CN113166411A - Polyimide resin, polyimide varnish, and polyimide film - Google Patents

Polyimide resin, polyimide varnish, and polyimide film Download PDF

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CN113166411A
CN113166411A CN201980077586.2A CN201980077586A CN113166411A CN 113166411 A CN113166411 A CN 113166411A CN 201980077586 A CN201980077586 A CN 201980077586A CN 113166411 A CN113166411 A CN 113166411A
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polyimide
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Inventor
安孙子洋平
星野舜
村谷孝博
关口慎司
高田贵文
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • 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

Abstract

A polyimide resin having a tetracarboxylic dianhydride-derived structural unit A and a diamine-derived structural unit B, wherein the structural unit A comprises at least one structural unit (A-1) selected from the group consisting of a structural unit (A-1-1) derived from a compound represented by the following formula (a-1-1) and a structural unit (A-1-2) derived from a compound represented by the following formula (a-1-2), the structural unit B comprises a structural unit (B-1) derived from a compound represented by the following formula (B-1) and a structural unit (B-2), and the structural unit (B-2) is a structural unit (B-2-1) selected from the group consisting of a structural unit (B-2-1) derived from a compound represented by the following formula (B-2-1), A structural unit (B-2-2) derived from a compound represented by the following formula (B-2-2)At least one member selected from the group consisting of a structural unit (B-2-3) derived from a compound represented by the following formula (B-2-3), a structural unit (B-2-4) derived from a compound represented by the following formula (B-2-4), and a structural unit (B-2-5) derived from a compound represented by the following formula (B-2-5), wherein the proportion of the structural unit (B-1) in the structural unit B is 70 mol% or more. (in the formula (b-2-2), R is each independently a hydrogen atom, a fluorine atom or a methyl group, and in the formula (b-2-4), R is1～R4Each independently a monovalent aliphatic group or a monovalent aromatic group, Z1And Z2Each independently is a divalent aliphatic group or a divalent aromatic group, and r is a positive integer. )

Description

Polyimide resin, polyimide varnish, and polyimide film
Technical Field
The present invention relates to a polyimide resin, a polyimide varnish, and a polyimide film.
Background
Polyimide resins have been studied for various uses in the fields of electric/electronic components and the like. For example, for the purpose of weight reduction and flexibility of devices, it is desired to replace glass substrates used in image display devices such as liquid crystal displays and OLED displays with plastic substrates, and studies have been made on polyimide films suitable for the plastic substrates.
In an image display device, when light emitted from a display element is emitted through a plastic substrate, the plastic substrate is required to have colorless transparency, and when light passes through a retardation film or a polarizing plate (for example, a liquid crystal display, a touch panel, or the like), the plastic substrate is required to have high optical isotropy (that is, low Rth) in addition to colorless transparency.
In order to satisfy the above-described required performance, various polyimide resins have been developed. For example, as a polyimide resin for providing a polyimide film which is colorless and transparent, has a low Rth, and is excellent in toughness, patent document 1 describes a polyimide resin produced by using a combination of a specific diamine (second diamine) such as 3,3 '-diaminodiphenyl sulfone (first diamine) and 4, 4' -diaminodiphenyl sulfone (second diamine) as a diamine component.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2016/158825
Disclosure of Invention
Problems to be solved by the invention
However, in order to adapt a polyimide film to a substrate, not only colorless transparency and optical isotropy but also chemical resistance (solvent resistance, acid resistance, and alkali resistance) are important physical properties.
For example, when a varnish for forming a resin layer is applied to a polyimide film in order to form another resin layer (for example, a color filter or a resist layer) on the polyimide film, the polyimide film is required to have resistance to a solvent contained in the varnish. When the solvent resistance of the polyimide film is insufficient, the film may lose its significance as a substrate due to dissolution and swelling of the film.
When a polyimide film is used as a substrate for forming an ITO (indium Tin oxide) film, the polyimide film is required to have resistance to an acid used for etching the ITO film. When the acid resistance of the polyimide film is insufficient, the film may be yellowed and the colorless transparency may be impaired.
In addition, in cleaning a support such as a glass plate (a support coated with a polyimide varnish) used in the production of a polyimide film, an alkaline aqueous solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution is mainly used. The washing with the alkali aqueous solution may be performed in a state where a polyimide film is formed on a support such as a glass plate. Therefore, the polyimide film also requires resistance to alkali.
However, in patent document 1, chemical resistance is not evaluated.
The present invention has been made in view of such a situation, and an object of the present invention is to provide: a polyimide resin capable of forming a film excellent in colorless transparency, optical isotropy, and chemical resistance (solvent resistance, acid resistance, and alkali resistance), and a polyimide varnish and a polyimide film comprising the polyimide resin.
Means for solving the problems
The inventors of the present invention found that: the above problems can be solved by a polyimide resin containing a combination of specific structural units, and the present invention has been completed.
That is, the present invention relates to the following [1] to [10 ].
[1]
A polyimide resin having a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine,
the structural unit A contains at least 1 structural unit (A-1) selected from the group consisting of a structural unit (A-1-1) derived from a compound represented by the following formula (a-1-1) and a structural unit (A-1-2) derived from a compound represented by the following formula (a-1-2),
the structural unit B contains a structural unit (B-1) derived from a compound represented by the following formula (B-1) and a structural unit (B-2), and the structural unit (B-2) is at least 1 selected from the group consisting of a structural unit (B-2-1) derived from a compound represented by the following formula (B-2-1), a structural unit (B-2-2) derived from a compound represented by the following formula (B-2-2), a structural unit (B-2-3) derived from a compound represented by the following formula (B-2-3), a structural unit (B-2-4) derived from a compound represented by the following formula (B-2-4), and a structural unit (B-2-5) derived from a compound represented by the following formula (B-2-5),
the proportion of the structural unit (B-1) in the structural unit B is 70 mol% or more.
Figure BDA0003082851470000031
(in the formula (b-2-2),
r is each independently a hydrogen atom, a fluorine atom or a methyl group,
in the formula (b-2-4),
R1～R4each independently a monovalent aliphatic group or a monovalent aromatic group,
Z1and Z2Each independently a divalent aliphatic group or a divalent aromatic group,
r is a positive integer. )
[2]
The polyimide resin according to the above [1], wherein the ratio of the structural unit (B-1) in the structural unit B is 70 to 97 mol%,
the proportion of the structural unit (B-2) in the structural unit B is 3 to 30 mol%.
[3]
The polyimide resin according to the above [1] or [2], wherein a ratio of the structural unit (A-1) in the structural unit A is 50 mol% or more.
[4]
The polyimide resin according to any one of the above [1] to [3], wherein the structural unit (B-2) is a structural unit (B-2-1).
[5]
The polyimide resin according to any one of the above [1] to [3], wherein the structural unit (B-2) is a structural unit (B-2-2).
[6]
The polyimide resin according to any one of the above [1] to [3], wherein the structural unit (B-2) is a structural unit (B-2-3).
[7]
The polyimide resin according to any one of the above [1] to [3], wherein the structural unit (B-2) is a structural unit (B-2-4).
[8]
The polyimide resin according to any one of the above [1] to [3], wherein the structural unit (B-2) is a structural unit (B-2-5).
[9]
A polyimide varnish comprising a polyimide resin according to any one of the above [1] to [8] dissolved in an organic solvent.
[10]
A polyimide film comprising the polyimide resin according to any one of the above [1] to [8 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can form a film excellent in colorless transparency, optical isotropy, and chemical resistance (solvent resistance, acid resistance, and alkali resistance).
Detailed Description
[ polyimide resin ]
The polyimide resin of the present invention has a tetracarboxylic dianhydride-derived structural unit A and a diamine-derived structural unit B, wherein the structural unit A comprises at least 1 structural unit (A-1) selected from the group consisting of a structural unit (A-1-1) derived from a compound represented by the following formula (a-1-1) and a structural unit (A-1-2) derived from a compound represented by the following formula (a-1-2), and the structural unit B comprises a structural unit (B-1) derived from a compound represented by the following formula (B-1), and a structural unit (B-2-2) selected from the group consisting of a structural unit (B-2-1) derived from a compound represented by the following formula (B-2-1), a structural unit (B-2-2) derived from a compound represented by the following formula (B-2-2), A structural unit (B-2) derived from at least 1 member of the group consisting of a structural unit (B-2-3) derived from a compound represented by the following formula (B-2-3), a structural unit (B-2-4) derived from a compound represented by the following formula (B-2-4), and a structural unit (B-2-5) derived from a compound represented by the following formula (B-2-5), wherein the ratio of the structural unit (B-1) in the structural unit B is 70 mol% or more.
Figure BDA0003082851470000061
(in the formula (b-2-2),
r is each independently a hydrogen atom, a fluorine atom or a methyl group,
in the formula (b-2-4),
R1～R4each independently a monovalent aliphatic group or a monovalent aromatic groupThe mass of the balls is obtained by mixing the raw materials,
Z1and Z2Each independently a divalent aliphatic group or a divalent aromatic group,
r is a positive integer. )
< structural Unit A >
The structural unit A is a structural unit derived from a tetracarboxylic dianhydride in a polyimide resin, and comprises at least 1 structural unit (A-1) selected from the group consisting of structural units (A-1-1) derived from a compound represented by the following formula (a-1-1) and structural units (A-1-2) derived from a compound represented by the following formula (a-1-2).
