WO2023013401A1 - Composition d'acide polyamique et composition de polyimide, film de polyimide et substrat de panneau d'affichage - Google Patents

Composition d'acide polyamique et composition de polyimide, film de polyimide et substrat de panneau d'affichage Download PDF

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WO2023013401A1
WO2023013401A1 PCT/JP2022/028046 JP2022028046W WO2023013401A1 WO 2023013401 A1 WO2023013401 A1 WO 2023013401A1 JP 2022028046 W JP2022028046 W JP 2022028046W WO 2023013401 A1 WO2023013401 A1 WO 2023013401A1
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formula
compound represented
polyamic acid
polyimide
tetracarboxylic dianhydride
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PCT/JP2022/028046
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English (en)
Japanese (ja)
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健一 福川
穣 久宗
達宣 浦上
佳広 坂田
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三井化学株式会社
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Priority to JP2023540232A priority Critical patent/JPWO2023013401A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets

Definitions

  • the present disclosure relates to polyamic acid compositions and polyimide compositions, polyimide films, and display panel substrates.
  • inorganic glass which is a transparent material
  • inorganic glass has a high specific gravity (weight) and low flexibility and impact resistance. Therefore, application of a polyimide film, which is excellent in lightness, impact resistance, workability and flexibility, to a panel substrate of a display device has been studied.
  • the panel substrate of the display device is required to have high transparency.
  • the panel substrate may be heated in the process of forming elements such as thin film transistors and transparent electrodes on the panel substrate. Therefore, the panel substrate is also required to have high heat resistance.
  • the diamine contains 2,2-bis(trifluoromethyl)benzidine (TFMB), and the tetracarboxylic dianhydride contains 3,3',4,4' Polyimide films derived from polyamic acids including -biphenyltetracarboxylic dianhydride (BPDA) and 9,9′-bis(3,4′-dicarboxyphenyl)fluoric dianhydride (BPAF) have been proposed.
  • BPDA -biphenyltetracarboxylic dianhydride
  • BPAF 9,9′-bis(3,4′-dicarboxyphenyl)fluoric dianhydride
  • a polyimide film obtained from a polyamic acid in which the diamine contains 2,2-bistrifluoromethylbenzidine (TFMB) and the tetracarboxylic dianhydride contains pyromellitic dianhydride (PMDA) has also been proposed.
  • TFMB 2,2-bistrifluoromethylbenzidine
  • PMDA pyromellitic dianhydride
  • low-CTE polyimides are polyimides derived from 2,3,6,7-naphthalenetetracarboxylic dianhydride (NTCDA) and 2,2-bis(trifluoromethyl)benzidine (TFMB).
  • NTCDA 2,3,6,7-naphthalenetetracarboxylic dianhydride
  • TFMB 2,2-bis(trifluoromethyl)benzidine
  • the polyimide film of Patent Document 1 did not have sufficiently low thermal expansion.
  • the polyimide film of Patent Document 2 has low thermal expansion, pyromellitic dianhydride (PMDA) tends to cause coloration and tends to increase the b * value.
  • PMDA pyromellitic dianhydride
  • excellent flexibility bending resistance
  • the polyimide film of Non-Patent Document 1 exhibits low thermal expansion, it has low bending resistance, and the b * value sometimes increases depending on the thermal imide temperature.
  • a polyamic acid composition capable of imparting a polyimide film having both sufficiently low thermal expansion and bending resistance without increasing the b * value
  • An object of the present invention is to provide a polyimide composition.
  • Another object of the present invention is to provide a polyimide film and a display panel substrate using the polyimide composition.
  • the polyamic acid composition of the present disclosure contains a polyamic acid, the polyamic acid contains a structural unit derived from a tetracarboxylic dianhydride and a structural unit derived from a diamine, and the tetracarboxylic acid di
  • the anhydride includes a compound represented by formula (a1) and a compound represented by formula (a2) and/or a compound represented by formula (a3), (In formula (a1), R 1 and R 2 are each independently an alkyl group having 1 to 4 carbon atoms, m and n are each an integer of 0 to 2, and m+n is 3 or less) (In formula (a3), R 3 and R 4 are each independently an alkyl group having 1 to 4 carbon atoms, o and p are each an integer of 0 to 3, and o+p is 3 or less)
  • the diamine contains a compound represented by formula (b1), The content of the compound represented by the formula (a1) is 10 mol% or more with respect to the
  • the content of the compound represented by the formula (a1) is 30 to 80 mol% with respect to the total amount of the tetracarboxylic dianhydride, according to any one of [1] to [4] polyamic acid composition.
  • the total amount of the compound represented by the formula (a2) and the compound represented by the formula (a3) is 10 to 70 mol% with respect to the total amount of the tetracarboxylic dianhydride, [ 1]
  • the tetracarboxylic dianhydride further includes a compound represented by formula (a4), or
  • the diamine further comprises a compound represented by formula (b2), (In formulas (a4) and (b2), R 5 , R 6 , R 7 and R 8 are each independently an alkyl group having 1 to 4 carbon atoms, q, r, s and t are each an integer from 0 to 3, and q+r and s+t are each 3 or less)
  • the polyamic acid composition according to any one of [1] to [6].
  • the total amount of the compound represented by the formula (a4) and the compound represented by the formula (b2) is 0.5 to 15 mol% with respect to the total of the diamine and the tetracarboxylic dianhydride.
  • the polyamic acid composition is thermally imidized at 350° C. to form a polyimide film having a thickness of 10 ⁇ m, the b * value in the L * a * b * color system is 8.0 or less.
  • the polyamic acid composition according to any one of to [9]. [11] The polyamic acid composition is thermally imidized at 350° C. to form a polyimide film having a thickness of 10 ⁇ m. The polyamic acid composition according to any one of [1] to [9].
