WO2022019226A1 - Résine polyimide, vernis polyimide, et film polyimide - Google Patents

Résine polyimide, vernis polyimide, et film polyimide Download PDF

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Publication number
WO2022019226A1
WO2022019226A1 PCT/JP2021/026768 JP2021026768W WO2022019226A1 WO 2022019226 A1 WO2022019226 A1 WO 2022019226A1 JP 2021026768 W JP2021026768 W JP 2021026768W WO 2022019226 A1 WO2022019226 A1 WO 2022019226A1
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structural unit
polyimide
mol
derived
polyimide resin
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PCT/JP2021/026768
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English (en)
Japanese (ja)
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菜摘 脇田
重之 廣瀬
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三菱瓦斯化学株式会社
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Priority to KR1020237001506A priority Critical patent/KR20230041690A/ko
Priority to CN202180060330.8A priority patent/CN116134072A/zh
Priority to JP2022537973A priority patent/JPWO2022019226A1/ja
Publication of WO2022019226A1 publication Critical patent/WO2022019226A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a polyimide resin, a polyimide varnish and a polyimide film.
  • Polyimide resins are obtained from aromatic tetracarboxylic acid anhydrides and aromatic diamines and generally have excellent heat resistance, chemical resistance, mechanical properties and electrical properties due to molecular rigidity, resonance stabilization and strong chemical bonds. Therefore, it is widely used in the fields of molding materials, composite materials, electrical / electronic parts, optical materials, displays, aerospace, and the like. In particular, the application to flexible devices is being studied by taking advantage of the fact that it is flexible with respect to glass materials that have been conventionally used for applications such as electric / electronic parts, optical materials, and displays.
  • Patent Document 1 describes a tetracarboxylic dianhydride component containing an alicyclic tetracarboxylic dianhydride and a fluorine-containing aromatic for the purpose of improving heat resistance, polyimide, flexibility, and transparency.
  • a composition for forming a flexible device substrate is disclosed, which comprises a polyimide which is a reaction product with a diamine component containing a diamine, and an organic solvent.
  • polyimide resin In recent years, the application of polyimide resin to applications of displays and front plates that protect them has been advancing, and from the viewpoint of substituting glass materials that have been conventionally used, good mechanical strength, that is, high strength and high elastic modulus. Polyimide resin is required. However, the conventional high-strength polyimide resin has a problem that the flexibility is not sufficient and many of them are inferior in colorless transparency. Recently, since it is also used as a display or protective plate for smartphones with a foldable structure, it is required to have higher strength and higher flexibility, and it is also necessary to have the property of recovering the shape after the polyimide film is deformed. There is. Therefore, a polyimide resin having these properties has been desired.
  • the problem to be solved by the present invention is a polyimide resin capable of forming a film having both mechanical properties and colorless transparency and having high strength and excellent deformation recovery, and both mechanical properties and colorless transparency. Further, it is an object of the present invention to provide a polyimide film having high strength and excellent deformation recovery property.
  • the structural unit A includes a structural unit (A1) derived from the compound represented by the following formula (a1) and a structural unit (A2) derived from the aliphatic tetracarboxylic dianhydride, and the structural unit B is the following formula.
  • the structural unit (A2) is a structural unit (A2-1) derived from a compound represented by the following formula (a2-1) and a configuration derived from a compound represented by the following formula (a2-2).
  • the structural unit (A2) is one of the above-mentioned [1] to [5], which is a structural unit (A2-2) derived from a compound represented by the following formula (a2-2).
  • a polyimide resin capable of forming a film having both mechanical properties and colorless transparency and having high strength and excellent deformation recovery properties, a polyimide varnish containing the polyimide resin, and mechanical properties and colorless transparency. It is possible to provide a polyimide film having both high strength and excellent deformation recovery.
  • the polyimide resin of the present invention is a polyimide resin having a structural unit A derived from tetracarboxylic acid dianhydride and a structural unit B derived from diamine, and the structural unit A is represented by the following formula (a1). Containing a structural unit (A1) derived from a compound and a structural unit (A2) derived from an aliphatic tetracarboxylic acid dianhydride, the structural unit B is a structural unit derived from a compound represented by the following formula (b1). (B1) and is included.
