Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present invention relates to a polyimide resin, a polyimide varnish, and a polyimide film.
• polyimide resins have excellent mechanical properties and heat resistance, and thus are being used in various fields such as electrical and electronic parts.
• a glass substrate used for an image display device such as a liquid crystal display or an OLED display
• a plastic substrate for the purpose of reducing the weight or flexibility of the device.
• the polyimide film for such use is required to be colorless and transparent.
• Patent Document 1 When a varnish applied on a glass support or a silicon wafer is heated and cured to form a polyimide film, residual stress is generated in the polyimide film. When the residual stress of the polyimide film is large, there arises a problem that the glass support or the silicon wafer is warped. Therefore, the polyimide film is also required to reduce the residual stress.
• 4,4′-oxydiphthalic dianhydride is used as a tetracarboxylic acid component as a polyimide resin that gives a film having low residual stress
• ⁇ , ⁇ -aminopropyl poly (ethylene) having a number average molecular weight of 1000 is used as a diamine component.
• a polyimide resin synthesized using dimethylsiloxane and 4,4′-diaminodiphenyl ether is disclosed.
• the polyimide film is required to have colorless transparency and low residual stress, but it is not easy to improve these characteristics while maintaining excellent mechanical properties and heat resistance.
• the present invention has been made in view of such circumstances, and the object of the present invention is a polyimide resin that is excellent in mechanical properties, heat resistance, and colorless transparency, and can form a film with low residual stress, Another object is to provide a polyimide varnish and a polyimide film containing the polyimide resin.
• the present inventors have found that a polyimide resin containing a combination of specific structural units can solve the above problems, and have completed the invention.
• the structural unit B includes a structural unit (B-1) derived from a compound represented by the following formula (b-1),
• the proportion of the structural unit (A-1) in the structural unit A is 50 to 90 mol%
• the polyimide resin according to [1] above, wherein the proportion of the structural unit (A-2) in the structural unit A is 10 to 50 mol%.
• the polyimide resin according to the above [1] or [2], wherein the proportion of the structural unit (B-1) in the structural unit B is 50 mol% or more.
• a polyimide film comprising the polyimide resin according to any one of [1] to [3] above.
• the polyimide resin of the present invention has a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from diamine, and the structural unit A is derived from a compound represented by the following formula (a-1). Including a structural unit (A-1) and a structural unit (A-2) derived from a compound represented by the following formula (a-2), wherein the structural unit B is represented by the following formula (b-1). The structural unit (B-1) derived from the compound is included, and the structural unit A does not include the structural unit (AX) derived from the compound represented by the following formula (ax).
• the structural unit A is a structural unit derived from tetracarboxylic dianhydride occupying the polyimide resin, the structural unit (A-1) derived from a compound represented by the following formula (a-1), and the following formula A structural unit (A-2) derived from the compound represented by (a-2), and a structural unit (AX) derived from the compound represented by the following formula (ax).
• the compound represented by the formula (a-1) is norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′ -tetracarboxylic Acid dianhydride.
• the compound represented by the formula (a-2) is biphenyltetracarboxylic dianhydride (BPDA), and specific examples thereof include 3,3 ′, 4, represented by the following formula (a-2s): 4′-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (a-BPDA) represented by the following formula (a-2a), Examples thereof include 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride (i-BPDA) represented by the following formula (a-2i).
• BPDA biphenyltetracarboxylic dianhydride
• the structural unit A includes both the structural unit (A-1) and the structural unit (A-2), the mechanical properties, heat resistance and colorless transparency of the film are improved, and the residual stress is decreased.
• the compound represented by the formula (ax) is 1,2,4,5-cyclohexanetetracarboxylic dianhydride.
• the structural unit A does not include the structural unit (AX) derived from the compound represented by the formula (ax). That is, the polyimide resin of the present invention does not contain a structural unit (AX).
• the ratio of the structural unit (A-1) in the structural unit A is preferably 50 to 90 mol%, more preferably 55 to 85 mol%, and still more preferably 60 to 80 mol%.
• the ratio of the structural unit (A-2) in the structural unit A is preferably 10 to 50 mol%, more preferably 15 to 45 mol%, and still more preferably 20 to 40 mol%.
