CN111133034A - Polyimide resin, polyimide varnish, and polyimide film - Google Patents
Polyimide resin, polyimide varnish, and polyimide film Download PDFInfo
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- CN111133034A CN111133034A CN201880062394.XA CN201880062394A CN111133034A CN 111133034 A CN111133034 A CN 111133034A CN 201880062394 A CN201880062394 A CN 201880062394A CN 111133034 A CN111133034 A CN 111133034A
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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
-
- 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
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives 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 C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—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 comprising a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, the structural unit A comprising a structural unit (A-1) derived from a compound represented by the following formula (a-1), the structural unit B comprising a structural unit (B-1) derived from a compound represented by the following formula (B-1) and a structural unit (B-2) derived from a compound represented by the following formula (B-2), the ratio of the structural unit (A-1) in the structural unit A being 50 mol% or more, the ratio of the structural unit (B-1) in the structural unit B being 45 mol% or more and 85 mol% or less, the structural unit B comprising a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, the structural unit A beingThe ratio of the structural unit (B-2) in (A) is 15 to 55 mol%. (in the formula (b-2), R independently represents a hydrogen atom, a fluorine atom or a methyl group.)
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 applications are being studied in the fields of electric/electronic components and the like. For example, it is desirable to replace a glass substrate used for an image display device such as a liquid crystal display or an OLED display with a plastic substrate for the purpose of weight reduction and flexibility of the device, and a polyimide resin suitable as the plastic material has been studied. The polyimide resin for such applications is also required to have colorless transparency, and further required to have high dimensional stability against heat (i.e., a low linear thermal expansion coefficient) in order to be able to cope with a high-temperature process in the production process of an image display device.
As a polyimide resin having a low linear thermal expansion coefficient, for example, patent document 1 describes a polyimide resin synthesized from a first tetracarboxylic acid component such as pyromellitic dianhydride, a second tetracarboxylic acid component such as 3,3 ', 4, 4' -diphenylsulfone tetracarboxylic dianhydride, and a toluidine sulfone skeleton diamine component, and patent document 2 describes a polyimide resin synthesized from a diamine compound containing a benzoxazolyl group and an aromatic tetracarboxylic acid dianhydride.
Documents of the prior art
Patent document
Patent document 1: japanese patent application laid-open No. 2010-053336
Patent document 2: japanese laid-open patent publication No. 2015-093915
Disclosure of Invention
Problems to be solved by the invention
Generally, polyimide resins are excellent in mechanical properties and heat resistance, but the structure of polyimide resins has been changed to improve colorless transparency and further to improve dimensional stability against heat, and as a result, these properties may be impaired.
The present invention addresses the problem of providing a polyimide resin that has good mechanical properties and heat resistance, and that has excellent colorless transparency and dimensional stability to heat.
Means for solving the problems
The present inventors have found that a polyimide resin containing a combination of specific structural units at a specific ratio can solve the above problems, and have completed the present invention.
That is, the present invention relates to the following [1] to [5 ].
[1] A polyimide resin comprising a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine,
the structural unit A comprises a structural unit (A-1) derived from a compound represented by the following formula (a-1),
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) derived from a compound represented by the following formula (B-2),
the proportion of the structural unit (A-1) in the structural unit A is 50 mol% or more,
the proportion of the structural unit (B-1) in the structural unit B is 45 mol% or more and 85 mol% or less,
the proportion of the structural unit (B-2) in the structural unit B is 15 mol% or more and 55 mol% or less.
(in the formula (b-2), R independently represents a hydrogen atom, a fluorine atom or a methyl group.)
[2] The polyimide resin according to [1], wherein the proportion of the structural unit (A-1) in the structural unit A is 100 mol%.
[3] The polyimide resin according to the above [1] or [2], wherein R represents a hydrogen atom.
[4] A polyimide varnish obtained by dissolving the polyimide resin according to any one of the above [1] to [3] in an organic solvent.
[5] A polyimide film comprising the polyimide resin according to any one of the above [1] to [3 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The polyimide resin of the present invention is excellent in mechanical properties and heat resistance, and is excellent in colorless transparency and dimensional stability against heat.
