imide moiety (I) and an amic acid moiety (A) represented by the following formula (1).
  • X 1 represents a tetravalent aliphatic group having 4 to 39 carbon atoms, an alicyclic group, an aromatic group or a combination thereof, and has a bonding group of —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—.
  • X 2 is a group consisting of a tetravalent aliphatic group having 4 to 39 carbon atoms different from X 1 , an alicyclic group, an aromatic group or a combination thereof, and has —O— or —SO 2 — as a bonding group.
  • Y 1 is a group consisting of a divalent aliphatic group having 4 to 39 carbon atoms, an alicyclic group, an aromatic group or a combination thereof, and has a bonding group of —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 a plurality of Y 1's have the same composition. Have. s and t are positive integers. )
  • the imide moiety (I) constituting the imide-amic acid copolymer of the present invention is a moiety represented by (I) in the above formula (1).
  • X 1 is a tetravalent aliphatic group having 4 to 39 carbon atoms, an alicyclic group, an aromatic group, or a combination thereof, and has —O— or — as a bonding group.
  • It may have at least one selected from the group consisting of SO 2 —, —CO—, —CH 2 —, —C(CH 3 ) 2 —, —C 2 H 4 O— and —S—, Among them, a C4-C39 tetravalent aliphatic group, an alicyclic group, or a group composed of a combination thereof is preferable, and a C4-C39 tetravalent alicyclic group is a group. Is more preferable.
  • X 1 is an aliphatic group or an alicyclic group, the transparency of the polyimide is good and the retardation is reduced, which is preferable. In addition, the elongation of the polyimide film is improved, which is preferable.
  • X 1 is obtained by removing two dicarboxylic acid anhydride moieties (four carboxy group moieties) from a tetracarboxylic acid dianhydride, which is a raw material of a structural unit IA derived from a tetracarboxylic acid dianhydride described later. Is preferred.
  • Y 1 is a divalent aliphatic group having 4 to 39 carbon atoms, an alicyclic group, an aromatic group, or a combination thereof, and has —O— or — as a bonding group. It may have at least one selected from the group consisting of SO 2 —, —CO—, —CH 2 —, —C(CH 3 ) 2 —, —C 2 H 4 O— and —S—, Among them, a divalent aromatic group having 4 to 39 carbon atoms, diaminoalkylcyclohexane, or a combination thereof is preferable.
  • the plurality of Y 1 have the same composition.
  • the "same composition", 1 if the type having a structure of Y 1 from diamine refers to Y 1 represented by the formula (1) having all the same structure, from multiple diamines of Y 1
  • each Y 1 represented by the above formula (1) has the same structure of Y 1 derived from each diamine. That is, in the case of having a structure of Y 1 derived from a plurality of diamines, even if each Y 1 is different in each molecule, all the Y 1 positions are at the same ratio in all the molecules even if each Y 1 is different.
  • Y 1 is preferably a diamine that is a raw material of a structural unit IB derived from a diamine described below, from which two amino group moieties have been removed.
  • s is the number of repeating units in the imide moiety (I) and is a positive integer. From the viewpoint of storage stability and moldability, s is preferably 1-20, more preferably 1-15, further preferably 1-10, and 1-5. Even more preferable.
  • the average number of repetitions of the imide moiety (I), that is, the average value of s is preferably 1 to 10, more preferably 1.5 to 9, and even more preferably 1.5 to 8. Even more preferably, it is 1.7 to 5.
  • the average number of repetitions of the imide moiety (I) is an average value of the number of repetitions of the imide moiety (I) of all imide-amic acid copolymers contained in the polyimide varnish or the polyimide film described later.
  • the average value means the average value of s of all the imide-amic acid copolymers contained in the polyimide varnish or polyimide film described later.
  • the amic acid moiety (A) constituting the imide-amic acid copolymer of the present invention is a moiety represented by (A) in the above formula (1).
  • X 2 is a tetravalent aliphatic group having 4 to 39 carbon atoms which is different from X 1 , an alicyclic group, an aromatic group, or a combination thereof, and is a bonding group.
  • a tetravalent aromatic group having 4 to 39 carbon atoms is preferable.
  • X 2 is an aromatic group because the heat resistance of the polyimide is improved.
  • X 2 is preferably one obtained by removing two carboxylic acid anhydride moieties from a tetracarboxylic acid dianhydride which is a raw material of a structural unit AA derived from a tetracarboxylic acid dianhydride described later.
  • Y 1 is the same as that described for the imide moiety (I).
  • Y 1 is preferably a diamine as a raw material of a structural unit AB derived from a diamine described below from which two amino group moieties have been removed.
  • t is the number of repeating units composed of the imide moiety (I) and the amic acid moiety (A) contained in the imide-amic acid copolymer of the present invention, and is a positive integer. From the viewpoint of storage stability and moldability, t is preferably 5 to 200, more preferably 6 to 150, and further preferably 10 to 120.
  • the average number of repeating units of the repeating unit composed of the imide moiety (I) and the amic acid moiety (A), that is, the average value of t is preferably 5 to 200, more preferably 6 to 150, and more preferably 10 It is more preferably from 120 to 120.
  • the average number of repeating units consisting of the imide moiety (I) and the amic acid moiety (A) is the same as that of all the imide moieties (I) of the imide-amic acid copolymer contained in the polyimide varnish or the polyimide film described below. It means the number of repetitions of the repeating unit composed of the amic acid moiety (A), and the average value of t is the average value of t of all imide-amic acid copolymers contained in the below-mentioned polyimide varnish or polyimide film.
  • the imide moiety and the amic acid moiety are randomly present, whereas in the imide-amic acid copolymer of the present invention, the imide moiety (I) and the amic acid moiety ( It is considered that the storage stability and the molding processability can be compatible with each other because A) has a specific structure.
  • the imide-amic acid copolymer of the present invention contains a repeating unit represented by the above formula (1) and composed of an imide moiety (I) and an amic acid moiety (A). It is shown below.
  • the imide moiety (I) comprises a structural unit IA derived from a tetracarboxylic dianhydride and a structural unit IB derived from a diamine.
  • the amic acid moiety (A) has a structural unit AA derived from a tetracarboxylic dianhydride and a structural unit AB derived from a diamine, and the structural unit IA is an alicyclic tetracarboxylic dianhydride.
  • the structural unit (A-1) derived from (a-1) is included, and the structural unit IB and the structural unit AB include a structural unit derived from an aromatic diamine having an ether bond.
  • the imide moiety (I) is a structural unit IA derived from tetracarboxylic dianhydride and a structural unit derived from diamine.
  • the amic acid moiety (A) has a structural unit AA derived from a tetracarboxylic dianhydride and a structural unit AB derived from a diamine, and the structural unit IA is an alicyclic tetracarboxylic acid dianhydride.
  • the structural unit (A-1) derived from the anhydride (a-1) is included, and the structural unit IB and the structural unit AB include structural units derived from a fluorine-containing aromatic diamine.
  • the structural unit IA is a structural unit derived from a tetracarboxylic dianhydride occupying the imide moiety (I) of the copolymer of the present invention, and includes a structural unit derived from an alicyclic tetracarboxylic dianhydride. It is preferable that the structural unit (A-1) derived from the alicyclic tetracarboxylic dianhydride (a-1) is contained.
  • the alicyclic tetracarboxylic dianhydride means a tetracarboxylic dianhydride in which at least one carbon atom to which four carboxy groups are bonded constitutes an alicyclic structure
  • an aromatic Group tetracarboxylic dianhydride means a tetracarboxylic dianhydride in which at least one of the carbon atoms to which four carboxy groups are bonded constitutes an aromatic ring structure
  • the aliphatic tetracarboxylic dianhydride is It refers to a tetracarboxylic dianhydride in which all of the carbon atoms to which the four carboxy groups are attached are aliphatic carbons.
  • the structural unit (A-1) is a structural unit derived from the alicyclic tetracarboxylic dianhydride (a-1).
  • the structural unit (A-1) is preferably a structural unit (A-1-1) derived from a compound represented by the following formula (a-1-1), or a structural unit (a-1-2) below.
  • the compound represented by the formula (a-1-1) is norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5'',6,6''-
  • the compound represented by the formula (a-1-3) which is tetracarboxylic dianhydride (CpODA), is 5,5′-bis-2-norbornene-5,5′,6,6′-tetracarboxylic acid.
  • the total ratio of the structural units (A-1-1) to (A-1-3) in the structural unit (A-1) is preferably 45 mol% or more, more preferably 70 mol% or more, and further preferably Is 90 mol% or more, particularly preferably 99 mol% or more.
  • the upper limit of the ratio is not particularly limited, that is, 100 mol%.
