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WO2019226641A9 - Vernis de polyimide présentant une résistance élevée à la chaleur et une excellente résistance mécanique - Google Patents

Vernis de polyimide présentant une résistance élevée à la chaleur et une excellente résistance mécanique Download PDF

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Publication number
WO2019226641A9
WO2019226641A9 PCT/US2019/033300 US2019033300W WO2019226641A9 WO 2019226641 A9 WO2019226641 A9 WO 2019226641A9 US 2019033300 W US2019033300 W US 2019033300W WO 2019226641 A9 WO2019226641 A9 WO 2019226641A9
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general formula
varnish
organic group
aromatic
represented
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WO2019226641A1 (fr
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Masahiko Miyauchi
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Kaneka Americas Holding Inc
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Kaneka Americas Holding Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1096—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors containing azo linkage in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a polyimide resin composition and a prepreg and a fiber- reinforced laminate including the composition, and specifically relates to member materials usable in various fields requiring excellent moldability and high heat resistance, including aircraft and apparatuses for the aerospace industry.
  • Aromatic polyimides are categorized into the highest level of heat resistance among polymers, also have excellent mechanical, electric, and other characteristics, and thus have been used as materials in various fields including the aerospace and the electronics.
  • thermal addition reactive polyimides are typically used as follows: the polyimides still having a low molecular weight is impregnated into fibers; and then the polyimides is crosslinked and cured in the final process.
  • PMR-15 (PMR: in-situ polymerization of monomer reactants) is exemplified as one of the representative examples of polyimide resins previously developed for fiber-reinforced composite materials. As illustrated in FIG. 1A and FIG. IB, a cross section microscopic view of PMR-15 demonstrates breakdown due to thermal cycle exposure. (Owens, G.A. et ah, Composites Science and Technology 1998, 33, 177-190).
  • the interlaminar shear strength (ILSS) decreases by about 50% after 1600 thermal cycles in PMR-15.
  • ILSS interlaminar shear strength
  • Wilson, D., 18 th International SAMPE Technical Conference, 1996, 242-253 A review of PMR-15, and its limitations can be found in Wilson, D., British Polymer Journal, 1988, 20, 405-416.
  • limitations of PMR-15 are reliable methods of quality control, prepreg batch to batch variability, microcracking of carbon fiber reinforced materials during thermal cycling, health and safety hazards, and high temperature cracking of carbon fiber reinforced materials.
  • the present invention has an object to provide a varnish with more than 65 % solid content in an organic solvent with a boiling point of 150°C or less at 1 atmosphere.
  • the varnish has an excellent solution storage stability and can be easily converted to modified imide oligomer with good moldability such as low melt viscosity, a solid imide resin composition including the terminally modified imide oligomer, and a cured product, a prepreg, an imide prepreg, and a fiber-reinforced composite material that are produced by using the solid imide resin composition and have high thermal and mechanical characteristics such as heat resistance, elastic modulus, tensile strength, and elongation.
  • the present invention provides a varnish including components (A) to (D).
  • the components (A), (B), and (C) are dissolved in the varnish at a solid content of more than 65 %;
  • the component (A) is an aromatic tetracarboxylic acid diester represented by General Formula (1) and is contained in an amount of 1 to 500 parts by weight;
  • the component (B) is 2-phenyl-4,4'-diaminodiphenyl ether and is contained in an amount of 1 to 450 parts by weight;
  • the component (C) is a 4-(2-phenylethynyl)phthalic acid monoester represented by General Formula (2) and is contained in an amount of 1 to 400 parts by weight;
  • the component (D) is an organic solvent having a boiling point of 150°C or less at 1 atmosphere or a mixture of two or more of the organic solvents which includes methanol, ethanol, 1- propanol, and 2-propanol and is contained in an amount of 100 parts by weight.
  • R j is an aromatic tetracarboxylic acid diester residue
  • R 2 and R 3 are the same or different and are an aliphatic organic group or an aromatic organic group
  • R 2 and R 3 are located in a cis configuration or a trans configuration
  • the compound is optionally a single isomer or a mixture of two isomers.
  • R4 and R 5 are a hydrogen atom, an aliphatic organic group, or an aromatic organic group; and one of R and R 5 is an aliphatic organic group or an aromatic organic group.
  • the aliphatic organic group represented by R 2 and R 3 in General Formula (1) is an organic group having an aliphatic chain, and the aromatic organic group is an organic group having an aromatic ring.
  • (1) is a tetravalent aromatic organic group formed by removing four carboxyl groups from an aromatic tetracarboxylic acid.
  • Ri is preferably a tetravalent residue of a 1,2,4,5-benzenetetracarboxylic acid or a tetravalent residue of a 3,3',4,4'-biphenyltetracarboxylic acid.
