WO2018066522A1 - Polyimide, résine de précurseur de polyimide, solution de ceux-ci, procédé de fabrication de polyimide, et film mettant en œuvre ce polyimide - Google Patents

Polyimide, résine de précurseur de polyimide, solution de ceux-ci, procédé de fabrication de polyimide, et film mettant en œuvre ce polyimide Download PDF

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WO2018066522A1
WO2018066522A1 PCT/JP2017/035847 JP2017035847W WO2018066522A1 WO 2018066522 A1 WO2018066522 A1 WO 2018066522A1 JP 2017035847 W JP2017035847 W JP 2017035847W WO 2018066522 A1 WO2018066522 A1 WO 2018066522A1
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polyimide
carbon atoms
repeating unit
film
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PCT/JP2017/035847
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Japanese (ja)
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大輔 渡部
貴大 長谷川
理恵子 藤代
亜紗子 京武
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Ｊｘｔｇエネルギー株式会社
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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

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  • the present invention relates to a polyimide, a polyimide precursor resin, a solution thereof, a method for producing polyimide, and a film using polyimide.
  • polyimide has been attracting attention as a light and flexible material having high heat resistance.
  • aromatic polyimide for example, trade name “Kapton” manufactured by DuPont
  • aromatic polyimide is a polyimide having sufficient flexibility and high heat resistance, it exhibits a brown color and can be used for glass replacement applications and optical applications that require light transmission. It wasn't.
  • Patent Document 1 discloses a polyimide having a repeating unit described by a specific general formula.
  • Patent Document 1 has sufficient light transmittance.
  • Patent Document 1 the alicyclic polyimide described in Patent Document 1 is not necessarily sufficient in terms of further improving the hardness.
  • the present invention has been made in view of the above-described problems of the prior art, and has a sufficiently high level of transparency and a sufficiently high level of hardness, and a polyimide thereof. It aims at providing the manufacturing method of the polyimide which can manufacture the polyimide solution which contains, the film using the polyimide, and the polyimide efficiently and reliably. Furthermore, an object of this invention is to provide the polyimide precursor resin solution which can be utilized suitably in order to manufacture the said polyimide, and the polyimide precursor resin solution containing the polyimide precursor resin.
  • the polyimide contains the following repeating unit (A1), the following repeating unit (B1), and the following repeating unit (C1). As a result, it has been found that it is possible to achieve a sufficiently high level of hardness while having sufficiently high transparency, and the present invention has been completed.
  • polyimide of the present invention has the following general formulas (1-1) to (1-2):
  • R 1, R 2, R 3 are each independently a hydrogen atom, represents one selected from the group consisting of alkyl groups and fluorine atoms having 1 to 10 carbon atoms
  • R 4 is Represents an arylene group having 6 to 40 carbon atoms
  • n represents an integer of 0 to 12
  • a plurality of R 6 each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group and a nitro group, or the same carbon
  • Two R 6 bonded to an atom may form a methylidene group together
  • R 7 and R 8 are each independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms.
  • R 4 represents an arylene group having 6 to 40 carbon atoms.
  • R 4 represents an arylene group having 6 to 40 carbon atoms.
  • X 1 represents a tetravalent saturated alicyclic hydrocarbon group having 4 to 16 carbon atoms
  • A may have a substituent and an aromatic ring 1 is selected from the group consisting of divalent aromatic groups having 6 to 30 carbon atoms, and each of the plurality of R 5 is independently a hydrogen atom or an alkyl having 1 to 10 carbon atoms.
  • 1 represents one selected from the group consisting of groups, and in formulas (4) to (5) and (101), R 4 represents an arylene group having 6 to 40 carbon atoms.
  • the polyimide precursor resin of the present invention has the following general formulas (6-1) to (6-3) and (6-4) to (6-6):
  • R 1 , R 2 and R 3 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom.
  • R 4 represents an arylene group having 6 to 40 carbon atoms, and Y 1 and Y 2 are each independently a group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkylsilyl group having 3 to 9 carbon atoms.
  • N represents an integer of 0 to 12
  • each of R 6 independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group and a nitro group Or two R 6 bonded to the same carbon atom may form together a methylidene group
  • R 7 and R 8 are each independently a hydrogen atom and an alkyl having 1 to 10 carbon atoms.
  • R 4 represents an arylene group having 6 to 40 carbon atoms
  • Y 1 and Y 2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and a carbon number; 1 type selected from the group consisting of 3 to 9 alkylsilyl groups.
  • R 4 represents an arylene group having 6 to 40 carbon atoms
  • Y 1 and Y 2 are each independently 1 type selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an alkylsilyl group having 3 to 9 carbon atoms.
  • X 1 represents a tetravalent saturated alicyclic hydrocarbon group having 4 to 16 carbon atoms
  • A has a substituent.
  • R 5 are independently selected from the group consisting of divalent aromatic groups having 6 to 30 carbon atoms that form an aromatic ring.
  • R 4 represents an arylene group having 6 to 40 carbon atoms
  • Y 1 and Y 2 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkylsilyl group having 3 to 9 carbon atoms.
  • the method for producing the polyimide of the present invention comprises: In the presence of a polymerization solvent, The following general formulas (11-1) to (11-2):
  • R 1 , R 2 , and R 3 each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and n Represents an integer from 0 to 12,
  • a plurality of R 6 each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group and a nitro group, or the same carbon
  • Two R 6 bonded to an atom may form a methylidene group together
  • R 7 and R 8 are each independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms.
  • At least one tetracarboxylic dianhydride (A) selected from the compounds represented by: The following general formulas (12) to (13):
  • At least one tetracarboxylic dianhydride (B) selected from the compounds represented by: The following general formulas (14) to (15) and (103):
  • X 1 represents a tetravalent saturated alicyclic hydrocarbon group having 4 to 16 carbon atoms
  • A may have a substituent and an aromatic ring 1 is selected from the group consisting of divalent aromatic groups having 6 to 30 carbon atoms, and each of the plurality of R 5 is independently a hydrogen atom or an alkyl having 1 to 10 carbon atoms. 1 type selected from the group which consists of groups is shown.
  • a tetracarboxylic dianhydride component comprising: The following general formula (16): H 2 N—R 4 —NH 2 (16) Wherein (16), R 4 represents an arylene group having 6 to 40 carbon atoms.
  • the polyimide solution of the present invention contains the polyimide of the present invention and an organic solvent.
  • the polyimide precursor resin solution of the present invention contains the polyimide precursor resin of the present invention and an organic solvent. According to such a resin solution (varnish) such as a polyimide solution or a polyimide precursor resin solution (for example, a polyamic acid solution), various forms of polyimide can be efficiently produced.
  • the polyimide film of the present invention is made of the polyimide of the present invention.
  • polyimide having a sufficiently high level of hardness while having a sufficiently high level of hardness a polyimide solution containing the polyimide, a film using the polyimide, and It is possible to provide a method for producing polyimide that can efficiently and reliably produce the polyimide. Furthermore, according to the present invention, it is possible to provide a polyimide precursor resin that can be suitably used for producing the polyimide, and a polyimide precursor resin solution containing the polyimide precursor resin. Become.
  • FIG. 2 is a graph showing an IR spectrum of polyimide obtained in Example 1.
  • the polyimide of the present invention comprises at least one repeating unit (A1) selected from repeating units represented by the general formulas (1-1) to (1-2), At least one repeating unit (B1) selected from repeating units represented by the general formulas (2) to (3); At least one repeating unit (C1) selected from repeating units represented by the general formulas (4) to (5) and (103); It contains.
  • A1 selected from repeating units represented by the general formulas (1-1) to (1-2)
  • At least one repeating unit (C1) selected from repeating units represented by the general formulas (4) to (5) and (103) It contains.
  • the repeating units (A1) to (C1) will be described.
  • the repeating unit (A1) contained in the polyimide of the present invention is at least one repeating unit selected from the repeating units represented by the general formulas (1-1) to (1-2) (note that In general formula (1-1), R 1 , R 2 , and R 3 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and n is 0 Represents an integer of ⁇ 12, R 4 represents an arylene group having 6 to 40 carbon atoms, and in the above formula (1-2), a plurality of R 6 are each independently a hydrogen atom or an alkyl having 1 to 10 carbon atoms.
  • R 6 1 type selected from the group consisting of a group, a hydroxyl group and a nitro group, or two R 6 bonded to the same carbon atom may be combined to form a methylidene group
  • 7 and R 8 are each independently a hydrogen atom and 1 to 1 represents one selected from the group consisting of 10 alkyl groups
  • R 4 represents an arylene group having 6 to 40 carbon atoms.
  • the alkyl group that can be selected as R 1 , R 2 , R 3 in the general formula (1-1) is an alkyl group having 1 to 10 carbon atoms. When the number of carbon atoms exceeds 10, the glass transition temperature is lowered and a sufficiently high heat resistance cannot be achieved. Further, the number of carbon atoms of the alkyl group that can be selected as R 1 , R 2 , or R 3 is preferably 1 to 6 and is preferably 1 to 5 from the viewpoint of easier purification. Is more preferably 1 to 4, particularly preferably 1 to 3. Further, such an alkyl group that can be selected as R 1 , R 2 , or R 3 may be linear or branched. Further, such an alkyl group is more preferably a methyl group or an ethyl group from the viewpoint of ease of purification.
  • R 1 , R 2 and R 3 in the general formula (1-1) are each independently a hydrogen atom or a carbon number of 1 from the viewpoint that higher heat resistance can be obtained when a polyimide is produced. It is more preferably an alkyl group of ⁇ 10, and among them, from the viewpoint of easy availability of raw materials and easier purification, they are each independently a hydrogen atom, methyl group, ethyl group, n-propyl group. Alternatively, an isopropyl group is more preferable, and a hydrogen atom or a methyl group is particularly preferable. Moreover, it is especially preferable that several R ⁇ 1 >, R ⁇ 2 >, R ⁇ 3 > in such a formula is the same from viewpoints, such as the ease of refinement
  • the arylene group that can be selected as R 4 in the general formula (1-1) is an arylene group having 6 to 40 carbon atoms. Such an arylene group preferably has 6 to 30 carbon atoms, more preferably 12 to 20 carbon atoms. If the number of carbon atoms is less than the lower limit, the heat resistance of the polyimide tends to be reduced. It tends to decrease.
  • Examples of the arylene group that can be selected as R 4 in the general formula (1-1) include the following general formulas (17) to (21):
  • Q has the formula: -C 6 H 4 -, - CONH-C 6 H 4 -NHCO -, - NHCO-C 6 H 4 -CONH -, - O-C 6 H 4 -CO —C 6 H 4 —O—, —OCO—C 6 H 4 —COO—, —OCO—C 6 H 4 —C 6 H 4 —COO—, —OCO—, —NC 6 H 5 —, —CO— C 4 H 8 N 2 —CO—, —C 13 H 10 —, — (CH 2 ) 5 —, —O—, —S—, —CO—, —CONH—, —SO 2 —, —C (CF 3 ) 2 —, —C (CH 3 ) 2 —, —CH 2 —, — (CH 2 ) 2 —, — (CH 2 ) 3 —, — (CH 2 ) 4 , — (CH 2 )
  • R 4 in the general formula (1-1) is a group represented by the general formula (21) from the viewpoint of high heat resistance, colorless transparency, good solubility, and high hardness. It is preferable that R 9 is a group represented by the above general formula (21), which is a trifluoromethyl group.
  • n represents an integer of 0 to 12.
  • the upper limit of the numerical value range of n in the general formula (1-1) is more preferably 5 and particularly preferably 3 from the viewpoint of easier purification.
  • the lower limit of the numerical value range of n in the general formula (1-1) is more preferably 1 and particularly preferably 2 from the viewpoint of the stability of the raw material compound.
  • n in the general formula (1-1) is particularly preferably an integer of 2 to 3.
  • the alkyl group that can be selected as R 6 in the general formula (1-2) is an alkyl group having 1 to 10 carbon atoms. When the number of carbon atoms exceeds 10, sufficiently high heat resistance cannot be achieved.
  • the number of carbon atoms of the alkyl group that can be selected as R 6 is preferably 1 to 6, more preferably 1 to 5, more preferably 1 to 5, from the viewpoint of easier purification. 4 is more preferable, and 1 to 3 is particularly preferable.
  • Such an alkyl group that can be selected as R 6 may be linear or branched. Further, such an alkyl group is more preferably a methyl group or an ethyl group from the viewpoint of ease of purification.
  • the plurality of R 6 in the general formula (1-2) includes higher heat resistance, easier acquisition (preparation) of raw materials, easier purification, etc. From the viewpoint, it is more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group.
  • the plurality of R 6 in such a formula may be the same or different from each other, but may be the same from the viewpoint of ease of purification and the like. preferable.
  • R 7 and R 8 are each independently one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms.
  • the alkyl group that can be selected as R 7 and R 8 is preferably 1 to 6, more preferably 1 to 5, from the viewpoint of obtaining higher heat resistance. It is more preferably 1 to 4, and particularly preferably 1 to 3. Further, such an alkyl group that can be selected as R 7 and R 8 may be linear or branched.
  • R 7 and R 8 in the general formula (1-2) can obtain higher heat resistance when the polymer is produced, the raw materials are easily obtained, and the purification is easier.