  • the structural unit (A-1) may contain at least one selected from the structural units (A-1-1) to (A-1-3), and the structural units (A-1-1) to (A-1-1) It may consist of only one selected from A-1-3).
  • the ratio of the structural unit (A-1-1) in the structural unit (A-1) is preferably 45 mol% or more, more preferably 70 mol% or more, even more preferably 90 mol% or more, particularly preferably It is 99 mol% or more.
  • the upper limit of the ratio is not particularly limited, that is, 100 mol%.
  • the structural unit (A-1) has a structural unit derived from an alicyclic tetracarboxylic dianhydride other than the compounds represented by the formulas (a-1-1) to (a-1-3). May be.
  • alicyclic tetracarboxylic dianhydride examples include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2, 4,5-Cyclohexanetetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, dicyclohexyltetracarboxylic dianhydride, etc.
  • structural units derived from alicyclic tetracarboxylic dianhydride other than the compounds represented by formulas (a-1-1) to (a-1-3) in structural unit (A-1) As the above, a structural unit derived from 1,2,4,5-cyclohexanetetracarboxylic dianhydride is preferable.
  • the alicyclic tetracarboxylic dianhydride (a-1) may be used alone or in combination of two or more.
  • the structural unit AA is a structural unit derived from tetracarboxylic dianhydride occupying the amic acid moiety (A) of the copolymer of the present invention, and is different from alicyclic tetracarboxylic dianhydride (a-1). It is more preferable to include the structural unit (A-2) derived from the tetracarboxylic dianhydride (a-2).
  • the structural unit (A-2) is a structural unit derived from the tetracarboxylic dianhydride (a-2) other than the alicyclic tetracarboxylic dianhydride (a-1).
  • the tetracarboxylic dianhydride (a-2) include one or more selected from the group consisting of aromatic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride. It is preferable to include dianhydride. That is, the structural unit (A-2) preferably contains a structural unit derived from an aromatic tetracarboxylic dianhydride.
  • the structural unit AA preferably contains a structural unit derived from an aromatic tetracarboxylic dianhydride.
  • the structural unit (A-2) is a structural unit (A-2-1) derived from a compound represented by the following formula (a-2-1), and the following formula A structural unit (A-2-2) derived from the compound represented by (a-2-2) and a structural unit (A-2-3) derived from the compound represented by the following formula (a-2-3): ), and at least one selected from the group consisting of structural units (A-2-4) derived from a compound represented by the following formula (a-2-4).
  • the compound represented by the formula (a-2-1) is biphenyltetracarboxylic dianhydride (BPDA), and specific examples thereof include 3,3 represented by the following formula (a-2-1s).
  • BPDA biphenyltetracarboxylic dianhydride
  • specific examples thereof include 3,3 represented by the following formula (a-2-1s).
  • s-BPDA ',4,4'-Biphenyltetracarboxylic dianhydride
  • a-2-1a) A-BPDA
  • i-BPDA 2,2′,3,3′-biphenyltetracarboxylic dianhydride
  • s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride represented by the following formula (a-2-1s) is preferable.
  • the compound represented by the formula (a-2-2) is p-phenylenebis(trimellitate) dianhydride (TAHQ).
  • the compound represented by the formula (a-2-3) is oxydiphthalic anhydride (ODPA), and specific examples thereof include 4,4′-oxydiphthalic acid represented by the following formula (a-2-3s).
  • Acid anhydride (s-ODPA), 3,4′-oxydiphthalic anhydride (a-ODPA) represented by the following formula (a-2-3a), represented by the following formula (a-2-3i) 3,3′-oxydiphthalic anhydride (i-ODPA) may be mentioned.
  • 4,4'-oxydiphthalic anhydride (s-ODPA) represented by the following formula (a-2-3s) is preferable.
  • the compound represented by the formula (a-2-4) is pyromellitic dianhydride (PMDA).
  • the structural unit (A-2) is at least one selected from the group consisting of the structural unit (A-2-1) and the structural unit (A-2-2) from the viewpoint of high heat resistance and low residual stress. It is preferable to include.
  • the structural unit (A-2-1) is preferable from the viewpoint of improving the heat resistance and thermal stability of the film and further reducing the residual stress, and the structural unit (A-2-2) has a low YI and is colorless and transparent. From the viewpoint of being more excellent, it is preferable.
  • the tetracarboxylic dianhydride (a-2) may contain a tetracarboxylic dianhydride other than the compounds represented by the formulas (a-2-1) to (a-2-4).
  • tetracarboxylic acid dianhydride examples include 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, 3,3′,4,4′-diphenylsulfone tetracarboxylic acid dianhydride, 3,3′, Aromatic aromatic compounds such as 4,4′-benzophenone tetracarboxylic dianhydride, 2,2′,3,3′-benzophenone tetracarboxylic dianhydride, and compounds represented by the following formula (a-2-5) And tetracarboxylic dianhydrides; and aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride.
  • the total ratio of the structural units (A-2-1) to (A-2-4) in the structural unit (A-2) is preferably 45 mol% or more, more preferably 70 mol% or more, and further preferably Is 90 mol% or more, particularly preferably 99 mol% or more.
  • the upper limit of the ratio is not particularly limited, that is, 100 mol%.
  • the structural unit (A-2) only needs to include at least one selected from the structural units (A-2-1) to (A-2-4), and the structural units (A-2-1) to (A-2-1) It may consist of only one selected from A-2-4).
  • the structural unit (A-2) contains two or more kinds of structural units selected from the structural units (A-2-1) to (A-2-4), each structural unit in the structural unit (A-2)
  • the ratio of the structural unit derived from the aromatic tetracarboxylic dianhydride in the structural unit (A-2) is preferably 45 mol% or more, more preferably 60 mol% or more, further preferably 85 mol% or more. is there.
  • the upper limit of the total content ratio is not particularly limited, that is, 100 mol%.
  • the molar ratio of the structural unit (A-1) to the structural unit (A-2) in the structural unit derived from the tetracarboxylic dianhydride of the imide-amic acid copolymer [(A-1)/(A -2) molar ratio] is preferably 10/90 to 90/10, more preferably 30/70 to 85/15, and further preferably 50/50 to 80/20.
  • the structural unit IB and the structural unit AB are structural units derived from the diamine in the imide moiety (I) and the amic acid moiety (A) of the copolymer of the present invention, respectively.
  • the structural unit IB and the structural unit AB are also collectively referred to as “structural unit B”.
  • the structural unit IB and the structural unit AB preferably include a structural unit derived from an aromatic diamine having an ether bond or a structural unit derived from a fluorine-containing aromatic diamine, and from the viewpoint of flexibility, an aromatic bond having an ether bond. It is more preferable to include a structural unit derived from a group diamine, and it is more preferable to include a structural unit derived from a fluorine-containing aromatic diamine from the viewpoint of transparency.
  • the structural unit IB and the structural unit AB have the same composition.
  • the "same composition” means that when it is composed of one kind of diamine-derived constitutional unit, the constitutional unit IB and the constitutional unit AB are all composed of the same constitutional unit, and when it is composed of a plurality of diamine-derived constitutional units, It means that the structural units derived from the respective diamines are present in the structural unit IB and the structural unit AB at the same ratio. That is, when it is composed of a plurality of constitutional units derived from diamine, even if the constitutional unit IB and the constitutional unit AB are different in each molecule, all the molecules are observed in the same proportion even if the constitutional units IB and AB are different. There is a structural unit of.
  • aromatic diamine having an ether bond which gives a structural unit derived from the aromatic diamine having an ether bond
  • 6FODA 2,2′-bis(trifluoromethyl)-4,4′-diaminodiphenyl ether
  • HFBAPP 2,2′-bis(trifluoromethyl)-4,4′-diaminodiphenyl ether
  • BAPS bis[4-(4-aminophenoxy)phenyl]sulfone
  • BAPS 2,2-bis[4-(4- Aminophenoxy)phenyl]propane
  • BAPP 4,4′-bis(4-aminophenoxy)biphenyl
  • ODA 4,4′-diaminodiphenyl ether
  • 3,4′-diaminodiphenyl ether and the like 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA) is preferred.
  • fluorine-containing aromatic diamine that provides the constitutional unit derived from the fluorine-containing aromatic diamine
  • examples of the fluorine-containing aromatic diamine that provides the constitutional unit derived from the fluorine-containing aromatic diamine include 2,2′-bis(trifluoromethyl)-4,4′-diaminodiphenyl ether (6FODA) and 2,2-bis[ 4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP) and the like can be mentioned, and 2,2′-bis(trifluoromethyl)-4,4′-diaminodiphenyl ether (6FODA) is preferable.
