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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
  • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
• • 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
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate

Definitions

• the present invention relates to a polyimide resin, a polyimide varnish, and a polyimide film.
• Polyimide resins are being studied for various uses in the fields of electrical and electronic parts. For example, it is desired to replace a glass substrate used for an image display device such as a liquid crystal display or an OLED display with a plastic substrate for the purpose of reducing the weight or flexibility of the device. Research is ongoing.
• the polyimide film for such use is required to be colorless and transparent.
• a thin film transistor In an image display device such as a liquid crystal display or an OLED display, a thin film transistor (TFT) is used as a pixel switching element.
• Polycrystalline silicon (polysilicon) having excellent crystallinity has a higher electron mobility than amorphous silicon, and thus TFT characteristics are greatly improved.
• One method of forming a polysilicon film is an excimer laser annealing (ELA) method.
• ELA excimer laser annealing
• the amorphous silicon dehydrogenation process in this method is a high temperature process. Therefore, in order to form a polysilicon film on a plastic substrate, the plastic substrate is required to have high heat resistance (that is, high glass transition temperature).
• the plastic substrate is also required to have high thermal stability for suppressing generation of outgas to the highest possible temperature range. Furthermore, when light passes through a retardation film or a polarizing plate (for example, a liquid crystal display, an OLED display, a touch panel, etc.), the plastic substrate is required to have high optical isotropy in addition to colorless transparency. Is done.
• a retardation film or a polarizing plate for example, a liquid crystal display, an OLED display, a touch panel, etc.
• Patent Document 1 as a polyimide resin having a low linear thermal expansion coefficient, a first tetracarboxylic acid component such as pyromellitic anhydride and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride are disclosed. A polyimide resin synthesized from a second tetracarboxylic acid component such as a tolidine sulfone skeleton diamine component is described.
• a first tetracarboxylic acid component such as pyromellitic anhydride and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride are disclosed.
• a polyimide resin synthesized from a second tetracarboxylic acid component such as a tolidine sulfone skeleton diamine component is described.
• the present invention has been made in view of such circumstances, and the object of the present invention is to form a film having excellent colorless transparency, heat resistance, thermal stability, optical isotropy, and dimensional stability against temperature cycling. It is in providing the polyimide resin which can be manufactured, its manufacturing method, and the polyimide varnish and polyimide film containing this polyimide resin.
• the present inventors have found that a polyimide resin containing a specific combination of structural units can solve the above-mentioned problems, and have completed the invention.
• a polyimide resin having a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from diamine The structural unit A includes a structural unit (A-1) derived from a compound represented by the following formula (a-1), Structural unit (B-1-1) derived from a compound represented by the following formula (b-1-1) as the structural unit B, structural unit derived from a compound represented by the following formula (b-1-2) A structural unit (B-1-2) and at least one selected from the group consisting of a structural unit (B-1-3) derived from a compound represented by the following formula (b-1-3) (B-1-2): -1) A polyimide resin in which no cyclohexane ring is present in the resin.
• each R is independently a hydrogen atom, a fluorine atom or a methyl group.
• the structural unit (B-1-3) is represented by the structural unit (B-1-31) derived from the compound represented by the following formula (b-1-31) and the following formula (b-1-32).
• polyimide resin according to any one of the above [1] to [11], wherein the structural unit B further comprises a structural unit derived from 2,2′-bis (trifluoromethyl) benzidine.
• the present invention it is possible to form a film having excellent colorless transparency, heat resistance, thermal stability, optical isotropy, and dimensional stability against a temperature cycle.
• 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).
