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WO2015052907A1 - Composition d'un dérivé de benzofuranne, composition d'un précurseur de polyimide, et procédé de production d'une résine de polyimide - Google Patents

Composition d'un dérivé de benzofuranne, composition d'un précurseur de polyimide, et procédé de production d'une résine de polyimide Download PDF

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WO2015052907A1
WO2015052907A1 PCT/JP2014/005070 JP2014005070W WO2015052907A1 WO 2015052907 A1 WO2015052907 A1 WO 2015052907A1 JP 2014005070 W JP2014005070 W JP 2014005070W WO 2015052907 A1 WO2015052907 A1 WO 2015052907A1
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group
polyimide precursor
bis
composition
benzofuran
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Japanese (ja)
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小林　正典
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JFE Chemical Corp
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JFE Chemical Corp
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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

Definitions

  • the present invention relates to a benzofuran derivative composition, a polyimide precursor composition, and a method for producing a polyimide resin.
  • Polyimide is one of the super engineering plastics. It boasts higher heat resistance than other polymer materials, and has extremely excellent performance in terms of mechanical strength and chemical resistance. In addition, since it has a low dielectric constant, excellent electrical insulation, excellent elongation characteristics, and a low thermal expansion coefficient, it has been widely used in industrial products such as an insulating layer of an electronic circuit and a binder carrying a conductive material.
  • polyimide has poor solubility in a solvent and is difficult to process, so it may be used in a composition containing a precursor and molded into a desired shape, and then heated to form a polyimide. Many.
  • Such a composition is usually often handled through coating, and in order to avoid viscosity modification and precipitation that hinder the film-forming property during coating over time, a solvent with high polarity and high dissolving power is used.
  • N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide and the like are widely used.
  • these solvents are pointed out as having large environmental burdens such as reproductive toxicity and generation of nitrogen oxides and sulfur oxides during incineration, and the problem is that they cannot be handled without special equipment and protective equipment.
  • polyimide precursors are often unstable to water, it is difficult to maintain properties suitable for coating without causing gelation or precipitation when water-based compositions using water as a solvent or dispersion medium are used. Problems arise in processability and storage stability when the composition is applied and dried.
  • aprotic polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide and the like used as a medium for a composition containing a polyimide precursor
  • a solvent with high environmental load such as high skin permeability derived from polar groups, biotoxicity, and generation of nitrogen oxides upon combustion.
  • these organic solvents are relatively expensive solvents, they also cause an increase in production cost.
  • Patent Documents 1 to 3 disclose means for producing an aqueous resin composition of a polyimide precursor by forming a salt of a polyimide precursor (polyamic acid) and a specific amine. If left for a long period of time, aggregates, precipitates, and gels are formed, and satisfactory coating stability cannot be obtained, such as inability to perform good coating.
  • Patent Document 4 discloses that a protective group is introduced via a hemiacetal ester bond by a reaction between a carboxy group of a polyamic acid, which is a polyimide precursor, and a vinyl ether compound. In the presence of water molecules, the bond easily decomposes even at room temperature, and transformation into acetaldehyde and alcohol occurs, so that practical storage stability cannot be obtained.
  • the present invention provides an aqueous composition of a polyimide precursor that is excellent in coating property and storage stability, and also excellent in solvent resistance and water resistance of a cured product, and a method for producing a polyimide resin (cured product). This is the issue.
  • An aqueous composition of a polyimide precursor (polyimide precursor composition) obtained by mixing a specific polyamine in an aqueous medium has excellent coating properties and storage stability, and is also resistant to polyimide resin obtained by curing. It was found that the solvent and water resistance were excellent, and the present invention was completed.
  • the present invention includes the following (1) to (4).
  • X is a tetravalent organic group (excluding those having a group reactive with an amino group)
  • R 3 , R 4 , R 5 and R 6 may be bonded to each other to show a cyclic structure.
  • X is a tetravalent organic group (excluding those having a group reactive with an amino group)
  • R 3 , R 4 , R 5 and R 6 may be bonded to each other to show a cyclic structure.
  • Y is an m-valent organic group (excluding those containing a group reactive with a carboxy group), and m is an integer of 2 or more.
