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WO2023249023A1 - ポリイミドワニスの製造方法 - Google Patents

ポリイミドワニスの製造方法 Download PDF

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Publication number
WO2023249023A1
WO2023249023A1 PCT/JP2023/022819 JP2023022819W WO2023249023A1 WO 2023249023 A1 WO2023249023 A1 WO 2023249023A1 JP 2023022819 W JP2023022819 W JP 2023022819W WO 2023249023 A1 WO2023249023 A1 WO 2023249023A1
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Prior art keywords
polyimide
reaction
compound represented
polyimide varnish
temperature
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PCT/JP2023/022819
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English (en)
French (fr)
Japanese (ja)
Inventor
修也 末永
晃久 松丸
健 杉戸
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三菱瓦斯化学株式会社
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Publication of WO2023249023A1 publication Critical patent/WO2023249023A1/ja

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a method for producing polyimide varnish.
  • polyimide resin Since polyimide resin has excellent mechanical properties and heat resistance, various uses are being considered in fields such as electrical and electronic parts. For example, it is desired to replace glass substrates used in image display devices such as liquid crystal displays and OLED displays with polyimide film substrates, and polyimide resins that satisfy the performance as optical materials are being developed. Varnish, which is a solution of polyimide soluble in a solvent, is used as a raw material for easily producing polyimide molded bodies such as polyimide films. Efforts have also been made to polyimide varnishes to improve the performance of the resulting polyimide molded bodies.
  • Patent Document 1 discloses that 1,2,4,5-cyclohexanetetracarboxylic dianhydride, a specific dicarboxylic acid anhydride, and a specific alicyclic diamine are used for the purpose of improving heat resistance, transparency, and toughness.
  • a solvent-soluble alicyclic polyimide copolymer and a varnish obtained by imidization reaction at a specific charging ratio are disclosed.
  • Polyimide varnishes that are soluble in solvents have excellent moldability as described above. Furthermore, although polyimide resin has excellent properties as described above, it is susceptible to discoloration such as yellowing during production. Recently, since it is also used for optical materials such as those mentioned above, higher colorlessness is required. Therefore, there has been a need for a method that can produce a varnish containing solvent-soluble polyimide and having excellent colorlessness.
  • the present invention has been made in view of these circumstances, and an object of the present invention is to produce a polyimide varnish that contains solvent-soluble polyimide, is free from coloration, and is capable of obtaining a varnish that is excellent in colorlessness. The purpose is to provide a method.
  • the present invention relates to the following [1] to [9].
  • [1] One or more tetracarboxylic dianhydrides and one or more diamines are polycondensed in an organic solvent at a reaction temperature of 160 to 220°C to obtain a reaction solution.
  • a method for producing a polyimide varnish comprising lowering the temperature of the reaction solution from the reaction temperature to 120°C at a rate of 4°C/min or more to stop the reaction.
  • the diamine further contains a compound represented by the following formula (3), and the molar ratio of the compound represented by the formula (2) to the compound represented by the formula (3) [(2)/(3) )] is 20/80 to 80/20, the method for producing a polyimide varnish according to [6] or [8].
  • the method for producing the polyimide varnish of the present invention involves polycondensing one or more tetracarboxylic dianhydrides and one or more diamines in an organic solvent at a reaction temperature of 160 to 220°C to obtain a reaction solution and diluting it.
  • the reaction is stopped by lowering the temperature of the reaction solution from the reaction temperature to 120° C. at a rate of 4° C./min or more by adding a solvent.
  • ⁇ Polycondensation step> In the method for producing a polyimide varnish of the present invention, first, one or more tetracarboxylic dianhydrides and one or more diamines are polycondensed in an organic solvent at a reaction temperature of 160 to 220°C to obtain a reaction liquid. .
  • the reaction solution contains polyimide after polycondensation. The polycondensation continues until the reaction is stopped in the next step, but the reaction is quickly stopped by adding a diluting solvent in the next step, so that the polyimide obtained in this step is substantially This becomes the polyimide contained in the final polyimide varnish.
  • the tetracarboxylic dianhydride to be subjected to polycondensation in this step is not particularly limited, but preferably includes an alicyclic tetracarboxylic dianhydride, and more preferably a compound represented by the following formula (1). including.
  • the tetracarboxylic dianhydride subjected to polycondensation in this step is preferably an alicyclic tetracarboxylic dianhydride, and more preferably a compound represented by the following formula (1).
