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
  • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
• • 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, and a polyimide varnish and a polyimide film containing the polyimide.
• Polyimides have excellent properties in mechanical properties, chemical resistance, electrical properties, etc. in addition to their excellent heat resistance, so films made of polyimides are molding materials, composite materials, electric and electronic parts And in the field of display devices and the like.
• studies are being actively made to realize reduction in the weight, thickness and flexibility of display devices by applying a plastic substrate instead of a glass substrate.
• the linear thermal expansion coefficients of the inorganic material and the film are significantly different, so the film on which the electronic device made of the inorganic material is formed is bent.
• an electronic element made of a material may be peeled off from the film. Therefore, in addition to transparency and heat resistance, a polyimide film is also required to have a low coefficient of linear thermal expansion.
• Patent Document 1 4,4 '-(hexafluoroisopropylidene) diphthalic acid is used as an acid component, and 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl is used as a diamine component.
• Polyimides are disclosed.
• the problem to be solved by the present invention is to provide a polyimide capable of forming a film having a low linear thermal expansion coefficient while maintaining high transparency and high heat resistance, and a polyimide varnish and a polyimide film containing the polyimide. It is.
• the present invention relates to the following [1] to [3].
• Structural unit A is a structural unit (A-1) derived from a compound represented by the following formula (a-1), and a structural unit (A-2) derived from a compound represented by the following formula (a-2)
• Structural unit B is a structural unit (B-2) derived from a compound represented by the following formula (b-1), and a structural unit (B-2) derived from a compound represented by the following formula (b-2) ), Including polyimide.
• each R independently represents a hydrogen atom, a fluorine atom or a methyl group.
• a polyimide capable of forming a film having a low linear thermal expansion coefficient while maintaining high transparency and high heat resistance, and a polyimide varnish and a polyimide film containing the polyimide.
• the polyimide of the present invention is a polyimide having a structural unit A derived from tetracarboxylic acid or a derivative thereof, and a structural unit B derived from a diamine
• Structural unit A is a structural unit (A-1) derived from the compound represented by the above formula (a-1), and a structural unit (A-2) derived from the compound represented by the above formula (a-2)
• Structural unit B is a structural unit (B-2) derived from the compound represented by the above formula (b-1), and a structural unit (B-2) derived from the compound represented by the above formula (b-2)
• the polyimide of the present invention has a specific structural unit (A-1), a structural unit (A-2), a structural unit (B-1), and a structural unit (B-2), so that the linear thermal expansion coefficient is low. Can be formed.
• the constituent unit A contained in the polyimide of the present invention is a constituent unit derived from tetracarboxylic acid or a derivative thereof.
• the tetracarboxylic acids or their derivatives can be used alone or in combination of two or more.
• Derivatives of tetracarboxylic acids include anhydrides or alkyl esters of tetracarboxylic acids.
• the alkyl ester of tetracarboxylic acid the carbon number of alkyl is preferably 1 to 3, and examples thereof include dimethyl ester, diethyl ester and dipropyl ester of tetracarboxylic acid.
• the constituent unit A in the present invention includes a constituent unit (A-1) derived from a compound represented by the following formula (a-1).
• the compound represented by the formula (a-1) is biphenyltetracarboxylic acid dianhydride.
• the structural unit A contains the structural unit (A-1)
• the heat resistance, mechanical properties (elastic modulus) and organic solvent resistance of the polyimide are improved.
• Examples of the compound represented by the formula (a-1) include 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride (s-BPDA) represented by the following formula (a-1-1): 2,3,3 ′, 4′-biphenyltetracarboxylic acid dianhydride (a-BPDA) represented by the following formula (a-1-2), and represented by the following formula (a-1-3) 2,2 ', 3,3'-biphenyltetracarboxylic acid dianhydride (i-BPDA) is mentioned, and among them, 3,3', 4,4'- represented by the following formula (a-1-1) Biphenyl tetracarboxylic dianhydride is preferred.
• the compounds represented by the formula (a-1) can be used alone or in combination of two or more.
• s-BPDA is preferable in terms of resistance to organic solvents
• a-BPDA and i-BPDA are preferable in terms of heat resistance and solution processability.