  • the structural unit B preferably contains the structural unit (B-1) derived from the compound represented by the following formula (b-1).
  • the structural unit (B-1) derived from the compound represented by the following formula (b-1).
  • the compound represented by the formula (b-1) is 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA).
  • the structural unit B preferably further contains a structural unit (B-3) derived from a compound represented by the following formula (b-3).
  • each R is independently selected from the group consisting of a hydrogen atom, a fluorine atom, and an alkyl group having 1 to 5 carbon atoms, and R is selected from a hydrogen atom, a fluorine atom, and a methyl group. It is preferably selected from the group consisting of, and more preferably a hydrogen atom.
  • Examples of the compound represented by the above formula (b-3) include 9,9-bis(4-aminophenyl)fluorene (BAFL), 9,9-bis(3-fluoro-4-aminophenyl)fluorene, and 9 , 9-bis(3-methyl-4-aminophenyl)fluorene, and the like.
  • the copolymer of the present invention has improved transparency and heat resistance by containing the structural unit (B-3).
  • the ratio of the structural unit (B-1) in the structural unit B is preferably 45 mol% or more, more preferably 48 mol% or more, even more preferably 85 mol% or more, even more preferably 88 mol% or more, It is preferably 100 mol% or less, more preferably 99.5 mol% or less, still more preferably 99.0 mol% or less.
  • the structural unit B may consist of the structural unit (B-1) only.
  • the ratio of the structural unit (B-3) in the structural unit B is preferably 5 mol% or more, more preferably 10 mol% from the viewpoint of low residual stress.
  • the structural unit B contains the structural unit (B-3)
  • the total ratio of the structural units (B-1) and (B-3) in the structural unit B is preferably 85.0 to 100 mol %, It is more preferably 88.0 to 99.5 mol%, and further preferably 92.0 to 99.0 mol%.
  • the ratio of the structural unit (B-1) in the structural unit B is also preferably in the same range as above.
  • the structural unit B may include a structural unit derived from an aromatic diamine having a sulfonyl group from the viewpoint of flexibility.
  • aromatic diamine having a sulfonyl group that provides a constitutional unit derived from the aromatic diamine having a sulfonyl group include 3,3′-diaminodiphenyl sulfone (3,3-DDS) and 4,4′-diaminodiphenyl sulfone ( 4,4-DDS), bis[4-(4-aminophenoxy)phenyl]sulfone (BAPS), bis[4-(3-aminophenoxy)phenyl]sulfone (BAPS-M) and the like.
  • the structural unit B is derived from the diamine exemplified as the structural unit derived from the aromatic diamine having an ether bond, the structural unit derived from the fluorine-containing aromatic diamine, and the structural unit derived from the aromatic diamine having a sulfonyl group. And other structural units derived from diamine other than the structural units (B-1) and (B-3).
  • the diamine which gives such a constitutional unit is not particularly limited, but 1,4-phenylenediamine, p-xylylenediamine, 3,5-diaminobenzoic acid, 1,5-diaminonaphthalene, 2,2′-dimethyl Biphenyl-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-aminophenyl)-2,3-dihydro-1,3,3-trimethyl- 1H-inden-5-amine, ⁇ , ⁇ ′-bis(4-aminophenyl)-1,4-diisopropylbenzene, N,
  • the constitutional unit derived from the other diamine optionally contained in the constitutional unit B may be one type or two or more types. From the viewpoint of achieving low retardation, the structural unit B preferably does not include a structural unit derived from 2,2′-bis(trifluoromethyl)benzidine.
  • the aromatic diamine means a diamine containing at least one aromatic ring
  • the alicyclic diamine means a diamine containing at least one alicyclic ring and containing no aromatic ring, and a fat.
  • Group diamine means a diamine containing neither an aromatic ring nor an alicyclic ring.
  • the imide-amic acid copolymer of the present invention may contain a structural unit other than the structural unit IA, the structural unit AA, the structural unit IB, and the structural unit AB.
  • the imide-amic acid copolymer of the present invention preferably further contains a structural unit (B-2) derived from a compound represented by the following general formula (b-2). By including the structural unit (B-2), the residual stress is reduced.
  • Z 1 and Z 2 each independently represent a divalent aliphatic group or a divalent aromatic group
  • R 1 and R 2 each independently represent a monovalent aromatic group
  • R 3 and R 4 each independently represent a monovalent aliphatic group
  • R 5 and R 6 each independently represent a monovalent aliphatic group or a monovalent aromatic group.
  • m and n each independently represent an integer of 1 or more
  • the sum of m and n represents an integer of 2 to 1000.
  • at least one of R 1 and R 2 represents a monovalent aromatic group.
  • two or more different repeating units described in parallel by [] may be repeated in any form and order of random, alternating or block.
  • the divalent aliphatic group or divalent aromatic group for Z 1 and Z 2 may be substituted with a fluorine atom or may contain an oxygen atom.
  • the carbon number shown below means all the carbon numbers contained in an aliphatic group or an aromatic group.
  • the divalent aliphatic group include divalent saturated or unsaturated aliphatic groups having 1 to 20 carbon atoms.
  • the divalent aliphatic group preferably has 3 to 20 carbon atoms.
  • Examples of the divalent saturated aliphatic group include alkylene groups and alkyleneoxy groups having 1 to 20 carbon atoms, and examples of the alkylene group include methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group and hexa Examples thereof include a methylene group, octamethylene group, decamethylene group and dodecamethylene group, and examples of the alkyleneoxy group include a propyleneoxy group and trimethyleneoxy group.
  • Examples of the divalent unsaturated aliphatic group include an alkylene group having 2 to 20 carbon atoms, and examples thereof include a vinylene group, a propenylene group, and an alkylene group having an unsaturated double bond at a terminal.
  • Examples of the divalent aromatic group include an arylene group having 6 to 20 carbon atoms and an aralkylene group having 7 to 20 carbon atoms.
  • Specific examples of the arylene group having 6 to 20 carbon atoms in Z 1 and Z 2 include o-phenylene group, m-phenylene group, p-phenylene group, 4,4′-biphenylylene group and 2,6-naphthylene group.
  • Z 1 and Z 2 a trimethylene group and a p-phenylene group are particularly preferable, and a trimethylene group is more preferable.
  • examples of the monovalent aliphatic group for R 1 to R 6 include monovalent saturated or unsaturated aliphatic groups.
  • examples of the monovalent saturated aliphatic group include an alkyl group having 1 to 22 carbon atoms, and examples thereof include a methyl group, an ethyl group and a propyl group.
  • examples of the monovalent unsaturated aliphatic group include alkenyl groups having 2 to 22 carbon atoms, and examples thereof include a vinyl group and a propenyl group. These groups may be substituted with a fluorine atom.
  • the monovalent aromatic group for R 1 , R 2 , R 5 and R 6 in the formula (b-2) is an aryl group having 6 to 20 carbon atoms, 7 to 30 carbon atoms and substituted with an alkyl group. Examples thereof include an aryl group and an aralkyl group having 7 to 30 carbon atoms. As the monovalent aromatic group, an aryl group is preferable, and a phenyl group is more preferable. At least one of R 1 and R 2 is a monovalent aromatic group, preferably R 1 and R 2 are both monovalent aromatic group, R 1 and R 2 are both phenyl Is more preferable.
  • R 3 and R 4 an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is more preferable.
  • R 5 and R 6 a monovalent aliphatic group is preferable, and a methyl group is more preferable.
  • m represents the number of repeating siloxane units to which at least one monovalent aromatic group is bonded
  • n represents the number of repeating siloxane units to which a monovalent aliphatic group is bonded.
  • m and n each independently represent an integer of 1 or more, and the sum (m+n) of m and n represents an integer of 2 to 1000.
  • the sum of m and n is preferably an integer of 3 to 500, more preferably 3 to 100, and further preferably 3 to 50.
  • the ratio of m/n is preferably 50/50 to 99/1, more preferably 60/40 to 90/10, still more preferably 70/30 to 80/20.
  • the functional group equivalent of the compound represented by the formula (b-2) is preferably 150 to 5,000 g/mol, more preferably 400 to 4,000 g/mol, and further preferably 500 to 3,000 g/mol. ..
  • the functional group equivalent means the mass of the compound represented by the formula (b-2) per mol of the functional group.
  • the compound represented by the general formula (b-2) may be the following general formula (b-21).
  • the ratio of the structural unit (B-2) to the total amount of the structural unit (B-2) and the structural unit B is preferably 0.01 to 15.0 mol%, more preferably 0.5 to 12.0 mol%. , And more preferably 1.0 to 8.0 mol %.
  • the content of the polyorganosiloxane unit with respect to the total of the constituent units constituting the imide-amic acid copolymer is preferably 5 to 45% by mass, more preferably 7 to 40% by mass, and further preferably 10 to 35% by mass. is there.