• the total ratio of the structural units (A-1) and (A-2) in the structural unit A is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more. And particularly preferably 99 mol% or more.
• the upper limit value of the total ratio of the structural units (A-1) and (A-2) is not particularly limited, that is, 100 mol%.
• the structural unit A may consist of only the structural unit (A-1) and the structural unit (A-2).
• the structural unit A may include structural units other than the structural units (A-1) and (A-2) (except for the structural unit (AX)).
• the tetracarboxylic dianhydride that gives such a structural unit is not particularly limited, but pyromellitic dianhydride, 9,9′-bis (3,4-dicarboxyphenyl) fluorene dianhydride, and 4 , 4 ′-(Hexafluoroisopropylidene) diphthalic anhydride and other aromatic tetracarboxylic dianhydrides (excluding compounds represented by the formula (a-2)); 1,2,3,4- Cycloaliphatic tetracarboxylic dianhydrides such as cyclobutanetetracarboxylic dianhydride (excluding compounds represented by formula (a-1) and compounds represented by formula (ax)); and 1 And aliphatic tetracarboxylic dianhydrides such as 2,3,4-butanetetracarboxylic dianhydride.
• an aromatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more aromatic rings
• an alicyclic tetracarboxylic dianhydride means one alicyclic ring.
• the tetracarboxylic dianhydride containing the above and containing no aromatic ring means an aliphatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing neither an aromatic ring nor an alicyclic ring.
• the structural units other than the structural units (A-1) and (A-2) optionally contained in the structural unit A may be one type or two or more types.
• the structural unit B is a structural unit derived from a diamine in the polyimide resin, and includes a structural unit (B-1) derived from a compound represented by the following formula (b-1).
• the compound represented by the formula (b-1) is 2,2′-bis (trifluoromethyl) benzidine.
• the structural unit B contains the structural unit (B-1)
• the colorless transparency and heat resistance of the film are improved, and the residual stress is reduced.
• the ratio of the structural unit (B-1) in the structural unit B is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol%. % Or more.
• the upper limit value of the ratio of the structural unit (B-1) is not particularly limited, that is, 100 mol%.
• the structural unit B may consist of only the structural unit (B-1).
• the structural unit B may include a structural unit other than the structural unit (B-1).
• the diamine which gives such a structural unit is not particularly limited, but 1,4-phenylenediamine, p-xylylenediamine, 3,5-diaminobenzoic acid, 1,5-diaminonaphthalene, 2,2′-dimethyl Biphenyl-4,4′-diamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4′-diaminodiphenylsulfone, 4 , 4'-diaminobenzanilide, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, ⁇ , ⁇ '-bis (4-aminophenyl) ) -1,4-di
• an aromatic diamine means a diamine containing one or more aromatic rings
• an alicyclic diamine means a diamine containing one or more alicyclic rings and no aromatic ring
• a group diamine means a diamine containing neither an aromatic ring nor an alicyclic ring.
• the number of structural units other than the structural unit (B-1) optionally included in the structural unit B may be one or more.
• 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 resulting polyimide film.
• the number average molecular weight of a polyimide resin can be calculated
• the polyimide resin of the present invention may contain a structure other than a polyimide chain (a structure in which the structural unit A and the structural unit B are imide-bonded).
• Examples of the structure other than the polyimide chain that can be included in the polyimide resin include a structure including an amide bond.
• the polyimide resin of the present invention preferably contains a polyimide chain (a structure in which the structural unit A and the structural unit B are imide-bonded) as a main structure. Therefore, the ratio of the polyimide chain in the polyimide resin of the present invention is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably 99% by mass. % Or more.
• the polyimide resin of the present invention By using the polyimide resin of the present invention, it is possible to form a film having excellent mechanical properties, heat resistance, and colorless transparency, and further having low residual stress, and suitable physical properties of the film are as follows. is there.
• the tensile elastic modulus is preferably 2.5 GPa or more, more preferably 3.0 GPa or more, and further preferably 3.5 GPa or more.
• the tensile strength is preferably 100 MPa or more, more preferably 120 MPa or more, and further preferably 150 MPa or more.