• the ratio of the structural unit (A-1) to the structural unit A is preferably 50 mol% or more, more preferably 55 mol% or more, and further preferably from the viewpoint of heat resistance, mechanical properties (elastic modulus) and organic solvent resistance. Is 60 mol% or more, more preferably 65 mol% or more, still more preferably 70 mol% or more, preferably 99 mol% or less, more preferably 95 mol% or less, still more preferably 90 mol% or less More preferably, it is 85 mol% or less, still more preferably 80 mol% or less.
• the structural unit A includes a structural unit (A-2) derived from a compound represented by the following formula (a-2).
• the compound represented by the formula (a-2) is 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride.
• the ratio of the structural unit (A-2) to the structural unit A is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, from the viewpoint of solubility and high transparency. It is preferably 15 mol% or more, more preferably 20 mol% or more, and from the viewpoint of high heat resistance, preferably 50 mol% or less, more preferably 45 mol% or less, still more preferably 40 mol% or less More preferably, it is 35 mol% or less, still more preferably 30 mol% or less.
• the ratio of the structural unit (A-1) and the structural unit (A-2) to the structural unit A is preferably 50 to 99% by mole of the structural unit (A-1) and 1 to 50 as the structural unit (A-2). %, More preferably 55 to 95 mol% of the structural unit (A-1), 5 to 45 mol% of the structural unit (A-2), and still more preferably 60 to 60 mol% of the structural unit (A-1). -90 mol%, 10-40 mol% of the structural unit (A-2), and still more preferably 65-85 mol% of the structural unit (A-1), 15-35 structural unit (A-2) More preferably, the structural unit (A-1) is 70 to 80 mol%, and the structural unit (A-2) is 20 to 30 mol%.
• the molar ratio [(A-1) / (A-2)] of the structural unit (A-1) to the structural unit (A-2) is 50/50 from the viewpoint of low linear thermal expansion coefficient and high transparency. -99/1 is preferable, 55/45 to 95/5 is more preferable, 60/40 to 90/10 is further preferable, 65/35 to 85/15 is still more preferable, 70/30 to 80/20 is more More preferable.
• the polyimide according to the present invention can be produced by using the structural unit A as a structural unit other than the structural unit (A-1) and the structural unit (A-2) as long as the effects of the present invention are not impaired.
• the structural unit derived from tetracarboxylic acid or its derivative (s) other than the compound represented by () and the compound represented by Formula (a-2) may be included, it is preferable not to contain.
• the proportion of the total of the structural unit (A-1) and the structural unit (A-2) in the structural unit A is 70 mol% or more from the viewpoint of low linear thermal expansion coefficient, high transparency, and organic solvent resistance Is preferably 85 mol% or more, more preferably 99 mol% or more, and still more preferably 100 mol%.
• the structural unit B contained in the polyimide of the present invention is a structural unit derived from a diamine.
• the structural unit B contains a structural unit (B-1) derived from a compound represented by the following formula (b-1).
• each R is independently selected from the group consisting of a hydrogen atom, a fluorine atom, and a methyl group, and is preferably a hydrogen atom.
• 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (3-fluoro-4-aminophenyl) fluorene, and 9,9- Bis (3-methyl-4-aminophenyl) fluorene and the like can be mentioned, and at least one selected from the group consisting of these three compounds is preferable, and 9,9-bis (4-aminophenyl) fluorene is more preferable.
• the polyimide of the present invention improves the transparency and heat resistance by including the structural unit (B-1).
• the ratio of the structural unit (B-1) to the structural unit B is preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 35 mol% or less from the viewpoint of low linear thermal expansion coefficient Still more preferably 30 mol% or less, still more preferably 25 mol% or less, and in view of high transparency and high heat resistance, preferably 5 mol% or more, more preferably 10 mol% or more. More preferably, it is 15 mol% or more, still more preferably 20 mol% or more.
• the constituent unit B in the present invention contains a constituent unit (B-2) derived from a compound represented by the following formula (b-2).
• the compound represented by the above formula (b-2) is 2,2'-bis (trifluoromethyl) benzidine (alias: 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl) is there.
• the polyimide of the present invention can improve mechanical properties (elastic modulus) and form a film having a low linear thermal expansion coefficient.
• the ratio of the structural unit (B-2) to the structural unit B is preferably 50 moles from the viewpoint of forming a film having a low linear thermal expansion coefficient while maintaining high transparency and high heat resistance.
• % More preferably 60 mol% or more, still more preferably 65 mol% or more, still more preferably 70 mol% or more, still more preferably 75 mol% or more, and preferably 95 mol% or less, more preferably It is 90 mol% or less, more preferably 85 mol% or less, still more preferably 80 mol% or less.
