WO2023080007A1 - Procédé de production de polyimide, polyimide, composition de résine de polyimide et produit durci associé - Google Patents

Procédé de production de polyimide, polyimide, composition de résine de polyimide et produit durci associé Download PDF

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WO2023080007A1
WO2023080007A1 PCT/JP2022/039608 JP2022039608W WO2023080007A1 WO 2023080007 A1 WO2023080007 A1 WO 2023080007A1 JP 2022039608 W JP2022039608 W JP 2022039608W WO 2023080007 A1 WO2023080007 A1 WO 2023080007A1
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polyimide
mass
bis
reaction
group
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PCT/JP2022/039608
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Japanese (ja)
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一瀬恵子
青島健太
浅野到
荒木斉
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東レ株式会社
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Priority to CN202280071046.5A priority Critical patent/CN118139912A/zh
Publication of WO2023080007A1 publication Critical patent/WO2023080007A1/fr

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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
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides

Definitions

  • the present invention relates to a method for producing a polyimide that can reduce the amount of organic solvent used and is suitable for surface protective films of electronic parts, interlayer insulating films, etc., the polyimide, a resin composition containing the polyimide, and a cured product thereof.
  • polyimide Due to its high heat resistance and excellent mechanical and electrical properties, polyimide is used for surface protective films and interlayer insulating films of electronic parts. Along with the recent demand for high performance electronic components, polyimide has improved reproducibility of pattern formation after development, high transmittance and neutral color appearance when made into a film, and cure shrinkage on the coated substrate. Small things are required.
  • NMP N-methyl-2-pyrrolidone
  • Patent Document 1 in order to efficiently remove NMP, a low boiling point solvent such as ethyl acetate and water are added to the NMP reaction solution of polyimide to separate it into an organic layer and an aqueous layer, and then the aqueous layer is removed.
  • a method for producing a polyimide precursor a method is disclosed in which the operation of removing NMP by rinsing is repeated about three times.
  • Patent Documents 2 to 5 as a method for producing polyimide that reduces the amount of organic solvent used, surface protective films and interlayer insulation of electronic parts are produced by reacting at a temperature exceeding 100 ° C. under high pressure in a water solvent. Techniques have been disclosed for polymerizing thermoplastic polyimides that are not intended for membranes.
  • Patent Document 1 discloses a method of preparing a nylon salt-type monomer from a tetracarboxylic acid and a diamine in a solvent and subjecting it to solid phase polymerization to obtain a polyimide.
  • Patent No. 6503341 Japanese Patent Application Laid-Open No. 2001-181389 Japanese Patent Application Laid-Open No. 2001-270945 Patent No. 4050458 Patent No. 6994946 JP 2015-98573 A
  • Non-Patent Document 1 and Patent Document 6 require higher temperature and longer time than the reaction using a solvent because the movement of molecules is controlled. It is considered that this is because the resulting polyimide has strong intermolecular interactions. Therefore, the obtained polyimide tends to have high crystallinity, and there is a problem that an insoluble and non-melting portion tends to occur.
  • the method for producing polyimide of the present invention has the following configuration. i.e. [1] Tetracarboxylic acid and/or tetracarboxylic dianhydride (a) and diamine (b) are mixed in a reaction solvent containing 60 to 100% by mass of water with respect to 100% by mass of the total reaction solvent, A method for producing a polyimide, comprising a step (2) of chain extension of the obtained polyimide after the step (1) of obtaining a polyimide by reacting it at a temperature range of 80 ° C. or more and 250 ° C.
  • R 5 and R 12 each independently represent an oxygen atom, C(CH 3 ) 2 , C(CF 3 ) 2 or SO 2 , R 6 and R 7 each independently , a hydrogen atom, a hydroxyl group, a sulfonic acid group or a thiol group, and R 8 , R 9 , R 10 , R 11 , R 13 and R 14 each independently represent a hydrogen atom, a hydroxyl group, a sulfonic acid group, a thiol group or Indicates an alkyl group having 1 to 6 carbon atoms.
  • a reaction solvent containing 60 to 100% by mass of water with respect to 100% by mass of the total reaction solvent a tetracarboxylic dianhydride (d) with a purity of 98% by mass or more and a A method for producing a polyimide, comprising the step (3) of reacting a diamine (e) in a temperature range of 100° C.
  • the polyimide of the present invention has the following constitution. i.e. [10] It has a structural unit represented by formula (2), contains an organic solvent of 1% by mass or less, has a yellowness of 0 to 3.0, and has a weight average molecular weight of 5,000 to 100. ,000 polyimide,
  • R 1 represents a 4- to 14-valent organic group having 5 to 40 carbon atoms
  • R 2 represents a 2- to 12-valent organic group having 5 to 40 carbon atoms
  • R 3 and R 4 are Each independently represents a hydroxyl group, a sulfonic acid group, a thiol group or an organic group having 1 to 20 carbon atoms
  • ⁇ and ⁇ each independently represents an integer from 0 to 10 satisfying ⁇ + ⁇ 1.
  • the polyimide resin composition of the present invention has the following constitution. i.e. [14] A polyimide resin composition containing the polyimide according to any one of [10] to [13], a photosensitizer and a solvent.
  • the cured product of the present invention has the following constitution. i.e. [15] A cured product obtained by curing the polyimide resin composition according to [14] above.
  • the present invention can reduce the amount of organic solvent used, has excellent solvent solubility, and has a low yellowness, and a method for producing a polyimide suitable for a surface protective film of an electronic component, an interlayer insulating film, etc., the polyimide, and the polyimide and a cured film formed from the resin composition.
  • the method for producing polyimide of the present invention has either the following first aspect or second aspect. i.e. Tetracarboxylic acid and/or tetracarboxylic dianhydride (a) and diamine (b) are heated at 80° C. or higher in a reaction solvent containing 60 to 100% by mass of water with respect to 100% by mass of the total reaction solvent.
  • a method for producing a polyimide comprising a step (1) of obtaining a polyimide by reaction in a temperature range of 250° C.
  • a step (2) of chain extension of the obtained polyimide or In a reaction solvent containing 60 to 100% by mass of water with respect to 100% by mass of the total reaction solvent, a tetracarboxylic dianhydride (d) with a purity of 98% by mass or more and a diamine (e) with a purity of 98% by mass or more ) in a temperature range of 100° C. or higher and 370° C. or lower to obtain a polyimide (3).
  • the polyimide referred to in the present invention is, for example, a structural unit derived from a tetracarboxylic acid and/or a tetracarboxylic dianhydride by reacting a tetracarboxylic acid and/or a tetracarboxylic dianhydride with a diamine.
  • Examples of the tetracarboxylic acid and/or tetracarboxylic dianhydride used in the method for producing a polyimide of the present invention include aromatic tetracarboxylic acid, alicyclic tetracarboxylic acid, and dianhydrides thereof. , but not limited to. Moreover, these may be used individually or in combination of 2 or more types.
  • tetracarboxylic acid and/or tetracarboxylic dianhydride (a) include 4- to 14-valent tetracarboxylic acids and tetracarboxylic dianhydrides having 5 to 40 carbon atoms, such as pyromellit acid, 3,3′,4,4′-biphenyltetracarboxylic acid, 2,3,3′,4′-biphenyltetracarboxylic acid, 2,2′,3,3′-biphenyltetracarboxylic acid, 3,3 ',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2 ,3-dicarboxyphenyl)propane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dica
  • the tetracarboxylic dianhydride preferably contains one or more selected from the group consisting of the compounds represented by formula (1).
  • R 5 and R 12 each independently represent an oxygen atom, C(CH 3 ) 2 , C(CF 3 ) 2 or SO 2
  • R 6 and R 7 each independently represents a hydrogen atom , a hydroxyl group, a sulfonic acid group or a thiol group ; It represents an alkyl group of numbers 1-6.
  • pyromellitic dianhydride bis(3,4-dicarboxyphenyl)sulfone dianhydride, 4,4′-oxydiphthalic anhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoro propane dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride or an alkyl group on the aromatic ring thereof or a halogen atom-substituted compound is particularly preferred. These are used alone or in combination of two or more.
  • diamines used in the production method of the present invention include, but are not limited to, aromatic diamines and alicyclic diamines. Moreover, these may be used individually or in combination of 2 or more types.
  • diamine (b) examples include diamines having 5 to 40 carbon atoms to 12-valent diamines, such as 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diamino Diphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'- Diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophen
  • the diamine contains one or more selected from the group consisting of compounds represented by formula (3).