• a structural unit (B-1-1) comprising the structural unit (A-1), wherein the structural unit B is derived from a compound represented by the following formula (b-1-1): Selected from the group consisting of a structural unit (B-1-2) derived from a compound represented by formula (B-1) and a structural unit (B-1-3) derived from a compound represented by the following formula (b-1-3) Which is at least one structural unit (B-1), provided that no cyclohexane ring is present in the resin.
• each R is independently a hydrogen atom, a fluorine atom or a methyl group.
• the thermal stability of a film improves because a polyimide resin does not contain a cyclohexane ring.
• the polyimide resin containing a cyclohexane ring generally tends to be excellent in colorless transparency
• the polyimide resin of the present invention is excellent in colorless transparency even if it does not contain a cyclohexane ring.
• the structural unit A is a structural unit derived from tetracarboxylic dianhydride in the polyimide resin, and includes a structural unit (A-1) derived from a compound represented by the following formula (a-1).
• the compound represented by the formula (a-1) is 9,9′-bis (3,4-dicarboxyphenyl) fluorene dianhydride.
• the structural unit A contains the structural unit (A-1)
• the heat resistance, thermal stability, optical isotropy, and dimensional stability against temperature cycles of the film are improved.
• the ratio of the structural unit (A-1) in the structural unit A is preferably 40% by mole or more, more preferably 50% by mole or more, still more preferably 60% by mole or more, and still more preferably 80% by mole. More preferably, it is 90 mol% or more, Most preferably, it is 99 mol% or more.
• the upper limit value of the ratio of the structural unit (A-1) is not particularly limited, that is, 100 mol%.
• the structural unit A may consist of only the structural unit (A-1). When the proportion of the structural unit (A-1) in the structural unit A is 40 mol% or more, particularly thermal stability and optical isotropy are improved, and colorless transparency is also improved.
• the structural unit A may include a structural unit other than the structural unit (A-1). However, since there is no cyclohexane ring in the polyimide resin of the present invention, a structural unit containing a cyclohexane ring is excluded as a structural unit other than the structural unit (A-1) optionally included in the structural unit A.
• the structural unit A preferably further includes a structural unit (A-2) derived from a compound represented by the following formula (a-2) in addition to the structural unit (A-1).
• 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 ratio of the structural unit (A-1) in the structural unit A is preferably 40 to 95 mol%, and more Preferably it is 45 to 90 mol%, more preferably 45 to 85 mol%, still more preferably 50 to 80 mol%, particularly preferably 50 to 70 mol%, and the constitution in the structural unit A
• the ratio of the unit (A-2) is preferably 5 to 60 mol%, more preferably 10 to 55 mol%, still more preferably 15 to 55 mol%, still more preferably 20 to 50 mol%. %, Particularly preferably 30 to 50 mol%.
• the ratio [(A-1) / (A-2)] (mol / mol) of the structural unit (A-1) to the structural unit (A-2) is preferably 30/70 to 90/10. More preferably, it is 40/60 to 70/30, and still more preferably 50/50 to 60/40.
• 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 further includes the structural unit (A-2), the dimensional stability with respect to the temperature cycle of the film is improved.
• the structural unit other than the structural unit (A-1) arbitrarily included in the structural unit A is not limited to the structural unit (A-2).
• the tetracarboxylic dianhydride that gives such an arbitrary structural unit is not particularly limited, but aromatic tetramethylene anhydride such as pyromellitic dianhydride and 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride.
• Carboxylic dianhydride (excluding the compound represented by the formula (a-1), the compound represented by the formula (a-2) and the compound containing a cyclohexane ring); 1,2,3,4-cyclobutane Alicyclic tetracarboxylic dianhydrides such as tetracarboxylic dianhydrides (excluding compounds containing a cyclohexane ring); and aliphatic tetra such as 1,2,3,4-butanetetracarboxylic dianhydrides Carboxylic dianhydrides are mentioned.
• 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 number of structural units other than the structural unit (A-1) optionally contained in the structural unit A may be one or more.