  • the ratio of the compound represented by the following formula (1) in the tetracarboxylic dianhydride used in this step is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more. It is mol% or more, and even more preferably 95 mol% or more.
  • the upper limit of the ratio of the compound represented by the following formula (1) is not particularly limited, and may be 100 mol% or less.
  • Examples of the alicyclic tetracarboxylic dianhydride include 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, norbornane-2-spiro- ⁇ -Cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene- 2,3,5,6-tetracarboxylic dianhydride, dicyclohexyltetracarboxylic dianhydride, 5,5'-(1,4-phenylene)-bis[hexahydro-4,7-Methanoisobenzofuran-1,3- dione], 5,5'-bis-2-norbornene-5,5',6,6'-tetracarboxylic acid-5,5',6,6'-dianhydride,
  • 1,2,4,5-cyclohexanetetracarboxylic dianhydride which is a compound represented by the above formula (1)
  • 1,2,4,5-cyclohexanetetracarboxylic dianhydride which is a compound represented by the above formula (1)
  • the resulting polyimide is soluble in a solvent, has no coloration, and has excellent colorlessness.
  • the compound represented by the formula (1) the resulting polyimide is soluble in a solvent, has less coloring, and has extremely excellent colorlessness.
  • the tetracarboxylic dianhydride may include a tetracarboxylic dianhydride other than the alicyclic tetracarboxylic dianhydride.
  • tetracarboxylic dianhydrides include, but are not particularly limited to, aromatic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides.
  • aromatic tetracarboxylic dianhydride examples include biphenyltetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, pyromellitic dianhydride, 3,3', 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride Examples include anhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, and the like.
  • aliphatic tetracarboxylic dianhydride examples include 1,2,3,4-butanetetracarboxylic dianhydride.
  • the number of tetracarboxylic dianhydrides may be one or more, and may be one or two or more.
  • aromatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more aromatic rings
  • alicyclic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more alicyclic rings.
  • aliphatic tetracarboxylic dianhydride refers to a tetracarboxylic dianhydride containing the above and not containing an aromatic ring
  • aliphatic tetracarboxylic dianhydride refers to a tetracarboxylic dianhydride containing neither an aromatic ring nor an alicyclic ring.
  • the diamine to be subjected to polycondensation in this step is not particularly limited, but preferably includes an aromatic diamine, more preferably a compound represented by the following formula (2) and a compound represented by the following formula (3).
  • the compound contains at least one selected from the group consisting of, and more preferably contains a compound represented by the following formula (2) and a compound represented by the following formula (3).
  • the diamine subjected to polycondensation in this step is preferably an aromatic diamine, and more preferably a compound represented by the following formula (2) or a compound represented by the following formula (3).
  • the total ratio of the compound represented by the following formula (2) and the compound represented by the following formula (3) in the diamine used in this step is preferably 50 mol% or more, more preferably 70 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more.
  • the upper limit of the total ratio of the compound represented by the following formula (2) and the following formula (3) is not particularly limited, and may be 100 mol% or less.
  • Aromatic diamines include 4,4'-bis(4-aminophenoxy)biphenyl, ⁇ , ⁇ '-bis(4-aminophenyl)-1,3-diisopropylbenzene, 1-(4-aminophenyl)-1 , 3,3-trimethylphenylindanamine, 4-aminophenyl-4-aminobenzoate, 2,2'-bis(trifluoromethyl)benzidine, 3,5-diaminobenzoic acid, 9,9-bis(4-amino phenyl)fluorene, 1,4-phenylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene, 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminodiphenylmethane, 1,4 -Bis[2-(4-aminophenyl)-2-propyl]benzene, 2,2-bis(4-aminoph
  • 4,4'-bis(4-aminophenoxy)biphenyl which is a compound represented by the above formula (2)
  • ⁇ , ⁇ '-bis which is a compound represented by the above formula (3)
  • At least one selected from the group consisting of (4-aminophenyl)-1,3-diisopropylbenzene is preferred.
  • an aromatic diamine By using an aromatic diamine, the resulting polyimide is soluble in a solvent, has no coloration, and has excellent colorlessness.
  • the compound represented by the above formula (2) and the above formula (3) the resulting polyimide is soluble in a solvent and has less coloration. It becomes extremely colorless.