  • each independently is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, more preferably a hydrogen atom or a methyl group.
  • R 7 and R 8 in the formula (1-2) may be the same or different from each other, but from the viewpoint of ease of purification and the like, they are the same. It is preferable that.
  • it is particularly preferable that all of the plurality of R 6 , R 7 and R 8 in the general formula (1-2) are hydrogen atoms.
  • R 4 in the formula (1-2) is the same as the R 4 in the general formula (1-1), The preferred one is also the same as R 4 in the general formula (1-1).
  • Such repeating units (A1) represented by general formulas (1-1) to (1-2) are compounds represented by the above general formulas (11-1) to (11-2) (note that wherein (11-1), R 1, R 2, R 3, n are as defined R 1, R 2, R 3 , n in the general formula (1-1) (also some its preferred And has the same meaning as R 1 , R 2 , R 3 , and n in the general formula (1-1), and R 6 , R 7 , and R 8 in the general formula (11-2) -2) R 6, R 7, the same meaning as R 8 in (the preferred ones also the general formula (1-2) the same meaning as R 6, R 7, R 8 in).) of On the basis of at least one tetracarboxylic dianhydride (A) selected from: and at least one aromatic diamine selected from the compounds represented by the general formula (16) It can be formed.
  • the method for producing such a compound represented by the general formula (11-1) (tetracarboxylic dianhydride (A)) is not particularly limited, and a known method can be appropriately employed.
  • the method for producing the compound represented by the general formula (11-2) (tetracarboxylic dianhydride (A)) is not particularly limited, and a known method can be appropriately employed. You may employ
  • such compounds represented by the general formulas (11-1) to (11-2) (tetracarboxylic dianhydride (A)) may be used singly or in combination of two or more. Also good.
  • the method for producing the compound (aromatic diamine) represented by the general formula (16) is not particularly limited, and a known method can be appropriately employed. Moreover, you may use a commercially available thing suitably as such aromatic diamine. Moreover, you may utilize the compound (aromatic diamine) represented by such General formula (16) individually by 1 type or in combination of 2 or more types.
  • the repeating unit (B1) contained in the polyimide of the present invention is at least one repeating unit selected from the repeating units represented by the general formulas (2) to (3) (note that the general formula (2 ) To (3), R 4 represents an arylene group having 6 to 40 carbon atoms.
  • Such a repeating unit (B1) includes at least one tetracarboxylic dianhydride (B) selected from the compounds represented by the general formulas (12) to (13), and the general formula ( It can be formed based on at least one aromatic diamine selected from the compounds represented by 16).
  • the compound represented by the general formula (12) used as the tetracarboxylic dianhydride (B) is pyromellitic anhydride (PMDA), and is represented by the general formula (13).
  • the compound is 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA).
  • the method for producing such tetracarboxylic dianhydride (B) is not particularly limited, and a known method can be appropriately employed. Moreover, as such a tetracarboxylic dianhydride (B), you may use a commercially available thing suitably. Further, such tetracarboxylic dianhydrides (B) may be used singly or in combination of two or more.
  • the repeating unit (C1) contained in the polyimide of the present invention is at least one repeating unit selected from the repeating units represented by the general formulas (4) to (5) and (101)
  • X 1 represents a tetravalent saturated alicyclic hydrocarbon group having 4 to 16 carbon atoms.
  • A may have a substituent and an aromatic ring. 1 is selected from the group consisting of divalent aromatic groups having 6 to 30 carbon atoms, and each of the plurality of R 5 is independently a hydrogen atom or an alkyl having 1 to 10 carbon atoms.
  • One of groups selected from the group consisting of groups, and R 4 in the general formulas (4) to (5) and (101) represents an arylene group having 6 to 40 carbon atoms.
  • X 1 in the general formula (4) is a tetravalent saturated alicyclic hydrocarbon group having 4 to 16 carbon atoms.
  • the number of carbon atoms of the saturated alicyclic hydrocarbon group that can be selected as X 1 is preferably 4 to 8, and preferably 4 to 6, from the viewpoint of good solubility of the resulting polyimide in a solvent. Is more preferable.
  • the saturated alicyclic hydrocarbon group having 4 to 16 carbon atoms that can be selected as X 1 is preferably a monocyclic cycloalkane, and one kind selected from cyclobutane, cyclopentane, and cyclohexane is used. More preferably, the following general formulas (22) to (24):
  • R 4 represents an arylene group having 6 to 40 carbon atoms.
  • More preferred is at least one repeating unit selected from repeating units represented by:
  • a in the general formula (101) is a divalent aromatic group which may have a substituent, and the number of carbons forming an aromatic ring contained in the aromatic group (here, The “number of carbons forming an aromatic ring” means that when the aromatic group has a substituent containing carbon (such as a hydrocarbon group), the number of carbons in the substituent does not include the aromatic group. This refers to the number of carbons in an aromatic ring in a group, for example, in the case of a 2-ethyl-1,4-phenylene group, the number of carbons forming the aromatic ring is 6. It is.
  • a in the general formula (101) is a divalent group (divalent aromatic group) which may have a substituent and has an aromatic ring having 6 to 30 carbon atoms. is there.
  • the polyimide obtained using the acid dianhydride of the general formula (101) as a raw material tends to be colored.
  • the number of carbon atoms forming the aromatic ring of the divalent aromatic group is more preferably 6-18, and further preferably 6-12. preferable.
  • Such a divalent aromatic group is not particularly limited as long as it satisfies the above condition of the number of carbons.
  • examples thereof include 1,4-phenylene group, 2,6-naphthylene group, 2,7-naphthylene group, 4,4′-biphenylene group, 9,10-anthracenylene group, and the like.
  • Groups in which at least one hydrogen atom in the residue is substituted with a substituent for example, 2,5-dimethyl-1,4-phenylene group, 2,3,5 6-tetramethyl-1,4-phenylene group
  • the position of the leaving hydrogen atom is not particularly limited.
  • the residue is a phenylene group, any of the ortho, meta, and para positions is used. It may be the position.
  • a phenylene group which may have a substituent, a biphenylene group which may have a substituent, A naphthylene group which may have a substituent, an anthracenylene group which may have a substituent, and a terphenylene group which may have a substituent are preferable, and each may have a substituent.
  • a phenylene group, a biphenylene group, a naphthylene group, and a terphenylene group are more preferable, and a phenylene group, a biphenylene group, and a naphthylene group, each of which may have a substituent, are further preferable.
  • the substituent that the divalent aromatic group may have is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, and a halogen atom. .
  • the solubility of polyimide in a solvent is improved, and from the viewpoint of obtaining higher processability, the number of carbon atoms is 1. More preferred are an alkyl group having ⁇ 10 and an alkoxy group having 1 to 10 carbon atoms. When the number of carbon atoms of the alkyl group and alkoxy group suitable as such a substituent exceeds 10, the heat resistance of the polyimide tends to decrease.
  • the number of carbon atoms of an alkyl group and an alkoxy group suitable as such a substituent is preferably 1 to 6 from the viewpoint of obtaining higher heat resistance when a polyimide is produced. 5 is more preferable, 1 to 4 is further preferable, and 1 to 3 is particularly preferable.
  • the alkyl group and alkoxy group which can be selected as such a substituent may be linear or branched, respectively.
  • the alkyl group that can be selected as R 5 in the general formula (101) is an alkyl group having 1 to 10 carbon atoms. When such a carbon number exceeds 10, when it uses as a monomer of a polyimide, the heat resistance of the polyimide obtained will fall. Further, the number of carbon atoms of the alkyl group that can be selected as R 5 is preferably 1 to 6, and preferably 1 to 5, from the viewpoint that higher heat resistance can be obtained when a polyimide is produced. More preferred is 1 to 4, still more preferred, and 1 to 3 is particularly preferred. Such an alkyl group that can be selected as R 5 may be linear or branched.
  • the plurality of R 5 in the general formula (101) it is possible to obtain higher heat resistance when the polyimide is produced, easy acquisition of raw materials, easier purification, and the like. Therefore, independently of each other, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are more preferable, and a hydrogen atom and a methyl group are particularly preferable.
  • a plurality of R 5 in such a formula may be the same or different from each other, but may be the same from the viewpoint of ease of purification and the like. preferable.
  • R 4 in the formulas (4) to (5) and (101) represents the above general formula (1- It is the same as R 4 in 1), and the preferred one is also the same as R 4 in the general formula (1-1).
  • Such a repeating unit (C1) includes at least one tetracarboxylic dianhydride (C) selected from the compounds represented by the general formulas (14) to (15) and (103), It can form based on the at least 1 sort (s) of aromatic diamine selected from the compound represented by the said General formula (16).
  • Examples of the compound represented by the general formula (14) used as the tetracarboxylic dianhydride (C) include 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA). ), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA), 1,2,3,4-cyclopentanetetracarboxylic Acid dianhydride, hexahydro-1H, 3H-4,8-methanobenzo [1,2-c: 4,5-c ′] difuran-1,3,5,7-tetraone (BHDA), hexahydro-1H, 3H -4,8-ethanobenzo [1,2-c: 4,5-c '] difuran-1,3,5,7-tetraone (BODA), decahydro-1H, 3H-4,10: 5,9-dimethanonaphth [2,3-c:
  • the method for producing such a tetracarboxylic dianhydride (C) is not particularly limited, and a known method can be appropriately employed.
  • a method for producing the compound represented by the general formula (103) a method described in International Publication No. 2015/163314 may be appropriately employed.
  • a tetracarboxylic dianhydride (C) you may use a commercially available thing suitably. Further, such tetracarboxylic dianhydrides (C) may be used singly or in combination of two or more.
  • the polyimide of the present invention contains the repeating unit (A1), the repeating unit (B1), and the repeating unit (C1).
  • the content of the repeating unit (A1) is 10 to 90 mol in terms of a molar ratio with respect to the total amount of the repeating unit (A1), the repeating unit (B1) and the repeating unit (C1) in the polyimide. %, More preferably 25 to 75 mol%, still more preferably 33 to 67 mol%. If the content of the repeating unit (A1) is less than the lower limit, the transparency, heat resistance, and hardness of the polyimide tend to decrease. On the other hand, if the content exceeds the upper limit, the solubility of the polyimide in the solvent tends to decrease. is there.
  • the content of the repeating unit (B1) is 5 to 50 mol in terms of a molar ratio with respect to the total amount of the repeating unit (A1), the repeating unit (B1) and the repeating unit (C1) in the polyimide. %, Preferably 10 to 40 mol%, more preferably 10 to 34 mol%. If the content of such a repeating unit (B1) is less than the lower limit, the heat resistance and hardness of the polyimide tend to be reduced. On the other hand, if the content exceeds the upper limit, the transparency of the polyimide and the solubility in the solvent tend to be reduced. is there.
  • the content of the repeating unit (C1) is 5 to 50 mol in terms of a molar ratio with respect to the total amount of the repeating unit (A1), the repeating unit (B1) and the repeating unit (C1) in the polyimide. %, More preferably 10 to 40 mol%, still more preferably 15 to 34 mol%.
  • the content of such a repeating unit (C1) is less than the lower limit, the transparency of the polyimide and the solubility in a solvent tend to decrease.
  • the content exceeds the upper limit the heat resistance and hardness of the polyimide tend to decrease. is there.
  • the total amount (total amount) of the repeating unit (A1), the repeating unit (B1), and the repeating unit (C1) is 90 mol with respect to all the repeating units contained in the polyimide. % Or more, more preferably 95 to 100 mol%, still more preferably 98 to 100 mol%.
  • the total amount (total amount) of the repeating unit (A1), the repeating unit (B1), and the repeating unit (C1) is less than the lower limit, the transparency of the polyimide, high heat resistance, good solubility in solvents, and high hardness. The balance tends to be lost.
  • Such a polyimide may contain other repeating units as long as the effects of the present invention are not impaired.
  • Such other repeating units are not particularly limited, and examples thereof include known repeating units that can be used as polyimide repeating units.
  • the polyimide of the present invention preferably has a 5% weight loss temperature of 400 ° C. or higher, more preferably 450 to 550 ° C. If such a 5% weight loss temperature is less than the lower limit, sufficient heat resistance tends to be difficult to achieve, and if it exceeds the upper limit, it tends to be difficult to produce a polyimide having such characteristics. It is in.
  • such 5% weight reduction temperature is heated gradually from 40 ° C. as a measurement start temperature after raising the temperature from room temperature (25 ° C.) to 40 ° C. while flowing nitrogen gas in a nitrogen gas atmosphere, It can be determined by measuring the temperature at which the weight of the sample used is reduced by 5%.
  • such a polyimide preferably has a glass transition temperature (Tg) of 250 ° C. or higher, more preferably 300 to 500 ° C. If the glass transition temperature (Tg) is less than the lower limit, sufficient heat resistance tends to be difficult to achieve, and if it exceeds the upper limit, it tends to be difficult to produce a polyimide having such characteristics. It is in.
  • Tg glass transition temperature
  • Such a glass transition temperature (Tg) can be measured in a tensile mode using a thermomechanical analyzer (trade name “TMA8310” manufactured by Rigaku).
