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
• • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions 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 C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
  • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
• • 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
  • C08G2150/00—Compositions for coatings

Definitions

• the present invention relates to a polyimide resin, a polyamic acid, a varnish and a polyimide film.
• Polyimide resin is being studied for various uses in the fields of electrical and electronic parts. For example, it is desired to replace a glass substrate used in 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 and flexibility of the device, and a polyimide film suitable as the plastic substrate is desired. Research is underway.
• Patent Document 1 describes an ester group-containing tetracarboxylic acid dianhydride and a diamine for the purpose of obtaining a polyimide having a low moisture absorption expansion coefficient and a low water absorption rate, which is particularly used as an insulating film for a flexible printed wiring substrate.
• the obtained polyesterimide precursor varnish and the polyesterimide film formed by imidizing the obtained varnish are disclosed.
• the device type of TFT which is being developed with the aim of increasing the definition of liquid crystal displays and OLED displays, is LTPS (low temperature polysilicon TFT) displays, which have a process temperature of over 400 ° C and are used as the polyimide substrate. Is required to have heat resistance to withstand a high temperature of 400 ° C. or higher. Further, it is also necessary to reduce the linear expansion coefficient because there is a risk of peeling at the joint surface and deformation of the product due to the difference in the linear thermal expansion coefficient from the inorganic layer constituting the device. Further, with the progress of display technology, a new form of display is being developed.
• LTPS low temperature polysilicon TFT
• the aromatic polyimide resin has excellent heat resistance to withstand high temperatures and a linear expansion coefficient, but has a problem of being easily yellowed, and a polyimide film having heat resistance, a low linear expansion coefficient, and a low yellowness is used. It was desired.
• the present invention has been made in view of such a situation, and the subject of the present invention is a polyimide resin capable of obtaining a polyimide film having a low yellowness while maintaining a low linear expansion coefficient and excellent heat resistance.
• the present invention is to provide a polyamic acid, a varnish and a polyimide film which are precursors thereof.
• the present inventors have found that a polyimide resin containing a combination of specific structural units can solve the above-mentioned problems, and have completed the invention.
• R independently represents a methyl group or a trifluoromethyl group, and n is an integer of 1 to 4).
• the structural unit AA includes a structural unit (AA1) derived from the compound represented by the following formula (a1).
• the polyimide resin of the present invention is 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 (A1) derived from a compound represented by the following formula (a1).
• the structural unit B includes a structural unit (B1) derived from the compound represented by the following formula (b1).
• R is independently a methyl group or a trifluoromethyl group, and n is an integer of 1 to 4).
• the structural unit A is a structural unit derived from the tetracarboxylic dianhydride in the polyimide resin.
• the structural unit A includes a structural unit (A1) derived from the compound represented by the following formula (a1). (In the formula, R is independently a methyl group or a trifluoromethyl group, and n is an integer of 1 to 4).
• R is independently a methyl group or a trifluoromethyl group, but is preferably a methyl group.
• n is an integer of 1 to 4, but preferably n is 3. That is, the structural unit (A1) derived from the compound represented by the formula (a1) is the structural unit (A11) derived from the compound represented by the following formula (a11) from the viewpoint of heat resistance and reduction of yellowness. It is preferable to include. Further, the structural unit (A1) derived from the compound represented by the formula (a1) is the structural unit (A11) derived from the compound represented by the following formula (a11) from the viewpoint of heat resistance and reduction of yellowness. Is more preferable.
• the compound represented by the formula (a11) is 2,2', 3,3', 5,5'-hexamethyl [1,1'-biphenyl] -4,4'-diyl-bis (1,3-dioxo). -1,3-Dihydro-2-benzofuran-5-carboxylate) (TMPBP-TME).
• the film of the present invention can have excellent heat resistance and a low coefficient of linear thermal expansion, and the yellowness can also be reduced.
• the ratio of the structural unit (A1) in the structural unit A is preferably 40 mol% or more, more preferably 50 mol% or more, from the viewpoint of maintaining a low coefficient of linear thermal expansion and maintaining a low yellowness. It is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more.
• the upper limit of the ratio is not particularly limited, but is 100 mol% or less.
• the ratio of the constituent unit (A1) in the constituent unit A may be 100 mol%, and it is also preferable that the constituent unit A is composed of only the constituent unit (A1).
• the ratio of the structural unit (A11) in the structural unit A is preferably 40 mol% or more. It is more preferably 50 mol% or more, further preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more.
• the upper limit of the ratio is not particularly limited, but is 100 mol% or less.
• the ratio of the constituent unit (A11) in the constituent unit A may be 100 mol%, and it is also preferable that the constituent unit A is composed of only the constituent unit (A11).
• the structural unit A may include a structural unit other than the structural unit (A1) as long as the effect of the present invention is not impaired.
• the tetracarboxylic acid dianhydride giving such a structural unit is not particularly limited, but is a compound represented by the following formula (a2), p-phenylenebis (trimeritate) anhydride (TAHQ), the following formula (a3).