  • R 15 represents an oxygen atom, C(CH 3 ) 2 , C(CF 3 ) 2 or SO 2
  • R 16 and R 17 each independently represents a hydrogen atom, a hydroxyl group, a sulfonic acid or a thiol group, especially when it is a hydroxyl group, the resulting polyimide is easily dissolved in an alkaline aqueous solution, and the dissolution rate in the alkaline aqueous solution, which is the developer used for development, increases, and the cured portion of the resin composition coating film and It is preferable because the dissolution contrast of the uncured portion is increased and fine pattern workability can be easily obtained.
  • the monoamine (c) is further reacted in the step (1).
  • the ends of the polymer main chain can be end-capped with monoamines. End capping can be achieved, for example, by substituting a monoamine for a portion of the diamine.
  • monoamines include, but are not limited to, aromatic monoamines and alicyclic monoamines. Moreover, these may be used individually or in combination of 2 or more types.
  • monoamines include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy -4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene , 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4 -aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4,6-dihydroxypyrimidine,
  • the monoamine (c) preferably has one or more substituents selected from the group consisting of hydroxyl groups, sulfonic acid groups and thiol groups.
  • the resin composition containing the polyimide of the present invention tends to exhibit excellent storage stability and good workability, which is preferable.
  • the process includes a step (1) of reacting anhydride (a) and diamine (b) in a temperature range of 80° C. or higher and 250° C. or lower to obtain a polyimide.
  • the reaction solvent used in step (1) of the present invention and step (3) described later contains 60 to 100% by mass of water with respect to 100% by mass of the reaction solvent as a whole.
  • a reaction solvent for example, alcohols such as ethanol, methanol, isopropyl alcohol and tert-butyl alcohol, glycols such as ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol and ethylene glycol ether, tetrahydrofuran, diethyl ether, dioxane, Ethers such as propylene glycol monomethyl ether, polar aprotic solvents such as ⁇ -butyrolactone, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, and diacetone alcohol, esters such as ethyl acetate, propylene glycol monomethyl ether acetate, and ethyl lactate.
  • Organic solvents such as aromatic hydrocarbons such as toluene and
  • polyimide is produced via polyamic acid, which is a polyimide precursor.
  • polyamic acid which is a polyimide precursor.
  • tetracarboxylic acid and/or tetracarboxylic dianhydride and diamine form a salt in the reaction solvent without going through the polyamic acid, and dehydration polycondensation takes place from this monomer salt. It is believed that it proceeds to produce polyimide.
  • the reaction solvent In order for the polyimide polymerization reaction to proceed without passing through the polyamic acid of the present invention, the reaction solvent must contain 60% by mass or more of water, preferably 70% by mass or more, more preferably 80% by mass or more, and further.
  • the organic solvent contained in the reaction solvent is less than 40% by mass, the organic solvent hardly remains in the polyimide obtained by the production method of the present invention. From this viewpoint, the organic solvent contained in the reaction solvent is less than 40% by mass, preferably less than 30% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and most preferably 0% by mass.
  • the total amount of tetracarboxylic acid and/or tetracarboxylic dianhydride, diamine, and monoamine, which are reaction raw materials used in step (1) and step (3) described later, is the reaction solvent, tetracarboxylic acid and/or tetracarboxylic acid, and Based on the total amount of 100% by mass of the acid dianhydride, diamine and monoamine, it is preferably 1% by mass or more from the viewpoint of easiness of the imide bond generation reaction, and more preferably 5% by mass or more. 10% by mass or more is more preferable. From the viewpoint of suppressing undesirable side reactions occurring during the reaction, the content is preferably 50% by mass or less, more preferably 40% by mass or less, and more preferably 35% by mass or less.
  • a catalyst may be used in step (1) of the present invention and step (3) described later.
  • the catalyst here is not particularly limited as long as it is a compound that has the effect of promoting the progress of the dehydration polycondensation reaction or suppressing the progress of side reactions such as cross-linking and oxidation.
  • Examples include organic base catalysts and acid catalysts. be done.
  • Organic base catalysts include triethylamine, tributylamine, tripentylamine, N,N-dimethylaniline, N,N-diethylaniline, pyridine, ⁇ -picoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2 ,6-lutidine, quinoline, isoquinoline and the like.
  • Acid catalysts include inorganic acids such as hydrochloric acid, hydrogen bromide, hydrogen iodide, sulfuric acid, sulfuric anhydride, nitric acid, phosphoric acid, phosphorous acid, phosphotungstic acid, and phosphomolybdic acid, as well as methanesulfonic acid, ethanesulfonic acid, and trifluoromethane.
  • inorganic acids such as hydrochloric acid, hydrogen bromide, hydrogen iodide, sulfuric acid, sulfuric anhydride, nitric acid, phosphoric acid, phosphorous acid, phosphotungstic acid, and phosphomolybdic acid, as well as methanesulfonic acid, ethanesulfonic acid, and trifluoromethane.
  • Sulfonic acids such as sulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; carboxylic acids such as acetic acid and oxalic acid; and halogenated carboxylic acids such as chloroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, difluoroacetic acid and trifluoroacetic acid. etc. can be exemplified. These catalysts may be used alone or in combination of two or more.
  • the reaction temperature in step (1) of the present invention must be a temperature at which the tetracarboxylic acid and/or tetracarboxylic dianhydride used in the reaction and the diamine react to form an imide bond, so the lower limit is 80°C. is.
  • the temperature is preferably 100° C. or higher, more preferably 120° C. or higher, from the viewpoint that a polyimide having a sufficiently high molecular weight can be obtained.
  • the upper limit of the reaction temperature is 250° C. in order to avoid progress of cross-linking and decomposition of the monomer. Since it is necessary to cope with the vapor pressure of the reaction solvent, which increases as the reaction temperature rises, the temperature is preferably 230° C.
  • the temperature is more preferably 200° C. or lower, still more preferably 160° C. or lower, and most preferably 140° C. or lower, from the viewpoint that the yellowness degree can easily be adjusted to the preferred range.
  • the reaction pressure is adjusted from the viewpoint that the tetracarboxylic acid and/or tetracarboxylic dianhydride used in the reaction and the diamine are likely to react to form an imide bond.
  • the reaction pressure it is preferably 20 MPa or less, more preferably 10 MPa or less, from the viewpoint of the pressure resistance of the reaction vessel and the handleability of the reaction.
  • the reaction time depends on the type and amount of raw materials used or the reaction temperature, and cannot be generally defined, but is preferably 0.1 hour or longer. , more preferably 0.5 hours or longer, and more preferably 1 hour or longer. When the time is longer than this preferable time, there is a tendency that unreacted raw material components can be sufficiently reduced. On the other hand, there is no particular upper limit to the reaction time, but the reaction proceeds sufficiently within 40 hours, preferably within 20 hours, and more preferably within 10 hours.
  • step (1) for producing a polyimide by the preferred method described above and the step (3) described later there are no particular restrictions on the method and order of adding the reaction raw materials and solvent, and if necessary, the catalyst, etc. to the reaction vessel, but each They may be added all at once, or the reaction raw materials soluble in the reaction solvent may be dissolved in the reaction solvent in advance and then added.
  • the method of carrying out the reaction is not particularly limited, but it is preferably carried out under stirring conditions.
  • the atmosphere in step (1) and step (3) to be described later is preferably a non-oxidizing atmosphere, preferably an atmosphere of an inert gas such as nitrogen, helium, and argon, which is economical and easy to handle. It is preferable to carry out in a nitrogen atmosphere.
  • the first aspect of the method for producing polyimide of the present invention includes step (2) for chain extension of the polyimide obtained in step (1).
  • the chain extension step referred to in the present invention is a step for increasing the molecular weight of the polyimide, and the weight average molecular weight of the polyimide obtained in the step (1) is higher than the weight average molecular weight of the polyimide obtained in the step (1) after the step (2).
  • the weight average molecular weight of the obtained polyimide becomes larger.
  • the weight average molecular weight is measured by a gel permeation chromatography method (GPC method) and calculated in terms of polystyrene.
  • reaction solvent containing 60 to 100% by mass of water with respect to the solid phase polymerization step (2a) and the total 100% by mass of the reaction solvent is more than the step (1).
  • a step (2b) of obtaining a polyimide by reaction at a high temperature can be preferably used.
  • the atmosphere in the solid phase polymerization step (2a) is preferably a non-oxidizing atmosphere or a reduced pressure.
  • non-oxidizing atmosphere refers to an atmosphere having an oxygen concentration of 5% by volume or less, preferably 2% by volume or less, more preferably substantially free of oxygen in the gas phase in contact with the polyimide to be subjected to solid phase polymerization, i.e. nitrogen, It refers to an atmosphere of an inert gas such as helium or argon, and among these, a nitrogen atmosphere is particularly preferable from the viewpoint of economy and ease of handling.