  • the content of the polyorganosiloxane unit is within the above range, both low retardation and low residual stress can be achieved at a higher level.
  • Examples of commercially available compounds represented by the formula (b-2) include “X-22-9409” and “X-22-1660B-3” manufactured by Shin-Etsu Chemical Co., Ltd.
  • the copolymer of the present invention is an imide repeating structural unit formed from a compound giving the structural unit (A-1) and a compound giving the structural unit (B-1), and a compound giving the structural unit (A-2). It is preferable to have an amic acid structural unit formed from a compound which gives the structural unit (B-1).
  • the copolymer of the present invention is a copolymer having structural units IA and AA derived from tetracarboxylic dianhydride, and structural units IB and AB derived from diamine,
  • the structural units IA and AA include a structural unit (A-1) derived from an alicyclic tetracarboxylic dianhydride (a-1) and a tetracyclic unit other than the alicyclic tetracarboxylic dianhydride (a-1).
  • a structural unit (A-2) derived from a carboxylic acid dianhydride (a-2), Structural units IB and AB include a structural unit (B-1) derived from a compound represented by the following formula (b-1),
  • the structural unit (A-2) is a structural unit (A-2-1) derived from a compound represented by the following formula (a-2-1), and a compound represented by the following formula (a-2-2)
  • a compound in which the copolymer has an imide repeating structural unit formed from a compound giving the structural unit (A-1) and a compound giving the structural unit (B-1), and gives the structural unit (A-2)
  • the copolymer of the present invention comprises an imide repeating structural unit formed from a compound other than the compound giving the structural unit (A-1) and a compound giving the structural unit B, and a compound giving the structural unit (A-1). It may have an imide repeating structural unit formed with a compound other than the compound giving the unit (B-1). Similarly, the copolymer of the present invention may have an amic acid structural unit formed from a compound other than the compound giving the structural unit (A-2) and a compound giving the structural unit (B-1). Good.
  • the imide-amic acid copolymer of the present invention By using the imide-amic acid copolymer of the present invention, it is possible to form a polyimide film which is excellent in colorless transparency and heat resistance, and has low residual stress and low retardation.
  • the suitable physical property values of the film are as follows.
  • the total light transmittance is preferably 87% or more, more preferably 89% or more, still more preferably 90% or more when a film having a thickness of 10 ⁇ m is formed.
  • the yellow index (YI) of the film having a thickness of 10 ⁇ m is preferably 7.0 or less, more preferably 4.0 or less, still more preferably 3.5 or less, still more preferably 3.0 or less. ..
  • the glass transition temperature (Tg) is preferably 220° C.
  • the absolute value of the thickness retardation (Rth) when the polyimide film has a thickness of 10 ⁇ m is preferably 200 nm or less, more preferably 150 nm or less, further preferably 110 nm or less, and particularly preferably 90 nm or less.
  • “low retardation” means that the thickness retardation (Rth) is low, and low retardation is preferable because the retardation due to birefringence is small.
  • the residual stress is preferably 26 MPa or less, more preferably 24 MPa or less, and further preferably 20 MPa or less.
  • Step 1 Step of Reacting Tetracarboxylic Acid Component Constituting Imide Moiety (I) with Diamine Component to Obtain Imide Oligomer
  • Step 2 Imide Oligomer Obtained in Step 1 and Amide Acid Moiety
  • A Reacting a tetracarboxylic acid component to obtain an imide-amic acid copolymer containing a repeating unit of the imide moiety (I) and the amic acid moiety (A) represented by the following formula (1):
  • X 1 represents a tetravalent aliphatic group having 4 to 39 carbon atoms, an alicyclic group, an aromatic group or a combination thereof, and has a bonding group of —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—.
  • X 2 is a group consisting of a tetravalent aliphatic group having 4 to 39 carbon atoms different from X 1 , an alicyclic group, an aromatic group or a combination thereof, and has —O— or —SO 2 — as a bonding group.
  • Y 1 is a group consisting of a divalent aliphatic group having 4 to 39 carbon atoms, an alicyclic group, an aromatic group or a combination thereof, and has a bonding group of —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 a plurality of Y 1's have the same composition. Have. s and t are positive integers. )
  • an imide-amic acid copolymer of the present invention it is possible to control the imide moiety and the amic acid moiety to have a specific structure, so that the conventional imide moiety and the amic acid moiety are randomly present. It is considered that, unlike the imide-amic acid copolymer, it is possible to obtain an imide-amic acid copolymer that can achieve both storage stability and molding processability.
  • preferred copolymers of the present invention include a compound giving the structural unit (A-1) and a tetracarboxylic acid component composed of a compound giving the structural unit (A-2), and a structural unit (B-1). It can be produced by reacting with a diamine component containing, and is preferably produced by a method having the following Step 1 and Step 2.
  • Step 1 a step of reacting a compound giving the structural unit (A-1) with a compound giving the structural unit (B-1) to obtain an oligomer having an imide repeating structural unit
  • Step 2 the oligomer obtained in Step 1 And a compound which gives the structural unit (A-2) are reacted to obtain a copolymer having an imide repeating structural unit and an amic acid structural unit.
  • a preferred method for producing a copolymer of the present invention is a method for producing a copolymer having the following Step 1 and Step 2,
  • the copolymer has a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from a diamine
  • the structural unit A is a structural unit (A-1) derived from an alicyclic tetracarboxylic dianhydride (a-1) and a tetracarboxylic acid other than the alicyclic tetracarboxylic dianhydride (a-1)
  • the structural unit B contains a structural unit (B-1) derived from a compound represented by the formula (b-1),
  • the structural unit (A-2) is derived from the compound represented by the formula (a-2-1) and the structural unit (A-2-1) derived from the compound represented by the formula (a-2-2).
  • Step 1 a step of reacting a compound giving the structural unit (A-1) with a compound giving the structural unit (B-1) to obtain an oligomer having an imide repeating structural unit
  • Step 2 the oligomer obtained in Step 1
  • Step 1 is a step of reacting a tetracarboxylic acid component forming the imide moiety (I) with a diamine component to obtain an imide oligomer.
  • the tetracarboxylic acid component forming the imide moiety (I) is an alicyclic tetracarboxylic acid component.
  • Step 1 is more preferably a step of reacting a compound giving the structural unit (A-1) with a compound giving the structural unit (B-1) to obtain an oligomer having an imide repeating structural unit.
  • the tetracarboxylic acid component used in Step 1 preferably contains a compound which gives the structural unit (A-1).
  • the structural unit (A-1) contains the structural unit (A-1-1)
  • the diamine component used in step 1 preferably contains a compound that gives the structural unit (B-1), and is a diamine component other than the compound that gives the structural unit (B-1) within a range that does not impair the effects of the present invention. May be included. Examples of such a compound include compounds that give the structural unit (B-3).
  • the diamine component with respect to the tetracarboxylic acid component is preferably 1.01 to 2 moles, more preferably 1.05 to 1.9 moles, and 1.1 to 1.7 moles. Is more preferable.
  • the method of reacting the tetracarboxylic acid component and the diamine component for obtaining 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 room temperature (about 20° C.) to 80° C. for 0.5 to 30 hours, and then heated.
  • a method of stirring for 0.5 to 30 hours and then raising the temperature to carry out the imidization reaction (3) charging a tetracarboxylic acid component, a diamine component, and a reaction solvent into a reactor and immediately raising the temperature to perform the imidization reaction. And the like.
  • the imidization reaction it is preferable to carry out the reaction using a Dean-Stark apparatus or the like while removing water produced during production. By performing such an operation, the degree of polymerization and the imidization ratio can be further increased.
  • a known imidization catalyst can be used.
  • the imidization catalyst include a base catalyst and an acid catalyst.
  • the base catalyst pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, imidazole, N,N
  • organic base catalysts such as dimethylaniline and N,N-diethylaniline
  • inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate, and sodium hydrogencarbonate.
  • the acid catalyst crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, paratoluenesulfonic acid, naphthalenesulfonic acid, etc.
  • the above imidization catalysts may be used alone or in combination of two or more.
  • a base catalyst is preferable, an organic base catalyst is more preferable, one or more selected from triethylamine and triethylenediamine is more preferable, and triethylamine is further more preferable, from the viewpoint of handleability.
  • 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 and the like.
  • the reaction time is preferably 0.5 to 10 hours after the start of distilling the produced water.
  • the imide oligomer obtained in Step 1 preferably has an imide repeating structural unit formed from a compound which gives the structural unit (A-1) and a compound which gives the structural unit (B-1).
  • the oligomer obtained in step 1 preferably has amino groups at both ends of the main chain of the molecular chain.
