CN116134071A - Polyimide resin, polyimide varnish and polyimide film - Google Patents
Polyimide resin, polyimide varnish and polyimide film Download PDFInfo
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Abstract
A polyimide resin having a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, wherein the structural unit A comprises a structural unit (A1) derived from 9, 9-bis (3, 4-dicarboxyphenyl) fluorenoic acid dianhydride and a structural unit (A2) derived from an aliphatic tetracarboxylic dianhydride, and the structural unit B comprises a structural unit (B1) derived from 2,2 '-bis (trifluoromethyl) -4,4' -diaminodiphenyl ether.
Description
Technical Field
The present invention relates to a polyimide resin, a polyimide varnish and a polyimide film.
Background
Polyimide resins are obtained from aromatic tetracarboxylic acid anhydrides and aromatic diamines, and generally have excellent heat resistance, chemical resistance, mechanical properties, and electrical characteristics due to the rigidity, resonance stabilization, and strong chemical bond of molecules, and therefore are widely used in the fields of molding materials, composite materials, electric/electronic parts, optical materials, displays, aerospace, and the like.
In particular, glass materials that have been used for electric/electronic parts, optical materials, displays, and the like have been studied for application to flexible devices by taking advantage of softness.
For example, patent document 1 discloses a composition for forming a flexible device substrate, which comprises a polyimide that is a reactant of a tetracarboxylic dianhydride component including an alicyclic tetracarboxylic dianhydride and a diamine component including a fluorinated aromatic diamine, and an organic solvent, for the purpose of improving heat resistance, retardation, flexibility, and transparency.
Prior art literature
Patent literature
Patent document 1: international publication No. 2018/097143
Disclosure of Invention
Problems to be solved by the invention
In recent years, polyimide resins have been particularly used for displays and front panels for protecting the displays, and polyimide resins having high mechanical strength have been demanded in order to replace glass materials used in the past. However, the flexibility of the high-strength polyimide resin is insufficient.
Recently, polyimide films have been used also as displays and protective plates for smart phones having a folded structure, and therefore, they are required to have high strength, higher flexibility, and properties such as shape recovery after deformation and film elongation.
Accordingly, polyimide resins having both of these properties are desired.
That is, an object of the present invention is to provide a polyimide resin capable of forming a film having high strength and excellent in recovery from deformation and elongation, and a polyimide film having high strength and excellent in recovery from deformation and elongation.
Solution for solving the problem
As a result of intensive studies, the inventors have found that a polyimide resin containing a combination of specific structural units can solve the above-mentioned problems, and have achieved the present invention.
That is, the present invention relates to the following [1] to [12].
[1] A polyimide resin having a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, wherein the structural unit A comprises a structural unit (A1) derived from a compound represented by the following formula (A1) and a structural unit (A2) derived from an aliphatic tetracarboxylic dianhydride, and the structural unit B comprises a structural unit (B1) derived from a compound represented by the following formula (B1).
[2] The polyimide resin according to the above [1], wherein the structural unit (A2) is a structural unit derived from alicyclic tetracarboxylic dianhydride.
[3] The polyimide resin according to the above [1] or [2], wherein the structural unit (A2) comprises at least one selected from the group consisting of a structural unit (A2-1) derived from a compound represented by the following formula (A2-1) and a structural unit (A2-2) derived from a compound represented by the following formula (A2-2).
[4] The polyimide resin according to the aforementioned [3], wherein the structural unit (A2) comprises the structural unit (A2-1).
[5] The polyimide resin according to the aforementioned [3], wherein the structural unit (A2) contains the structural unit (A2-2).
[6] The polyimide resin according to any one of the above [1] to [5], wherein the ratio of the total of the structural units (A1) and (A2) relative to the structural unit A is 50 mol% or more.
[7] The polyimide resin according to any one of the above [1] to [6], wherein the molar ratio [ (A1)/(A2) ] of the structural unit (A1) to the structural unit (A2) in the structural unit A is 20/80 to 99/1.
[8] The polyimide resin according to the above [4], wherein the molar ratio [ (A1)/(A2-1) ] of the structural unit (A1) to the structural unit (A2-1) is 50/50 to 95/5.
[9] The polyimide resin according to [5], wherein the molar ratio [ (A1)/(A2-2) ] of the structural unit (A1) to the structural unit (A2-2) in the structural unit A is 20/80 to 50/50.
[10] The polyimide resin according to any one of the above [1] to [9], wherein the proportion of the structural unit (B1) to the structural unit B is 60 mol% or more.
[11] A polyimide varnish prepared by dissolving the polyimide resin according to any one of the above [1] to [10] in an organic solvent.
[12] A polyimide film comprising the polyimide resin according to any one of the foregoing [1] to [10 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a polyimide resin which can form a film having high strength and excellent recovery from deformation and elongation, a polyimide varnish containing the polyimide resin, and a polyimide film having high strength and excellent recovery from deformation and elongation can be provided.