  • the polyimide resin of the present invention will be described.
  • the structural unit A contained in the polyimide of the present invention is a structural unit derived from the tetracarboxylic dianhydride in the polyimide resin.
  • the structural unit A includes a structural unit (A1) derived from the compound represented by the formula (a1) and a structural unit (A2) derived from the aliphatic tetracarboxylic dianhydride.
  • the compound represented by the formula (a1) is 9,9-bis (3,4-dicarboxyphenyl) fluorenic acid dianhydride (BPAF).
  • BPAF 9,9-bis (3,4-dicarboxyphenyl) fluorenic acid dianhydride
  • the structural unit (A2) is a structural unit derived from the aliphatic tetracarboxylic acid dianhydride, and the structural unit (A2) preferably contains a structural unit derived from the alicyclic tetracarboxylic acid dianhydride, and more. It preferably contains a structural unit derived from a tetracarboxylic acid dianhydride having an alicyclic having 4 to 25 carbon atoms.
  • a structural unit derived from a tetracarboxylic dianhydride having an alicyclic ring By containing a structural unit derived from a tetracarboxylic dianhydride having an alicyclic ring, deformation recovery and colorless transparency are improved while maintaining mechanical strength.
  • the aliphatic tetracarboxylic acid dianhydride means a tetracarboxylic acid dianhydride containing no aromatic ring
  • the alicyclic tetracarboxylic acid dianhydride means an aliphatic tetracarboxylic acid dianhydride.
  • it means a tetracarboxylic acid dianhydride containing one or more alicyclics.
  • the "alicyclic” refers to a cyclic hydrocarbon structure excluding an aromatic ring among the structures in which carbon atoms are cyclically bonded
  • the number of carbon atoms in the alicyclic ring refers to the number of carbons constituting the ring.
  • alicyclic tetracarboxylic acid dianhydride examples include 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and norbornan-2.
  • -Spiro- ⁇ -cyclopentanone- ⁇ '-Spiro-2''-norbornan-5,5'', 6,6''-tetracarboxylic acid dianhydride bicyclo [2.2.2] octa-7 -En-2,3,5,6-tetracarboxylic acid dianhydride, dicyclohexyltetracarboxylic acid dianhydride, position isomers thereof and the like can be mentioned.
  • Specific examples of the aliphatic tetracarboxylic acid dianhydride other than the alicyclic tetracarboxylic acid dianhydride include 1,2,3,4-butanetetracarboxylic acid dianhydride.
  • the structural unit (A2) derived from the aliphatic tetracarboxylic dianhydride includes the structural unit (A2-1) derived from the compound represented by the following formula (a2-1) and the following formula (A2-1). At least one selected from the structural unit (A2-2) derived from the compound represented by a2-2) and the structural unit (A2-3) derived from the compound represented by the following formula (a2-3). It is preferably contained, and more preferably it contains a structural unit (A2-2) derived from a compound represented by the following formula (a2-2).
  • the structural unit (A2) derived from the aliphatic tetracarboxylic acid dianhydride is a structural unit (A2-1) derived from the compound represented by the following formula (a2-1), and the following formula (a2-2). It is preferably at least one selected from the structural unit (A2-2) derived from the compound represented by the above and the structural unit (A2-3) derived from the compound represented by the following formula (a2-3). , It is more preferable that it is a structural unit (A2-2) derived from a compound represented by the following formula (a2-2).
  • the compound represented by the formula (a2-1) is 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA).
  • the compound represented by the formula (a2-2) is 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA).
  • the compound represented by the above formula (a2-3) is norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5'', 6,6''-tetra. It is a carboxylic dianhydride (CpODA).
  • the structural unit A includes the structural unit (A2), the deformation recovery property and the colorless transparency are improved while maintaining the mechanical strength.
  • the polyimide resin and the polyimide film of the present invention have both mechanical properties and colorless transparency.
  • the reason why it is excellent in deformation recovery while having high strength is not clear, but it is considered to be derived from the rigidity of the fluorene group and the degree of freedom of the aliphatic compound.
  • the ratio of the constituent unit (A1) to the constituent unit A is preferably 30 to 90 mol%, more preferably 40 to 90 mol%, still more preferably 50 to 90 mol%, still more preferably 50. ⁇ 80 mol%.