Detailed Description
[ polyimide resin ]
The polyimide resin of the present invention comprises a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, the structural unit A comprising a structural unit (A-1) derived from a compound represented by the following formula (a-1), and the structural unit B comprising a structural unit (B-1) derived from a compound represented by the following formula (B-1) and a structural unit (B-2) derived from a compound represented by the following formula (B-2). The ratio of the structural unit (A-1) in the structural unit A is 50 mol% or more, the ratio of the structural unit (B-1) in the structural unit B is 45 mol% or more and 85 mol% or less, and the ratio of the structural unit (B-2) in the structural unit B is 15 mol% or more and 55 mol% or less.
(in the formula (b-2), R independently represents a hydrogen atom, a fluorine atom or a methyl group.)
< structural unit A >)
The structural unit A is a structural unit derived from a tetracarboxylic dianhydride and comprises a structural unit (A-1) derived from a compound represented by the formula (a-1) the compound represented by the formula (a-1) is norbornane-2-spiro- α -cyclopentanone- α '-spiro-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride, and the structural unit A comprises the structural unit (A-1), whereby the heat resistance, the colorless transparency and the dimensional stability are improved.
The proportion of the structural unit (A-1) in the structural unit A is 50 mol% or more. When the proportion of the structural unit (A-1) is less than 50 mol%, there is a possibility that heat resistance, colorless transparency and dimensional stability are deteriorated. The proportion of the structural unit (A-1) is preferably 70 mol% or more, more preferably 90 mol% or more. The upper limit of the content ratio of the structural unit (A-1) is not particularly limited, i.e., 100 mol%. The structural unit A may be composed of only the structural unit (A-1).
The structural unit A may contain a structural unit other than the structural unit (A-1). The tetracarboxylic dianhydrides forming the structural units other than the structural unit (a-1) are not particularly limited, and examples thereof include aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride, 3 ', 4,4 ' -biphenyltetracarboxylic dianhydride, and 4,4 ' - (hexafluoroisopropylidene) diphthalic anhydride; alicyclic tetracarboxylic dianhydrides such as 1,2,3, 4-cyclobutanetetracarboxylic dianhydride and 1,2,4, 5-cyclohexanetetracarboxylic 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 no aromatic rings and no alicyclic rings.
The structural unit (a) may be any of 1 or 2 or more structural units contained in the structural unit a (i.e., structural units other than the structural unit (a-1)).
< structural unit B >
The structural unit B is a diamine-derived structural unit and comprises a structural unit (B-1) derived from the compound represented by the formula (B-1) and a structural unit (B-2) derived from the compound represented by the formula (B-2).
The compound represented by the formula (b-1) is 2, 2' -bis (trifluoromethyl) benzidine. By including the structural unit (B-1) in the structural unit B, mechanical characteristics and dimensional stability are improved.
In the formula (b-2), each R is independently selected from the group consisting of a hydrogen atom, a fluorine atom and a methyl group, and is preferably a hydrogen atom. Examples of the compound represented by the formula (b-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. By including the structural unit (B-2) in the structural unit B, heat resistance is improved.
The proportion of the structural unit (B-1) in the structural unit B is 45 mol% or more and 85 mol% or less. When the ratio of the structural unit (B-1) is less than 45 mol%, there is a fear that mechanical properties and/or dimensional stability are deteriorated, and when it exceeds 85%, there is a fear that heat resistance is deteriorated. The proportion of the structural unit (B-1) is preferably 50 mol% or more and 80 mol% or less.
The proportion of the structural unit (B-2) in the structural unit B is 15 mol% or more and 55 mol% or less. When the ratio of the structural unit (B-1) is less than 15 mol%, the heat resistance may deteriorate, and when it exceeds 55%, the mechanical properties and/or dimensional stability may deteriorate. The proportion of the structural unit (B-2) is preferably 20 mol% or more and 50 mol% or less.