Figure BDA0003082851470000071
The compound represented by the formula (a-1-1) is 1,2,4, 5-cyclohexanetetracarboxylic dianhydride.
When the structural unit A contains the structural unit (A-1-1) as the structural unit (A-1), the colorless transparency and the optical isotropy of the film can be improved.
The compound represented by the formula (a-1-2) is 4, 4' -oxydiphthalic anhydride.
By including the structural unit (A) as the structural unit (A-1) in the structural unit A, the chemical resistance of the film can be improved.
The proportion of the structural unit (a-1) in the structural unit a is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably 99 mol% or more. The upper limit of the ratio of the structural unit (A-1) is not particularly limited, i.e., 100 mol%. The structural unit A may contain only the structural unit (A-1).
The structural unit (A-1) may be only the structural unit (A-1-1) or may be only the structural unit (A-1-2). Further, the structural unit (A-1) may be a combination of the structural unit (A-1-1) and the structural unit (A-1-2).
When the structural unit (A-1) is a combination of the structural unit (A-1-1) and the structural unit (A-1-2), the molar ratio of the structural unit (A-1-1)/the structural unit (A-1-2) is preferably 5/95 to 95/5, more preferably 20/80 to 90/10, and still more preferably 50/50 to 90/10, from the viewpoints of colorless transparency, optical isotropy, and chemical resistance. Further, it is more preferably 20/80 to 70/30 particularly from the viewpoint of toughness of the obtained film, and is more preferably 60/40 to 95/5 particularly from the viewpoint of improving optical isotropy of the obtained film, more preferably 70/30 to 95/5, and more preferably 85/15 to 95/5.
The structural unit A may contain a structural unit other than the structural unit (A-1). The tetracarboxylic dianhydride providing such a structural unit is not particularly limited, and examples thereof include aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride, 9 '-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, and 4, 4' - (hexafluoroisopropylidene) phthalic anhydride (except for the compound represented by the formula (a-1-2)); alicyclic tetracarboxylic dianhydrides such as 1,2,3, 4-cyclobutanetetracarboxylic dianhydride and norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 ″ -norbornane-5, 5 ″,6,6 ″ -tetracarboxylic dianhydride (except for the compound represented by the formula (a-1-1)); and aliphatic tetracarboxylic acid dianhydrides such as 1,2,3, 4-butanetetracarboxylic acid dianhydride.
In the present specification, an aromatic tetracarboxylic dianhydride refers to a tetracarboxylic dianhydride containing 1 or more aromatic rings, an alicyclic tetracarboxylic dianhydride refers to a tetracarboxylic dianhydride containing 1 or more alicyclic rings and no aromatic rings, and an aliphatic tetracarboxylic dianhydride refers to a tetracarboxylic dianhydride containing no aromatic rings and no alicyclic rings.
The structural unit(s) optionally contained in the structural unit a (i.e., structural units other than the structural unit (a-1)) are optionally 1 or 2 or more.
< structural Unit B >
The structural unit B is a diamine-derived structural unit in the polyimide resin, and comprises a structural unit (B-1) derived from a compound represented by the following formula (B-1) and a structural unit (B-2), and the structural unit (B-2) is at least one selected from the group consisting of a structural unit (B-2-1) derived from a compound represented by the following formula (B-2-1), a structural unit (B-2-2) derived from a compound represented by the following formula (B-2-2), a structural unit (B-2-3) derived from a compound represented by the following formula (B-2-3), a structural unit (B-2-4) derived from a compound represented by the following formula (B-2-4), and a structural unit (B-2-5) derived from a compound represented by the following formula (B-2-5) 1 kind of the Chinese medicinal composition.
Figure BDA0003082851470000091
(in the formula (b-2-2),
r is each independently a hydrogen atom, a fluorine atom or a methyl group,
in the formula (b-2-4),
R1～R4each independently a monovalent aliphatic group or a monovalent aromatic group,
Z1and Z2Each independently a divalent aliphatic group or a divalent aromatic group,
r is a positive integer. )
The compound represented by the formula (b-1) is 3, 3' -diaminodiphenyl sulfone.
The compound represented by the formula (b-2-1) is 4,4 '-diamino-2, 2' -bistrifluoromethyldiphenyl ether. Particularly, from the viewpoint of toughness and acid resistance of the film, the structural unit (B-2) preferably contains the structural unit (B-2-1) derived from the compound represented by the formula (B-2-1), and the structural unit B preferably contains the structural unit (B-2-1) derived from the compound represented by the formula (B-2-1).
In the formula (b-2-2), R is each independently a hydrogen atom, a fluorine atom, or a methyl group, preferably a hydrogen atom. Examples of the compound represented by the formula (b-2-2) include 9, 9-bis (4-aminophenyl) fluorene, 9-bis (3-fluoro-4-aminophenyl) fluorene, and 9, 9-bis (3-methyl-4-aminophenyl) fluorene, and 9, 9-bis (4-aminophenyl) fluorene is preferable. Particularly, from the viewpoint of heat resistance and optical isotropy of the film, the structural unit (B-2) preferably contains the structural unit (B-2-2) derived from the compound represented by the formula (B-2-2), and the structural unit B preferably contains the structural unit (B-2-2) derived from the compound represented by the formula (B-2-2).
The compound represented by the formula (b-2-3) is 2, 2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane. In particular, from the viewpoint of colorless transparency of the film, the structural unit (B-2) preferably contains the structural unit (B-2-3) derived from the compound represented by the formula (B-2-3), and the structural unit B preferably contains the structural unit (B-2-3) derived from the compound represented by the formula (B-2-3).
R in the formula (b-2-4)1、R2、R3And R4Each independently represents a monovalent aliphatic group or a monovalent aromatic group, which may be substituted with a fluorine atom. Examples of the monovalent aliphatic group include a monovalent saturated hydrocarbon group and a monovalent unsaturated hydrocarbon group. Examples of the monovalent saturated hydrocarbon group include alkyl groups having 1 to 22 carbon atoms, and examples thereof include methyl, ethyl and propyl. The monovalent unsaturated hydrocarbon group includes an alkenyl group having 2 to 22 carbon atoms, and examples thereof include an ethenyl group and an propenyl group. Examples of the monovalent aromatic group include aryl groups and aralkyl groups having 6 to 24 carbon atoms. As R1、R2、R3And R4Particularly preferred is a methyl group or a phenyl group.
In addition, Z1And Z2Each independently represents a divalent aliphatic group or a divalent aromatic group, which may be substituted with a fluorine atom or may contain an oxygen atom. When the oxygen atom is contained as an ether bond, the carbon number shown below refers to all the carbon numbers contained in the aliphatic group or the aromatic group. Examples of the divalent aliphatic group include a divalent saturated hydrocarbon group and a divalent unsaturated hydrocarbon group. Examples of the divalent saturated hydrocarbon group include an alkylene group having 1 to 22 carbon atoms and an alkyleneoxy group, and examples of the alkylene group include a methylene group, an ethylene group and a propylene group. Examples of the divalent unsaturated hydrocarbon group include unsaturated hydrocarbon groups having 2 to 22 carbon atoms, examples of which include an ethenylene group, an propenylene group, and an alkylene group having an unsaturated double bond at the terminal, and examples of the alkyleneoxy group include a propyleneoxy group and a trimethyleneoxy group. Examples of the divalent aromatic group include phenylene groups having 6 to 24 carbon atoms, phenylene groups substituted with alkyl groups, and aralkylene groups. As Z1And Z2Propylene, phenylene and aralkylene are particularly preferable.
R represents a positive integer, preferably an integer of 10 to 10000.
Examples of the compound represented by the formula (b-2-4) include 1, 3-bis (3-aminopropyl) -1,1,2, 2-tetramethyldisiloxane, 1, 3-bis (3-aminobutyl) -1,1,2, 2-tetramethyldisiloxane, bis (4-aminophenoxy) dimethylsilane, 1, 3-bis (4-aminophenoxy) tetramethyldisiloxane, 1,3, 3-tetramethyl-1, 3-bis (4-aminophenyl) disiloxane, 1,3, 3-tetraphenoxy-1, 3-bis (2-aminoethyl) disiloxane, 1,3, 3-tetraphenyl-1, 3-bis (2-aminoethyl) disiloxane, 1,1,3, 3-tetraphenyl-1, 3-bis (3-aminopropyl) disiloxane, 1,3, 3-tetramethyl-1, 3-bis (2-aminoethyl) disiloxane, 1,3, 3-tetramethyl-1, 3-bis (3-aminopropyl) disiloxane, 1,3, 3-tetramethyl-1, 3-bis (4-aminobutyl) disiloxane, 1, 3-dimethyl-1, 3-dimethoxy-1, 3-bis (4-aminobutyl) disiloxane, 1,3,3,5, 5-hexamethyl-1, 5-bis (4-aminophenyl) trisiloxane, 1,5, 5-tetraphenyl-3, 3-dimethyl-1, 5-bis (3-aminopropyl) trisiloxane, 1,5, 5-tetraphenyl-3, 3-dimethoxy-1, 5-bis (4-aminobutyl) trisiloxane, 1,5, 5-tetraphenyl-3, 3-dimethoxy-1, 5-bis (5-aminopentyl) trisiloxane, 1,5, 5-tetramethyl-3, 3-dimethoxy-1, 5-bis (2-aminoethyl) trisiloxane, 1,5, 5-tetramethyl-3, 3-dimethoxy-1, 5-bis (4-aminobutyl) trisiloxane, 5-bis (5-aminopentyl) trisiloxane, 1,3,3,5, 5-hexamethyl-1, 5-bis (3-aminopropyl) trisiloxane, 1,3,3,5, 5-hexaethyl-1, 5-bis (3-aminopropyl) trisiloxane, 1,3,3,5, 5-hexapropyl-1, 5-bis (3-aminopropyl) trisiloxane and the like. The above-mentioned compounds may be used alone or in combination of two or more.