• the ratio of the structural units (B-1) and (B-2) to the structural unit B is preferably 5 to 50 mol% of the structural unit (B-1) and 50 to 95 mol% of the structural unit (B-2) More preferably, the structural unit (B-1) is 10 to 40 mol%, the structural unit (B-2) is 60 to 90 mol%, and still more preferably the structural unit (B-1) is 15 to 35 Mol%, the structural unit (B-2) is 65 to 85 mol%, more preferably 15 to 30 mol% of the structural unit (B-1), 70 to 85 mol% of the structural unit (B-2) More preferably, the structural unit (B-1) is 20 to 25 mol%, and the structural unit (B-2) is 75 to 80 mol%.
• the molar ratio [(B-1) / (B-2)] of the structural unit (B-1) to the structural unit (B-2) has low linear thermal expansion while maintaining high transparency and high heat resistance. From the viewpoint of forming a film having a coefficient, 50/50 to 5/95 is preferable, 40/60 to 10/90 is more preferable, 35/65 to 15/85 is more preferable, and 30/70 to 15/85 is Still more preferred is 25/75 to 20/80.
• the polyimide of the present invention contains a structural unit derived from a diamine other than the compounds represented by the formulas (b-1) to (b-2) in the structural unit B, as long as the effects of the present invention are not impaired. Although it may be contained, it is preferable not to contain.
• the ratio of the total of the structural unit (B-1) and the structural unit (B-2) in the structural unit B forms a film having a low linear thermal expansion coefficient while maintaining high transparency and high heat resistance. In light of the above, 70 mol% or more is preferable, 85 mol% or more is more preferable, 99 mol% or more is more preferable, and 100 mol% is still more preferable.
• the polyimide of the present invention can be obtained by reacting the tetracarboxylic acid component giving the constitutional unit A and the diamine component giving the constitutional unit B.
• tetracarboxylic acid component examples include tetracarboxylic acids or their derivatives.
• the tetracarboxylic acid components can be used alone or in combination of two or more.
• Derivatives of tetracarboxylic acids include anhydrides or alkyl esters of the tetracarboxylic acids.
• the alkyl ester of tetracarboxylic acid the carbon number of alkyl is preferably 1 to 3, and examples thereof include dimethyl ester, diethyl ester and dipropyl ester of tetracarboxylic acid.
• the tetracarboxylic acid component used in the present invention includes biphenyl tetracarboxylic acid or its derivative, and 4,4 '-(hexafluoroisopropylidene) diphthalic acid or its derivative.
• biphenyltetracarboxylic acid dianhydride [the above formula (a-1)] and 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride [the above formula (a-2)] are preferably included, 3 It is more preferable to contain 4,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride [formula (a-1-1)] and 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride .
• the amount of the biphenyltetracarboxylic acid or derivative thereof used is preferably 50 to 99 mol%, more preferably 55 to 95 mol%, still more preferably 60 to 90 mol%, still more preferably, relative to all tetracarboxylic acid components. Is more preferably 65 to 85 mol%, still more preferably 70 to 80 mol%.
• the amount of 4,4 '-(hexafluoroisopropylidene) diphthalic acid or a derivative thereof to be used is preferably 1 to 50 mol%, more preferably 5 to 45 mol%, still more preferably 1 to 50 mol%, relative to all tetracarboxylic acid components.
• the total amount of biphenyltetracarboxylic acid, 4,4 '-(hexafluoroisopropylidene) diphthalic acid, and derivatives thereof to be used is preferably 70 to 100 mol%, more preferably 70 to 100 mol%, based on all tetracarboxylic acid components. It is 85 to 100 mol%, more preferably 99 to 100 mol%, still more preferably 100 mol%.
• the tetracarboxylic acid component used in the present invention may contain a bicarboxylic acid and a tetracarboxylic acid component other than 4,4 '-(hexafluoroisopropylidene) diphthalic acid or derivatives thereof.
• the tetracarboxylic acid component include at least one selected from the group consisting of tetracarboxylic acids containing an aromatic ring or derivatives thereof, and tetracarboxylic acids containing an alicyclic hydrocarbon structure or derivatives thereof.
• the tetracarboxylic acid components can be used alone or in combination of two or more.