  • the ratio of the constituent unit (A2) to the constituent unit A is preferably 10 to 70 mol%, more preferably 10 to 60 mol%, still more preferably 10 to 50 mol%, still more preferably 20. ⁇ 50 mol%.
  • the total ratio of the structural unit (A1) and the structural unit (A2) in the structural unit A is preferably 50 mol% or more, more preferably 70 mol% or more, and further preferably 90 mol% or more.
  • the upper limit of the ratio of the total of the constituent units (A1) and the constituent units (A2) is not particularly limited, and is 100 mol% or less.
  • the constituent unit A may be composed of only the constituent unit (A1) and the constituent unit (A2).
  • the molar ratio [(A1) / (A2)] of the structural unit (A1) and the structural unit (A2) in the structural unit A is preferably 20/80 from the viewpoint of improving mechanical properties, colorless transparency and deformation recovery. It is ⁇ 90/10, more preferably 30/70 to 90/10, further preferably 40/60 to 80/20, and even more preferably 50/50 to 70/30. Especially from the viewpoint of improving the deformation recovery at high temperature, it is preferably 40/60 to 80/20, more preferably 40/60 to 70/30, and further preferably 40/60 to 60/40. Is.
  • the polyimide resin of the present invention contains a constituent unit derived from a tetracarboxylic dianhydride other than the constituent unit (A1) and the constituent unit (A2) in the constituent unit A as long as the effect of the present invention is not impaired. You may.
  • the tetracarboxylic acid dianhydride that gives a structural unit other than the structural unit (A1) and the structural unit (A2) is not particularly limited, but is pyromellitic anhydride, 2,3,5,6-toluenetetracarboxylic dianhydride. Examples thereof include aromatic tetracarboxylic acid dianhydrides such as 1,4,5,8-naphthalenetetracarboxylic acid dianhydride. These can be used alone or in combination of two or more.
  • aromatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more aromatic rings.
  • the structural unit B contained in the polyimide of the present invention is a structural unit derived from diamine.
  • the structural unit B includes a structural unit (B1) derived from the compound represented by the following formula (b1).
  • the compound represented by the formula (b1) is 2,2'-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane (HFBAPP).
  • HFBAPP 2,2'-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane
  • the ratio of the constituent unit (B1) to the constituent unit B is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, still more preferably 50 mol% or more. Is. In particular, from the viewpoint of improving the elongation of the obtained polyimide film, it is more preferably 70 mol% or more, still more preferably 90 mol% or more. Further, the upper limit of the ratio of the constituent unit (B1) is not particularly limited, and is 100 mol% or less.
  • the structural unit B may be composed of only the structural unit (B1).
  • the polyimide resin of the present invention contains a diamine other than the compound represented by the general formula (b1) as a structural unit other than the structural unit (B1) in the structural unit B as long as the effect of the present invention is not impaired. It may contain the building blocks from which it is derived.
  • the diamine other than the compound represented by the above general formula (b1) is not particularly limited, but is limited to 3,5-diaminobenzoic acid (3,5-DABA) and bis [4- (3-aminophenoxy) phenyl] sulfone.
  • 3,5-diaminobenzoic acid (3,5-DABA) and bis [4- (3-aminophenoxy) phenyl] sulfone At least one selected from the group consisting of BAPS-M) and 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is preferred.
  • the aromatic diamine means a diamine containing one or more aromatic rings
  • the aliphatic diamine means a diamine not containing an aromatic ring
  • the aliphatic diamine means an aliphatic diamine.
  • the number average molecular weight of the polyimide resin of the present invention is preferably 5,000 to 100,000 from the viewpoint of the mechanical strength of the obtained polyimide film.
  • the number average molecular weight of the polyimide resin can be measured by gel filtration chromatography or the like.
  • the polyimide resin of the present invention may be further mixed with various additives as long as the effects of the present invention are not impaired.
  • the additive include antioxidants, light stabilizers, surfactants, flame retardants, plasticizers, polymer compounds other than the polyimide resin, and the like.