Commercially available products of the compound represented by the formula (B-2-4) include "X-22-9409", "X-22-1660B", "X-22-161A" and "X-22-161B", which are available from shin-Etsu chemical Co.
The structural unit (B-2) preferably contains the structural unit (B-2-4) derived from the compound represented by the formula (B-2-4), and the structural unit B preferably contains the structural unit (B-2-4) derived from the compound represented by the formula (B-2-4), particularly from the viewpoint of acid resistance and transparency of the film.
The compound represented by the formula (b-2-5) is 2, 2' -bis (trifluoromethyl) benzidine. In particular, from the viewpoint of toughness, heat resistance and optical isotropy of the film, the structural unit (B-2) preferably contains the structural unit (B-2-5) derived from the compound represented by the formula (B-2-5), and the structural unit B preferably contains the structural unit (B-2-5) derived from the compound represented by the formula (B-2-5).
As described above, the structural unit B preferably contains at least 1 selected from the group consisting of the structural unit (B-2-1) derived from the compound represented by the formula (B-2-1), the structural unit (B-2-2) derived from the compound represented by the formula (B-2-2), the structural unit (B-2-3) derived from the compound represented by the formula (B-2-3), the structural unit (B-2-4) derived from the compound represented by the formula (B-2-4), and the structural unit (B-2-5) derived from the compound represented by the formula (B-2-5) as the structural unit (B-2) from the viewpoint of improving various properties of the film, particularly from the viewpoint of improving the colorless transparency and the optical isotropy of the film, the structural unit B preferably contains the structural unit (B-2-3) derived from the compound represented by the formula (B-2-3).
By including both the structural unit (B-1) and the structural unit (B-2) in the structural unit B and further setting the ratio of the structural unit (B-1) in the structural unit B to 70 mol% or more, the colorless transparency, the optical isotropy, and the chemical resistance of the film can be improved. Among them, the acid resistance and the solvent resistance can be particularly improved.
The proportion of the structural unit (B-1) in the structural unit B is 70 mol% or more. The ratio is preferably 70 to 97 mol%, more preferably 75 to 97 mol%, even more preferably 80 to 97 mol%, from the viewpoint of acid resistance and solvent resistance, and is even more preferably 90 to 97 mol%, even more preferably 93 to 97 mol%, from the viewpoint of acid resistance.
The proportion of the structural unit (B-2) in the structural unit B is preferably 3 to 30 mol%, more preferably 3 to 25 mol%, and still more preferably 3 to 20 mol%. In particular, when the structural unit (B-2) is at least 1 member selected from the group consisting of the structural units (B-2-1), (B-2-2), (B-2-3) and (B-2-5), the ratio of the structural unit (B-2) is more preferably 10 to 25 mol%, and still more preferably 10 to 20 mol%. In particular, when the structural unit (B-2) is the structural unit (B-2-4), the proportion of the structural unit (B-2) is more preferably 3 to 15 mol%, still more preferably 3 to 10 mol%, and still more preferably 3 to 7 mol%.
The total ratio of the constituent units (B-1) and (B-2) in the constituent unit B is preferably 75 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more. The upper limit of the total ratio of the structural units (B-1) and (B-2) is not particularly limited, i.e., 100 mol%. The structural unit B may contain only the structural unit (B-1) and the structural unit (B-2).
The structural unit (B-2) may be only the structural unit (B-2-1), may be only the structural unit (B-2-2), may be only the structural unit (B-2-3), may be only the structural unit (B-2-4), or may be only the structural unit (B-2-5).
Further, the structural unit (B-2) may be a combination of 2 or more structural units selected from the group consisting of the structural units (B-2-1) to (B-2-5).
The structural unit B may include structural units other than the structural units (B-1) and (B-2). The diamine providing such a structural unit is not particularly limited, and examples thereof include 1, 4-phenylenediamine, p-xylylenediamine, 3, 5-diaminobenzoic acid, 1, 5-diaminonaphthalene, 2 ' -dimethylbiphenyl-4, 4 ' -diamine, 4 ' -diaminodiphenyl ether, 4 ' -diaminodiphenylmethane, 2-bis (4-aminophenyl) hexafluoropropane, 4 ' -diaminodiphenylsulfone, 4 ' -diaminobenzanilide, 1- (4-aminophenyl) -2, 3-dihydro-1, 3, 3-trimethyl-1H-indene-5-amine, α ' -bis (4-aminophenyl) -1, 4-diisopropylbenzene, and, Aromatic diamines such as N, N '-bis (4-aminophenyl) terephthalamide, 4' -bis (4-aminophenoxy) biphenyl, and 2, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane (excluding compounds represented by the formula (b-1) and compounds represented by the formulae (b-2-1) to (b-2-5)); alicyclic diamines such as 1, 3-bis (aminomethyl) cyclohexane and 1, 4-bis (aminomethyl) cyclohexane; and aliphatic diamines such as ethylenediamine and hexamethylenediamine (except for the compound represented by the formula (b-2-4)).
In the present specification, an aromatic diamine refers to a diamine containing 1 or more aromatic rings, an alicyclic diamine refers to a diamine containing 1 or more alicyclic rings and no aromatic rings, and an aliphatic diamine refers to a diamine containing no aromatic rings and no alicyclic rings.
The structural units optionally contained in the structural unit B (i.e., structural units other than the structural units (B-1) and (B-2)) are optionally 1 or 2 or more.
The number average molecular weight of the polyimide resin of the present invention is preferably 5000 to 200000 from the viewpoint of mechanical strength of the polyimide film to be obtained. The number average molecular weight of the polyimide resin can be determined, for example, by a standard polymethyl methacrylate (PMMA) conversion value measured by gel filtration chromatography.
The polyimide resin of the present invention may have a structure other than a polyimide chain (a structure in which the structural unit a and the structural unit B are imide-bonded). Examples of the structure other than the polyimide chain that can be contained in the polyimide resin include, for example, a structure containing an amide bond.
The polyimide resin of the present invention preferably has a main structure of a polyimide chain (a structure in which a structural unit a and a structural unit B are imide-bonded). Therefore, the ratio of the polyimide chain in the polyimide resin of the present invention is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and particularly preferably 99% by mass or more.
By using the polyimide resin of the present invention, a film having excellent colorless transparency, optical isotropy, and chemical resistance can be formed, and the film has the following preferable physical property values.
When a film having a thickness of 10 μm is formed, the total light transmittance is preferably 88% or more, more preferably 88.5% or more, and still more preferably 89% or more.
When a film having a thickness of 10 μm is formed, the Yellowness Index (YI) is preferably 4.0 or less, more preferably 2.5 or less, and still more preferably 2.0 or less.
When a film having a thickness of 10 μm is formed, b is preferably 2.0 or less, more preferably 1.2 or less, and still more preferably 1.0 or less.
When a film having a thickness of 10 μm is formed, the absolute value of the retardation in thickness (Rth) is preferably 70nm or less, more preferably 60nm or less, and still more preferably 50nm or less.
When a film having a thickness of 10 μm is formed, the mixed acid Δ YI is preferably 1.5 or less, more preferably 1.3 or less, and still more preferably 1.0 or less.
When a film having a thickness of 10 μm is formed, the mixed acid Δ b is preferably 0.8 or less, more preferably 0.6 or less, and still more preferably 0.5 or less.
The mixed acid Δ YI and the mixed acid Δ b*Respectively refer to the difference in YI before and after immersion when the polyimide film is immersed in a mixture of phosphoric acid, nitric acid and acetic acid, and b*The difference (c) can be measured specifically by the method described in examples. Δ YI and Δ b*Smaller means more excellent acid resistance. By using the polyimide resin of the present invention, a film having excellent chemical resistance can be formed, and excellent resistance to acids can be exhibited. Particularly, the composition exhibits excellent resistance to a mixed acid (for example, a mixed solution of 50 to 97% by mass of phosphoric acid, 1 to 20% by mass of nitric acid, 1 to 10% by mass of acetic acid, and 1 to 20% by mass of water, preferably a mixed solution of 63 to 87% by mass of phosphoric acid, 5 to 15% by mass of nitric acid, 3 to 7% by mass of acetic acid, and 5 to 15% by mass of water).