• the glass transition temperature (Tg) is preferably 320 ° C. or higher, more preferably 350 ° C. or higher, and still more preferably 365 ° C. or higher.
• the total light transmittance is preferably 88% or more, more preferably 89% or more, and still more preferably 90% or more when a film having a thickness of 10 ⁇ m is formed.
• the yellow index (YI) is preferably 3.5 or less, more preferably 3.0 or less, and even more preferably 2.8 or less when a film having a thickness of 10 ⁇ m is formed.
• the residual stress is preferably 18.0 MPa or less, more preferably 17.0 MPa or less, and further preferably 15.0 MPa or less.
• the said physical-property value in this invention can be specifically measured by the method as described in an Example.
• the polyimide resin of the present invention contains the compound that gives the structural unit (A-1) and the compound that gives the structural unit (A-2), but does not contain the compound that gives the structural unit (AX). It can be produced by reacting a tetracarboxylic acid component with a diamine component containing a compound that gives the structural unit (B-1).
• Examples of the compound that provides the structural unit (A-1) include compounds represented by the formula (a-1), but are not limited thereto, and may be derivatives thereof within a range that provides the same structural unit.
• Examples of the derivative include tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a-1) (that is, norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′). -Norbornane-5,5 ′′, 6,6 ′′ -tetracarboxylic acid), and alkyl esters of the tetracarboxylic acid.
• examples of the compound that provides the structural unit (A-2) include compounds represented by the formula (a-2), but are not limited thereto and may be derivatives thereof within a range that provides the same structural unit. .
• examples of the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a-2) and an alkyl ester of the tetracarboxylic acid.
• a-2 a compound represented by the formula (a-2) (that is, dianhydride) is preferable.
• the tetracarboxylic acid component does not include a compound that provides the structural unit (AX). Therefore, the tetracarboxylic acid component does not include the compound represented by the formula (ax), and does not include the derivative as long as the same structural unit is provided.
• the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (ax) and an alkyl ester of the tetracarboxylic acid.
• the tetracarboxylic acid component preferably contains 50 to 90 mol%, more preferably 55 to 85 mol%, still more preferably 60 to 80 mol% of the compound that gives the structural unit (A-1).
• the tetracarboxylic acid component preferably contains 10 to 50 mol%, more preferably 15 to 45 mol%, and still more preferably 20 to 40 mol% of the compound giving the structural unit (A-2).
• the tetracarboxylic acid component contains, in total, a compound that provides the structural unit (A-1) and a compound that provides the structural unit (A-2), preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably Contains 90 mol% or more, particularly preferably 99 mol% or more.
• the upper limit of the total content of the compound that provides the structural unit (A-1) and the compound that provides the structural unit (A-2) is not particularly limited, that is, 100 mol%.
• the tetracarboxylic acid component may consist only of a compound that provides the structural unit (A-1) and a compound that provides the structural unit (A-2).
• the tetracarboxylic acid component may contain a compound other than the compound that gives the structural unit (A-1) and the compound that gives the structural unit (A-2) (except for the compound that gives the structural unit (AX)).
• the compound includes the above-mentioned aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aliphatic tetracarboxylic dianhydride, and derivatives thereof (tetracarboxylic acid, tetracarboxylic acid Alkyl ester etc.).
• the compound other than the compound giving the structural unit (A-1) and the compound giving the structural unit (A-2) optionally contained in the tetracarboxylic acid component may be one kind or two or more kinds.
• Examples of the compound that provides the structural unit (B-1) include compounds represented by the formula (b-1), but are not limited thereto, and may be derivatives thereof within a range that provides the same structural unit.
• Examples of the derivative include diisocyanates corresponding to the diamine represented by the formula (b-1).
• a compound represented by the formula (b-1) that is, a diamine is preferable.
• the diamine component preferably contains 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, particularly preferably 99 mol% or more of the compound that gives the structural unit (B-1). .
• the upper limit of the content of the compound that gives the structural unit (B-1) is not particularly limited, that is, 100 mol%.
• the diamine component may consist only of a compound that provides the structural unit (B-1).
• the diamine component may contain a compound other than the compound that gives the structural unit (B-1).