  • the polyimide composition of the present disclosure includes a polyimide, the polyimide includes a structural unit derived from a tetracarboxylic dianhydride and a structural unit derived from a diamine, and the tetracarboxylic dianhydride is , a compound represented by formula (a1) and a compound represented by formula (a2) and/or a compound represented by formula (a3), (In formula (a1), R 1 and R 2 are each independently an alkyl group having 1 to 4 carbon atoms, m and n are each an integer of 0 to 2, and m+n is 3 or less) (In formula (a3), R 3 and R 4 are each independently an alkyl group having 1 to 4 carbon atoms, o and p are each an integer of 0 to 3, and o+p is 3 or less)
  • the diamine contains a compound represented by formula (b1), The content of the compound represented by the formula (a1) is 10 mol% or more with respect to the total amount of the total
  • the content of the compound represented by the formula (a1) is 30 to 80 mol% relative to the total amount of the tetracarboxylic dianhydride, according to any one of [12] to [15] polyimide composition.
  • the total amount of the compound represented by the formula (a2) and the compound represented by the formula (a3) is 10 to 70 mol% with respect to the total amount of the tetracarboxylic dianhydride,
  • the polyimide composition according to any one of [16].
  • the tetracarboxylic dianhydride further includes a compound represented by formula (a4), or
  • the diamine further comprises a compound represented by formula (b2), (In formulas (a4) and (b2), R 5 , R 6 , R 7 and R 8 are each independently an alkyl group having 1 to 4 carbon atoms, q, r, s and t are each an integer from 0 to 3, and q+r and s+t are each 3 or less) [12]
  • the polyimide composition according to any one of [17].
  • the total amount of the compound represented by the formula (a4) and the compound represented by the formula (b2) is 0.5 to 15 mol% with respect to the sum of the diamine and the tetracarboxylic dianhydride.
  • the polyimide composition according to any one of [12] to [20] which has a linear thermal expansion coefficient of ⁇ 10 to 30 ppm/K at 100 to 350° C. when formed into a film.
  • [23] comprising the polyimide composition according to any one of [12] to [22], polyimide film.
  • a display panel substrate comprising the polyimide film according to any one of [23] to [25].
  • a polyamic acid composition and a polyimide composition capable of imparting a polyimide film having both sufficiently low thermal expansion and bending resistance while suppressing an increase in the b * value.
  • a polyimide film and a display panel substrate using the polyimide composition can also be provided.
  • a numerical range represented using “ ⁇ ” means a range that includes the numerical values before and after " ⁇ " as lower and upper limits, respectively.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise.
  • the present inventors have found that by containing the compound represented by the formula (a1) as a tetracarboxylic dianhydride, while suppressing the coloring of the resulting polyimide film (without increasing the b * value), It has been found that the CTE can be lowered.
  • the naphthalene ring has a rigid structure and tends to increase the orientation, the CTE of the film can be easily lowered.
  • the benzene ring easily absorbs light due to the formation of an intermolecular charge transfer complex accompanying the donor-acceptor with two adjacent acid dianhydride sites, and 1,4,5,8-naphthalenetetracarboxylic acid Dianhydrides and condensed rings in which three or more benzene rings are condensed (for example, 3,4,9,10-perylenetetracarboxylic dianhydride, etc.) have a structure similar to a dye compound, and the ⁇ electrons in the molecule Since the conjugated system is extended, it is easy to absorb light.
  • the naphthalene ring is less likely to form an intermolecular charge-transfer complex associated with the donor/acceptor that causes light absorption, and is less likely to cause coloration because the ⁇ -electron conjugation in the molecule does not spread much. .
  • the compound represented by formula (a1) can contribute to lowering the CTE while suppressing coloration, but the bending resistance of the film is likely to be impaired.
  • the present inventors have found that by further including at least one of the compound represented by formula (a2) and the compound represented by formula (a3), bending resistance can be ensured while maintaining a low CTE.
  • a compound represented by formula (a1), a tetracarboxylic dianhydride containing a compound represented by formula (a2) and/or a compound represented by formula (a3), and a specific diamine (TFMB ) can provide a polyimide film that can achieve both low CTE and high bending resistance while suppressing coloration (while having transparency).
  • TFMB specific diamine
  • polyamic Acid composition of the present disclosure contains a polyamic acid and may optionally further contain other optional ingredients such as a solvent.
  • Polyamic acid contains structural units derived from tetracarboxylic dianhydride and structural units derived from diamine.
  • the tetracarboxylic dianhydride includes a compound represented by formula (a1) and a compound represented by formula (a2) and/or a compound represented by formula (a3).
  • R 1 and R 2 are each independently an alkyl group having 1 to 4 carbon atoms.
  • the number of carbon atoms in the alkyl group is preferably 1 or 2.
  • m and n are each an integer of 0 to 2, and m+n is 3 or less. From the viewpoint of easily lowering the CTE, it is preferable that the orientation (molecular linearity) is high, and m and n are preferably 0.
  • the compound represented by formula (a1) and the compound represented by formula (a2) can lower the CTE of the polyimide film.
  • the compound represented by formula (a2) can lower the CTE without coloring the resulting polyimide film (without increasing the b * value) than the compound represented by formula (a1). .
  • Examples of the compound represented by formula (a1) include 2,3,6,7-naphthalenetetracarboxylic dianhydride (NTCDA) and those partially substituted with alkyl groups. 3,6,7-Naphthalenetetracarboxylic dianhydride (NTCDA) is preferred.
  • Examples of compounds represented by formula (a2) include pyromellitic dianhydride (1,2,4,5-benzenetetracarboxylic acid, PMDA).
  • R 3 and R 4 are each independently an alkyl group having 1 to 4 carbon atoms.
  • the number of carbon atoms in the alkyl group is preferably 1 or 2.
  • o and p are each an integer from 0 to 3, and o+p is 3 or less.
  • the compound represented by formula (a3) can increase the bending resistance of the polyimide film.
  • Examples of compounds represented by formula (b1) include compounds represented by formula (a3-1) and compounds represented by formula (a3-2).
  • Examples of compounds represented by formula (a3-1) include 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA).
  • Examples of compounds represented by formula (a3-2) include 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA).
  • the compound represented by formula (a3-1) is preferred, and 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) is more preferred, from the viewpoint of increasing bending resistance.
  • the compound represented by the formula (a3-2) is preferable, and 2,3,3′,4′-biphenyltetracarboxylic dianhydride (a-BPDA) is more preferable. preferable.
  • the tetracarboxylic dianhydride preferably contains a compound represented by the formula (a1) and a compound represented by the formula (a3).
  • a compound represented by formula (a2) That is, the compound represented by formula (a2) can have intermediate properties between the compound represented by formula (a1) and the compound represented by formula (a3).