• tetracarboxylic acid containing an aromatic ring or a derivative thereof pyromellitic acid, 3,3 ′, 4,4′-diphenyl sulfone tetracarboxylic acid, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 4, 4'-oxydiphthalic acid, 2,2 ', 3,3'-benzophenonetetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (2,3-dicarboxyphenyl) ) Propane, 2,2-bis (3,4-dicarboxyphenoxyphenyl) propane, 1,1-bis (2,3-dicarboxyphenyl) ethane, 1,2-bis (2,3-dicarboxyphenyl) Ethane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 1,2-bis (3,4-dicarboxyphenyl) ethane, bis
• tetracarboxylic acids containing an alicyclic hydrocarbon structure or derivatives thereof include 1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,4,5-cyclopentane tetracarboxylic acid, 1,2,4, 5-cyclohexanetetracarboxylic acid, bicyclo [2.2.2] octa-7-ene-2,3,5,6-tetracarboxylic acid, dicyclohexyltetracarboxylic acid, cyclopentanone bis-spironorbornane tetracarboxylic acid or their compounds Regioisomers and their derivatives are included.
• the amount of the biphenyltetracarboxylic acid or derivative thereof and the tetracarboxylic acid component other than 4,4 '-(hexafluoroisopropylidene) diphthalic acid or derivative thereof is preferably 30% by mole based on all tetracarboxylic acid components.
• the following content is more preferably 15 mol% or less, still more preferably 1 mol% or less, and still more preferably 0 mol%.
• the diamine component used in the present invention includes the compound represented by the above formula (b-1) and 2,2′-bis (trifluoromethyl) benzidine [the above formula (b-2)].
• a diamine component which gives the structural unit B it is not restricted to a diamine, although the derivative (diisocyanate etc.) may be sufficient in the range in which the same structural unit is formed, a diamine is preferable.
• the amount of the compound represented by the above formula (b-1) is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, still more preferably 10 to 35 mol based on all diamine components.
• the amount of 2,2'-bis (trifluoromethyl) benzidine used is preferably 50 to 95 mol%, more preferably 60 to 90 mol%, still more preferably 65 to 90 mol based on the total diamine components. %, Still more preferably 70 to 85 mol%, still more preferably 75 to 85 mol%, still more preferably 75 to 80 mol%.
• the total amount of the compound represented by the above formula (b-1) and 2,2′-bis (trifluoromethyl) benzidine is preferably 70 to 100 mol%, more preferably about all diamine components. It is 85 to 100 mol%, more preferably 99 to 100 mol%, still more preferably 100 mol%.
• the diamine component used in the present invention may contain a diamine component other than the compound represented by the above formula (b-1) and 2,2′-bis (trifluoromethyl) benzidine.
• the diamine component include at least one selected from the group consisting of aromatic diamines and aliphatic diamines.
• the diamine components can be used alone or in combination of two or more.
• aromatic diamine refers to a diamine in which an amino group is directly bonded to an aromatic ring, and an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group as part of the structure thereof And other substituents (for example, a halogen atom, a sulfonyl group, a carbonyl group, an oxygen atom, etc.) may be included.
• aliphatic diamine refers to a diamine in which an amino group is directly bonded to an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and an aromatic hydrocarbon group or aliphatic hydrocarbon group as part of its structure
• alicyclic hydrocarbon groups and other substituents for example, halogen atoms, sulfonyl groups, carbonyl groups, oxygen atoms, etc.
• aromatic diamines include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, benzidine, o-tolidine, m-tolidine, octafluorobenzidine, 3,3'- Dihydroxy-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4 '-Diaminobiphenyl, 2,6-diaminonaphthalene, 1,5-diaminonaphthalene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl
• aliphatic diamines include ethylene diamine, hexamethylene diamine, polyethylene glycol bis (3-aminopropyl) ether, polypropylene glycol bis (3-aminopropyl) ether, 1,3-bis (aminomethyl) cyclohexane, 1,4- Bis (aminomethyl) cyclohexane, metaxylylenediamine, paraxylylenediamine, 1,4-bis (2-amino-isopropyl) benzene, 1,3-bis (2-amino-isopropyl) benzene, isophorone diamine, norbornane Diamine, siloxane diamine, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodicyclohexylmethane, 3,3
• the amount of use of the compound represented by the above formula (b-1) and diamine components other than 2,2′-bis (trifluoromethyl) benzidine is preferably 30 mol% or less, more preferably to all diamine components. Is 15 mol% or less, more preferably 1 mol% or less, and still more preferably 0 mol%.