  • a benzofuran derivative composition production process in which a benzofuran compound represented by the following formula (A), a tetracarboxylic acid represented by the following formula (B), and an aqueous medium are mixed and stirred.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom, a halogen atom or a monovalent organic group (reactive with an amino group or a carboxy group) R 3 , R 4 , R 5 and R 6 may be bonded to each other to show a cyclic structure.
  • X is a tetravalent organic group (excluding those containing a group reactive with an amino group).
  • Y is an m-valent organic group (excluding those containing a group reactive with a carboxy group), and m is an integer of 2 or more.
  • the polyimide resin aqueous composition excellent in the solvent resistance and water resistance of a polyimide resin, and the manufacturing method of a polyimide resin can be provided. .
  • One feature of the present invention is that in the polyimide precursor, a carboxy group derived from tetracarboxylic acid has a hemiacetal ester bond formed by an addition reaction with a benzofuran compound.
  • the hemiacetal bond formed by the reaction of a benzofuran compound and a carboxy group has resistance to hydrolysis, and deprotection due to elimination of the protective group of the carboxy group does not easily occur, so polyimide in an aqueous medium
  • the stability of the precursor is high, and the storage stability of the polyimide precursor composition is excellent.
  • the inventor has found that the hemiacetal ester bond formed by the reaction of a vinyl ether compound and a carboxy group as described in Patent Document 4 can have a planar structure for resistance to hydrolysis.
  • the hemiacetal ester bond formed by the reaction of the benzofuran compound and the carboxy group is sterically hindered by the five-membered ring of the benzofuran compound, so that the hemiacetal bond is planar. It is presumed that the resistance to hydrolysis is increased due to the inability to add water to the structure. Furthermore, it is considered that not only the stability in an aqueous medium is high, but also the stability in an organic solvent is high.
  • the hemiacetal bond formed by the reaction between the benzofuran compound and the carboxy group is rapidly decomposed by heating to 170 ° C. or higher, and the benzofuran compound is eliminated.
  • the carboxy group can be protected until just before.
  • the detached benzofuran compound is vaporized during heating, the polyimide after imidization has very little residual benzofuran compound, and does not impair the solvent resistance and water resistance of the polyimide resin.
  • the manufacturing method of the polyimide resin of this invention is equipped with a benzofuran derivative composition manufacturing process, a polyimide precursor composition manufacturing process, and a polyimide resin manufacturing process.
  • a benzofuran derivative composition manufacturing process a benzofuran derivative composition containing a benzofuran derivative and an aqueous medium is manufactured
  • a polyimide precursor composition manufacturing process a polyimide precursor containing a benzofuran derivative composition, a polyamine, and an aqueous medium.
  • a composition is produced.
  • the benzofuran derivative composition manufacturing process is a process in which a benzofuran compound, a tetracarboxylic acid, and an aqueous medium are mixed and stirred to produce an aqueous composition of a benzofuran derivative (benzofuran derivative composition). is there.
  • the benzofuran compound used in the manufacturing process of the benzofuran derivative composition is represented by the following formula (A), and the tetracarboxylic acid is represented by the following formula (B).
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom, a halogen atom or a monovalent organic group (reactive with an amino group or a carboxy group).
  • R 3 , R 4 , R 5 and R 6 may be bonded to each other to represent a cyclic structure.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are determined depending on the benzofuran compound.
  • Examples of the monovalent organic group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group ( aryl group) and the like.
  • an alkyl group is preferable, a C 1-3 alkyl group selected from a methyl group, an ethyl group, a propyl group, and an isopropyl group is more preferable, and a methyl group is more preferable.
  • an arbitrary hydrogen atom may be substituted with a halogen atom.
  • halogen atom a fluorine atom is preferable. However, it is not limited to these.
  • Examples of the organic group having reactivity with the amino group include, but are not limited to, a carboxy group, a carboxylic anhydride group, a carbonyl group, an aldehyde group, a halogeno-carbonyl group, and the like.
  • Examples of the organic group having reactivity with the carboxy group include, but are not limited to, an amino group, a hydroxy group, a carboxy group, and a vinyloxy group.