  • the compound represented by the formula (2) and the compound represented by the formula (3) are preferably 20/80 to 80/20, more preferably 30/70 to 70/30, even more preferably The ratio is 40/60 to 60/40.
  • the diamine subjected to polycondensation in this step may include diamines other than aromatic diamines.
  • diamines include, but are not limited to, alicyclic diamines and aliphatic diamines.
  • the alicyclic diamine include 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane.
  • aliphatic diamines include ethylene diamine and hexamethylene diamine.
  • the number of diamines subjected to polycondensation in this step may be one or more, and may be one or two or more.
  • aromatic diamine means a diamine containing one or more aromatic rings
  • alicyclic diamine means a diamine containing one or more alicyclic rings and no aromatic ring
  • Group diamine means a diamine containing neither aromatic ring nor alicyclic ring.
  • This step is a step of polycondensing one or more tetracarboxylic dianhydrides and one or more diamines in an organic solvent at a reaction temperature of 160 to 220°C to obtain a reaction solution.
  • the polycondensation reaction is preferably carried out as follows.
  • the polycondensation reaction in this step is performed in an organic solvent.
  • the organic solvent used in the polycondensation reaction may be any solvent as long as it can dissolve the polyimide produced, and examples thereof include aprotic solvents, phenol solvents, ether solvents, carbonate solvents, etc. At least one selected from the group consisting of phenolic solvents, ether solvents, and carbonate solvents is preferred.
  • the aprotic solvent include amide solvents such as cyclic amides and chain amides, phosphorus-containing amide solvents, sulfur-containing solvents, ketone solvents, and ester solvents containing cyclic esters.
  • the organic solvent preferably contains at least one selected from the group consisting of a cyclic amide, a chain amide, and a cyclic ester, and more preferably at least one selected from the group consisting of a chain amide and a cyclic ester. , more preferably linear amides and cyclic esters.
  • the organic solvent is preferably at least one selected from the group consisting of a cyclic amide, a chain amide, and a cyclic ester, and more preferably at least one selected from the group consisting of a chain amide and a cyclic ester, More preferred are linear amides and cyclic esters.
  • Examples of the cyclic amide include N-methyl-2-pyrrolidone, N-methylcaprolactam, and 1,3-dimethylimidazolidinone, with N-methyl-2-pyrrolidone being preferred.
  • Examples of the chain amide include N,N-dimethylformamide, N,N-dimethylacetamide, and tetramethylurea.
  • Examples of the cyclic ester include ⁇ -butyrolactone and ⁇ -valerolactone.
  • Other ester solvents include acetic acid (2-methoxy-1-methylethyl) and the like.
  • Examples of the phosphorus-containing amide solvent include hexamethylphosphoric amide, hexamethylphosphine triamide, and the like.
  • Examples of the sulfur-containing solvent include dimethylsulfone, dimethylsulfoxide, and sulfolane.
  • Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, and the like.
  • phenolic solvents 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, etc.
  • ether solvents include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, and bis[2-(2-methoxyethoxy)ethyl]. Examples include ether, tetrahydrofuran, 1,4-dioxane and the like.
  • carbonate solvents include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate, and the like.
  • the organic solvent preferably contains at least one selected from the group consisting of ⁇ -butyrolactone, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone, and more preferably ⁇ -butyrolactone.
  • - Contains at least one member selected from the group consisting of butyrolactone and N,N-dimethylacetamide, preferably ⁇ -butyrolactone and N,N-dimethylacetamide.
  • the organic solvent is preferably at least one selected from the group consisting of ⁇ -butyrolactone, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, more preferably ⁇ -butyrolactone and N,N-dimethyl It is at least one selected from the group consisting of acetamides, and more preferably ⁇ -butyrolactone and N,N-dimethylacetamide.
  • the above organic solvents may be used alone or in combination of two or more.
  • the method for polycondensing the tetracarboxylic dianhydride and diamine is not particularly limited, and any known method can be used.
  • a specific reaction method (1) a solution containing a diamine and an organic solvent and a tetracarboxylic dianhydride are charged into a reactor, and stirred at 10 to 110°C for 0.5 to 30 hours as necessary, (2) A method in which a solution containing a diamine and an organic solvent and a tetracarboxylic dianhydride are charged into a reactor and the temperature is immediately raised to carry out a polycondensation reaction. Can be mentioned.