• the ratio by weight of the tetracarboxylic acid component to the diamine component is preferably 0.9 to 1.1 moles of the diamine component to 1 mole of the tetracarboxylic acid component.
• terminal blocker other than the said tetracarboxylic acid component and the said diamine component.
• the end capping agent monoamines or dicarboxylic acids are preferable.
• the preparation amount of the end capping agent to be introduced is preferably 0.0001 to 0.1 mol, and more preferably 0.001 to 0.06 mol, per 1 mol of the tetracarboxylic acid component.
• Examples of monoamines end capping agents include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3- Ethyl benzylamine, aniline, 3-methylaniline, 4-methylaniline and the like are recommended. Among these, benzylamine and aniline can be suitably used.
• dicarboxylic acid end capping agent dicarboxylic acids are preferable, and some of them may be ring-closed.
• phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenonedicarboxylic acid, 3,4-benzophenonedicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclopentane-1,2 -Dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, etc. are recommended.
• phthalic acid and phthalic anhydride can be suitably used.
• tetracarboxylic acid component and a diamine component are made to react
• a well-known method can be used.
• a specific reaction method (1) a tetracarboxylic acid component, a diamine component, and a reaction solvent are charged in a reactor, and stirred at room temperature to 80 ° C. for 0.5 to 30 hours, and then heated to imidation Method for carrying out the reaction, (2) The diamine component and the reaction solvent are charged into the reactor and dissolved, and then the tetracarboxylic acid component is charged, and if necessary, stirred for 0.5 to 30 hours at room temperature to 80 ° C. (3) The tetracarboxylic acid component, the diamine component, and the reaction solvent are charged into a reactor, and the temperature is raised immediately to perform the imidization reaction.
• the reaction solvent used for producing the polyimide may be any solvent which can dissolve the polyimide to be produced without inhibiting the imidization reaction.
• aprotic solvents phenol solvents, ether solvents, carbonate solvents and the like can be mentioned.
• aprotic solvent examples include N, N-dimethylisobutyramide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethyl Amide solvents such as imidazolidinone and tetramethylurea, lactone solvents such as ⁇ -butyrolactone and ⁇ -valerolactone, phosphorus-containing amide solvents such as hexamethylphosphoric amide and hexamethylphosphine triamide, dimethyl sulfone, Sulfur-containing solvents such as dimethylsulfoxide and sulfolane, ketone solvents such as acetone, cyclohexanone and methylcyclohexanone, amine solvents such as picoline and pyridine, ester solvents such as acetic acid (2-methoxy-1-methylethyl) It can be mentioned.
• phenolic solvents 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] Ether, tetrahydrofuran, 1,4-dioxane and the like can be mentioned.
• reaction solvents diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, a propylene carbonate etc. are mentioned as a specific example of a carbonate type solvent.
• aprotic solvents are preferable, and amide solvents or lactone solvents are more preferable.
• the above reaction solvents may be used alone or in combination of two or more.
• the imidization reaction it is preferable to carry out the reaction while removing water generated at the time of production using a Dean-Stark apparatus or the like. By performing such an operation, the degree of polymerization and the imidation ratio can be further increased.
• the imidation catalyst includes a base catalyst or an acid catalyst.
• a base catalyst pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, imidazole, N, N-dimethylaniline
• organic base catalysts such as N, N-diethylaniline
• inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate.
• an acid catalyst crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, paratoluenesulfonic acid, naphthalenesulfonic acid, etc.
• the above imidation catalysts may be used alone or in combination of two or more.
• a base catalyst is preferable, an organic base catalyst is more preferable, and triethylamine is more preferable.
• the temperature of the imidization reaction is preferably 120 to 250 ° C., more preferably 160 to 190 ° C., and still more preferably 180 to 190 ° C. from the viewpoint of reaction rate and suppression of gelation etc. is there.
• the reaction time is preferably 0.5 to 10 hours after the start of distillation of the produced water.
• the temperature of the imidation reaction when no catalyst is used is preferably 200 to 350.degree.
• a polyimide solution containing at least a polyimide and a reaction solvent can be obtained after completion of the imidization reaction.
• the weight average molecular weight of the polyimide of the present invention is preferably 500 to 1,000,000, more preferably 5,000 to 100,000, from the viewpoint of the mechanical strength of the resulting polyimide film.
