CN111741996B - Polyimide resin, polyimide varnish, and polyimide film - Google Patents
Polyimide resin, polyimide varnish, and polyimide film Download PDFInfo
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- CN111741996B CN111741996B CN201980014291.0A CN201980014291A CN111741996B CN 111741996 B CN111741996 B CN 111741996B CN 201980014291 A CN201980014291 A CN 201980014291A CN 111741996 B CN111741996 B CN 111741996B
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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
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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
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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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
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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
- C08G73/1057—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
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- 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
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- 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
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- 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
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Abstract
The present invention provides a polyimide resin, wherein a constituent unit A derived from tetracarboxylic dianhydride comprises a constituent unit (A-1) derived from a compound represented by the formula (a-1); the diamine-derived constituent unit B contains a constituent unit (B-1) derived from a compound represented by the formula (B-1) and a constituent unit (B-2), and the constituent unit (B-2) is at least 1 selected from the group consisting of a constituent unit (B-2-1) derived from a compound represented by the formula (B-2-1), a constituent unit (B-2-2) derived from a compound represented by the formula (B-2-2), and a constituent unit (B-2-3) derived from a compound represented by the formula (B-2-3). (in the formula (b-1), R 1 ～R 4 Each independently a monovalent aliphatic group or a monovalent aromatic group, Z 1 And Z 2 Each independently is a divalent aliphatic group or a divalent aromatic group, and r is a positive integer. )
Description
Technical Field
The present invention relates to a polyimide resin, a polyimide varnish, and a polyimide film.
Background
Polyimide resins have excellent mechanical properties and heat resistance, and therefore, various uses thereof in the fields of electric/electronic components and the like have been studied. For example, it is desired to replace a glass substrate used in an image display device such as a liquid crystal display or an OLED display with a plastic substrate, and studies have been made on a polyimide film suitable for the plastic substrate. Polyimide films for such applications are required to have excellent colorless transparency.
In addition, in order to be suitable as a plastic substrate for use in an image display device (for example, a liquid crystal display) in which light emitted from a display element passes through a retardation film or a polarizing plate, the polyimide film is required to have not only excellent colorless transparency but also excellent optical isotropy.
In order to satisfy the required performance as described above, various polyimide resins have been developed. For example, patent document 1 discloses a polyimide resin synthesized using 1,2,4,5-cyclohexanetetracarboxylic dianhydride as a tetracarboxylic acid component and 9,9-bis (3-methyl-4-aminophenyl) fluorene and 4,4' -diaminodiphenyl ether as diamine components, as a polyimide resin having excellent transparency, heat resistance and optical isotropy.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 6010533
Disclosure of Invention
Problems to be solved by the invention
One of the purposes of replacing a glass substrate used in an image display device with a plastic substrate is to make the device flexible. In contrast to glass, it can be said that polyimide resin is a material having high flexibility (i.e., low elastic modulus). However, since the main chain of the polyimide resin is generally rigid, the polyimide resin tends to have a higher elastic modulus than other plastic materials. Therefore, in the case of using a polyimide film as a flexible substrate, the low elastic modulus is 1 problem, and it is not easy to achieve the low elastic modulus while maintaining excellent colorless transparency and optical isotropy.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide: a polyimide resin which can form a film having excellent colorless transparency and optical isotropy and a low elastic modulus.
Means for solving the problems
The present inventors have found that: the above problems can be solved by a polyimide resin containing a combination of specific constituent units, and the present invention has been completed.
That is, the present invention relates to the following [1] to [8].
[1]
A polyimide resin having a constituent unit A derived from a tetracarboxylic dianhydride and a constituent unit B derived from a diamine,
wherein the constituent unit A comprises a constituent unit (A-1) derived from a compound represented by the following formula (a-1),
the constituent unit B includes a constituent unit (B-1) derived from a compound represented by the following formula (B-1) and a constituent unit (B-2), and the constituent unit (B-2) is at least 1 selected from the group consisting of a constituent unit (B-2-1) derived from a compound represented by the following formula (B-2-1), a constituent unit (B-2-2) derived from a compound represented by the following formula (B-2-2), and a constituent unit (B-2-3) derived from a compound represented by the following formula (B-2-3).
(in the formula (b-1),
R 1 ～R 4 each independently a monovalent aliphatic group or a monovalent aromatic group,
Z 1 and Z 2 Each independently a divalent aliphatic group or a divalent aromatic group,
r is a positive integer. )
[2]
The polyimide resin according to [1], wherein the proportion of the constituent unit (A-1) in the constituent unit A is 50 mol% or more.
[3]
The polyimide resin according to the above [1] or [2], wherein the proportion of the constituent unit (B-1) in the constituent unit B is 10 to 50 mol%,
the proportion of the constituent unit (B-2) in the constituent unit B is 50 to 90 mol%.
[4]
The polyimide resin according to any one of the above [1] to [3], wherein the constituent unit (B-2) is a constituent unit (B-2-1).
[5]
The polyimide resin according to any one of the above [1] to [3], wherein the constituent unit (B-2) is a constituent unit (B-2-2).
[6]
The polyimide resin according to any one of the above [1] to [3], wherein the constituent unit (B-2) is a constituent unit (B-2-3).
[7]
A polyimide varnish comprising the polyimide resin according to any one of the above [1] to [6] dissolved in an organic solvent.
[8]
A polyimide film comprising the polyimide resin according to any one of the above [1] to [6 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a film having excellent colorless transparency and optical isotropy and a low elastic modulus.
Detailed Description
[ polyimide resin ]
The polyimide resin of the present invention has a constituent unit A derived from a tetracarboxylic dianhydride and a constituent unit B derived from a diamine, wherein the constituent unit A includes a constituent unit (A-1) derived from a compound represented by the following formula (a-1), the constituent unit B includes a constituent unit (B-1) derived from a compound represented by the following formula (B-1) and a constituent unit (B-2), and the constituent unit (B-2) is at least 1 selected from the group consisting of a constituent unit (B-2-1) derived from a compound represented by the following formula (B-2-1), a constituent unit (B-2-2) derived from a compound represented by the following formula (B-2-2), and a constituent unit (B-2-3) derived from a compound represented by the following formula (B-2-3).
(in the formula (b-1),
R 1 ～R 4 each independently a monovalent aliphatic group or a monovalent aromatic group,
Z 1 and Z 2 Each independently a divalent aliphatic group or a divalent aromatic group,
r is a positive integer. )
< constituent Unit A >
The constituent unit A is a constituent unit derived from a tetracarboxylic dianhydride in a polyimide resin, and includes a constituent unit (A-1) derived from a compound represented by the following formula (a-1).