  • benzofuran compound examples include 1-benzofuran (2,3-benzofuran), 2,3-dimethylbenzofuran, psoralen, angelicin and the like. Among these, 1-benzofuran or 2,3-dimethylbenzofuran is preferable, and 1-benzofuran is more preferable.
  • a benzofuran compound can be used alone or in combination of two or more.
  • X is a tetravalent organic group (excluding those containing a group reactive with an amino group). X is determined depending on the tetracarboxylic acid.
  • Examples of the tetravalent organic group include a compound having a chain hydrocarbon such as ethylene and propane in the basic skeleton, a compound having a cyclic hydrocarbon such as cyclohexane in the basic skeleton, and an aromatic hydrocarbon such as benzene and naphthalene.
  • a compound having a basic skeleton a compound having a benzophenone skeleton such as benzophenone, a compound having a diphenyl ether skeleton such as diphenyl ether, a compound having a diphenyl sulfone skeleton such as diphenyl sulfone, a compound having a biphenyl skeleton such as biphenyl, etc.
  • Examples include a group from which a hydrogen atom has been removed. However, it is not limited to these.
  • Examples of the group having reactivity with the amino group include, but are not limited to, a carboxy group, a carboxylic acid anhydride group, a carbonyl group, an aldehyde group, a halogenocarbonyl group, and the like.
  • tetracarboxylic acid examples include, for example, 1,2,4,5-benzenetetracarboxylic acid (1,2,4,5-benzenetetracarboxylic acid) (1,2,3).
  • 4-Benzenetetracarboxylic acid (melophanoic acid) 2,3,6,7-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid 3,4,9,10-perylenetetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,7,8-phenanthrenetetracarboxylic acid (phenanthrene-1,2,7,8 -tetracarboxylic acid, 3,3 ', 4,4'-benzophenone-3,3', 4,4'-tetracarboxylic acid, 2,2 ', 3,3'-benzophenone tetracarboxylic acid, 2,
  • the tetracarboxylic acid is preferably an aromatic tetracarboxylic acid from the viewpoint of the heat resistance and linear thermal expansion coefficient of a polyimide resin obtained by drying and curing the polyimide precursor composition, and 1,2,4,5- Benzenetetracarboxylic acid (pyromellitic acid), 1,2,3,4-benzenetetracarboxylic acid (melophanoic acid), 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′, 4,4 '-Biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 2,3,2 ', 3'-biphenyltetracarboxylic acid, 2,2', 6,6'-biphenyltetracarboxylic acid Acid, bis (3,4-dicarboxyphenyl) ether, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,
  • tetracarboxylic acids examples include 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,3 from the viewpoint of the stability of the hemiacetal ester bond. 2,2 ′, 3′-biphenyltetracarboxylic acid or bis (3,4-dicarboxyphenyl) ether is preferred.
  • Tetracarboxylic acid can be used alone or in combination of two or more.
  • the aqueous medium is a medium mainly composed of water.
  • water ion exchange water, distilled water, deionized distilled water, RO water (reverse osmosis-treated water) and the like can be used.
  • “having water as a main component” means containing 60 mass% or more, preferably 75 mass% or more, more preferably 90 mass% or more of water.
  • the aqueous medium may contain a known alcohol or ether that has a small environmental load and does not adversely affect the volatility and drying of water for the purpose of imparting wettability to the substrate and preserving effect.
  • a known alcohol or ether that has a small environmental load and does not adversely affect the volatility and drying of water for the purpose of imparting wettability to the substrate and preserving effect.
  • methanol, ethanol, n-propanol, 2-propanol (isopropyl alcohol), n-butanol, isobutanol, t-butanol, butyl cellosolve, propylene glycol monomethyl ether, 1- (2-hydroxyethyl) -2-pyrrolidone, etc. Can be mentioned.
  • These alcohols or ethers can be used singly or in combination of two or more.
  • the ratio of the alcohol in the aqueous medium is preferably 1% by mass or more and less than 40% by mass, and more preferably 5% by mass or more and 25% by mass or less.
  • the alcohol ratio is 1% by mass or more, the effect of improving the wettability of the coating composition with respect to the substrate is exhibited, and the repellency of the coating composition on the substrate is suppressed.