The total content ratio of the structural unit (B-1) and the structural unit (B-2) in the structural unit B is 60 mol% or more, preferably 70 mol% or more, and more preferably 80% or more. The upper limit of the total content ratio of the structural unit (B-1) and the structural unit (B-2) is not particularly limited, i.e., 100 mol%. The structural unit B may be composed of only the structural unit (B-1) and the structural unit (B-2).
The diamine forming such a structural unit may include structural units other than the structural units (B-1) and (B-2), and examples thereof include, but are not particularly limited to, 1, 4-phenylenediamine, p-xylylenediamine, 3, 5-diaminobenzoic acid, 2 ' -dimethylbiphenyl-4, 4 ' -diamine, 4 ' -diaminodiphenyl ether, 4 ' -diaminodiphenylmethane, 2-bis (4-aminophenyl) hexafluoropropane, bis (4-aminophenyl) sulfone, 4 ' -diaminobenzanilide, 1- (4-aminophenyl) -2, 3-dihydro-1, 3, 3-trimethyl-1H-indene-5-amine, α ' -bis (4-aminophenyl) -1, 4-diisopropylbenzene, N ' -bis (4-aminophenyl) terephthalamide, 4 ' -bis (4-aminophenoxy) biphenyl, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane and 2, 2-bis (4-aminophenoxy) p-phenylene), 4 ' -bis (4-aminophenoxy) benzene, 2-diamine, and aliphatic diamines such as those represented by formula (B), and aliphatic diamines such as represented by formula (B), and (2, 2-bis (4-aminophenyl) hexamethylenediamine represented by formula (B), and alicyclic diamine represented by formula (B), and (1, 4-methyl) cyclohexane, 2-bis (B).
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 arbitrarily contained in the structural unit B, that is, the structural units other than the structural units (B-1) and (B-2), may be 1 kind or 2 or more kinds.
The polyimide resin of the present invention preferably has a number average molecular weight of 5000 to 100000 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 has good mechanical properties and heat resistance, and is excellent in colorless transparency and dimensional stability against heat, and thus can have the following physical property values.
The tensile strength of the polyimide resin of the present invention is preferably 80MPa or more, more preferably 85MPa or more, still more preferably 90MPa or more, and particularly preferably 95MPa or more.
The tensile modulus of the polyimide resin of the present invention is preferably 2.2GPa or more, more preferably 2.4GPa or more, still more preferably 2.5GPa or more, and particularly preferably 2.8GPa or more.
The glass transition temperature (Tg) of the polyimide resin of the present invention is preferably 350 ℃ or higher, more preferably 380 ℃ or higher, still more preferably 400 ℃ or higher, and particularly preferably 430 ℃ or higher.
The polyimide resin of the present invention has a total light transmittance of preferably 85% or more, more preferably 88% or more, further preferably 90% or more, and particularly preferably 91% or more, when formed into a polyimide film having a thickness of 10 μm.
The polyimide resin of the present invention has a Yellowness Index (YI) of preferably 3.0 or less, more preferably 2.0 or less, still more preferably 1.5 or less, and particularly preferably 1.2 or less when formed into a polyimide film having a thickness of 10 μm.
The polyimide resin of the present invention has a coefficient of linear thermal expansion (CTE) of preferably 25 ppm/DEG C or less, more preferably 20 ppm/DEG C or less, still more preferably 15 ppm/DEG C or less, and particularly preferably 10 ppm/DEG C or less, as the CTE of 100 to 200 ℃; the CTE of 100 to 350 ℃ is preferably 30 ppm/DEG C or less, more preferably 25 ppm/DEG C or less, still more preferably 20 ppm/DEG C or less, and particularly preferably 15 ppm/DEG C or less.
In the present invention, the tensile modulus, tensile strength, glass transition temperature (Tg), total light transmittance, Yellowness Index (YI), and coefficient of linear thermal expansion (CTE) 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 diamine component with a tetracarboxylic acid component containing a compound that imparts the structural unit (a-1); the diamine component contains a compound that imparts the structural unit (B-1) and a compound that imparts the structural unit (B-2).