The compound represented by the formula (a-1) is 1,2,4, 5-cyclohexanetetracarboxylic dianhydride.
When the constituent unit A contains the constituent unit (A-1), the colorless transparency of the film is improved.
The proportion of the constituent unit (a-1) in the constituent unit a is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more. The upper limit of the ratio of the constituent unit (A-1) is not particularly limited, and is 100 mol%. The constituent unit A may contain only the constituent unit (A-1).
The constituent unit A may include constituent units other than the constituent unit (A-1). The tetracarboxylic dianhydrides providing such constituent units are not particularly limited, and examples thereof include aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride, 3', 4' -biphenyltetracarboxylic dianhydride, 9 '-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, and 4,4' - (hexafluoroisopropylidene) phthalic anhydride; alicyclic tetracarboxylic dianhydrides such as 1,2,3, 4-cyclobutanetetracarboxylic dianhydride and norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 ″ -norbornane-5, 5 ″,6 ″ -tetracarboxylic dianhydride (except for the compound represented by the formula (a-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 neither aromatic rings nor alicyclic rings.
The constituent unit (a) may optionally include 1 or 2 or more constituent units other than the constituent unit (a-1).
In addition, as an embodiment of the polyimide resin of the present invention, there is exemplified a polyimide resin in which the constituent unit a does not contain a constituent unit derived from 9,9' -bis (3, 4-dicarboxyphenyl) fluorene dianhydride.
< constituent Unit B >
The constituent unit B is a diamine-derived constituent unit in the polyimide resin, and comprises a constituent unit (B-1) derived from a compound represented by the following formula (B-1) and a constituent unit (B-2), and the constituent unit (B-2) is at least 1 selected from the group consisting of a constituent unit (B-2-1) derived from a compound represented by the following formula (B-2-1), a constituent unit (B-2-2) derived from a compound represented by the following formula (B-2-2), and a constituent unit (B-2-3) derived from a compound represented by the following formula (B-2-3).
(in the formula (b-1),
R 1 ～R 4 each independently a monovalent aliphatic group or a monovalent aromatic group,
Z 1 and Z 2 Each independently a divalent aliphatic group or a divalent aromatic group,
r is a positive integer. )
R in the formula (b-1) 1 、R 2 、R 3 And R 4 Each independently represents a monovalent aliphatic group or a monovalent aromatic group, at least one of these groupsA portion of the hydrogen atoms are optionally substituted with fluorine atoms. Examples of the monovalent aliphatic group include a monovalent saturated hydrocarbon group, a monovalent unsaturated hydrocarbon group, and a monovalent hydrocarbonoxy 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. Examples of the monovalent unsaturated hydrocarbon group include alkenyl groups having 2 to 22 carbon atoms, and examples thereof include a vinyl group and a propenyl group. Examples of the monovalent hydrocarbonoxy group include alkoxy groups having 1 to 22 carbon atoms, and examples thereof include the 1-valent groups in which the above-mentioned alkyl groups are bonded to oxygen atoms. Examples of the monovalent aromatic group include an aryl group having 6 to 24 carbon atoms, an aralkyl group having 7 to 24 carbon atoms, and an aryloxy group having 6 to 24 carbon atoms, and examples thereof include a phenyl group and a phenoxy group. As R 1 、R 2 、R 3 And R 4 Particularly preferred is a methyl group or a phenyl group.
In addition, Z 1 And Z 2 Each independently represents a divalent aliphatic group or a divalent aromatic group, at least a part of hydrogen atoms of these groups being optionally substituted by fluorine atoms. 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 alkylene groups having 1 to 22 carbon atoms, and examples thereof include methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene, octamethylene, decamethylene, and dodecamethylene. Examples of the divalent unsaturated hydrocarbon group include unsaturated hydrocarbon groups having 2 to 22 carbon atoms, and examples thereof include an ethenylene group, an propenylene group, and an alkylene group having an unsaturated double bond at a terminal. Examples of the divalent aromatic group include an arylene group having 6 to 24 carbon atoms, an aralkylene group (arylalkylene) having 7 to 24 carbon atoms, and an aryloxylene group having 6 to 24 carbon atoms. At least a part of hydrogen atoms constituting the aromatic ring in these groups is optionally substituted with an alkyl group. As Z 1 And Z 2 Specific examples of the arylene group having 6 to 24 carbon atoms in the above-mentioned group include o-phenylene, m-phenylene, p-phenylene, 4' -biphenylene and 2, 6-naphthylene. Specific examples of the aralkylene group having 7 to 24 carbon atoms include a benzylene group and a phenethylene group. Specific examples of the aryloxy ene group having 6 to 24 carbon atoms include the aforementioned exemplary aryloxy enesA 2-valent group in which the group is bonded to an oxygen atom. As Z 1 And Z 2 Propylene, trimethylene, tetramethylene, p-phenylene and benzylidene are preferred, and trimethylene, tetramethylene and p-phenylene are more preferred.
R represents a positive integer, preferably an integer of 2 to 50. When R is 2 or more, plural R 1 And R 2 Each of which is optionally the same or different from each other.
<xnotran> (b-1) , 1,3- (3- ) -1,1,2,2- ,1,3- (3- ) -1,1,2,2- ,1,3- (4- ) ,1,1,3,3- -1,3- (4- ) ,1,1,3,3- -1,3- (2- ) ,1,1,3,3- -1,3- (2- ) ,1,1,3,3- -1,3- (3- ) ,1,1,3,3- -1,3- (2- ) ,1,1,3,3- -1,3- (3- ) ,1,1,3,3- -1,3- (4- ) ,1,3- -1,3- -1,3- (4- ) ,1,1,3,3,5,5- -1,5- (4- ) ,1,1,5,5- -3,3- -1,5- (3- ) ,1,1,5,5- -3,3- -1,5- (4- ) , </xnotran> <xnotran> 1,1,5,5- -3,3- -1,5- (5- ) ,1,1,5,5- -3,3- -1,5- (2- ) ,1,1,5,5- -3,3- -1,5- (4- ) ,1,1,5,5- -3,3- -1,5- (5- ) ,1,1,3,3,5,5- -1,5- (3- ) ,1,1,3,3,5,5- -1,5- (3- ) ,1,1,3,3,5,5- -1,5- (3- ) . </xnotran> The compounds represented by the formula (b-1) may be used alone or in combination of two or more.