• BP-TME 4,4'-Bis (1,3-dioxobenzofuran-5-ylcarbonyloxy) biphenyl
• BPAF 4,4'-Bis (1,3-dioxobenzofuran-5-ylcarbonyloxy) biphenyl
• BPAF 4,4'-Bis (1,3-dioxobenzofuran-5-ylcarbonyloxy) biphenyl
• BPAF 4,4'-Bis (1,3-dioxobenzofuran-5-ylcarbonyloxy) biphenyl
• BPAF 4,4'-Bis (1,3-dioxobenzofuran-5-ylcarbonyloxy) biphenyl
• BPAF 4,4'-Bis (1,3-dioxobenzofuran-5-ylcarbonyloxy) biphenyl
• BPAF 4,4'-Bis (1,3-dioxobenzofuran-5-ylcarbonyloxy
• an aromatic tetracarboxylic acid dianhydride and more preferably a p-phenylenebis (trimeritate) anhydride (TAHQ), which is a compound represented by the following formula (a2), represented by the following formula (a3).
• TAHQ p-phenylenebis (trimeritate) anhydride
• BP-TME 4,4'-Bis (1,3-dioxobenzofuran-5-ylcarbonyloxy) biphenyl
• 9,9 which is a compound represented by the following formula (a4).
• -At least one selected from the group consisting of bis (3,4-dicarboxyphenyl) fluorennic acid anhydride (BPAF), and more preferably a compound represented by the following formula (a2) from the viewpoint of elongation.
• BPAF bis (3,4-dicarboxyphenyl) fluorennic acid anhydride
• a2 p-Phenylenebis (trimeritate) anhydride
• TAHQ 4,4'-bis (1,3-dioxo) which is a compound represented by the following formula (a3). It is at least one selected from the group consisting of benzofuran-5-ylcarbonyloxy) biphenyl (BP-TME), and is more preferably a compound represented by the following formula (a2) from the viewpoint of strength and elongation.
• It is p-phenylene bis (trimeritate) anhydrate (TAHQ).
• TAHQ p-phenylene bis (trimeritate) anhydride
• a3 4,4'-bis (1,3-dioxo
• Benzofuran-5-ylcarbonyloxy) biphenyl (BP-TME) and 9,9-bis (3,4-dicarboxyphenyl) fluorennic anhydride (BPAF) which is a compound represented by the above formula (a4).
• the structural unit derived from at least one compound selected from the group consisting of the above is defined as the structural unit (A2).
• the ratio of the constituent unit (A2) in the constituent unit A is preferably 1 to 60 mol from the viewpoint of maintaining a low coefficient of linear thermal expansion and maintaining a low yellowness. %, More preferably 10 to 50 mol%, still more preferably 10 to 30 mol%.
• the structural unit other than the structural unit (A1) arbitrarily included in the structural unit A may be one type or two or more types.
• the aromatic tetracarboxylic acid dianhydride means a tetracarboxylic acid dianhydride containing one or more aromatic rings, and the alicyclic tetracarboxylic acid dianhydride has one alicyclic ring.
• the tetracarboxylic acid dianhydride containing the above and containing no aromatic ring is meant, and the aliphatic tetracarboxylic acid dianhydride means a tetracarboxylic acid dianhydride containing neither an aromatic ring nor an alicyclic ring.
• the structural unit B includes a structural unit (B1) derived from the compound represented by the following formula (b1). By including the structural unit (B1), the structural unit B has excellent heat resistance, a low coefficient of linear thermal expansion, and excellent thermal properties, but has low yellowness, high colorlessness, and low residual stress. It is considered that
• the compound represented by the formula (b1) is 4-aminophenyl-4'-aminobenzoate (4-BAAB).
• the ratio of the structural unit (B1) in the structural unit B is preferably 50 mol% or more, more preferably 70, from the viewpoint of improving low yellowness, low residual stress, low coefficient of linear thermal expansion, and heat resistance. It is mol% or more, more preferably 90 mol% or more, and particularly preferably 99 mol% or more. The upper limit of the ratio is not particularly limited and is 100 mol% or less.
• the ratio of the constituent unit (B1) in the constituent unit B may be 100 mol%, and it is also preferable that the constituent unit B is composed of only the constituent unit (B1).
• the structural unit B may include a structural unit other than the structural unit (B1).
• the diamine that gives such a structural unit is not particularly limited, but is a compound represented by the following formula (b2), 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA).
• 4,4'-Diaminodiphenyl ether 9,9-bis (4-aminophenyl) fluorene, 2,2'-bis (trifluoromethyl) benzidine, 1,4-phenylenediamine, p-xylylene diamine, 3, 5-Diaminobenzoic acid, 1,5-diaminonaphthalene, 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminodiphenylmethane, 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl ether, 1- (4-aminophenyl) -2, 3-Dihydro-1,3,3-trimethyl-1H-inden-5-amine, ⁇ , ⁇ '
• the ratio of the constituent unit (B2) in the constituent unit B is preferably 1 to 50 mol%, more preferably 10 to 30 mol% from the viewpoint of transparency. %.
• the aromatic diamine means a diamine containing one or more aromatic rings
• the alicyclic diamine means a diamine containing one or more alicyclic rings and does not contain an aromatic ring, and is a fat.
• the group diamine means a diamine that does not contain an aromatic ring or an alicyclic ring.
• the structural unit other than the structural unit (B1) arbitrarily included in the structural unit B may be one type or two or more types.
• the polyimide resin of the present invention may contain a structure other than the 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 contained in the polyimide resin include a structure containing an amide bond and the like.