The film formed by using the polyimide resin of the present invention has good mechanical properties and the following preferable physical property values.
The tensile strength is preferably 60MPa or more, more preferably 70MPa or more, and still more preferably 80MPa or more.
The tensile elastic modulus is preferably 2.0GPa or more, more preferably 2.5GPa or more, and still more preferably 3.0GPa or more.
The film formed using the polyimide resin according to one embodiment of the present invention has good heat resistance and the following preferable physical property values.
The glass transition temperature (Tg) is preferably 230 ℃ or higher, more preferably 250 ℃ or higher, and still more preferably 270 ℃ or higher.
The physical property values in the present invention can be measured specifically by the methods described in examples.
[ method for producing polyimide resin ]
The polyimide resin of the present invention can be produced by reacting a tetracarboxylic acid component containing a compound that provides the structural unit (A-1) with a diamine component containing 70 mol% or more of a compound that provides the structural unit (B-1) and a compound that provides the structural unit (B-2).
Examples of the compound that can provide the structural unit (A-1) include a compound represented by the formula (a-1-1) and a compound represented by the formula (a-1-2), but the compound is not limited thereto, and derivatives thereof may be provided as long as the same structural unit is provided. Examples of the derivative include a tetracarboxylic acid corresponding to a tetracarboxylic dianhydride represented by the formula (a-1-1) or the formula (a-1-2) and an alkyl ester of the tetracarboxylic acid. As the compound providing the structural unit (A-1), compounds represented by the formulae (a-1-1) and (a-1-2) (i.e., dianhydrides) are preferable.
The tetracarboxylic acid component preferably contains 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more of the compound that provides the structural unit (a-1). The upper limit of the content ratio of the compound providing the structural unit (A-1) is not particularly limited, i.e., 100 mol%. The tetracarboxylic acid component may also contain only the compound which provides the structural unit (A-1).
The compound providing the structural unit (A-1) may be only the compound providing the structural unit (A-1-1), or may be only the compound providing the structural unit (A-1-2). Further, the compound providing the structural unit (A-1) may be a combination of a compound providing the structural unit (A-1-1) and a compound providing the structural unit (A-1-2).
When the compound that provides the structural unit (A-1) is a combination of the compound that provides the structural unit (A-1-1) and the compound that provides the structural unit (A-1-2), the content ratio of the compound that provides the structural unit (A-1-1)/the compound that provides the structural unit (A-1-2) is preferably 5/95 to 95/5 in terms of a molar ratio, and is more preferably 20/80 to 90/10, and is even more preferably 50/50 to 90/10, from the viewpoints of colorless transparency, optical isotropy, and chemical resistance. Further, it is more preferably 20/80 to 70/30 particularly from the viewpoint of toughness of the obtained film, and is more preferably 60/40 to 95/5 particularly from the viewpoint of improving optical isotropy of the obtained film, more preferably 70/30 to 95/5, and more preferably 85/15 to 95/5.
The tetracarboxylic acid component may contain a compound other than the compound providing the structural unit (a-1), and examples of the compound include the above-mentioned aromatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and aliphatic tetracarboxylic acid dianhydride, and derivatives thereof (e.g., tetracarboxylic acid, alkyl ester of tetracarboxylic acid, etc.).
The tetracarboxylic acid component optionally contains 1 or 2 or more compounds (i.e., compounds other than the compound providing the structural unit (A-1)).
Examples of the compound that can provide the structural unit (B-1) include compounds represented by the formula (B-1), but the compound is not limited thereto, and derivatives thereof may be included within the range that provides the same structural unit. Examples of the derivative include diisocyanates corresponding to the diamines represented by the formula (b-1). As the compound providing the structural unit (B-1), a compound represented by the formula (B-1) (i.e., diamine) is preferable.
Examples of the compound that can provide the structural unit (B-2) include a compound represented by the formula (B-2-1), a compound represented by the formula (B-2-2), a compound represented by the formula (B-2-3), a compound represented by the formula (B-2-4), and a compound represented by the formula (B-2-5), but the compound is not limited thereto, and derivatives thereof may be included as long as the same structural unit can be formed. Examples of the derivative include diisocyanates corresponding to diamines represented by the formulae (b-2-1) to (b-2-5). As the compound providing the structural unit (B-2), compounds represented by the formulae (B-2-1) to (B-2-5) (i.e., diamines) are preferable.
The diamine component contains 70 mol% or more of a compound that provides the structural unit (B-1). The diamine component preferably contains 70 to 97 mol%, more preferably 75 to 97 mol%, even more preferably 80 to 97 mol% of the compound that provides the structural unit (B-1), and still more preferably 90 to 97 mol%, even more preferably 93 to 97 mol%, from the viewpoint of acid resistance.
The diamine component preferably contains 3 to 30 mol%, more preferably 3 to 25 mol%, and still more preferably 3 to 20 mol% of a compound that provides the structural unit (B-2). In particular, when the compound providing the structural unit (B-2) is at least 1 selected from the group consisting of the compound providing the structural unit (B-2-1), the compound providing the structural unit (B-2-2), the compound providing the structural unit (B-2-3) and the compound providing the structural unit (B-2-5), the diamine component preferably contains 10 to 25 mol%, more preferably 10 to 20 mol%, of the compound providing the structural unit (B-2). In particular, when the compound that provides the structural unit (B-2) is the compound that provides the structural unit (B-2-4), the diamine component preferably further contains 3 to 15 mol%, more preferably 3 to 10 mol%, and even more preferably 3 to 7 mol% of the compound that provides the structural unit (B-2).
The diamine component preferably contains 75 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more of the compound that provides the structural unit (B-1) and the compound that provides the structural unit (B-2) in total. The upper limit of the total content ratio of the compound that provides the structural unit (B-1) and the compound that provides the structural unit (B-2) is not particularly limited, i.e., 100 mol%. The diamine component may contain only the compound that provides the structural unit (B-1) and the compound that provides the structural unit (B-2).
The compound that provides the structural unit (B-2) may be only the compound that provides the structural unit (B-2-1), may be only the compound that provides the structural unit (B-2-2), may be only the compound that provides the structural unit (B-2-3), may be only the compound that provides the structural unit (B-2-4), or may be only the compound that provides the structural unit (B-2-5).
Further, the compound providing the structural unit (B-2) may be a combination of 2 or more compounds selected from the group consisting of compounds providing the structural units (B-2-1) to (B-2-5).
The diamine component may contain compounds other than the compound that provides the structural unit (B-1) and the compound that provides the structural unit (B-2), and examples of the compounds include the above-mentioned aromatic diamine, alicyclic diamine, and aliphatic diamine, and derivatives thereof (e.g., diisocyanate).
The diamine component optionally contains 1 or 2 or more compounds (i.e., compounds other than the compound providing the structural unit (B-1) and the compound providing the structural unit (B-2)).
In the present invention, the amount ratio of the tetracarboxylic acid component and the diamine component to be used for producing the polyimide resin is preferably 0.9 to 1.1 mol based on 1 mol of the tetracarboxylic acid component.
In the present invention, in addition to the tetracarboxylic acid component and the diamine component described above, an end-capping agent may be used in the production of the polyimide resin. As the end-capping agent, monoamines or dicarboxylic acids are preferred. The amount of the end-capping agent to be introduced is preferably 0.0001 to 0.1 mol, and particularly preferably 0.001 to 0.06 mol, based on 1 mol of the tetracarboxylic acid component. As the monoamine-type blocking agent, for example, 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. Among these, benzylamine and aniline can be suitably used. As the dicarboxylic acid-based end capping agent, dicarboxylic acids are preferred, and a part thereof may be ring-closed. For example, phthalic acid, phthalic 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, and the like are recommended. Among these, phthalic acid and phthalic anhydride can be suitably used.
The method for reacting the tetracarboxylic acid component with the diamine component is not particularly limited, and a known method can be used.
Specific examples of the reaction method include (1) a method in which a tetracarboxylic acid component, a diamine component, and a reaction solvent are charged into a reactor, stirred at room temperature (about 20 ℃) to 80 ℃ for 0.5 to 30 hours, and then heated to carry out an imidization reaction, (2) a method in which a diamine component and a reaction solvent are charged into a reactor to dissolve them, then a tetracarboxylic acid component is charged, stirred at room temperature (about 20 ℃) to 80 ℃ for 0.5 to 30 hours, and then heated to carry out an imidization reaction, and (3) a method in which a tetracarboxylic acid component, a diamine component, and a reaction solvent are charged into a reactor, and directly heated to carry out an imidization reaction.
The reaction solvent used in the production of the polyimide resin may be any solvent which can dissolve the polyimide produced without inhibiting the imidization reaction. Examples thereof include aprotic solvents, phenol solvents, ether solvents, carbonate solvents and the like.
Specific examples of the aprotic solvent include amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1, 3-dimethylimidazolidinone, and tetramethylurea, lactone solvents such as γ -butyrolactone and γ -valerolactone, phosphorus-containing amide solvents such as hexamethylphosphoramide and hexamethylphosphinotriamide, sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide, and sulfolane, ketone solvents such as acetone, cyclohexanone, and methylcyclohexanone, amine solvents such as picoline and pyridine, and ester solvents such as acetic acid (2-methoxy-1-methylethyl).