• the compound include the above-mentioned aromatic diamine, alicyclic diamine, and aliphatic diamine, and derivatives thereof (such as diisocyanate). Is mentioned.
• the compound other than the compound that provides the structural unit (B-1) optionally contained in the diamine component may be one kind or two or more kinds.
• the charging ratio of the tetracarboxylic acid component and the diamine component used for the production of the polyimide resin is preferably 0.9 to 1.1 mol of the diamine component relative to 1 mol of the tetracarboxylic acid component.
• a terminal blocking agent may be used in addition to the aforementioned tetracarboxylic acid component and diamine component.
• end-capping agents monoamines or dicarboxylic acids are preferred.
• the amount of the terminal blocking agent introduced is preferably 0.0001 to 0.1 mol, particularly preferably 0.001 to 0.06 mol, per 1 mol of the tetracarboxylic acid component.
• Examples of monoamine end-capping agents include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3- Ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline and the like are recommended. Of these, benzylamine and aniline can be preferably used.
• dicarboxylic acid end-capping agent dicarboxylic acids are preferable, and a part of them may be closed.
• phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenone dicarboxylic acid, 3,4-benzophenone dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclopentane-1,2 -Dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid and the like are recommended.
• phthalic acid and phthalic anhydride can be suitably used.
• a well-known method can be used. Specifically, (1) a tetracarboxylic acid component, a diamine component, and a reaction solvent are charged into a reactor, stirred at room temperature to 80 ° C. for 0.5 to 30 hours, and then heated to imidize. Method of performing the reaction, (2) The diamine component and the reaction solvent are charged into the reactor and dissolved, then the tetracarboxylic acid component is charged, and if necessary, stirred at room temperature to 80 ° C. for 0.5 to 30 hours, and then (3) A method in which a tetracarboxylic acid component, a diamine component, and a reaction solvent are charged into a reactor and the temperature is immediately raised to carry out an imidization reaction.
• the reaction solvent used for the production of the polyimide resin may be any solvent that does not inhibit the imidization reaction and can dissolve the produced polyimide.
• an aprotic solvent, a phenol solvent, an ether solvent, a carbonate solvent, and the like can be given.
• aprotic solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethylimidazolidinone, tetramethylurea, etc.
• Amide solvents lactone solvents such as ⁇ -butyrolactone and ⁇ -valerolactone, phosphorus-containing amide solvents such as hexamethylphosphoric amide and hexamethylphosphine triamide, sulfur-containing dimethylsulfone, dimethylsulfoxide, sulfolane and the like
• solvents such as ketone solvents such as acetone, cyclohexanone and methylcyclohexanone, amine solvents such as picoline and pyridine, and ester solvents such as acetic acid (2-methoxy-1-methylethyl).
• phenol 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.
• ether solvents include 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, 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.
• amide solvents or lactone solvents are preferable.
• the imidization reaction it is preferable to perform the reaction using a Dean Stark apparatus or the like while removing water generated during production. By performing such an operation, the degree of polymerization and the imidization rate can be further increased.
• a known imidation catalyst can be used.
• the imidization catalyst include a base catalyst and an acid catalyst.
• Base catalysts include pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, imidazole, N, N -Organic base catalysts such as dimethylaniline and N, N-diethylaniline, and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate.
• 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, p-toluenesulfonic acid, naphthalenesulfonic acid, etc. Is mentioned.
• the above imidation catalysts may be used alone or in combination of two or more. Among these, from the viewpoint of handleability, it is preferable to use a base catalyst, more preferably an organic base catalyst, still more preferably triethylamine, and particularly preferably a combination of triethylamine and triethylenediamine.
• the temperature of the imidization reaction is preferably 120 to 250 ° C., more preferably 160 to 200 ° C., from the viewpoint of suppressing the reaction rate and gelation.
• the reaction time is preferably 0.5 to 10 hours after the start of distillation of the produced water.
• 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 is not particularly limited as long as it dissolves the polyimide resin, but it is preferable to use the above-described compounds alone or in combination of two or more as the reaction solvent used in the production of the polyimide resin.