• the polyimide resin of the present invention preferably contains a polyimide chain (a structure in which a structural unit A and a structural unit B are imide-bonded) as a main structure. Therefore, the ratio of the polyimide chain to 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, and may be 100% by mass.
• Suitable physical property values of the polyimide resin of the present invention are as follows.
• the following physical property values at a film thickness of 10 ⁇ m are physical property values when the polyimide resin of the present invention is molded into a film having a thickness of 10 ⁇ m.
• the total light transmittance at a film thickness of 10 ⁇ m is preferably 80% or more, more preferably 83% or more, and further preferably 85% or more.
• the yellow index (YI) at a film thickness of 10 ⁇ m is preferably 20 or less, more preferably 15 or less, and further preferably 12 or less.
• the coefficient of linear expansion (CTE) is preferably in the range of 100-400 ° C., preferably 25 ppm / ° C. or less, more preferably 23 ppm / ° C. or less, 20 ppm / ° C. or less, still more preferably 18 ppm / ° C. or less. be.
• the glass transition temperature (Tg) is preferably 400 ° C. or higher, more preferably 420 ° C. or higher, still more preferably 430 ° C. or higher.
• the above-mentioned physical property values in the present invention can be specifically measured by the method described in Examples.
• the polyimide resin of the present invention can be produced by reacting a tetracarboxylic acid component containing the compound giving the above-mentioned structural unit A with a diamine component containing the above-mentioned compound giving the structural unit (B1).
• the polyimide resin of the present invention is preferably produced by a method of imidizing (dehydrating and ring-closing) the polyamic acid which is the precursor of the polyimide resin. Specifically, it is preferable to apply or mold the polyamic acid contained in the varnish described later on the support, remove the organic solvent by heating, and imidize (dehydrate and ring) by heating to obtain a polyimide resin.
• the production of the polyimide film which is a film-shaped polyimide resin, will be described later.
• the polyamic acid is a product of a heavy addition reaction between the above-mentioned tetracarboxylic acid component and the above-mentioned diamine component. That is, the polyamic acid used as a precursor of the polyimide resin of the present invention is a polyamic acid having a structural unit AA derived from tetracarboxylic acid dianhydride and a structural unit BA derived from diamine, and the structural unit AA is as follows.
• the polyamic acid contains a structural unit (AA1) derived from the compound represented by the formula (a1), and the structural unit BA contains a structural unit (BA1) derived from the compound represented by the following formula (b1). preferable.
• R is independently a methyl group or a trifluoromethyl group, and n is an integer of 1 to 4).
• R is independently a methyl group or a trifluoromethyl group, but is preferably a methyl group.
• n is an integer of 1 to 4, but preferably n is 3.
• preferred compounds include the compound represented by the formula (a1), which is the compound that gives the above-mentioned structural unit (A1).
• the derivative may be used as long as it gives the same structural unit.
• examples of the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a1) and an alkyl ester of the tetracarboxylic acid.
• the compound represented by the formula (a1) that is, dianhydride
• the compound represented by the formula (a11) is more preferable.
• the tetracarboxylic acid component may contain a compound other than the compound giving the structural unit (A1), and the compound includes the above-mentioned aromatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and fat. Examples thereof include group tetracarboxylic acid dianhydrides and derivatives thereof (tetracarboxylic acids, alkyl esters of tetracarboxylic acids, etc.). Among them, as a compound other than the compound giving the structural unit (A1), p-phenylenebis (trimeritate) is preferably an aromatic tetracarboxylic acid dianhydride, and more preferably a compound represented by the formula (a2).
• TAHQ 4,4'-bis (1,3-dioxobenzofuran-5-ylcarbonyloxy) biphenyl
• BPAF 9,9-bis (3,4-dicarboxyphenyl) fluorennic acid anhydride
• the compound other than the compound arbitrarily contained in the tetracarboxylic dian component and given the structural unit (A1) may be one kind or two or more kinds.
• the tetracarboxylic acid component (acid dianhydride component) contains a compound that gives a constituent unit (A1), and the ratio of the compound that gives a constituent unit (A1) to the tetracarboxylic acid component is preferably 40 mol% or more. It is more preferably 50 mol% or more, further preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more. The upper limit of the ratio is not particularly limited and is 100 mol% or less.
• the ratio of the compound giving the structural unit (A1) in the tetracarboxylic acid component may be 100 mol%, and the tetracarboxylic acid component is preferably composed only of the compound giving the structural unit (A1).
• the ratio of the compound represented by the formula (a11) in the tetracarboxylic acid component is preferably 40. It is mol% or more, more preferably 50 mol% or more, further preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more. The upper limit of the ratio is not particularly limited, but is 100 mol% or less.
• the ratio of the compound represented by the formula (a11) in the tetracarboxylic acid component may be 100 mol%, and it is also preferable that the tetracarboxylic acid component comprises only the compound represented by the formula (a11).
• the film of the present invention can have excellent heat resistance and a low coefficient of linear thermal expansion, and can also reduce the yellowness.
• TAHQ p-phenylene bis (trimeritate) anhydride
• a3 4,4'-bis (1,3-dioxo
• Benzofuran-5-ylcarbonyloxy) biphenyl (BP-TME) and 9,9-bis (3,4-dicarboxyphenyl) fluorennic anhydride (BPAF) which is a compound represented by the above formula (a4).