Drawings
FIG. 1 is a schematic view showing a method for measuring the deformation recovery of a polyimide film.
Detailed Description
[ polyimide resin ]
The polyimide resin of the present invention is a polyimide resin having a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from diamine,
the structural unit a includes a structural unit (A1) derived from a compound represented by the following formula (A1) and a structural unit (A2) derived from an aliphatic tetracarboxylic dianhydride, and the structural unit B includes a structural unit (B1) derived from a compound represented by the following formula (B1).
Hereinafter, the polyimide resin of the present invention will be described.
(structural unit A)
The structural unit a contained in the polyimide of the present invention is a structural unit derived from tetracarboxylic dianhydride, which is contained in a polyimide resin.
The structural unit A includes a structural unit (A1) derived from the compound represented by the aforementioned formula (A1) and a structural unit (A2) derived from an aliphatic tetracarboxylic dianhydride.
The compound represented by the above formula (a 1) is 9, 9-bis (3, 4-dicarboxyphenyl) fluorenoic acid dianhydride (BPAF).
By including the structural unit (A1) in the structural unit a, the mechanical strength of the obtained polyimide resin is improved.
The structural unit (A2) is a structural unit derived from an aliphatic tetracarboxylic dianhydride, and the structural unit (A2) preferably contains a structural unit derived from an alicyclic tetracarboxylic dianhydride, more preferably contains a structural unit derived from a tetracarboxylic dianhydride having an alicyclic ring having 4 to 15 carbon atoms. By including the structural unit derived from the tetracarboxylic dianhydride having an alicyclic structure, elongation is improved, and deformation recovery and transparency are improved.
In the present specification, the aliphatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing no aromatic ring, and the alicyclic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing 1 or more alicyclic rings.
Here, "alicyclic ring" means a cyclic aliphatic hydrocarbon structure other than an aromatic ring in the structure in which carbon atoms are bonded in a cyclic manner, and the number of carbon atoms of the alicyclic ring means the number of carbon atoms constituting the ring.
Specific examples of the alicyclic tetracarboxylic dianhydride include 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, norbornane-2-spiro- α -cyclopentanone- α '-spiro-2' -norbornane-5, 5", 6" -tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, dicyclohexyltetracarboxylic dianhydride, and positional isomers thereof.
Specific examples of aliphatic tetracarboxylic dianhydrides other than alicyclic tetracarboxylic dianhydrides include 1,2,3, 4-butane tetracarboxylic dianhydride, and the like.
Among them, as the structural unit (A2) derived from the aliphatic tetracarboxylic dianhydride, at least one selected from the structural unit (A2-1) derived from the compound represented by the following formula (A2-1) and the structural unit (A2-2) derived from the compound represented by the following formula (A2-2) is preferably contained, and at least one selected from the structural unit (A2-1) derived from the compound represented by the following formula (A2-1) and the structural unit (A2-2) derived from the compound represented by the following formula (A2-2) is more preferably contained.
The compound represented by the above formula (a 2-1) is 1,2,3, 4-cyclobutane tetracarboxylic dianhydride (CBDA).
The compound represented by the above formula (a 2-2) is 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (HPMDA).
Since the structural unit a includes the structural unit (A2), elongation is improved, and deformation recovery and transparency are improved.
In this way, the reason why the polyimide resin and the polyimide film of the present invention have high strength but excellent recovery from deformation and elongation is not clear, because the structural unit a derived from the structural unit of tetracarboxylic dianhydride has the structural units (A1) and (A2), but it is considered that the rigidity of the fluorenyl group and the degree of freedom of the aliphatic compound are due.
The proportion of the structural unit (A1) relative to the structural unit a is preferably 20 to 99 mol%, more preferably 30 to 97 mol%, still more preferably 40 to 96 mol%, still more preferably 50 to 95 mol%.
The proportion of the structural unit (A2) relative to the structural unit a is preferably 1 to 80 mol%, more preferably 3 to 70 mol%, still more preferably 4 to 60 mol%, still more preferably 5 to 50 mol%.
The ratio of the total of the structural units (A1) and (A2) in the structural unit a is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more. The upper limit of the total ratio of the structural units (A1) and (A2) is not particularly limited, but is 100 mol% or less. The structural unit a may be composed of only the structural unit (A1) and the structural unit (A2).
The molar ratio [ (A1)/(A2) ] of the structural unit (A1) to the structural unit (A2) in the structural unit A is preferably 20/80 to 99/1, more preferably 30/70 to 97/3, still more preferably 40/60 to 96/4, still more preferably 50/50 to 95/5, from the viewpoint of improving mechanical properties and deformation recovery.
Among them, from the viewpoint of improving the deformation recovery property in particular, 60/40 to 99/1 is preferable, 80/20 to 99/1 is more preferable, and 80/20 to 97/3 is still more preferable.