Examples of the substances obtainable AS commercially available products of the compound represented by the formula (B-1) include "X-22-9409", "X-22-1660B", "X-22-161AS", "X-22-161A" and "X-22-161B" manufactured by shin-Etsu chemical Co., ltd.
The inclusion of the constituent unit (B-1) in the constituent unit (B) contributes to an improvement in optical isotropy and a reduction in elastic modulus of the film.
The compound represented by the formula (b-2-1) is 2, 2-bis [ 4- (4-aminophenoxy) phenyl ] hexafluoropropane.
The compound represented by the formula (b-2-2) is 2, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane.
The compound represented by the formula (b-2-3) is 1- (4-aminophenyl) -2, 3-dihydro-1, 3-trimethyl-1H-indene-5-amine.
In the present invention, the constituent unit B can control the glass transition temperature of the thin film by incorporating the constituent unit (B-2) in combination with the constituent unit (B-1). The constituent unit (B-1) contributes to improvement of optical isotropy and lowering of elastic modulus of the film, but on the other hand, it has a side of lowering the glass transition temperature. Thus, the constituent element B includes the constituent element (B-2), whereby the glass transition temperature of the thin film can be controlled by reducing the lowering width of the glass transition temperature based on the constituent element (B-1). In addition, from the viewpoint of obtaining a film having excellent colorless transparency and excellent optical isotropy, it is also preferable that the constituent unit (B-2) is contained in the constituent unit B.
The constituent unit (B-2) may be only the constituent unit (B-2-1), may be only the constituent unit (B-2-2), or may be only the constituent unit (B-2-3).
Further, the constituent unit (B-2) may be a combination of the constituent unit (B-2-1) and the constituent unit (B-2-2), a combination of the constituent unit (B-2-2) and the constituent unit (B-2-3), or a combination of the constituent unit (B-2-1) and the constituent unit (B-2-3).
Further, the constituent unit (B-2) may be a combination of the constituent unit (B-2-1), the constituent unit (B-2-2) and the constituent unit (B-2-3).
The proportion of the constituent unit (B-1) in the constituent unit B is preferably 10 to 50 mol%, more preferably 10 to 40 mol%, still more preferably 15 to 30 mol%, and particularly preferably 15 to 25 mol%.
The proportion of the constituent unit (B-2) in the constituent unit B is preferably 50 to 90 mol%, more preferably 60 to 90 mol%, still more preferably 70 to 85 mol%, and particularly preferably 75 to 85 mol%.
The total ratio of the constituent unit (B-1) and the constituent unit (B-2) in the constituent unit B is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more. The upper limit of the total ratio of the constituent unit (B-1) and the constituent unit (B-2) is not particularly limited, and is 100 mol%. The constituent unit B may include only the constituent unit (B-1) and the constituent unit (B-2).
The constituent unit B may include constituent units other than the constituent units (B-1) and (B-2). <xnotran> , , 1,4- , ,3,5- ,2,2 ' - -4,4' - ,2,2 ' - ( ) ,4,4' - ,4,4' - ,2,2- (4- ) , (4- ) ,4,4' - , α, α ' - (4- ) -1,4- , N, N ' - (4- ) ,4,4' - (4- ) , 9,9- (4- ) (, (b-1) , (b-2-1) , (b-2-2) (b-2-3) ); </xnotran> 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-1)).
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 neither aromatic rings nor alicyclic rings.
The constituent unit (B) may optionally contain 1 or 2 or more constituent units other than the constituent units (B-1) and (B-2).
The number average molecular weight of the polyimide resin of the present invention is preferably 5000 to 100000 from the viewpoint of the mechanical strength of the polyimide film to be obtained. The number average molecular weight of the polyimide resin can be determined, for example, from a value converted to standard polymethyl methacrylate (PMMA) measured by gel filtration chromatography.
By using the polyimide resin of the present invention, a film having excellent colorless transparency and optical isotropy and a low elastic modulus can be formed. Preferred physical property values of the film obtained by using the polyimide resin of the present invention are as follows.
The tensile modulus is preferably 2.1GPa or less, more preferably 2.0GPa or less, and still more preferably 1.8GPa or less.
The tensile strength is preferably 40MPa or more, more preferably 50MPa or more, and still more preferably 60MPa or more.
The total light transmittance is preferably 85% or more, more preferably 88% or more, and further preferably 90% or more, when a film having a thickness of 30 μm is formed.
The haze is preferably 1.0% or less, more preferably 0.5% or less, and further preferably 0.3% or less when a film having a thickness of 30 μm is formed.
The Yellowness Index (YI) is preferably 6.0 or less, more preferably 3.0 or less, and still more preferably 1.5 or less when a film having a thickness of 30 μm is formed.
The absolute value of the retardation in thickness (Rth) is preferably 100nm or less, more preferably 50nm or less, and still more preferably 30nm or less when a film having a thickness of 30 μm is formed.
The glass transition temperature (Tg) is preferably from 150 to 300 ℃, more preferably from 150 to 280 ℃, and still more preferably from 150 to 250 ℃.
In the present invention, the tensile elastic modulus, tensile strength, total light transmittance, haze, yellowness Index (YI), retardation in thickness (Rth), and glass transition temperature (Tg) 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 providing the above-mentioned constituent unit (a-1) with a diamine component containing: a compound which provides the above constituent unit (B-1) and a compound which provides the above constituent unit (B-2).
Examples of the compound that provides the constituent unit (A-1) include compounds represented by the formula (a-1), but the compound is not limited thereto, and derivatives thereof may be provided as long as the same constituent unit is provided. Examples of the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a-1) (i.e., 1,2,4, 5-cyclohexanetetracarboxylic acid) and an alkyl ester of the tetracarboxylic acid. As the compound providing the constituent unit (A-1), a compound represented by the formula (a-1) (i.e., dianhydride) is 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 constituent unit (a-1). The upper limit of the content of the compound constituting the unit (A-1) is not particularly limited, i.e., 100 mol%. The tetracarboxylic acid component may contain only a compound that provides the constituent unit (A-1).
The tetracarboxylic acid component may contain a compound other than the compound providing the constituent 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 may optionally contain 1 or 2 or more compounds other than the compound providing the constituent unit (A-1).