  • the ratio of the amounts of tetracarboxylic dianhydride and diamine used for producing the polyimide resin is preferably 0.9 to 1.1 mol of diamine per 1 mol of tetracarboxylic dianhydride. .
  • water since water is produced by imidization, it is preferable to carry out the reaction while removing water produced during production using a Dean-Stark apparatus or the like. By performing such an operation, the degree of polymerization and the imidization rate can be further increased.
  • imidization catalysts include base catalysts and acid catalysts.
  • Base catalysts include pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, imidazole, N,N
  • organic base catalysts such as -dimethylaniline and N,N-diethylaniline
  • inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, and sodium hydrogen carbonate.
  • examples of acid catalysts include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, etc. can be mentioned.
  • the above imidization catalysts may be used alone or in combination of two or more.
  • base catalysts are preferred, organic base catalysts are more preferred, one or more selected from triethylamine and triethylenediamine are still more preferred, and triethylamine is even more preferred.
  • the reaction temperature of the polycondensation reaction in this polycondensation step is 160 to 220°C. From the viewpoint of reaction rate and suppression of gelation, etc., the temperature is preferably 160 to 250°C, more preferably 160 to 230°C, and even more preferably 170 to 200°C. Further, the reaction time is preferably 0.5 to 10 hours after the start of distillation of the produced water. Moreover, it is preferable that this polycondensation step is performed under an inert gas atmosphere such as nitrogen.
  • the concentration of polyimide in the resulting reaction solution is usually 1 to 50% by weight, preferably 3 to 35% by weight, and more preferably 5 to 30% by weight.
  • the weight average molecular weight (Mw) of the polyimide obtained in this step is 200,000 or more, preferably 300,000 or more, and more preferably 400,000 or more from the viewpoint of mechanical properties of the polyimide obtained. . Although there is no upper limit to the upper limit, it is preferably 1,000,000 or less, more preferably 700,000 or less. Further, from the same viewpoint, the number average molecular weight is preferably 50,000 to 500,000. Note that the weight average molecular weight and number average molecular weight of the polyimide can be determined from standard polystyrene (PS) equivalent values determined by gel filtration chromatography measurement.
  • PS polystyrene
  • a terminal capping agent may be used in addition to the above-mentioned tetracarboxylic dianhydride and diamine.
  • the terminal capping agent monoamines or dicarboxylic acids are preferable.
  • the amount of the terminal capping agent to be introduced is preferably 0.0001 to 0.1 mol, particularly preferably 0.001 to 0.06 mol, per 1 mol of the tetracarboxylic acid component.
  • Examples of monoamine terminal capping 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 are preferred. Among these, benzylamine and aniline can be preferably used.
  • dicarboxylic acid terminal capping agent dicarboxylic acids are preferred, and a portion thereof may be ring-closed.
  • phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenone dicarboxylic acid, 3,4-benzophenone dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1 , 2-dicarboxylic acid, etc. are recommended.
  • phthalic acid and phthalic anhydride can be preferably used.
  • ⁇ Reaction termination step> In the method for producing a polyimide varnish of the present invention, the polycondensation reaction is stopped by lowering the temperature of the reaction solution from the reaction temperature to 120° C. at a rate of 4° C./min or more by adding a diluting solvent. That is, in order to stop the polycondensation in the polycondensation step, a diluting solvent is added and the reaction temperature is lowered from 160 to 220°C to 120°C. This step will be described below as a reaction termination step.
  • the diluting solvent used in this step may be any solvent as long as it can dissolve the polyimide produced, and the organic solvent used in the polycondensation reaction can be suitably used.
  • Specific examples include aprotic solvents, phenolic solvents, ether solvents, carbonate solvents, etc., and at least one solvent selected from the group consisting of aprotic solvents, phenolic solvents, ether solvents, and carbonate solvents. Seeds are preferred.
  • the aprotic solvent include amide solvents such as cyclic amides and chain amides, phosphorus-containing amide solvents, sulfur-containing solvents, ketone solvents, and ester solvents containing cyclic esters.
  • the diluting solvent preferably contains at least one selected from the group consisting of a cyclic amide, a chain amide, and a cyclic ester, and more preferably at least one selected from the group consisting of a chain amide and a cyclic ester. It contains a species, more preferably a chain amide.
  • the diluting solvent is preferably at least one selected from the group consisting of cyclic amides, chain amides, and cyclic esters, and more preferably at least one selected from the group consisting of chain amides and cyclic esters. , more preferably a linear amide.