  • thermomechanical analyzer (trade name “TMA8310” manufactured by Rigaku) is used as a measuring device, and a polyimide film having a size of 20 mm in length and 5 mm in width (the thickness of the film does not affect the measured value). Although it is not particularly limited, it is preferably 5 to 80 ⁇ m.) Is formed as a measurement sample, and the conditions are a nitrogen atmosphere, a tensile mode (49 mN), and a heating rate of 5 ° C./min.
  • the TMA curve can be obtained by measurement and extrapolated before and after the inflection point of the TMA curve resulting from the glass transition.
  • such a polyimide preferably has a softening temperature of 300 ° C. or higher, more preferably 350 to 550 ° C. If the softening temperature is less than the lower limit, sufficient heat resistance tends to be difficult to achieve, and if it exceeds the upper limit, it tends to be difficult to produce a polyimide having such characteristics.
  • a softening temperature can be measured by a penetration mode using a thermomechanical analyzer (trade name “TMA8310” manufactured by Rigaku). In measurement, the sample size (vertical, horizontal, thickness, etc.) does not affect the measured value, so it can be attached to the jig of the thermomechanical analyzer to be used (trade name “TMA8310” manufactured by Rigaku). The sample size may be appropriately adjusted to a suitable size.
  • Such a polyimide preferably has a thermal decomposition temperature (Td) of 450 ° C. or higher, more preferably 480 to 600 ° C. If the thermal decomposition temperature (Td) is less than the lower limit, it tends to be difficult to achieve sufficient heat resistance. On the other hand, if the thermal decomposition temperature (Td) exceeds the upper limit, a polyimide having such characteristics can be produced. It tends to be difficult.
  • Td thermal decomposition temperature was measured using a TG / DTA220 thermogravimetric analyzer (manufactured by SII Nanotechnology Co., Ltd.) in a nitrogen atmosphere under a heating rate of 10 ° C./min. It can be determined by measuring the temperature at the intersection of the tangent lines drawn on the decomposition curve before and after thermal decomposition under the conditions of
  • the polyimide of the present invention preferably has a hardness of H to 9H, more preferably a hardness of 2H to 5H. If the hardness is less than the lower limit, it tends to be difficult to obtain a sufficiently high level of hardness. It tends to be difficult.
  • a pencil hardness value can be obtained by measuring in accordance with a method defined in JIS K5600-5-4 issued in 1999.
  • the number average molecular weight (Mn) of such a polyimide is preferably 1,000 to 1,000,000, more preferably 10,000 to 500,000 in terms of polystyrene. If such a number average molecular weight is less than the lower limit, it is difficult to achieve sufficient heat resistance, it does not sufficiently precipitate from the polymerization solvent during production, and it tends to be difficult to obtain polyimide efficiently, When the upper limit is exceeded, the viscosity increases, and it takes a long time to dissolve or requires a large amount of solvent, which tends to make processing difficult.
  • the weight average molecular weight (Mw) of such a polyimide is preferably 1000 to 5000000 in terms of polystyrene.
  • a weight average molecular weight (Mw) it is more preferable that it is 5000, It is further more preferable that it is 10,000, It is especially preferable that it is 20000.
  • an upper limit of the numerical range of a weight average molecular weight (Mw) it is more preferable that it is 5000000, It is further more preferable that it is 500,000, It is especially preferable that it is 100,000.
  • the weight average molecular weight is less than the lower limit, it is difficult not only to achieve sufficient heat resistance, but also does not sufficiently precipitate from the polymerization solvent during production, and it tends to be difficult to obtain polyimide efficiently, If the upper limit is exceeded, the viscosity will increase and it will take a long time to dissolve, and a large amount of solvent will tend to make processing difficult.
  • the molecular weight distribution (Mw / Mn) of such polyimide is preferably 1.1 to 5.0, and more preferably 1.5 to 3.0. If the molecular weight distribution is less than the lower limit, it tends to be difficult to produce, while if it exceeds the upper limit, it tends to be difficult to obtain a uniform film.
  • the molecular weight (Mw or Mn) and molecular weight distribution (Mw / Mn) of such a polyimide are measured by a gel permeation chromatography (GPC) measuring device (Degasser: DG-2080-54 manufactured by JASCO, Liquid pump: PU-2080 manufactured by JASCO, interface: LC-NetII / ADC manufactured by JASCO, column: GPC column KF-806M (x2) manufactured by Shodex, column oven: 860-CO manufactured by JASCO, RI detector : Data measured using RI-2031 manufactured by JASCO, column temperature 40 ° C., chloroform solvent (flow rate 1 mL / min.) Can be obtained by conversion with polystyrene.
  • GPC gel permeation chromatography
  • such a polyimide preferably has a linear expansion coefficient (CTE) of 0 to 100 ppm / K, more preferably 10 to 70 ppm / K.
  • CTE linear expansion coefficient
  • the linear expansion coefficient exceeds the upper limit, peeling tends to occur due to thermal history when combined with a metal or an inorganic material having a linear expansion coefficient range of 5 to 20 ppm / K.
  • the linear expansion coefficient is less than the lower limit, the solubility and the film characteristics tend to be lowered.
  • a polyimide film having a size of 20 mm in length and 5 mm in width is not particularly limited because it does not affect the measured value, but is preferably 5 to 80 ⁇ m).
  • a thermomechanical analyzer (trade name “TMA8310”, manufactured by Rigaku) as a measuring device, the conditions of the tension mode (49 mN) and the temperature increase rate of 5 ° C./min are measured. Adopted, raised from room temperature to 200 ° C (first temperature rise), allowed to cool to 30 ° C or less, then raised from that temperature to 400 ° C (second temperature rise).
  • the change in the length of the sample in the vertical direction is measured.
  • 1 in the temperature range of 100 ° C. to 200 ° C. is used.
  • the average value of the change in length per ° C is obtained, and the obtained value is measured as the linear expansion coefficient of polyimide.
  • a value obtained by calculating the average value of the length change per 1 ° C. in the temperature range of 100 ° C. to 200 ° C. based on the TMA curve is adopted. To do.
  • such a polyimide preferably has a sufficiently high transparency when a film is formed, and has a total light transmittance of 80% or more (more preferably 85% or more, particularly preferably 87% or more). ) Is more preferable. Such total light transmittance can be easily achieved by appropriately selecting the type of polyimide or the like.
  • such a polyimide has a haze (turbidity) of 5 to 0 (more preferably 4 to 0, particularly preferably 3 to 0) from the viewpoint of obtaining a higher degree of colorless transparency. preferable. If the haze value exceeds the upper limit, it tends to be difficult to achieve a higher level of colorless transparency.
  • a polyimide those having a yellowness (YI) of 5 to 0 (more preferably 4 to 0, particularly preferably 3 to 0) are obtained from the viewpoint of obtaining a higher degree of colorless transparency. preferable. When such yellowness exceeds the upper limit, it tends to be difficult to achieve a higher level of colorless transparency.
  • YI yellowness
  • Such total light transmittance, haze (turbidity) and yellowness (YI) are measured by a product name “Haze Meter NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd. or manufactured by Nippon Denshoku Industries Co., Ltd.
  • the total light transmittance and haze were measured using a product name “Spectral Color Meter SD6000” (trade name “Haze Meter NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd.).
  • the value measured by using a film made of polyimide having a thickness of 5 to 100 ⁇ m as a sample for measurement can be used.
  • the vertical and horizontal sizes of the measurement sample may be any size that can be arranged at the measurement site of the measurement apparatus, and the vertical and horizontal sizes may be appropriately changed.
  • such total light transmittance is obtained by measuring according to JIS K7361-1 (issued in 1997), and haze (turbidity) is measured according to JIS K7136 (issued in 2000).
  • the yellowness (YI) is obtained by performing measurement in accordance with ASTM E313-05 (issued in 2005).
  • the absolute value of retardation (Rth) in the thickness direction measured at a wavelength of 590 nm is preferably 150 nm or less, more preferably 100 nm or less, and more preferably 50 nm or less in terms of a thickness of 10 ⁇ m. More preferably, it is particularly preferably 25 nm or less. That is, the retardation (Rth) value is preferably ⁇ 150 nm to 150 nm (more preferably ⁇ 100 nm to 100 nm, still more preferably ⁇ 50 to 50 nm, particularly preferably ⁇ 25 to 25 nm).
  • the absolute value of retardation (Rth) in the thickness direction exceeds the upper limit, when used in a display device, the contrast tends to decrease and the viewing angle tends to decrease.
  • the absolute value of the retardation (Rth) falls within the above range, when used in a display device, the effect of suppressing the decrease in contrast and the effect of improving the viewing angle tend to be more advanced.
  • the absolute value of the retardation (Rth) in the thickness direction is from the viewpoint that the reduction in contrast can be suppressed to a higher degree and the viewing angle can be further improved. A lower value is preferred.
  • Such “absolute value of thickness direction retardation (Rth)” is the value of the refractive index (589 nm) of the polyimide film measured as described below using the product name “AxoScan” manufactured by AXOMETRICS as a measuring device. After input to the measuring device, the retardation in the thickness direction of the polyimide film was measured using light with a wavelength of 590 nm under the conditions of temperature: 25 ° C. and humidity: 40%, and the measured value of retardation in the thickness direction thus obtained. Obtain a value (converted value) converted to a retardation value per 10 ⁇ m thickness of the film based on (measured value by automatic measurement (automatic calculation) of the measuring device) and calculate an absolute value from the converted value. Can do.
  • the “absolute value of retardation (Rth) in the thickness direction” can be obtained by calculating the absolute value (
  • the size of the polyimide film of the measurement sample is not particularly limited as long as it is larger than the photometric part (diameter: about 1 cm) of the stage of the measuring instrument. However, the length is 76 mm, the width is 52 mm, and the thickness is 5 to 20 ⁇ m. It is preferable to do.
  • the value of “refractive index of polyimide film (589 nm)” used for the measurement of retardation (Rth) in the thickness direction is an unstretched film made of the same type of polyimide as the polyimide forming the film to be measured for retardation. After forming the film, such an unstretched film is used as a measurement sample (in the case where the film to be measured is an unstretched film, the film can be used as a measurement sample as it is), and measurement is performed.
  • the size of the polyimide film of the measurement sample is not particularly limited as long as it is a size that can be used in the refractive index measurement device, and may be 1 cm square (1 cm in length and width) and 5 to 20 ⁇ m in thickness.
  • the shape of such a polyimide is not particularly limited, and may be, for example, a film shape or a powder shape, or may be a pellet shape by extrusion.
  • the polyimide of the present invention can be formed into a film shape, formed into a pellet shape by extrusion molding, or can be appropriately formed into various shapes by a known method.
  • polyimides are flexible wiring board films, heat-resistant insulating tapes, wire enamels, semiconductor protective coating agents, liquid crystal alignment films, transparent conductive films for organic EL, flexible board films, flexible transparent conductive films, organic Transparent conductive film for thin film solar cell, transparent conductive film for dye-sensitized solar cell, flexible gas barrier film, film for touch panel, TFT substrate film for flat panel detector, seamless polyimide belt for copying machine (so-called transfer belt), Transparent electrode substrate (transparent electrode substrate for organic EL, transparent electrode substrate for solar cell, transparent electrode substrate for electronic paper, etc.), interlayer insulating film, sensor substrate, image sensor substrate, light emitting diode (LED) reflector (LED lighting) Reflector: LED Shot plate), LED illumination cover, LED reflector illumination cover, cover lay film, high ductility composite substrate, semiconductor resist, lithium ion battery, organic memory substrate, organic transistor substrate, organic semiconductor substrate, It is particularly useful as a material for producing a color filter substrate and the like.
  • LED light emitting diode
  • such a polyimide can be formed into a powder or various molded bodies, for example, for automobile parts, aerospace parts, bearing parts, seals, etc. It can also be used as appropriate for materials, bearing parts, gear wheels and valve parts.
  • the polyimide precursor resin of the present invention is at least one selected from repeating units represented by the general formulas (6-1) to (6-3) and (6-4) to (6-6).
  • the repeating units (A2) to (C2) will be described first.
  • the repeating unit (A2) contained in the polyimide precursor resin (more preferably, polyamic acid) of the present invention has the above general formulas (6-1) to (6-3) and (6-4) to (6-6). It is at least 1 sort (s) of repeating units selected from the repeating units represented by these.
  • R 1 , R 2 , R 3 , R 4 and n in the general formulas (6-1) to (6-3) are the same as those in the general formula (1-1) in the repeating unit (A1).
  • R 1 , R 2 , R 3 , R 4 and n are the same as those described above, and preferable examples thereof are also the same as R 1 , R 2 , R 3 , R 4 and n in the general formula (1-1).
  • the repeating units represented by the general formulas (6-1) to (6-3) are obtained by imidizing the repeating unit (for example, when the polyimide precursor resin is a polyamic acid, To form a repeating unit represented by the general formula (1-1). Further, R 6 in the general formula (1-2) in the above general formula (6-4) ⁇ R 6, R 7 in (6-6), R 8 and R 4 is the aforementioned repeating unit (A1), The same as R 7 , R 8 and R 4, and the preferred ones are also the same as R 6 , R 7 , R 8 and R 4 in the general formula (1-2).