Examples of the compound that can provide the constituent unit (B-1) include compounds represented by the formula (B-1), but the compound is not limited thereto, and derivatives thereof may be provided as long as the same constituent unit is provided. The derivative is a diisocyanate corresponding to the diamine represented by the formula (b-1). As the compound providing the constituent unit (B-1), a compound represented by the formula (B-1) (i.e., diamine) is preferred.
As the compound providing the constituent unit (B-2), at least 1 selected from the group consisting of a compound providing the constituent unit (B-2-1), a compound providing the constituent unit (B-2-2), and a compound providing the constituent unit (B-2-3) is used.
Examples of the compound that can provide the constituent unit (B-2-1), the compound that can provide the constituent unit (B-2-2), and the compound that can provide the constituent unit (B-2-3) include, but are not limited to, compounds represented by the formula (B-2-1), compounds represented by the formula (B-2-2), and compounds represented by the formula (B-2-3), respectively, and derivatives thereof may be provided in the range where the same constituent unit is provided. Examples of the derivative include a diisocyanate corresponding to a diamine represented by the formula (b-2-1), a diisocyanate corresponding to a diamine represented by the formula (b-2-2), and a diisocyanate corresponding to a diamine represented by the formula (b-2-3). As the compound that provides the constituent unit (B-2-1), the compound that provides the constituent unit (B-2-2), and the compound that provides the constituent unit (B-2-3), compounds represented by the formula (B-2-1) (i.e., diamines), compounds represented by the formula (B-2-2) (i.e., diamines), and compounds represented by the formula (B-2-3) (i.e., diamines) are preferable, respectively.
As the compound that provides the constituent unit (B-2), only the compound that provides the constituent unit (B-2-1), only the compound that provides the constituent unit (B-2-2), or only the compound that provides the constituent unit (B-2-3) may be used.
Further, as the compound which can provide the constituent unit (B-2), a combination of a compound which can provide the constituent unit (B-2-1) and a compound which can provide the constituent unit (B-2-2), a combination of a compound which can provide the constituent unit (B-2-2) and a compound which can provide the constituent unit (B-2-3), or a combination of a compound which can provide the constituent unit (B-2-1) and a compound which can provide the constituent unit (B-2-3) can be used.
Further, as the compound which can provide the constituent unit (B-2), a combination of a compound which can provide the constituent unit (B-2-1), a compound which can provide the constituent unit (B-2-2) and a compound which can provide the constituent unit (B-2-3) can be used.
The diamine component preferably contains 10 to 50 mol%, more preferably 10 to 40 mol%, still more preferably 15 to 30 mol%, particularly preferably 15 to 25 mol% of the compound that provides the constituent unit (B-1).
The diamine component preferably contains 50 to 90 mol%, more preferably 60 to 90 mol%, even more preferably 70 to 85 mol%, and particularly preferably 75 to 85 mol% of the compound that provides the constituent unit (B-2).
The diamine component preferably contains 50 mol% or more, more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably 99 mol% or more of the total of the compound that provides the constituent unit (B-1) and the compound that provides the constituent unit (B-2). The upper limit of the total content of the compound that provides the constituent unit (B-1) and the compound that provides the constituent unit (B-2) is not particularly limited, i.e., 100 mol%. The diamine component may contain only the compound that provides the constituent unit (B-1) and the compound that provides the constituent unit (B-2).
The diamine component may contain compounds other than the compound providing the constituent unit (B-1) and the compound providing the constituent 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 may optionally contain 1 or 2 or more compounds other than the compound that provides the constituent unit (B-1) and the compound that provides the constituent unit (B-2).
In the present invention, the input amount ratio of the tetracarboxylic acid component and the diamine component used for producing the polyimide resin is preferably: the diamine component is 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. The dicarboxylic acid-based end capping agent is preferably a dicarboxylic acid, and a part of the dicarboxylic acid-based end capping agent may be ring-closed. For example, phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2, 3-benzophenonedicarboxylic acid, 3, 4-benzophenonedicarboxylic acid, cyclohexane-1, 2-dicarboxylic acid, cyclopentane-1, 2-dicarboxylic acid, 4-cyclohexene-1, 2-dicarboxylic acid, 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 the following methods: (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 to 80 ℃ for 0.5 to 30 hours, and then heated to effect imidization; (2) A method in which a diamine component and a reaction solvent are put into a reactor and dissolved, and then a tetracarboxylic acid component is put into the reactor, and if necessary, the mixture is stirred at room temperature to 80 ℃ for 0.5 to 30 hours, and then heated to carry out imidization; (3) A method of charging a tetracarboxylic acid component, a diamine component, and a reaction solvent into a reactor, and directly raising the temperature to perform an imidization reaction.
The reaction solvent used for producing 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, ethyl methyl carbonate, ethylene carbonate, and propylene carbonate.
Among the above reaction solvents, an amide solvent or a lactone solvent is preferable. The reaction solvent may be used alone or in combination of two or more.
In the imidization reaction, it is preferable to use a dean-Stark apparatus or the like, and to carry out the reaction while removing the water produced during the production. By performing such an operation, the polymerization degree 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 hydrogen carbonate and sodium hydrogen carbonate.
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 basic catalyst is preferred, the use of an organic basic catalyst is more preferred, the use of triethylamine is further preferred, and the use of a combination of triethylamine and triethylenediamine 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, and the polyimide resin is dissolved in the organic solvent.
The organic solvent is not particularly limited as long as it can dissolve the polyimide resin, and the reaction solvent used for producing the polyimide resin is preferably 2 or more of the above compounds alone or in combination.
The polyimide varnish of the present invention may be a polyimide solution itself in which a polyimide resin obtained by a polymerization method is dissolved in a reaction solvent, or a polyimide solution in which a diluting solvent is further added 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 stably 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, and more preferably 5 to 150 pas. The viscosity of the polyimide varnish was measured at 25 ℃ using an E-type viscometer.
The polyimide varnish of the present invention may further contain various additives such as an inorganic filler, an adhesion promoter, a release agent, a flame retardant, an ultraviolet absorber, a surfactant, a leveling agent, an antifoaming agent, a fluorescent whitening agent, a crosslinking agent, a polymerization initiator, and a photosensitizer, within a range that does not impair the required properties of the polyimide film. That is, the polyimide resin of the present invention may be configured as a resin composition to which the above-described additive is added, as required.
The method for producing the polyimide varnish of the present invention is not particularly limited, and a known method can be applied.