  • Examples of the cyclic amide include N-methyl-2-pyrrolidone, N-methylcaprolactam, and 1,3-dimethylimidazolidinone, with N-methyl-2-pyrrolidone being preferred.
  • Examples of the chain amide include N,N-dimethylformamide, N,N-dimethylacetamide, and tetramethylurea.
  • Examples of the cyclic ester include ⁇ -butyrolactone and ⁇ -valerolactone.
  • Other ester solvents include acetic acid (2-methoxy-1-methylethyl) and the like.
  • Examples of the phosphorus-containing amide solvent include hexamethylphosphoric amide, hexamethylphosphine triamide, and the like.
  • Examples of the sulfur-containing solvent include dimethylsulfone, dimethylsulfoxide, and sulfolane.
  • Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, and the like.
  • phenolic solvents 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, etc.
  • ether solvents include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, and bis[2-(2-methoxyethoxy)ethyl]. Examples include ether, tetrahydrofuran, 1,4-dioxane and the like.
  • carbonate solvents include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate, and the like.
  • the diluting solvent preferably contains at least one selected from the group consisting of ⁇ -butyrolactone, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone, and more preferably contains at least one member selected from the group consisting of ⁇ -butyrolactone and N,N-dimethylacetamide, preferably N,N-dimethylacetamide.
  • the diluting solvent is preferably at least one selected from the group consisting of ⁇ -butyrolactone, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, more preferably ⁇ -butyrolactone and N,N- It is at least one selected from the group consisting of dimethylacetamide, and more preferably N,N-dimethylacetamide.
  • the above diluting solvents may be used alone or in combination of two or more.
  • the temperature of the diluting solvent is preferably 50° C. or lower at the time it is added to the reaction solution obtained in the polycondensation reaction. By keeping the temperature of the diluting solvent low, the temperature of the reaction solution can be efficiently lowered and the reaction can be stopped quickly.
  • the temperature of the diluting solvent is preferably 40°C or lower, still more preferably 30°C or lower, even more preferably 25°C or lower at the time of adding it to the reaction solution obtained in the polycondensation reaction. be. There is no lower limit, but it is usually 0°C or higher.
  • the rate of decrease in temperature of the reaction solution (temperature decrease rate) when the reaction is stopped by adding the diluting solvent is 4° C./min or more. By quickly stopping the temperature of the reaction solution, it is possible to obtain a varnish that contains solvent-soluble polyimide but is free from coloration and has excellent colorlessness.
  • the rate of decrease in temperature of the reaction solution (temperature decreasing rate) when stopping the reaction by adding a diluting solvent is preferably 5°C/min or more, more preferably 7°C/min or more, and even more preferably 8°C/min or more. C/min or more, more preferably 9 C/min or more. There is no upper limit, but it is usually 30°C/min or less.
  • the time required to bring the temperature of the reaction solution to 120°C is preferably 1 hour or less, more preferably 30 minutes or less, from the start of adding the diluting solvent.
  • the time is preferably 12 minutes or less, and even more preferably 10 minutes or less.
  • the polyimide is uniformly dissolved, and the concentration (solid content) of the polyimide is preferably 5 to 40% by mass, more preferably 10 to 40% by mass. It is 30% by mass.
  • the viscosity (25° C.) of the polyimide solution is preferably 1 to 200 Pa ⁇ s, more preferably 1 to 100 Pa ⁇ s. Since the solution obtained in this step contains polyimide, it may be used as it is as a polyimide varnish, or the concentration may be adjusted by adding or removing an organic solvent.
  • the solution obtained in this step contains polyimide.
  • the polyimide includes a structural unit derived from the tetracarboxylic dianhydride and a structural unit derived from the diamine.
  • the polyimide preferably contains a structural unit derived from an alicyclic tetracarboxylic dianhydride, and more preferably contains a structural unit derived from a compound represented by the following formula (1).
  • the ratio of the structural unit derived from the compound represented by the following formula (1) in the structural unit derived from tetracarboxylic dianhydride is preferably 50 mol% or more, more preferably 70 mol% or more. It is more preferably 90 mol% or more, even more preferably 95 mol% or more.
  • the upper limit of the ratio of the structural units derived from the compound represented by the following formula (1) is not particularly limited, and may be 100 mol% or less.
  • the resulting polyimide is soluble in a solvent, has less coloring, and has extremely excellent colorlessness.