  • the content of the compound represented by formula (a1) is preferably 10 mol % or more relative to the total amount of the tetracarboxylic dianhydride.
  • the content of the compound represented by the formula (a1) is 10 mol % or more, it is possible to suppress the coloring of the polyimide film and lower the b * value while lowering the CTE.
  • the content of the compound represented by formula (a1) is more preferably 30 to 80 mol% with respect to the total amount of tetracarboxylic dianhydride, and 40 to 65 mol%. is more preferred.
  • the content of the compound represented by formula (a1) is preferably larger than that of the compound represented by formula (a2) from the viewpoint of further lowering the CTE while suppressing the coloration of the film.
  • the ratio of the content of the compound represented by formula (a1) to the total amount of the compound represented by formula (a1) and the compound represented by formula (a2) (a1/(a1+a2)) is preferably 0.5 to 1.0, more preferably 0.6 to 1.0.
  • the amount of the compound represented by formula (a3) is preferably 10 mol % or more relative to the total amount of the tetracarboxylic dianhydride. That is, the compound represented by formula (a3) has a slightly non-planar structure. Therefore, in addition to the compound represented by the formula (a1), when 10 mol% or more of the compound represented by the formula (a3) is further included, the resulting polyimide structure derived from the compound represented by the formula (a1) The intermolecular interaction between the unit and the structural unit derived from the compound represented by formula (a3) tends to moderately weaken. As a result, the coloring and b * value of the polyimide film can be further reduced, and the bending performance of the film can be further improved.
  • the compound represented by formula (a3) is preferably 10 to 70 mol%, more preferably 20 to 65 mol%, relative to the total amount of tetracarboxylic dianhydride. , 30 to 60 mol %.
  • the total amount (a1+a2) of the compound represented by formula (a1) and the compound represented by formula (a2) is preferably 30 to 80 mol% relative to the total amount of tetracarboxylic dianhydride.
  • the total amount is 30 mol % or more, the CTE of the film can be sufficiently lowered, and when it is 80 mol % or less, the bending resistance of the film is hardly impaired.
  • the above total amount is more preferably 30 to 70 mol %, more preferably 40 to 65 mol %, relative to the total amount of tetracarboxylic dianhydride.
  • the total amount (a2+a3) of the compound represented by the formula (a2) and the compound represented by the formula (a3) is preferably 10 to 80 mol% with respect to the total amount of the tetracarboxylic dianhydride. .
  • the total amount is 10 mol% or more, the bending resistance of the film tends to be increased, and when it is 80 mol% or less, an excessive increase in CTE can be suppressed.
  • the total amount is more preferably 10 to 70 mol%, more preferably 23 to 60 mol%, and 40 to 60 mol% with respect to the total amount of tetracarboxylic dianhydride. is particularly preferred.
  • the total amount (a1+a2) of the compound represented by the formula (a1) and the compound represented by the formula (a2), the compound represented by the formula (a2) and the compound represented by the formula (a3) ) is preferably 4 or less, preferably 2 or less, more preferably 1 or less, and particularly preferably 0.9 or less.
  • (a1 + a2) / (a2 + a3) is preferably 0.4 or more, preferably 0.6 or more, and more preferably 0.8 or more.
  • it is more preferably 1 or more.
  • (a1+a2)/(a2+a3) is preferably 0.4 to 4, more preferably 0.4 to 2, still more preferably 0.4 to 1, further preferably 0.6 to 1, and 0 0.6 to 0.9 are particularly preferred.
  • the tetracarboxylic dianhydride preferably further contains a compound represented by formula (a4).
  • R 5 and R 6 in formula (a4) each independently represent an optionally substituted alkyl group having 1 to 4 carbon atoms or a fluorine atom.
  • the number of carbon atoms in the alkyl group is preferably 1 or 2.
  • substituents that the alkyl group may have include a fluorine atom and the like.
  • q and r each represent an integer of 0 to 3; However, q+r is 3 or less.
  • the compound represented by formula (a4) can not only impart high transparency and heat resistance when formed into a film, but also reduce the birefringence ⁇ n of the film.
  • the compound represented by formula (a4) is preferably 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF).
  • the content of the compound represented by the formula (a4) is the total amount of the tetracarboxylic anhydride having a fluorene skeleton and the diamine (the total amount of the compound represented by the formula (a4) and the compound represented by the formula (b2) amount) is preferably set within the range described later.
  • the tetracarboxylic dianhydride may further contain other tetracarboxylic dianhydrides other than the above, as long as the effects of the present disclosure are not impaired.
  • examples of other tetracarboxylic dianhydrides include aromatic tetracarboxylic dianhydrides other than those mentioned above, alicyclic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides.
  • the content of other tetracarboxylic dianhydrides can be 10 mol % or less with respect to the total amount of tetracarboxylic dianhydrides.
  • Diamines include compounds represented by formula (b1).
  • the compound represented by formula (b1) is 2,2'-bis(trifluoromethyl)benzidine (TFMB).
  • TFMB 2,2'-bis(trifluoromethyl)benzidine
  • the diamine preferably further contains a compound represented by the formula (b2), for example, from the viewpoint of increasing the heat resistance of the film or reducing the birefringence ⁇ n.
  • R 7 and R 8 in formula (b2) each independently represent an optionally substituted alkyl group having 1 to 4 carbon atoms or a fluorine atom.
  • the number of carbon atoms in the alkyl group is preferably 1 or 2.
  • substituents that the alkyl group may have include a fluorine atom and the like.
  • s and t each represents an integer of 0 to 3; However, s+t is 3 or less.
  • Examples of compounds represented by formula (b2) include 9,9-bis(4-aminophenyl)fluorene (BAFL), 9,9-bis(4-amino-3-methylphenyl)fluorene (FFDA), 9,9-bis(aminofluorophenyl)fluorene is included.
  • BAFL 9,9-bis(4-aminophenyl)fluorene
  • FFDA 9,9-bis(4-amino-3-methylphenyl)fluorene
  • 9,9-bis(aminofluorophenyl)fluorene is included.
  • the content of the compound represented by formula (b1) is preferably 80 mol % or more with respect to the total amount of diamine.