Any suitable ultraviolet absorber can be used as the ultraviolet absorber exemplified as the additive. Specific examples thereof include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, triazine-based ultraviolet absorbers, hindered amine-based ultraviolet absorbers, inorganic particle-based ultraviolet absorbers, and organic ultraviolet absorbers such as oxalic acid aniline-based ultraviolet absorbers and malonate-based ultraviolet absorbers. Only one kind of ultraviolet absorber may be used, or two or more kinds may be used in combination. Among them, benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers are preferable, and benzotriazole-based ultraviolet absorbers are more preferable.
The amount of the ultraviolet absorber added to the resin composition is preferably 0.01 to 6 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.5 to 4 parts by mass, per 100 parts by mass of the polyimide resin of the present invention. When the amount of the ultraviolet absorber is large, the properties of the polyimide resin such as optical properties and heat resistance may be deteriorated, and haze may be generated in the film.
In the present invention, the ultraviolet absorber can achieve the effect of the ultraviolet absorber in the resin composition. Therefore, the compound added as the ultraviolet absorber may be present in the resin composition as it is, or the compound may be modified by heat treatment to a modified product still having an ultraviolet absorbing effect. In addition, the ultraviolet absorber is preferably uniformly mixed with the polyimide resin of the present invention in the resin composition.
[ 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 and optical isotropy, and has a low elastic modulus. 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. Examples thereof include: a method of applying the polyimide varnish of the present invention to a smooth support such as a glass plate, a metal plate, or a plastic, or forming the polyimide varnish into a film, and then removing an organic solvent such as a reaction solvent or a dilution solvent contained in the varnish by heating. If necessary, a release agent may be applied in advance to the surface of the support.
As a method for removing the organic solvent contained in the varnish by heating, the following method is preferable. Namely, preferably: the polyimide film is produced by evaporating an organic solvent at a temperature of 120 ℃ or lower to form a self-supporting film, peeling the self-supporting film from a support, fixing the end of the self-supporting film, and drying the film at a temperature of the boiling point of the organic solvent used or higher. Further, it is preferable to perform drying under a nitrogen atmosphere. The pressure of the drying atmosphere may be reduced pressure, normal pressure or increased pressure. The heating temperature for producing the polyimide film by drying the self-supporting film is not particularly limited, and is preferably 200 to 400 ℃.
The thickness of the polyimide film of the present invention may be appropriately selected depending on the application, and is preferably in the range of 1 to 250. Mu.m, more preferably 5 to 100. Mu.m, and still more preferably 10 to 80 μm. The film having a thickness of 1 to 250 μm 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 is particularly suitable for use as a substrate for an image display device such as a liquid crystal display, an OLED display, or the like.
Examples
The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples.
The solid content concentration of the polyimide varnish and the physical properties of the polyimide film obtained in the examples and comparative examples were measured by the following methods.
(1) Concentration of solid component
The sample was heated at 320 ℃ for 120 minutes in a small electric furnace "MMF-1" manufactured by AS ONE CORPORATION, and the solid content concentration was calculated from the mass difference between the sample before and after heating.
(2) Thickness of film
The film thickness was measured using a micrometer manufactured by Sanfeng corporation.
(3) Tensile modulus of elasticity and tensile strength
The tensile modulus and tensile strength were measured according to JIS K7127 using a tensile tester "Strogaph VG-1E" manufactured by Toyo Seiki Seisaku-Sho.
(4) Total light transmittance, yellowness Index (YI), haze
The total light transmittance, YI and haze were measured by using a color/haze simultaneous measuring instrument "COH400" manufactured by Nippon Denshoku industries Co., ltd. The total light transmittance and YI were measured according to JIS K7361-1:1997, haze was measured according to JIS K7136:2000.
(5) Thickness phase difference (Rth)
The thickness retardation (Rth) was measured using an ellipsometer "M-220" manufactured by Nippon spectral Co., ltd. The thickness retardation value at a measurement wavelength of 550nm was measured. When nx is the maximum value and ny is the minimum value among the in-plane refractive indices of the polyimide film, nz is the refractive index in the thickness direction, and d is the thickness of the film, rth is expressed by the following formula.
Rth＝[{(nx+ny)/2}-nz]×d
(6) Glass transition temperature (Tg)
The residual stress was removed by heating to a temperature at which the residual stress was sufficiently removed under conditions of a specimen size of 2mm × 20mm, a load of 0.1N, and a heating rate of 10 ℃/min in a tensile mode using a thermomechanical analyzer "TMA/SS6100" manufactured by Hitachi High-Tech Science co. Thereafter, the elongation of the test piece was measured under the same conditions as those of the treatment for removing the residual stress, and the temperature at which the inflection point of the elongation was confirmed was determined as the glass transition temperature.
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))
< diamine component >
X-22-9409: both terminal amino group-modified silicone oil "X-22-9409" (manufactured by shin-Etsu chemical Co., ltd.; compound represented by formula (b-1))
HFBAPP:2, 2-bis [ 4- (4-aminophenoxy) phenyl ] hexafluoropropane (manufactured by Kyowa 124751245212459
BAPP:2, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane (manufactured by Union corporation, inc./124751245212459; compound represented by the formula (b-2-2)
TMDA:1- (4-aminophenyl) -2, 3-dihydro-1, 3-trimethyl-1H-indene-5-amine (manufactured by Nippon Kanji Kagaku K.K.; compound represented by formula (b-2-3))
BAPS: bis [ 4- (4-aminophenoxy) phenyl ] sulfone (manufactured by\124751245212459manufacturedby Kyoho K.K.
< example 1>
To a 0.3L 5-neck glass round-bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen introduction tube, a dean-Stark apparatus equipped with a condenser tube, a thermometer, and a glass end cap were added HFBAPP 29.034g (0.056 mol), X-22-9409 (18.014 mol), gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) 50g, triethylenediamine (manufactured by Tokyo chemical Co., ltd.) as a catalyst 0.039g, and triethylamine (manufactured by Kanto chemical Co., ltd.) 3.54g, and the mixture was stirred at 200rpm under a nitrogen atmosphere to obtain a solution. To this solution, 15.692g (0.070 mol) of HPMDA and 13.5g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation) were added in one portion, and then the mixture was heated with a mantle heater to raise the temperature in the reaction system to 200 ℃ over about 20 minutes. The distilled components were collected, and the temperature in the reaction system was maintained at 200 ℃ for 3 hours. 78.76g of N, N-dimethylacetamide (manufactured by Mitsubishi gas chemical) was added thereto, and the mixture was stirred at about 100 ℃ for about 1 hour to obtain a uniform polyimide varnish having a solid content of 30 mass%.