Specific examples of the phenol solvent 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.
Specific examples of the ether solvent include 1, 2-dimethoxyethane, bis (2-methoxyethyl) ether, 1, 2-bis (2-methoxyethoxy) ethane, bis [ 2- (2-methoxyethoxy) ethyl ] ether, tetrahydrofuran, and 1, 4-dioxane.
Specific examples of the carbonate-based solvent include diethyl carbonate, methylethyl carbonate, ethylene carbonate, and propylene carbonate.
Among the above reaction solvents, an amide solvent or a lactone solvent is preferable. The reaction solvents may be used alone or in combination of two or more.
In the imidization reaction, it is preferable to carry out the reaction while removing water produced during the production using a dean-Stark apparatus or the like. By performing such an operation, the degree of polymerization and the imidization ratio can be further increased.
In the imidization reaction, a known imidization catalyst can be used. Examples of the imidization catalyst include an alkali catalyst and an acid catalyst.
Examples of the base catalyst include organic base catalysts such as pyridine, quinoline, isoquinoline, α -picoline, β -picoline, 2, 4-lutidine, 2, 6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, imidazole, N-dimethylaniline and N, N-diethylaniline, and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate and sodium hydrogencarbonate.
Examples of the acid catalyst include crotonic acid, acrylic acid, trans-3-hexanoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, hydroxybenzoic acid, terephthalic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, and the like. The imidization catalyst may be used singly or in combination of two or more.
Among the above, from the viewpoint of handling properties, the use of a base catalyst is preferred, the use of an organic base catalyst is more preferred, the use of triethylamine is further preferred, and the use of triethylamine and triethylenediamine in combination is particularly preferred.
The temperature of the imidization reaction is preferably 120 to 250 ℃ and more preferably 160 to 200 ℃ from the viewpoint of suppressing the reactivity, gelation, and the like. The reaction time is preferably 0.5 to 10 hours after the start of distillation of the product water.
[ polyimide varnish ]
The polyimide varnish of the present invention is obtained by dissolving the polyimide resin of the present invention in an organic solvent. That is, the polyimide varnish of the present invention comprises the polyimide resin of the present invention and an organic solvent in which the polyimide resin is dissolved.
The organic solvent may be any solvent that dissolves the polyimide resin, and is not particularly limited, and it is preferable to use 2 or more of the above compounds alone or in combination as a reaction solvent used for producing the polyimide resin.
The polyimide varnish of the present invention may be a polyimide solution itself obtained by dissolving a polyimide resin obtained by a polymerization method in a reaction solvent, or may be one obtained by further adding a diluting solvent to the polyimide solution.
The polyimide resin of the present invention has solvent solubility, and therefore can be used as a varnish having a high concentration and being stable at room temperature. The polyimide varnish of the present invention preferably contains 5 to 40% by mass, more preferably 10 to 30% by mass of the polyimide resin of the present invention. The viscosity of the polyimide varnish is preferably 1 to 200 pas, more preferably 2 to 100 pas. The viscosity of the polyimide varnish was measured at 25 ℃ using an E-type viscometer.
The polyimide varnish of the present invention may contain various additives such as inorganic fillers, adhesion promoters, release agents, flame retardants, ultraviolet stabilizers, surfactants, leveling agents, defoaming agents, fluorescent whitening agents, crosslinking agents, polymerization initiators, and photosensitizers, as long as the required properties of the polyimide film are not impaired.
The method for producing the polyimide varnish of the present invention is not particularly limited, and a known method can be applied.
[ polyimide film ]
The polyimide film of the present invention comprises the polyimide resin of the present invention. Therefore, the polyimide film of the present invention is excellent in colorless transparency, optical isotropy, and chemical resistance (solvent resistance, acid resistance, and alkali resistance). The polyimide film of the present invention has the preferred physical property values as described above.
The method for producing the polyimide film of the present invention is not particularly limited, and a known method can be used. For example, the polyimide varnish of the present invention is applied to a smooth support such as a glass plate, a metal plate or a plastic, or formed into a film, and then the organic solvent such as a reaction solvent or a diluting solvent contained in the varnish is removed by heating.
Examples of the coating method include known coating methods such as spin coating, slit coating, and blade coating. Among them, slit coating is preferable from the viewpoint of controlling the intermolecular orientation and improving the chemical resistance and handling properties.
The organic solvent contained in the varnish is preferably removed by heating, and after evaporating the organic solvent at a temperature of 150 ℃ or lower to prevent it from sticking to the hands, the varnish is dried at a temperature of 200 to 500 ℃ or higher (not particularly limited) than the boiling point of the organic solvent used. Further, it is preferable to dry under an air atmosphere or a nitrogen atmosphere. The pressure of the drying atmosphere may be reduced pressure, normal pressure or increased pressure.
The method for peeling the polyimide film formed on the support from the support is not particularly limited, and examples thereof include a laser peeling method and a method using a sacrificial layer for peeling (a method in which a release agent is applied to the surface of the support in advance).
The polyimide film of the present invention can also be produced using a polyamic acid varnish in which a polyamic acid is dissolved in an organic solvent.
The polyamic acid contained in the polyamic acid varnish is a precursor of the polyimide resin of the present invention, and is a product of addition polymerization of a tetracarboxylic acid component containing a compound that provides the structural unit (A-1) and a diamine component containing 70 mol% or more of a compound that provides the structural unit (B-1) and a compound that provides the structural unit (B-2). The polyimide resin of the present invention can be obtained as a final product by imidizing (dehydrating ring closure) the polyamic acid.
As the organic solvent contained in the polyamic acid varnish, the organic solvent contained in the polyimide varnish of the present invention can be used.
In the present invention, the polyamic acid varnish may be a polyamic acid solution itself obtained by addition polymerization of a tetracarboxylic acid component and a diamine component in a reaction solvent, or may be a polyamic acid solution to which a diluting solvent is further added.
The method for producing the polyimide film using the polyamic acid varnish is not particularly limited, and a known method can be used. For example, a polyamic acid varnish may be applied to a smooth support such as a glass plate, a metal plate, or a plastic, or formed into a film, an organic solvent such as a reaction solvent or a diluting solvent contained in the varnish may be removed by heating to obtain a polyamic acid film, and the polyamic acid in the polyamic acid film may be imidized by heating to produce a polyimide film.
The heating temperature for drying the polyamic acid varnish to obtain a polyamic acid film is preferably 50 to 120 ℃. The heating temperature for imidizing the polyamic acid by heating is preferably 200 to 400 ℃.
The method of imidization is not limited to thermal imidization, and chemical imidization may be applied.
The thickness of the polyimide film of the present invention can be suitably selected depending on the application, and is preferably 1 to 250. mu.m, more preferably 5 to 100. mu.m, and still more preferably 10 to 80 μm. The film has a thickness of 1 to 250 μm and 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 viscosity of the polyimide varnish.
The polyimide film of the present invention can be suitably used as a film for various members such as color filters, flexible displays, semiconductor components, and optical members. The polyimide film of the present invention can be suitably used as a substrate for an image display device such as a liquid crystal display and an OLED display.
Examples
The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples.
In examples and comparative examples, physical properties were measured by the methods shown below.
(1) Thickness of film
The film thickness was measured using a micrometer manufactured by Sanfeng corporation.
(2) Tensile Strength and tensile elastic modulus
According to JIS K7127: 1999, tensile strength and tensile modulus were measured using a tensile tester "StrongGraph VG-1E" manufactured by Toyo Seiki Seisaku-Sho. The distance between the chucks was set to 50mm, the test piece size was set to 10mm × 70mm, and the test speed was set to 20 mm/min.
(3) Glass transition temperature (Tg)
The residual stress was removed by heating to a temperature sufficient for removing the residual stress in a tensile mode under conditions of a specimen size of 2mm × 20mm, a load of 0.1N, and a heating rate of 10 ℃/min using a thermomechanical analyzer "TMA/SS 6100" manufactured by Hitachi High-Tech Science Corporation, and then cooling to room temperature. Thereafter, the elongation of the test piece was measured under the same conditions as in the treatment for removing the residual stress, and the inflection point where the elongation was observed was determined as the glass transition temperature.
(4) Total light transmittance, Yellow Index (YI), b*
According to JIS K7105: 1981 Total light transmittance, YI and b were measured using a color/turbidity simultaneous measuring instrument "COH 400" manufactured by Nippon Denshoku industries Co., Ltd*。
(5) Thickness retardation (Rth)
The thickness retardation (Rth) was measured using an ellipsometer "M-220" manufactured by Nippon spectral Co., Ltd. The value of thickness retardation at a wavelength of 590nm was measured. When nx is the maximum value, ny is the minimum value, nz is the refractive index in the thickness direction, and d is the thickness of the film among the in-plane refractive indices of the polyimide film, Rth is expressed by the following formula.
Rth＝[{(nx+ny)/2}-nz]×d
(6) Solvent resistance
On the polyimide film formed on the glass plate, a solvent was dropped at room temperature to confirm whether or not the film surface was changed. As the solvent, Propylene Glycol Monomethyl Ether Acetate (PGMEA) was used.