  • the content of the compound represented by the formula (b1) is 80 mol% or more, it is easy to suppress the coloration of the film (easy to lower the b * value).
  • the content of the compound represented by formula (b1) is preferably 90 mol % or more, and may be 100 mol %.
  • the content of the compound represented by the formula (b2) is such that the total amount of the compound represented by the formula (a4) and the compound represented by the formula (b2) (the content of the component having a fluorene skeleton) is equal to the diamine and It is set to be 0 to 15 mol %, preferably 0.5 to 15 mol %, based on the total amount of tetracarboxylic dianhydride.
  • the total amount is 0.15 mol % or more, the birefringence ⁇ n tends to be lowered, and when it is 15 mol % or less, an increase in CTE is easily suppressed. From the same point of view, the above total amount is more preferably 2 to 8 mol %.
  • the diamine may further contain diamines other than the above as long as the effects of the present disclosure are not impaired.
  • diamines include bis(3-aminophenyl)sulfone (3,3-DAS), 4,4′-diaminodiphenylsulfone (4,4-DAS), 1,5-diaminonaphthalene (15DAN), 4,4′-diaminobenzanilide (DABA), m-diaminobenzene (MDA) and other aromatic diamines other than the above, 1,2-cyclohexanediamine (DACH) and 1,3-bis(aminomethyl)cyclohexane, Included are cycloaliphatic diamines such as 1,4-bis(aminomethyl)cyclohexane, and aliphatic diamines such as ethylenediamine and hexamethylenediamine.
  • the content of other diamines can be 10 mol % or less with respect to the total amount of diamines.
  • the intrinsic viscosity ( ⁇ ) of the polyamic acid is not particularly limited, it is preferably 0.3 to 2.0 dL/g, more preferably 0.6 to 1.6 dL/g.
  • the intrinsic viscosity ( ⁇ ) of the polyamic acid varnish is within the above range, it is easy to achieve both coatability and film formability.
  • the intrinsic viscosity ( ⁇ ) of polyamic acid can be adjusted by adjusting the amount ratio (molar ratio) of tetracarboxylic dianhydride and diamine when preparing polyamic acid. For example, when the acid dianhydride/diamine ratio is equimolar, the intrinsic viscosity ( ⁇ ) tends to increase.
  • the intrinsic viscosity ( ⁇ ) is a value measured at 25° C. with an Ubbelohde viscosity tube when the polyamic acid concentration in N-methyl-2-pyrrolidone (NMP) is 0.5 g/dL.
  • the polyamic acid composition of the present disclosure may, if necessary, further contain components other than the polyamic acid described above.
  • the polyamic acid composition may further contain a solvent.
  • the solvent may be a solvent used for preparing the polyamic acid composition described later, and is not particularly limited as long as it can dissolve the diamine component and the tetracarboxylic dianhydride component described above.
  • an aprotic polar solvent, an alcoholic solvent, or the like can be used.
  • aprotic polar solvents examples include N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), N,N- Amide solvents such as dimethylformamide (DMF), N,N-diethylformamide (DEF), hexamethylphosphoramide (HMPA); dimethylsulfoxide; and 2-methoxyethanol, 2-ethoxyethanol, 2-(methoxymethoxy) ethoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monoethyl ether, tetraethylene glycol, 1 - methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, di
  • alcoholic solvents include methanol, ethanol, 1-propanol, 2-propanol, tert-butyl alcohol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1 ,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, 1,2,6-hexanetriol, Diacetone alcohol and the like are included.
  • solvents may contain only one type, or may be a combination of two or more types.
  • N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone (DMI) or a mixed solvent thereof is preferable.
  • the polyamic acid content is not particularly limited, but from the viewpoint of coatability, it is 5 to 30% by mass, preferably 10 to 25% by mass, based on the total amount of the polyamic acid composition.
  • the resin concentration of the polyamic acid composition may be the same as the solution concentration during preparation of the polyamic acid composition.
  • a film (polyimide film) obtained by imidating the polyamic acid composition of the present disclosure is inhibited from being colored and has good bending resistance.
  • the b * value in the L * a * b * color system of a polyimide film having a thickness of 10 ⁇ m obtained by thermally imidizing a polyamic acid composition at 350° C. is preferably 8.0 or less, more preferably 6.0 or less. , and more preferably 4.0 or less.
  • the b * value represents the yellowness of the film, and a smaller value indicates less yellowness. Therefore, the lower limit of the b * value is usually about 1.0, preferably 0.
  • a polyimide film having a b * value of 8.0 or less is less colored and has excellent transparency, and is suitable for optical films, ie, panel substrates for various display devices.
  • the b * value is obtained by thermally curing (imidizing) the polyamic acid composition at 350 ° C.
  • the b * value of a polyimide film having a thickness of 10 ⁇ m is measured by a colorimeter (for example, Suga Test Instruments Co., Ltd. tristimulus value direct reading type measurement It is the value when measured using a colorimeter (Colour Cute CC-i model) in transmission mode (when using the above equipment, transmission mode is set to 0°di).
  • the b * value can be adjusted by the monomer composition of the polyamic acid. For example, if the content ratio of the compound (TFMB) represented by the formula (b1) in the diamine is increased, or the content ratio of the compound (PMDA) represented by the formula (a2) in the acid anhydride is decreased, , b * values tend to be small.
  • a polyimide film having a thickness of 10 ⁇ m obtained by thermally imidizing a polyamic acid composition at 350° C. has a folding endurance in the MIT folding endurance test of, for example, preferably 10,000 times or more, and preferably 40,000 times or more. is more preferable, 100,000 times or more is more preferable, and 200,000 times or more is even more preferable.
  • the MIT folding endurance test can be performed by the following procedure.
  • a polyimide film (10 ⁇ m thick) is cut into a shape of 120 mm long ⁇ 15 mm wide to obtain a test piece.
  • One end of this test piece is set in an MIT folding endurance tester (307 type) manufactured by Yasuda Seiki Seisakusho, and the other end is held, with a curvature radius of 0.38 mm, a load of 0.5 kg, and a bending accuracy of 270 degrees (left and right 135 degrees). degree) and the bending speed is 175 times/min.
  • the measurement conditions can be as described in Examples below.
  • the thickness of the polyimide film is not restricted to 9 to 12 ⁇ m depending on the thickness of the film.