Examples of the compound to be added to the structural unit (A-1) include the compounds represented by the formula (a-1), but are not limited thereto and may be derivatives thereof insofar as they can form the same structural unit.A tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a-1) (i.e., norbornane-2-spiro- α -cyclopentanone- α '-spiro-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic acid) and an alkyl ester of the tetracarboxylic acid are mentioned as the derivative.A compound to be added to the structural unit (A-1) is preferably the compound represented by the formula (a-1) (i.e., dianhydride).
The compound to which the structural unit (B-1) is added may be a compound represented by the formula (B-1), but is not limited thereto, and may be a derivative thereof insofar as the same structural unit can be formed. As the derivative, a diisocyanate corresponding to the diamine represented by the formula (b-1) can be mentioned. As the compound to which the structural unit (B-1) is imparted, a compound represented by the formula (B-1) (i.e., diamine) is preferable.
The compound to which the structural unit (B-2) is added is not limited to the compound represented by the formula (B-2), and may be a derivative thereof insofar as the same structural unit can be formed. As the derivative, a diisocyanate corresponding to the diamine represented by the formula (b-2) can be mentioned. As the compound to which the structural unit (B-2) is imparted, a compound represented by the formula (B-2) (i.e., diamine) is preferable.
The tetracarboxylic acid component contains 50 mol% or more of the compound that imparts the structural unit (A-1), preferably 70 mol% or more, and more preferably 90 mol% or more. The upper limit of the content ratio of the compound to be imparted to the structural unit (A-1) is not particularly limited, i.e., 100 mol%. The tetracarboxylic acid component may be composed of only the compound having the structural unit (A-1).
The tetracarboxylic acid component may contain a compound other than the compound that imparts 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 compound (i.e., a compound other than the compound imparting the structural unit (A-1)) optionally contained in the tetracarboxylic acid component may be 1 or 2 or more.
The diamine component contains 45 to 85 mol% of the compound that imparts the structural unit (B-1), and preferably 50 to 80 mol%. The diamine component contains 15 to 55 mol% of the compound having the structural unit (B-2), and preferably 20 to 50 mol%.
The diamine component contains 60 mol% or more of the compound having the structural unit (B-1) and the compound having the structural unit (B-2) in total, preferably 70 mol% or more, and more preferably 80 mol% or more. The upper limit of the total content ratio of the compound having the structural unit (B-1) and the compound having the structural unit (B-2) is not particularly limited, that is, 100 mol%. The diamine component may be composed of only the compound having the structural unit (B-1) and the compound having the structural unit (B-2).
The diamine component may contain compounds other than the compound having the structural unit (B-1) and the compound having 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 number of compounds (i.e., compounds other than the compound providing the structural unit (B-1) and the compound providing the structural unit (B-2)) optionally contained in the diamine component may be 1 or 2 or more.
In the present invention, the input amount ratio of the tetracarboxylic acid component and the diamine component for producing the polyimide resin is preferably: the diamine component is 0.9 to 1.1 mol relative to 1 mol of the tetracarboxylic acid component.
In the present invention, in the production of the polyimide resin, an end-capping agent may be used in addition to the tetracarboxylic acid component and the diamine component. 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. Of these, benzylamine and aniline can be suitably used. As the dicarboxylic acid-based end capping agent, dicarboxylic acids are preferred, and a part of the ring may be 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 put into a reactor, stirred at room temperature to 80 ℃ for 0.5 to 30 hours, and then heated to carry out imidization; (2) a method in which a diamine component and a reaction solvent are put into a reactor to be dissolved, and then a tetracarboxylic acid component is put into the reactor, and the mixture is stirred at room temperature to 80 ℃ for 0.5 to 30 hours as required, and then heated to carry out imidization; (3) a method in which a tetracarboxylic acid component, a diamine component and a reaction solvent are charged into a reactor, and the temperature is immediately raised to effect imidization.
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 2-methoxy-1-methylethyl) acetate.
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 use a dean-Stark trap or the like, and the reaction is carried out while removing the water produced during the production. By performing such an operation, the degree of polymerization and the imidization ratio can be further increased.