Subsequently, the obtained polyimide varnish was coated on a PET substrate, and the substrate was kept at 100 ℃ for 30 minutes to evaporate the solvent, thereby obtaining a colorless transparent primary dried film having self-supporting properties. The film was fixed on a stainless steel frame, and dried at 230 ℃ for 2 hours in a nitrogen atmosphere to remove the solvent, thereby obtaining a film having a thickness of 30 μm. The FT-IR analysis of the obtained film confirmed the disappearance of the raw material peak and the appearance of the peak derived from the imide skeleton. The evaluation results of the polyimide film are shown in table 1.
< example 2>
A0.5L 5-neck glass round-bottomed flask equipped with a stainless steel crescent-shaped stirring blade, a nitrogen introduction tube, a dean-Stark apparatus equipped with a condenser tube, a thermometer, and a glass end cap was charged with 65.683g (0.160 mol) of BAPP, 53.600g (0.040 mol) of X-22-9409, 200g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation), and 10.12g of triethylamine (manufactured by Kanto chemical Co., ltd.) as a catalyst, and the mixture was stirred at 200rpm under a nitrogen atmosphere to obtain a solution. To this solution, 144.834g (0.200 mol) of HPMDA and 46.2g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) were added in one portion, and then the mixture was heated with a mantle heater to raise the temperature in the reaction system to 200 ℃ over about 20 minutes. The distilled components were collected, and the temperature in the reaction system was maintained at 200 ℃ for 5 hours. 120.0g of N, N-dimethylacetamide (manufactured by Mitsubishi gas chemical corporation) was added thereto, and the mixture was stirred at about 100 ℃ for about 1 hour to obtain a uniform polyimide varnish having a solid content of 30 mass%.
Subsequently, the obtained polyimide varnish was coated on a PET substrate, and the substrate was kept at 100 ℃ for 30 minutes to evaporate the solvent, thereby obtaining a colorless transparent primary dried film having self-supporting properties. The film was fixed on a stainless steel frame, and dried at 230 ℃ for 2 hours in a nitrogen atmosphere to remove the solvent, thereby obtaining a film having a thickness of 30 μm. The FT-IR analysis of the obtained film confirmed the disappearance of the raw material peak and the appearance of the peak derived from the imide skeleton. The evaluation results of the polyimide film are shown in table 1.
< example 3>
To a 0.5L 5-neck glass round-bottom flask equipped with a stainless steel semilunar stirring blade, a nitrogen inlet tube, a dean-Stark apparatus equipped with a condenser tube, a thermometer, and a glass end cap were added 14.906g (0.056 mol) of TMDA, 18.76g (0.014 mol) of X-22-9409, 30g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation), 0.031g of triethylenediamine (manufactured by Tokyo chemical Co., ltd.) as a catalyst, and 3.54g of triethylamine (manufactured by Kanto chemical Co., ltd.) and the mixture was stirred at 200rpm under a nitrogen atmosphere to obtain a solution. To this solution, 15.692g (0.070 mol) of HPMDA and 10.4g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation) were added in one portion, and then the mixture was heated with a mantle heater to raise the temperature in the reaction system to 200 ℃ over about 20 minutes. The distilled components were collected, the temperature in the reaction system was maintained at 200 ℃ for 2.5 hours, and 10.91g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added thereto, followed by stirring for 50 minutes. Then, 10.7g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added thereto, and the mixture was stirred for 75 minutes. Then, 13.9g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added thereto, and the mixture was stirred for 4 hours. Finally, 35.24g of N, N-dimethylacetamide (manufactured by Mitsubishi gas chemical) was added thereto and the mixture was stirred at about 100 ℃ for about 1 hour to obtain a uniform polyimide varnish having a solid content of 30 mass%.
Subsequently, the obtained polyimide varnish was coated on a PET substrate, and the substrate was kept at 100 ℃ for 30 minutes to evaporate the solvent, thereby obtaining a colorless transparent primary dried film having self-supporting properties. The film was fixed on a stainless steel frame, and dried at 230 ℃ for 2 hours in a nitrogen atmosphere to remove the solvent, thereby obtaining a film having a thickness of 24 μm. The FT-IR analysis of the obtained film confirmed the disappearance of the raw material peak and the appearance of the peak derived from the imide skeleton. The evaluation results of the polyimide film are shown in table 1.
< example 4>
To a 3.0L 5-neck glass round-bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen inlet tube, a dean-Stark apparatus equipped with a condenser tube, a thermometer, and a glass end cap were added 355.41g (0.684 mol) of HFBAPP, 295.347g (0.216 mol) of X-22-9409, gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) 500g, and as catalysts, 0.501g of triethylenediamine (manufactured by Tokyo chemical Co., ltd.) and 45.54g of triethylamine (manufactured by Kanto chemical Co., ltd.) and the mixture was stirred at 150rpm under a nitrogen atmosphere to obtain a solution. To this solution, 201.96g (0.900 mol) of HPMDA and 192.0g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation) were added in one portion, and then the mixture was heated with a mantle heater to raise the temperature in the reaction system to 200 ℃ over about 50 minutes. The distilled-off components were collected, and the temperature in the reaction system was maintained at 200 ℃ for 3.75 hours. Finally, 1205.9g of N, N-dimethylacetamide (manufactured by Mitsubishi gas chemical) was added thereto and the mixture was stirred at about 100 ℃ for about 1 hour to obtain a uniform polyimide varnish having a solid content of 30 mass%.
Subsequently, the obtained polyimide varnish was coated on a PET substrate, and the substrate was kept at 100 ℃ for 30 minutes to evaporate the solvent, thereby obtaining a colorless transparent primary dried film having self-supporting properties. The film was fixed on a stainless steel frame, and dried at 190 ℃ for 20 minutes in an air atmosphere to remove the solvent, thereby obtaining a film having a thickness of 38 μm. By FT-IR analysis of the obtained film, disappearance of the raw material peak and appearance of the peak derived from the imide skeleton were confirmed. The evaluation results of the polyimide film are shown in table 1.