The evaluation criteria for solvent resistance are as follows.
A: the surface of the film is unchanged.
B: the film surface had slight cracks.
C: cracks exist on the surface of the film, or the surface of the film is dissolved.
(7) Acid resistance (Mixed acid. DELTA. YI and Mixed acid. DELTA. b)*)
A polyimide film formed on a glass plate was immersed in a mixed acid (H) heated to 40 ℃3PO4(70% by mass) + HNO3(10% by mass) + CH3COOH (5 mass%) + H2Mixed solution of O (15 mass%)) for 4 minutes, and then washed with water. After washing with water, the water was removed, and the mixture was heated at 240 ℃ for 50 minutes on a hot plate and dried. Determination of YI and b before and after the test*The changes (Δ YI and Δ b) were determined*). Here, YI measurement and b*The measurement was performed in a state where a polyimide film was formed on a glass plate (state of glass plate + polyimide film).
(8) Alkali resistance
The polyimide film formed on the glass plate was immersed in a 3 mass% potassium hydroxide aqueous solution at room temperature for 5 minutes, and then washed with water. After washing, the presence or absence of change in the film surface was confirmed.
The alkali resistance was evaluated as follows.
A: the surface of the film is unchanged.
B: the film surface had slight cracks.
C: cracks exist on the surface of the film, or the surface of the film is dissolved.
The tetracarboxylic acid component and the diamine component used in the examples and comparative examples, and their abbreviations are as follows.
< tetracarboxylic acid component >
HPMDA: 1,2,4, 5-Cyclohexanetetracarboxylic dianhydride (manufactured by Mitsubishi gas chemical Co., Ltd.; Compound represented by the formula (a-1-1))
ODPA: 4, 4' -oxydiphthalic anhydride (manufactured by Manac Inc.; Compound represented by formula (a-1-2))
< diamine component >
3, 3' -DDS: 3, 3' -diaminodiphenyl sulfone (Seika Co., Ltd.; product of Ltd.; Compound represented by the formula (b-1))
6 FODA: 4,4 '-diamino-2, 2' -bistrifluoromethyldiphenyl ether (ChinaTech Chemical (Tianjin) Co., Ltd.; Compound represented by the formula (b-2-1))
BAFL: 9, 9-bis (4-aminophenyl) fluorene (produced by Taokra chemical industries Co., Ltd.; Compound represented by the formula (b-2-2))
HFBAPP: 2, 2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane (Seika Co., Ltd.; manufactured by Ltd.; Compound represented by the formula (b-2-3))
X-22-9409: both terminal amino-modified Silicone oil "X-22-9409" (Compound represented by the formula (b-2-4, manufactured by shin-Etsu chemical Co., Ltd.))
TFMB: 2, 2' -bis (trifluoromethyl) benzidine (Seika Co., Ltd.; product of Ltd.; Compound represented by the formula (b-2-5))
1, 3-BAC: 1, 3-bis (aminomethyl) cyclohexane (manufactured by Mitsubishi gas chemical Co., Ltd.)
4, 4' -DDS: 4, 4' -diaminodiphenyl sulfone (Seika Co., Ltd.)
< example 1>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube, a condenser tube, a thermometer, and a glass end cap was charged with 3, 3' -DDS 24.931g (0.100 mol), X-22-94096.373 g (0.005 mol), and N-methylpyrrolidone (manufactured by Mitsubishi chemical corporation) 62.335g, and stirred at a system temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution were added ODPA 32.468g (0.105 mol) and N-methylpyrrolidone 15.589g (Mitsubishi chemical corporation), 0.529g of triethylamine (Kanto chemical corporation) as an imidization catalyst was charged, and the mixture was heated with a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted in accordance with the increase in viscosity, and the temperature in the reaction system was maintained at 190 ℃ and the mixture was refluxed for 5 hours.
Thereafter, 162.057g of N-methylpyrrolidone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 300 ℃ for 30 minutes in a hot air dryer under a nitrogen atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
< example 2>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube, a condenser tube, a thermometer, and a glass end cap was charged with 3, 3' -DDS 23.121g (0.093 mol), X-22-94099.527 g (0.007 mol), and N-methylpyrrolidone (62.182 g, available from Mitsubishi chemical corporation), and the mixture was stirred at a system temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution were added ODPA 30.948g (0.100 mol) and N-methylpyrrolidone 15.545g (manufactured by Mitsubishi chemical corporation), 0.505g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was added, and the mixture was heated with a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted in accordance with the increase in viscosity, and the temperature in the reaction system was maintained at 190 ℃ and the mixture was refluxed for 5 hours.
Thereafter, 162.273g of N-methylpyrrolidone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 300 ℃ for 30 minutes in a hot air dryer under a nitrogen atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
< example 3>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube and a condenser tube, a thermometer and a glass end cap was charged with 3, 3' -DDS 26.174g (0.105 mol), BAFL 9.155g (0.026 mol) and γ -butyrolactone (manufactured by Mitsubishi chemical corporation) 63.287g, and stirred at a system temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution were added 29.396g (0.131 mol) of HPMDA and 15.822g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation), 0.663g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was added, and the mixture was heated by a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted in accordance with the increase in viscosity, and the temperature in the reaction system was maintained at 190 ℃ and the mixture was refluxed for 5 hours.
Thereafter, 160.859g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
< example 4>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube, a condenser tube, a thermometer, and a glass end cap was charged with 3, 3' -DDS 24.363g (0.098 mol), HFBAPP 12.673g (0.024 mol), and γ -butyrolactone (manufactured by Mitsubishi chemical corporation) 62.967g, and stirred at a rotation speed of 200rpm under a nitrogen atmosphere at a system temperature of 70 ℃ to obtain a solution.
To this solution were added 27.362g (0.122 mol) of HPMDA and 15.742g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation), 0.617g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was added, and the mixture was heated with a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted according to the increase in viscosity, and the reaction system was refluxed for 5 hours while maintaining the temperature at 190 ℃.
Thereafter, 161.291g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
< example 5>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube and a condenser, a thermometer and a glass end cap was charged with 3, 3' -DDS 26.319g (0.105 mol), 6FODA 8.873g (0.026 mol) and γ -butyrolactone (manufactured by Mitsubishi chemical Co., Ltd.) 63.312g, and stirred at a rotation speed of 200rpm under a nitrogen atmosphere at a system temperature of 70 ℃ to obtain a solution.
To this solution were added 29.559g (0.132 mol) of HPMDA and 15.828g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation), 0.667g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was added, and the mixture was heated with a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted according to the increase in viscosity, and the reaction system was refluxed for 5 hours while maintaining the temperature at 190 ℃.
Thereafter, 160.860g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
< example 6>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube and a condenser tube, a thermometer and a glass end cap was charged with 3, 3' -DDS 26.505g (0.106 mol), TFMB 8.513g (0.027 mol) and γ -butyrolactone (manufactured by Mitsubishi chemical corporation) 63.345g, and stirred at a system temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution were added 29.768g (0.133 mol) of HPMDA and 15.836g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation), 0.672g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was charged, and the mixture was heated with a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted according to the increase in viscosity, and the reaction system was refluxed for 5 hours while maintaining the temperature at 190 ℃.
Thereafter, 160.819g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
< comparative example 1>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube, a condenser tube, a thermometer, and a glass end cap was charged with 3, 3' -DDS 28.588g (0.115 mol) and gamma-butyrolactone (Mitsubishi chemical corporation) 62.704g, and stirred at a system temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution were added ODPA 35.541g (0.115 mol) and gamma-butyrolactone 15.676g (Mitsubishi chemical corporation), 0.580g of triethylamine (Kanto chemical corporation) was added as an imidization catalyst, and the mixture was heated with a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted according to the increase in viscosity, and the reaction system was refluxed for 5 hours while maintaining the temperature at 190 ℃.
Thereafter, 161.620g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
< comparative example 2>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube and a condenser tube, a thermometer and a glass end cap was charged with 3, 3' -DDS 15.901g (0.064 mol), 1,3-BAC 9.156g (0.064 mol) and γ -butyrolactone (manufactured by Mitsubishi chemical corporation) 63.157g, and stirred at a rotation speed of 200rpm at a temperature of 70 ℃ in the system under a nitrogen atmosphere to obtain a solution.
To this solution were added ODPA 39.536g (0.127 mol) and gamma-butyrolactone 15.789g (Mitsubishi chemical corporation), 0.967g of triethylamine (Kanto chemical corporation) as an imidization catalyst was added, and the mixture was heated with a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted according to the increase in viscosity, and the reaction system was refluxed for 5 hours while maintaining the temperature at 190 ℃.
Thereafter, 159.801g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
< comparative example 3>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube and a condenser tube, a thermometer and a glass end cap was charged with 3, 3' -DDS 13.053g (0.052 mol), BAFL 18.263g (0.052 mol) and γ -butyrolactone (manufactured by Mitsubishi chemical corporation) 62.353g, and stirred at a system temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution were added ODPA 32.455g (0.105 mol) and γ -butyrolactone 15.588g (Mitsubishi chemical corporation), 0.529g of triethylamine (Kanto chemical corporation) as an imidization catalyst was added, and the mixture was heated with a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted according to the increase in viscosity, and the reaction system was refluxed for 5 hours while maintaining the temperature at 190 ℃.