  • Bending resistance can be adjusted by the monomer composition of polyimide. For example, among the acid dianhydrides, the total amount (a2 + a3) of the compound represented by the formula (a2) and the compound represented by the formula (a3) is increased (or (a1 + a2) / (a2 + a3) is decreased) When the content of the compound represented by the formula (a3) is increased, the bending resistance tends to increase.
  • the polyamic acid composition can be obtained by reacting a tetracarboxylic dianhydride component and a diamine component in a solvent.
  • the types of solvent, tetracarboxylic dianhydride component, and diamine component to be used and their quantitative ratios are as described above.
  • the reaction for obtaining the polyamic acid composition is preferably carried out by heating the above tetracarboxylic dianhydride and diamine in a solvent at a relatively low temperature (a temperature at which imidization does not occur). .
  • a temperature at which imidization does not occur can be 5 to 120°C, more preferably 25 to 80°C.
  • the reaction is preferably carried out in an environment in which an imidization catalyst (for example, triethylamine, etc.) is substantially absent.
  • the content of the tetracarboxylic dianhydride and the diamine in the solution is not particularly limited, but from the viewpoint of promoting intermolecular cross-linking during imidization, it is preferably high, and the coating properties are not impaired. From the viewpoint of making The concentration of the solution can be 5 to 30% by mass, preferably 10 to 25% by mass, from the viewpoint of coatability.
  • the above reaction can be performed by a known method. For example, a container equipped with a stirrer and a nitrogen inlet tube is prepared, and the solvent is introduced into the container which is purged with nitrogen. Then, diamine is added so that the final polyamic acid concentration falls within the above range, and the temperature is adjusted and stirred. A predetermined amount of tetracarboxylic dianhydride is added to the solution. Then, the mixture is stirred for about 1 to 50 hours while adjusting the temperature.
  • the ratio (y/x) of the total molar amount x of the diamine and the total molar amount y of the tetracarboxylic dianhydride is, for example, 0.9 to 1.1, preferably 0.95 to 1.05.
  • the polyimide composition of the present disclosure includes a specific polyimide obtained by imidating the polyamic acid contained in the polyamic acid composition.
  • Polyimide The polyimide is obtained by imidizing the polyamic acid, and includes structural units derived from the tetracarboxylic dianhydride and structural units derived from the diamine. Polyimide compositions (eg, polyimide films) containing such polyimides have reduced coloration (low b * values), low CTE, and good bending resistance.
  • the polyimide composition may be in the form of powder, pellets, or film. Among them, a film is preferable from the viewpoint of ease of use as a display substrate.
  • the polyimide composition and the polyimide film containing the same have little coloration, low CTE, and good bending resistance.
  • the polyimide composition and the polyimide film containing it preferably satisfy one or more of the following physical properties.
  • the total light transmittance (Total Transmittance: TT) of the polyimide film depends on the thermal imidization conditions (especially the heating temperature), but is for example 80% or more, preferably 85% or more, more preferably 87% or more, and more preferably 89% or more.
  • the upper limit of the total light transmittance is preferably 100%, but usually about 92% or 90%.
  • a polyimide film having such a high total light transmittance is suitable for optical films, ie, panel substrates (transparent substrates) for various display devices.
  • the total light transmittance (TT) indicates the average transmittance in the entire wavelength range (300 to 830 nm) of D65, which is a standard light source. From the viewpoint of further improving visibility, the transmittance at a wavelength of 450 nm (T@450 nm) is preferably 60% or more, more preferably 75% or more.
  • the total light transmittance of the polyimide film is measured with light source D65 according to JIS-K7361-1.
  • the light transmittance at a wavelength of 450 nm can be obtained by measuring the UV-visible spectrum in the wavelength range of 300 to 800 nm and calculating the transmittance of light at a wavelength of 450 nm as T@450 nm.
  • the total light transmittance of the polyimide film and the transmittance at a wavelength of 450 nm can be adjusted by the monomer composition of the polyimide.
  • the content ratio of the compound represented by the formula (b1) (TFMB) in the diamine or the content ratio of the compound represented by the formula (a4) in the acid anhydride (for example, BPAF) is high, the total light transmission efficiency and transmittance at a wavelength of 450 nm tend to be high.
  • the b * value in the L * a * b * color system of a polyimide film is preferably 16.0 or less, more preferably 8.0 or less, still more preferably 6.0 or less, especially Preferably it is 4.0 or less.
  • the lower limit of the b * value is usually about 1.0, preferably 0.
  • a polyimide film having a b * value of 16.0 or less, preferably 8.0 or less is less colored and has excellent transparency, and is suitable for optical films, ie, panel substrates for various display devices.
  • the method for measuring and adjusting the b * value is as described above.
  • the thickness of the polyimide film is not restricted to 9 to 12 ⁇ m depending on the thickness of the film.
  • the thickness direction birefringence ⁇ n of the polyimide film at a wavelength of 633 nm is not particularly limited, but is preferably 0.19 or less, more preferably 0.1 or less.
  • the birefringence ⁇ n is within the above range, when the polyimide film is used as a display substrate, the image displayed on the display device is less likely to be distorted, and the display characteristics can be improved.
  • the birefringence ⁇ n in the thickness direction can be measured by the following method. Using a Metricon prism coupler (model 2010), a laser beam with a wavelength of 633 nm is incident on the sample through a coupling prism, and the refractive index (nTE) in TE polarized light and the refractive index (nTM) in TM polarized light are measured, Subtract nTM from nTE to calculate birefringence.
  • nTE refractive index
  • nTM refractive index
  • the birefringence ⁇ n in the thickness direction can be adjusted by the monomer composition of polyimide. For example, if the total amount of the compound represented by the formula (a4) and the compound represented by the formula (b2) with respect to the total of the tetracarboxylic dianhydride and the diamine constituting the polyimide (a component containing a fluorene skeleton) is large, The birefringence ⁇ n of the polyimide film tends to be low. This is probably because the many aromatic rings of the compound containing a fluorene skeleton show different orientations and tend to act in a direction that cancels out the optical anisotropy.
  • the glass transition temperature (Tg) of the polyimide film is preferably 370°C or higher, more preferably 400°C or higher.
  • the film can be applied to substrates for TFT arrays and the like.