The imidization reaction may use a known imidization catalyst. Examples of the imidization catalyst include a basic catalyst and an acid catalyst.
Examples of the basic catalyst include organic basic catalysts such as pyridine, quinoline, isoquinoline, α -methylpyridine, β -methylpyridine, 2, 4-lutidine, 2, 6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, imidazole, N-dimethylaniline and N, N-diethylaniline, and inorganic basic 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, o-hydroxybenzoic acid, terephthalic acid, benzenesulfonic acid, p-toluenesulfonic acid, and naphthalenesulfonic acid. The imidization catalyst may be used singly or in combination of two or more.
Among the above, from the viewpoint of handling properties, a basic catalyst is preferably used, an organic basic catalyst is more preferably used, triethylamine is further preferably used, and triethylamine and triethylenediamine are particularly preferably used in combination.
The temperature of the imidization reaction is preferably 120 to 250 ℃ and more preferably 160 to 200 ℃ from the viewpoints of the reaction rate, the suppression of gelation, and the like. The reaction time is preferably 0.5 to 10 hours after the start of distillation to produce 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 is not particularly limited as long as it dissolves the polyimide resin, and as a reaction solvent for producing the polyimide resin, two or more of the above-mentioned compounds are preferably used alone or in combination.
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 5 to 150 pas.
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 used.
[ 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 mechanical properties and heat resistance, and is excellent in colorless transparency and dimensional stability against heat.
The method for producing the polyimide film of the present invention is not particularly limited, and a known method can be used. For example, a method of applying or molding the polyimide varnish of the present invention in a film form and then removing the organic solvent may be mentioned.
The polyimide film of the present invention is excellent in mechanical properties and heat resistance, and excellent in colorless transparency and dimensional stability against heat, and therefore can be suitably used as a film for various members such as color filters, flexible displays, semiconductor members, and optical members. The polyimide film of the present invention can be particularly suitably used 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 described in detail with reference to examples. The present invention is not limited to these examples.
The solid content concentration of the polyimide varnish obtained in the examples and comparative examples and the physical properties of the polyimide film were measured by the following methods.
(1) Concentration of solid component
For the measurement of the solid content concentration of the polyimide varnish, a sample was heated at 320 ℃ for 120 minutes by a small electric furnace "MMF-1" manufactured by AS ONE Corporation, and the measurement was calculated based on the mass difference between the sample before and after heating.
(2) Thickness of film
The film thickness was measured using a micrometer manufactured by Mitutoyo Corporation.
(3) Tensile Strength and tensile modulus
The measurement was carried out in accordance with JIS K7127 using a tensile tester "StrographVG-1E" manufactured by Toyo Seiki Kagaku K.K.
(4) Glass transition temperature (Tg)
The residual stress was removed by heating to Tg or higher under the 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/SS 6100" manufactured by Hitachi High-Tech Science Corporation, and then TMA measurement was performed under the same conditions from 50 ℃ to 500 ℃ to determine Tg.
(5) Total light transmittance, Yellow Index (YI)
According to JIS K7361-1, the measurement was carried out using a color/turbidity simultaneous measurement apparatus "COH 400" manufactured by Nippon Denshoku industries Co., Ltd.
(6) Coefficient of linear thermal expansion (CTE)
TMA measurement was performed in a tensile mode under conditions of a specimen size of 2mm × 20mm, a load of 0.1N, and a temperature rise rate of 10 ℃/min using a thermomechanical analyzer "TMA/SS 6100" manufactured by Hitachi High-Tech Science Corporation, and the CTE of 100 to 200 ℃ and the CTE of 100 to 350 ℃ were determined.