  • the alcohol ratio is less than 40% by mass, crystals do not precipitate on the polyimide precursor composition, and it becomes easy to dispose the coating composition on the substrate in a film form. If the ratio of alcohol is less than 1% by mass, the improvement effect by adding alcohol becomes insufficient, and the desired effect may not be obtained.
  • the alcohol ratio is 40% by mass or more, crystals may be deposited on the polyimide precursor composition, which may make it difficult to dispose the coating composition on the substrate. .
  • An aqueous composition of a benzofuran derivative is produced by mixing and stirring a benzofuran compound, a tetracarboxylic acid, and an aqueous medium. According to this method, it is not necessary to use an organic solvent with a high environmental load, and an aqueous composition of a benzofuran derivative can be obtained by a reaction between a benzofuran compound and a tetracarboxylic acid in an aqueous medium. It is not necessary to collect the benzofuran derivative, which is a product, and mix it in an aqueous medium, thereby reducing the number of steps.
  • the number of moles of the benzofuran compound is usually preferably 0.5 to 4 times, more preferably 1 to 2 times the number of moles of tetracarboxylic acid.
  • the method of mixing the benzofuran compound, the tetracarboxylic acid, and the aqueous medium is not particularly limited.
  • the aqueous composition containing the benzofuran compound and the aqueous medium, and the aqueous composition containing the tetracarboxylic acid and the aqueous medium are examples of the aqueous composition containing the benzofuran compound and the aqueous medium.
  • a method of mixing and stirring a product a method of adding a benzofuran compound to an aqueous composition containing a tetracarboxylic acid and an aqueous medium and stirring, a tetracarboxylic acid in an aqueous composition containing a benzofuran compound and an aqueous medium
  • the method of adding and stirring is mentioned.
  • the temperature at the time of mixing and stirring is not particularly limited as long as it is a temperature at which addition reaction can be performed, but is preferably 5 to 45 ° C, more preferably 20 to 30 ° C, and further about 25 ° C. preferable.
  • the stirring time is not particularly limited as long as the addition reaction is sufficiently performed, but is preferably 30 minutes to 6 hours, more preferably 1 hour to 3 hours, and further preferably about 2 hours.
  • the atmosphere for producing the benzofuran derivative composition is not particularly limited, and an atmosphere such as an air atmosphere, a nitrogen atmosphere, an inert gas atmosphere, or the like can be used.
  • the continuous type may be sufficient as the format for manufacturing a benzofuran derivative composition, and a batch type may be sufficient as it.
  • the mixed liquid obtained by mixing the benzofuran compound, the tetracarboxylic acid, and the aqueous medium may further contain a catalyst for promoting the reaction between the benzofuran compound and the tetracarboxylic acid.
  • a catalyst for promoting the reaction between the benzofuran compound and the tetracarboxylic acid include a catalyst for promoting the addition reaction between the double bond of the five-membered ring of the benzofuran compound and the carboxy group of the tetracarboxylic acid.
  • Such catalysts are not particularly limited, and specific examples include those that promote the formation of enols such as titanium tetrachloride and tin tetrachloride, which are more acidic than carboxylic acids.
  • a catalyst can be used individually by 1 type or in combination of 2 or more types.
  • a benzofuran derivative composition containing a benzofuran derivative represented by the following formula (1) and an aqueous medium is produced by the above-described method for producing a benzofuran derivative composition.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are respectively R 1 , R 2 , R 3 , R 4 , R 5 and R 6 in formula (A). It is synonymous and X is synonymous with X in Formula (B).
  • X is synonymous with X in Formula (B).
  • the benzofuran derivative composition in addition to the benzofuran derivative represented by the formula (1) and an aqueous medium, 2 to 4 molecules of benzofuran compound are added to one molecule of unreacted benzofuran compound, tetracarboxylic acid, or tetracarboxylic acid. A benzofuran derivative or the like may be contained.
  • Polyimide precursor composition manufacturing process mixes and stirs a benzofuran derivative, a polyamine, and an aqueous medium, and manufactures the aqueous composition (polyimide precursor composition) of a polyimide precursor. It is a process.
  • the benzofuran derivative is synthesized in the benzofuran derivative composition manufacturing process, and is an aqueous composition when reacted in an aqueous medium.