• the structural unit B is a structural unit derived from a diamine in the polyimide resin, and is derived from a compound represented by the following formula (b-1-1) (B-1-1), -1-2) derived from the compound represented by the compound (B-1-2), and derived from the compound represented by the following formula (b-1-3) (B-1-3)
• each R is independently a hydrogen atom, a fluorine atom, or a methyl group, and preferably a hydrogen atom.
• the compound represented by the formula (b-1) include 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (3-fluoro-4-aminophenyl) fluorene, and 9,9-bis. Examples include (3-methyl-4-aminophenyl) fluorene, and 9,9-bis (4-aminophenyl) fluorene is preferred.
• the compound represented by the formula (b-1-2) is 4,4′-diamino-2,2′-bistrifluoromethyldiphenyl ether.
• Examples of the compound represented by the formula (b-1-3) include a compound represented by the following formula (b-1-31) (that is, 4,4′-diaminodiphenylsulfone) and the following formula (b-1- 32) (that is, 3,3′-diaminodiphenylsulfone) and the like.
• the structural unit (B-1-3) is a structural unit (B-1-31) derived from a compound represented by the formula (b-1-31) and a compound represented by the formula (b-1-32) It is preferably at least one selected from the group consisting of structural units derived from (B-1-32).
• the structural unit (B-1-3) may be the structural unit (B-1-31) alone, the structural unit (B-1-32) alone, or the structural unit (B-1 -31) and a structural unit (B-1-32).
• a polyimide resin in which the structural unit B does not include the structural unit (B-1-32) can be given.
• the structural unit B includes the structural unit (B-1), the colorless transparency, heat resistance, and thermal stability of the film are improved. Further, when the structural unit (B-1-1) is included as the structural unit (B-1), the structural unit (B-1-1) is particularly excellent in heat resistance and thermal stability, and is also excellent in optical isotropy.
• the structural unit (B-1) may be the structural unit (B-1-1) alone, the structural unit (B-1-2) alone, or the structural unit (B-1-3). ) Only.
• the structural unit (B-1) may be a combination of the structural unit (B-1-1) and the structural unit (B-1-2).
• the structural unit (B-1-2) and the structural unit It may be a combination of (B-1-3), or a combination of a structural unit (B-1-1) and a structural unit (B-1-3).
• the structural unit (B-1) may be a combination of the structural unit (B-1-1), the structural unit (B-1-2), and the structural unit (B-1-3).
• 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 80 mol% or more, and still more preferably 90 mol%. It is at least mol%, particularly preferably at least 99 mol%.
• 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). However, since a cyclohexane ring does not exist in the polyimide resin of the present invention, a structural unit containing a cyclohexane ring is excluded as a structural unit other than the structural unit (B-1) optionally included in the structural unit B.
• the diamine that gives the structural unit other than the structural unit (B-1) optionally contained in the structural unit B is not particularly limited, but is 1,4-phenylenediamine, p-xylylenediamine, 3,5-diaminobenzoic acid.
• 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 300,000, more 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 total light transmittance is preferably 85% or more, more preferably 88% or more, and still more preferably 89% or more when a film having a thickness of 10 ⁇ m is formed.
• the yellow index (YI) is preferably 6.5 or less, more preferably 5.5 or less, still more preferably 3.5 or less, and even more preferably when a film having a thickness of 10 ⁇ m is formed. 2.0 or less.
• the glass transition temperature (Tg) is preferably 330 ° C. or higher, more preferably 360 ° C.
• the 1% weight loss temperature is preferably 480 ° C. or higher, more preferably 500 ° C. or higher, and still more preferably 520 ° C. or higher.
• the 2% weight loss temperature is preferably 510 ° C or higher, more preferably 520 ° C or higher, and further preferably 530 ° C or higher.
• the 3% weight loss temperature is preferably 520 ° C. or higher, more preferably 540 ° C. or higher, and further preferably 550 ° C. or higher.
• the 5% weight loss temperature is preferably 530 ° C. or higher, more preferably 540 ° C. or higher, and further preferably 550 ° C. or higher.
• weight loss rate is preferably 1.10% or less, more preferably 0.80% or less, and still more preferably 0.50% or less.
• the weight loss rate at 480 ° C. is preferably 4.00% or less, more preferably 2.50% or less, and still more preferably 1.00% or less.
• the absolute value of the thickness retardation (Rth) is preferably 250 nm or less, more preferably 180 nm or less, still more preferably 120 nm or less, and still more preferably 90 nm or less when a film having a thickness of 10 ⁇ m is formed. And more preferably 30 nm or less.