  • the pressure-reduced condition means that the pressure in the reaction system is lower than the atmospheric pressure, and the upper limit is preferably 50 kPa or less, more preferably 20 kPa or less, and even more preferably 10 kPa or less. As a lower limit, 0.1 Pa or more can be exemplified. This tends to suppress the occurrence of undesirable side reactions such as cross-linking reaction and decomposition reaction of polyimide.
  • the temperature in step (2a) is not particularly limited as long as it is a temperature at which the polyimide obtained in step (1) is increased in molecular weight. Carrying out the reaction at 80° C. or higher facilitates sufficiently increasing the molecular weight, which is preferable. It is more preferably 100° C. or higher, still more preferably 120° C. or higher, particularly preferably 150° C. or higher, and most preferably 180° C. or higher.
  • the solid polyimide obtained in step (1) maintains a substantially solid state and is performed at a temperature at which the shape does not change. . It is more preferably 280° C. or lower, still more preferably 260° C. or lower, and most preferably 250° C. or lower.
  • the time in step (2a) is not particularly limited as long as the polyimide obtained in step (1) is sufficiently high in molecular weight.
  • the above is preferable, and 72 hours or less is preferable from the viewpoint that undesirable side reactions such as cross-linking reaction and decomposition reaction can be suppressed. It is more preferably 5 hours or more and 48 hours or less, still more preferably 10 hours or more and 36 hours or less, and most preferably 12 hours or more and 24 hours or less.
  • step (2b) of obtaining a polyimide by reacting it in the reaction solvent at a temperature higher than that in the step (1) after recovering the polyimide obtained in the step (1) from the reaction solvent, adding it again to the reaction solvent, the step It is also possible to carry out the reaction at a higher temperature than in (1), and it is also possible to carry out the reaction at a higher temperature without recovering or cooling the polyimide after step (1). From the viewpoint of simplicity of the process, it is preferable to continue the reaction at elevated temperature without recovering or cooling the polyimide after the process (1).
  • the reaction temperature in step (2b) is higher than in step (1), preferably 10° C. or higher and 200° C. or lower, more preferably 20° C. or higher and 180° C. or lower than the reaction temperature in step (1), It is more preferably 30°C or higher and 150°C or lower, and most preferably 50°C or higher and 120°C or lower.
  • the reaction time is preferably 0.1 hours or longer, more preferably 0.5 hours or longer, and even more preferably 1 hour or longer.
  • the time is longer than this preferable time, there is a tendency that the molecular weight is sufficiently increased.
  • there is no upper limit to the reaction time but the reaction proceeds sufficiently within 40 hours, preferably within 20 hours, more preferably within 10 hours.
  • the method of carrying out the reaction is not particularly limited, but it is preferably carried out under stirring conditions.
  • the atmosphere in step (2b) is desirably a non-oxidizing atmosphere, preferably under an inert gas atmosphere such as nitrogen, helium, and argon, and from the viewpoint of economic efficiency and ease of handling, it is preferable to carry out under a nitrogen atmosphere. is preferred.
  • a tetracarboxylic dianhydride having a purity of 98% by mass or more in a reaction solvent containing 60 to 100% by mass of water with respect to 100% by mass of the total reaction solvent. and a step (3) of reacting the substance (d) with a diamine (e) having a purity of 98% by mass or more in a temperature range of 100° C. or higher and 370° C. or lower to obtain a polyimide.
  • the tetracarboxylic dianhydride used in the step (3) of the present invention includes, but is not limited to, the same compounds as the tetracarboxylic dianhydride described above in the explanation of step (1).
  • the structure of the tetracarboxylic dianhydride is not particularly limited, it has a purity of 98% by mass or more, preferably a purity of 99% by mass or more, and more preferably a purity of 99.5% by mass or more.
  • a tetracarboxylic dianhydride with a purity of 98% by mass or more a polyimide with reduced yellowness can be obtained.
  • the purity is less than 98% by mass, the resulting polyimide has a high degree of yellowness.
  • the yellowness referred to here means that a polyimide solution in which polyimide is dissolved in an organic solvent is applied onto a substrate, and the solvent is removed by drying to prepare a polyimide film having a thickness of 10 ⁇ m. Shows a value calculated by measuring with a spectrophotometer.
  • Purity can be determined by, for example, high performance liquid chromatography analysis, gas chromatography analysis, and 1 H-NMR analysis.
  • the peak area attributed to the main component in the sample is the peak area attributed to the sample-derived peak when the sample is divided into components by high-performance liquid chromatography equipped with a UV detector. It can be calculated as a percentage.
  • the qualitative properties of each peak obtained by component separation by high-performance liquid chromatography can be performed by separating each peak by preparative liquid chromatography and performing absorption spectrum and mass spectrometry in infrared spectroscopic analysis.
  • Impurities contained in the tetracarboxylic dianhydride (d) having a purity of 98% by mass or more used in the present invention mainly originate from the production of the tetracarboxylic dianhydride, such as raw material carboxylic acids and carboxylic acid esters, Catalysts such as lower carboxylic acids (eg, formic acid, acetic acid, propionic acid, etc.), acetic anhydride, p-toluenesulfonic acid, sulfonic acid-type ion exchange resins, etc., and hydrolysates of tetracarboxylic dianhydrides.
  • the tetracarboxylic dianhydride such as raw material carboxylic acids and carboxylic acid esters, Catalysts such as lower carboxylic acids (eg, formic acid, acetic acid, propionic acid, etc.), acetic anhydride, p-toluenesulfonic acid, s
  • the diamine used in the step (3) of the present invention includes the same compounds as the diamine described in the explanation of the step (1), but is not limited to these.
  • the diamine (e) having a purity of 98% by mass or more contains one or more selected from the group consisting of compounds represented by formula (3).
  • R 15 represents an oxygen atom, C(CH 3 ) 2 , C(CF 3 ) 2 or SO 2
  • R 16 and R 17 each independently represents a hydrogen atom, a hydroxyl group, a sulfonic acid or a thiol group.
  • the obtained polyimide is easily dissolved in an alkaline aqueous solution, the dissolution rate in the alkaline aqueous solution which is the developer used for development increases, and the dissolution contrast between the cured part and the uncured part of the resin composition coating film is improved. It is preferable because it becomes large and fine pattern workability is easily obtained.
  • the structure of the diamine is not particularly limited, it has a purity of 98% by mass or more, preferably a purity of 99% by mass or more, and more preferably a purity of 99.5% by mass or more.
  • a diamine having a purity of 98% by mass or more a polyimide with suppressed yellow coloration can be obtained. If the purity is less than 98% by mass, the resulting polyimide tends to have a high degree of yellowness.
  • Impurities contained in the diamine (e) with a purity of 98% by mass or more used in the present invention include mainly compounds derived from the production of the diamine.
  • a monoamine (f) having a purity of 97% by weight or more is further reacted in the step (3).
  • the ends of the polymer main chain can be end-capped with monoamines. End capping can be achieved, for example, by substituting a monoamine for a portion of the diamine.
  • monoamines include, but are not limited to, aromatic monoamines and alicyclic monoamines. Moreover, these may be used individually or in combination of 2 or more types.
  • monoamines include, but are not limited to, compounds similar to those described above in the description of step (1).
  • two or more of these monoamines may be used in combination.
  • the structure of the monoamine is not particularly limited, but preferably has a purity of 97% by mass or more, more preferably a purity of 98% by mass or more, still more preferably a purity of 99% by mass or more, and particularly preferably a purity of 99.5% by mass or more. is.
  • a diamine having a purity of 97% by mass or more a polyimide with suppressed yellow coloration can be obtained.
  • Impurities contained in the monoamine (f) with a purity of 97% by mass or more used in the present invention include mainly compounds derived from the production of the monoamine.
  • a tetracarboxylic dianhydride (d) having a purity of 98% by mass or more in a reaction solvent containing 60 to 100% by mass of water with respect to 100% by mass of the total reaction solvent A step of reacting a diamine (e) having a purity of 98% by mass or more in a temperature range of 100° C. or higher and 370° C. or lower to produce a polyimide.
  • the reaction temperature in the second aspect of the method for producing a polyimide of the present invention must be a temperature at which the tetracarboxylic dianhydride and diamine used in the reaction react to form an imide bond, so the lower limit is 100°C. be.
  • the temperature is preferably 110° C. or higher, more preferably 120° C. or higher, still more preferably 160° C. or higher, and most preferably 180° C. or higher.
  • the upper limit of the reaction temperature is 370° C. in order to avoid progress of cross-linking and decomposition of the monomer.
  • the vapor pressure of the reaction solvent that increases as the reaction temperature rises it is preferably 310° C. or lower, more preferably 250° C. or lower, and still more preferably 250° C. or lower, from the viewpoint of the pressure resistance of the reaction vessel and the handleability of the reaction. is below 230°C.