• the polyimide varnish of the present invention may be a polyimide solution itself in which a polyimide resin obtained by a polymerization method is dissolved in a reaction solvent, or may be a solution obtained by adding a dilution solvent to the polyimide solution.
• the polyimide varnish of the present invention preferably contains 5 to 40% by mass of the polyimide resin of the present invention, more preferably 10 to 30% by mass.
• the viscosity of the polyimide varnish is preferably 1 to 200 Pa ⁇ s, more preferably 5 to 150 Pa ⁇ s.
• the viscosity of the polyimide varnish is a value measured at 25 ° C. using an E-type viscometer.
• the polyimide varnish of the present invention is an inorganic filler, adhesion promoter, release agent, flame retardant, UV stabilizer, surfactant, leveling agent, antifoaming agent, fluorescent enhancement, as long as the required properties of the polyimide film are not impaired.
• Various additives such as a whitening agent, a crosslinking agent, a polymerization initiator, and a photosensitizer may be included.
• the manufacturing method of the polyimide varnish of this invention is not specifically limited, A well-known method is applicable.
• the polyimide film of the present invention contains the polyimide resin of the present invention. Therefore, the polyimide film of the present invention is excellent in mechanical properties, heat resistance, and colorless transparency, and has a low residual stress.
• the preferred physical properties of the polyimide film of the present invention are as described above.
• a release agent may be applied to the surface of the support in advance.
• a method for removing the organic solvent contained in the varnish by heating the following method is preferable. That is, after evaporating the organic solvent at a temperature of 120 ° C. or less to form a self-supporting film, the self-supporting film is peeled off from the support, the ends of the self-supporting film are fixed, and the organic solvent used It is preferable to produce a polyimide film by drying at a temperature equal to or higher than the boiling point. Moreover, it is preferable to dry in nitrogen atmosphere. The pressure in the dry atmosphere may be any of reduced pressure, normal pressure, and increased pressure.
• the heating temperature for producing the polyimide film by drying the self-supporting film is not particularly limited, but is preferably 200 to 400 ° C.
• the polyimide film of this invention can also be manufactured using the polyamic-acid varnish formed by melt
• the polyamic acid contained in the polyamic acid varnish is a precursor of the polyimide resin of the present invention, and includes a compound that provides the structural unit (A-1) and a compound that provides the structural unit (A-2). And a product of a polyaddition reaction of a tetracarboxylic acid component not containing the compound giving the structural unit (AX) and a diamine component containing the compound giving the structural unit (B-1).
• imidizing (dehydrating and ring-closing) this polyamic acid the final product, the polyimide resin of the present invention, is obtained.
• the organic solvent contained in the polyamic acid varnish As the organic solvent contained in the polyamic acid varnish, the organic solvent contained in the polyimide varnish of the present invention can be used.
• the polyamic acid varnish includes a compound that provides the structural unit (A-1) and a compound that provides the structural unit (A-2), and a compound that provides the structural unit (AX). It may be a polyamic acid solution itself obtained by polyaddition reaction of a tetracarboxylic acid component not contained and a diamine component containing the compound giving the structural unit (B-1) in a reaction solvent, or the polyamide What added the dilution solvent further with respect to an acid solution may be used.
• a well-known method can be used.
• a polyamic acid varnish is coated on a smooth support such as a glass plate, a metal plate, or a plastic, or formed into a film, and an organic solvent such as a reaction solvent or a diluting solvent contained in the varnish is removed by heating.
• a polyimide film can be produced by obtaining a polyamic acid film and imidizing the polyamic acid in the polyamic acid film by heating.
• the heating temperature for obtaining the polyamic acid film by drying the polyamic acid varnish is preferably 50 to 120 ° C.
• the heating temperature for imidizing the polyamic acid by heating is preferably 200 to 400 ° C.
• the imidization method is not limited to thermal imidization, and chemical imidization can also be applied.
• the thickness of the polyimide film of the present invention can be appropriately selected depending on the application and the like, but is preferably in the range of 1 to 250 ⁇ m, more preferably 5 to 100 ⁇ m, and still more preferably 10 to 80 ⁇ m. When the thickness is 1 to 250 ⁇ m, practical use as a self-supporting film becomes possible.