  • the aqueous medium is as described above.
  • the polyamine used in the polyimide precursor composition manufacturing process is represented by the following formula (C).
  • Y is an m-valent organic group (excluding those containing a group reactive with a carboxy group), and m is an integer of 2 or more.
  • the upper limit of m is not particularly limited, but is preferably 600.
  • Y and m are determined depending on the polyamine.
  • Examples of m-valent organic groups include compounds having a chain hydrocarbon such as ethylene and propane in the basic skeleton, compounds having a cyclic hydrocarbon such as cyclohexane in the basic skeleton, and aromatic hydrocarbons such as benzene and naphthalene.
  • Examples include a group in which a hydrogen atom has been removed. However, it is not limited to these.
  • Examples of the group having reactivity with the carboxy group include, but are not limited to, an amino group, a hydroxy group, a carboxy group, and a vinyloxy group.
  • polyamine examples include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'- Diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'--
  • the polyamine is a substituent selected from the group consisting of a fluorine atom, a methyl group, a methoxy group, a trifluoromethyl group, and a trifluoromethoxy group, with some or all of the hydrogen atoms on the aromatic ring of the polyamine described above. Substituted polyamines can also be used.
  • polyamine in addition to the above-described polyamine, a polymer having two or more primary amino groups (—NH 2 ) in one molecule (including groups reactive to carboxy groups other than primary amino groups) May be used).
  • examples of such polyamines include those in which the main chain or side chain of polystyrene, polyacrylic acid, polyurethane, polyamide, polyimide or the like is modified with two or more primary amino groups. More specifically, a primary amino group-containing acrylic polymer, tetracarboxylic acid obtained by grafting ethyleneimine to the side chain of an acrylic acid copolymer by utilizing the reactivity between the carboxy group of the polymer side chain and ethyleneimine.
  • group having reactivity with the carboxy group include, but are not limited to, a hydroxy group, a carboxy group, and a vinyloxy group.
  • the polyamine further includes an ethynyl group, a benzocyclobuten-4-yl group, and a vinyl group that serve as crosslinking points when a crosslinking reaction is performed after the polyimide is formed.
  • group), an allyl group (allyl group), a cyano group (cyano group), and an isopropenyl group are bonded to some or all of the hydrogen atoms on the aromatic ring of the polyamine. Even if it introduce
  • the polyamine can be selected depending on the desired physical properties. If a rigid diamine such as p-phenylenediamine is used, the finally obtained polyimide has a low expansion coefficient.
  • p-phenylenediamine, m-phenylenediamine, 1,4-diaminonaphthalene (1,4-diaminonaphthalene) is a diamine having two amino groups bonded to the same aromatic ring. ), 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 1,4-diaminoanthracene and the like.
  • a dendrimer such as polyamidoamine may also be used.
  • polyamines include polyamines in which two or more aromatic rings are bonded by a single bond, and two or more amino groups are bonded to separate aromatic rings either directly or as part of a substituent.
  • Specific examples include benzidine, tolidine and the like.
  • a polyamine having a substituent on the benzene ring can also be used as the polyamine.
  • These substituents are monovalent organic groups, but they may be bonded to each other. Specific examples include 2,2'-dimethyl-4,4'-diaminobiphenyl and 2,2'-ditrifluoromethyl-4,4'-diamino.
  • Biphenyl (2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl), 3,3'-dichloro-4,4'-diaminobiphenyl (3,3'-dichloro-4,4'-diaminobiphenyl), 3,3 '-Dimethoxy-4,4'-diaminobiphenyl (3,3'-dimethoxy-4,4'-diaminobiphenyl), 3,3'-dimethyl-4,4'-diaminobiphenyl (3,3'-dimethyl-4 , 4'-diaminobiphenyl) and the like.
  • the polyamine selected is preferably an aromatic polyamine from the viewpoint of heat resistance, but the aliphatic diamine or siloxane is within a range not exceeding 60 mol%, preferably 40 mol% of the total of the diamine depending on the desired physical properties.
  • Non-aromatic diamines such as diamines may be used.
  • the polyamine may form a hydrohalide salt, for example, a salt such as hydrochloride or hydrobromide.