  • the polyimide of the present invention is a polyimide having a structural unit represented by formula (2).
  • R 1 represents a 4- to 14-valent organic group having 5 to 40 carbon atoms
  • R 2 represents a 2- to 12-valent organic group having 5 to 40 carbon atoms
  • R 3 and R 4 are Each independently represents a hydroxyl group, a sulfonic acid group, a thiol group, or an organic group having 1 to 20 carbon atoms
  • ⁇ and ⁇ are integers from 0 to 10 that satisfy ⁇ + ⁇ 1.
  • R 1 in formula (2) represents a residue derived from a tetracarboxylic dianhydride, which is a tetravalent to 14valent organic group having 5 to 40 carbon atoms.
  • R 2 represents a residue derived from a diamine, and the diamine is a divalent to 14-valent organic group having 5 to 40 carbon atoms.
  • Any one of R 1 and R 2 preferably contains at least one group selected from 1,1,1,3,3,3-hexafluoropropyl group, ether group, thioether group and SO 2 group, Both R 1 and R 2 may be contained.
  • both R 1 and R 2 preferably have at least one group selected from 1,1,1,3,3,3-hexafluoropropyl group, ether group, thioether group and SO 2 group.
  • R 3 and R 4 each independently represent a hydroxyl group, a sulfonic acid group, a thiol group or an organic group having 1 to 20 carbon atoms, and ⁇ and ⁇ are integers from 0 to 10 satisfying ⁇ + ⁇ 1 indicates From the viewpoint of imparting solvent solubility to the resulting polyimide, it is particularly preferred that R 3 and R 4 are hydroxyl groups.
  • R 1 in formula (2) is a residue derived from a tetracarboxylic acid dianhydride having 5 to 40 carbon atoms and 4 to 14 valences.
  • tetracarboxylic dianhydride residues include pyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, Carboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3 '-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1, 1-bis
  • R 2 in formula (2) is a residue derived from a diamine to 12-valent diamine having 5 to 40 carbon atoms.
  • Diamine residues include, for example, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3, 4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzine, m -phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-
  • At least one of the main chain ends of the polyimide of the present invention preferably contains a structure blocked with a terminal blocking agent.
  • a residue derived from monoamine can be preferably exemplified.
  • Monoamine residues include, for example, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4- aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1- Carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid
  • the introduction ratio of the terminal blocking agent to the polyimide terminal is in the range of 0.1 to 60 mol% with respect to the total amine component when converted to the primary monoamine component of the terminal blocking agent, which is the original component. It is preferably 5 to 50 mol %, more preferably 5 to 50 mol %.
  • an aliphatic compound having a siloxane structure in R 1 and R 2 in the formula (3) is used within a range that does not reduce the heat resistance.
  • the groups may be copolymerized.
  • Specific examples of the diamine component include those obtained by copolymerizing 1 to 10 mol % of bis(3-aminopropyl)tetramethyldisiloxane, bis(p-amino-phenyl)octamethylpentasiloxane, or the like.
  • the polyimide of the present invention preferably has a weight average molecular weight of 1,000 or more and 200,000 or less, more preferably 5,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less. is more preferred. Within this range, good workability, mechanical properties, and heat resistance can be obtained.
  • the weight average molecular weight is measured by a gel permeation chromatography method (GPC method) and calculated in terms of polystyrene.
  • the polyimide of the present invention is preferably solvent-soluble.
  • Alkali-soluble is particularly preferred.
  • the solvent-soluble resin as used herein refers to a resin that dissolves at 25° C. in an amount of 0.1 g or more in 100 g of an organic solvent or an alkaline aqueous solution.
  • Organic solvents include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, dimethylsulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, Butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, toluene, xylene, N- methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, 1,
  • alkaline aqueous solutions include tetramethylammonium hydroxide (TMAH), diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylamino Aqueous solutions of ethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like can be mentioned.
  • TMAH tetramethylammonium hydroxide
  • diethanolamine diethylaminoethanol
  • sodium hydroxide sodium hydroxide
  • potassium hydroxide sodium carbonate
  • potassium carbonate potassium carbonate
  • triethylamine diethylamine
  • methylamine dimethylamine
  • dimethylaminoethyl acetate dimethylamino Aqueous solutions of ethanol, dimethylaminoe
  • the polyimide is solvent-soluble
  • a photosensitive resin composition using a polyimide solution in which the polyimide is dissolved can be developed, and from the viewpoint that an alkaline solution can be used as a developer, it is particularly alkali-soluble.
  • an alkaline solution can be used as a developer, it is particularly alkali-soluble.
  • the polyimide of the present invention preferably has a hydroxyl group, a sulfonic acid group, a thiol group, or an organic group having 1 to 20 carbon atoms as described above, and the dissolution rate in an alkaline aqueous solution as a developer is A hydroxyl group is particularly preferable from the viewpoint that it becomes larger, the dissolution contrast between the cured portion and the uncured portion of the resin composition coating film increases, and fine pattern workability can be easily obtained.
  • the polyimide of the present invention preferably has a light transmittance of 90% or more, more preferably 95% or more, and even more preferably 99% or more at a wavelength of 365 nm per 1 ⁇ m film thickness. Within this range, fine pattern workability can be expressed even in a thick film of 20 ⁇ m or more when the photosensitive resin composition is formed.
  • the polyimide of the present invention has a yellowness in the range of 0 to 3.0. If the yellowness is out of this range, the transparency will be impaired and the appearance will be poor, making it unsuitable for use in semiconductor devices and circuit boards.
  • the yellowness referred to here means that a polyimide solution in which polyimide is dissolved in an organic solvent is applied onto a substrate, and the solvent is removed by drying to prepare a polyimide film, and the obtained film is measured by a C light source color meter. Indicates a value calculated by measurement.
  • the yellowness index preferably ranges from 0 to 2.8, more preferably from 0 to 2.5.
  • the polyimide of the present invention has an organic solvent content of 1% by mass or less and does not substantially contain an organic solvent.
  • the content is preferably 0.1% by mass or less, and more preferably 0% by mass.
  • 0% by mass means that the organic solvent is not contained at all.
  • the content of organic solvents can be calculated by high-performance liquid chromatography, gas chromatography, and measuring the total organic carbon concentration (TOC).
  • TOC total organic carbon concentration
  • water-soluble components are extracted from polyimide obtained by polymerization using distilled water, and the concentration of extracted organic carbon is measured to calculate the content of organic solvent in the sample.
  • the polyimide resin composition of the present invention contains the polyimide represented by the formula (2), a photosensitizer and a solvent.
  • a photoacid generator As the photosensitizer, a photoacid generator, a photobase generator, a photopolymerization initiator, etc. can be used.
  • a photoacid generator When a photoacid generator is used, an acid is generated in the light-irradiated portion of the resin composition, and the solubility of the light-irradiated portion in an alkaline developer increases, so that a positive pattern in which the light-irradiated portion dissolves is obtained. be able to.
  • a photopolymerization initiator When a photopolymerization initiator is used, radicals are generated in the light-irradiated portion of the resin composition, radical polymerization proceeds, and the resin composition becomes insoluble in an alkaline developer, thereby forming a negative pattern. .
  • UV curing during exposure is accelerated, and sensitivity can be improved.
  • a quinonediazide compound can be exemplified as the photoacid generator, and a compound in which a sulfonic acid of naphthoquinonediazide is bonded to a compound having a phenolic hydroxyl group via an ester is preferable.
  • Examples of compounds having a phenolic hydroxyl group used here include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, and BisP-MZ.
  • BisP-EZ Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (tetrakis P-DO-BPA), TrisP -HAP, TrisP-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, methylene tris- FR-CR, BisRS-26X, BisRS-OCHP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC- F, 4PC, BIR-BIPC-F, TEP-BIP-A (trade names, manufactured by Asahi Organic
  • Preferable examples are those obtained by introducing 4-naphthoquinonediazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid into these compounds having a phenolic hydroxyl group via an ester bond, and compounds other than these can also be used.
  • Photopolymerization initiators include compounds containing polymerizable unsaturated functional groups. Examples include unsaturated triple bond functional groups such as propargyl, and among these, conjugated vinyl groups, acryloyl groups, and methacryloyl groups are preferred from the standpoint of polymerizability.
  • the number of functional groups contained is preferably 1 to 4 from the standpoint of stability, and the groups do not have to be the same. Further, the compound referred to herein means one having a molecular weight of 30-800.