  • step 2 in the production method of the present invention the imide oligomer obtained in step 1 is reacted with the tetracarboxylic acid component constituting the amic acid moiety (A), and the imide moiety (represented by the following formula (1) ( It is a step of obtaining an imide-amic acid copolymer containing a repeating unit consisting of I) and an amic acid moiety (A).
  • the tetracarboxylic acid component constituting the amic acid moiety (A) used in Step 2 is preferably an aromatic tetracarboxylic acid component, and more preferably contains a compound giving the structural unit (A-2). It may contain a compound giving the unit (A-1).
  • the tetracarboxylic acid component used in Step 2 does not contain a compound that provides the structural unit (A-1-1).
  • a diamine containing a polyorganosiloxane unit or a tetracarboxylic acid dianhydride may be reacted with the polyorganosiloxane unit. It is preferable to react a diamine containing a siloxane unit, and it is more preferable to react a compound giving the structural unit (B-2).
  • the method for reacting the tetracarboxylic acid component and the imide oligomer obtained in step 1 for obtaining the imide-amic acid copolymer in step 2 is not particularly limited, and a known method can be used.
  • a specific reaction method (1) the imide oligomer obtained in step 1, the tetracarboxylic acid component and the solvent are charged into a reactor and the temperature is 0 to 120° C., preferably 5 to 80° C. for 1 to 72 hours.
  • the imide-amic acid copolymer obtained by the production method of the present invention is a product of a polyaddition reaction of the tetracarboxylic acid component in step 2, the diamine component in step 2, and the oligomer obtained in step 1.
  • the imide-amic acid copolymer of the present invention has an imide repeating structural unit formed from a compound which gives the structural unit (A-1) and a compound which gives the structural unit (B-1) in step 1, and In Step 2, it is preferable to have an amic acid structural unit formed from a compound which gives the structural unit (A-2) and a compound which gives the structural unit (B-1).
  • a copolymer solution containing an imide-amic acid copolymer dissolved in a solvent can be obtained.
  • the concentration of the copolymer in the obtained copolymer solution is usually 1 to 50% by mass, preferably 3 to 35% by mass, more preferably 10 to 30% by mass.
  • 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 mechanical strength of the obtained polyimide film.
  • the weight average molecular weight (Mw) is preferably 10,000 to 800,000, more preferably 100,000 to 300,000.
  • the number average molecular weight of the copolymer can be determined, for example, from a standard polymethylmethacrylate (PMMA) conversion value measured by gel filtration chromatography. Next, raw materials and the like used in this manufacturing method will be described.
  • ⁇ Tetracarboxylic acid component> The tetracarboxylic acid component used as a raw material of the imide-amic acid copolymer in the present production method is described in (Structural Unit IA) and (Structural Unit AA) of the above-mentioned ⁇ Imido-amic acid copolymer embodiment>. It is preferable to use a compound that gives each structural unit.
  • the compound providing the structural unit (A-1) includes, but is not limited to, an alicyclic tetracarboxylic dianhydride (a-1), and a derivative thereof within the range of providing the same structural unit Good.
  • Examples of the derivative include an alicyclic tetracarboxylic acid corresponding to the alicyclic tetracarboxylic dianhydride (a-1) and an alkyl ester of the alicyclic tetracarboxylic acid.
  • the compound providing the structural unit (A-1) is preferably an alicyclic tetracarboxylic acid dianhydride (a-1).
  • examples of the compound that provides the structural unit (A-2) include, but are not limited to, tetracarboxylic dianhydride (a-2), and a derivative thereof may be used as long as the same structural unit is provided. ..
  • Examples of the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride (a-2) and an alkyl ester of the tetracarboxylic acid.
  • a-2 tetracarboxylic dianhydride
  • a-2 tetracarboxylic dianhydride
  • the molar ratio of the compound giving the structural unit (A-1) to the compound giving the structural unit (A-2) [( A-1)/(A-2) molar ratio] is preferably 10/90 to 90/10, more preferably 30/70 to 85/15, and further preferably 50/50 to 80/20. Is.
  • Examples of the compound that provides the structural unit (A-1) include a compound that provides the structural unit (A-1-1), a compound that provides the structural unit (A-1-2), and a structural unit (A-1-3).
  • the compound which gives the structural unit (A-1-1) is more preferable.
  • the ratio of the total of the compounds giving the structural units (A-1-1) to (A-1-3) in the compound giving the structural unit (A-1) is preferably 45 mol% or more, more preferably 70 mol% or more. It is at least mol%, more preferably at least 90 mol%, and particularly preferably at least 99 mol%.
  • the upper limit of the ratio is not particularly limited, that is, 100 mol %, and the ratio of the compound providing the structural unit (A-1-1) in the compound providing the structural unit (A-1) is preferably Is 45 mol% or more, more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably 99 mol% or more.
  • the upper limit of the ratio is not particularly limited, that is, 100 mol%.
  • As the compound giving the structural unit (A-2), a compound giving the structural unit (A-2-1), a compound giving the structural unit (A-2-2), and a structural unit (A-2-3) are given.
  • One or more compounds selected from the group consisting of compounds and compounds providing the structural unit (A-2-4) are preferred.
  • the ratio of the total of the compounds providing the structural units (A-2-1) to (A-2-4) in the compound providing the structural unit (A-2) is preferably 45 mol% or more, more preferably 70 mol% or more. It is at least mol%, more preferably at least 90 mol%, and particularly preferably at least 99 mol%. The upper limit of the ratio is not particularly limited, that is, 100 mol%.
  • the tetracarboxylic acid component includes structural units (A-1-1), structural units (A-1-2), structural units (A-1-3), structural units (A-2-1), structural units ( A-2-2), the structural unit (A-2-3), and a compound other than the compound providing the structural unit (A-2-4) may be included, and the compound may be one kind or two kinds. It may be more than.
  • Examples of the compound that provides the structural unit B include a diamine, but the compound is not limited thereto, and a derivative thereof may be used as long as the same structural unit is provided. Examples of the derivative include diisocyanates corresponding to diamines.
  • diamine is preferable.
  • a compound represented by the formula (b-1) that is, diamine
  • a compound represented by the formula (b-3) that is, diamine
  • the diamine component preferably contains the compound giving the structural unit (B-1) in an amount of 45 mol% or more, more preferably 48 mol% or more, still more preferably 85 mol% or more, still more preferably 88 mol% or more, preferably Is 100 mol% or less, more preferably 99.5 mol% or less, still more preferably 99.0 mol% or less.
  • the diamine component may consist of only the compound which gives the structural unit (B-1).
  • the compound providing the structural unit (B-3) is included as the diamine component, the compound providing the structural unit (B-3) is preferably contained in an amount of 5 to 65 mol%, more preferably 10 to 55 mol%, based on the entire diamine component. , More preferably 25 to 50 mol %.
  • the diamine component may be composed of a combination of a compound providing the structural unit (B-1) and at least one compound selected from the compounds providing the structural unit (B-3).
  • the total content ratio of the compound which gives the structural unit (B-1) and the compound which gives the structural unit (B-3) is preferably 45 mol% or more, more preferably 60 mol% or more, further preferably still more preferably 60 mol% or more in all diamine components. Is 85 mol% or more.
  • the upper limit of the total content ratio is not particularly limited, that is, 100 mol%.
  • the diamine component may include a compound that provides the structural unit B other than the compound that provides the structural unit (B-1) and the compound that provides the structural unit (B-3).
  • examples of such compounds include the aromatic diamines described above, Examples thereof include alicyclic diamine, aliphatic diamine, and their derivatives (diisocyanate and the like).
  • the compound other than the compound which gives the structural units (B-1) and (B-3) optionally contained in the diamine component may be one kind or two or more kinds.
  • the compound which gives the structural unit (B-2) is added to the total amount of the compound which gives the structural unit (B-2) and the diamine component. %, preferably 0.01 to 15.0 mol %, more preferably 0.5 to 12.0 mol %, still more preferably 1.0 to 8.0 mol %.
  • tetracarboxylic acid used in all steps of the production of the copolymer including step 1, step 2 and reaction with other components such as a compound which gives the structural unit (B-2) after completion of step 2
  • the ratio of the amounts of the component and the diamine component charged is preferably 0.9 to 1.1 mol of the diamine component with respect to 1 mol of the tetracarboxylic acid component.
  • an end-capping agent may be used in addition to the above-mentioned tetracarboxylic acid component and diamine component in the production of the imide-amic acid copolymer.
  • the terminal blocking agent monoamines or dicarboxylic acids are preferable.