  • the polymer compound include polyimides other than the polyimide resin of the present invention, polyesters such as polycarbonate, polystyrene, polyamide, polyamideimide and polyethylene terephthalate, polyethersulfone, polycarboxylic acid, polyacetylene, polyphenylene ether, polysulfone, polybutylene, polypropylene and poly. Examples include acrylamide, polyvinyl chloride and the like.
  • the polyimide resin of the present invention is obtained by reacting a tetracarboxylic acid component containing the above-mentioned compound giving the structural unit (A1) and the compound giving (A2) with a diamine component containing the compound giving the structural unit (B1). Can be manufactured.
  • Examples of the compound giving the structural unit (A1) include the compound represented by the formula (a1), but the compound is not limited to this, and may be a derivative thereof as long as the same structural unit is given.
  • Examples of the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a1) and an alkyl ester of the tetracarboxylic acid.
  • the compound represented by the formula (a1) that is, dianhydride
  • dianhydride is preferable.
  • examples of the compound giving the structural unit (A2) include an aliphatic tetracarboxylic dianhydride, preferably an alicyclic tetracarboxylic dianhydride, and more preferably a formula (a2-1) and a formula (a2-1).
  • examples thereof include the compound represented by a2-2) or the formula (a2-3), but the compound is not limited to this, and may be a derivative thereof as long as the same structural unit is given.
  • Examples of the derivative of the compound represented by the formula (a2-1), the formula (a2-2) or the formula (a2-3) include the formula (a2-1), the formula (a2-2) or the formula (a2-3).
  • Examples thereof include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by and an alkyl ester of the tetracarboxylic acid.
  • a compound represented by the formula (a2-1), the formula (a2-2) or the formula (a2-3) that is, a dianhydride is preferable.
  • the tetracarboxylic acid component contains, preferably 30 to 90 mol%, more preferably 40 to 90 mol%, still more preferably 50 to 90 mol%, and even more preferably 50, the compound giving the structural unit (A1). Contains ⁇ 80 mol%.
  • the tetracarboxylic acid component contains, preferably 10 to 70 mol%, more preferably 10 to 60 mol%, still more preferably 10 to 50 mol%, and even more preferably 20 to the compound giving the structural unit (A2). Contains ⁇ 50 mol%.
  • the total content ratio of the compound giving the structural unit (A1) and the compound giving the structural unit (A2) is preferably 50 mol% or more, more preferably 70 mol% or more, in the total tetracarboxylic acid component. More preferably, it is 90 mol% or more.
  • the upper limit of the total content ratio of the compound giving the structural unit (A1) and the compound giving the structural unit (A2) is not particularly limited and is 100 mol% or less.
  • the tetracarboxylic dian component may consist only of a compound that gives a constituent unit (A1) and a compound that gives a constituent unit (A2).
  • the molar ratio [(A1) / (A2)] of the compound giving the constituent unit (A1) to the compound giving the constituent unit (A2) in the tetracarboxylic acid component improves mechanical properties, colorless transparency and deformation recovery. From the viewpoint, it is preferably 20/80 to 90/10, more preferably 30/70 to 90/10, still more preferably 40/60 to 80/20, and even more preferably 50/50 to 70. / 30. Especially from the viewpoint of improving the deformation recovery at high temperature, it is preferably 40/60 to 80/20, more preferably 40/60 to 70/30, and further preferably 40/60 to 60/40. Is.
  • the tetracarboxylic acid component may contain a compound other than the compound giving the structural unit (A1) and the compound giving the structural unit (A2), and the compound includes the above-mentioned aromatic tetracarboxylic dianhydride and derivatives thereof.
  • Tetracarboxylic acid, alkyl ester of tetracarboxylic acid, etc. can be mentioned.
  • the compound arbitrarily contained in the tetracarboxylic acid component (that is, a compound other than the compound giving the structural unit (A1) and the structural unit (A2)) may be one kind or two or more kinds.
  • Examples of the compound giving the structural unit (B1) include the compound represented by the formula (b1), but the compound is not limited to this, and may be a derivative thereof as long as the same structural unit is given.
  • Examples of the derivative include diisocyanates corresponding to the diamine represented by the formula (b1).
  • the compound represented by the formula (b1) that is, a diamine is preferable.