  • benzophenones such as benzophenone, Michler's ketone, 4,4,-bis(diethylamino)benzophenone, 3,3,4,4,-tetra(t-butylperoxycarbonyl)benzophenone, and 3,5- benzylidenes such as bis(diethylaminobenzylidene)-N-methyl-4-piperidone, 3,5-bis(diethylaminobenzylidene)-N-ethyl-4-piperidone, 7-diethylamino-3-thenonylcoumarin, 4,6- dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis(7-diethylaminocoumarin), 7-diethylamino-3-(1-methylmethylbenzimidazolyl)coumarin, 3-(2-benzothiazolyl)-7-diethylaminocoumarin, etc.
  • benzophenones such as benzophenone, Michler's ketone, 4,4,-bis(
  • anthraquinones such as 2-t-butylanthraquinone, 2-ethylanthraquinone, 1,2-benzanthraquinone, benzoins such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, 2,4-dimethylthioxanthone, 2 Thioxanthones such as ,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-isopropylthioxanthone, ethylene glycol di(3-mercaptopropionate), 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, 2-mercapto mercaptos such as benzimidazole, glycines such as N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-(p-chlorophenyl)g
  • the content of the photosensitizer is not particularly limited, but is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and 0.7 parts by mass with respect to 100 parts by mass of the polyimide in the resin composition.
  • the above is more preferable, and 1 part by mass or more is particularly preferable.
  • the content of the photosensitive agent is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 17 parts by mass or less, with respect to 100 parts by mass of the polyimide in the resin composition.
  • the resolution after development can be improved as content of a photosensitive agent is in the said range.
  • Solvents contained in the polyimide resin composition of the present invention include, for example, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, dimethylsulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetone, methyl ethyl ketone.
  • cyclopentanone cyclohexanone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, diacetone alcohol, 3-methyl-3 -methoxybutanol, toluene, xylene, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropylene urea, 1,3-dimethylisobutyramide, methoxy-N,N-dimethylpropionamide, butoxy-N,N-dimethylpropionamide, dimethylsulfoxide, and the like, but are not limited to these.
  • solvents that pose health or environmental concerns specifically solvents that are subject to regulations in each country such as REACH regulations, N-methyl-2-pyrrolidone, N,N-dimethylformamide, For example, N,N-dimethylacetamide is not used.
  • the polyimide resin composition of the present invention contains 0% by mass of solvents that pose health and environmental concerns that are subject to regulations in various countries such as REACH regulations. be.
  • 0% by mass means that no organic solvent is contained.
  • the content of the solvent is not particularly limited, it is preferably 100 parts by mass or more and 10,000 parts by mass or less, more preferably 100 parts by mass or more and 5,000 parts by mass or less, relative to 100 parts by mass of the polyimide in the resin composition. 100 parts by mass or more and 2,000 parts by mass or less is particularly preferable.
  • the content of the solvent is preferable in terms of being able to form a coating film having a thickness of 1 ⁇ m or more with excellent coatability and flatness of the coating film.
  • the polyimide resin composition of the present invention can also contain additives such as cross-linking agents, cross-linking accelerators, sensitizers, dissolution modifiers, surfactants, stabilizers and antifoaming agents, if necessary.
  • the cured product of the present invention is a cured product obtained by curing the polyimide resin composition.
  • the method for obtaining the cured product of the present invention includes the steps of applying a polyimide resin composition on a substrate and drying to form a polyimide resin film on the substrate, exposing the photosensitive resin film, and the polyimide
  • a method including a step of removing an unexposed portion of the resin film with a developer and developing the film, and a step of heat-treating the polyimide resin film after the development to obtain a cured product can be exemplified.
  • the step of applying the polyimide resin composition onto a substrate and drying to form a polyimide resin film on the substrate includes, for example, applying the polyimide resin composition to a spin coater, a spray coater, a screen coater, a blade coater, and a die coater. , calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, slit die coater, etc., and dried at a temperature of 50 ° C or higher and 150 ° C or lower for 1 minute or more and several hours or less.
  • Polyimide Examples include, but are not limited to, a step of forming a resin film.
  • 365 nm i-line, 405 nm h-line, and 432 nm g-line of a high pressure mercury lamp are exposed at 50 mJ or more and 3,000 mJ or less. but not limited to this.
  • the polyimide resin film exposed by the above process may be baked after exposure. Post-exposure baking is preferably performed at 50° C. or higher from the viewpoint of curability and adhesion to the substrate, and preferably at 150° C. or lower from the viewpoint of resolution.
  • the step of removing the unexposed portion of the polyimide resin film with a developer for development includes, for example, spraying the developer onto the surface of the polyimide resin film, heaping the developer onto the film surface, immersing the film in the developer, Alternatively, a process of immersing and applying ultrasonic waves may be mentioned, but is not limited to these.
  • Developing conditions such as the developing time and the temperature of the developer in the developing step may be any conditions as long as the exposed portion can be removed and the pattern can be formed.
  • an alkali developer when an alkali developer is used, an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylamino acetate.
  • Aqueous solutions of alkaline compounds such as ethyl, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine are preferred.
  • the developer at this time includes N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, hexa
  • a polar solvent such as methyl phosphortriamide alone or in combination with methanol, ethanol, isopropyl alcohol, xylene, water, methyl carbitol, ethyl carbitol, or the like can be used.
  • alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing.
  • esters such as ethyl lactate and propylene glycol monomethyl ether acetate
  • an alcohol such as ethanol or isopropyl alcohol, ethyl lactate, propylene glycol monomethyl ether acetate, or the like may be added to water for rinsing.
  • the heat treatment is performed at a temperature of 150° C. or higher and 500° C. or lower for 5 minutes or more and 5 hours or less to advance the thermal cross-linking reaction. but not limited thereto.
  • a method of selecting a temperature and increasing the temperature stepwise or a method of selecting a certain temperature range and increasing the temperature continuously can be selected.
  • the former includes, for example, a method of heat-treating at 130° C. and 200° C. for 30 minutes each, but is not limited to this.
  • the latter includes, but is not limited to, a method of linearly increasing the temperature from room temperature to 400° C. over 2 hours.
  • the resin composition was applied on a copper substrate using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.), and a hot plate (SCW manufactured by Dainippon Screen Co., Ltd.) -636) and dried by heating at 100° C. for 3 minutes to form a coating film of 10 ⁇ m.
  • TMAH tetramethylammonium hydroxide
  • the patterned portion was observed using an FPD microscope (MX61, manufactured by Olympus Corporation) to determine the minimum pattern size free from abnormalities such as development residues, and fine pattern processability was evaluated based on the following criteria. It was determined that the smaller the minimum pattern size, the better the pattern workability.
  • Viscosity increase rate is less than 5%
  • B Viscosity increase rate is 5% or more and less than 10%
  • C Viscosity increase rate is 10% or more.
  • Purity is the ratio of the peak area attributed to the main component in the sample to the peak area attributed to the sample-derived peak when the components are divided.
  • Purity main component weight / (main component weight + impurity weight ).
  • ODPA-1 4,4'-oxydiphthalic anhydride purity 98% by mass
  • ODPA-2 4,4'-oxydiphthalic anhydride purity 95% by mass
  • ODPA-2 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride purity 99 mass%
  • TDA-1 Bis (3,4-dicarboxyphenyl) sulfonic acid dianhydride purity 98% by mass
  • BAHF-1 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane purity 95 mass%
  • BAHF-2) 1,3-bis(3-aminopropyl)tetramethyld
  • Example 1 31.02 g (0.1 mol) of 4,4′-oxydiphthalic anhydride (ODPA-2) and 2,2-bis(3-amino-4-hydroxyphenyl)hexanone were placed in a stainless steel autoclave equipped with a stirrer. 36.63 g (0.1 mol) of fluoropropane (BAHF-1) and 255 g of deionized water were charged. After the reaction vessel was sealed under nitrogen gas at room temperature and normal pressure, the temperature was raised from room temperature to 100° C. while stirring at 150 rpm. The pressure in the reaction system at this stage was 0.1 MPa in gauge pressure. After being held at 100° C. for 10 hours, it was allowed to cool to around room temperature.
  • ODPA-2 4,4′-oxydiphthalic anhydride
  • BAHF-1 fluoropropane
  • the resulting content was filtered using a filter paper with a pore size of 1 ⁇ m to recover the solid content.
  • the obtained solid content was subjected to vacuum drying at 50° C. for 12 hours to obtain polyimide (P1).
  • P1 was measured by infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 . Moreover, the weight average molecular weight was 6,000.
  • the obtained P1 was placed in a heat dryer, and after a reduced pressure atmosphere (133 Pa), the temperature was raised to 180°C. After being held at 180° C. for 12 hours, it was allowed to cool to around room temperature to obtain polyimide (P1′).
  • P1′ was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the obtained P1′ was evaluated according to the evaluation methods (1), (2), (3) and (4) above.