  • Ri may be a combination of two or more of a tetravalent aromatic tetracarboxylic acid diester represented by a tetravalent residue of a 1,2,4,5- benzenetetracarboxylic acid, an aromatic tetracarboxylic acid diester represented by a tetravalent residue of a 3,3',4,4'-biphenyltetracarboxylic acid, and an aromatic tetracarboxylic acid diester represented by a tetravalent residue of a bis(3,4-carboxyphenyl) ether.
  • a tetravalent aromatic tetracarboxylic acid diester represented by a tetravalent residue of a 1,2,4,5- benzenetetracarboxylic acid
  • an aromatic tetracarboxylic acid diester represented by a tetravalent residue of a 3,3',4,4'-biphenyltetracarboxylic acid
  • the aliphatic organic group represented by R or R 5 in General Formula (2) is an organic group having an aliphatic chain, and the aromatic organic group is an organic group having an aromatic ring.
  • the present invention also provides a solid imide resin composition represented by
  • the solid imide resin composition is produced by heating the varnish to remove the organic solvent.
  • R 6 and R 7 are each a hydrogen atom or a phenyl group; one of R 6 and R 7 is a phenyl group; R 8 and R 9 are the same or different and are a divalent aromatic diamine residue; R 10 and Rn are the same or different and are a tetravalent aromatic tetracarboxylic acid residue; m and n satisfy relations of m > 1, n > 0, 1 ⁇ m + n ⁇ 10, and 0.05 ⁇ m/(m + n) ⁇ 1; and repeating units are optionally arranged in a block sequence or a random sequence.
  • the present invention further provides a molded article of a polymerized imide resin composition, in which the polymerized imide resin composition is obtained by heating the solid imide resin composition in a molten state.
  • the imide resin composition has a glass transition temperature (Tg) of 300°C or more, more preferably 330°C or more, and even more preferably 350°C or more.
  • the present invention also provides a film obtained from the molded article of the imide resin composition.
  • the film preferably has a tensile elongation at break of 10% or more, more preferably 15% or more, and even more preferably 20% or more.
  • the present invention further provides a prepreg including the varnish and fibers into which the varnish is impregnated.
  • the present invention provides both a wet prepreg that contains a solvent and a dry prepreg from which a solvent is substantially completely removed.
  • the present invention also provides an imide prepreg obtained by further heating the prepreg.
  • the present invention provides both a semidried imide wet prepreg that partially contains a solvent and an imide dry prepreg from which a solvent is substantially completely removed.
  • the present invention also provides a fiber-reinforced composite material obtained by stacking the prepregs, the imide prepregs, or a combination of the prepregs and the imide prepregs and thermally curing the stacked prepregs.
  • the fiber-reinforced composite material preferably has a Tg of 300°C or more and more preferably 330°C or more.
  • the present invention also provides a fiber-reinforced composite material showing no generation of microcracks inside and maintaining greater than about 70 %, preferably about more than 80 %, and even more preferably 90 % initial interlaminar shear strength (ILSS) or short beam shear (SBS) strength as measured at room temperature (25 °C), and about 200 to about 250 °C, preferably about 232 °C after thermal cycling in the temperature range between about -60 and about 250 °C, preferably between about -54 and 232 °C, preferably for 500 cycles or more.
  • ILSS interlaminar shear strength
  • SBS short beam shear
  • the present invention further provides a method of producing the varnish.
  • the method includes heating an aromatic tetracarboxylic anhydride and 4-(2-phenylethynyl)phthalic anhydride in a state the aromatic tetracarboxylic anhydride and the 4-(2-phenylethynyl)phthalic anhydride are dissolved in an organic solvent having a boiling point of 150°C or less at 1 atmosphere, to prepare an aromatic tetracarboxylic acid diester represented by General Formula (1); preparing a solution of an organic solvent having a boiling point of 150°C or less at 1 atmosphere, which contains the aromatic tetracarboxylic acid diester represented by General Formula (1) and a 4-(2-phenylethynyl)phthalic acid monoester represented by General Formula (2); adding a diamine including 2 -phenyl-4, 4'- diaminodiphenyl ether to the solution; and uniformly dissolving, in the solution, the diamine including 2- phenyl-4,
  • the present invention can provide the varnish having excellent solubility at a solid content of more than 65 wt % and long-term storage stability because of the effect of 2 -phenyl-4, 4'- diaminodiphenyl ether which has an asymmetric chemical structure.
  • the present invention can also provide the solid imide resin composition having excellent melt flowability at high temperature and molding processability, by heating the varnish to give a particular terminally modified imide oligomer component having 2-phenyl-4,4'-diaminodiphenyl ether.
  • the present invention can provide the imide resin molded article having both high heat resistance and excellent breaking elongation, by further heating the solid imide resin composition to polymerize the terminally modified imide oligomer component.
  • the present invention can provide the imide prepreg having excellent preservability and handling properties and achieving excellent adhesion properties between prepregs, by infiltrating the varnish into fibers.