  • the diamine component contains the compound giving the constituent unit (B1) in an amount of preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, still more preferably 50 mol% or more. Including the above. In particular, from the viewpoint of improving the elongation of the obtained polyimide film, it is more preferably contained in an amount of 70 mol% or more, and further preferably contained in an amount of 90 mol% or more. Further, the upper limit of the ratio of the compound giving the structural unit (B1) is not particularly limited, and is 100 mol% or less.
  • the diamine component may consist only of the compound giving the structural unit (B1).
  • the diamine component may contain a compound other than the compound giving the structural unit (B1), and the compound includes the above-mentioned aromatic diamine, alicyclic diamine, aliphatic diamine, modified silicone diamine, and derivatives thereof (diisocyanate). Etc.).
  • the compound arbitrarily contained in the diamine component (that is, a compound other than the compound giving the structural unit (B1)) may be one kind or two or more kinds.
  • the charging amount ratio of the tetracarboxylic acid component and the diamine component is preferably 0.9 to 1.1 mol of the diamine component with respect to 1 mol of the tetracarboxylic acid component. ..
  • an end-capping agent may be used in addition to the tetracarboxylic acid component and the diamine component.
  • the terminal encapsulant monoamines or dicarboxylic acids are preferable.
  • the amount of the terminal encapsulant to be introduced is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.06 mol, based on 1 mol of the tetracarboxylic acid component.
  • Preferred monoamine terminal encapsulants include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine and 3-ethyl.
  • Benzylamine, aniline, 3-methylaniline, 4-methylaniline and the like can be mentioned. Of these, benzylamine and aniline are more preferable.
  • dicarboxylic acid terminal encapsulant dicarboxylic acids are preferable, and a part thereof may be ring-closed.
  • Preferred dicarboxylic acids include phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenone dicarboxylic acid, 3,4-benzophenone dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid and cyclopentane. Examples thereof include -1,2-dicarboxylic acid and 4-cyclohexene-1,2-dicarboxylic acid. Of these, phthalic acid and phthalic anhydride are more preferable.
  • the method for reacting the above-mentioned tetracarboxylic acid component and the diamine component is not particularly limited, and a known method can be used.
  • a specific reaction method (1) a tetracarboxylic acid component, a diamine component, and a reaction solvent are charged in a reactor, stirred at 10 to 110 ° C. for 0.5 to 30 hours, and then heated to imidize. Method of carrying out the reaction, (2) The diamine component and the reaction solvent are charged into a reactor and dissolved, then the tetracarboxylic acid component is charged, and if necessary, the mixture is stirred at 10 to 110 ° C. for 0.5 to 30 hours, and then.
  • Examples thereof include a method of carrying out an imidization reaction by raising the temperature to (3) a method of charging a tetracarboxylic acid component, a diamine component and a reaction solvent into a reactor and immediately raising the temperature to carry out the imidization reaction.
  • the reaction solvent used for producing the polyimide resin may be any one that does not inhibit the imidization reaction and can dissolve the produced polyimide resin.
  • an aprotic solvent, a phenol solvent, an ether solvent, a carbonate solvent and the like can be mentioned.
  • aprotonic solvent examples include N, N-dimethylisobutylamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethyl.
  • Amide solvents such as imidazolidinone and tetramethylurea, lactone solvents such as ⁇ -butyrolactone and ⁇ -valerolactone, phosphorus-containing amide solvents such as hexamethylphosphoric amide and hexamethylphosphintriamide, dimethyl sulfone, Sulfur-containing solvents such as dimethyl sulfoxide and sulfolane, ketone solvents such as acetone, cyclohexanone and methylcyclohexane, amine solvents such as picolin and pyridine, ester solvents such as acetic acid (2-methoxy-1-methylethyl), etc. Can be mentioned.
  • phenolic solvent examples include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4. -Xylenol, 3,5-xylenol and the like can be mentioned.
  • ether solvent examples include 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, and bis [2- (2-methoxyethoxy) ethyl]. Examples include ether, tetrahydrofuran, 1,4-dioxane and the like.
  • the carbonate solvent examples include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate and the like.
  • an amide solvent or a lactone solvent is preferable. Further, the above reaction solvent may be used alone or in combination of two or more.