• the structural unit derived from at least one compound selected from the group consisting of the above is defined as the structural unit (A2).
• the tetracarboxylic acid component may contain a compound that gives a constituent unit (A2), and when the tetracarboxylic acid component contains a compound that gives a constituent unit (A2), the constituent unit (A2) in the tetracarboxylic acid component.
• the ratio of the compound giving the above is preferably 1 to 60 mol%, more preferably 10 to 50 mol%, still more preferably 10 to 10 to 60 mol%, from the viewpoint of maintaining a low linear thermal expansion coefficient and maintaining a low yellowness. It is 30 mol%.
• examples of the compound that gives the structural unit (B1) include, but are not limited to, the compound represented by the formula (b1), and the same structural unit. It may be a derivative thereof as long as it gives. Examples of the derivative include diisocyanates corresponding to the compound represented by the formula (b1).
• the compound represented by the formula (b1) that is, a diamine is preferable.
• the diamine component may contain a compound other than the compound giving the structural unit (B1), and examples of the compound include the above-mentioned aromatic diamines, alicyclic diamines, and aliphatic diamines, and diisocyanates corresponding thereto. .. Among them, it is preferably an aromatic diamine, and more preferably 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA), which is a compound represented by the formula (b2).
• 6FODA 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether
• the diamine component contains the compound giving the constituent unit (B1) in an amount of 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. Is.
• the upper limit of the ratio is not particularly limited and is 100 mol% or less.
• the ratio of the compound giving the structural unit (B1) in the diamine component may be 100 mol%, and the diamine component is preferably composed only of the compound giving the structural unit (B1).
• the diamine component may contain a compound that gives a constituent unit (B2), and when the diamine component contains a compound that gives a constituent unit (B2), the ratio of the compound that gives the constituent unit (B2) to the diamine component is From the viewpoint of transparency, it is preferably 1 to 50 mol%, more preferably 10 to 30 mol%.
• the compound that gives the constituent unit AA in the above-mentioned polyamic acid has the same preferable compound and ratio as the compound that gives the constituent unit A in the polyimide of the present invention described in this section, and the constituent unit BA in the above-mentioned polyamic acid.
• the compound giving the above is the same as the compound giving the structural unit B in the polyimide of the present invention described in this section, and the preferable compound and the ratio are the same.
• the charging amount ratio of the tetracarboxylic acid component and the diamine component used in the production of the polyimide resin is preferably 0.9 to 1.1 mol of the diamine component with respect to 1 mol of the tetracarboxylic acid component, and is 0. It is more preferably .95 to 1.10 mol, further preferably 1.00 to 1.08 mol, and even more preferably 1.01 to 1.08 mol. It is preferable to use the above-mentioned charging amount ratio because the stability of the polyamic acid can be improved.
• a terminal encapsulant may be used in addition to the above-mentioned tetracarboxylic acid component and diamine component for the production of the polyimide resin.
• the terminal encapsulant monoamines or dicarboxylic acids are preferable.
• the amount of the terminal encapsulant to be introduced is preferably 0.0001 to 0.1 mol, particularly preferably 0.001 to 0.06 mol, based on 1 mol of the tetracarboxylic acid component.
• Examples of the monoamine terminal encapsulant 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 terminal encapsulant dicarboxylic acids are preferable, and a part thereof may be ring-closed.
• phthalic acid, phthalic acid anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenonedicarboxylic acid, 3,4-benzophenonedicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1. , 2-Dicarboxylic acid, etc. are recommended.
• phthalic acid and phthalic anhydride can be preferably used.
• the method for reacting the above-mentioned tetracarboxylic acid component and the diamine component for obtaining the polyamic acid is not particularly limited, and a known method can be used.
• a specific reaction method a method in which a tetracarboxylic acid component, a diamine component, and a solvent are charged in a reactor and stirred at 0 to 120 ° C., preferably 5 to 80 ° C. for 1 to 72 hours can be exemplified.
• the reaction is carried out at 80 ° C. or lower, the molecular weight of the obtained polyamic acid does not fluctuate depending on the temperature history at the time of polymerization, and the progress of thermal imidization can be suppressed, so that the polyamic acid can be stably produced. can.
• the solvent used for producing the polyamic acid may be any solvent that can dissolve the polyamic acid to be produced.
• an aprotic solvent, a phenol solvent, an ether solvent, a carbonate solvent and the like can be mentioned.
• aprotonic solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactum, 1,3-dimethylimidazolidinone, tetramethylurea and the like.
• Amide-based solvent lactone-based solvent such as ⁇ -butyrolactone and ⁇ -valerolactone, phosphorus-containing amide-based solvent such as hexamethylphosphoric amide and hexamethylphosphintriamide, and sulfur-containing solvent such as dimethylsulfone, dimethylsulfoxide, and sulfolane.
• Examples thereof include a system solvent, a ketone solvent such as acetone, methyl ethyl ketone, cyclohexanone and methylcyclohexanone, and an ester solvent such as acetic acid (2-methoxy-1-methylethyl).
• a system solvent such as acetone, methyl ethyl ketone, cyclohexanone and methylcyclohexanone
• an ester solvent such as acetic acid (2-methoxy-1-methylethyl).