  • the repeating units represented by the general formulas (6-4) to (6-6) are obtained by imidizing the repeating unit (for example, when the polyimide precursor resin is a polyamic acid, To form a repeating unit represented by the general formula (1-2).
  • Such a repeating unit (A2) is based on the tetracarboxylic dianhydride (A) and at least one aromatic diamine selected from the compounds represented by the general formula (16). Can be formed.
  • Y 1 and Y 2 are each independently a hydrogen atom, having 1 to 6 carbon atoms (preferably Either an alkyl group having 1 to 3 carbon atoms or an alkylsilyl group having 3 to 9 carbon atoms.
  • Y 1 and Y 2 can change the type of the substituent and the introduction rate of the substituent by appropriately changing the production conditions.
  • Y 1 and Y 2 are both hydrogen atoms (when they become so-called polyamic acid repeating units), the polyimide tends to be easily produced.
  • Y 1 and Y 2 each have 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms). When it is an alkyl group, the storage stability of the polyimide precursor resin tends to be more excellent. When Y 1 and Y 2 are alkyl groups having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), Y 1 and Y 2 are more preferably methyl groups or ethyl groups.
  • Y 1 and Y 2 in the general formulas (6-1) to (6-3) and (6-4) to (6-6) are alkylsilyl groups having 3 to 9 carbon atoms
  • a polyimide precursor The solubility of the body resin tends to be superior.
  • Y 1 and Y 2 are alkylsilyl groups having 3 to 9 carbon atoms
  • Y 1 and Y 2 are more preferably trimethylsilyl groups or t-butyldimethylsilyl groups.
  • the introduction rate of a group other than a hydrogen atom is not particularly limited, but among Y 1 and Y 2
  • each of Y 1 and Y 2 in the repeating unit (A2) is 25% or more of the total amount (more preferably 50% or more, still more preferably 75%).
  • the above is preferably an alkyl group and / or an alkylsilyl group (in this case, Y 1 and Y 2 other than the alkyl group and / or the alkylsilyl group are hydrogen atoms).
  • Y 1 and Y 2 in the repeating unit (A2) the storage stability of the polyimide precursor tends to be more excellent by making 25% or more of the total amount an alkyl group and / or an alkylsilyl group. It is in.
  • the repeating unit (B2) contained in the polyimide precursor resin (more preferably polyamic acid) of the present invention has the above general formulas (7-1) to (7-2) and (8-1) to (8-3). It is at least 1 sort (s) of repeating units selected from the repeating units represented by these.
  • R 4 in such general formulas (7-1) to (7-2) and (8-1) to (8-3) represents the above general formula (2) described in the repeating unit (B1).
  • ⁇ (3) it is similar to the R 4, and also the same as R 4 in the general formula (2) to (3) as its preferred.
  • Y 1 and Y 2 are the general formulas (6-1) to (6-3), respectively.
  • the repeating units represented by the general formulas (7-1) to (7-2) can be converted to the repeating units represented by the general formula (2) by imidizing the repeating units and dehydrating and cyclizing the repeating units.
  • Such repeating units represented by the general formulas (8-1) to (8-3) can be formed by imidizing the repeating unit (for example, the polyimide precursor).
  • the repeating unit represented by the general formula (3) can be formed by imidization and dehydration and ring closure.
  • Such a repeating unit (B2) is based on the tetracarboxylic dianhydride (B) and at least one aromatic diamine selected from the compounds represented by the general formula (16). Can be formed.
  • the repeating unit (C2) contained in the polyimide precursor resin (more preferably polyamic acid) of the present invention has the general formulas (9), (10-1) to (10-3) and (102-1) to (102-1) 102-3) at least one kind of repeating unit selected from the repeating units represented by 102-3).
  • X 1 in the general formula (9), A and R 5 in the general formulas (102-1) to (102-3), and the general formulas (9), (10-1) to (10) 10-3) and R 4 in (102-1) to (102-3) are X 1 in the general formula (4) described in the above repeating unit (C1), and the general formula (101).
  • a and R 5, as well as in the general formula (4) to (5) and (101) in is similar to the R 4, its preferred are also the general formula (4) to (5) and The same as X 1 , A, R 5 and R 4 in (101).
  • Y 1 and Y 2 in the general formulas (9), (10-1) to (10-3) and (102-1) to (102-3) are represented by the general formula (6-1), respectively.
  • the same as Y 1 and Y 2 in (6-3) (the preferable conditions (including the introduction rate of a group (functional group) other than a hydrogen atom) are also the same).
  • such a repeating unit represented by the general formula (9) is obtained by imidizing this (for example, by imidizing and dehydrating and closing a ring when the polyimide precursor resin is a polyamic acid).
  • the repeating units represented by the general formula (4) can be formed, and the repeating units represented by the general formulas (10-1) to (10-3) are: By imidizing this (for example, when the polyimide precursor resin is a polyamic acid, imidizing and dehydrating and ring-closing), the repeating unit represented by the general formula (5) can be formed. It is possible.
  • repeating units represented by the general formulas (102-1) to (102-3) are imidized (for example, when the polyimide precursor resin is a polyamic acid, an imide And the dehydration ring closure), the repeating unit represented by the general formula (101) can be formed.
  • Such a repeating unit (C2) is based on the tetracarboxylic dianhydride (C) and at least one aromatic diamine selected from the compounds represented by the general formula (16). Can be formed.
  • the polyimide precursor resin of the present invention contains the repeating unit (A2), the repeating unit (B2), and the repeating unit (C2).
  • Such polyimide precursor resin the repeating unit (A2), (B2), (C2) depending on the type of Y 1, Y 2 substituents in, 1) a polyamic acid (in the general formula of the repeating units Y 1 and Y 2 are both hydrogen atoms), 2) polyamic acid ester (Y 1 , Y 2 is at least partly an alkyl group), 3) polyamic acid silyl ester (Y 1 , Y 2 is at least part of Alkylsilyl group), and the like.
  • all of Y 1 and Y 2 in the general formulas of the repeating units (A2), (B2) and (C2) are hydrogen atoms. Some polyamic acids are more preferred.
  • the content of the repeating unit (A2) is such that the repeating unit (A2) in the polyimide precursor resin (more preferably, polyamic acid) is repeated.
  • the molar ratio with respect to the total amount of the unit (B2) and the repeating unit (C2) is preferably 10 to 90 mol%, more preferably 25 to 75 mol%, still more preferably 33 to 67 mol%. . If the content of the repeating unit (A2) is less than the lower limit, the transparency, heat resistance, and hardness of the polyimide tend to decrease. On the other hand, if the content exceeds the upper limit, the solubility of the polyimide in the solvent tends to decrease. is there.
  • the content of the repeating unit (B2) is such that the repeating unit (A2) in the polyimide precursor resin (more preferably, polyamic acid) is repeated.
  • the molar ratio with respect to the total amount of the unit (B2) and the repeating unit (C2) is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, still more preferably 10 to 34 mol%. . If the content of such a repeating unit (B2) is less than the lower limit, the heat resistance and hardness of the polyimide tend to be reduced. is there.
  • the content of the repeating unit (C2) is such that the repeating unit (A2) in the polyimide precursor resin (more preferably polyamic acid) is repeated.
  • the molar ratio with respect to the total amount of the unit (B2) and the repeating unit (C2) is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, still more preferably 15 to 34 mol%. . If the content of such a repeating unit (C2) is less than the lower limit, the transparency of the polyimide and the solubility in a solvent tend to decrease. On the other hand, if the upper limit is exceeded, the heat resistance and hardness of the polyimide tend to decrease. is there.
  • the total amount (total amount) of the repeating unit (A2), the repeating unit (B2), and the repeating unit (C2) is a polyimide precursor. It is preferably 90 mol% or more, more preferably 95 to 100 mol%, further preferably 98 to 100 mol%, based on all repeating units contained in the resin (more preferably, polyamic acid). preferable.
  • the total amount (total amount) of the repeating unit (A2), the repeating unit (B2), and the repeating unit (C2) is less than the lower limit, the transparency of the polyimide, high heat resistance, good solubility in solvents, and high hardness The balance tends to be lost.
  • Y 1 and Y 2 is an alkyl group and / or an alkylsilyl group, the total amount of Y 1 and Y 2 in all repeating units It is preferable to introduce 25% or more (more preferably 50% or more, more preferably 75% or more) as an alkyl group and / or an alkylsilyl group.
  • such a polyimide precursor resin may contain other repeating units as long as the effects of the present invention are not impaired.
  • Such other repeating units are not particularly limited and include known repeating units that can be used as polyimide precursor resins (more preferably, repeating units of polyamic acid).
  • the intrinsic viscosity [ ⁇ ] is preferably 0.05 to 3.0 dL / g, and preferably 0.1 to 2.0 dL / g. Is more preferable.
  • the intrinsic viscosity [ ⁇ ] is smaller than 0.05 dL / g, when a film-like polyimide is produced using the intrinsic viscosity [ ⁇ ], the resulting film tends to be brittle, while 3.0 dL / g is reduced. When it exceeds, the viscosity is too high and the processability is lowered, and for example, when a film is produced, it is difficult to obtain a uniform film.
  • Such intrinsic viscosity [ ⁇ ] can be measured as follows.
  • N, N-dimethylacetamide is used as a solvent, and the polyamic acid is dissolved in the N, N-dimethylacetamide so as to have a concentration of 0.5 g / dL, and a measurement sample (solution) is obtained. obtain.
  • the viscosity of the measurement sample is measured using a kinematic viscometer under a temperature condition of 30 ° C., and the obtained value is adopted as the intrinsic viscosity [ ⁇ ].
  • an automatic viscosity measuring device (trade name “VMC-252”) manufactured by Koiso Co., Ltd. is used.
  • such a polyimide precursor resin (more preferably, polyamic acid) can be suitably used when producing the polyimide of the present invention.
  • such a polyimide precursor resin (more preferably a polyamic acid) can be obtained as a reaction intermediate (precursor) in producing the polyimide of the present invention.
  • polyimide precursor resin (more preferably polyamic acid) of this invention was demonstrated, hereafter, manufacture of the polyimide of this invention which can be utilized suitably as a method for manufacturing the said polyimide of this invention. A method will be described.
  • the method for producing the polyimide of the present invention includes: In the presence of a polymerization solvent, At least one tetracarboxylic dianhydride (A) selected from the compounds represented by the general formulas (11-1) to (11-2); At least one tetracarboxylic dianhydride (B) selected from the compounds represented by the general formulas (12) to (13); At least one tetracarboxylic dianhydride (C) selected from the compounds represented by the general formulas (14) to (15) and (103); A tetracarboxylic dianhydride component comprising: The following general formula (16): H 2 N—R 4 —NH 2 (16) Wherein (16), R 4 represents an arylene group having 6 to 40 carbon atoms.
  • the specific steps for obtaining a polyimide by reacting the tetracarboxylic dianhydride component with the aromatic diamine are not particularly limited.
  • Such a method for producing a polyimide of the present invention includes, for example, at least one selected from the tetracarboxylic dianhydride component and the compound represented by the general formula (16) in the presence of a polymerization solvent.
  • Y 1 and Y 2 in the general formula are both hydrogen atoms
  • Y 1 and Y 2 in the general formula are both hydrogen atoms.
  • Polyamic acid containing the repeating unit (B2) and the repeating unit (C2) in which Y 1 and Y 2 in the general formula are both hydrogen atoms (polyamic acid suitable as the polyimide precursor resin of the present invention) And (I) to obtain Step (II) of imidizing the polyamic acid to obtain a polyimide (polyimide of the present invention) containing the repeating unit (A1), the repeating unit (B1), and the repeating unit (C1); It is good also as a method including.
  • steps (I) and (II) that can be suitably used in the method for producing a polyimide of the present invention will be described.
  • the tetracarboxylic dianhydride component is reacted with at least one aromatic diamine selected from the compounds represented by the general formula (16) in the presence of a polymerization solvent. And obtaining the polyamic acid.
  • the tetracarboxylic dianhydride (A) used as the tetracarboxylic dianhydride component is at least one selected from the compounds represented by the general formulas (11-1) to (11-2). It is a compound of this.
  • R 1 , R 2 and R 3 in the formula (11-1) are each independently It is one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and n is an integer of 0 to 12.
  • R 1 in the general formula (11-1) R 2, R 3, n is, R 1 in the general formula (1-1) in which described in the polyimide of the present invention described above, R 2, R 3 and n are the same as those of R 1 , R 2 , R 3 and n in the general formula (1-1).
  • the method for producing the compound represented by the general formula (11-1) (tetracarboxylic dianhydride (A)) used in such step (I) is not particularly limited, and is publicly known. For example, the methods described in Synthesis Example 1, Example 1 and Example 2 of International Publication No. 2011/099518 can be appropriately employed.
  • a plurality of R 6 are each independently a hydrogen atom or a carbon number of 1 1 to 10 selected from the group consisting of alkyl groups, hydroxyl groups and nitro groups, or two R 6 bonded to the same carbon atom together form a methylidene group
  • R 7 and R 8 are each independently one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms.
  • R 8 has the same meaning as R 6, R 7, R 8 in the general formula (1-2), also the general ones that suitable It has the same meaning as R 6 , R 7 and R 8 in formula (1-2).