  • the imidization reaction it is preferable to carry out the reaction while removing water generated during production using a Dean-Stark apparatus or the like. By performing such an operation, the degree of polymerization and the imidization rate can be further increased.
  • a known imidization catalyst can be used.
  • the imidization catalyst include a base catalyst or an acid catalyst.
  • Base catalysts include pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, imidazole, N, N-dimethylaniline. , N, N-diethylaniline and the like, organic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate, sodium hydrogencarbonate and the like.
  • the acid catalyst examples include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, paratoluenesulfonic acid, naphthalenesulfonic acid and the like. Can be mentioned.
  • the above imidization catalyst may be used alone or in combination of two or more. Of the above, from the viewpoint of handleability, it is preferable to use a base catalyst, more preferably an organic base catalyst, and even more preferably triethylamine.
  • the temperature of the imidization reaction is preferably 120 to 250 ° C., more preferably 160 to 190 ° C., still more preferably 180 to 190 ° C. from the viewpoint of suppressing the reaction rate and gelation. be.
  • the reaction time is preferably 0.5 to 10 hours after the start of distillation of the produced water.
  • the temperature of the imidization reaction when no catalyst is used is preferably 200 to 350 ° C.
  • the polyimide varnish of the present invention is obtained by dissolving the polyimide resin of the present invention in an organic solvent. That is, the polyimide varnish of the present invention contains the polyimide resin of the present invention and an organic solvent, and the polyimide resin is dissolved in the organic solvent.
  • the organic solvent may be any one that dissolves the polyimide resin, and is not particularly limited, but it is preferable to use the above-mentioned compounds alone or in combination of two or more as the reaction solvent used for producing the polyimide resin.
  • the polyimide varnish of the present invention preferably contains 5 to 60% by mass of the polyimide resin of the present invention, and more preferably 5 to 45% by mass.
  • the viscosity of the polyimide varnish is preferably 0.1 to 200 Pa ⁇ s, more preferably 0.5 to 150 Pa ⁇ s.
  • the polyimide film of the present invention contains the above-mentioned polyimide resin. Further, the polyimide film of the present invention is preferably made of the above-mentioned polyimide resin. That is, it has a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from diamine, and the structural unit A is a structural unit (A1) derived from the compound represented by the formula (a1).
  • the polyimide film of the present invention has both mechanical properties and colorless transparency, and is excellent in deformation recovery while having high strength.
  • the method for producing the polyimide film of the present invention is not particularly limited, and a known method can be used.
  • a solution containing the polyimide resin of the present invention or a solution containing the solution containing the polyimide resin of the present invention and the various additives described above is applied onto a smooth support such as a glass plate, a metal plate, or plastic.
  • a method of removing a solvent component such as an organic solvent contained in the solution after molding into a film can be mentioned.
  • the solution containing the polyimide resin may be the polyimide resin solution itself obtained by the polymerization method. Further, at least one selected from the compounds exemplified above as a solvent for dissolving the polyimide resin in the polyimide resin solution may be mixed. By adjusting the solid content concentration and viscosity of the solution containing the polyimide resin as described above, the thickness of the polyimide film of the present invention can be easily controlled.
  • a mold release agent may be applied to the surface of the support.
  • the following method is preferable as a method of applying the polyimide resin or a solution containing the polyimide resin composition to the support and then heating to evaporate the solvent component. That is, after evaporating the solvent at a temperature of 120 ° C. or lower to form a self-supporting film, the self-supporting film was peeled off from the support, the end portion of the self-supporting film was fixed, and the solvent component used was used. It is preferable to produce a polyimide film by drying at a temperature equal to or higher than the boiling point and 350 ° C. or lower. Further, it is preferable to dry in a nitrogen atmosphere. The pressure in the dry atmosphere may be reduced pressure, normal pressure, or pressurized pressure.
  • the thickness of the polyimide film of the present invention can be appropriately selected depending on the intended use and the like, but is preferably in the range of 1 to 250 ⁇ m, more preferably 5 to 100 ⁇ m, and further preferably 10 to 80 ⁇ m. When the thickness is 1 to 250 ⁇ m, it can be practically used as a self-supporting film.
  • the polyimide film containing the polyimide resin of the present invention is suitably used as a film for various members such as color filters, flexible displays, semiconductor parts, and optical members.