• phenolic solvent examples include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4. -Xylenol, 3,5-xylenol and the like can be mentioned.
• ether solvent examples include 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, and bis [2- (2-methoxyethoxy) ethyl]. Examples include ether, tetrahydrofuran, 1,4-dioxane and the like.
• the carbonate solvent examples include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate and the like.
• an amide solvent or a lactone solvent is preferable, an amide solvent is more preferable, and N-methyl-2-pyrrolidone is further preferable.
• the above reaction solvent may be used alone or in combination of two or more.
• a polyamic acid solution containing polyamic acid dissolved in a solvent can be obtained.
• the concentration of the polyamic acid in the obtained polyamic acid solution is usually 1 to 50% by mass, preferably 3 to 35% by mass, and more preferably 10 to 30% by mass in the polyamic acid solution.
• the number average molecular weight of the polyamic acid is preferably 5,000 to 300,000 from the viewpoint of the mechanical strength of the obtained polyimide film.
• the number average molecular weight of the polyamic acid can be obtained from, for example, a standard polymethylmethacrylate (PMMA) conversion value measured by gel filtration chromatography.
• PMMA polymethylmethacrylate
• the polyamic acid obtained as described above is a polyamic acid having a structural unit AA derived from tetracarboxylic dianhydride and a structural unit BA derived from diamine, and the structural unit AA is the above formula. It is preferable that the structural unit (AA1) derived from the compound represented by (a1) is contained, and the structural unit BA contains the structural unit (BA1) derived from the compound represented by the formula (b1).
• the structural unit (AA1) derived from the compound represented by the formula (a1) includes the structural unit (AA11) derived from the compound represented by the formula (a11) from the viewpoint of heat resistance and reduction of yellowness. Is preferable. Further, the structural unit (AA1) derived from the compound represented by the formula (a1) is a structural unit (AA11) derived from the compound represented by the formula (a11) from the viewpoint of heat resistance and reduction of yellowness. Is more preferable.
• the ratio of the structural unit (AA1) in the structural unit AA is preferably 40 mol% or more, more preferably 50 mol% or more, from the viewpoint of maintaining a low coefficient of linear thermal expansion and maintaining a low yellowness. It is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more.
• the upper limit of the ratio is not particularly limited, but is 100 mol% or less.
• the ratio of the constituent unit (AA1) in the constituent unit AA may be 100 mol%, and it is also preferable that the constituent unit A is composed of only the constituent unit (AA1).
• the ratio of the structural unit (AA11) in the structural unit A is preferably 40 mol% or more. It is more preferably 50 mol% or more, further preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more.
• the upper limit of the ratio is not particularly limited, but is 100 mol% or less.
• the ratio of the constituent unit (AA11) in the constituent unit AA may be 100 mol%, and it is also preferable that the constituent unit AA is composed of only the constituent unit (AA11).
• the ratio of the structural unit (BA1) in the structural unit BA is preferably 50 mol% or more, more preferably 70, from the viewpoint of improving low yellowness, low residual stress, low coefficient of linear thermal expansion, and heat resistance. It is mol% or more, more preferably 90 mol% or more, and particularly preferably 99 mol% or more. The upper limit of the ratio is not particularly limited and is 100 mol% or less.
• the ratio of the constituent unit (BA1) in the constituent unit BA may be 100 mol%, and it is also preferable that the constituent unit BA is composed of only the constituent unit (BA1).
• the varnish of the present invention is obtained by dissolving the above-mentioned polyamic acid, which is a precursor of the polyimide resin of the present invention, in an organic solvent. That is, the varnish of the present invention contains a polyamic acid and an organic solvent which are precursors of the polyimide resin of the present invention, and the polyamic acid is dissolved in the organic solvent.
• the organic solvent may be any one that dissolves the polyamic acid, and is not particularly limited, but it is preferable to use the above-mentioned compounds alone or in combination of two or more as the solvent used for producing the polyamic acid.
• the varnish of the present invention may be the above-mentioned polyamic acid solution itself, or may be obtained by further adding a diluting solvent to the polyamic acid solution.
• the varnish of the present invention can further contain an imidization catalyst and a dehydration catalyst from the viewpoint of efficiently advancing the imidization of the polyamic acid of the present invention.
• the imidization catalyst may be any imidization catalyst having a boiling point of 40 ° C. or higher and 180 ° C. or lower, and an amine compound having a boiling point of 180 ° C. or lower is preferable. If the imidization catalyst has a boiling point of 180 ° C. or lower, the film will be colored when dried at a high temperature after the film is formed, and the appearance will not be impaired. Further, if the imidization catalyst has a boiling point of 40 ° C. or higher, the possibility of volatilization before the imidization proceeds sufficiently can be avoided.
• Examples of the amine compound preferably used as an imidization catalyst include pyridine and picoline.
• the above imidization catalyst may be used alone or in combination of two or more.
• Examples of the dehydration catalyst include acid anhydrides such as acetic anhydride, propionic acid anhydride, n-butyric acid anhydride, benzoic acid anhydride and trifluoroacetic anhydride; carbodiimide compounds such as dicyclohexylcarbodiimide; and the like. These may be used alone or in combination of two or more.
• the varnish of the present invention preferably contains 3 to 40% by mass of polyamic acid, and more preferably 5 to 30% by mass.