• the weight average molecular weight of the polyimide can be measured by gel filtration chromatography or the like.
• a method of measuring an absolute molecular weight with a light scattering detector using N, N-dimethylformamide as a developing solvent can be mentioned.
• the polyimide of the present invention may further be mixed with various additives as long as the effects of the present invention are not impaired.
• the additive include an antioxidant, a light stabilizer, a surfactant, a flame retardant, a plasticizer, an inorganic filler, and a polymer compound other than the polyimide.
• polymer compound polyimide other than the polyimide of the present invention, polycarbonate, polystyrene, polyamide, polyamide imide, polyester such as polyethylene terephthalate, polyether sulfone, polycarboxylic acid, polyacetal, polyphenylene ether, polysulfone, polybutylene, polypropylene, polyacrylamide And polyvinyl chloride.
• the polyimide varnish of the present invention is obtained by dissolving the polyimide of the present invention in an organic solvent. That is, the polyimide varnish of the present invention contains the polyimide of the present invention and an organic solvent, and the polyimide is dissolved in the organic solvent.
• the organic solvent is not particularly limited as long as it dissolves the polyimide, but it is preferable to use one or more of the compounds described above as the reaction solvent used for producing the polyimide. Since the polyimide of the present invention has solvent solubility, it can be a highly concentrated varnish stable at room temperature.
• the polyimide varnish may be a polyimide solution itself in which a polyimide obtained by a polymerization method is dissolved in a reaction solvent. Moreover, what mixed at least 1 sort (s) chosen from the solvent illustrated above as a solvent which a polyimide melt
• the solid content concentration of the polyimide varnish of the present invention can be appropriately selected according to the workability at the time of forming a polyimide film to be described later, etc., and the reaction solvent used for producing the polyimide of the present invention is volatilized and condensed. Alternatively, the solid content concentration and viscosity of the polyimide varnish of the present invention may be adjusted by adding an organic solvent as a dilution solvent.
• the organic solvent is not particularly limited as long as it can dissolve polyimide.
• the solid content concentration of the polyimide varnish of the present invention is preferably 5 to 45% by mass, more preferably 5 to 35% by mass, and still more preferably 5 to 25% by mass.
• the viscosity of the polyimide varnish of the present invention is preferably 0.1 to 200 Pa ⁇ s, more preferably 0.5 to 180 Pa ⁇ s, and still more preferably 1 to 150 Pa ⁇ s.
• the viscosity of the polyimide varnish is a value measured at 25 ° C. using an E-type viscometer.
• the polyimide film of the present invention is characterized by containing the polyimide of the present invention, and has a low linear thermal expansion coefficient while maintaining high transparency and high heat resistance.
• the polyimide film of the present invention preferably comprises the polyimide of the present invention.
• a polyimide varnish containing the polyimide of the present invention is coated on a smooth support such as a glass plate, metal plate or plastic, or a film And the like, and a method of removing solvent components such as a reaction solvent and a dilution solvent contained in the varnish.
• a smooth support such as a glass plate, metal plate or plastic, or a film And the like
• solvent components such as a reaction solvent and a dilution solvent contained in the varnish.
• a release agent may be applied to the surface of the support, if necessary.
• a method of heating and evaporating a solvent component after applying the said polyimide varnish to the said support body the following method is preferable. That is, after the solvent is evaporated at a temperature of 120 ° C. or less to form a self-supporting film, the self-supporting film is peeled from the support to fix the end portion of the self-supporting film, and It is preferable to produce a polyimide film by drying at a temperature not lower than the boiling point and not higher than 350 ° C. Moreover, it is preferable to dry under nitrogen atmosphere.
• the pressure of the drying atmosphere may be any of reduced pressure, normal pressure and increased pressure.
• the thickness of the polyimide film of the present invention can be appropriately selected according to the application etc., but is preferably in the range of 1 to 250 ⁇ m, more preferably 5 to 100 ⁇ m, still more preferably 7 to 90 ⁇ m, still more preferably 10 to 80 ⁇ m. It is.
• the thickness of 1 to 250 ⁇ m enables practical use as a free standing film.
• a polyimide film having a total light transmittance of preferably 80% or more, more preferably 85% or more, still more preferably 88% or more, still more preferably 89% or more at a thickness of 10 ⁇ m can be formed.