In particular, from the viewpoint of improving strength, it is preferably 60/40 to 99/1, more preferably 80/20 to 99/1, still more preferably 92/8 to 99/1.
From the viewpoint of further improving the elongation, it is preferably 20/80 to 92/8, more preferably 30/70 to 80/20, still more preferably 40/60 to 60/40.
The molar ratio [ (A1)/(A2-1) ] of the structural unit (A1) to the structural unit (A2-1) in the structural unit A is preferably 40/60 to 99/1, more preferably 45/55 to 96/4, still more preferably 50/50 to 95/5 from the viewpoint of improving mechanical properties and deformation recovery.
Among them, from the viewpoint of improving the deformation recovery property in particular, 60/40 to 99/1 is preferable, 80/20 to 99/1 is more preferable, and 80/20 to 97/3 is still more preferable.
In particular, from the viewpoint of improving strength, it is preferably 60/40 to 99/1, more preferably 80/20 to 99/1, still more preferably 92/8 to 99/1.
From the viewpoint of further improving the elongation, it is preferably 20/80 to 92/8, more preferably 30/70 to 80/20, still more preferably 40/60 to 60/40.
The molar ratio [ (A1)/(A2-2) ] of the structural unit (A1) to the structural unit (A2-2) in the structural unit A is preferably 20/80 to 99/1, more preferably 20/80 to 60/40, still more preferably 20/80 to 50/50 from the viewpoint of improving mechanical properties and recovery from deformation.
Among them, from the viewpoint of improving the recovery from deformation, it is preferable that 20/80 to 60/40, more preferable that 20/80 to 50/50, and still more preferable that 20/80 to 40/60 are used.
In particular, from the viewpoint of improving strength, it is preferably 20/80 to 92/8, more preferably 30/70 to 80/20, still more preferably 40/60 to 60/40.
From the viewpoint of further improving the elongation, it is preferably 20/80 to 92/8, more preferably 30/70 to 80/20, still more preferably 40/60 to 60/40.
The polyimide resin of the present invention may contain structural units derived from tetracarboxylic dianhydrides other than the structural unit (A1) and the structural unit (A2) in the structural unit a within a range that does not impair the effects of the present invention.
The tetracarboxylic dianhydrides providing the structural units other than the structural units (A1) and (A2) are not particularly limited, and examples thereof include aromatic tetracarboxylic dianhydrides such as pyromellitic anhydride, 2,3,5, 6-toluene tetracarboxylic dianhydride, and 1,4,5, 8-naphthalene tetracarboxylic dianhydride. They may be used singly or in combination of two or more.
In the present specification, the aromatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more aromatic rings.
Structural unit B
The structural unit B contained in the polyimide of the present invention is a structural unit derived from diamine.
The structural unit B includes a structural unit (B1) derived from a compound represented by the following formula (B1).
The compound represented by the above formula (b 1) is 2,2 '-bis (trifluoromethyl) -4,4' -diaminodiphenyl ether (6 FODA).
The structural unit B includes the structural unit (B1), and thus, in addition to physical properties such as transparency of the obtained polyimide resin, mechanical strength can be improved while maintaining elongation and deformation recovery.
The proportion of the structural unit (B1) relative to the structural unit B is preferably 30 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, still more preferably 60 mol% or more, still more preferably 70 mol% or more, still more preferably 90 mol% or more. The upper limit of the proportion of the structural unit (B1) is not particularly limited, but is 100 mol% or less. The structural unit B may be constituted only by the structural unit (B1).
The polyimide resin of the present invention may contain, as the structural unit other than the structural unit (B1), structural units derived from diamines other than the compounds represented by the general formula (B1) in the structural unit B within a range that does not impair the effects of the present invention.
The diamines other than the compounds represented by the above general formula (b 1) are not particularly limited, and examples thereof include 1, 4-phenylenediamine, paraxylylenediamine, 1, 5-diaminonaphthalene, 2 '-dimethylbiphenyl-4, 4' -diamine, 2 '-dimethylbiphenyl-4, 4' -diamine, 4 '-diaminodiphenylmethane, 1, 4-bis [2- (4-aminophenyl) -2-propyl ] benzene, 2-bis (4-aminophenyl) hexafluoropropane, 4' -diaminobenzanilide, aromatic diamines such as 1- (4-aminophenyl) -2, 3-dihydro-1, 3-trimethyl-1H-inden-5-amine, α '-bis (4-aminophenyl) -1, 4-diisopropylbenzene, N' -bis (4-aminophenyl) terephthalamide, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and 1, 4-bis (4-aminophenoxy) benzene; alicyclic diamines such as 1, 3-bis (aminomethyl) cyclohexane and 1, 4-bis (aminomethyl) cyclohexane; aliphatic diamines such as ethylenediamine and hexamethylenediamine; and modified silicone diamine. They may be used singly or in combination of two or more.