  • the method for producing the compound represented by the above general formula (11-2) (tetracarboxylic dianhydride (A)) used in the step (I) is not particularly limited, and is publicly known. The method described in International Publication No. 2017/030019 may be employed as appropriate.
  • the tetracarboxylic dianhydride (B) used as the tetracarboxylic dianhydride component is at least one compound selected from the compounds represented by the general formulas (12) to (13).
  • the compound represented by the general formula (12) is pyromellitic anhydride (PMDA), and the compound represented by the general formula (13) is 3,3 ′, 4,4′-biphenyl.
  • the production method of such a compound (tetracarboxylic dianhydride (B)) is not particularly limited, and a known method can be appropriately employed. Moreover, as a tetracarboxylic dianhydride (B), you may utilize a commercial item suitably.
  • the tetracarboxylic dianhydride (C) used as the tetracarboxylic dianhydride component is at least one selected from the compounds represented by the general formulas (14) to (15) and (103).
  • X 1 in the formula (14) is a tetravalent saturated alicyclic group having 4 to 16 carbon atoms. It is a hydrocarbon group.
  • X 1 in the general formula (14) in is the same as the X 1 in the general formula (4) described in the polyimides of the present invention described above, the preferred ones also the general formula (4 ) in the same as the preferred ones of X 1 in.
  • Examples of such a compound represented by the general formula (14) include 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,3,4-cyclopentanetetracarboxylic acid.
  • CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • HPMDA 1,2,4,5-cyclohexanetetracarboxylic dianhydride
  • the compound represented by the general formula (15) is 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA).
  • examples of such tetracarboxylic dianhydrides (C) include 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 1, from the viewpoint of transparency of polyimide and good solubility in solvents.
  • CBDA 2,3,4-cyclobutanetetracarboxylic dianhydride
  • HPMDA 1,2,4,5-cyclohexanetetracarboxylic dianhydride
  • hexahydro-1H, 3H-4,8-methanobenzo 1, 2-c: 4,5-c ′] difuran-1,3,5,7-tetraone, 5,5-bi (hexahydro-4,7-methanoisobenzofuran-1,3-dione) is more preferable.
  • the method for producing the compounds represented by the general formulas (14) to (15) and (103) is not particularly limited, and known methods can be appropriately employed.
  • a manufacturing method of such a compound represented with General formula (103) you may employ
  • the content of the acid dianhydride (A) is preferably 10 to 90% by mole, more preferably 25 to 75% by mole, and still more preferably 33 to 67% by mole. . If the content of the tetracarboxylic dianhydride (A) is less than the lower limit, the transparency, heat resistance, and hardness of the polyimide tend to decrease. It tends to decrease.
  • the content of the acid dianhydride (B) is preferably 5 to 50% by mole, more preferably 10 to 40% by mole, and still more preferably 10 to 34% by mole. . If the content of tetracarboxylic dianhydride (B) is less than the lower limit, the heat resistance and hardness of the polyimide tend to decrease. On the other hand, if the content exceeds the upper limit, the transparency of the polyimide and the solubility in the solvent are high. It tends to decrease.
  • the content of the acid dianhydride (C) is preferably 5 to 50% by mole, more preferably 10 to 40% by mole, and still more preferably 15 to 34% by mole. . If the content of tetracarboxylic dianhydride (C) is less than the lower limit, the transparency of the polyimide and the solubility in the solvent tend to decrease. On the other hand, if the upper limit is exceeded, the heat resistance and hardness of the polyimide are low. It tends to decrease.
  • R 4 in the general formula (16) is the same as the R 4 in the general formula described in the polyimide of the present invention described above (1-1) Preferred examples thereof are also the same as those preferred for R 4 in the general formula (1-1). It does not restrict
  • the polymerization solvent according to the present invention is preferably an organic solvent capable of dissolving both the tetracarboxylic dianhydride component and the aromatic diamine.
  • organic solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, propylene carbonate, tetramethylurea, 1,3- Aprotic polar solvents such as dimethyl-2-imidazolidinone, hexamethylphosphoric triamide, pyridine; phenol solvents such as m-cresol, xylenol, phenol, halogenated phenol; tetrahydrofuran, dioxane, cellosolve, glyme And ether solvents such as benzene, toluene and xylene, ketone solvents such as cyclopentanone and cyclohexanone, and nitrile
  • a polymerization solvent it is more preferable to use an aprotic polar solvent from the viewpoint of solubility in tetracarboxylic dianhydride and aromatic diamine, and among them, N, N-dimethylacetamide and ⁇ - It is particularly preferable to use butyrolactone in combination.
  • N, N-dimethylacetamide and ⁇ -butyrolactone are used in combination as the polymerization solvent, these are excellent in solubility in tetracarboxylic dianhydride and aromatic diamine. It becomes possible to make the polymerization reaction proceed more efficiently (becomes a state in which the reaction is more likely to proceed), thereby making it possible to obtain a polyamic acid varnish having a high degree of polymerization in a shorter time.
  • a tetracarboxylic dianhydride component comprising the tetracarboxylic dianhydride (A), the tetracarboxylic dianhydride (B), and the tetracarboxylic dianhydride (C);
  • the ratio of use with the aromatic diamine is all the tetracarboxylic dianhydride used in the reaction with respect to 1 equivalent of the amino group in the aromatic diamine.
  • the amount of the acid anhydride group is preferably 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents.
  • the total amount of the said tetracarboxylic dianhydride component and the said aromatic diamine (compound represented by General formula (16)) is reaction.
  • the amount is preferably 0.1 to 50% by mass (more preferably 10 to 30% by mass) with respect to the total amount of the solution. If the amount of the organic solvent used is less than the lower limit, the polyamic acid tends not to be obtained efficiently. On the other hand, if it exceeds the upper limit, stirring tends to be difficult due to the increase in viscosity.
  • the tetracarboxylic dianhydride component (tetracarboxylic dianhydrides (A) to (C)) and a compound represented by the general formula (16) are selected.
  • a basic compound may be further added to the organic solvent from the viewpoint of improving the reaction rate and obtaining a polyamic acid having a high degree of polymerization.
  • Such basic compounds are not particularly limited, and examples thereof include triethylamine, tetrabutylamine, tetrahexylamine, 1,8-diazabicyclo [5.4.0] -undecene-7, pyridine, isoquinoline, ⁇ -picoline and the like. Can be mentioned.
  • the amount of the base compound used is preferably 0.001 to 10 equivalents relative to 1 equivalent of the tetracarboxylic dianhydride represented by the general formula (5), preferably 0.01 to More preferably, it is 0.1 equivalent. If the amount of such a basic compound used is less than the lower limit, the effect of addition tends to be lost. On the other hand, if it exceeds the upper limit, it tends to cause coloring or the like.
  • step (I) the tetracarboxylic dianhydride component (tetracarboxylic dianhydrides (A) to (C)) and the aromatic diamine (compound represented by the general formula (16))
  • the reaction temperature at the time of reaction may be appropriately adjusted to a temperature at which these compounds can be reacted, and is not particularly limited, and is preferably ⁇ 40 to 450 ° C. depending on the case. It is more preferably from ⁇ 400 ° C., even more preferably from ⁇ 20 to 200 ° C., particularly preferably from 0 to 100 ° C.
  • tetracarboxylic dianhydride components tetracarboxylic dianhydrides (A) to (C)
  • aromatic diamine represented by the general formula (16)
  • a known method capable of conducting a polymerization reaction of tetracarboxylic dianhydride and aromatic diamine can be appropriately used, and is not particularly limited.
  • reaction temperature or reaction time is less than the lower limit, it tends to be difficult to cause sufficient reaction.
  • the upper limit is exceeded, the probability of mixing a substance (such as oxygen) that degrades the polymer increases and the molecular weight increases. It tends to decrease.
  • the repeating unit Y 1 and Y 2 in the general formula are both a hydrogen atom (B2 )
  • the repeating unit (C2) in which Y 1 and Y 2 in the general formula are both hydrogen atoms can be obtained.
  • the polyamic acid obtained in this way is the same as the polyamic acid described in the polyimide precursor resin of the present invention (when Y 1 and Y 2 are both hydrogen atoms).
  • the repeating unit (A2) in which both Y 1 and Y 2 in the general formula are hydrogen atoms is the same as that described in the polyimide precursor resin of the present invention (the above general formula (6 -1) to (6-3) and at least one repeating unit selected from repeating units represented by (6-4) to (6-6), wherein Y 1 and Y 2 is a repeating unit in which both are hydrogen atoms), and the repeating unit (A2) in which Y 1 and Y 2 in the general formula are both hydrogen atoms includes the tetracarboxylic dianhydride (A), It can form based on the at least 1 sort (s) of aromatic diamine selected from the compound represented by the said General formula (16).
  • the repeating unit (B2) in which both Y 1 and Y 2 in the general formula are hydrogen atoms is also the same as that described in the polyimide precursor resin of the present invention (the above general formula (7-1) At least one repeating unit selected from the repeating units represented by (7-2) and (8-1) to (8-3), wherein Y 1 and Y 2 And the repeating unit (B2) in which both Y 1 and Y 2 in the general formula are hydrogen atoms are the tetracarboxylic dianhydride (B) and the above general formula. It can be formed based on at least one aromatic diamine selected from the compounds represented by (16).
  • the repeating unit (C2) in which Y 1 and Y 2 in the general formula are both hydrogen atoms is the same as that described in the polyimide precursor resin of the present invention (the above general formula (9), ( 10-1) to (10-3) and at least one repeating unit selected from repeating units represented by (102-1) to (102-3), wherein Y 1 and Y 2 is a repeating unit in which both are hydrogen atoms), and the repeating unit (C2) in which both Y 1 and Y 2 in the general formula are hydrogen atoms is the tetracarboxylic dianhydride (C) and And at least one aromatic diamine selected from the compounds represented by the general formula (16).
  • the polyamic acid can be obtained by performing the step (I).
  • the polyimide obtained by the present invention contains other repeating units together with the repeating units (A1), (B1) and (C1), for example, in the step (I), the tetracarboxylic
  • other tetracarboxylic dianhydrides may be used and reacted with the aromatic diamine, or other diamines together with the aromatic diamine represented by the general formula (16). These may be reacted with the tetracarboxylic dianhydride component, and furthermore, polyimides may be produced by appropriately using both such other tetracarboxylic dianhydrides and other diamines. May be.
  • known ones used for the production of polyimide can be used as appropriate.
  • Step (II) is a step of imidizing the polyamic acid to obtain a polyimide containing the repeating unit (A1), the repeating unit (B1), and the repeating unit (C1).
  • the imidization method of the polyamic acid is not particularly limited as long as it is a method capable of imidizing the polyamic acid, and a known method can be appropriately employed.
  • the polyamic acid can be used as a so-called condensing agent.
  • the polyamic acid when adopting a method of imidizing the polyamic acid using an imidizing agent such as a so-called condensing agent, it is preferable to imidize the polyamic acid in a solvent in the presence of the condensing agent. .
  • a solvent the thing similar to the polymerization solvent (organic solvent) used for the manufacturing method of the said polyamic acid can be used conveniently.
  • the polyamic acid is chemically imidized using an imidizing agent such as a condensing agent in the polymerization solvent. It is preferable to employ a step of obtaining the polyimide.
  • the imidization step described in the step (II) is performed using a dehydrating condensing agent (carboxylic acid anhydride) as the condensing agent. More preferably, the polyamic acid is dehydrated and cyclized and imidized using a compound, carbodiimide, acid azide, active esterifying agent, etc.) and a reaction accelerator (tertiary amine, etc.).
  • a dehydrating condensing agent carboxylic acid anhydride
  • the polyamic acid is dehydrated and cyclized and imidized using a compound, carbodiimide, acid azide, active esterifying agent, etc.) and a reaction accelerator (tertiary amine, etc.).
  • reaction obtained by reacting the tetracarboxylic dianhydride component with the aromatic diamine in a polymerization solvent (organic solvent) in step (I) After obtaining a liquid (a reaction liquid containing a polyamic acid containing the repeating unit (A2), the repeating unit (B2), and the repeating unit (C2)), the reaction liquid is used as it is for condensation. Chemical imidization using an agent may be performed.
  • the polyamic acid may be isolated, and the polyamic acid may be separately added to a polymerization solvent and then subjected to chemical imidization.
  • the condensing agent used in the case of employing chemical imidization in such step (II) may be any one that can be used when condensing the polyamic acid to form a polyimide, and will be described later.
  • a known compound used as a so-called “imidizing agent” can be appropriately used.
  • Such a condensing agent is not particularly limited, and examples thereof include carboxylic anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride, carbodiimides such as N, N′-dicyclohexylcarbodiimide (DCC), and diphenyl phosphoric acid.
  • Examples thereof include acid azides such as azide (DPPA), active esterifying agents such as Laudoreagent, and dehydrating condensation agents such as 2-chloro-4,6-dimethoxytriazine (CDMT).
  • acid azides such as azide (DPPA)
  • active esterifying agents such as Laudo reagent
  • dehydrating condensation agents such as 2-chloro-4,6-dimethoxytriazine (CDMT).
  • condensing agents acetic anhydride, propionic anhydride, and trifluoroacetic anhydride are preferable, acetic anhydride and propionic anhydride are more preferable, and acetic anhydride is still more preferable from the viewpoint of reactivity, availability, and practicality.