< example 1 >
A300 mL 5-neck round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube, a dean-Stark trap equipped with a cooling tube, a thermometer, and a glass end cap was charged with 16.012g (0.050 mol) of 2, 2' -bis (trifluoromethyl) benzidine (manufactured by Hill Seiki Kaisha), 17.423g (0.050 mol) of 9, 9-bis (4-aminophenyl) fluorene (manufactured by Taoka chemical Co., Ltd.) and 85.688g of γ -butyrolactone (manufactured by Mitsubishi chemical Co., Ltd.) and stirred at a system internal temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution, 38.438g (0.100 mol) of norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6,6 "-tetracarboxylic dianhydride (manufactured by JX energy corporation) and 21.422g of γ -butyrolactone (manufactured by mitsubishi chemical corporation) were added at once, and then 0.506g of triethylamine (manufactured by kanto chemical corporation) and 0.056g of triethylenediamine (manufactured by tokyo chemical corporation) were added as imidization catalysts, and heating was performed by a jacketed resistance heater (mantle heater) for about 20 minutes to raise the internal temperature of the reaction system to 190 ℃.
Then, 169.87g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added, the internal temperature of the reaction system was cooled to 120 ℃, and the mixture was stirred for about 3 hours to be homogenized, thereby obtaining a polyimide varnish having a solid content of 20 mass%. Subsequently, the obtained polyimide varnish was coated on a glass plate, and the plate was kept at 80 ℃ for 20 minutes, and then heated at 400 ℃ for 30 minutes in a hot air dryer under a nitrogen atmosphere to evaporate the solvent, thereby obtaining a film having a thickness of 10 μm. The results are shown in Table 1.
< example 2 >
Into a 300mL 5-neck round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube, a dean-stark trap equipped with a cooling tube, a thermometer, and a glass end cap were charged 25.619g (0.080 mol) of 2,2 '-bis (trifluoromethyl) benzidine (manufactured by singham's industries co., ltd.), 6.969g (0.020 mol) of 9, 9-bis (4-aminophenyl) fluorene (manufactured by Taoka chemical co., ltd.), and 86.703g of γ -butyrolactone (manufactured by mitsubishi chemical corporation), and the mixture was stirred at a system internal temperature of 70 ℃ and a rotation speed of 200rpm in a nitrogen atmosphere to obtain a solution.
To this solution, 38.438g (0.100 mol) of norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6,6 "-tetracarboxylic dianhydride (manufactured by JX energy corporation) and 21.676g of γ -butyrolactone (manufactured by mitsubishi chemical corporation) were added at once, and then 0.506g of triethylamine (manufactured by kanto chemical corporation) and 0.056g of triethylenediamine (manufactured by tokyo chemical corporation) were added as imidization catalysts, and heating was performed by a jacketed resistance heater for about 20 minutes to raise the internal temperature of the reaction system to 190 ℃.
Then, 169.82g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added, the internal temperature of the reaction system was cooled to 120 ℃, and the mixture was stirred for about 3 hours to be homogenized, thereby obtaining a polyimide varnish having a solid content of 20 mass%. The obtained polyimide varnish was coated on a glass plate, and the plate was kept at 80 ℃ for 20 minutes, and then heated at 400 ℃ for 30 minutes in a hot air dryer under a nitrogen atmosphere to evaporate the solvent, thereby obtaining a film having a thickness of 10 μm. The results are shown in Table 1.
< example 3 >
Into a 300mL 5-neck round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube, a dean-stark trap equipped with a cooling tube, a thermometer, and a glass end cap were charged 22.417g (0.070 mol) of 2,2 '-bis (trifluoromethyl) benzidine (manufactured by singham's industries co., ltd.), 10.454g (0.030 mol) of 9, 9-bis (4-aminophenyl) fluorene (manufactured by Taoka chemical co., ltd.), and 85.570g of γ -butyrolactone (manufactured by mitsubishi chemical corporation), and the mixture was stirred at a system internal temperature of 70 ℃ and a rotation speed of 200rpm in a nitrogen atmosphere to obtain a solution.
To this solution, 38.438g (0.100 mol) of norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6,6 "-tetracarboxylic dianhydride (manufactured by JX energy corporation) and 21.392g of γ -butyrolactone (manufactured by mitsubishi chemical corporation) were added at once, and then 0.506g of triethylamine (manufactured by kanto chemical corporation) and 0.056g of triethylenediamine (manufactured by tokyo chemical corporation) were added as imidization catalysts, and heating was performed by a jacketed resistance heater for about 20 minutes to raise the internal temperature of the reaction system to 190 ℃.