In the present specification, an aromatic diamine means a diamine containing 1 or more aromatic rings, an aliphatic diamine means a diamine containing no aromatic rings, and an alicyclic diamine means a diamine containing 1 or more alicyclic rings among the aliphatic diamines.
(characteristics of polyimide resin, etc.)
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 obtained polyimide film. The number average molecular weight of the polyimide resin can be measured by gel filtration chromatography or the like.
The polyimide resin of the present invention may be blended with various additives within a range that does not impair the effects of the present invention. Examples of the additives include antioxidants, light stabilizers, surfactants, flame retardants, plasticizers, and polymer compounds other than the polyimide resins.
Examples of the polymer compound include polyimide other than the polyimide resin of the present invention, polyester such as polycarbonate, polystyrene, polyamide, polyamideimide and polyethylene terephthalate, polyether sulfone, polycarboxylic acid, polyacetal, polyphenylene oxide, polysulfone, polybutene, polypropylene, polyacrylamide and polyvinyl chloride.
(method for producing polyimide resin)
The polyimide resin of the present invention can be produced by reacting a tetracarboxylic acid component comprising the compound providing the structural unit (A1) and the compound providing the structural unit (A2) with a diamine component comprising the compound providing the structural unit (B1).
The compound providing the structural unit (A1) may be a compound represented by the formula (A1), but is not limited thereto, and may be a derivative thereof within a range in which the same structural unit is provided. Examples of the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a 1) and an alkyl ester of the tetracarboxylic acid. As the compound providing the structural unit (A1), a compound represented by the formula (A1) (i.e., dianhydride) is preferable.
Similarly, the compound providing the structural unit (A2) may be an aliphatic tetracarboxylic dianhydride, preferably an alicyclic tetracarboxylic dianhydride, and more preferably a compound represented by the formula (A2-1) or the formula (A2-2), but the present invention is not limited thereto, and may be a derivative thereof within the range where the same structural unit is provided. The derivative of the compound represented by the formula (a 2-1) or the formula (a 2-2) includes a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a 2-1) or the formula (a 2-2) and an alkyl ester of the tetracarboxylic acid. As the compound providing the structural unit (A2), a compound represented by the formula (A2-1) or the formula (A2-2) (i.e., dianhydride) is preferable.
The tetracarboxylic acid component preferably contains 20 to 99 mol%, more preferably 30 to 97 mol%, still more preferably 40 to 96 mol%, still more preferably 50 to 95 mol% of the compound having the structural unit (A1) provided therein.
The tetracarboxylic acid component preferably contains 1 to 80 mol%, more preferably 3 to 70 mol%, still more preferably 4 to 60 mol%, still more preferably 5 to 50 mol% of the compound providing the structural unit (A2).
The total content ratio of the compound providing the structural unit (A1) and the compound providing the structural unit (A2) in the total tetracarboxylic acid component is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more. The upper limit of the total content ratio of the compound providing the structural unit (A1) and the compound providing the structural unit (A2) is not particularly limited, and is 100 mol% or less. The tetracarboxylic acid component may be composed of only the compound providing the structural unit (A1) and the compound providing the structural unit (A2).
The molar ratio [ (A1)/(A2) ] of the compound providing the structural unit (A1) and the compound providing the structural unit (A2) in the tetracarboxylic acid component is preferably 20/80 to 99/1, more preferably 30/70 to 97/3, still more preferably 40/60 to 96/4, still more preferably 50/50 to 95/5, from the viewpoint of improving mechanical properties and deformation recovery.
Among them, from the viewpoint of improving the deformation recovery property in particular, 60/40 to 99/1 is preferable, 80/20 to 99/1 is more preferable, and 80/20 to 97/3 is still more preferable.
In particular, from the viewpoint of improving strength, it is preferably 60/40 to 99/1, more preferably 80/20 to 99/1, still more preferably 92/8 to 99/1.
From the viewpoint of further improving the elongation, it is preferably 20/80 to 92/8, more preferably 30/70 to 80/20, still more preferably 40/60 to 60/40.
The tetracarboxylic acid component may contain a compound other than the compound providing the structural unit (A1) and the compound providing the structural unit (A2), and examples of the compound include the aromatic tetracarboxylic dianhydride and its derivatives (tetracarboxylic acid, alkyl esters of tetracarboxylic acid, and the like).
The number of compounds (i.e., compounds other than the compounds providing the structural unit (A1) and the structural unit (A2)) arbitrarily contained in the tetracarboxylic acid component may be 1 or 2 or more.
The compound providing the structural unit (B1) may be a compound represented by the formula (B1), but is not limited thereto, and may be a derivative thereof within a range in which the same structural unit is provided. The derivative may be a diisocyanate corresponding to the diamine represented by the formula (b 1). As the compound providing the structural unit (B1), a compound represented by the formula (B1) (i.e., diamine) is preferable.