• the viscosity of the varnish is preferably 0.1 to 100 Pa ⁇ s, more preferably 0.1 to 20 Pa ⁇ s.
• the viscosity of the varnish is a value measured at 25 ° C. using an E-type viscometer.
• the varnish of the present invention has an inorganic filler, an adhesion accelerator, a release agent, a flame retardant, an ultraviolet stabilizer, a surfactant, a leveling agent, an antifoaming agent, and an optical brightener as long as the required characteristics of the polyimide film are not impaired. It may contain various additives such as an agent, a cross-linking agent, a polymerization initiator, and a photosensitizer.
• the varnish of the present invention is an arbitrary additive, particularly from the viewpoint of reducing the linear expansion coefficient, but preferably further contains tetraalkoxysilane, and more preferably further contains a compound represented by the following formula (y1). That is, the varnish of the present invention preferably contains a polyamic acid, a tetraalkoxysilane and an organic solvent which are precursors of the polyimide resin of the present invention, and the polyamic acid and the tetraalkoxysilane are dissolved in the organic solvent.
• the varnish of the present invention more preferably contains a polyamic acid which is a precursor of the polyimide resin of the present invention, a compound represented by the above formula (y1) and an organic solvent, and is represented by the polyamic acid and the above formula (y1).
• the compound is dissolved in the organic solvent.
• the compound represented by the formula (y1) is tetraethoxysilane.
• tetraalkoxysilane examples include tetramethoxysilane, tetraethoxysilane (compound represented by the above formula (y1)), tetrapropoxysilane, tetraisopropoxysilane, and tetrabutoxysilane, and tetramethoxysilane and tetraethoxysilane ( At least one selected from the group consisting of the compound represented by the formula (y1) and tetraisopropoxysilane is preferable, and from the group consisting of tetramethoxysilane and tetraethoxysilane (compound represented by the formula (y1)). At least one selected is more preferable, and tetraethoxysilane (compound represented by the above formula (y1)) is further preferable.
• the degree of yellowness can be reduced. Above all, the linear expansion coefficient can be greatly reduced.
• the amount of tetraalkoxysilane is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass with respect to 100 parts by mass of polyamic acid. It is more preferably 3 to 15 parts by mass, and even more preferably 5 to 12 parts by mass.
• the amount of the compound represented by the formula (y1) is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the polyamic acid. It is more preferably 2 to 20 parts by mass, further preferably 3 to 15 parts by mass, and even more preferably 5 to 12 parts by mass.
• the method for producing the varnish of the present invention is not particularly limited, and a known method can be applied.
• the polyimide film of the present invention contains the polyimide resin of the present invention. That is, it has a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from diamine, and the structural unit A includes a structural unit (A1) derived from the compound represented by the above formula (a1). , Containing a polyimide resin, wherein the structural unit B contains a structural unit (B1) derived from the compound represented by the above formula (b1). Further, it is preferable that the polyimide film of the present invention is substantially made of the polyimide resin of the present invention.
• the polyimide film of the present invention has a low degree of yellowness while maintaining a low coefficient of linear expansion and excellent heat resistance.
• the suitable physical property values of the polyimide film of the present invention are as described above.
• the polyimide film of the present invention is preferably produced using a varnish in which the above-mentioned polyamic acid is dissolved in an organic solvent. Further, the polyimide film of the present invention is more preferably produced by using a varnish in which the above-mentioned polyamic acid is dissolved in an organic solvent and contains tetraalkoxysilane. It is more preferable to use a varnish containing the compound represented by y1).
• the method for producing a polyimide film using the varnish of the present invention is not particularly limited, and a known method can be used. Among them, the method of applying the varnish of the present invention on the support and heating is preferable, and specifically, the varnish of the present invention is applied or in the form of a film on a smooth support such as a glass plate, a metal plate, or a plastic.
• the organic solvent such as the reaction solvent and the diluting solvent contained in the varnish is removed by heating to obtain a polyamic acid film, and the polyamic acid in the polyamic acid film is imidized by heating (dehydration ring closure). Then, the polyimide film can be produced by peeling from the support.
• the polyimide film of the present invention is preferably obtained by applying the varnish of the present invention on a support and heating the film.
• the heating temperature for drying the polyamic acid varnish (varnish containing polyamic acid) to obtain a polyamic acid film is preferably 50 to 150 ° C.
• the heating temperature for imidizing the polyamic acid by heating is preferably 350 to 450 ° C, more preferably 380 to 420 ° C.
• the heating time is usually 1 minute to 6 hours, preferably 5 minutes to 2 hours, and more preferably 15 minutes to 1 hour. By setting such a temperature and time, the physical characteristics of the obtained polyimide film become good.
• Examples of the heating atmosphere include air gas, nitrogen gas, oxygen gas, hydrogen gas, and nitrogen / hydrogen mixed gas. In order to suppress the coloring of the obtained polyimide resin, nitrogen gas and hydrogen concentration having an oxygen concentration of 100 ppm or less are used. A nitrogen / hydrogen mixed gas containing 0.5% or less is preferable.
• 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 intended use and the like, but is preferably 1 to 250 ⁇ m, more preferably 5 to 100 ⁇ m, and further preferably 7 to 50 ⁇ m. When the thickness is 1 to 250 ⁇ m, it can be practically used as a self-supporting film. The thickness of the polyimide film can be easily controlled by adjusting the solid content concentration and the viscosity of the varnish.