  • a polyamine can be used individually by 1 type or in combination of 2 or more types.
  • ⁇ Method for producing polyimide precursor composition The aqueous composition of a polyimide precursor is manufactured by mixing and stirring a benzofuran derivative, a polyamine, and an aqueous medium. According to this method, similarly to the method for producing a benzofuran derivative composition, it is not necessary to use an organic solvent having a high environmental load, and the number of steps can be reduced.
  • the method for mixing the benzofuran derivative, the polyamine, and the aqueous medium is not particularly limited. For example, the aqueous composition containing the benzofuran derivative and the aqueous medium is mixed with the aqueous composition containing the polyamine and the aqueous medium.
  • a stirring method a method of adding a polyamine to an aqueous composition containing a benzofuran derivative and an aqueous medium, and stirring.
  • the temperature at the time of mixing and stirring is not particularly limited, but is preferably 5 to 45 ° C, more preferably 20 to 30 ° C, and further preferably about 25 ° C.
  • the stirring time is not particularly limited, but is preferably 30 minutes to 6 hours, more preferably 1 hour to 3 hours, and further preferably about 2 hours.
  • the atmosphere at the time of manufacturing the polyimide precursor composition is not particularly limited, and an atmosphere such as an air atmosphere, a nitrogen atmosphere, an inert gas atmosphere, or the like can be used.
  • the form for producing the polyimide precursor composition may be a continuous type or a batch type.
  • the polyimide precursor composition of the present invention contains a benzofuran derivative represented by the above formula (1), a polyamine represented by the above formula (C), and an aqueous medium.
  • the polyimide precursor composition of the present invention may be a mixture thereof, or a salt structure represented by the following formula (2) in which carboxylate and ammonium are paired.
  • the polyimide precursor composition may contain a small amount of volatile amine for the purpose of supplementing the stability of the composition in water.
  • a volatile amine is desirably an amount that does not exceed the number of moles of a carboxy group that is not used in the addition reaction between a benzofuran compound and a tetracarboxylic acid.
  • ammonia, trimethylamine, triethylamine, and tributylamine are preferable.
  • a volatile amine can be used individually by 1 type or in combination of 2 or more types.
  • the polyimide precursor composition may further comprise reinforcing materials, fillers, anti-aging agents, antioxidants, light stabilizers, anti-scorch agents, other cross-linking retarders, plasticizers, processing aids, lubricants, adhesives as necessary. Additives such as an agent, a lubricant, a flame retardant, an antifungal agent, an antistatic agent, a colorant, and a surfactant can be blended. Furthermore, as long as the characteristics of the polyimide precursor composition are not impaired, resin components such as other polymers and elastomers can be blended as necessary. In the polyimide precursor composition of this invention, it can prepare by mix
  • the polyimide precursor composition is substantially free of organic solvents except for organic solvents such as alcohols and ethers contained in aqueous media, organic solvents contained in volatile amines, and trace amounts of organic solvents inevitably mixed in. .
  • organic solvents include N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylcaprolactam, acetone, ⁇ -butyrolactone, methyl ethyl ketone, methyl isobutyl.
  • Organic solvents with high environmental impact such as ketones can be mentioned.
  • the viscosity of the polyimide precursor composition according to the present invention is not particularly limited as long as the coating property is not impaired, but the viscosity at 20 ° C. is in the range of 50 mPa ⁇ s to 200 Pa ⁇ s, It is practically preferable to adjust the viscosity at 22 ° C. to a range of 10 mPa ⁇ s to 200 Pa ⁇ s.
  • the polyimide resin production process is a process of producing a polyimide resin by heat-treating and curing a polyimide precursor composition containing a polyimide precursor and an aqueous medium.
  • the polyimide precursor is obtained in the polyimide precursor composition manufacturing process, and becomes an aqueous composition when mixed and stirred in an aqueous medium.
  • the aqueous medium is as described above.
  • the aqueous medium which the polyimide precursor composition manufactured at the polyimide precursor composition manufacturing process contains may be sufficient.