  • the Tg of the polyimide film is preferably 350° C. or higher when used for manufacturing a TFT array using IGZO (an oxide semiconductor composed of indium, gallium, zinc, and oxygen), and 390° C. It is more preferably 400° C. or higher when used for manufacturing a TFT array using low-temperature polysilicon.
  • the display device can be used even under the working environment during fabrication of each TFT array, and a highly reliable display device can be easily obtained.
  • the upper limit of the Tg of the polyimide film is not particularly limited, it can be, for example, about 500° C. from the viewpoint of moldability.
  • a sample with a width of 5 mm and a length of 20 mm was measured in a nitrogen atmosphere at a temperature of 25 to 450 ° C., a heating rate of 3 ° C./min, a frequency of 1 Hz,
  • the dynamic viscoelasticity is measured under the measurement condition of an initial load of 5.0 kg/cm 2 per cross-sectional area, and the loss tangent (value obtained by dividing the loss elastic modulus by the storage elastic modulus, tan ⁇ ) is obtained.
  • the temperature at which tan ⁇ shows the maximum value above the firing temperature is defined as the glass transition temperature.
  • the coefficient of linear thermal expansion (CTE) of the polyimide film depends on the thermal imidization conditions (especially the heating temperature), but is preferably -10 to 50 ppm/K, more preferably -10 to 30 ppm/K. It is preferably -5 to 20 ppm/K, and particularly preferably 0 to 10 ppm/K.
  • the coefficient of linear thermal expansion is within the above range, the polyimide film is less likely to deform even at high temperatures when used as a panel substrate for various display devices, and warping due to the high temperature environment in the process of forming electric elements on the substrate. It is easy to suppress misalignment and breakage of electric elements due to thermal deformation such as, and it is easy to stack various elements.
  • CTE coefficient of linear thermal expansion
  • the coefficient of linear thermal expansion (CTE) can be adjusted by the monomer composition of polyimide (or its precursor polyamic acid). For example, among the acid dianhydrides, the total amount (a1 + a2) (or (a1 + a2) / (a2 + a3)) of the compound represented by the formula (a1) and the compound represented by the formula (a2) is increased, or the formula When the content of the compound represented by (a1) is increased, the CTE tends to be lowered.
  • the tensile strength of the polyimide film is preferably 160 MPa or more, for example.
  • the tensile elongation is preferably 4-15%, for example.
  • Tensile strength and tensile elongation can be measured by the following procedures.
  • a dumbbell-shaped punched test piece is prepared from the polyimide film and measured with a tensile tester (EZ-S, manufactured by Shimadzu Corporation) under the conditions of a marked line width of 5 mm, a sample length of 30 mm, and a tensile speed of 30 mm/min. From the obtained stress-strain curve, the strength and elongation at the breaking point are defined as tensile strength and tensile elongation, respectively, and the average values of five measurements are determined as tensile strength TS and tensile elongation EL.
  • the number of folding endurance of the polyimide film in the MIT folding endurance test is, for example, preferably 10,000 times or more, more preferably 40,000 times or more, further preferably 100,000 times or more, and 200,000 times. It is more preferable that it is above.
  • a film having a folding endurance number in the above range in the MIT folding endurance test has high flexibility and is therefore suitable as a flexible display substrate.
  • the method of the MIT folding endurance test and the method of adjusting the bending endurance are as described above.
  • the thickness of the polyimide film is not particularly limited, and is appropriately selected according to the use of the film.
  • the thickness of the polyimide film is, for example, 1-100 ⁇ m, preferably 5-50 ⁇ m, more preferably 5-20 ⁇ m.
  • the polyimide film of the present disclosure has high transparency, low CTE, and high bending resistance. Therefore, it is suitable for substrates for electronic devices.
  • substrates for electronic devices include transparent substrates (display panel substrates) for display devices such as touch panels, liquid crystal displays, and organic EL displays; and substrates for mounting sensors for fingerprint authentication and face authentication.
  • transparent substrates display panel substrates
  • substrates for mounting sensors for fingerprint authentication and face authentication For example, for substrate applications where sensors for fingerprint authentication and face authentication are mounted, it is required to have flexibility, high transparency that does not block the light that is the object of measurement, and little coloring. heat resistance (low CTE) is required.
  • the polyimide film of the present disclosure is also suitable for such uses.
  • the polyimide film of the present disclosure includes: 1) a step of applying the polyamic acid composition of the present disclosure to a substrate to form a coating film; ) is obtained through the step of
  • step 1) varnish application
  • the varnish containing the polyamic acid and solvent is applied to the surface of various substrates to form a coating film.
  • the base material to which the varnish is applied is not particularly limited as long as it has solvent resistance and heat resistance. Any substrate can be used as long as the obtained polyimide film can be easily peeled off, and a flexible substrate such as a glass plate, a metal film, or a heat-resistant polymer film is preferable.
  • Examples of flexible substrates made of metals include copper, aluminum, stainless steel, iron, silver, palladium, nickel, chromium, molybdenum, tungsten, zirconium, gold, cobalt, titanium, tantalum, zinc, lead, tin, silicon, bismuth. , indium, or alloys thereof.
  • the metal foil surface may be coated with a release agent.
  • Examples of flexible substrates made of heat-resistant polymer films include polyimide films, aramid films, polyetheretherketone films, and polyethersulfone films.
  • the flexible base material made of a heat-resistant polymer film may contain a releasing agent or an antistatic agent, or may be coated with a releasing agent or an antistatic agent.
  • the base material is preferably a polyimide film because it has good film releasability and high heat resistance and solvent resistance.
  • the shape of the substrate is appropriately selected according to the shape of the polyimide film to be produced, and may be in the form of a single leaf sheet or in the form of an elongated sheet.
  • the thickness of the substrate is preferably 5-150 ⁇ m, more preferably 10-70 ⁇ m. When the thickness of the substrate is 5 ⁇ m or more, the substrate is less likely to wrinkle or split during application of the varnish.
  • the method of applying the varnish to the substrate is not particularly limited as long as it can be applied with a uniform thickness.
  • coating methods include methods using a die coater, a comma coater, a roll coater, a gravure coater, a curtain coater, a spray coater, a lip coater and the like.