• the linear thermal expansion coefficient (CTE) is preferably 45 ppm / ° C. or less, more preferably 40 ppm / ° C. or less, and further preferably 30 ppm / ° C. or less as CTE of 100 to 200 ° C.
• a film that can be formed by using the polyimide resin of the present invention has good mechanical properties and has the following suitable physical properties.
• the tensile elastic modulus is preferably 2.0 GPa or more, more preferably 2.5 GPa or more, and further preferably 3.0 GPa or more.
• the tensile strength is preferably 80 MPa or more, more preferably 90 MPa or more, and further preferably 100 MPa or more.
• 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 is produced by reacting a tetracarboxylic acid component containing a compound giving the structural unit (A-1) with a diamine component containing a compound giving the structural unit (B-1). can do. More specifically, the method for producing a polyimide resin of the present invention comprises a reaction solvent comprising a tetracarboxylic acid component containing a compound giving the structural unit (A-1) and a diamine component containing the compound giving the structural unit (B-1). The imidization reaction is carried out by heating in the presence.
• 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 a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a-1), and an alkyl ester of the tetracarboxylic acid.
• a compound represented by the formula (a-1) that is, dianhydride
• a-1 that is, dianhydride
• the tetracarboxylic acid component preferably contains 40 mol% or more, more preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 80 mol% of the compound that gives the structural unit (A-1). Including, more preferably 90 mol% or more, particularly preferably 99 mol% or more.
• the upper limit of the content of the compound giving the structural unit (A-1) 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).
• the tetracarboxylic acid component may contain a compound other than the compound that provides the structural unit (A-1).
• the tetracarboxylic acid component preferably further contains a compound giving the structural unit (A-2) in addition to the compound giving the structural unit (A-1).
• 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 compound represented by the formula (a-2) that is, dianhydride
• the tetracarboxylic acid component includes a compound that provides the structural unit (A-1) and a compound that provides the structural unit (A-2), the tetracarboxylic acid component is preferably a compound that provides the structural unit (A-1). Containing 40 to 95 mol%, more preferably 45 to 90 mol%, still more preferably 45 to 85 mol%, still more preferably 50 to 80 mol%, particularly preferably 50 to 70 mol%, The compound giving (A-2) is preferably contained in an amount of 5 to 60 mol%, more preferably 10 to 55 mol%, further preferably 15 to 55 mol%, particularly preferably 20 to 50 mol%.
• 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 compound other than the compound that provides the structural unit (A-1) optionally contained in the tetracarboxylic acid component is not limited to the compound that provides the structural unit (A-2).
• Such optional compounds include the above-mentioned aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides, and derivatives thereof (tetracarboxylic acids, tetra And alkyl esters of carboxylic acids).
• the compound other than the compound giving the structural unit (A-1) 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 a compound that provides the structural unit (B-1-1), a compound that provides the structural unit (B-1-2), and a structural unit (B-1-3). At least one selected from the group consisting of compounds to be given is used.
• the compound that gives the structural unit (B-1-1), the compound that gives the structural unit (B-1-2), and the compound that gives the structural unit (B-1-3) are each represented by the formula (b-1- 1), a compound represented by the formula (b-1-2), and a compound represented by the formula (b-1-3), but are not limited thereto. Those derivatives may be used within the range given.
• Examples of the derivative include a diisocyanate corresponding to the diamine represented by the compound represented by the formula (b-1-1), and a diisocyanate corresponding to the diamine represented by the compound represented by the formula (b-1-2). And a diisocyanate corresponding to the diamine represented by the compound represented by the formula (b-1-3).