  • ⁇ Heat treatment / curing> By heat treatment, drying of the polyimide precursor composition, deprotection of the carboxy group of the benzofuran derivative (that is, elimination of the benzofuran compound from the benzofuran derivative) and imidation of tetracarboxylic acid and polyamine (by polyamic acid formation and dehydration ring closure) Curing by polyimide generation).
  • the heat treatment includes a step of drying the polyimide precursor composition, a step of deprotecting the carboxy group of the benzofuran derivative, and a step of curing by imidation of tetracarboxylic acid and polyamine (polyamide acid generation and polyimide generation by dehydration ring closure).
  • the heating temperature is usually 80 ° C. or higher, preferably 80 to 100 ° C.
  • the heating time is preferably several minutes to 1 hour, more preferably 15 minutes to 45 minutes. By performing drying, the moldability of the composition can be enhanced.
  • the heating temperature is preferably 170 ° C. or higher and lower than 200 ° C.
  • the heating time is preferably several minutes to 1 hour, more preferably 15 minutes to 45 minutes.
  • 200 to 400 ° C. is preferred.
  • the heating time is preferably several minutes to several hours, more preferably 10 to 50 minutes.
  • a heating method an appropriate method such as press heating, steam heating, oven heating, hot air heating and the like can be adopted. Usually, after heating and reacting in a predetermined shape, steam heating, oven heating, hot air is performed. Further reaction by heating or the like.
  • the present invention improves storage stability by using, as a polyimide raw material, a benzofuran derivative having a protective group introduced via a hemiacetal ester bond formed by a reaction between a benzofuran compound and a carboxy group, and a polyamine. And by heating these, deprotection of the carboxy group of the benzofuran derivative (that is, elimination of the benzofuran compound from the benzofuran derivative) and imidation of the tetracarboxylic acid and the polyamine (dehydration ring closure: that is, polyimide after the formation of the polyamic acid) It is characterized in that a polyimide resin from which the benzofuran compound is eliminated is finally obtained by curing by the production.
  • Polyimide resin produced by the production method of the present invention is used in a wide range of fields such as transportation equipment such as automobiles, general equipment / devices, electronics / electricity, and architecture, sealing materials, buffering / protecting materials, wire coating materials, industrial use. Useful as belts, hoses, sheets, airbags, etc.
  • Example 1 (1) Production of polyimide precursor composition In a separable flask (200 mL; cylinder type) equipped with a stirrer, 1,2,4,5-benzenetetracarboxylic acid (11.1 g) and water (45.1 g) After stirring for 10 minutes at 25 ° C., 2,3-benzofuran (4.9 g) was added and further stirred and mixed at 25 ° C. for 30 minutes to obtain an aqueous dispersion of the benzofuran derivative.
  • Viscosity measurement The viscosity at 22 ° C. immediately after production of the obtained polyimide precursor composition was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., model number TV-22). The measurement results are shown in the column of “Initial viscosity (22 ° C.)” in Table 1.
  • the polyimide precursor composition was collected in a glass bottle and immediately placed in a thermostatic chamber at 25 ° C.
  • a glass substrate with a cured film was prepared by the following procedure using the polyimide precursor composition 1 day, 3 days, and 7 days after the standing day, and a solvent resistance test was performed.
  • the polyimide precursor composition was applied so that the dry coating film had a thickness of 40 ⁇ m.
  • heat treatment is performed at 90 ° C. for 30 minutes using a hot plate, and then heat treatment is performed at 250 ° C. for 30 minutes using a constant temperature drying oven, on one surface of the glass substrate.
  • a cured film made of polyimide resin was formed.
  • a cured film made of polyimide resin was formed.
  • the glass substrate on which the cured film was formed was immersed in hot water at 90 ° C. and allowed to stand for 10 minutes, then the cured film was visually observed, and the water resistance of the cured film was evaluated based on the following evaluation criteria.
  • the evaluation results are shown in the column of “Water resistance test” in Table 3. (Evaluation criteria) A: No change B: Whitening or swelling occurs in the cured film C: At least a part of the glass substrate is exposed or coating is poor
  • Example 2 (1) Production of polyimide precursor composition A separable flask (200 mL; cylindrical type) equipped with a stirrer was charged with 1,2,4,5-benzenetetracarboxylic acid (11.1 g) and water (44.5 g). Further, after stirring and mixing at 25 ° C. for 10 minutes, 3-methylbenzofuran (5.5 g) was added, and further stirring and mixing at 25 ° C. for 30 minutes to obtain an aqueous dispersion of a benzofuran derivative.