Thereafter, 162.059g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
< comparative example 4>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube and a condenser tube, a thermometer and a glass end cap was charged with 4, 4' -DDS 28.535g (0.115 mol) and gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) 62.710g, and stirred at a system temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution were added 35.600g (0.115 mol) of ODPA and 15.678g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation), 0.581g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was charged, and the mixture was heated by a mantle heater, whereby the reaction solution was cloudy and no varnish was obtained.
< comparative example 5>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube, a condenser tube, a thermometer, and a glass end cap was charged with 3, 3' -DDS 34.192g (0.137 mol) and gamma-butyrolactone (Mitsubishi chemical corporation) 63.495g, and stirred at a system temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution were added 30.746g (0.137 mol) of HPMDA and 15.874g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation), 0.693g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was added, and the mixture was heated with a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted according to the increase in viscosity, and the reaction system was refluxed for 5 hours while maintaining the temperature at 190 ℃.
Thereafter, 160.631g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
< comparative example 6>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube and a condenser tube, a thermometer and a glass end cap was charged with 15.819g (0.063 mol) of 3, 3' -DDS, 20.323g (0.063 mol) of TFMB and 63.134g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation), and the mixture was stirred at a rotation speed of 200rpm under a nitrogen atmosphere at a temperature of 70 ℃ in the system to obtain a solution.
To this solution were added 28.427g (0.127 mol) of HPMDA and 15.784g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation), 0.641g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was added, and the mixture was heated with a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted according to the increase in viscosity, and the reaction system was refluxed for 5 hours while maintaining the temperature at 190 ℃.
Thereafter, 161.082g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
< comparative example 7>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube and a condenser tube, a thermometer and a glass end cap was charged with 3, 3' -DDS 15.356g (0.062 mol), BAFL 21.485g (0.062 mol) and γ -butyrolactone (manufactured by Mitsubishi chemical corporation) 63.004g, and stirred at a system temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution were added 27.594g (0.123 mol) of HPMDA and 15.751g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation), 0.623g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was added, and the mixture was heated with a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted according to the increase in viscosity, and the reaction system was refluxed for 5 hours while maintaining the temperature at 190 ℃.
Thereafter, 161.246g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
< comparative example 8>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube and a condenser, a thermometer and a glass end cap was charged with 4, 4' -DDS 34.155g (0.137 mol) and gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) 63.507g, and stirred at a system temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution were added 30.795g (0.137 mol) of HPMDA and 15.877g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation) together, 0.695g of triethylamine (manufactured by Kanto chemical corporation) was added as an imidization catalyst, and the mixture was heated by a hood heater, whereby the reaction solution was cloudy and no varnish was obtained.
< example 7>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube and a condenser tube, a thermometer and a glass end cap was charged with 3, 3' -DDS 23.921g (0.096 mol), BAFL 8.367g (0.024 mol) and γ -butyrolactone (manufactured by Mitsubishi chemical Co., Ltd.) 62.889g, and stirred at a system temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution were added HPMDA 13.444g (0.060 mol), ODPA 18.587g (0.060 mol) and γ -butyrolactone (15.722 g, Mitsubishi chemical corporation) in combination, and then 0.606g of triethylamine (manufactured by Kanto chemical Co., Ltd.) as an imidization catalyst was charged, and the mixture was heated by a mantle heater to raise the internal temperature of the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted according to the increase in viscosity, and the reaction system was refluxed for 5 hours while maintaining the temperature at 190 ℃.
Thereafter, 161.389g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 2.
< example 8>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen gas inlet tube and a condenser tube, a thermometer and a glass end cap was charged with 3, 3' -DDS 22.397g (0.090 mol), HFBAPP 11.657g (0.022 mol) and γ -butyrolactone (manufactured by Mitsubishi chemical corporation) 62.620g, and stirred at a rotation speed of 200rpm under a nitrogen atmosphere at a system temperature of 70 ℃ to obtain a solution.
To this solution were added 12.587g (0.056 mol) of HPMDA, 17.402g (0.056 mol) of ODPA and 15.655g of gamma-butyrolactone (Mitsubishi chemical corporation), 0.568g of triethylamine (Kanto chemical corporation) was added as an imidization catalyst, and the mixture was heated with a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted according to the increase in viscosity, and the reaction system was refluxed for 5 hours while maintaining the temperature at 190 ℃.
Thereafter, 161.725g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 2.
< example 9>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube and a condenser, a thermometer and a glass end cap was charged with 3, 3' -DDS 24.042g (0.096 mol), 6FODA 8.106g (0.024 mol) and γ -butyrolactone (manufactured by Mitsubishi chemical Co., Ltd.) 62.910g, and stirred at a rotation speed of 200rpm under a nitrogen atmosphere at a system temperature of 70 ℃ to obtain a solution.
To this solution were added 13.512g (0.060 mol) of HPMDA, 18.681g (0.060 mol) of ODPA and 15.728g of γ -butyrolactone (Mitsubishi chemical corporation), 0.609g of triethylamine (Kanto chemical corporation) was added as an imidization catalyst, and the mixture was heated with a mantle heater to raise the internal temperature of the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted in accordance with the increase in viscosity, and the temperature in the reaction system was maintained at 190 ℃ and the mixture was refluxed for 5 hours.
Thereafter, 161.362g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 2.
< example 10>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube, a condenser tube, a thermometer, and a glass end cap was charged with 3, 3' -DDS 25.353g (0.102 mol), 6FODA 8.547g (0.025 mol), and γ -butyrolactone 63.142g (manufactured by Mitsubishi chemical corporation), and stirred at a rotation speed of 200rpm under a nitrogen atmosphere at a system temperature of 70 ℃ to obtain a solution.
To this solution were added HPMDA 22.797g (0.102 mol), ODPA 7.880g (0.025 mol) and γ -butyrolactone 15.785g (Mitsubishi chemical corporation) in combination, and then 0.643g of triethylamine (Kanto chemical corporation) as an imidization catalyst was charged, and the mixture was heated with a mantle heater to raise the internal temperature of the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted according to the increase in viscosity, and the reaction system was refluxed for 5 hours while maintaining the temperature at 190 ℃.
Thereafter, 161.073g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 2.
< example 11>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube, a condenser tube, a thermometer, and a glass end cap was charged with 3, 3' -DDS 23.530g (0.094 mol), HFBAPP 12.247g (0.024 mol), and γ -butyrolactone (manufactured by Mitsubishi chemical corporation) 62.820g, and stirred at a rotation speed of 200rpm under a nitrogen atmosphere at a system temperature of 70 ℃ to obtain a solution.
To this solution were added 21.158g (0.094 mol) of HPMDA, 7.313g (0.024 mol) of ODPA and 15.705g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation), 0.596g of triethylamine (manufactured by Kanto chemical Co., Ltd.) was added as an imidization catalyst, and the mixture was heated with a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted according to the increase in viscosity, and the reaction system was refluxed for 5 hours while maintaining the temperature at 190 ℃.
Thereafter, 161.475g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 2.
< example 12>
In a 300mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube and a condenser tube, a thermometer and a glass end cap, 3' -DDS 25.218g (0.101 mol), BAFL 8.821g (0.025 mol) and γ -butyrolactone (manufactured by Mitsubishi chemical Co., Ltd.) 63.118g were charged, and the mixture was stirred at a system temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution were added 22.676g (0.101 mol) of HPMDA, 7.838g (0.025 mol) of ODPA7 and 15.780g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation), 0.639g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was added, and the mixture was heated by a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted according to the increase in viscosity, and the reaction system was refluxed for 5 hours while maintaining the temperature at 190 ℃.
Thereafter, 161.102g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 2.
< example 13>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube, a condenser tube, a thermometer, and a glass end cap was charged with 3, 3' -DDS 23.933g (0.096 mol), HFBAPP 12.457g (0.024 mol), and γ -butyrolactone (manufactured by Mitsubishi chemical corporation) 62.891g, and stirred at a rotation speed of 200rpm under a nitrogen atmosphere at a system temperature of 70 ℃ to obtain a solution.
To this solution were added HPMDA 24.211g (0.108 mol), ODPA 3.719g (0.012 mol) and γ -butyrolactone (15.723 g, Mitsubishi chemical corporation) in combination, and then 0.607g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was charged, and the mixture was heated by a mantle heater to raise the internal temperature of the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted according to the increase in viscosity, and the reaction system was refluxed for 5 hours while maintaining the temperature at 190 ℃.
Thereafter, 161.386g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 2.
< example 14>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube and a condenser, a thermometer and a glass end cap was charged with 3, 3' -DDS 25.822g (0.103 mol), 6FODA 8.706g (0.026 mol) and γ -butyrolactone (manufactured by Mitsubishi chemical Co., Ltd.) 63.225g, and stirred at a rotation speed of 200rpm under a nitrogen atmosphere at a system temperature of 70 ℃ to obtain a solution.