• the compound that gives the structural unit (B-1-1), the compound that gives the structural unit (B-1-2), and the compound that gives the structural unit (B-1-3) are each represented by the formula (b-1- 1) a compound represented by formula (ie, diamine), a compound represented by formula (b-1-2) (ie, diamine), and a compound represented by formula (b-1-3) (ie, diamine) ) Is preferred.
• the compound giving the structural unit (B-1) only the compound giving the structural unit (B-1-1) may be used, or only the compound giving the structural unit (B-1-2) may be used, Alternatively, only the compound giving the structural unit (B-1-3) may be used. Further, as the compound giving the structural unit (B-1), a combination of a compound giving the structural unit (B-1-1) and a compound giving the structural unit (B-1-2) may be used. A combination of a compound giving B-1-2) and a compound giving structural unit (B-1-3) may be used, or a compound giving structural unit (B-1-1) and structural unit (B-1 A combination of compounds giving -3) may be used. In addition, as a compound that provides the structural unit (B-1), a compound that provides the structural unit (B-1-1), a compound that provides the structural unit (B-1-2), and a structural unit (B-1-3) Combinations of the given compounds may be used.
• the diamine component preferably contains 50 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and still more preferably 90 mol% or more of the compound that gives the structural unit (B-1). Including, particularly preferably 99 mol% or more.
• 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, 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).
• N, N-dimethylacetamide, N-methyl-2-pyrrolidone and N-methylcaprolactam are preferable, and N-methyl-2-pyrrolidone is more preferable.
• lactone solvents ⁇ -butyrolactone is preferred.
• 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.
• the reaction solvents amide solvents and / or lactone solvents are preferable, and lactone solvents are more 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 5 to 30% by mass, and still more preferably 10 to 30% by mass.
• the viscosity of the polyimide varnish is preferably 1 to 200 Pa ⁇ s, more preferably 1 to 150 Pa ⁇ s, and still 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 colorless transparency, heat resistance, thermal stability, optical isotropy, and dimensional stability against temperature cycles.
• 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 500 ° C, more 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 tetracarboxylic acid component containing a compound that gives the structural unit (A-1) and the structural unit (B-1 ) Is a product of a polyaddition reaction with a diamine component containing a compound that gives.
• 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 comprises a tetracarboxylic acid component containing a compound giving the structural unit (A-1) and a diamine component containing a compound giving the structural unit (B-1) in a reaction solvent.
• the polyamic acid solution itself obtained by the polyaddition reaction may be used, or a diluting solvent may be further added to the polyamic acid solution.
• 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 500 ° C, more preferably 200 to 480 ° C, still more preferably 200 to 450 ° C, and still more preferably 200 to 400 ° C. ° 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, still more preferably 8 to 80 ⁇ m, and still more preferably 10 to 80 ⁇ m. It is. 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.
• Tg Glass transition temperature (Evaluation of heat resistance) Residual stress is removed using the thermomechanical analyzer "TMA / SS6100" manufactured by Hitachi High-Tech Science Co., Ltd. under the conditions of sample size 2 mm x 20 mm, load 0.1 N, and heating rate 10 ° C / min. The temperature was raised to a sufficient temperature to remove residual stress, and then cooled to room temperature. Thereafter, the measurement of the elongation of the test piece was performed under the same conditions as the treatment for removing the residual stress, and the place where the inflection point of the elongation was observed was determined as the glass transition temperature.
• Tg The larger the value of Tg, the better the heat resistance.
• a differential thermothermal gravimetric simultaneous measurement device “TG / DTA6200” manufactured by Hitachi High-Tech Science Co., Ltd. was used. The sample was heated to 40 to 550 ° C. at a heating rate of 10 ° C./min, and the temperature when the weight decreased by 1, 2, 3, and 5% compared to the weight at 300 ° C. was 1%, 2%, respectively. %, 3%, and 5% weight loss temperatures. The greater the value of each weight reduction temperature, the better the thermal stability. Further, the sample was heated from 40 ° C.
• Thickness retardation (Rth) (Evaluation of optical isotropy) The thickness retardation (Rth) was measured using an ellipsometer “M-220” manufactured by JASCO Corporation.