  • the amount of the terminal blocking agent introduced is preferably 0.0001 to 0.1 mol, and particularly preferably 0.001 to 0.06 mol, per 1 mol of the tetracarboxylic acid component.
  • Examples of the monoamine end capping agent include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3- Ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline and the like are recommended. Of these, benzylamine and aniline can be preferably used.
  • dicarboxylic acid end capping agent dicarboxylic acids are preferable, and a part thereof may be ring-closed.
  • phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenone dicarboxylic acid, 3,4-benzophenone dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1 , 2-dicarboxylic acid and the like are recommended.
  • phthalic acid and phthalic anhydride can be preferably used.
  • the solvent used in the method for producing the copolymer of the present invention may be any solvent that can dissolve the imide-amide copolymer produced.
  • an aprotic solvent, a phenol solvent, an ether solvent, a carbonate solvent, etc. are mentioned.
  • aprotic solvent examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethylimidazolidinone and tetramethylurea.
  • Amide solvents lactone solvents such as ⁇ -butyrolactone and ⁇ -valerolactone, phosphorus-containing amide solvents such as hexamethylphosphoric amide and hexamethylphosphinetriamide, and sulfur-containing dimethyl sulfone, dimethyl sulfoxide, sulfolane, etc.
  • the solvent examples include ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and methylcyclohexanone, and ester solvents such as acetic acid (2-methoxy-1-methylethyl).
  • ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and methylcyclohexanone
  • ester solvents such as acetic acid (2-methoxy-1-methylethyl).
  • phenolic 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, 3,5-xylenol and the like can be mentioned.
  • 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 can be mentioned.
  • the carbonate-based solvent examples include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate and the like.
  • amide solvents or lactone solvents are preferable, amide solvents are more preferable, and N-methyl-2-pyrrolidone is further preferable. You may use the said reaction solvent individually or in mixture of 2 or more types.
  • the varnish of the present invention comprises the imide-amic acid copolymer of the present invention, which is a precursor of a polyimide resin, dissolved in an organic solvent. That is, the varnish of the present invention contains the copolymer of the present invention and an organic solvent, and the copolymer is dissolved in the organic solvent.
  • the organic solvent is not particularly limited as long as it can dissolve 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 alone or in combination of two or more. It is preferable to use.
  • the varnish of the present invention may be the above-mentioned copolymer solution itself, or may be one obtained by further adding a diluting solvent to the copolymer solution.
  • the varnish of the present invention may further contain an imidization catalyst and a dehydration catalyst from the viewpoint of efficiently promoting the imidization of the amic acid site in the copolymer of the present invention.
  • the imidization catalyst may be any imidization catalyst having a boiling point of 40° C. or higher and 180° C. or lower, and an amine compound having a boiling point of 180° C. or lower is preferred.
  • the imidization catalyst has a boiling point of 180° C. or less, there is no fear that the film will be colored and the appearance will be impaired when the film is formed and dried at high temperature. Further, if the imidization catalyst has a boiling point of 40° C. or higher, it is possible to avoid the possibility of volatilization before the imidization sufficiently proceeds.
  • Pyridine or picoline is mentioned as an amine compound used suitably as an imidization catalyst.
  • the above imidization catalysts may be used alone or in combination of two or more.
  • the dehydration catalyst include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, trifluoroacetic anhydride, and other acid anhydrides; dicyclohexylcarbodiimide and other carbodiimide compounds; and the like. You may use these individually or in combination of 2 or more types.
  • the varnish of the present invention preferably contains the copolymer of the present invention in an amount of 3 to 40% by mass, more preferably 5 to 40% by mass, and further preferably 10 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 is 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 whitening agent within a range that does not impair the required properties of a polyimide film.
  • Various additives such as agents, cross-linking agents, polymerization initiators and photosensitizers may be included.
  • the method for producing the varnish of the present invention is not particularly limited, and a known method can be applied.
  • the polyimide film of the present invention contains a polyimide resin obtained by imidizing the amide acid site in the imide-amic acid copolymer of the present invention. Therefore, the polyimide film of the present invention can achieve both storage stability and molding processability, is more excellent in colorless transparency and heat resistance, and exhibits low retardation and low residual stress. Suitable physical properties of the polyimide film of the present invention are as described above.
  • the polyimide film of the present invention can be produced using a varnish obtained by dissolving the above-mentioned copolymer in an organic solvent.
  • the method for producing a polyimide film using the varnish of the present invention is not particularly limited, and a known method can be used.
  • a glass plate, a metal plate, the varnish of the present invention is applied onto a smooth support such as plastic, or after being formed into a film, an organic solvent such as a reaction solvent or a diluting solvent contained in the varnish is heated.
  • a polyimide film is produced by removing and obtaining a copolymer film, imidizing (dehydrating and ring-closing) the amic acid site of the copolymer in the copolymer film by heating, and then peeling from the support. 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, and more preferably 30,000 to 500,000, from the viewpoint of mechanical strength of the film. , And more preferably 50,000 to 400,000, 100,000 to 300,000.
  • the number average molecular weight of the copolymer can be determined, for example, from a standard polymethylmethacrylate (PMMA) conversion value measured by gel filtration chromatography.
  • the heating temperature when the varnish of the present invention is dried to obtain a copolymer film is preferably 50 to 150°C.
  • the heating temperature at the time of imidizing the copolymer of the present invention by heating can be selected from the range of preferably 200 to 500°C, more preferably 250 to 450°C, further preferably 300 to 400°C.
  • the heating time is usually 1 minute to 6 hours, preferably 5 minutes to 2 hours, and more preferably 15 minutes to 1 hour.
  • Examples of the heating atmosphere include air gas, nitrogen gas, oxygen gas, hydrogen gas, nitrogen/hydrogen mixed gas, etc.
  • nitrogen gas having an oxygen concentration of 100 ppm or less hydrogen concentration Nitrogen/hydrogen mixed gas containing 0.5% or less is preferable.
  • 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 according to the application etc., but is preferably in the range of 1 to 250 ⁇ m, more preferably 5 to 100 ⁇ m, and further preferably 7 to 50 ⁇ m. When the thickness is 1 to 250 ⁇ m, it can be practically used as a self-supporting film. The thickness of the polyimide film can be easily controlled by adjusting the solid content concentration and viscosity of the varnish.
  • the polyimide film of the present invention is preferably used as a film for various members such as color filters, flexible displays, semiconductor parts and optical members.
  • the polyimide film of the present invention is particularly preferably used as a substrate for image display devices such as liquid crystal displays and OLED displays.
  • the viscosity of the varnish immediately after production and the viscosity of the varnish after storage for 1 week were measured, and the viscosity of the varnish after storage for 1 week was divided by the viscosity of the varnish immediately after production to obtain the rate of change in viscosity (viscosity after storage/viscosity immediately after production). ) was calculated.
  • the smaller the rate of change that is, the rate of increase in viscosity or the rate of decrease in viscosity, the better the storage stability.
  • the evaluation standard was A when the rate of change was 10% or less, and B when the rate of change exceeded 10%.
  • the viscosity was measured at 23° C. using an E-type viscometer.
  • Total light transmittance, yellow index (YI) The total light transmittance and YI were measured using a color/turbidity simultaneous measuring device “COH400” manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K7105:1981.
  • Glass transition temperature (Tg) Using a thermomechanical analyzer "TMA/SS6100” manufactured by Hitachi High-Tech Science Co., Ltd., sample size 3 mm x 20 mm, load 0.1 N, nitrogen flow (flow rate 200 mL/min), temperature rising rate 10°C in tensile mode. The temperature was raised to a temperature sufficient to remove the residual stress under the condition of /min to remove the residual stress, and then cooled to room temperature. Thereafter, the elongation of the test piece was measured under the same conditions as the treatment for removing the residual stress, and the point where the inflection point of the elongation was observed was determined as the glass transition temperature.
  • ⁇ Tetracarboxylic acid component> CpODA: norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride (manufactured by JX Energy Corporation; Compound represented by formula (a-1-1)) HPMDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride (a compound corresponding to alicyclic tetracarboxylic dianhydride (a-1)) s-BPDA: 3,3′,4,4′-biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation, compound represented by formula (a-2-1s)) TAHQ: p-phenylenebis(trimellitate) dianhydride (mana)
  • NMP N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation)
  • TEA triethylamine (manufactured by Kanto Chemical Co., Inc.)
  • Example 1 32.858 g (0.0977 mol) of 6FODA was placed in a 500 mL 5-neck round bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen introduction tube, a Dean Stark equipped with a cooling tube, a thermometer, and a glass end cap. And 90.000 g of NMP were added, and the solution was obtained by stirring at a system internal temperature of 70° C. and a nitrogen atmosphere at a rotation speed of 200 rpm.