The diamine component preferably contains 30 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, still more preferably 60 mol% or more, still more preferably 70 mol% or more, still more preferably 90 mol% or more of the compound providing the structural unit (B1). The upper limit of the proportion of the compound providing the structural unit (B1) is not particularly limited, but is 100 mol% or less. The diamine component may be composed of only the compound providing the structural unit (B1).
The diamine component may contain a compound other than the compound providing the structural unit (B1), and examples of the compound include the above aromatic diamine, alicyclic diamine, aliphatic diamine, modified silicone diamine, and derivatives thereof (diisocyanate, etc.).
The number of compounds (i.e., compounds other than the compound providing the structural unit (B1)) optionally contained in the diamine component may be 1 or 2 or more.
In the production of the polyimide resin of the present invention, the ratio of the amount of the tetracarboxylic acid component to the amount of the diamine component to be added is preferably 0.9 to 1.1 mol based on 1 mol of the tetracarboxylic acid component.
In the production of the polyimide resin of the present invention, a capping agent may be used in addition to the tetracarboxylic acid component and the diamine component. As the blocking agent, monoamines or dicarboxylic acids are preferred. The amount of the blocking agent to be introduced is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.06 mol, based on 1 mol of the tetracarboxylic acid component. Preferable monoamine type blocking agents include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3-ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline, and the like. Among these, benzylamine and aniline are more preferable. As the dicarboxylic acid-based capping agent, dicarboxylic acids, a part of which may be closed-loop, are preferable. Preferred dicarboxylic acids include phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2, 3-benzophenone dicarboxylic acid, 3, 4-benzophenone dicarboxylic acid, cyclohexane-1, 2-dicarboxylic acid, cyclopentane-1, 2-dicarboxylic acid, and 4-cyclohexene-1, 2-dicarboxylic acid. Among these, phthalic acid and phthalic anhydride are more preferable.
The method for reacting the tetracarboxylic acid component and the diamine component is not particularly limited, and a known method can be used.
Specific reaction methods include the following: adding a tetracarboxylic acid component, a diamine component and a reaction solvent into a reactor, stirring for 0.5-30 hours at 10-110 ℃, and then heating to perform imidization; adding diamine component and reaction solvent into a reactor to dissolve the diamine component and the reaction solvent, adding tetracarboxylic acid component, stirring for 0.5-30 hours at 10-110 ℃ according to the need, and heating to perform imidization reaction; the method (3) comprises the steps of charging a tetracarboxylic acid component, a diamine component and a reaction solvent into a reactor, immediately heating the mixture, and carrying out imidization; etc.
The reaction solvent used in the production of the polyimide resin may be one which does not interfere with the imidization reaction and which can dissolve the polyimide resin to be produced. Examples thereof include aprotic solvents, phenolic solvents, ether solvents, and carbonate solvents.
Specific examples of the aprotic solvent include amide solvents such as N, N-dimethylisobutyl amide, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1, 3-dimethylimidazolidone, and tetramethylurea, lactone solvents such as γ -butyrolactone and γ -valerolactone, phosphoramide solvents such as hexamethylphosphoramide and hexamethylphosphoric triamide, sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide, and sulfolane, ketone solvents such as acetone, cyclohexanone, and methylcyclohexane, amine solvents such as picoline, and amine solvents such as (2-methoxy-1-methylethyl) acetate, and the like.
Specific examples of the phenol-based solvent include phenol, o-cresol, m-cresol, p-cresol, 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 2, 6-xylenol, 3, 4-xylenol, and 3, 5-xylenol.
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-based solvent or a lactone-based solvent is preferable. The reaction solvent may be used alone or in combination of 2 or more kinds.
In the imidization reaction, the reaction is preferably performed while removing water generated during the production, using a dean-stark trap device or the like. By performing such an operation, the polymerization degree and the imidization rate can be further increased.
In the imidization reaction, a known imidization catalyst may be used. Examples of the imidization catalyst include a base 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, imidazole, N-dimethylaniline, and N, N-diethylaniline, and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate.
Examples of the acid catalyst include crotonic acid, acrylic acid, trans-3-hexenedioic 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 alone or in combination of 2 or more.
Among the above, from the viewpoint of operability, a base catalyst is preferably used, an organic base catalyst is more preferably used, and triethylamine is more preferably used.
When the catalyst is used, the temperature of the imidization reaction is preferably 120 to 250 ℃, more preferably 160 to 190 ℃, and even more preferably 180 to 190 ℃ from the viewpoints of the reaction rate, gelation inhibition, and the like. The reaction time is preferably 0.5 to 10 hours after the start of distillation of the produced water.
The imidization reaction temperature when no catalyst is used is preferably 200 to 350 ℃.
[ polyimide varnish ]
The polyimide varnish of the present invention is prepared by dissolving the polyimide resin of the present invention in an organic solvent. That is, the polyimide varnish of the present invention contains 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 it is preferable to use the above-mentioned compounds alone or in combination of 2 or more as a reaction solvent used in the production of the polyimide resin.