• the thickness retardation value at a measurement wavelength of 590 nm was measured.
• Rth is expressed by the following formula when the maximum refractive index in the plane of the polyimide film is nx, the minimum refractive index is ny, the refractive index in the thickness direction is nz, and the thickness of the film is d. Is. The smaller the absolute value of Rth, the better the optical isotropy.
• Example 1 34.845 g (0.100 mol) of BAFL 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 ⁇ -butyrolactone (manufactured by Mitsubishi Chemical Corporation) were added in an amount of 98.826 g and stirred at a system temperature of 70 ° C. in a nitrogen atmosphere at a rotation speed of 150 rpm to obtain a solution.
• ⁇ -butyrolactone manufactured by Mitsubishi Chemical Corporation
• Example 2 A polyimide varnish was prepared in the same manner as in Example 1 except that BAFL 34.845 g (0.100 mol) was changed to 6FODA 33.620 g (0.100 mol), and a solid content concentration of 10.0% by mass was obtained. Got. 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 10 ⁇ m. The results are shown in Table 1.
• Example 3 A polyimide varnish was prepared in the same manner as in Example 1 except that BAFL 34.845 g (0.100 mol) was changed to 4,4-DDS 24.830 g (0.100 mol), and the solid content concentration was 10.0 mass. % Polyimide varnish was obtained. 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 10 ⁇ m. The results are shown in Table 1.
• Example 4 The same as Example 1 except that the amount of BPAF was changed from 45.843 g (0.100 mol) to 36.674 g (0.080 mol) and 4.884 g (0.020 mol) of s-BPDA was added.
• a polyimide varnish was prepared by the above method to obtain a polyimide varnish having a solid content concentration of 10.0% by mass.
• a film was produced in the same manner as in Example 1 to obtain a film having a thickness of 10 ⁇ m. The results are shown in Table 1.
• Example 5 Example 1 except that the amount of BPAF was changed from 45.843 g (0.100 mol) to 22.922 g (0.050 mol) and 14.711 g (0.050 mol) of s-BPDA was added.
• a polyimide varnish was prepared by the above method 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 10 ⁇ m. The results are shown in Table 1.
• Example 6 17.423 g (0.050 mol) of BAFL in a 1 L 5-neck round bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen inlet tube, a Dean Stark fitted with a cooling tube, a thermometer, and a glass end cap And DAN (7.910 g, 0.050 mol) and ⁇ -butyrolactone (Mitsubishi Chemical Co., Ltd.) (105.746 g) were added, and the system temperature was 70 ° C. and stirred at a rotation speed of 150 rpm in a nitrogen atmosphere to obtain a solution. It was.
• DAN 7.910 g, 0.050 mol
• ⁇ -butyrolactone Mitsubishi Chemical Co., Ltd.
• Example 7 The amount of BPAF was changed from 45.843 g (0.100 mol) to 22.922 g (0.050 mol), 14.711 g (0.050 mol) of s-BPDA was added, and 7.910 g of DAN (0.050 mol) was added.
• a polyimide varnish was produced in the same manner as in Example 6 except that 16.012 g (0.050 mol) of TFMB was added in place of (mol) 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 9.5 ⁇ m. The results are shown in Table 1.
• Example 8> The amount of BPAF was changed from 45.843 g (0.100 mol) to 22.922 g (0.050 mol), 14.711 g (0.050 mol) of s-BPDA was added, and the amount of BAFL was 17.423 g. (0.050 mol) was changed to 27.876 g (0.080 mol), and instead of DAN 7.910 g (0.050 mol), TFMB was added in an amount of 6.405 g (0.020 mol).
• a polyimide varnish was prepared by the same method as in Example 6 to obtain a polyimide varnish having a solid content concentration of 10.0% by mass.
• Example 9 A polyimide varnish was prepared in the same manner as in Example 6 except that 16.012 g (0.050 mol) of TFMB was added instead of 7.910 g (0.050 mol) of DAN, and the solid content concentration was 10.0% by mass. The polyimide varnish was obtained. 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 10 ⁇ m. The results are shown in Table 1.
• Example 10 The amount of BPAF was changed from 45.843 g (0.100 mol) to 22.922 g (0.050 mol), 14.711 g (0.050 mol) of a-BPDA was added, and 7.910 g (0.050 DAN) of DAN was added.
• a polyimide varnish was prepared in the same manner as in Example 6 except that the amount of BAFL was changed from 17.423 g (0.050 mol) to 34.845 g (0.100 mol) instead of A polyimide varnish having a concentration of 10.0% by mass was obtained. 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 9 ⁇ m. The results are shown in Table 1.