  • condensing agents may be used singly or in combination of two or more.
  • the reaction accelerator is not particularly limited as long as it can be used when the polyamic acid is condensed to form a polyimide, and a known compound can be appropriately used.
  • a reaction accelerator can also function as an acid scavenger that supplements the acid by-produced during the reaction. Therefore, by using such a reaction accelerator, acceleration of the reaction and the reverse reaction due to the by-product acid are suppressed, and the reaction can proceed efficiently.
  • Such a reaction accelerator is not particularly limited, but more preferably also serves as an acid scavenger.
  • DMAP 4-dimethylaminopyridine
  • DABCO 1,4-diazabicyclo [2.2.2] octane
  • DBN diazabicyclononene
  • DBU diazabicycloundecene
  • reaction accelerators triethylamine, diisopropylethylamine, N-methylpiperidine, and pyridine are preferable from the viewpoint of reactivity, availability, and practicality, triethylamine, pyridine, and N-methylpiperidine are more preferable, and triethylamine, N More preferred is methylpiperidine.
  • Such reaction accelerators may be used alone or in combination of two or more.
  • an azeotropic dehydrating agent benzene, toluene, xylene, etc.
  • water generated when the polyamic acid becomes an imide is removed by azeotropic dehydration. It may be imidized.
  • an azeotropic dehydrating agent may be appropriately used together with the reaction accelerator.
  • Such an azeotropic dehydrating agent is not particularly limited, and may be appropriately selected from known azeotropic dehydrating agents according to the type of material used in the reaction.
  • the polyamic acid obtained after implementing step (I) is isolated from the viewpoint of more efficiently producing polyimide.
  • Reaction obtained by reacting the tetracarboxylic dianhydride component (a mixture of tetracarboxylic dianhydrides (A) to (C)) with the aromatic diamine in a polymerization solvent (organic solvent) It is more preferable to employ a method in which the liquid (reaction liquid containing the polyamic acid) is used as it is, and a condensing agent (imidizing agent) and a reaction accelerator are added to the reaction liquid and imidized.
  • the temperature condition during such chemical imidation is preferably ⁇ 40 ° C. to 200 ° C., more preferably ⁇ 20 ° C. to 150 ° C., and still more preferably 0 to 150 ° C. 50 to 100 ° C. is particularly preferable. If such a temperature exceeds the upper limit, an undesirable side reaction tends to proceed and polyimide cannot be obtained. On the other hand, if the temperature is lower than the lower limit, the reaction rate of chemical imidation decreases or the reaction itself does not proceed. Tend not to be obtained. As described above, when chemical imidization is employed, imidization can be performed in a relatively low temperature range of ⁇ 40 ° C. to 200 ° C., thereby reducing the environmental load. It becomes.
  • reaction time for such chemical imidation is preferably 0.1 to 48 hours. If the reaction temperature or time is less than the lower limit, it tends to be difficult to imidize sufficiently. On the other hand, if the upper limit is exceeded, the mixing probability of substances (such as oxygen) that degrade the polymer is increased. The molecular weight tends to decrease.
  • the amount of the condensing agent used is not particularly limited, but is preferably 0.05 to 4.0 mol, preferably 1 to 2 mol with respect to 1 mol of the repeating unit in the polyamic acid. Is more preferable. If the amount of such a condensing agent (imidizing agent) is less than the lower limit, the reaction rate of chemical imidization tends to decrease, or the reaction itself does not proceed sufficiently and polyimide cannot be obtained sufficiently, When the upper limit is exceeded, an undesirable side reaction proceeds, and thus polyimide cannot be obtained efficiently.
  • the amount of the reaction accelerator used in the chemical imidation is not particularly limited, but is preferably 0.05 to 4.0 mol with respect to 1 mol of the repeating unit in the polyamic acid. More preferably, it is 2 mol. If the amount of the reaction accelerator used is less than the lower limit, the reaction rate of chemical imidization decreases, or the reaction itself does not proceed sufficiently and polyimide cannot be obtained sufficiently. On the other hand, it exceeds the upper limit. As a result, an undesirable side reaction proceeds, and thus polyimide cannot be obtained efficiently.
  • the pressure conditions for performing such chemical imidation are not particularly limited, but are preferably 0.01 hPa to 1 MPa, more preferably 0.1 hPa to 0.3 MPa. If such pressure is less than the lower limit, the solvent, the condensing agent, and the reaction accelerator are gasified, the stoichiometry is lost, the reaction is adversely affected, and the reaction tends to be difficult to proceed sufficiently. On the other hand, when the upper limit is exceeded, an undesirable side reaction proceeds, or the solubility of the polyamic acid tends to decrease and precipitate.
  • the polyamic acid is subjected to a treatment (heating treatment) for heating at a temperature of 60 to 450 ° C. (more preferably 80 to 400 ° C.). It is also possible to adopt a method of making it.
  • the reaction tends to be delayed when the heating temperature is less than the lower limit, and on the other hand, when the upper limit is exceeded, coloring or thermal decomposition causes molecular weight. There is a tendency to decrease.
  • the reaction time (heating time) in the case of employing the method of imidizing by performing the heat treatment is preferably 0.5 to 5 hours. If such a reaction time is less than the lower limit, it tends to be difficult to sufficiently imidize. On the other hand, if it exceeds the upper limit, it tends to be colored or decrease in molecular weight due to thermal decomposition.
  • reaction accelerator In the case of imidization by performing the heat treatment, a so-called reaction accelerator may be used to promote high molecular weight and imidization.
  • a reaction accelerator include known reaction accelerators (triethylamine, diisopropylethylamine, N-methylpiperidine, pyridine, collidine, lutidine, 2-hydroxypyridine, 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo [2.2.2]
  • DMAP 1,4-diazabicyclo [2.2.2]
  • a tertiary amine such as octane (DABCO), diazabicyclononene (DBN), diazabicycloundecene (DBU), etc.
  • DABCO octane
  • DBN diazabicyclononene
  • DBU diazabicycloundecene
  • reaction accelerators triethylamine, diisopropylethylamine, N-methylpiperidine, and pyridine are preferable from the viewpoint of reactivity, availability, and practicality, triethylamine, pyridine, and N-methylpiperidine are more preferable, and triethylamine is preferable. N-methylpiperidine is more preferred.
  • Such reaction accelerators may be used alone or in combination of two or more.
  • the amount of the reaction accelerator used is not particularly limited. The amount is preferably 4.0 mol, more preferably 0.05 to 2.0 mol, and still more preferably 0.05 to 1.0 mol.
  • step (I ) when a method including such steps (I) and (II) is used, and when a method of imidizing by applying the heat treatment during imidization is employed, the step (I ), And a reaction solution obtained by reacting the tetracarboxylic dianhydride component and the aromatic diamine in an organic solvent without isolating the polyamic acid (containing the polyamic acid).
  • the reaction solution may be used as it is, and after the solvent is removed by subjecting the reaction solution to evaporation removal (solvent removal treatment), imidization may be adopted by performing the heat treatment. .
  • solvent removal treatment solvent removal treatment
  • the temperature condition in such a method of evaporating and removing the solvent is preferably 0 to 180 ° C., more preferably 30 to 150 ° C. If the temperature condition in such a solvent removal treatment is less than the lower limit, it tends to be difficult to remove the solvent sufficiently by evaporation, whereas if the upper limit is exceeded, the solvent will boil and the film contains bubbles and voids. Tend to be.
  • the reaction solution obtained may be applied as it is on a substrate (for example, a glass plate), and the solvent may be removed by evaporation and heat treatment, It becomes possible to produce a film-like polyimide by a simple method.
  • the isolation method is not particularly limited, and a known method capable of isolating the polyamic acid can be appropriately employed. Alternatively, a method of isolating as a reprecipitate may be adopted.
  • the step (II) and the step (II) may be performed simultaneously as a series of steps.
  • a method of simultaneously performing the step (I) and the step (II) as a series of steps for example, a process of heating from the step of reacting the tetracarboxylic dianhydride component and the aromatic diamine is performed.
  • the formation of polyamic acid (intermediate) and the subsequent formation of polyimide (imidation) can proceed at the same time, and a method of simultaneously applying the step (I) and the step (II) can be employed.
  • the tetracarboxylic dianhydride component (tetracarboxylic dianhydrides (A) to (C)) and the aromatic diamine (compound represented by the general formula (16)) are reacted in this way.
  • the tetracarboxylic dianhydride component (tetracarboxylic dianhydride (A) is added in the presence of a polymerization solvent.
  • the aromatic diamine (compound represented by the above general formula (16)) are used in the presence of the polymerization solvent and the reaction accelerator.
  • a polyimide By heating and reacting the carboxylic dianhydride component (tetracarboxylic dianhydrides (A) to (C)) and the aromatic diamine (compound represented by the general formula (16)), a polyimide is obtained. Form It is preferable.
  • generation of the polyamic acid in process (I) and imidation of the polyamic acid in process (II) are caused continuously by heating.
  • polyimide is prepared in a solvent.
  • the reaction rate of polyamic acid and imidization can be greatly increased, and the molecular weight can be increased. It becomes.
  • step (I) and the step (II) are simultaneously performed by heating using the reaction accelerator, the reaction between the tetracarboxylic dianhydride and the aromatic diamine proceeds by heating. Since water generated by the reaction can be removed by evaporation, the reaction can be efficiently advanced without using a so-called condensing agent (dehydration condensing agent).
  • condensing agent dehydration condensing agent
  • the tetracarboxylic dianhydride components tetracarboxylic dianhydrides (A) to (C)
  • the aromatic diamine in the general formula (16)
  • the heating The temperature condition is preferably 100 to 250 ° C., more preferably 120 to 250 ° C., and still more preferably 150 to 220 ° C.
  • the reaction temperature is lower than the boiling point of water, so water does not evaporate, the presence of water hinders the progress of the reaction, and the molecular weight of the polyimide is increased.
  • the upper limit is exceeded, side reactions such as thermal decomposition of the solvent occur, and the amount of impurities in the mixed liquid (varnish) of the polyimide and organic solvent obtained after heating increases. When a film is formed using this, the physical properties of the resulting polyimide film tend to deteriorate.
  • the reaction accelerator used in the step includes triethylamine, diisopropylethylamine, N-methylpiperidine, pyridine, Collidine, lutidine, 2-hydroxypyridine, 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo [2.2.2] octane (DABCO), diazabicyclononene (DBN), diazabicycloundecene (DBU)
  • DMAP 1,4-diazabicyclo [2.2.2] octane
  • DBN diazabicyclononene
  • DBU diazabicycloundecene
  • triethylamine, diisopropylethylamine, N-methylpiperidine, and pyridine are preferable, and triethylamine, pyridine, and N-methylpiperidine are more preferable, and triethylamine is preferable.
  • N-methylpi Lysine is more preferable.
  • Such reaction accelerators may be used alone or in combination of two or more.
  • the usage-amount of the reaction accelerator is the tetracarboxylic dianhydride component (tetracarboxylic dianhydride).
  • the total amount (total amount) of the products (A) to (C)) and the aromatic diamine (the compound represented by the general formula (16)) is set to 0.01 to 10 parts by mass.
  • the content is 0.05 to 2 parts by mass.
  • the repeating unit (A1) is the same as described in the polyimide of the present invention (at least selected from repeating units represented by the general formulas (1-1) to (1-2))
  • the repeating unit (A1) is at least one fragrance selected from the tetracarboxylic dianhydride (A) and the compound represented by the general formula (16). Can be formed on the basis of a group diamine.
  • the repeating unit (B1) is the same as that described in the polyimide of the present invention (at least one repeating unit selected from repeating units represented by the above general formulas (2) to (3)). And the repeating unit (B1) includes the tetracarboxylic dianhydride (B) and at least one aromatic diamine selected from the compounds represented by the general formula (16). Can be formed based on. Further, the repeating unit (C1) is the same as that described in the polyimide of the present invention (at least one repeating unit selected from the repeating units represented by the general formulas (4) to (5)). And the repeating unit (C1) includes the tetracarboxylic dianhydride (C) and at least one aromatic diamine selected from the compounds represented by the general formula (16). Can be formed based on.
  • the reaction liquid reaction containing the said polyimide obtained
  • a heating Liquid
  • the heating condition in such a heat curing step is preferably a condition of heating at a temperature of 50 to 350 ° C. (more preferably 50 to 300 ° C.) for 1 to 5 hours.
  • heating conditions temperature and time conditions
  • the solvent cannot be sufficiently dried, and the heat resistance of the film tends to be lowered.
  • the upper limit is exceeded, the drying time is long. As a result, the probability that a side reaction such as oxidation of the terminal amino group proceeds increases, and the transparency tends to decrease.
  • a method for manufacturing a polyimide precursor resin for that can be suitably used a method for manufacturing a polyimide precursor resin of the present invention, the aforementioned polyimide precursor resin classification: 1) Y 1, Y 2 of the polyamic acid (in the general formula of the repeating units Are all hydrogen atoms); 2) polyamic acid ester (Y 1 and Y 2 are at least partly alkyl groups); 3) polyamic acid silyl ester (at least part of Y 1 and Y 2 are alkylsilyl groups); Briefly explained.