< example 5>
To a 0.3L 5-neck glass round-bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen inlet tube, a dean-Stark apparatus equipped with a condenser tube, a thermometer, and a glass end cap were added HFBAPP 28.708g (0.055 mol), X-22-9409 (12.010 mol), gamma-butyrolactone (Mitsubishi chemical corporation, inc.) 44.9g, triethylenediamine (Tokyo chemical Co., ltd.) as a catalyst 0.036g, and triethylamine (Kanto chemical Co., ltd.) 3.29g, and the mixture was stirred at 200rpm under a nitrogen atmosphere to obtain a solution. To this solution, 14.586g (0.065 mol) of HPMDA and 11.2g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) were added in one portion, and then the mixture was heated with a mantle heater, and the temperature in the reaction system was increased to 180 ℃ over about 20 minutes. The distilled components were collected, and the temperature in the reaction system was maintained at 180 ℃ for 4 hours. 69.3g of N, N-dimethylacetamide (manufactured by Mitsubishi gas chemical corporation) was added thereto, and the mixture was stirred at about 100 ℃ for about 1 hour to obtain a uniform polyimide varnish having a solid content of 30 mass%.
Subsequently, the obtained polyimide varnish was coated on a PET substrate, and the substrate was kept at 100 ℃ for 30 minutes to evaporate the solvent, thereby obtaining a colorless transparent primary dried film having self-supporting properties. The film was fixed on a stainless steel frame, dried at 240 ℃ for 10 minutes in an air atmosphere, and then further dried at 250 ℃ for 10 minutes in an air atmosphere, to remove the solvent, thereby obtaining a film having a thickness of 36 μm. By FT-IR analysis of the obtained film, disappearance of the raw material peak and appearance of the peak derived from the imide skeleton were confirmed. The evaluation results of the polyimide film are shown in table 1.
< example 6>
A film having a thickness of 33 μm was obtained in the same manner as in example 1, except that 0.5 part by mass of Tinuvin234 (manufactured by BASF Japan K.K., benzotriazole-based ultraviolet absorber) as an ultraviolet absorber was added to 100 parts by mass of the polyimide resin in the polyimide varnish obtained in the same manner as in example 1. The evaluation results of the polyimide film are shown in table 1.
< example 7>
A film having a thickness of 25 μm was obtained in the same manner as in example 1, except that 4.0 parts by mass of Tinuvin234 (product of BASF Japan, benzotriazole-based ultraviolet absorber) as an ultraviolet absorber was added to 100 parts by mass of the polyimide resin in the polyimide varnish obtained in the same manner as in example 1. The evaluation results of the polyimide film are shown in table 1.
< comparative example 1>
In a 0.3L 5-neck glass round-bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen inlet tube, a dean-Stark apparatus equipped with a condenser tube, a thermometer, and a glass end cap, 41.477g (0.080 mol) of HFBAPP, 70g of γ -butyrolactone (manufactured by Mitsubishi chemical Co., ltd.), and 0.405g of triethylamine (manufactured by Kanto chemical Co., ltd.) as a catalyst were added, and the mixture was stirred at 200rpm under a nitrogen atmosphere to obtain a solution. 17.952g (0.080 mol) of HPMDA and 19.1g of gamma-butyrolactone (produced by Mitsubishi chemical corporation) were added to the solution at a time, and then the mixture was heated by a mantle heater to raise the temperature in the reaction system to 180 ℃ over about 20 minutes. The distilled components were collected, and the temperature in the reaction system was held at 180 ℃ for 4 hours, 89.12g of N, N-dimethylacetamide (manufactured by Mitsubishi gas chemical Co., ltd.) was added thereto, and the mixture was stirred at about 100 ℃ for about 1 hour to obtain a uniform polyimide varnish having a solid content of 20 mass%.
Subsequently, the obtained polyimide varnish was coated on a PET substrate, and the substrate was kept at 100 ℃ for 30 minutes to evaporate the solvent, thereby obtaining a colorless transparent primary dried film having self-supporting properties. The film was fixed on a stainless steel frame, and dried at 230 ℃ for 2 hours under a nitrogen atmosphere to remove the solvent, thereby obtaining a film having a thickness of 35 μm. The FT-IR analysis of the obtained film confirmed the disappearance of the raw material peak and the appearance of the peak derived from the imide skeleton. The evaluation results of the polyimide film are shown in table 1. The polyimide film was not measured for Tg.
< comparative example 2>
In a 0.3L 5-neck glass round-bottom flask equipped with a stainless steel semilunar stirring blade, a nitrogen inlet tube, a dean-Stark apparatus equipped with a condenser tube, a thermometer, and a glass end cap, 20.76g (0.048 mol) of BAPS, 16.408g (0.012 mol) of X-22-9409, 32g of gamma-butyrolactone (manufactured by Mitsubishi chemical Co., ltd.), and 3.04g of triethylamine (manufactured by Kanto chemical Co., ltd.) as a catalyst were added, and the mixture was stirred at 200rpm under a nitrogen atmosphere to obtain a solution. To this solution, 13.450g (0.060 mol) of HPMDA and 18g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) were added in one portion, and then the mixture was heated by a mantle heater to raise the temperature in the reaction system to 200 ℃ for about 20 minutes. The distilled components were collected, and the temperature in the reaction system was maintained at 200 ℃ for 3.5 hours. 62.0g of N, N-dimethylacetamide (manufactured by Mitsubishi gas chemical corporation) was added thereto, and the mixture was stirred at about 100 ℃ for about 1 hour to obtain a uniform polyimide varnish having a solid content of 30 mass%.
Subsequently, the obtained polyimide varnish was coated on a PET substrate, and the substrate was kept at 100 ℃ for 30 minutes to evaporate the solvent, thereby obtaining a colorless transparent primary dried film having self-supporting properties. The film was fixed on a stainless steel frame, and dried at 230 ℃ for 2 hours in a nitrogen atmosphere to remove the solvent, thereby obtaining a film having a thickness of 46 μm. By FT-IR analysis of the obtained film, disappearance of the raw material peak and appearance of the peak derived from the imide skeleton were confirmed. The evaluation results of the polyimide film are shown in table 1.
[ Table 1]
TABLE 1
*1: relative to 100 parts by mass of the polyimide resin
As shown in Table 1, the films of examples 1 to 7 were excellent in colorless transparency and optical isotropy, and had low elastic modulus.
From the comparison of the film of example 1 with the film of comparative example 1, it was confirmed that the polyimide resin decreased in elastic modulus by containing the constituent unit (B-1).
From the comparison of the films of examples 1 to 7 with the film of comparative example 2, it was confirmed that the polyimide resin exhibited excellent colorless transparency by including the constituent unit (B-2).