Then, gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) 163.855 was added to the reaction system, and after the internal temperature of the reaction system was cooled to 120 ℃, the reaction system was stirred for about 3 hours to homogenize the reaction system, thereby obtaining a polyimide varnish having a solid content of 20 mass%. The obtained polyimide varnish was coated on a glass plate, and the plate was kept at 80 ℃ for 20 minutes, and then heated at 400 ℃ for 30 minutes in a hot air dryer under a nitrogen atmosphere to evaporate the solvent, thereby obtaining a film having a thickness of 10 μm. The results are shown in Table 1.
< comparative example 1 >
Into a 300mL 5-neck round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube, a dean-stark trap equipped with a cooling tube, a thermometer, and a glass end cap were charged 34.845g (0.100 mol) of 9, 9-bis (4-aminophenyl) fluorene (manufactured by taoka chemical co., ltd.) and 88.395g of γ -butyrolactone (manufactured by mitsubishi chemical corporation) and the mixture was stirred at a system internal temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution, 38.438g (0.100 mol) of norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6,6 "-tetracarboxylic dianhydride (manufactured by JX energy corporation) and 22.099g of γ -butyrolactone (manufactured by mitsubishi chemical corporation) were added at once, and then 0.506g of triethylamine (manufactured by kanto chemical corporation) and 0.056g of triethylenediamine (manufactured by tokyo chemical corporation) were added as imidization catalysts, and heating was performed by a jacketed resistance heater for about 20 minutes to raise the internal temperature of the reaction system to 190 ℃.
Then, 169.74g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added, the internal temperature of the reaction system was cooled to 120 ℃, and the mixture was stirred for about 3 hours to be homogenized, thereby obtaining a polyimide varnish having a solid content of 20 mass%. The obtained polyimide varnish was coated on a glass plate, and the plate was kept at 80 ℃ for 20 minutes, and then heated at 400 ℃ for 30 minutes in a hot air dryer under a nitrogen atmosphere to evaporate the solvent, thereby obtaining a film having a thickness of 10 μm. The results are shown in Table 1.
< comparative example 2 >
Into a 300mL 5-neck round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube, a dean-stark trap equipped with a cooling tube, a thermometer, and a glass end cap were charged 3.202g (0.010 mol) of 2,2 '-bis (trifluoromethyl) benzidine (manufactured by singham's industries co., ltd.), 31.361g (0.090 mol) of 9, 9-bis (4-aminophenyl) fluorene (manufactured by Taoka chemical co., ltd.) and 87.601g of γ -butyrolactone (manufactured by mitsubishi chemical corporation), and the mixture was stirred at a system internal temperature of 70 ℃ and a rotation speed of 200rpm in a nitrogen atmosphere to obtain a solution.
To this solution, 38.438g (0.100 mol) of norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6,6 "-tetracarboxylic dianhydride (manufactured by JX energy corporation) and 21.900 g of γ -butyrolactone (manufactured by mitsubishi chemical corporation) were added at once, and then 0.506g of triethylamine (manufactured by kanto chemical corporation) and 0.056g of triethylenediamine (manufactured by tokyo chemical corporation) were added as imidization catalysts, and heating was performed by a jacketed resistance heater for about 20 minutes to raise the internal temperature of the reaction system to 190 ℃.
Then, 168.086g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added, the internal temperature of the reaction system was cooled to 120 ℃, and the mixture was stirred for about 3 hours to be homogenized, thereby obtaining a polyimide varnish having a solid content of 20 mass%. The obtained polyimide varnish was coated on a glass plate, and the plate was kept at 80 ℃ for 20 minutes, and then heated at 400 ℃ for 30 minutes in a hot air dryer under a nitrogen atmosphere to evaporate the solvent, thereby obtaining a film having a thickness of 10 μm. The results are shown in Table 1.