  • step 2) (imidation of polyamic acid)
  • the coating film of the polyamic acid composition is heated to imidize (ring-close) the polyamic acid.
  • the coating film of the varnish is heated while increasing the temperature from 150°C or lower to over 200°C, thereby imidizing the polyamic acid while removing the solvent in the coating film. After the temperature is raised to a predetermined temperature, the material is heated at that temperature for a predetermined time.
  • the temperature at which polyamic acid imidates is 150-200°C. Therefore, when the temperature of the coating film is rapidly raised to 200° C. or higher, the polyamic acid on the coating film surface is imidized before the solvent volatilizes from the coating film. As a result, the solvent remaining in the coating film causes air bubbles or irregularities on the surface of the coating film. Therefore, it is preferable to gradually raise the temperature of the coating film in the temperature range of 150 to 200°C.
  • the temperature increase rate in the temperature range of 150 to 200° C. is preferably 0.25 to 50° C./min, more preferably 1 to 40° C./min, and 2 to 30° C./min. It is more preferable that
  • the temperature may be raised continuously or stepwise (sequentially), but it is preferable to raise the temperature continuously from the viewpoint of suppressing appearance defects of the resulting polyimide film.
  • the rate of temperature increase may be constant over the entire temperature range described above, or may be changed in the middle.
  • An example of a method of heating a single-leaf coating film while raising the temperature is to raise the temperature inside the oven.
  • the heating rate is adjusted by setting the oven.
  • a plurality of heating furnaces for heating the coating film are arranged along the conveying (moving) direction of the substrate; Vary for each heating furnace.
  • the temperature of each heating furnace may be increased along the moving direction of the substrate.
  • the heating rate is adjusted by the conveying speed of the substrate.
  • the heating temperature is not particularly limited, it is preferably a temperature at which the amount of solvent in the film is 0.5% by mass or less.
  • the solvent can be easily removed by making the temperature higher than the Tg of polyimide.
  • the heating temperature is preferably 250° C. or higher, more preferably 300° C. or higher, still more preferably 340° C. or higher, and may be 400° C. or higher.
  • the heating time can usually be about 0.5 to 2 hours.
  • TFTs for display substrates if the TFT device type is the low temperature polysilicon (LTPS) type, a higher process temperature (e.g., 400°C or higher) is required compared to conventional amorphous silicon or IGZO types. There is Even after such a high-temperature thermal history, damage to the device can be reduced.
  • LTPS low temperature polysilicon
  • Polyimide is easily oxidized when heated at a temperature exceeding 200°C.
  • the obtained polyimide film turns yellow and the total light transmittance of the polyimide film decreases. Therefore, in the temperature range exceeding 200° C., it is preferable to (i) use an inert gas atmosphere as the heating atmosphere, or (ii) reduce the pressure of the heating atmosphere.
  • the heating atmosphere is an inert gas atmosphere
  • the oxidation reaction of polyimide is suppressed.
  • the type of inert gas is not particularly limited, and may be argon gas, nitrogen gas, or carbon dioxide gas.
  • the oxygen concentration in the temperature range exceeding 200 ° C. is preferably 1% by volume or less, more preferably 0.1% by volume (1000 ppm) or less, and 0.01% by volume (100 ppm) or less. is more preferred.
  • the oxygen concentration in the atmosphere is measured by a commercially available oxygen concentration meter (for example, a zirconia oxygen concentration meter).
  • the oxidation reaction of polyimide is also suppressed by reducing the pressure of the heating atmosphere.
  • the pressure in the atmosphere is preferably 15 kPa or less, more preferably 5 kPa or less, and even more preferably 1 kPa or less.
  • the heating atmosphere is decompressed, the coating film is heated in a decompression oven or the like.
  • a polyimide film is obtained by peeling off the base material.
  • Tetracarboxylic dianhydrides and diamines used in Examples and Comparative Examples are as follows.
  • NTCDA 2,3,6,7-naphthalenetetracarboxylic dianhydride
  • PMDA pyromellitic dianhydride
  • BPAF fluorenylidene bisphthalic anhydride
  • s-BPDA 3,3',4,4'-biphenyltetra Carboxylic acid dianhydride
  • test 1 2-1 Preparation of varnish (Preparation of polyamic acid varnishes 1 to 15)
  • a flask equipped with a thermometer, a condenser, a nitrogen inlet tube and a stirrer was charged with the diamine and N-methyl-2-pyrrolidinone (NMP) from Table 1 (the weight of NMP was previously added so that the total concentration of all monomers was 20% by mass). calculated) was added and stirred under a nitrogen atmosphere to form a uniform solution.
  • NMP N-methyl-2-pyrrolidinone
  • a predetermined amount of the corresponding tetracarboxylic acid dianhydride in Table 1 was added to the solution as powder, stirred at room temperature for 30 minutes, and then the solution temperature was raised to 85 to 90 ° C. for 1 hour. After stirring for a period of time, a uniform solution was obtained. Thereafter, the mixture was cooled to room temperature, and stirring was continued overnight at room temperature to obtain a pale yellow viscous polyamic acid varnish (polyamic
  • the intrinsic viscosity ⁇ of the obtained varnish was measured with an Ubbelohde viscosity tube at a polymer concentration of 0.5 g/dL, NMP, and 25°C.
  • Table 1 shows the preparation conditions and physical properties of the polyamic acid varnish.
  • thermal properties linear thermal expansion coefficient (CTE) and tan ⁇
  • optical properties total light transmittance, b * value, birefringence ⁇ n
  • mechanical properties Teensile strength, elongation and MIT folding endurance
  • Thermophysical properties (tan ⁇ of DMA (dynamic viscoelasticity measurement)) Using RSA-III manufactured by TA Instruments, a sample with a width of 5 mm and a length of 20 mm was measured in a nitrogen atmosphere at a temperature of 25 to 450 ° C., a temperature increase rate of 3 ° C./min, a frequency of 1 Hz, and an initial load per cross-sectional area.
  • the dynamic viscoelasticity was measured under the measurement condition of 0 kg/cm 2 to obtain the loss tangent (value obtained by dividing the loss elastic modulus by the storage elastic modulus, tan ⁇ ).
  • CTE Coefficient of linear thermal expansion
  • total light transmittance The total light transmittance (TT) of the obtained polyimide film was measured with a light source D65 according to JIS-K7361 using a haze meter NDH2000 manufactured by Nippon Denshoku Industries.