  • Example 2 26.953 g (0.0802 mol) of 6FODA was added to a 500 mL 5-neck round bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen introduction tube, a Dean Stark equipped with a cooling tube, a thermometer, and a glass end cap. , And NMP (56.000 g) were added, and the solution was obtained by stirring at a system temperature of 70° C. and a nitrogen atmosphere at a rotation speed of 200 rpm.
  • Example 3 25.096 g (0.0746 mol) of 6FODA was placed in a 500 mL 5-neck round bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen introduction tube, a Dean Stark equipped with a cooling tube, a thermometer, and a glass end cap. , And NMP (56.000 g) were added, and the solution was obtained by stirring at a system internal temperature of 70° C. and a nitrogen atmosphere at a rotation speed of 200 rpm.
  • Example 4 14.806 g (0.044 mol) of 6FODA was placed in a 500 mL 5-neck round bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen introduction tube, a Dean Stark equipped with a cooling tube, a thermometer, and a glass end cap. , BAFL (15.343 g (0.044 mol)) and NMP (56.000 g) were charged, and the solution was obtained by stirring at a system internal temperature of 70° C. and a nitrogen atmosphere at a rotation speed of 200 rpm.
  • Example 5 26.235 g (0.0780 mol) of 6FODA was placed in a 500 mL 5-neck round bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen introduction tube, a Dean Stark equipped with a cooling tube, a thermometer, and a glass end cap. , And NMP (56.000 g) were added, and the solution was obtained by stirring at a system temperature of 70° C. and a nitrogen atmosphere at a rotation speed of 200 rpm.
  • Example 6 26.250 g (0.0781 mol) of 6FODA was placed in a 500 mL 5-neck round bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen introduction tube, a Dean Stark equipped with a cooling tube, a thermometer, and a glass end cap. And 60.000 g of NMP were added and stirred at a system temperature of 70° C. under a nitrogen atmosphere at a rotation speed of 200 rpm to obtain a solution.
  • Example 7 24.408 g (0.0726 mol) of 6FODA was placed in a 500 mL 5-neck round bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen introduction tube, a Dean Stark equipped with a cooling tube, a thermometer, and a glass end cap. And 60.000 g of NMP were added, and the solution was obtained by stirring at a system internal temperature of 70° C. and a nitrogen atmosphere at a rotation speed of 200 rpm.
  • Example 8 34.383 g (0.1023 mol) of 6FODA was placed in a 500 mL 5-neck round bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen introduction tube, a Dean Stark equipped with a cooling tube, a thermometer, and a glass end cap. , And NMP (56.000 g) were added, and the solution was obtained by stirring at a system internal temperature of 70° C. and a nitrogen atmosphere at a rotation speed of 200 rpm.
  • the temperature in the reaction system was raised to 190°C.
  • the components to be distilled off were collected, and the temperature in the reaction system was kept at 190° C. and refluxed for 1 hour while adjusting the number of rotations according to the increase in viscosity.
  • 85.806 g of NMP was added, the temperature in the reaction system was cooled to 50° C., and a solution containing an oligomer having an imide repeating structural unit was obtained.
  • 11.417 g (0.0388 mol) of s-BPDA and 7.527 g of NMP were added all at once, and the mixture was stirred at 50° C. for 5 hours.
  • Example 11 29.073 g (0.0865 mol) of 6FODA was placed in a 500 mL 5-neck round bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen introduction tube, a Dean Stark equipped with a cooling tube, a thermometer, and a glass end cap. , And NMP in an amount of 56.000 g and stirred at a system temperature of 70° C. under a nitrogen atmosphere at a rotation speed of 200 rpm to obtain a solution.
  • Example 12 29.554 g (0.0879 mol) of 6FODA was placed in a 500 mL 5-neck round bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen introduction tube, a Dean Stark equipped with a cooling tube, a thermometer, and a glass end cap. , And NMP in an amount of 56.000 g and stirred at a system temperature of 70° C. under a nitrogen atmosphere at a rotation speed of 200 rpm to obtain a solution.
  • the components to be distilled off were collected, and the temperature in the reaction system was maintained at 190° C. and refluxed for 3 hours while adjusting the number of rotations according to the increase in viscosity. Then, 125.000 g of NMP was added so that the solid content concentration was about 15% by mass, the temperature in the reaction system was cooled to 100° C., and the mixture was further stirred for about 1 hour to homogenize to obtain a polyimide varnish. It was Subsequently, the obtained polyimide varnish was applied onto a glass plate by spin coating, kept at 80° C. for 20 minutes on a hot plate, and then heated in a hot air dryer at 350° C. for 30 minutes to evaporate the solvent. Then, a polyimide film was obtained.
  • PAA polyamic acid
  • the polyamic acid obtained in Comparative Example 4 has only an amic acid repeating structural unit formed from s-BPDA and 6FODA. The said polyamic acid is called "PAA.”
  • the imide-amic acid copolymers of the examples can achieve both storage stability and molding processability. Further, as shown in Table 1, the polyimide films of Examples 1 to 16 formed from a copolymer having a specific imide repeating structural unit and an amic acid structural unit are excellent in colorless transparency and heat resistance and It was excellent in retardation and low residual stress.

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Abstract

L'invention concerne un copolymère d'imide-acide amique comprenant une unité répétitive composée d'un résidu imide (I) et d'un résidu acide amique (A), et représenté par la formule (1). (Dans la formule (1), X1 représente un groupe aliphatique, un groupe alicyclique ou un groupe aromatique, chacun ayant une valence de 4 et comprenant 4 à 39 atomes de carbone, ou un groupe formé à partir de la combinaison d'un ou de plusieurs de ces groupes, le groupe pouvant comprendre au moins un groupe sélectionné dans le groupe constitué par -O-, -SO2-, -CO-, -CH2-, -C(CH3)2-, -C2H4O- et -S- en tant que groupe de liaison ; X2 représente un groupe aliphatique, un groupe alicyclique ou un groupe aromatique, chacun ayant une valence de 4 et comprenant 4 à 39 atomes de carbone, ou un groupe formé à partir de la combinaison d'un ou de plusieurs de ces groupes, le groupe étant différent de X1 et pouvant comprendre au moins un groupe sélectionné dans le groupe constitué par -O-, -SO2-, -CO-, -CH2-, -C(CH3)2-, -C2H4O- et -S- en tant que groupe de liaison ; Y1 représente un groupe aliphatique, un groupe alicyclique ou un groupe aromatique, chacun ayant une valence de 2 et comprenant 4 à 39 atomes de carbone, ou un groupe formé à partir de la combinaison d'un ou de plusieurs de ces groupes, le groupe pouvant comprendre au moins un groupe sélectionné dans le groupe constitué par -O-, -SO2-, -CO-, -CH2-, -C(CH3)2-, -C2H4O- et -S- en tant que groupe de liaison ; un grand nombre des Y1 présentant une composition identique entre eux ; et s et t représentant chacun un nombre entier positif.)