  • a resin composition was prepared by pressure filtration using a 1 ⁇ m filter. The prepared resin composition was evaluated according to the evaluation methods (5) and (6) above.
  • Example 2 31.02 g (0.1 mol) of ODPA-2, 30.03 g (0.082 mol) of BAHF-1 and 1,3-bis(3-aminopropyl)tetramethyl are placed in a stainless steel autoclave equipped with a stirrer. 1.24 g (0.005 mol) of disiloxane (SiDA-1), 2.73 (0.025 mol) of 3-aminophenol (MAP-1) and 255 g of deionized water were charged. After the reaction vessel was sealed under nitrogen gas at room temperature and normal pressure, the temperature was raised from room temperature to 120° C. while stirring at 150 rpm. The pressure in the reaction system at this stage was 0.2 MPa in gauge pressure. After being held at 120° C.
  • the obtained P2 was placed in a heat dryer and heated to 220° C. under a nitrogen stream. After being held at 220° C. for 10 hours, it was allowed to cool to around room temperature to obtain polyimide (P2′).
  • P2′ was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the resulting P2' was evaluated according to the evaluation methods (1), (2), (3) and (4) above.
  • a resin composition was prepared in the same manner as in Example 1, except that P2' was used instead of P1'.
  • the prepared resin composition was evaluated according to the evaluation methods (5) and (6) above.
  • Example 3 A stainless steel autoclave equipped with a stirrer was charged with 31.02 g (0.1 mol) of ODPA-2, 32.96 g (0.09 mol) of BAHF-1, and 1.0 g of p-aminobenzoic acid (AA-1). 51 g (0.01 mol) and 255 g of deionized water were charged. After the reaction vessel was sealed under nitrogen gas at room temperature and normal pressure, the temperature was raised from room temperature to 160° C. while stirring at 150 rpm. The pressure in the reaction system at this stage was 0.6 MPa in gauge pressure. After being held at 160° C. for 4 hours, it was allowed to cool to near room temperature.
  • the obtained contents were separated by filtration using filter paper with a pore size of 1 ⁇ m, and the solid content was recovered.
  • the obtained solid content was subjected to vacuum drying at 50° C. for 12 hours to obtain polyimide (P3).
  • P3 was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the weight average molecular weight was 10,300.
  • the obtained P3 was placed in a heat dryer, and after a reduced pressure atmosphere (133 Pa), the temperature was raised to 120°C. After being held at 120° C. for 24 hours, it was allowed to cool to around room temperature to obtain polyimide (P3′).
  • P3′ was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the resulting P3' was evaluated according to the evaluation methods (1), (2), (3) and (4) above.
  • a resin composition was prepared in the same manner as in Example 1, except that P3' was used instead of P1'.
  • the prepared resin composition was evaluated according to the evaluation methods (5) and (6) above.
  • Example 4 A stainless steel autoclave equipped with a stirrer was charged with 35.83 g (0.1 mol) of bis(3,4-dicarboxyphenyl)sulfonic dianhydride (BCSA-1) and 30.03 g (0.1 mol) of BAHF-1. 085 mol), 2.33 g (0.025 mol) of aniline (A-1), and 255 g of deionized water were charged. After the inside of the reaction vessel was replaced with nitrogen gas at room temperature and normal pressure, the temperature was raised from room temperature to 180° C. while stirring at 150 rpm. The pressure in the reaction system at this stage was 1.0 MPa in gauge pressure. After being held at 180° C. for 4 hours, it was allowed to cool to around room temperature.
  • BCSA-1 bis(3,4-dicarboxyphenyl)sulfonic dianhydride
  • the obtained contents were separated by filtration using filter paper with a pore size of 1 ⁇ m, and the solid content was recovered.
  • the obtained solid content was subjected to vacuum drying at 50° C. for 12 hours to obtain polyimide (P4).
  • P4 was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 . Moreover, the weight average molecular weight was 13,400.
  • the obtained P4 was placed in a heat dryer, and after a reduced pressure atmosphere (133 Pa), the temperature was raised to 240°C. After being held at 240° C. for 5 hours, it was allowed to cool to around room temperature to obtain polyimide (P4′).
  • a resin composition was prepared in the same manner as in Example 1, except that P4' was used instead of P1'.
  • the prepared resin composition was evaluated according to the evaluation methods (5) and (6) above.
  • Example 5 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride (TDA-1) was placed in a stainless steel autoclave equipped with a stirrer. 30.03 g (0.1 mol) of , 32.96 g (0.09 mol) of BAHF-1, 2.18 g (0.02 mol) of MAP-1, and 255 g of deionized water were charged. After the reaction vessel was sealed under nitrogen gas at room temperature and normal pressure, the temperature was raised from room temperature to 150° C. while stirring at 150 rpm. The pressure in the reaction system at this stage was 0.5 MPa in gauge pressure.
  • TDA-1 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride
  • P5′ polyimide
  • P5′ was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the resulting P5' was evaluated according to the evaluation methods (1), (2), (3) and (4) above.
  • a resin composition was prepared in the same manner as in Example 1, except that P5' was used instead of P1'.
  • the prepared resin composition was evaluated according to the evaluation methods (5) and (6) above.
  • Example 6 A stainless steel autoclave equipped with a stirrer was charged with 31.02 g (0.1 mol) of ODPA-2, 33.43 g (0.1 mol) of BAHF-1, and 255 g of deionized water. After the reaction vessel was sealed under nitrogen gas at room temperature and normal pressure, the temperature was raised from room temperature to 120° C. while stirring at 150 rpm. The pressure in the reaction system at this stage was 0.2 MPa in gauge pressure. After being held at 120° C. for 4 hours, it was allowed to cool to around room temperature. The obtained contents were separated by filtration using filter paper with a pore size of 1 ⁇ m, and the solid content was recovered. The obtained solid content was subjected to vacuum drying at 50° C.
  • polyimide (P6).
  • P6 was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 . Moreover, the weight average molecular weight was 12,000.
  • the obtained P6 was placed in a heat dryer and heated to 180° C. under a nitrogen stream. After being held at 180° C. for 12 hours, it was allowed to cool to around room temperature to obtain polyimide (P6′).
  • P6′ was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the resulting P6' was evaluated according to the evaluation methods (1), (2), (3) and (4) above.
  • a resin composition was prepared in the same manner as in Example 1, except that P6' was used instead of P1'.
  • the prepared resin composition was evaluated according to the evaluation methods (5) and (6) above.
  • Example 7 31.02 g (0.1 mol) of ODPA-2, 28.41 g (0.085 mol) of BAHF-1, and 2.33 g (0.025 mol) of A-1 in a stainless steel autoclave equipped with a stirrer , 255 g of ion-exchanged water was charged. After the reaction vessel was sealed under nitrogen gas at room temperature and normal pressure, the temperature was raised from room temperature to 160° C. while stirring at 150 rpm. The pressure in the reaction system at this stage was 0.6 MPa in gauge pressure. After being held at 160° C. for 4 hours, it was allowed to cool to near room temperature. The obtained contents were separated by filtration using filter paper with a pore size of 1 ⁇ m, and the solid content was recovered.
  • the obtained solid content was subjected to vacuum drying at 50° C. for 12 hours to obtain polyimide (P7).
  • P7 was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the weight average molecular weight was 11,500.
  • the obtained P7 was placed in a heat dryer and heated to 180° C. under a nitrogen stream. After being held at 180° C. for 24 hours, it was allowed to cool to around room temperature to obtain polyimide (P7′).
  • P7′ was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the resulting P7' was evaluated according to the evaluation methods (1), (2), (3) and (4) above.
  • a resin composition was prepared in the same manner as in Example 1, except that P7' was used instead of P1'.
  • the prepared resin composition was evaluated according to the evaluation methods (5) and (6) above.
  • Example 8 31.02 g (0.1 mol) of ODPA-2, 28.41 g (0.085 mol) of BAHF-1, and 2.73 g (0.025 mol) of MAP-1 in a stainless steel autoclave equipped with a stirrer , 255 g of ion-exchanged water was charged. After the reaction vessel was sealed under nitrogen gas at room temperature and normal pressure, the temperature was raised from room temperature to 160° C. while stirring at 150 rpm. The pressure in the reaction system at this stage was 0.6 MPa in gauge pressure. After being held at 160° C. for 4 hours, it was allowed to cool to around room temperature. The obtained contents were separated by filtration using filter paper with a pore size of 1 ⁇ m, and the solid content was recovered.
  • the obtained solid content was subjected to vacuum drying at 50° C. for 12 hours to obtain polyimide (P8).
  • P8 was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the weight average molecular weight was 10,800.
  • the obtained P8 was placed in a heat dryer and heated to 180° C. under a nitrogen stream. After holding at 180° C. for 24 hours, it was allowed to cool to around room temperature to obtain polyimide (P8′).