< comparative example 3 >
Into a 300mL 5-neck round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube, a dean-stark trap equipped with a cooling tube, a thermometer, and a glass end cap were charged 9.607g (0.030 mol) of 2,2 '-bis (trifluoromethyl) benzidine (manufactured by singham's industries co., ltd.), 24.392g (0.070 mol) of 9, 9-bis (4-aminophenyl) fluorene (manufactured by Taoka chemical co., ltd.), and 86.924g of γ -butyrolactone (manufactured by mitsubishi chemical corporation), and the mixture was stirred at a system internal temperature of 70 ℃ and a rotation speed of 200rpm in a nitrogen atmosphere to obtain a solution.
To this solution, 38.438g (0.100 mol) of norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6,6 "-tetracarboxylic dianhydride (manufactured by JX energy corporation) and 21.731g of γ -butyrolactone (manufactured by mitsubishi chemical corporation) were added at once, and then 0.506g of triethylamine (manufactured by kanto chemical corporation) and 0.056g of triethylenediamine (manufactured by tokyo chemical corporation) were added as imidization catalysts, and heating was performed by a jacketed resistance heater for about 20 minutes to raise the internal temperature of the reaction system to 190 ℃.
Then, 166.676g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added, the internal temperature of the reaction system was cooled to 120 ℃, and the mixture was stirred for about 3 hours to be homogenized, thereby obtaining a polyimide varnish having a solid content of 20 mass%. The obtained polyimide varnish was coated on a glass plate, and the plate was kept at 80 ℃ for 20 minutes, and then heated at 400 ℃ for 30 minutes in a hot air dryer under a nitrogen atmosphere to evaporate the solvent, thereby obtaining a film having a thickness of 10 μm. The results are shown in Table 1.
[ Table 1]
TABLE 1
Abbreviations in the table are as follows.
CpODA norbornane-2-spiro- α -cyclopentanone- α '-spiro-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride (Compound represented by the formula (a-1))
TFMB: 2, 2' -bis (trifluoromethyl) benzidine (Compound represented by the formula (b-1))
BAFL: 9, 9-bis (4-aminophenyl) fluorene (compound represented by the formula (b-2))
As shown in Table 1, the polyimide films of examples 1 to 3 were excellent in mechanical properties and heat resistance, and were excellent in colorless transparency and dimensional stability against heat. On the other hand, the polyimide films of comparative examples 1 to 3 are excellent in heat resistance, but very poor in dimensional stability against heat.
Claims (5)
1. A polyimide resin comprising a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine,
the structural unit A comprises a structural unit (A-1) derived from a compound represented by the following formula (a-1),
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) derived from a compound represented by the following formula (B-2),
the proportion of the structural unit (A-1) in the structural unit A is 50 mol% or more,
the proportion of the structural unit (B-1) in the structural unit B is 45 mol% or more and 85 mol% or less,
the proportion of the structural unit (B-2) in the structural unit B is 15 mol% or more and 55 mol% or less,
in the formula (b-2), R independently represents a hydrogen atom, a fluorine atom or a methyl group.
2. The polyimide resin according to claim 1, wherein the proportion of the structural unit (a-1) in the structural unit a is 100 mol%.
3. The polyimide resin according to claim 1 or 2, wherein R represents a hydrogen atom.
4. A polyimide varnish obtained by dissolving the polyimide resin according to any one of claims 1 to 3 in an organic solvent.
5. A polyimide film comprising the polyimide resin according to any one of claims 1 to 3.
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| CN113372554A (en) * | 2021-06-10 | 2021-09-10 | 中国科学院宁波材料技术与工程研究所 | Semi-alicyclic polyimide and application of film thereof in gas separation |
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| KR20200052309A (en) | 2020-05-14 |
| TW201920370A (en) | 2019-06-01 |
| CN111133034B (en) | 2022-08-09 |
| JP7255489B2 (en) | 2023-04-11 |
| TWI774848B (en) | 2022-08-21 |
| WO2019065522A1 (en) | 2019-04-04 |
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