• Example 11 A polyimide varnish was prepared in the same manner as in Example 7 except that the reaction solvent and the diluted solvent after refluxing for 3 hours were changed from ⁇ -butyrolactone (Mitsubishi Chemical Corporation) to N-methylpyrrolidone (Mitsubishi Chemical Corporation). A polyimide varnish having a solid content concentration of 10.0% by mass was obtained. Subsequently, the obtained polyimide varnish was applied onto a glass plate, kept at 80 ° C. for 20 minutes on a hot plate, and then heated at 420 ° C. for 30 minutes in a hot air dryer under a nitrogen atmosphere to evaporate the solvent and have a thickness of 10 ⁇ m. Film was obtained. The results are shown in Table 1.
• Example 12 A polyimide varnish was prepared in the same manner as in Example 9, except that the reaction solvent and the diluted solvent after refluxing for 3 hours were changed from ⁇ -butyrolactone (Mitsubishi Chemical Corporation) to N-methylpyrrolidone (Mitsubishi Chemical Corporation). A polyimide varnish having a solid content concentration of 10.0% by mass was obtained. Subsequently, the obtained polyimide varnish was applied onto a glass plate, kept on a hot plate at 80 ° C. for 20 minutes, and then heated in a hot air dryer at 420 ° C. for 30 minutes in a nitrogen atmosphere to evaporate the solvent and have a thickness of 9 ⁇ m. Film was obtained. The results are shown in Table 1.
• Example 13 A polyimide varnish was prepared in the same manner as in Example 5 except that the diluting solvent after refluxing for 3 hours was changed from ⁇ -butyrolactone (Mitsubishi Chemical Corporation) to N-methylpyrrolidone (Mitsubishi Chemical Corporation), A polyimide varnish having a solid content concentration of 10.0% by mass was obtained. Subsequently, the obtained polyimide varnish was applied onto a glass plate, kept on a hot plate at 80 ° C. for 20 minutes, and then heated in a hot air dryer at 450 ° C. for 30 minutes in a nitrogen atmosphere to evaporate the solvent and have a thickness of 9 ⁇ m. Film was obtained. The results are shown in Table 1.
• Example 14 A polyimide varnish was prepared in the same manner as in Example 10 except that the reaction solvent and the diluted solvent after refluxing for 3 hours were changed from ⁇ -butyrolactone (Mitsubishi Chemical Corporation) to N-methylpyrrolidone (Mitsubishi Chemical Corporation). A polyimide varnish having a solid content concentration of 10.0% by mass was obtained. Subsequently, the obtained polyimide varnish was applied onto a glass plate, held at 80 ° C. for 20 minutes on a hot plate, and then heated at 450 ° C. for 30 minutes in a hot air dryer under a nitrogen atmosphere to evaporate the solvent, and the thickness was 8 ⁇ m. Film was obtained. The results are shown in Table 1.
• Example 1 A polyimide varnish was prepared in the same manner as in Example 1 except that 45.843 g (0.100 mol) of BPAF was changed to 22.417 g (0.100 mol) of HPMDA, and a polyimide varnish having a solid content concentration of 10.0% by mass was prepared. Got. 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 11 ⁇ m. The results are shown in Table 1.
• the polyimide films of Examples 1 to 14 produced using a specific tetracarboxylic acid component and a specific diamine component are colorless and transparent, heat resistant, heat stable, optically isotropic and Excellent dimensional stability against temperature cycle.
• the polyimide film of Comparative Example 1 manufactured using HPMDA instead of BPAF as the tetracarboxylic acid component is 1%, 2%, 3%, and 5% by weight as compared with the polyimide film of Example 1. The decrease temperature was low, and the weight loss rates at 450 ° C and 480 ° C were large.
• the polyimide film of Comparative Example 2 produced by using BPAF and HPMDA together as the tetracarboxylic acid component is also 1%, 2%, 3%, and 5% weight loss temperature as compared with the polyimide film of Example 1.
• the weight loss rate at 450 ° C. and 480 ° C. was large. Therefore, even if it replaced with BPAF as a tetracarboxylic acid component, or was the form used together with BPAF, the thermal stability of the polyimide film deteriorated by using HPMDA.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Non-Metallic Protective Coatings For Printed Circuits (AREA)
• Wire Bonding (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=68061715

Family Applications (1)

Country Status (5)

Cited By (6)

Families Citing this family (2)

Citations (6)

Family Cites Families (2)

• 2019
  • 2019-03-13 CN CN201980021801.7A patent/CN111936553A/zh active Pending
  • 2019-03-13 JP JP2020509876A patent/JP7424284B2/ja active Active
  • 2019-03-13 KR KR1020207026439A patent/KR20200135953A/ko not_active Application Discontinuation
  • 2019-03-13 WO PCT/JP2019/010357 patent/WO2019188305A1/ja active Application Filing
  • 2019-03-18 TW TW108109022A patent/TWI802662B/zh active

Patent Citations (6)

Also Published As

Similar Documents

Legal Events