  • MIT folding endurance (bending endurance)
  • the polyimide film prepared above was cut into a shape of length 120 mm ⁇ width 15 mm to obtain a test piece.
  • One end of this test piece is set in an MIT folding endurance tester (307 type) manufactured by Yasuda Seiki Seisakusho, and the other end is held, with a curvature radius of 0.38 mm, a load of 0.5 kg, and a bending angle of 270 degrees (left and right 135 degree), and the bending rate was 175 times/minute, and the number of times until breakage was measured.
  • the measurement conditions were as follows.
  • Table 2 shows the evaluation results of polyimide films 1 to 15.
  • polyimide films obtained from polyamic acid varnishes 1 and 15, in which the tetracarboxylic dianhydride contains NTCDA (a1) but does not contain both PMDA (a2) and BPDA (a3) have poor flexibility.
  • NTCDA NTCDA
  • BPDA BPDA
  • the polyimide film obtained from the polyamic acid varnish 13 in which the tetracarboxylic dianhydride is composed only of PMDA (a2) has poor flexibility.
  • the polyimide film obtained from the polyamic acid varnish 4 in which the tetracarboxylic dianhydride does not contain BPDA (a3) has poor flexibility.
  • test 2 3-1 Preparation of polyimide film Using the polyamic acid varnish shown in Table 3, a glass substrate (non-alkali glass, OA11 made by NEG, thickness 0.5 mm) was spin-coated and placed in an inert oven (manufactured by Koyo Thermo Systems, model INH21CD). ) is used to adjust the oxygen concentration in the chamber to 20 ppm or less, and the glass substrate and the polyimide resin having a thickness shown in Table 3 or 4 are baked under the following conditions A) or B). A laminate of membranes (polyimide films) was produced.
  • Condition A The temperature was raised from 50°C to 430°C at a temperature elevation rate of 2°C/min, and the temperature was maintained at 430°C for 30 minutes.
  • Condition B The temperature was raised from 50°C to 450°C at a temperature elevation rate of 2°C/min. Hold at 450°C for 30 minutes
  • Table 3 shows the evaluation results of the polyimide film produced under condition A
  • Table 4 shows the evaluation result of the polyimide film produced under condition B).
  • "-" indicates unmeasured.
  • TFMB as a diamine
  • NTCDA (a1) and BPDA (a3) as tetracarboxylic dianhydrides
  • the total amount of NTCDA and PMDA (a1 + a2) is within a predetermined range
  • the polyimide films obtained from polyamic acid varnishes 5, 6, 8, 15 had lower b * values than the polyimide films obtained from polyamic acid varnish 1 (comparative example), and polyamic acid varnish 15 (comparative It can be seen that the CTE is lower than that of the polyimide film obtained from Example).
  • the polyimide film obtained from polyamic acid varnish 6 had an MIT folding endurance of more than 1,000,000 times, showing excellent flexibility.
  • test 3 Some of the laminates obtained under the condition A) were evaluated for the LLO peel test and the properties after the LLO peel test.
  • the polyamic acid compositions of the present disclosure can impart polyimide films with both sufficiently low thermal expansion and bending resistance without increasing the b * value. Such films are applicable to substrates for various electronic devices.

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Abstract

La présente invention concerne une composition d'acide polyamique qui contient un acide polyamique. Un dianhydride d'acide tétracarboxylique constituant l'acide polyamique contient un composé représenté par la formule (a1) et un composé représenté par la formule (a2) et/ou un composé représenté par la formule (a3), et une diamine constituant l'acide polyamique contient un composé représenté par la formule (b1). La teneur en composé représenté par la formule (a1) est de 10 % en moles ou plus par rapport à la quantité totale de dianhydrides d'acide, et la quantité combinée des composés représentés par les formules (a1) et (a2) est de 30 à 80 % en moles par rapport à la quantité totale des dianhydrides d'acide.　[Composé 1] [Composé 2] [Composé 3] [Composé 4]
PCT/JP2022/028046 2021-08-06 2022-07-19 Composition d'acide polyamique et composition de polyimide, film de polyimide et substrat de panneau d'affichage WO2023013401A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05216039A (ja) * 1992-02-05 1993-08-27 Canon Inc 液晶素子
CN101591521A (zh) * 2009-07-08 2009-12-02 北京航空航天大学 一种含芴聚酰亚胺胶粘剂及其制备方法
WO2014097633A1 (fr) * 2012-12-21 2014-06-26 日立化成デュポンマイクロシステムズ株式会社 Précurseur polyimide, composition de résine photosensible contenant ce précurseur polyimide ainsi que procédé de fabrication d'un film durci à motif mettant en oeuvre cette composition et dispositif à semi-conducteurs associé
WO2014129464A1 (fr) * 2013-02-19 2014-08-28 新日鉄住金化学株式会社 Corps stratifié, élément de cellule solaire, cellule solaire, élément de dispositif d'affichage, dispositif d'affichage, et procédé de fabrication de corps stratifié
JP2016204457A (ja) * 2015-04-17 2016-12-08 Ｊｆｅケミカル株式会社 ポリアミド酸組成物およびポリイミド組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05216039A (ja) * 1992-02-05 1993-08-27 Canon Inc 液晶素子
CN101591521A (zh) * 2009-07-08 2009-12-02 北京航空航天大学 一种含芴聚酰亚胺胶粘剂及其制备方法
WO2014097633A1 (fr) * 2012-12-21 2014-06-26 日立化成デュポンマイクロシステムズ株式会社 Précurseur polyimide, composition de résine photosensible contenant ce précurseur polyimide ainsi que procédé de fabrication d'un film durci à motif mettant en oeuvre cette composition et dispositif à semi-conducteurs associé
WO2014129464A1 (fr) * 2013-02-19 2014-08-28 新日鉄住金化学株式会社 Corps stratifié, élément de cellule solaire, cellule solaire, élément de dispositif d'affichage, dispositif d'affichage, et procédé de fabrication de corps stratifié
JP2016204457A (ja) * 2015-04-17 2016-12-08 Ｊｆｅケミカル株式会社 ポリアミド酸組成物およびポリイミド組成物

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