  • the method for manufacturing the polyimide precursor resin of this invention is not limited to the following manufacturing methods.
  • Polyamic acid A method that can be suitably used for producing the polyamic acid will be briefly described below. Although it does not restrict
  • Monomer component containing the diester dicarboxylic acid chloride thus obtained (the diester derived from at least one tetracarboxylic dianhydride of tetracarboxylic dianhydrides (A) to (C))
  • a polyimide precursor resin comprising a polyamic acid ester containing repeating units (A2) to (C2) whose part is an alkyl group is obtained.
  • the reaction is carried out at a temperature of 80 ° C. or higher during stirring, the molecular weight tends to fluctuate depending on the temperature history at the time of polymerization, and imidation may proceed due to heat. It tends to be difficult to stably produce the resin.
  • the polyimide precursor resin which consists of the said polyamic acid ester can also be obtained simply by dehydrating and condensing diester dicarboxylic acid and the said aromatic diamine using a phosphorus-type condensing agent, a carbodiimide condensing agent, etc. Since the polyimide precursor comprising a polyamic acid ester obtained by such a method is stable, it can be purified by reprecipitation by adding a solvent such as water or alcohol.
  • the following method can be adopted as a method that can be suitably used for producing the polyamic acid silyl ester. That is, first, the aromatic diamine and a silylating agent are reacted to obtain the silylated aromatic diamine. In addition, you may refine
  • a polyimide precursor resin comprising a polyamic acid silyl ester containing repeating units (A2) to (C2) in which at least a part of Y 1 and Y 2 is an alkylsilyl group can be obtained.
  • the reaction at such a stirring temperature is 80 ° C. or higher, the molecular weight is likely to vary depending on the temperature history at the time of polymerization, and imidization may proceed due to heat, It tends to be difficult to stably produce a polyimide precursor resin.
  • silylating agent which does not contain a chlorine atom it is preferable to use as the silylating agent.
  • a silylating agent that does not contain a chlorine atom in this way, it is not necessary to purify the silylated aromatic diamine, so that the process can be further simplified.
  • silylating agents not containing a chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide, and hexamethyldisilazane.
  • the silylating agent is particularly preferably N, O-bis (trimethylsilyl) acetamide or hexamethyldisilazane because it does not contain a fluorine atom and is low in cost.
  • an amine catalyst such as pyridine, piperidine or triethylamine can be used to accelerate the reaction.
  • an amine catalyst can be used as it is as a polymerization catalyst for the polyimide precursor.
  • a method that can be suitably used for producing the polyamic acid described in the column of “1) Polyamic acid” described above was carried out, and obtained after the reaction.
  • the reaction solution is prepared as it is as a polyamic acid solution.
  • a silylating agent is mixed into the obtained polyamic acid solution and stirred for 1 to 72 hours in the range of 0 to 120 ° C. (preferably 5 to 80 ° C.), whereby the polyimide comprising the polyamic acid silyl ester is prepared.
  • a precursor resin can be obtained (direct method). When the reaction is carried out at a temperature of 80 ° C.
  • a silylating agent that can be used in such a direct method a silylated polyamic acid or a silylating agent that does not contain a chlorine atom can be used because it is not necessary to purify the obtained polyimide.
  • silylating agents not containing a chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide, and hexamethyldisilazane.
  • N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferable because they do not contain a fluorine atom and are low in cost.
  • any of the above-described methods for producing the polyimide precursor resin of the present invention can be carried out in an organic solvent.
  • the polyimide precursor resin solution (varnish of polyimide precursor resin) of the present invention can be easily obtained.
  • the manufacturing method of the polyimide of this invention and the method which can be utilized suitably in order to manufacture the polyimide precursor resin (including polyamic acid) of this invention were demonstrated, hereafter, the polyimide of this invention is demonstrated.
  • the precursor resin solution will be described.
  • the polyimide precursor resin solution of the present invention contains the polyimide precursor resin (preferably polyamic acid) of the present invention and an organic solvent.
  • an organic solvent used for such a polyimide precursor resin solution resin solution: varnish
  • the same solvent as the above-mentioned polymerization solvent can be suitably used.
  • the polyimide precursor resin solution (preferably the polyamic acid solution) of the present invention is a method for producing the above-described polyimide precursor resin of the present invention (for example, when the polyimide precursor is a polyamic acid, the polyamic acid A method that can be suitably used for producing (a method of performing the step (I))) is performed, and the reaction solution obtained after the reaction is used as it is as a polyimide precursor resin solution (for example, a polyimide precursor).
  • a polyamic acid solution may be prepared.
  • the content of the polyimide precursor resin (preferably polyamic acid) in the polyimide precursor resin solution (preferably polyamic acid solution) is not particularly limited, but is preferably 1 to 80% by mass. More preferably, it is mass%. If such a content is less than the lower limit, the production of the polyimide film tends to be difficult. On the other hand, if the content exceeds the upper limit, the production of the polyimide film tends to be difficult.
  • such a polyimide precursor resin solution preferably a polyamic acid solution
  • such a polyimide precursor resin solution preferably a polyamic acid solution
  • the polyimide precursor resin solution of the present invention has been described above. Next, the polyimide solution of the present invention will be described.
  • the polyimide solution of the present invention contains the polyimide of the present invention and an organic solvent.
  • an organic solvent used for such a polyimide solution the same solvent as the polymerization solvent described above can be suitably used.
  • the polyimide solution of the present invention can be used after the reaction when the polyimide obtained by carrying out the above-described method for producing the polyimide of the present invention is sufficiently soluble in the polymerization solvent (organic solvent) used during the production.
  • the obtained reaction solution may be used as a polyimide solution as it is (for example, as an organic solvent (polymerization solvent), by using a material that can sufficiently dissolve the obtained polyimide, and by forming the polyimide in the solvent, after the reaction
  • the obtained reaction liquid can be used as a polyimide solution as it is.
  • the organic solvent used in the polyimide solution of the present invention the same solvents as those described in the above polymerization solvent can be suitably used.
  • an organic solvent used for the polyimide solution of the present invention for example, from the viewpoint of transpiration and removability of the solvent when the polyimide solution is used as a coating solution, a halogen-based solvent having a boiling point of 200 ° C.
  • Dichloromethane (boiling point 40 ° C), trichloromethane (boiling point 62 ° C), carbon tetrachloride (boiling point 77 ° C), dichloroethane (boiling point 84 ° C), trichloroethylene (boiling point 87 ° C), tetrachloroethylene (boiling point 121 ° C), tetrachloroethane (boiling point) 147 ° C), chlorobenzene (boiling point 131 ° C), o-dichlorobenzene (boiling point 180 ° C), etc.).
  • N-methyl-2-pyrrolidone, N, N are used from the viewpoint of solubility, film forming property, productivity, industrial availability, existence of existing equipment, and price.
  • -Dimethylacetamide, ⁇ -butyrolactone, propylene carbonate, tetramethylurea, 1,3-dimethyl-2-imidazolidinone are preferred
  • N-methyl-2-pyrrolidone, N, N-dimethylacetamide, ⁇ -butyrolactone, tetramethyl Urea is more preferable
  • N, N-dimethylacetamide and ⁇ -butyrolactone are particularly preferable.
  • such a polyimide solution can be suitably used as a coating solution for producing various processed products.
  • the polyimide solution of the present invention is used as a coating liquid, and this is coated on a substrate to obtain a coating film, and then the solvent is removed to remove the polyimide film. It may be formed.
  • a coating method is not particularly limited, and a known method (spin coating method, bar coating method, dip coating method, etc.) can be appropriately used.
  • the content (dissolution amount) of the polyimide is not particularly limited, but is preferably 1 to 75% by mass, and more preferably 10 to 50% by mass.
  • the content is less than the lower limit, the film thickness after film formation tends to be thin when used for film formation and the like.
  • the content exceeds the upper limit a part tends to be insoluble in the solvent. .
  • such a polyimide solution includes an antioxidant (phenolic, phosphite, thioether, etc.), ultraviolet absorber, hindered amine light stabilizer, nucleating agent, resin additive ( Additives such as fillers, talc, glass fibers, etc.), flame retardants, processability improvers and lubricants may be further added.
  • an antioxidant phenolic, phosphite, thioether, etc.
  • ultraviolet absorber hindered amine light stabilizer
  • nucleating agent resin additive
  • Additives such as fillers, talc, glass fibers, etc.
  • flame retardants such as fillers, talc, glass fibers, etc.
  • processability improvers and lubricants may be further added.
  • limit especially as these additives A well-known thing can be utilized suitably, and a commercially available thing may be utilized.
  • the polyimide film of the present invention is made of the polyimide of the present invention.
  • the polyimide film of the present invention may be a film made of polyimide described as the polyimide of the present invention.
  • the thickness of the polyimide film of the present invention is not particularly limited, but is preferably 1 to 500 ⁇ m, and more preferably 10 to 200 ⁇ m. If the thickness is less than the lower limit, the strength tends to be reduced and handling tends to be difficult.On the other hand, if the upper limit is exceeded, multiple coatings may be required or processing may be complicated. Tend to occur.
  • the form of such a polyimide film is not particularly limited as long as it is in the form of a film, and can be appropriately designed into various shapes (disk shape, cylindrical shape (film processed into a cylindrical shape), etc.) When manufactured using a polyimide solution, the design can be changed more easily.
  • the method for preparing such a polyimide film of the present invention is not particularly limited.
  • the reaction liquid (polyamic acid solution) obtained by the above step (I) is applied on a substrate to remove the solvent.
  • a method of preparing a polyimide film by imidization may be employed, or a method of preparing a polyimide film by applying the polyimide solution of the present invention on a substrate and removing the solvent is employed. May be.
  • such a polyimide film of the present invention is composed of the polyimide of the present invention, it is possible not only to have sufficiently excellent transparency but also to have sufficiently high hardness. is there. Therefore, such a polyimide film of the present invention includes, for example, a film for a flexible wiring substrate, a film used for a liquid crystal alignment film, a transparent conductive film for organic EL, a film for organic EL lighting, a flexible substrate film, and a substrate for flexible organic EL.
  • Film flexible transparent conductive film, transparent conductive film, transparent conductive film for organic thin film solar cell, transparent conductive film for dye-sensitized solar cell, flexible gas barrier film, film for touch panel, front film for flexible display, Back film for flexible display, TFT substrate film for flat panel detector, polyimide belt, coating agent, barrier film, sealing material, interlayer insulating material, passivation film, TAB (Tape Auto) ated Bonding) tape, an optical waveguide, a color filter substrate, a semiconductor coating agent, it can be appropriately utilized heat insulating tape, for applications such as wire enamels.
  • TAB TAB
  • Identification of the molecular structure of the compound obtained in each example or the like was performed by infrared absorption spectrum measurement (IR measurement). Note that an IR measuring device (manufactured by JASCO Corporation, trade name: FT / IR-4100) was used as the measuring apparatus.
  • the total light transmittance value (unit:%), haze (turbidity: HAZE) and yellowness (YI) of the polyimide obtained in each example etc. are used for measuring the film obtained in each example as it is.
  • the measurement is performed using a product name “Haze Meter NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd. or a product name “Spectral Color Meter SD6000” manufactured by Nippon Denshoku Industries Co., Ltd. as a measuring device.
  • ⁇ Measurement of 5% weight loss temperature> The 5% weight loss temperature of the compound obtained in each example, etc., was measured using a thermogravimetric analyzer (“TG / DTA220” manufactured by SII Nanotechnology Co., Ltd.) using the polyimide film produced in each example. The temperature was raised from room temperature to 40 ° C. while flowing nitrogen gas. The temperature was determined by measuring the temperature at which the weight of the sample used was reduced by 5%.
  • Pencil hardness was measured using the polyimide film obtained in each example. That is, with respect to the polyimide film obtained in each Example etc., the hardness of the surface of the polyimide film was measured using a pencil hardness tester (trade name “TQC Pencil Scratch Hardness Tester”) manufactured by Cortemac Co., Ltd. in 1999. It was determined by measuring each in accordance with the method specified in JIS K5600-5-4 issued in 2009.
  • a polyimide solution a viscous uniform light yellow reaction liquid (polyimide solution).
  • a polyimide derived from the aromatic diamine (TFMB) and the tetracarboxylic dianhydride component (a mixture of CpODA, s-BPDA, and HPMDA) was prepared by a heating step, and a reaction solution (polyimide) was prepared. Solution).
  • the reaction between the aromatic diamine (TFMB) and the tetracarboxylic dianhydride component mixture of CpODA, s-BPDA, and HPMDA
  • the imidization proceeds to form a polyimide.
  • the reaction solution was spin-coated on a glass plate (length: 75 mm, width 50 mm, thickness 1.3 mm) to form a coating film on the glass plate.
  • the glass plate on which the coating film was formed was put into an oven, and after standing in a nitrogen atmosphere at a temperature condition of 60 ° C. for 4 hours, the temperature was raised from 60 ° C. to 250 ° C., The coating film is cured by allowing it to stand for 1 hour under a temperature condition of 250 ° C. (hereinafter referred to as “second temperature (firing temperature)” for convenience), and a thin film (polyimide film) made of polyimide on a glass plate. ) was obtained.