Further, it was confirmed from the comparison of the film of example 1 with the film of comparative example 1 that the optical isotropy of the film was improved by the polyimide resin containing the constituent unit (B-1), and from the comparison of the films of examples 1 to 7 with the film of comparative example 2 that the polyimide resin exhibited particularly excellent optical isotropy by containing both the constituent unit (B-1) and the constituent unit (B-2).
Claims (6)
1. A polyimide resin having a constituent unit A derived from a tetracarboxylic dianhydride and a constituent unit B derived from a diamine,
wherein the constituent unit A contains a constituent unit (A-1) derived from a compound represented by the following formula (a-1), the proportion of the constituent unit (A-1) in the constituent unit A is 50 mol% or more,
the constituent unit B contains a constituent unit (B-1) derived from a compound represented by the following formula (B-1) and a constituent unit (B-2), the constituent unit (B-2) is at least 1 selected from the group consisting of a constituent unit (B-2-1) derived from a compound represented by the following formula (B-2-1), a constituent unit (B-2-2) derived from a compound represented by the following formula (B-2-2), and a constituent unit (B-2-3) derived from a compound represented by the following formula (B-2-3), the ratio of the constituent unit (B-1) in the constituent unit B is 10 to 50 mol%, the ratio of the constituent unit (B-2) in the constituent unit B is 50 to 90 mol%,
in the formula (b-1), the compound (A),
R 1 ～R 4 each independently a monovalent aliphatic group or a monovalent aromatic group,
Z 1 and Z 2 Each independently a divalent aliphatic group or a divalent aromatic group,
r is a positive integer.
2. The polyimide resin according to claim 1, wherein the constituent unit (B-2) is a constituent unit (B-2-1).
3. The polyimide resin according to claim 1, wherein the constituent unit (B-2) is a constituent unit (B-2-2).
4. The polyimide resin according to claim 1, wherein the constituent unit (B-2) is a constituent unit (B-2-3).
5. A polyimide varnish obtained by dissolving the polyimide resin according to any one of claims 1 to 4 in an organic solvent.
6. A polyimide film comprising the polyimide resin according to any one of claims 1 to 4.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2018031246 | 2018-02-23 | ||
| JP2018-031246 | 2018-02-23 | ||
| PCT/JP2019/006333 WO2019163830A1 (en) | 2018-02-23 | 2019-02-20 | Polyimide resin, polyimide varnish and polyimide film |
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| CN111741996B true CN111741996B (en) | 2023-04-07 |
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| JP (1) | JP7306371B2 (en) |
| KR (1) | KR20200124670A (en) |
| CN (1) | CN111741996B (en) |
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| CN115135702A (en) * | 2020-02-21 | 2022-09-30 | 三菱瓦斯化学株式会社 | Method for producing polyimide film |
| WO2022004857A1 (en) * | 2020-07-02 | 2022-01-06 | 住友化学株式会社 | Optical film |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003155342A (en) * | 2001-11-19 | 2003-05-27 | Nippon Steel Chem Co Ltd | Polyimide copolymer having alicyclic structure |
| JP2012167169A (en) * | 2011-02-14 | 2012-09-06 | Mitsubishi Gas Chemical Co Inc | Colored light-blocking polyimide film |
| CN104769021A (en) * | 2012-11-08 | 2015-07-08 | 旭化成电子材料株式会社 | Substrate for flexible device, flexible device and method for producing same, laminate and method for producing same, and resin composition |
| JP2015136868A (en) * | 2014-01-23 | 2015-07-30 | 旭化成イーマテリアルズ株式会社 | Substrate which can be applied to flexible electronic device with specified structure, and production method of the substrate |
| JP2018003009A (en) * | 2016-06-23 | 2018-01-11 | ユニチカ株式会社 | Polyimide solution for forming porous polyimide film, process for producing porous polyimide film, and porous polyimide film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS6010533B2 (en) | 1977-04-05 | 1985-03-18 | 株式会社日立製作所 | Molding resin composition |
| US8580913B2 (en) * | 2006-07-07 | 2013-11-12 | Mitsubishi Gas Chemical Company, Inc. | Polyimide resin |
| KR101423361B1 (en) * | 2007-05-24 | 2014-07-24 | 미츠비시 가스 가가쿠 가부시키가이샤 | Process and apparatus for production of colorless transparent resin film |
| JP5501672B2 (en) * | 2008-06-26 | 2014-05-28 | サンワ化学工業株式会社 | Photosensitive polyimide, photosensitive polyimide ink composition, and insulating film |
| KR101387031B1 (en) * | 2013-02-28 | 2014-04-18 | 한국과학기술원 | Manufacturing method of colorless and transparent polyimide substrate embedded with glass fabric for flexible display |
| JP2017222745A (en) * | 2016-06-14 | 2017-12-21 | 信越化学工業株式会社 | Solventless silicone-modified polyimide resin composition |
-
2019
- 2019-02-20 JP JP2020500997A patent/JP7306371B2/en active Active
- 2019-02-20 WO PCT/JP2019/006333 patent/WO2019163830A1/en active Application Filing
- 2019-02-20 CN CN201980014291.0A patent/CN111741996B/en active Active
- 2019-02-20 KR KR1020207023995A patent/KR20200124670A/en not_active Application Discontinuation
- 2019-02-22 TW TW108105906A patent/TW201936721A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003155342A (en) * | 2001-11-19 | 2003-05-27 | Nippon Steel Chem Co Ltd | Polyimide copolymer having alicyclic structure |
| JP2012167169A (en) * | 2011-02-14 | 2012-09-06 | Mitsubishi Gas Chemical Co Inc | Colored light-blocking polyimide film |
| CN104769021A (en) * | 2012-11-08 | 2015-07-08 | 旭化成电子材料株式会社 | Substrate for flexible device, flexible device and method for producing same, laminate and method for producing same, and resin composition |
| JP2015136868A (en) * | 2014-01-23 | 2015-07-30 | 旭化成イーマテリアルズ株式会社 | Substrate which can be applied to flexible electronic device with specified structure, and production method of the substrate |
| JP2018003009A (en) * | 2016-06-23 | 2018-01-11 | ユニチカ株式会社 | Polyimide solution for forming porous polyimide film, process for producing porous polyimide film, and porous polyimide film |
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| JP7306371B2 (en) | 2023-07-11 |
| WO2019163830A1 (en) | 2019-08-29 |
| JPWO2019163830A1 (en) | 2021-03-11 |
| KR20200124670A (en) | 2020-11-03 |
| TW201936721A (en) | 2019-09-16 |
| CN111741996A (en) | 2020-10-02 |
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