To this solution were added HPMDA 26.121g (0.116 mol), ODPA 4.013g (0.013 mol) and γ -butyrolactone 15.806g (Mitsubishi chemical corporation) in combination, and then 0.654g of triethylamine (Kanto chemical corporation) as an imidization catalyst was charged, and the mixture was heated with a mantle heater to raise the internal temperature of the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted according to the increase in viscosity, and the reaction system was refluxed for 5 hours while maintaining the temperature at 190 ℃.
Thereafter, 160.969g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 2.
< example 15>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube and a condenser, a thermometer and a glass end cap was charged with 26.000g (0.104 mol) of 3, 3' -DDS, 8.351g (0.026 mol) of TFMB and 63.256g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation), and stirred at a rotation speed of 200rpm under a nitrogen atmosphere at a system temperature of 70 ℃ to obtain a solution.
To this solution were added HPMDA 26.302g (0.117 mol), ODPA 4.041g (0.013 mol) and γ -butyrolactone (15.814 g, Mitsubishi chemical corporation) in combination, and then 0.659g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was charged, and the mixture was heated with a mantle heater to raise the internal temperature of the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted according to the increase in viscosity, and the reaction system was refluxed for 5 hours while maintaining the temperature at 190 ℃.
Thereafter, 160.930g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 2.
< comparative example 9>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube and a condenser tube, a thermometer and a glass end cap was charged with BAFL36.092g (0.103 mol) and gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) 63.309g, and stirred at a system temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution were added 11.598g (0.052 mol) of HPMDA, 16.035g (0.052 mol) of ODPA and 15.577g of γ -butyrolactone (Mitsubishi chemical corporation), 0.523g of triethylamine (Kanto chemical corporation) was added as an imidization catalyst, and the mixture was heated with a mantle heater for about 20 minutes to raise the temperature in the reaction system to 190 ℃. The distilled components were collected, and the rotational speed was adjusted according to the increase in viscosity, and the reaction system was refluxed for 5 hours while maintaining the temperature at 190 ℃.
Thereafter, 162.113g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 2.
< comparative example 10>
A300 mL five-necked round-bottomed flask equipped with a dean-Stark apparatus equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube and a condenser tube, a thermometer and a glass end cap was charged with 3, 3' -DDS 14.109g (0.057 mol), BAFL 19.740g (0.057 mol) and γ -butyrolactone (manufactured by Mitsubishi chemical corporation) 62.651g, and stirred at a system temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution were added 12.687g (0.057 mol) of HPMDA, 17.540g (0.057 mol) of ODPA and 15.663g of gamma-butyrolactone (Mitsubishi chemical corporation), 0.572g of triethylamine (Kanto chemical corporation) was added as an imidization catalyst, and the mixture was heated with a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted according to the increase in viscosity, and the reaction system was refluxed for 5 hours while maintaining the temperature at 190 ℃.
Thereafter, 161.686g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 20 mass%, the temperature in the reaction system was cooled to 100 ℃, and the mixture was further stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes by a hot plate, and thereafter, the plate was heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 2.
[ Table 1]
Figure BDA0003082851470000411
In comparative examples 4 and 8, the reaction solution was clouded during the synthesis of the polyimide resin, and no varnish was obtained. Therefore, the physical properties of the film could not be measured.
In addition, since the film of comparative example 5 was immersed in a mixed acid in the acid resistance test and the result was remarkably deteriorated, YI and b after immersion could not be measured. Therefore, Δ YI and Δ b of comparative example 5 could not be obtained.
[ Table 2]
Figure BDA0003082851470000431
As shown in Table 1, the polyimide films of examples 1 to 6 were produced using HPMDA or ODPA as the tetracarboxylic acid component and 3, 3' -DDS in combination with a specific second diamine (6FODA, BAFL, HFBAPP, X-22-9409, or TFMB) as the diamine component. As a result, the resultant composition is excellent in colorless transparency, optical isotropy, and chemical resistance (solvent resistance, acid resistance, and alkali resistance).
On the other hand, in comparative examples 1 to 4, ODPA was used as the tetracarboxylic acid component, but the diamine component did not have the structure of the present invention. The polyimide film of comparative example 1, which was produced using only 3, 3' -DDS as the diamine component, was poor in colorless transparency and optical isotropy. The polyimide film of comparative example 2 produced by using 3, 3' -DDS in combination with a diamine other than the specific second diamine (1, 3-BAC) as the diamine component was inferior in solvent resistance. Although the polyimide film of comparative example 3 was produced by using 3,3 '-DDS and a specific second diamine (BAFL) in combination as the diamine component, the polyimide film of comparative example 3 in which the ratio of 3, 3' -DDS was less than 70 mol% had poor colorless transparency (total light transmittance), optical isotropy, and acid resistance. In comparative example 4 in which 4, 4' -DDS was used as the diamine component, the reaction solution was cloudy during the synthesis of the polyimide resin, and no varnish could be obtained.
In comparative examples 5 to 8, HPMDA was used as the tetracarboxylic acid component, but the diamine component did not have the structure of the present invention. The polyimide film of comparative example 5, which was produced using only 3, 3' -DDS as the diamine component, had poor acid resistance. Although the polyimide film of comparative example 6 was produced by using 3,3 '-DDS and a specific second diamine (TFMB) in combination as the diamine components, the polyimide film of comparative example 6 in which the ratio of 3, 3' -DDS was less than 70 mol% had poor solvent resistance. Although the polyimide film was produced by using 3,3 '-DDS and a specific second diamine (BAFL) in combination as the diamine component, the polyimide film of comparative example 7 in which the ratio of 3, 3' -DDS was less than 70 mol% had poor acid resistance. In comparative example 8 in which 4, 4' -DDS was used as the diamine component, the reaction solution was cloudy during the synthesis of the polyimide resin, and no varnish could be obtained.
Further, as shown in table 2, the polyimide films of examples 7 to 15 produced by using HPMDA and ODPA in combination as tetracarboxylic acid components were also excellent in colorless transparency, optical isotropy, and chemical resistance (solvent resistance, acid resistance, and alkali resistance).
On the other hand, in comparative examples 9 and 10, HPMDA and ODPA were used in combination as the tetracarboxylic acid component, but the diamine component did not have the structure of the present invention. The polyimide film of comparative example 9, which was produced using only BAFL as the diamine component, had poor acid resistance. Although the polyimide film of comparative example 10 was produced by using 3,3 '-DDS and a specific second diamine (BAFL) in combination as the diamine component, the polyimide film of comparative example 10 in which the ratio of 3, 3' -DDS was less than 70 mol% had poor optical isotropy and acid resistance.

Claims (10)

1. A polyimide resin having a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine,
the structural unit A contains a structural unit (A-1), the structural unit (A-1) is at least one selected from the group consisting of a structural unit (A-1-1) derived from a compound represented by the following formula (a-1-1) and a structural unit (A-1-2) derived from a compound represented by the following formula (a-1-2),
the structural unit B contains a structural unit (B-1) derived from a compound represented by the following formula (B-1) and a structural unit (B-2), and the structural unit (B-2) is at least one selected from the group consisting of a structural unit (B-2-1) derived from a compound represented by the following formula (B-2-1), a structural unit (B-2-2) derived from a compound represented by the following formula (B-2-2), a structural unit (B-2-3) derived from a compound represented by the following formula (B-2-3), a structural unit (B-2-4) derived from a compound represented by the following formula (B-2-4), and a structural unit (B-2-5) derived from a compound represented by the following formula (B-2-5),
the proportion of the structural unit (B-1) in the structural unit B is 70 mol% or more,
Figure FDA0003082851460000011
in the formula (b-2-2),
r is each independently a hydrogen atom, a fluorine atom or a methyl group,
in the formula (b-2-4),
R1～R4each independently a monovalent aliphatic group or a monovalent aromatic group,
Z1and Z2Each independently a divalent aliphatic radical or a divalent aromatic radical,
r is a positive integer.
2. The polyimide resin according to claim 1, wherein the proportion of the structural unit (B-1) in the structural unit B is 70 to 97 mol%,
the proportion of the structural unit (B-2) in the structural unit B is 3 to 30 mol%.
3. The polyimide resin according to claim 1 or 2, wherein a ratio of the structural unit (a-1) in the structural unit a is 50 mol% or more.
4. The polyimide resin according to any one of claims 1 to 3, wherein the structural unit (B-2) is a structural unit (B-2-1).
5. The polyimide resin according to any one of claims 1 to 3, wherein the structural unit (B-2) is a structural unit (B-2-2).
6. The polyimide resin according to any one of claims 1 to 3, wherein the structural unit (B-2) is a structural unit (B-2-3).
7. The polyimide resin according to any one of claims 1 to 3, wherein the structural unit (B-2) is a structural unit (B-2-4).
8. The polyimide resin according to any one of claims 1 to 3, wherein the structural unit (B-2) is a structural unit (B-2-5).
9. A polyimide varnish prepared by dissolving the polyimide resin according to any one of claims 1 to 8 in an organic solvent.
10. A polyimide film comprising the polyimide resin according to any one of claims 1 to 8.
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