  • the physical characteristics of the polyimide films obtained in the following Examples and Comparative Examples were measured by the methods shown below.
  • Film thickness The film thickness was measured using a micrometer manufactured by Mitutoyo Co., Ltd.
  • Tensile strength and tensile elastic modulus were measured in accordance with JIS K7127 using a tensile tester "Strograph VG1E” manufactured by Toyo Seiki Co., Ltd.
  • Tensile breaking elongation rate The tensile breaking elongation rate was measured by a tensile test (measurement of elongation rate) in accordance with JIS K7127.
  • the test piece used had a width of 10 mm and a thickness of 10 to 70 ⁇ m.
  • Example 1 A 300 mL five-necked round-bottom flask equipped with a stainless half-moon stirring blade, a nitrogen inlet tube, a Dean-Stark apparatus with a cooling tube, a thermometer, and a glass end cap, and 2,2'-bis as a diamine component.
  • 4- (4-Aminophenoxy) phenyl] Hexafluoropropane manufactured by Seika Co., Ltd., hereinafter HFBAPP
  • HFBAPP Hexafluoropropane
  • GBL ⁇ -butyrolactone
  • a polyimide solution was obtained by collecting the components to be distilled off, maintaining the temperature inside the reaction system at 190 ° C., and refluxing for 2 hours while adjusting the rotation speed according to the increase in viscosity. After that, when the temperature inside the reaction system is cooled to 120 ° C., N, N-dimethylacetamide (manufactured by Mitsubishi Gas Chemical Company, Inc., hereinafter DMAc) is added so as to have a predetermined solid content concentration, and the mixture is further stirred for about 3 hours to make it uniform. A polyimide varnish (A) having a solid content concentration of 20.0% by mass was obtained.
  • N, N-dimethylacetamide manufactured by Mitsubishi Gas Chemical Company, Inc., hereinafter DMAc
  • the polyimide varnish (A) is applied onto a PET substrate, held at 60 ° C. for 20 minutes, 80 ° C. for 20 minutes, and 100 ° C. for 30 minutes to volatilize the solvent to provide self-supporting transparent primary.
  • a dried film was obtained, and the film was further fixed to a stainless steel frame and dried at 220 ° C. in an air atmosphere for 20 minutes to remove the solvent to obtain a polyimide film.
  • Table 1 shows the measurement results and evaluation results of the physical properties.
  • Example 2 The amount of HFBAPP is set to 24.25 g (0.047 mol), and 1.78 g (0.012 mol) of 3,5-diaminobenzoic acid (manufactured by Nippon Junyaku Ryohin Co., Ltd., hereinafter 3,5-DABA) is added.
  • the same method as in Example 1 except that the amount of TEA was changed to 0.296 g, the amount of BPAF was changed to 13.40 g (0.029 mol), and the amount of HPMDA was changed to 6.55 g (0.029 mol). Obtained a polyimide varnish (B) having a solid content concentration of 15.0% by mass. Using the obtained polyimide varnish (B), a polyimide film was obtained by the same method as in Example 1. Table 1 shows the measurement results and evaluation results of the physical properties.
  • Example 3 The amount of HFBAPP is 14.58 g (0.028 mol), and 12.16 g (0.028 mol) of bis [4- (3-aminophenoxy) phenyl] sulfone (manufactured by Seika Co., Ltd., hereinafter BAPS-M) is added.
  • BAPS-M bis [4- (3-aminophenoxy) phenyl] sulfone
  • Example 4 The amount of HFBAPP is 19.15 g (0.037 mol), and 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether (ChinaTech Chemical (Taijin) Co., Ltd., hereinafter 6FODA). 12.42 g (0.037 mol) was added, the amount of TEA was changed to 0.296 g, the amount of BPAF was 16.93 g (0.037 mol), and the amount of HPMDA was 8.28 g (0.037 mol).
  • a polyimide varnish (D) having a solid content concentration of 18.5% by mass was obtained by the same method as in Example 1 except that the solid content was changed to 18.5% by mass. Using the obtained polyimide varnish (D), a film was obtained by the same method as in Example 1. Table 1 shows the measurement results and evaluation results of the physical properties.