  • the structural unit derived from tetracarboxylic dianhydride may include a structural unit derived from tetracarboxylic dianhydride other than the structural unit derived from alicyclic tetracarboxylic dianhydride.
  • Such structural units derived from tetracarboxylic dianhydrides are not particularly limited, but include structural units derived from aromatic tetracarboxylic dianhydrides, and structural units derived from aliphatic tetracarboxylic dianhydrides. Examples include structural units that The number of structural units derived from tetracarboxylic dianhydride may be one or more, and may be one or two or more.
  • the polyimide preferably contains a structural unit derived from an aromatic diamine, more preferably a structural unit derived from a compound represented by the following formula (2), and a structural unit derived from a compound represented by the following formula (3).
  • a structural unit containing at least one selected from the group consisting of structural units, more preferably a structural unit derived from a compound represented by the following formula (2) and a structure derived from a compound represented by the following formula (3). Contains units.
  • the total ratio of the structural units derived from the compound represented by the following formula (2) and the structural units derived from the compound represented by the following formula (3) in the diamine-derived structural units is preferably The content is 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, even more preferably 95 mol% or more.
  • the upper limit of the total ratio of the structural units derived from the compound represented by the following formula (2) and the structural units derived from the compound represented by the following formula (3) is not particularly limited, and is 100 mol% or less That's fine. It is soluble in a solvent by containing either or both of the structural unit derived from the compound represented by the above formula (2) and the structural unit derived from the compound represented by the above formula (3).
  • the compound represented by the formula (2) is derived from the compound represented by the formula (2).
  • the molar ratio [(2)/(3)] of the structural unit derived from the compound represented by formula (3) is preferably 20/80 to 80/20, more preferably 30/80 to 80/20. /70 to 70/30, more preferably 40/60 to 60/40.
  • the structural unit derived from a diamine may include a structural unit derived from a diamine other than the structural unit derived from an aromatic diamine.
  • Such structural units derived from diamines include, but are not particularly limited to, structural units derived from alicyclic diamines and structural units derived from aliphatic diamines.
  • the number of structural units derived from diamine may be one or more, and may be one or two or more.
  • the polyimide varnish obtained by the above production method contains a solvent-soluble polyimide, is free from coloration, and provides a method for producing a polyimide varnish that can yield a varnish with excellent colorlessness.
  • the polyimide varnish contains polyimide and an organic solvent.
  • As the polyimide preferably the above-mentioned polyimide is used.
  • the organic solvent contained in the polyimide varnish is the same as the organic solvent used in the polycondensation step or the reaction termination step.
  • the solution obtained in the reaction termination step may be used as it is as a polyimide varnish, or the solution obtained in the reaction termination step may be adjusted to a polyimide concentration (solid content) suitable for polyimide varnish in the reaction termination step. can be used as is as a polyimide varnish.
  • the polyimide varnish has polyimide dissolved therein uniformly, and the concentration (solid content) of the polyimide is preferably 5 to 40% by mass, more preferably 10 to 30% by mass.
  • the viscosity (25° C.) of the polyimide varnish is preferably 1 to 200 Pa ⁇ s, more preferably 1 to 100 Pa ⁇ s.
  • the polyimide varnish may contain inorganic fillers, adhesion promoters, release agents, flame retardants, ultraviolet stabilizers, surfactants, leveling agents, antifoaming agents, optical brighteners, etc., to the extent that the effects of the present invention are not impaired. It may also contain various additives such as a crosslinking agent, a polymerization initiator, and a photosensitizer.
  • the polyimide varnish obtained by the production method of the present invention is suitably used as a raw material for various members such as color filters, flexible displays, semiconductor parts, and optical members.
  • the polyimide varnish obtained by the production method of the present invention is particularly suitably used as a raw material for image display devices such as liquid crystal displays and OLED displays.
  • Yellow index (yellowness, YI) The yellowness (YI) of the polyimide varnish obtained in Examples and Comparative Examples was determined by placing the polyimide varnish in a measuring cell with a cell length (measurement thickness) of 10 mm, and measuring color and turbidity simultaneously (manufactured by Nippon Denshoku Kogyo Co., Ltd.). Measurement was performed using a measuring device "COH7700". The smaller the yellow index (YI), the better the colorlessness.