  • second temperature firing temperature
  • the polyimide-coated glass thus obtained is immersed in water at 90 ° C. for 0.5 hours, and the polyimide film is recovered by peeling off the polyimide film from the glass substrate.
  • a film (polyimide film) was obtained.
  • the film thickness of the polyimide film thus obtained was 23 ⁇ m.
  • Example 2 The amount of the compound (CpODA) represented by the general formula (28) is changed from 1.29 g (3.35 mmol) to 1.92 g (4.99 mmol), and the compound represented by the general formula (30) Implementation was performed except that the amount of (HPMDA) used was changed from 0.75 g (3.35 mmol) to 0.38 g (1.69 mmol) and the amount of dimethylacetamide used was changed from 11.9 g to 13.0 g.
  • a colorless transparent film (polyimide film) made of polyimide was obtained in the same manner as in Example 1. The film thickness of the polyimide film thus obtained was 27 ⁇ m.
  • Example 3 The amount of the compound (CpODA) represented by the general formula (28) is changed from 1.29 g (3.35 mmol) to 1.92 g (5.00 mmol), and the compound represented by the general formula (13)
  • the amount of (s-BPDA) used was changed from 0.99 g (3.35 mmol) to 0.73 g (2.49 mmol), and the amount of the compound represented by the general formula (30) (HPMDA) was changed to 0.
  • a colorless transparent film (polyimide film) was obtained.
  • the film thickness of the polyimide film thus obtained was 25 ⁇ m.
  • Example 4 The amount of the compound (CpODA) represented by the general formula (28) is changed from 1.29 g (3.35 mmol) to 2.30 g (5.98 mmol), and the compound represented by the general formula (13) The amount of (s-BPDA) used was changed from 0.99 g (3.35 mmol) to 0.58 g (1.98 mmol), and the amount of the compound represented by the above general formula (30) (HPMDA) was changed to 0.8. It is made of polyimide in the same manner as in Example 1, except that 75 g (3.35 mmol) is changed to 0.45 g (2.02 mmol) and the amount of dimethylacetamide used is changed from 11.9 g to 13.3 g. A colorless transparent film (polyimide film) was obtained. The film thickness of the polyimide film thus obtained was 33 ⁇ m.
  • Example 5 The amount of the compound (CpODA) represented by the general formula (28) was changed from 1.29 g (3.35 mmol) to 2.54 g (6.61 mmol), and the compound represented by the general formula (13) The amount of (s-BPDA) used was changed from 0.99 g (3.35 mmol) to 0.42 g (1.41 mmol), and the amount of the compound represented by the general formula (30) (HPMDA) was changed to 0. It is made of polyimide in the same manner as in Example 1 except that 75 g (3.35 mmol) is changed to 0.44 g (1.97 mmol) and the amount of dimethylacetamide used is changed from 11.9 g to 13.5 g. A colorless transparent film (polyimide film) was obtained. The film thickness of the polyimide film thus obtained was 31 ⁇ m.
  • Example 2 In the same manner as in Example 1 except that 0.65 g (3.30 mmol) of a compound represented by the formula (Tokyo Chemical Industry Co., Ltd .: 1,2,3,4-cyclobutanetetracarboxylic dianhydride: CBDA) was used. A colorless transparent film (polyimide film) made of polyimide was obtained. The film thickness of the polyimide film thus obtained was 14 ⁇ m.
  • a compound represented by the formula Tokyo Chemical Industry Co., Ltd .: 1,2,3,4-cyclobutanetetracarboxylic dianhydride: CBDA
  • Example 7 The amount of the compound (CpODA) represented by the general formula (28) is changed from 1.29 g (3.35 mmol) to 1.93 g (5.02 mmol), and the compound represented by the general formula (13) Instead of using a product manufactured by Tokyo Chemical Industry Co., Ltd.
  • (s-BPDA) a product manufactured by Mitsubishi Chemical Corporation (trade name “BPDA (3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride)”
  • the amount of the compound (s-BPDA) represented by the general formula (13) was changed from 0.99 g (3.35 mmol) to 0.73 g (2.49 mmol), and the general formula (30 ) Instead of using 0.75 g (3.35 mmol) of the compound (HPMDA) represented by the above formula (15), a compound represented by the above general formula (15) (produced by Tokyo Chemical Industry Co., Ltd.
  • Polyimide in the same manner as in Example 1, except that 1.11 g (2.50 mmol) of (den) diphthalic anhydride: 6FDA) was used and the amount of dimethylacetamide was changed from 11.9 g to 15.0 g. A colorless transparent film (polyimide film) was obtained, and the film thickness of the polyimide film thus obtained was 20 ⁇ m.
  • Example 8 The amount of the compound (CpODA) represented by the general formula (28) is changed from 1.29 g (3.35 mmol) to 2.54 g (6.61 mmol), and the compound represented by the general formula (30) The amount of (HPMDA) used was changed from 0.75 g (3.35 mmol) to 0.45 g (1.99 mmol), and 0.99 g of the compound (s-BPDA) represented by the above general formula (13) was used. (3.35 mmol) In the same manner as in Example 1 except that 0.31 g (1.41 mmol) of the compound represented by the above general formula (12) (pyromellitic anhydride: PMDA) was used instead of using it. A colorless transparent film (polyimide film) made of polyimide was obtained. The film thickness of the polyimide film thus obtained was 22 ⁇ m.
  • Example 9 The amount of the compound (CpODA) represented by the general formula (28) is changed from 1.29 g (3.35 mmol) to 1.92 g (5.00 mmol), and the compound represented by the general formula (30) The amount of (HPMDA) used was changed from 0.75 g (3.35 mmol) to 0.37 g (1.67 mmol), and the amount of compound (s-BPDA) represented by the general formula (13) was changed to It consists of polyimide like Example 1 except having changed from 0.99g (3.35mmol) to 0.98g (3.33mmol) and having changed the usage-amount of dimethylacetamide from 11.9g to 13g. A colorless transparent film (polyimide film) was obtained. The film thickness of the polyimide film thus obtained was 24 ⁇ m.
  • Example 10 The amount of the compound (CpODA) represented by the general formula (28) is changed from 1.29 g (3.35 mmol) to 0.96 g (2.50 mmol), and the compound represented by the general formula (13)
  • the amount of (s-BPDA) used was changed from 0.99 g (3.35 mmol) to 0.74 g (2.50 mmol)
  • the compound (HPMDA) represented by the general formula (30) was changed to 0.75 g (3 .35 mmol) 2.22 g of the compound represented by the above general formula (15) (manufactured by Tokyo Chemical Industry Co., Ltd .: 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride: 6FDA) instead of using (5 mmol) 0.0000) and a transparent and colorless film made of polyimide in the same manner as in Example 1 except that the amount of dimethylacetamide used was changed from 11.9 g to 15.6 g. Polyimide film) was obtained.
  • the tetracarboxylic dianhydride (BzDA) represented by these was prepared.
  • Example 11 The amount of the compound (CpODA) represented by the general formula (28) is changed from 1.29 g (3.35 mmol) to 1.28 g (3.33 mmol), and the compound represented by the general formula (13)
  • the amount of (s-BPDA) used was changed from 0.99 g (3.35 mmol) to 0.98 g (3.33 mmol), and the compound represented by the general formula (30) (HPMDA) was changed to 0.75 g (3 .35 mmol) 1.35 g (3.33 mmol) of the compound (BzDA) represented by the general formula (111) obtained in Synthesis Example 2 was used instead of using 11.9 g of dimethylacetamide.
  • a colorless transparent film (polyimide film) made of polyimide was obtained in the same manner as in Example 1 except that the amount was changed from 14.6 g to 14.6 g.
  • the film thickness of the polyimide film thus obtained was 34 ⁇ m.
  • Example 12 The amount of the compound (CpODA) represented by the general formula (28) is changed from 1.29 g (3.35 mmol) to 0.96 g (2.50 mmol), and the compound represented by the general formula (13)
  • the amount of (s-BPDA) used was changed from 0.99 g (3.35 mmol) to 0.74 g (2.50 mmol), and the compound (HPMDA) represented by the general formula (30) was changed to 0.75 g (3 .35 mmol)
  • the amount of dimethylacetamide used was changed from 11.9 g to 9 0.2 g and a colorless transparent film made of polyimide (polyimide) in the same manner as in Example 1 except that the amount of ⁇ -butyrolactone used was changed from 12.9 g to 6.9 g. Irumu) was obtained.
  • the film thickness of the polyimide film thus obtained was
  • BNBDA tetracarboxylic dianhydride
  • Example 14 The amount of the compound (TFMB) represented by the general formula (29) is changed from 3.20 g (9.98 mmol) to 6.45 g (20.1 mmol), and the compound represented by the general formula (28) Instead of using 1.29 g (3.35 mmol) of (CpODA), 3.30 g (10.0 mmol) of the compound (BNBDA) represented by the above general formula (121) was used, and represented by the above general formula (13). The amount of the compound (s-BPDA) used is changed from 0.99 g (3.35 mmol) to 1.47 g (5.00 mmol), and the amount of the compound represented by the general formula (30) (HPMDA) is changed.
  • a colorless transparent film (polyimide film) made of polyimide was obtained in the same manner as in Example 1 except that the coating was changed to bar coating.
  • the film thickness of the polyimide film thus obtained was 16 ⁇ m.
  • Example 15 The amount of the compound (TFMB) represented by the following general formula (29) was changed from 3.20 g (9.98 mmol) to 5.76 g (18.0 mmol), and the compound represented by the above general formula (28) Instead of using 1.29 g (3.35 mmol) of (CpODA), 1.98 g (6.00 mmol) of the compound (BNBDA) represented by the above general formula (121) was used, and represented by the above general formula (13). The amount of the compound (s-BPDA) used is changed from 0.99 g (3.35 mmol) to 1.77 g (6.00 mmol), and the amount of the compound represented by the general formula (30) (HPMDA) is changed.
  • a colorless transparent film (polyimide film) made of polyimide was obtained in the same manner as in Example 1 except that the coating was changed to bar coating.
  • the film thickness of the polyimide film thus obtained was 23 ⁇ m.
  • the polyimides obtained in Examples 1 to 8 in Examples 1 to 8, the repeating unit (A1), the repeating unit (B1), and the repeating unit (C1)
  • the total light transmittance is 89% or more
  • HAZE is 0.8 or less
  • YI was confirmed to be 3.0 or less.
  • the polyimides obtained in Examples 9 to 13 in Examples 9 to 13, the repeating unit (A1), the repeating unit (B1), and the repeating unit ( The formation of a polyimide containing C1) is apparent from the type of compound used, etc.
  • the total light transmittance is 90% or more, and HAZE is 0.8 or less.
  • YI was confirmed to be 3.7 or less.
  • the polyimides obtained in Examples 14 to 15 polyimides containing the repeating unit (A1), the repeating unit (B1), and the repeating unit (C1)
  • the total light transmittance is 90% or more, HAZE is 1.0 or less, and YI is 2.9 or less. It was confirmed that.
  • a polyimide that has a sufficiently high level of hardness while having a sufficiently high level of transparency a polyimide solution containing the polyimide, and the polyimide It becomes possible to provide a method for producing a polyimide that can efficiently and reliably produce the polyimide using the film. Furthermore, according to the present invention, it is possible to provide a polyimide precursor resin that can be suitably used for producing the polyimide, and a polyimide precursor resin solution containing the polyimide precursor resin. Become.
  • Such a polyimide of the present invention includes, for example, a film for a flexible wiring board, a heat-resistant insulating tape, a wire enamel, a semiconductor protective coating agent, a liquid crystal alignment film, a transparent conductive film for organic EL, a flexible substrate film, and a flexible transparent conductive material.
  • Films transparent conductive films for organic thin film solar cells, transparent conductive films for dye-sensitized solar cells, various gas barrier film substrates (flexible gas barrier films, etc.), touch panel films, flat panel detector TFT substrate films, copying Seamless polyimide belts for machines (so-called transfer belts), transparent electrode substrates (transparent electrode substrates for organic EL, transparent electrode substrates for solar cells, transparent electrode substrates for electronic paper, etc.), interlayer insulating films, sensor substrates, image sensor substrates, Light emitting diode (ED) reflector (LED illumination reflector: LED reflector), LED illumination cover, LED reflector illumination cover, coverlay film, high ductility composite substrate, semiconductor resist, lithium ion battery, organic memory It is useful as a material for manufacturing a substrate for an organic transistor, a substrate for an organic transistor, a substrate for an organic semiconductor, a color filter base material and the like.
  • ED Light emitting diode
  • LED illumination reflector LED illumination reflector: LED reflector
  • LED illumination cover LED reflect

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Abstract

L'invention concerne un polyimide qui comprend une unité de répétition (A1) spécifique, une unité de répétition (B1) spécifique, et une unité de répétition (C1) spécifique.
PCT/JP2017/035847 2016-10-07 2017-10-02 Polyimide, résine de précurseur de polyimide, solution de ceux-ci, procédé de fabrication de polyimide, et film mettant en œuvre ce polyimide WO2018066522A1 (fr)

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WO2022054850A1 (fr) * 2020-09-09 2022-03-17 Ｋｊケミカルズ株式会社 Solvant destiné à la synthèse de résine et procédé de production de résine synthétique à l'aide dudit solvant
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