  • P8′ was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the resulting P8' was evaluated according to the evaluation methods (1), (2), (3) and (4) above.
  • a resin composition was prepared in the same manner as in Example 1, except that P8' was used instead of P1'.
  • the prepared resin composition was evaluated according to the evaluation methods (5) and (6) above.
  • Example 9 31.02 g (0.1 mol) of ODPA-2, 28.41 g (0.085 mol) of BAHF-1, and 3-aniline sulfonic acid (AS-1) were placed in a stainless steel autoclave equipped with a stirrer. 33 g (0.025 mol) and 255 g of deionized water were charged. After the reaction vessel was sealed under nitrogen gas at room temperature and normal pressure, the temperature was raised from room temperature to 160° C. while stirring at 150 rpm. The pressure in the reaction system at this stage was 0.6 MPa in gauge pressure. After being held at 160° C. for 4 hours, it was allowed to cool to around room temperature.
  • the obtained contents were separated by filtration using filter paper with a pore size of 1 ⁇ m, and the solid content was recovered.
  • the obtained solid content was subjected to vacuum drying at 50° C. for 12 hours to obtain a polyimide (P9).
  • P9 was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the weight average molecular weight was 9,500.
  • the obtained P9 was placed in a heat dryer and heated to 180° C. under a nitrogen stream. After being held at 180° C. for 24 hours, it was allowed to cool to around room temperature to obtain polyimide (P9′).
  • P9′ was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the resulting P9' was evaluated according to the evaluation methods (1), (2), (3) and (4) above.
  • a resin composition was prepared in the same manner as in Example 1, except that P9' was used instead of P1'.
  • the prepared resin composition was evaluated according to the evaluation methods (5) and (6) above.
  • Example 10 31.02 g (0.1 mol) of ODPA, 28.41 g (0.085 mol) of BAHF-1, 3.13 g (AB-1) of 3-aminobenzenethiol (AB-1) were added to a stainless steel autoclave equipped with a stirrer. 0.025 mol) and 255 g of ion-exchanged water were charged. After the reaction vessel was sealed under nitrogen gas at room temperature and normal pressure, the temperature was raised from room temperature to 160° C. while stirring at 150 rpm. The pressure in the reaction system at this stage was 0.6 MPa in gauge pressure. After being held at 160° C. for 4 hours, it was allowed to cool to around room temperature.
  • the obtained contents were separated by filtration using filter paper with a pore size of 1 ⁇ m, and the solid content was recovered.
  • the obtained solid content was subjected to vacuum drying at 50° C. for 12 hours to obtain polyimide (P10).
  • P10 was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the weight average molecular weight was 10,800.
  • the obtained P10 was placed in a heat dryer and heated to 180° C. under a nitrogen stream. After holding at 180° C. for 24 hours, it was allowed to cool to around room temperature to obtain polyimide (P10′).
  • P10′ was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the obtained P10′ was evaluated according to the evaluation methods (1), (2), (3) and (4) above.
  • a resin composition was prepared in the same manner as in Example 1, except that P10' was used instead of P1'.
  • the prepared resin composition was evaluated according to the evaluation methods (5) and (6) above.
  • Example 11 31.02 g (0.1 mol) of ODPA-2, 30.03 g (0.082 mol) of BAHF-1, and 1.24 g (0.005 mol) of SiDA-1 in a stainless steel autoclave equipped with a stirrer , 2.73 (0.025 mol) of MAP-1, 204 g of deionized water, and 51 g of methanol were charged. After the reaction vessel was sealed under nitrogen gas at room temperature and normal pressure, the temperature was raised from room temperature to 120° C. while stirring at 150 rpm. The pressure in the reaction system at this stage was 0.3 MPa in gauge pressure. After being held at 120° C. for 4 hours, it was allowed to cool to near room temperature.
  • the obtained contents were separated by filtration using filter paper with a pore size of 1 ⁇ m, and the solid content was recovered.
  • the obtained solid content was subjected to vacuum drying at 50° C. for 12 hours to obtain polyimide (P11).
  • P11 was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 . Moreover, the weight average molecular weight was 7,000.
  • the obtained P11 was placed in a heat dryer, and after a reduced pressure atmosphere (133 Pa), the temperature was raised to 180°C. After holding at 180° C. for 12 hours, it was allowed to cool to around room temperature to obtain polyimide (P11′).
  • P11′ was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the obtained P11′ was evaluated according to the evaluation methods (1), (2), (3) and (4) above.
  • a resin composition was prepared in the same manner as in Example 1, except that P11' was used instead of P1'.
  • the prepared resin composition was evaluated according to the evaluation methods (5) and (6) above.
  • Example 12 A stainless steel autoclave equipped with a stirrer was charged with 31.02 g (0.1 mol) of ODPA-2, 36.63 g (0.1 mol) of BAHF-1, and 255 g of deionized water. After the reaction vessel was sealed under nitrogen gas at room temperature and normal pressure, the temperature was raised from room temperature to 80° C. while stirring at 150 rpm. The pressure in the reaction system at this stage was 0.0 MPa in gauge pressure. After being held at 80° C. for 10 hours, it was allowed to cool to near room temperature. The obtained contents were separated by filtration using filter paper with a pore size of 1 ⁇ m, and the solid content was recovered. The obtained solid content was subjected to vacuum drying at 50° C.
  • polyimide (P12).
  • P12 was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 . Moreover, the weight average molecular weight was 4,000.
  • the obtained P12 was placed in a heat dryer, and after a reduced pressure atmosphere (133 Pa), the temperature was raised to 180°C. After holding at 180° C. for 12 hours, it was allowed to cool to around room temperature to obtain polyimide (P12′).
  • P12′ was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the resulting P12' was evaluated according to the evaluation methods (1), (2), (3) and (4) above.
  • a resin composition was prepared in the same manner as in Example 1, except that P12' was used instead of P1'.
  • the prepared resin composition was evaluated according to the evaluation methods (5) and (6) above.
  • Example 13 31.02 g (0.1 mol) of ODPA-2, 30.03 g (0.082 mol) of BAHF-1, and 1.24 g (0.005 mol) of SiDA-1 in a stainless steel autoclave equipped with a stirrer , 2.73 (0.025 mol) of MAP-1 and 255 g of deionized water were charged. After the reaction vessel was sealed under nitrogen gas at room temperature and normal pressure, the temperature was raised from room temperature to 100° C. while stirring at 150 rpm. The pressure in the reaction system at this stage was 0.0 MPa in gauge pressure. After being held at 100° C. for 5 hours, it was allowed to cool to around room temperature.
  • the obtained contents were separated by filtration using filter paper with a pore size of 1 ⁇ m, and the solid content was recovered.
  • the obtained solid content was subjected to vacuum drying at 50° C. for 12 hours to obtain polyimide (P13).
  • P13 was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the weight average molecular weight was 5,7000.
  • a resin composition was prepared in the same manner as in Example 1, except that P13' was used instead of P1'.
  • the prepared resin composition was evaluated according to the evaluation methods (5) and (6) above.
  • the obtained P14 was placed in a heat dryer and heated to 220° C. under a nitrogen stream. After holding at 220° C. for 24 hours, it was allowed to cool to around room temperature to obtain polyimide (P14′).
  • P14′ was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the resulting P14' was evaluated according to the evaluation methods (1), (2), (3) and (4) above.
  • the obtained contents were separated by filtration using filter paper with a pore size of 1 ⁇ m, and the solid content was recovered.
  • the obtained solid content was subjected to vacuum drying at 50° C. for 12 hours to obtain polyimide (P15).
  • P15 polyimide
  • absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the weight average molecular weight was 23,500.
  • the obtained P15 was placed in a heat dryer, and after a reduced pressure atmosphere (133 Pa), the temperature was raised to 180°C. After being held at 180° C. for 12 hours, it was allowed to cool to around room temperature to obtain polyimide (P15′).
  • P15′ was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the obtained P15′ was evaluated according to the evaluation methods (1), (2), (3) and (4) above.
  • a resin composition was prepared in the same manner as in Example 1, except that P15' was used instead of P1'.
  • the prepared resin composition was evaluated according to the evaluation methods (5) and (6) above.
  • the reaction solution was poured into 3 L of ion-exchanged water, and the precipitate was collected by filtration using a filter paper with a pore size of 1 ⁇ m. After the collected precipitate was washed with water three times, it was subjected to vacuum drying at 50° C. for 12 hours to obtain polyimide (P16).
  • P16 was measured by infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 . Moreover, the weight average molecular weight was 13,100.