PCT/JP2019/051293 2018-12-28 2019-12-26 Copolymère d'imide-(acide amique) et son procédé de production, vernis et film de polyimide WO2020138360A1 (fr)

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* Cited by examiner, † Cited by third party
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WO2021085283A1 (fr) * 2019-10-31 2021-05-06 住友化学株式会社 Résine de polyamide-imide
WO2021132197A1 (fr) * 2019-12-27 2021-07-01 三菱瓦斯化学株式会社 Résine de polyimide, vernis et film de polyimide
WO2021210640A1 (fr) * 2020-04-16 2021-10-21 三菱瓦斯化学株式会社 Copolymère d'imide-acide amique et son procédé de production, vernis et film de polyimide
WO2021210641A1 (fr) * 2020-04-16 2021-10-21 三菱瓦斯化学株式会社 Copolymère d'imide-acide amique et son procédé de production, vernis et film de polyimide
CN114599708A (zh) * 2019-10-31 2022-06-07 住友化学株式会社 聚酰胺酰亚胺树脂
WO2022210274A1 (fr) * 2021-03-31 2022-10-06 Ｅｎｅｏｓ株式会社 Dianhydride tétracarboxylique, composé carbonyle, composé contenant un groupe anhydride d'acide, procédés de production de ceux-ci, polyimide et résine précurseur de polyimide
WO2022211086A1 (fr) * 2021-04-02 2022-10-06 旭化成株式会社 Polyimide, composition de résine, film de polyimide et procédé de production associé

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* Cited by examiner, † Cited by third party
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Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07157560A (ja) * 1993-12-02 1995-06-20 P I Zairyo Kenkyusho:Kk ポリイミドブロック共重合体の製造方法及びその溶液組成物
JPH08231719A (ja) * 1994-10-31 1996-09-10 Korea Res Inst Of Chem Technol ポリ（イミド−アミックエステル）及びその製造方法並びにそれを用いたポリイミド、ポリイミドフィルム、ポリイミドファイバー及びそれらの製造方法
JPH09185064A (ja) * 1995-12-28 1997-07-15 Japan Synthetic Rubber Co Ltd イミド基含有ポリアミック酸およびその製造方法並びに液晶配向剤
JP2002201271A (ja) * 2000-12-21 2002-07-19 E I Du Pont De Nemours & Co 溶融加工性半晶質ブロックコポリイミド
JP2006016592A (ja) * 2004-06-04 2006-01-19 Fuji Xerox Co Ltd ポリアミック酸組成物、ポリイミド無端ベルト及びその製造方法、画像形成装置
JP2008222969A (ja) * 2007-03-15 2008-09-25 Ube Ind Ltd アミック酸構造の繰返単位の一部がイミド構造になっている共重合体、およびその製造方法
JP2010018802A (ja) * 2008-07-09 2010-01-28 Lg Chem Ltd ポリイミド−ポリアミド酸共重合体、その製造方法、それを含む感光性組成物およびこれにより提供される保護膜
JP2015229691A (ja) * 2014-06-03 2015-12-21 旭化成イーマテリアルズ株式会社 ポリイミド前駆体組成物及びポリイミドフィルム
CN105273189A (zh) * 2015-10-29 2016-01-27 阜新泓扬光电材料有限公司 具有阻隔紫外线作用的透明聚酰亚胺薄膜及其制备和应用
JP2017119868A (ja) * 2015-12-31 2017-07-06 ドンジン セミケム カンパニー リミテッドＤｏｎｇｊｉｎ Ｓｅｍｉｃｈｅｍ Ｃｏ．， Ｌｔｄ． ポリイミド高分子組成物とその製造方法、及びそれを用いたポリイミドフィルムの製造方法
WO2017191822A1 (fr) * 2016-05-06 2017-11-09 三菱瓦斯化学株式会社 Résine de polyimide
JP2018030994A (ja) * 2013-03-18 2018-03-01 旭化成株式会社 樹脂前駆体及びそれを含有する樹脂組成物、樹脂フィルム及びその製造方法、並びに、積層体及びその製造方法
JP2018048344A (ja) * 2014-06-25 2018-03-29 旭化成株式会社 空隙を有するポリイミドフィルム及びその製造方法
JP2018526675A (ja) * 2015-11-11 2018-09-13 エルジー・ケム・リミテッド 液晶配向膜の製造方法、これを利用した液晶配向膜および液晶表示素子
US20180273711A1 (en) * 2017-03-23 2018-09-27 Wuhan China Star Optoelectronics Technology Co., Ltd. Modified polyimide thin film and manufacturing method thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005232383A (ja) 2004-02-20 2005-09-02 Asahi Kasei Electronics Co Ltd ポリアミド酸誘導体
JP2008231327A (ja) 2007-03-22 2008-10-02 Ihara Chem Ind Co Ltd 高透明性を有するポリイミドおよびその製造方法
KR20210014751A (ko) 2012-12-21 2021-02-09 아사히 가세이 이-매터리얼즈 가부시키가이샤 폴리이미드 전구체 및 그것을 함유하는 수지 조성물
JP6485996B2 (ja) 2013-06-14 2019-03-20 ソマール株式会社 ポリイミド共重合体オリゴマー、ポリイミド共重合体、およびそれらの製造方法
CN103755959B (zh) 2014-01-22 2016-03-02 江苏亚宝绝缘材料股份有限公司 一种柔性透明聚酰亚胺薄膜
CN103756317B (zh) 2014-01-24 2016-05-11 江苏亚宝绝缘材料股份有限公司 一种柔性导电聚酰亚胺薄膜
CN104558605A (zh) 2014-12-14 2015-04-29 南京新月材料科技有限公司 一种透明聚酰亚胺薄膜及其制备方法
CN106893125A (zh) * 2017-03-23 2017-06-27 武汉华星光电技术有限公司 一种改性聚酰亚胺薄膜及其制备方法

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07157560A (ja) * 1993-12-02 1995-06-20 P I Zairyo Kenkyusho:Kk ポリイミドブロック共重合体の製造方法及びその溶液組成物
JPH08231719A (ja) * 1994-10-31 1996-09-10 Korea Res Inst Of Chem Technol ポリ（イミド−アミックエステル）及びその製造方法並びにそれを用いたポリイミド、ポリイミドフィルム、ポリイミドファイバー及びそれらの製造方法
JPH09185064A (ja) * 1995-12-28 1997-07-15 Japan Synthetic Rubber Co Ltd イミド基含有ポリアミック酸およびその製造方法並びに液晶配向剤
JP2002201271A (ja) * 2000-12-21 2002-07-19 E I Du Pont De Nemours & Co 溶融加工性半晶質ブロックコポリイミド
JP2006016592A (ja) * 2004-06-04 2006-01-19 Fuji Xerox Co Ltd ポリアミック酸組成物、ポリイミド無端ベルト及びその製造方法、画像形成装置
JP2008222969A (ja) * 2007-03-15 2008-09-25 Ube Ind Ltd アミック酸構造の繰返単位の一部がイミド構造になっている共重合体、およびその製造方法
JP2010018802A (ja) * 2008-07-09 2010-01-28 Lg Chem Ltd ポリイミド−ポリアミド酸共重合体、その製造方法、それを含む感光性組成物およびこれにより提供される保護膜
JP2018030994A (ja) * 2013-03-18 2018-03-01 旭化成株式会社 樹脂前駆体及びそれを含有する樹脂組成物、樹脂フィルム及びその製造方法、並びに、積層体及びその製造方法
JP2015229691A (ja) * 2014-06-03 2015-12-21 旭化成イーマテリアルズ株式会社 ポリイミド前駆体組成物及びポリイミドフィルム
JP2018048344A (ja) * 2014-06-25 2018-03-29 旭化成株式会社 空隙を有するポリイミドフィルム及びその製造方法
CN105273189A (zh) * 2015-10-29 2016-01-27 阜新泓扬光电材料有限公司 具有阻隔紫外线作用的透明聚酰亚胺薄膜及其制备和应用
JP2018526675A (ja) * 2015-11-11 2018-09-13 エルジー・ケム・リミテッド 液晶配向膜の製造方法、これを利用した液晶配向膜および液晶表示素子
JP2017119868A (ja) * 2015-12-31 2017-07-06 ドンジン セミケム カンパニー リミテッドＤｏｎｇｊｉｎ Ｓｅｍｉｃｈｅｍ Ｃｏ．， Ｌｔｄ． ポリイミド高分子組成物とその製造方法、及びそれを用いたポリイミドフィルムの製造方法
WO2017191822A1 (fr) * 2016-05-06 2017-11-09 三菱瓦斯化学株式会社 Résine de polyimide
US20180273711A1 (en) * 2017-03-23 2018-09-27 Wuhan China Star Optoelectronics Technology Co., Ltd. Modified polyimide thin film and manufacturing method thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021085283A1 (fr) * 2019-10-31 2021-05-06 住友化学株式会社 Résine de polyamide-imide
CN114599708A (zh) * 2019-10-31 2022-06-07 住友化学株式会社 聚酰胺酰亚胺树脂
WO2021132197A1 (fr) * 2019-12-27 2021-07-01 三菱瓦斯化学株式会社 Résine de polyimide, vernis et film de polyimide
WO2021210640A1 (fr) * 2020-04-16 2021-10-21 三菱瓦斯化学株式会社 Copolymère d'imide-acide amique et son procédé de production, vernis et film de polyimide
WO2021210641A1 (fr) * 2020-04-16 2021-10-21 三菱瓦斯化学株式会社 Copolymère d'imide-acide amique et son procédé de production, vernis et film de polyimide
WO2022210274A1 (fr) * 2021-03-31 2022-10-06 Ｅｎｅｏｓ株式会社 Dianhydride tétracarboxylique, composé carbonyle, composé contenant un groupe anhydride d'acide, procédés de production de ceux-ci, polyimide et résine précurseur de polyimide
WO2022211086A1 (fr) * 2021-04-02 2022-10-06 旭化成株式会社 Polyimide, composition de résine, film de polyimide et procédé de production associé
JP7174199B1 (ja) * 2021-04-02 2022-11-17 旭化成株式会社 ポリイミド、樹脂組成物、ポリイミドフィルム、及び、その製造方法
KR20230147181A (ko) 2021-04-02 2023-10-20 아사히 가세이 가부시키가이샤 폴리이미드, 수지 조성물, 폴리이미드 필름, 및, 그 제조 방법

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