The polyimide varnish of the present invention preferably contains 5 to 60 mass%, more preferably 5 to 45 mass% of the polyimide resin of the present invention. The viscosity of the polyimide varnish is preferably 0.1 to 200pa·s, more preferably 0.5 to 150pa·s.
[ polyimide film ]
The polyimide film of the present invention contains the aforementioned polyimide resin. The polyimide film of the present invention is preferably composed of the polyimide resin.
Specifically, the polyimide resin comprises a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, wherein the structural unit A comprises a structural unit (A1) derived from a compound represented by the formula (A1) and a structural unit (A2) derived from an aliphatic tetracarboxylic dianhydride, and the structural unit B comprises a structural unit (B1) derived from a compound represented by the formula (B1).
By containing such a polyimide resin, the polyimide film of the present invention has high strength and also has excellent elongation and deformation recovery.
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 in which a solution containing the polyimide resin of the present invention, a solution containing the polyimide resin of the present invention and the above-mentioned various additives are applied to a smooth support such as a glass plate, a metal plate, or a plastic, or formed into a film, and then the solvent component such as an organic solvent contained in the solution is removed.
The solution containing a polyimide resin may be a polyimide resin solution itself obtained by a polymerization method. In addition, at least one compound selected from the above-mentioned examples as a solvent for dissolving the polyimide resin may be mixed with the polyimide resin solution. As described above, the thickness of the polyimide film of the present invention can be easily controlled by adjusting the solid concentration and viscosity of the solution containing the polyimide resin.
The surface of the support may be coated with a release agent as needed. The following method is preferable as a method of applying a solution containing the polyimide resin or the polyimide resin composition to the support and then heating and evaporating the solvent component. That is, it is preferable that the self-supporting film is formed by evaporating the solvent at a temperature of 120 ℃ or lower, then the self-supporting film is peeled off from the support, the end of the self-supporting film is fixed, and the polyimide film is produced by drying at a temperature of 350 ℃ or lower and above the boiling point of the solvent component used. In addition, the drying is preferably performed under a nitrogen atmosphere. The pressure of the drying atmosphere may be reduced, normal pressure or increased.
The thickness of the polyimide film of the present invention may be appropriately selected depending on the application, etc., and is preferably in the range of 1 to 250. Mu.m, more preferably 5 to 100. Mu.m, still more preferably 10 to 80. Mu.m. The thickness of 1-250 μm makes practical use as a free-standing film possible.
The polyimide film containing the polyimide resin of the present invention is suitable for use as a film for various members such as color filters, flexible displays, semiconductor parts, optical members, and the like.
Examples
The present invention is specifically described below with reference to examples. The present invention is not limited by these examples.
The physical properties of the polyimide films obtained in the following examples and comparative examples were measured by the methods shown below.
(1) Film thickness
The film thickness was measured using a micrometer manufactured by Mitutoyo Corporation.
(2) Tensile modulus, tensile Strength
The measurement was performed based on JIS K7127 using the tensile tester "Stroggraph VG1E" manufactured by Toyo Seisakusho Co.
(3) Elongation at tensile break (evaluation of elongation)
The tensile elongation at break was measured according to the tensile test (measurement of elongation) based on JIS K7127. The test piece used was 10mm wide and 10 to 70 μm thick.
(4) Recovery from deformation
As shown in fig. 1 (a), a polyimide film 1 cut into a width of 10mm×a length of 100mm was fixed with a jig so as to have r=3 mm, and left to stand for 24 hours or 100 hours at 65 ℃ under a relative humidity of 90%, or 70 ℃ under a dry condition. Then, the jig was removed at 23℃and a relative humidity of 50%, and after standing for 170 hours, the deformation recovery was evaluated by measuring an angle θ shown in FIG. 1 (b) for recovery of the film. The smaller the measured angle is, the more excellent the deformation recovery is, and the smaller the value is preferably.
Example 1
Into a 300mL five-necked round-bottom flask equipped with a stainless steel half-moon shaped stirring blade, a nitrogen inlet pipe, a dean-Stark trap equipped with a condenser, a thermometer, and a glass end cap, 20.22g (0.060 mol) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminodiphenyl ether (ChinaTech Chemical (Taijin) co., ltd. Manufactured by Taijin), 56.7g of gamma-butyrolactone (manufactured by Mitsubishi chemical Co., ltd., hereinafter referred to as GBL) as an organic solvent, and 0.309g of triethylamine (manufactured by Guandon chemical Co., ltd., hereinafter referred to as TEA) as an imidization catalyst were charged, and stirred at a temperature of 70℃under a nitrogen atmosphere and a rotation speed of 150rpm in the system to obtain a solution. To this, 26.18g (0.057 mol) of 9, 9-bis (3, 4-dicarboxyphenyl) fluorenoic acid dianhydride (manufactured by JFE chemical Co., ltd., hereinafter referred to as BPAF) and 0.59g (0.003 mol) of 1,2,3, 4-cyclobutane tetracarboxylic dianhydride (manufactured by Wako pure chemical industries, ltd., hereinafter referred to as CBDA) as tetracarboxylic acid components and 30.5g of GBL were simultaneously added, and then heated in a covered heater to raise the temperature in the reaction system to 190 ℃ for about 20 minutes. The distilled component was collected, the rotation speed was adjusted according to the viscosity rise, and the temperature in the reaction system was kept at 190℃and refluxed for 2 hours, thereby obtaining a polyimide solution. Thereafter, the reaction system was cooled to 120℃and N, N-dimethylacetamide (DMAC, manufactured by Mitsubishi gas chemical Co., ltd., hereinafter abbreviated as DMAC) was added thereto so as to have a predetermined solid content concentration, and the mixture was further stirred for about 3 hours to homogenize the mixture, thereby obtaining a polyimide varnish (A) having a solid content concentration of 15.0 mass%.