• the polyimide film of the present invention is suitably used as a film for various members such as color filters, flexible displays, semiconductor parts, and optical members.
• the polyimide film of the present invention is particularly preferably used as a substrate for an image display device such as a liquid crystal display or an OLED display.
• the polyimide film of the present invention is excellent in heat resistance and can be suitably used for a LTPS-TFT (low temperature polysilicon TFT) substrate that requires a process temperature at a high temperature. That is, the polyimide film of the present invention is preferably a polyimide film for a LTPS-TFT (low temperature polysilicon TFT) substrate.
• the LTPS-TFT (Low Temperature Polysilicon TFT) substrate containing the polyimide film of the present invention is a laminate in which at least one selected from the group consisting of the polyimide film, a metal film layer, a semiconductor film layer, and an insulating film layer is laminated. Consists of. Since the LTPS-TFT (low temperature polysilicon TFT) substrate contains the polyimide film of the present invention, it has a feature of being excellent in transparency. That is, the LTPS-TFT (low temperature polysilicon TFT) substrate is suitable for a transparent display or a display using UDC (under display camera) technology. Further, the polyimide film of the present invention is suitable for a LTPS-TFT (low temperature polysilicon TFT) substrate used for a transparent display or a display using UDC (under display camera) technology.
• CTE Coefficient of linear thermal expansion
• tetracarboxylic acid component and diamine component used in Examples and Comparative Examples, and their abbreviations and the like are as follows.
• TAHQ p-phenylenebis (trimeritate) anhydride
• BP-TME (manufactured by Honshu Chemical Industry Co., Ltd .; compound represented by formula (a3))
• s-BPDA 3,3', 4,4'-biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation)
• NMP N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation)
• TEOS Tetraethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., compound represented by formula (y1))
• Example 1 10.107 g (0.044 mol) of 4-BAAB in a 300 mL five-necked round-bottom flask equipped with a stainless half-moon stirring blade, a Dean Stark with a nitrogen inlet tube, a thermometer, and a glass end cap. ), NMP 170.000 g was added, the temperature inside the system was raised to 80 ° C. with a mantle heater, and the mixture was stirred at a rotation speed of 200 rpm under a nitrogen atmosphere to obtain a solution. 27.393 g (0.044 mol) of TMPBP-TME and 42.500 g of NMP were collectively added to this solution and kept at an in-system temperature of 80 ° C. for 10 minutes.
• the mixture was cooled to 25 ° C. and stirred at 25 ° C. for 5 hours to obtain a polyamic acid varnish having a solid content concentration of 15% by mass.
• the obtained polyamic acid varnish was applied onto a glass plate by spin coating, held at 80 ° C. for 20 minutes on a hot plate, and then heated at 400 ° C. in a hot air dryer for 60 minutes under a nitrogen atmosphere (ascending). The temperature was 5 ° C./min), the solvent was evaporated, and the mixture was further thermally imidized to obtain a polyimide film.
• Table 1 The results are shown in Table 1.
• Example 2 4-BAAB 7.885 g (0.035 mol) in a 300 mL five-necked round-bottom flask equipped with a stainless half-moon stirring blade, a Dean Stark with a nitrogen inlet tube, a thermometer, and a glass end cap. ), 6FODA 2.904 g (0.009 mol) and NMP 170.000 g were added, the temperature was raised to 80 ° C. in the system with a mantle heater, and the mixture was stirred at a rotation speed of 200 rpm under a nitrogen atmosphere to obtain a solution.
• Example 3 4-BAAB 10.636 g (0.047 mol) in a 300 mL five-necked round-bottom flask equipped with a stainless half-moon stirring blade, a Dean Stark with a nitrogen inlet tube, a thermometer, and a glass end cap. ), NMP 170.000 g was added, the temperature inside the system was raised to 80 ° C. with a mantle heater, and the mixture was stirred at a rotation speed of 200 rpm under a nitrogen atmosphere to obtain a solution.
• Example 4 4-BAAB 11.164 g (0.049 mol) in a 300 mL five-necked round-bottom flask equipped with a stainless half-moon stirring blade, a Dean Stark with a nitrogen inlet tube, a thermometer, and a glass end cap. ), 170.000 g of NMP was added, the temperature inside the system was raised to 80 ° C. with a mantle heater, and the mixture was stirred at a rotation speed of 200 rpm under a nitrogen atmosphere to obtain a solution.
• Example 5 10.312 g (0.045 mol) of 4-BAAB in a 300 mL five-necked round-bottom flask equipped with a stainless half-moon stirring blade, a Dean Stark with a nitrogen inlet tube, a thermometer, and a glass end cap. ), NMP 170.000 g was added, the temperature inside the system was raised to 80 ° C. with a mantle heater, and the mixture was stirred at a rotation speed of 200 rpm under a nitrogen atmosphere to obtain a solution.
• Example 6 4-BAAB 10.505 g (0.046 mol) in a 300 mL five-necked round-bottom flask equipped with a stainless half-moon stirring blade, a Dean Stark with a nitrogen inlet tube, a thermometer, and a glass end cap. ), NMP 170.000 g was added, the temperature inside the system was raised to 80 ° C. with a mantle heater, and the mixture was stirred at a rotation speed of 200 rpm under a nitrogen atmosphere to obtain a solution.