  • Example 5 The amount of HFBAPP is 12.08 g (0.023 mol), the amount of 6FODA is 18.28 g (0.054 mol), the amount of BPAF is 17.80 g (0.039 mol), and the amount of HPMDA is 8.70 g (.
  • a polyimide varnish (E) having a solid content concentration of 18.5% by mass was obtained by the same method as in Example 4 except that the content was changed to 0.039 mol). Using the obtained polyimide varnish (E), a film was obtained by the same method as in Example 1. Table 1 shows the measurement results and evaluation results of the physical properties.
  • Example 6 The amount of HFBAPP is 18.19 g (0.035 mol), the amount of 6FODA is 11.79 g (0.035 mol), the amount of BPAF is 22.51 g (0.049 mol), and the amount of HPMDA is 4.72 g (.
  • a polyimide varnish (F) having a solid content concentration of 18.5% by mass was obtained by the same method as in Example 4 except that the content was changed to 0.021 mol). Using the obtained polyimide varnish (F), a film was obtained by the same method as in Example 1. Table 1 shows the measurement results and evaluation results of the physical properties.
  • Example 7 The amount of HFBAPP was changed to 33.49 g (0.065 mol), the amount of BPAF was changed to 14.81 g (0.032 mol), and Norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ was not used.
  • Add 12.42 g (0.032 mol) of'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride manufactured by JXTG Energy Co., Ltd., hereinafter CpODA.
  • a polyimide varnish (G) having a solid content concentration of 20.0% by mass was obtained by the same method as in Example 1. Using the obtained polyimide varnish (G), a film was obtained by the same method as in Example 1. Table 1 shows the measurement results and evaluation results of the physical properties.
  • Example 2 The amount of HFBAPP is 39.23 g (0.076 mol), the amount of 3,5-DABA is 2.88 g (0.019 mol), and the amount of HPMDA is 21.20 g (0.095 mol) without using BPAF.
  • a polyimide varnish was produced by the same method as in Example 2 except that the solid content concentration was changed to (I), and a polyimide varnish (I) having a solid content concentration of 20% by mass was obtained. Using the obtained polyimide varnish (I), a film was obtained by the same method as in Example 1.
  • the polyimide films of Examples 1 to 7 have both mechanical properties and colorless transparency, and are excellent in deformation recovery under both high humidity conditions and dry conditions while having high strength. ..

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention concerne une résine polyimide possédant: une unité structurelle (A) dérivée de dianhydride tétracarboxylique et une unité structurelle (B) dérivée de diamine. L'unité structurelle (A) contient une unité structurelle (A1) dérivée de dianhydride d'acide 9,9-bis(3,4-dicarboxyphényl)fluorénique, et une unité structurelle (A2) dérivée de dianhydride tétracarboxylique aliphatique; et l'unité structurelle (B) contient une unité structurelle (B1) dérivée de 2,2'-bis[4-(4-aminophénoxy)phényl] hexafluoropropane.
PCT/JP2021/026768 2020-07-21 2021-07-16 Résine polyimide, vernis polyimide, et film polyimide WO2022019226A1 (fr)

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JP2013069505A (ja) * 2011-09-21 2013-04-18 Dexerials Corp 電池用セパレータシート及び電池
WO2020110948A1 (fr) * 2018-11-28 2020-06-04 三菱瓦斯化学株式会社 Résine polyimide, vernis polyimide et film de polyimide
JP2020193325A (ja) * 2019-05-27 2020-12-03 信越化学工業株式会社 有機膜形成用材料、半導体装置製造用基板、有機膜の形成方法、及びパターン形成方法

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WO2018097143A1 (fr) 2016-11-24 2018-05-31 日産化学工業株式会社 Composition pour former un substrat de dispositif flexible

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013069505A (ja) * 2011-09-21 2013-04-18 Dexerials Corp 電池用セパレータシート及び電池
WO2020110948A1 (fr) * 2018-11-28 2020-06-04 三菱瓦斯化学株式会社 Résine polyimide, vernis polyimide et film de polyimide
JP2020193325A (ja) * 2019-05-27 2020-12-03 信越化学工業株式会社 有機膜形成用材料、半導体装置製造用基板、有機膜の形成方法、及びパターン形成方法

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