Next, the polyimide varnish (a) was applied to a PET substrate, held at 60 ℃ for 20 minutes, held at 80 ℃ for 20 minutes, and held at 100 ℃ for 30 minutes, and the solvent was volatilized to obtain a transparent primary-dried film having self-supporting properties, and the film was further fixed to a stainless steel frame and dried at 220 ℃ in an air atmosphere for 20 minutes, whereby the solvent was removed to obtain a polyimide film. The measurement results and evaluation results of the physical properties are shown in table 1.
Example 2
A polyimide varnish (B) having a solid content concentration of 15.0 mass% was obtained in the same manner as in example 1, except that the amount of 6FODA was changed to 20.54g (0.061 mol), the amount of BPAF was changed to 25.21g (0.055 mol), and the amount of CBDA was changed to 1.20g (0.006 mol). Using the obtained polyimide varnish (B), a polyimide film was obtained in the same manner as in example 1. The measurement results and evaluation results of the physical properties are shown in table 1.
Example 3
A polyimide varnish (C) having a solid content concentration of 15.0 mass% was obtained in the same manner as in example 1, except that the amount of 6FODA was changed to 21.88g (0.065 mol), the amount of BPAF was changed to 20.88g (0.046 mol), and the amount of CBDA was changed to 3.83g (0.020 mol). Using the obtained polyimide varnish (C), a polyimide film was obtained in the same manner as in example 1. The measurement results and evaluation results of the physical properties are shown in table 1.
Example 4
A polyimide varnish (D) having a solid content of 15.0 mass% was obtained in the same manner as in example 1, except that the amount of 6FODA was changed to 23.41g (0.070 mol), the amount of BPAF was changed to 15.96g (0.035 mol), and the amount of CBDA was changed to 6.83g (0.035 mol). Using the obtained polyimide varnish (D), a film was obtained in the same manner as in example 1. The measurement results and evaluation results of the physical properties are shown in table 1.
Example 5
A polyimide varnish (E) having a solid content of 15.0% by mass was obtained in the same manner as in example 1 except that the amount of 6FODA was changed to 22.93g (0.068 mol) and the amount of BPAF was changed to 15.63g (0.034 mol), and that no CBDA was used and 7.64g (0.034 mol) of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (HPMDA, mitsubishi gas chemical Co., ltd.) was added. Using the obtained polyimide varnish (E), a film was obtained in the same manner as in example 1. The measurement results and evaluation results of the physical properties are shown in table 1.
Example 6
A polyimide varnish (F) having a solid content of 20.0% by mass was obtained in the same manner as in example 1 except that the amount of 6FODA was changed to 32.52g (0.097 mol) and the amount of BPAF was changed to 13.30g (0.029 mol), and that HPMA15.17 g (0.068 mol) was added without using CBDA. Using the obtained polyimide varnish (F), a film was obtained in the same manner as in example 1. The measurement results and evaluation results of the physical properties are shown in table 1.
Example 7
A polyimide varnish (G) having a solid content of 18.5% by mass was obtained in the same manner as in example 1 except that the amount of 6FODA was changed to 11.75G (0.035 mol), 9-bis [4- (aminophenoxy) phenyl ] fluorene (manufactured by JFE chemical Co., ltd., hereinafter referred to as BPF-AN) (0.035 mol), the amount of BPAF was changed to 22.43G (0.049 mol), and the amount of CBDA was changed to 4.11G (0.021 mol). Using the obtained polyimide varnish (G), a polyimide film was obtained in the same manner as in example 1. The measurement results and evaluation results of the physical properties are shown in table 1.
Comparative example 1
A polyimide varnish (H) having a solid content of 15.0 mass% was obtained in the same manner as in example 1, except that the amount of 6FODA was changed to 19.93g (0.059 mol) and the amount of BPAF was changed to 27.18g (0.059 mol), and CBDA was not used. Using the obtained polyimide varnish (H), a film was obtained in the same manner as in example 1. The measurement results and evaluation results of the physical properties are shown in table 1.