  • the polyimide varnish used for the measurement of yellowness index (YI) was stored at room temperature (25°C) for 16 hours after adding N,N-dimethylacetamide as a diluting solvent and confirming that it was homogeneous. was used.
  • Example 1 ⁇ , ⁇ '-bis (4- 113.751 g (0.331 mol) of 4,4'-bis(4-aminophenoxy) 121.330 g (0.331 mol) of biphenyl (compound represented by formula (2), manufactured by Wakayama Seika Kogyo Co., Ltd.) and 460.6 g of ⁇ -butyrolactone (manufactured by Mitsubishi Chemical Corporation) were added, and the temperature was 70°C. A solution was obtained by stirring at 100 rpm under a nitrogen atmosphere.
  • N,N-dimethylacetamide at a temperature of 25°C was added to the obtained reaction solution at 180°C so that the temperature inside the reaction system was lowered at a rate of 10°C/min, and the temperature of the reaction solution was lowered to 120°C. And so.
  • the amount of N,N-dimethylacetamide added was adjusted to obtain a uniform polyimide varnish with a solid content concentration of 20% by mass. Table 1 shows the evaluation results of the obtained polyimide varnish.
  • Example 2 A polycondensation reaction was carried out in the same manner as in Example 1 to obtain a reaction solution. N,N-dimethylacetamide at a temperature of 25°C was added to the obtained reaction solution at 180°C so that the temperature inside the reaction system was lowered at a rate of 7.2°C/min, and the temperature of the reaction solution was lowered. The temperature was 120°C. The amount of N,N-dimethylacetamide added was adjusted to obtain a uniform polyimide varnish with a solid content concentration of 20% by mass. Table 1 shows the evaluation results of the obtained polyimide varnish.
  • Example 3 A polycondensation reaction was carried out in the same manner as in Example 1 to obtain a reaction solution. N,N-dimethylacetamide at a temperature of 25°C was added to the resulting reaction solution at 180°C so that the temperature inside the reaction system was lowered at a rate of 5.1°C/min, and the temperature of the reaction solution was lowered. The temperature was 120°C. The amount of N,N-dimethylacetamide added was adjusted to obtain a uniform polyimide varnish with a solid content concentration of 20% by mass. Table 1 shows the evaluation results of the obtained polyimide varnish.
  • Comparative example 1 A polycondensation reaction was carried out in the same manner as in Example 1 to obtain a reaction solution. N,N-dimethylacetamide at a temperature of 25°C was added to the obtained reaction solution at 180°C so that the temperature inside the reaction system was lowered at a rate of 1.3°C/min, and the temperature of the reaction solution was lowered. The temperature was 120°C. The amount of N,N-dimethylacetamide added was adjusted to obtain a uniform polyimide varnish with a solid content concentration of 20% by mass. Table 1 shows the evaluation results of the obtained polyimide varnish.
  • Comparative example 2 A polycondensation reaction was carried out in the same manner as in Example 1 to obtain a reaction solution. N,N-dimethylacetamide at a temperature of 25°C was added to the resulting reaction solution at 180°C so that the temperature inside the reaction system was lowered at a rate of 3.5°C/min, and the temperature of the reaction solution was lowered. The temperature was 120°C. The amount of N,N-dimethylacetamide added was adjusted to obtain a uniform polyimide varnish with a solid content concentration of 20% by mass. Table 1 shows the evaluation results of the obtained polyimide varnish.
  • the polyimide varnish obtained by the production method of the present invention is uniform and has low yellowness, which indicates that it contains solvent-soluble polyimide, is not colored, and has excellent colorlessness. Recognize. For this reason, the polyimide varnish obtained by the production method of the present invention can be suitably used as a material for image display devices.

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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WO2019116940A1 (ja) * 2017-12-15 2019-06-20 三菱瓦斯化学株式会社 ポリイミド樹脂、ポリイミドワニス及びポリイミドフィルム
WO2020196103A1 (ja) * 2019-03-25 2020-10-01 三菱瓦斯化学株式会社 無色透明樹脂フィルムの製造方法

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* Cited by examiner, † Cited by third party
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WO2019116940A1 (ja) * 2017-12-15 2019-06-20 三菱瓦斯化学株式会社 ポリイミド樹脂、ポリイミドワニス及びポリイミドフィルム
WO2020196103A1 (ja) * 2019-03-25 2020-10-01 三菱瓦斯化学株式会社 無色透明樹脂フィルムの製造方法

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