• Example 7 4-BAAB 10.472 g (0.046 mol) in a 300 mL five-necked round-bottom flask equipped with a stainless half-moon stirring blade, a Dean Stark with a nitrogen inlet tube, a thermometer, and a glass end cap. ), NMP 170.000 g was added, the temperature inside the system was raised to 80 ° C. with a mantle heater, and the mixture was stirred at a rotation speed of 200 rpm under a nitrogen atmosphere to obtain a solution. 27.028 g (0.044 mol) of TMPBP-TME and 42.500 g of NMP were collectively added to this solution and kept at an in-system temperature of 80 ° C. for 10 minutes.
• Example 1 After confirming the dissolution, the mixture was cooled to 25 ° C. and stirred at 25 ° C. for 5 hours to obtain a polyamic acid varnish having a solid content concentration of 15% by mass. Using the obtained varnish, a film was obtained by the same method as in Example 1.
• Example 8 4-BAAB 10.543 g (0.046 mol) in a 300 mL five-necked round-bottom flask equipped with a stainless half-moon stirring blade, a Dean Stark with a nitrogen inlet tube, a thermometer, and a glass end cap. ), NMP 170.000 g was added, the temperature inside the system was raised to 80 ° C. with a mantle heater, and the mixture was stirred at a rotation speed of 200 rpm under a nitrogen atmosphere to obtain a solution. 26.957 g (0.044 mol) of TMPBP-TME and 42.500 g of NMP were collectively added to this solution and kept at an in-system temperature of 80 ° C. for 10 minutes.
• Example 1 After confirming the dissolution, the mixture was cooled to 25 ° C. and stirred at 25 ° C. for 5 hours to obtain a polyamic acid varnish having a solid content concentration of 15% by mass. Using the obtained varnish, a film was obtained by the same method as in Example 1.
• Example 9 To 100 g of the polyamic acid varnish having a solid content concentration of 15% by mass obtained in Example 1, TEOS was added so that the TEOS was 10 parts by mass with respect to 100 parts by mass of the polyamic acid, and the mixture was stirred for 30 minutes to homogenize. I got a varnish. Using the obtained varnish, a film was obtained by the same method as in Example 1.
• Comparative Example 1 4-BAAB 11.223g (0.049mol) in a 300mL five-necked round-bottom flask equipped with a stainless half-moon stirring blade, a Dean Stark with a nitrogen inlet tube, a thermometer, and a glass end cap. ), NMP 170.000 g was added, the temperature inside the system was raised to 80 ° C. with a mantle heater, and the mixture was stirred at a rotation speed of 200 rpm under a nitrogen atmosphere to obtain a solution. 26.277 g (0.049 mol) of BP-TME and 42.500 g of NMP were collectively added to this solution and kept at an in-system temperature of 80 ° C. for 10 minutes.
• Example 1 After confirming the dissolution, the mixture was cooled to 25 ° C. and stirred at 25 ° C. for 5 hours to obtain a polyamic acid varnish having a solid content concentration of 15% by mass. Using the obtained varnish, a film was obtained by the same method as in Example 1.
• Comparative Example 2 4-BAAB 16.383 g (0.072 mol) in a 300 mL five-necked round-bottom flask equipped with a stainless half-moon stirring blade, a Dean Stark with a nitrogen inlet tube, a thermometer, and a glass end cap. ), NMP 170.000 g was added, the temperature inside the system was raised to 80 ° C. with a mantle heater, and the mixture was stirred at a rotation speed of 200 rpm under a nitrogen atmosphere to obtain a solution. 21.117 g (0.072 mol) of s-BPDA and 42.500 g of NMP were collectively added to this solution and kept at an in-system temperature of 80 ° C. for 10 minutes.
• Example 1 After confirming the dissolution, the mixture was cooled to 25 ° C. and stirred at 25 ° C. for 5 hours to obtain a polyamic acid varnish having a solid content concentration of 15% by mass. Using the obtained varnish, a film was obtained by the same method as in Example 1.
• Comparative Example 3 12.467 g (0.055 mol) of 4-BAAB in a 300 mL five-necked round-bottom flask equipped with a stainless half-moon stirring blade, a Dean Stark with a nitrogen inlet tube, a thermometer, and a glass end cap. ), NMP 170.000 g was added, the temperature inside the system was raised to 80 ° C. with a mantle heater, and the mixture was stirred at a rotation speed of 200 rpm under a nitrogen atmosphere to obtain a solution. 25.033 g (0.055 mol) of TAHQ and 42.500 g of NMP were collectively added to this solution, and the mixture was kept at an in-system temperature of 80 ° C. for 10 minutes.
• Example 1 After confirming the dissolution, the mixture was cooled to 25 ° C. and stirred at 25 ° C. for 5 hours to obtain a polyamic acid varnish having a solid content concentration of 15% by mass. Using the obtained varnish, a film was obtained by the same method as in Example 1.
• the polyimide film containing the polyimide resin of the present invention is a film made of an aromatic polyimide resin having excellent heat resistance and a low coefficient of linear expansion, but has a low yellowness and is yellow. The change is suppressed.
• Example 9 when TEOS is used as an additive, it shows a particularly low linear expansion coefficient.

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