• the thickness of the polyimide film can be easily controlled by adjusting the solid content concentration and viscosity of the polyimide varnish.
• the polyimide film of the present invention is suitably used as a film for various members such as a color filter, a flexible display, a semiconductor component, and an optical member.
• the polyimide film of the present invention is particularly preferably used as a substrate for image display devices such as liquid crystal displays and OLED displays.
• Solid content concentration The solid content concentration of the varnish was calculated from the difference in mass of the sample before and after heating by heating the sample at 320 ° C. ⁇ 120 min in a small electric furnace “MMF-1” manufactured by AS ONE Corporation.
• Film thickness The film thickness was measured using a micrometer manufactured by Mitutoyo Corporation.
• Tensile Elastic Modulus and Tensile Strength The tensile elastic modulus and tensile strength were measured using a tensile tester “Strograph VG-1E” manufactured by Toyo Seiki Co., Ltd. in accordance with JIS K7127. The distance between chucks was 10 mm ⁇ 50 mm, and the test speed was 20 mm / min.
• Total light transmittance, yellow index (YI) The total light transmittance and YI were measured using a color / turbidity simultaneous measuring device “COH400” manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K7361-1: 1997. The closer the total light transmittance is to 100%, the better YI is.
• Residual stress A polyimide varnish was measured on a 4-inch silicon wafer having a thickness of 525 ⁇ m ⁇ 25 ⁇ m, in which the “warping amount” was measured in advance using a residual stress measuring device “FLX-2320” manufactured by KLA-Tencor Corporation. Alternatively, polyamic acid varnish was applied using a spin coater and prebaked.
• a heat curing treatment was performed at 400 ° C. for 1 hour in a nitrogen atmosphere, and a silicon wafer with a polyimide film having a thickness of 8 to 20 ⁇ m after curing was produced.
• the amount of warpage of the wafer was measured using the above-described residual stress measuring device, and the residual stress generated between the silicon wafer and the polyimide film was evaluated. The smaller the numerical value, the better the residual stress.
• tetracarboxylic acid component > CpODA: Norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′ -tetracarboxylic dianhydride (manufactured by JX Energy Corporation; Compound represented by formula (a-1)) BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation; compound represented by formula (a-2)) ⁇ Diamine> TFMB: 2,2′-bis (trifluoromethyl) benzidine (Wakayama Seika Kogyo Co., Ltd .; compound represented by formula (b-1))
• Example 1 32.024 g (0.100 mol) of TFMB in a 1 L 5-neck round bottom flask equipped with a stainless steel half-moon stirring blade, a Dean Stark fitted with a nitrogen inlet tube, a cooling tube, a thermometer, and a glass end cap And N-methylpyrrolidone (Mitsubishi Chemical Co., Ltd.) were added in an amount of 82.391 g, and the system temperature was 70 ° C. and a nitrogen atmosphere was stirred at a rotation speed of 150 rpm to obtain a solution.
• N-methylpyrrolidone Mitsubishi Chemical Co., Ltd.
• Example 2 The amount of CpODA was changed from 30.750 g (0.080 mol) to 23.063 g (0.060 mol), and the amount of BPDA was changed from 5.884 g (0.020 mol) to 11.769 g (0.040 mol). Except for the above, a polyimide varnish was produced in the same manner as in Example 1 to obtain a polyimide varnish having a solid content concentration of 10.0% by mass. Using the obtained polyimide varnish, a film was produced in the same manner as in Example 1 to obtain a film having a thickness of 7 ⁇ m. The results are shown in Table 1.
• N-methylpyrrolidone manufactured by Mitsubishi Chemical Corporation
• the polyimide films of Examples 1 and 2 were excellent in mechanical properties, heat resistance, and colorless transparency, and further had low residual stress.
• the polyimide film of Comparative Example 1 produced using only CpODA as the tetracarboxylic acid component was inferior in tensile modulus and heat resistance and high in residual stress as compared with the polyimide films of Examples 1 and 2.
• the polyimide film of Comparative Example 2 produced using only BPDA as the tetracarboxylic acid component was inferior in heat resistance and colorless transparency and high in residual stress as compared with the polyimide films of Examples 1 and 2. .

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