  • the obtained P16 was placed in a heat dryer and heated to 180° C. under a nitrogen stream. After holding at 180° C. for 12 hours, it was allowed to cool to around room temperature to obtain polyimide (P16′).
  • P16′ was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the resulting P16' was evaluated according to the evaluation methods (1), (2), (3) and (4) above.
  • a resin composition was prepared in the same manner as in Example 1, except that P16' was used instead of P1'.
  • the prepared resin composition was evaluated according to the evaluation methods (5) and (6) above.
  • the obtained solid content was subjected to vacuum drying at 50° C. for 12 hours to obtain a product (P17).
  • P17 was measured by infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the weight average molecular weight was 1,000.
  • the obtained P17 was placed in a heat dryer and heated to 220° C. under a nitrogen stream. After being kept at 220° C. for 24 hours, it was allowed to cool to around room temperature to obtain a polyimide (P17′).
  • P17′ was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the resulting P17' was evaluated according to the evaluation methods (1), (2), (3) and (4) above.
  • Table 1 shows the evaluation results of Examples 1 to 13 and Comparative Examples 1 to 4.
  • Example 14 A stainless steel autoclave equipped with a stirrer was charged with ODPA-1 (31.02 g, 0.1 mol), BAHF-1 (36.63 g, 0.1 mol), and 255 g of deionized water. After the reaction vessel was sealed under nitrogen gas at room temperature and normal pressure, the temperature was raised from room temperature to 195° C. over about 1.5 hours while stirring at 150 rpm. The pressure in the reaction system at this stage was 1.5 MPa in gauge pressure. After being held at 195° C. for 4 hours, it was allowed to cool to around room temperature. The obtained contents were separated by filtration using filter paper with a pore size of 1 ⁇ m, and the solid content was recovered. The obtained solid content was subjected to vacuum drying at 80° C.
  • P18 polyimide
  • P18 was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 . Moreover, the weight average molecular weight was 27,500.
  • the obtained P18 was evaluated according to the evaluation methods (2), (3) and (4) above.
  • ODPA-1 31.02 g, 0.1 mol
  • BAHF-1 (30.03 g, 0.082 mol)
  • SiDA-1 1.24 g, 0.005 mol
  • MAP-1 2.73 g, 0.025 mol
  • 255 g of deionized water were charged.
  • the temperature was raised from room temperature to 210° C. over about 1.5 hours while stirring at 150 rpm.
  • the pressure in the reaction system at this stage was 2.0 MPa in gauge pressure. After being held at 210° C. for 4 hours, it was allowed to cool to near room temperature.
  • the obtained contents were separated by filtration using filter paper with a pore size of 1 ⁇ m, and the solid content was recovered.
  • the obtained solid content was subjected to vacuum drying at 80° C. for 12 hours to obtain a polyimide (P19).
  • P19 was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 . Moreover, the weight average molecular weight was 29,300.
  • the obtained P19 was evaluated according to the evaluation methods (2), (3) and (4) above.
  • the obtained contents were separated by filtration using filter paper with a pore size of 1 ⁇ m, and the solid content was recovered.
  • the obtained solid content was subjected to vacuum drying at 80° C. for 12 hours to obtain polyimide (P20).
  • P20 was measured by infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the weight average molecular weight was 32,400.
  • the obtained P20 was evaluated according to the evaluation methods (2), (3) and (4) above.
  • TDA-1 (30.03 g, 0.1 mol), BAHF-1 (32.96 g, 0.09 mol), MAP-1 (2.18 g, 0.02 mol) were placed in a stainless steel autoclave equipped with a stirrer. , and charged with 255 g of ion-exchanged water. After the reaction vessel was sealed under nitrogen gas at room temperature and normal pressure, the temperature was raised from room temperature to 190° C. over about 1.5 hours while stirring at 150 rpm. The pressure in the reaction system at this stage was 1.2 MPa in gauge pressure. After being held at 190° C. for 4 hours, it was allowed to cool to near room temperature.
  • the obtained contents were separated by filtration using filter paper with a pore size of 1 ⁇ m, and the solid content was recovered.
  • the obtained solid content was subjected to vacuum drying at 80° C. for 12 hours to obtain polyimide (P21).
  • P21 was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 .
  • the weight average molecular weight was 24,400.
  • the obtained P21 was evaluated according to the evaluation methods (2), (3) and (4) above.
  • the reaction solution was poured into 3 L of ion-exchanged water, and the precipitate was collected by filtration using a filter paper with a pore size of 1 ⁇ m. After the collected precipitate was washed with water three times, it was subjected to vacuum drying at 80° C. for 12 hours to obtain polyimide (P22).
  • P22 was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 . Moreover, the weight average molecular weight was 28,800.
  • the obtained P22 was evaluated according to the evaluation methods (2), (3) and (4) above.
  • the obtained contents were separated by filtration using filter paper with a pore size of 1 ⁇ m, and the solid content was recovered.
  • the obtained solid content was subjected to vacuum drying at 80° C. for 12 hours to obtain polyimide (P23).
  • P23 was measured by an infrared absorption spectrum, absorption peaks of an imide structure due to polyimide were detected near 1,780 cm ⁇ 1 and 1,377 cm ⁇ 1 . Moreover, the weight average molecular weight was 29,300.
  • the obtained P23 was evaluated according to the evaluation methods (2), (3) and (4) above.
  • Table 2 shows the evaluation results of Examples 14 to 17 and Comparative Examples 5 and 6.
  • a cured product obtained by curing a polyimide resin composition containing polyimide obtained by the present invention can be suitably used as an insulating film or a protective film constituting electronic parts. Furthermore, since it does not substantially contain solvents that pose health and environmental concerns, it can greatly contribute to the provision of sustainable industrial products.
  • electronic components include active components having semiconductors such as transistors, diodes, integrated circuits (ICs) and memories, and passive components such as resistors, capacitors and inductors.
  • the electronic components also include packages sealed for the purpose of improving the durability of these components, and modules in which a plurality of components are integrated.
  • An electronic component using a semiconductor is also called a semiconductor device or a semiconductor package.
  • a touch sensor panel etc. are mentioned.
  • cured products in electronic components include passivation films for semiconductors, surface protective films for semiconductor elements or TFTs (Thin Film Transistors), and interlayer insulation between rewiring in multilayer wiring for high-density mounting of 2 to 10 layers. It is suitably used for applications such as interlayer insulating films such as films, interlayer insulating films for passive components such as thin film capacitors, piezoelectric elements, and signal filters, insulating films for touch panels, and protective films.
  • the cured product of the present invention can be used for each member of an image display device such as an organic EL display and a liquid crystal display.
  • a planarizing layer a wiring planarizing layer, a TFT protective layer, an electrode protective layer, a wiring protective layer, a gate insulating layer, a color filter, a black matrix, or a black column spacer. It is not limited to this, and can be used for various purposes.

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Abstract

La présente invention concerne : un procédé de production de polyimide comprenant une étape (1) pour obtenir un polyimide en provoquant une réaction entre (b) une diamine et (a) un acide tétracarboxylique et/ou un dianhydride d'acide tétracarboxylique dans une plage de température de 80 à 250 °C dans un solvant de réaction contenant de 60 à 100 % en masse d'eau par rapport à un total de 100 % en masse du solvant de réaction, et une étape (2) pour réaliser une extension de chaîne du polyimide obtenu ; ou un procédé de production de polyimide comprenant une étape (3) pour obtenir un polyimide en provoquant une réaction entre (e) une diamine ayant une pureté supérieure ou égale à 98 % en masse et (d) un dianhydride d'acide tétracarboxylique ayant une pureté de 98 % en masse ou plus dans une plage de température de 100 à 370 °C dans un solvant de réaction contenant de 60 à 100 % en masse d'eau par rapport à un total de 100 % en masse du solvant de réaction.　L'invention concerne : un procédé qui permet de produire un polyimide approprié pour un film d'isolation intercouche et un film de protection de surface pour des composants électroniques, etc., et qui permet de réduire la quantité d'utilisation de solvants organiques ; ledit polyimide, une composition de résine contenant ledit polyimide ; et un produit durci formé à partir de la composition de résine.
PCT/JP2022/039608 2021-11-02 2022-10-25 Procédé de production de polyimide, polyimide, composition de résine de polyimide et produit durci associé WO2023080007A1 (fr)

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US20190177483A1 (en) * 2016-08-19 2019-06-13 Technische Universität Wien Method for producing polyimides
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CN117806123A (zh) * 2024-02-29 2024-04-02 明士(北京)新材料开发有限公司 一种化学增幅型负性光敏聚酰亚胺组合物及其应用
CN117806123B (zh) * 2024-02-29 2024-05-31 明士(北京)新材料开发有限公司 一种化学增幅型负性光敏聚酰亚胺组合物及其应用

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