Comparative example 2
A polyimide varnish was produced in the same manner as in example 5 except that the amount of 6FODA was changed to 38.45g (0.11 mol) and the amount of HPMDA was changed to 25.63g (0.11 mol), and BPAF was not used, to obtain a polyimide varnish (I) having a solid content concentration of 20 mass%. Using the obtained polyimide varnish (I), a film was obtained in the same manner as in example 1.
Comparative example 3
A polyimide varnish (J) having a solid content of 15.0% by mass was obtained in the same manner as in example 5, except that the amount of 6FODA was changed to 19.44g (0.058 mol) and the amount of HPMDA was changed to 5.18g (0.023 mol), and 2,2', 3', 5' -hexamethyl [1,1' -biphenyl ] -4,4' -diyl=bis (1, 3-dioxo-1, 3-dihydro-2-benzofuran-5-carboxylate) (hereinafter referred to as TMPBP-TME, manufactured by Benzhou chemical Co., ltd.) was used instead of BPAF. Using the obtained polyimide varnish (J), a film was obtained in the same manner as in example 1. The measurement results and evaluation results of the physical properties are shown in table 1.
TABLE 1
TABLE 1
As is clear from Table 1, the polyimide films of examples 1 to 7 were excellent in the recovery from deformation and elongation, although they were high in strength.
Claims (12)
1. A polyimide resin having a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, wherein the structural unit A comprises a structural unit (A1) derived from a compound represented by the following formula (A1) and a structural unit (A2) derived from an aliphatic tetracarboxylic dianhydride, the structural unit B comprises a structural unit (B1) derived from a compound represented by the following formula (B1),
2. the polyimide resin according to claim 1, wherein the structural unit (A2) is a structural unit derived from alicyclic tetracarboxylic dianhydride.
3. The polyimide resin according to claim 1 or 2, wherein the structural unit (A2) comprises at least one selected from the group consisting of a structural unit (A2-1) derived from a compound represented by the following formula (A2-1) and a structural unit (A2-2) derived from a compound represented by the following formula (A2-2),
4. a polyimide resin according to claim 3, wherein the structural unit (A2) comprises the structural unit (A2-1).
5. A polyimide resin according to claim 3, wherein the structural unit (A2) comprises the structural unit (A2-2).
6. The polyimide resin according to any one of claims 1 to 5, wherein the ratio of the total of the structural units (A1) and (A2) relative to the structural units a is 50 mol% or more.
7. The polyimide resin according to any one of claims 1 to 6, wherein the molar ratio [ (A1)/(A2) ] of the structural unit (A1) to the structural unit (A2) in the structural unit a is 20/80 to 99/1.
8. The polyimide resin according to claim 4, wherein the molar ratio [ (A1)/(A2-1) ] of the structural unit (A1) to the structural unit (A2-1) in the structural unit A is 50/50 to 95/5.
9. The polyimide resin according to claim 5, wherein the molar ratio [ (A1)/(A2-2) ] of the structural unit (A1) to the structural unit (A2-2) in the structural unit A is 20/80 to 50/50.
10. The polyimide resin according to any one of claims 1 to 9, wherein the proportion of the structural unit (B1) to the structural unit B is 60 mol% or more.
11. A polyimide varnish prepared by dissolving the polyimide resin according to any one of claims 1 to 10 in an organic solvent.
12. A polyimide film comprising the polyimide resin according to any one of claims 1 to 10.
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| JP2020124771 | 2020-07-21 | ||
| JP2020-124771 | 2020-07-21 | ||
| PCT/JP2021/026767 WO2022019225A1 (en) | 2020-07-21 | 2021-07-16 | Polyimide resin, polyimide varnish, and polyimide film |
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| KR102207439B1 (en) * | 2013-09-27 | 2021-01-26 | 도레이 카부시키가이샤 | Polyimide precursor, polyimide resin film produced from said polyimide precursor, display element, optical element, light-receiving element, touch panel and circuit board each equipped with said polyimide resin film, organic el display, and methods respectively for producing organic el element and color filter |
| JP7011231B2 (en) | 2016-11-24 | 2022-01-26 | 日産化学株式会社 | Composition for forming a flexible device substrate |
| WO2019069723A1 (en) * | 2017-10-04 | 2019-04-11 | 三菱瓦斯化学株式会社 | Polyimide resin, polyimide varnish, and polyimide film |
| CN111205457B (en) * | 2018-11-22 | 2022-09-23 | 达迈科技股份有限公司 | Method for producing polyimide film |
| KR20210096064A (en) * | 2018-11-28 | 2021-08-04 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Polyimide resins, polyimide varnishes and polyimide films |
| CN110951078A (en) * | 2019-11-27 | 2020-04-03 | 安徽国风塑业股份有限公司 | Polyimide precursor, polyimide, transparent polyimide film and preparation method thereof |
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