• a polyimide film having a yellow index (YI value) of preferably 6.0 or less, more preferably 5.0 or less, and still more preferably 4.5 or less can be formed.
• a polyimide film having a haze of preferably 1.0 or less, more preferably 0.8 or less, and even more preferably 0.5 or less can be formed.
• a polyimide film having a glass transition temperature of preferably 250 ° C. or more, more preferably 300 ° C. or more, still more preferably 350 ° C. or more can be formed.
• a polyimide film having a linear thermal expansion coefficient of preferably 40 ppm / ° C. or less, more preferably 35 ppm / ° C. or less, further preferably 30 ppm / ° C. or less can be formed.
• a polyimide film having a tensile elastic modulus (measurement temperature: 23 ° C., humidity: 50% RH) of preferably 3.0 GPa or more, more preferably 3.5 GPa or more can be formed.
• the total light transmittance, the YI value, the haze, the glass transition temperature, the linear thermal expansion coefficient, and the tensile modulus of elasticity of the polyimide film can be specifically measured by the method described in the examples.
• the polyimide film containing the polyimide of the present invention is excellent in transparency and heat resistance, and has a low coefficient of linear thermal expansion so that the dimensional change due to heat is small, and films for various members such as color filters, flexible displays, semiconductor parts, optical members, etc. Are preferably used. Since the polyimide film of the present invention has high dimensional stability, it can correspond to the high temperature process of the manufacturing process of the image display device. Therefore, for example, the polyimide film of the present invention can be used for at least a part of an image display device such as a liquid crystal display or an organic EL display.
• Solid content concentration The solid content concentration of the polyimide varnish or the polyimide precursor varnish was measured by heating the sample at 320 ° C. for 120 minutes in a small electric furnace MMF-1 manufactured by As One Co., Ltd., and calculating from the mass difference of the sample before and after heating.
• Film thickness The polyimide film thickness was measured using a micrometer manufactured by Mitutoyo Corporation.
• Total light transmittance, yellow index (YI), haze It carried out using Nippon Denshoku Kogyo Co., Ltd. color and turbidity simultaneous measurement apparatus "COH400". The measurement of total light transmittance and YI conformed to JIS K7361-1: 1997, and the measurement of haze conformed to JIS K7136: 2000.
• Example 1 Stainless steel half-moon-type stirring blade, nitrogen introduction pipe, Dean Stark device equipped with a cooling pipe, thermometer, 5-neck round bottom flask equipped with a glass end cap, 2, 2 '-bis (trifluoromethyl) benzidine 29.462 g (0.092 mol) (manufactured by Wakayama Seika Kogyo Co., Ltd.), 8.014 g (0.023 mol) of 9,9-bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical Industry Co., Ltd.), N 111.263 g of methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation) was charged, and the solution was obtained by stirring at a rotation speed of 200 rpm under a nitrogen atmosphere at a system temperature of 70 ° C.
• Example 2 Stainless steel half-moon-type stirring blade, nitrogen introduction pipe, Dean Stark device equipped with a cooling pipe, thermometer, 5-neck round bottom flask equipped with a glass end cap, 2, 2 '-bis (trifluoromethyl) benzidine 19.685 g (0.061 mol) (manufactured by Wakayama Seika Kogyo Co., Ltd.), 5.343 g (0.015 mol) of 9,9-bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical Industry Co., Ltd.), N 75.897 g of methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation) was charged, and the solution was obtained by stirring at a rotation speed of 200 rpm under a nitrogen atmosphere at a system temperature of 70 ° C.
• the obtained polyimide varnish is applied onto a glass plate, held at 80 ° C. for 30 minutes with a hot plate, and then heated at 300 ° C. for 30 minutes in a hot air dryer under nitrogen purge to evaporate the solvent A film of 10 ⁇ m was obtained.
• Table 1 The results are shown in Table 1.
• the polyimide films of Examples 1 and 2 have a low coefficient of linear thermal expansion in addition to high transparency and high heat resistance, so all of these properties are good and balanced.
• the polyimide films of Comparative Examples 1 and 2 are excellent in heat resistance, they have a high coefficient of linear thermal expansion, and the polyimide films of Comparative Example 2 are also inferior in transparency, so these polyimide films are highly transparent. In addition to the properties and high heat resistance, it has not been possible to obtain films with a low linear thermal expansion coefficient.

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