  • Viscosity measurement and storage stability test were conducted in the same manner as in Example 1 using the obtained polyimide precursor composition. However, since the polyimide precursor composition gelled on the seventh day after standing in a temperature-controlled room in the storage stability test, the viscosity measurement could not be performed.
  • the viscosity measurement results immediately after production of the obtained polyimide precursor composition are shown in the column of “Initial viscosity (22 ° C.)” in Table 1, and the viscosity measurement results in the storage stability test are shown in “Storage stability (25 In the column of “Viscosity (22 ° C.)” of “° C.)”, the observation results of the appearance are shown in the “Appearance (visual)” column of “Storage stability (25 ° C.)” of Table 2.
  • polyimide precursor composition a polyimide precursor solution (polyimide precursor composition).
  • polyimide precursor composition a polyimide precursor solution
  • Viscosity measurement, storage stability test, solvent resistance test, water resistance test In the same manner as in Example 1, viscosity measurement, storage stability test, solvent resistance test and water resistance test were performed.
  • the obtained polyimide precursor composition showed a solution state on the first day of preparation, but crystals were deposited on the third day and thereafter, so the coating film test was not performed. The results are shown in Table 1, Table 2, and Table 3.
  • the polyimide precursor compositions of Example 1 and Example 2 have low viscosity and excellent coatability.
  • the polyimide precursor composition containing the polyimide precursor which added the vinyl ether compound instead of the benzofuran compound of the comparative example 2 is also low viscosity, and is excellent in coating property.
  • the polyimide precursor composition in the N-methyl-2-pyrrolidone solution instead of the polyimide precursor aqueous dispersion of Comparative Example 3 has a low initial viscosity and excellent coatability. However, it has a high environmental load and is disadvantageous in terms of cost.
  • the polyimide precursor compositions of Example 1 and Example 2 have a low viscosity and do not impair the coatability even after a period after production.
  • the polyimide precursor composition containing a polyimide precursor to which a vinyl ether compound is added instead of the benzofuran compound of Comparative Example 2 has a low initial viscosity and excellent coatability, but the appearance changes after a period after manufacture. At the same time, the viscosity increases and the coatability is impaired.
  • the polyimide precursor composition in the N-methyl-2-pyrrolidone solution, not the aqueous dispersion of the polyimide precursor in Comparative Example 3 has a low initial viscosity and excellent coatability, but after 3 days Will precipitate and become unusable.
  • the polyimide resin obtained by heat-processing is excellent in solvent resistance and water resistance.
  • the polyimide precursor composition containing the polyimide precursor which added the vinyl ether compound instead of the benzofuran compound of the comparative example 2 is a solvent-resistant polyimide resin obtained by heat-processing when the period after manufacture passes. And water resistance becomes inferior.
  • the polyimide resin obtained by heat-treating the composition one day after preparation is excellent in solvent resistance and water resistance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

[Problème] Fournir une composition aqueuse d'un précurseur de polyimide et un procédé de production d'une résine de polyimide (produit durci), qui ont d'excellentes propriétés de revêtement et de stabilité au stockage, et dont le produit durci a une bonne résistance aux solvants et une bonne résistance à l'eau. [Solution] Composition de précurseur de polyimide comprenant un dérivé de benzofuranne représenté par la formule (1), une polyamine représentée par la formule (C), et un milieu aqueux, et procédé de production d'une résine de polyimide par durcissement de la composition de précurseur de polyimide sous l'effet d'un traitement thermique. Nothing to translate
PCT/JP2014/005070 2013-10-10 2014-10-06 Composition d'un dérivé de benzofuranne, composition d'un précurseur de polyimide, et procédé de production d'une résine de polyimide Ceased WO2015052907A1 (fr)

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WO2018159064A1 (fr) * 2017-02-28 2018-09-07 Ｊｆｅケミカル株式会社 Composition de précurseur de polyimide, procédé pour la production de résine de polyimide et résine de polyimide
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