  • the prepreg or the imide prepreg of the present invention can readily yield a high quality fiber-reinforced composite material having excellent heat resistance and mechanical characteristics and containing no large voids in the material because the organic solvent having a low boiling point used in the varnish is readily removed from a composite material prepared by stacking the prepregs or the imide prepregs, in a step of thermoforming the composite material.
  • the fiber-reinforced composite material shows an excellent thermal cycle resistance because of both high heat resistance and excellent breaking elongation of the molded imide resin involved inside.
  • Fig. 1A is a cross sectional microscope observation of a prior art fabric composite prior to thermal cycle exposure.
  • Fig. IB is a cross sectional microscope observation of a prior art fabric composite after
  • Fig. 2 is a plot of interlaminar shear strength (IFSS) strength of a prior art fabric composite as a function of thermal cycling.
  • IFSS interlaminar shear strength
  • Fig. 3 is a graph representing the short beam strength (SBS) strength of fiber composites after thermal cycling exposure in accordance with embodiments of Example 13.
  • SBS short beam strength
  • Figs. 4A-4B are a cross sectional microscope observation of fiber composites before and after thermal cycle exposure in accordance with embodiments of Example 13.
  • a varnish of the present invention is characterized by including the following components (A) to (D), and the components (A), (B), and (C) are dissolved in the varnish at a solid content of more than 65 %.
  • the component (A) is an aromatic tetracarboxylic acid diester represented by General
  • Formula (1) and is contained in an amount of 1 to 500 parts by weight;
  • the component (B) is 2-phenyl-4,4'-diaminodiphenyl ether and is contained in an amount of 1 to 450 parts by weight;
  • the component (C) is a 4-(2-phenylethynyl)phthalic acid monoester represented by General Formula (2) and is contained in an amount of 1 to 400 parts by weight;
  • the component (D) is an organic solvent having a boiling point of 150°C or less at 1 atmosphere or a mixture of two or more of the organic solvents which includes methanol, ethanol, 1- propanol, and 2-propanol and is contained in an amount of 100 parts by weight.
  • Ri is an aromatic tetracarboxylic acid diester residue
  • R 2 and R 3 are the same or different and are an aliphatic organic group or an aromatic organic group
  • R 2 and R 3 are located in a cis configuration or a trans configuration
  • the compound is optionally a single isomer or a mixture of two isomers.
  • R 4 and R 5 are a hydrogen atom, an aliphatic organic group, or an aromatic organic group; and one of R 4 and R 5 is an aliphatic organic group or an aromatic organic group Component (Aj
  • the aromatic tetracarboxylic acid diester represented by General Formula (1) is used as a component of the varnish of the present invention.
  • the aromatic tetracarboxylic acid diester represented by General Formula (1) is a component that reacts with the components (B) and (C) to form a part of the skeleton of the terminally modified imide oligomer represented by General Formula (3).
  • the aromatic tetracarboxylic acid constituting the aromatic tetracarboxylic acid diester residue represented by Rl in General Formula (1) is exemplified by tetravalent residues of 1, 2,4,5- benzenetetracarboxylic acids, tetravalent residues of 3,3',4,4'-biphenyltetracarboxylic acids, and tetravalent residues of bis(3,4-carboxyphenyl) ethers.
  • the aromatic tetracarboxylic acid diester residue represented by Ri in General Formula (1) is preferably a tetravalent residue of a 1,2,4,5-benzenetetracarboxylic acid, a tetravalent residue of a 3, 3', 4,4'- biphenyltetracarboxylic acid, or a tetravalent residue of a bis(3,4-carboxyphenyl) ether, and more preferably a tetravalent residue of a 1,2,4,5-benzenetetracarboxylic acid or a tetravalent residue of a 3,3',4,4'-biphenyltetracarboxylic acid because a molded article of an imide resin composition can achieve a high glass transition temperature (Tg), long-term thermal stability, and anti-oxidation stability at high temperature.
  • Tg glass transition temperature
  • the combination of tetravalent aromatic tetracarboxylic acids include a combination partially containing a tetravalent residue of a 1,2,4,5-benzenetetracarboxylic acid and containing a tetravalent residue of a 3,3',4,4'-biphenyltetracarboxylic acid as the remainder; a combination partially containing a tetravalent residue of a 1,2,4,5-benzenetetracarboxylic acid and containing a tetravalent residue of a bis(3,4-carboxyphenyl) ether as the remainder; and a combination partially containing a tetravalent residue of a 3,3',4,4'-biphenyltetracarboxylic acid and containing a tetravalent residue of a bis(3,4-carboxyphenyl) ether as the remainder
  • General Formula (1) is preferably an organic group having 1 to 12 carbon atoms, more preferably an organic group having 1 to 9 carbon atoms, and even more preferably an organic group having 1 to 6 carbon atoms because an alcohol component that is generated and eliminated by amic acid formation reaction with a diamine by heat preferably has a low boiling point in order to be immediately volatilized and removed during production of the imide resin composition or molding of the composite material.
  • the aromatic tetracarboxylic acid diester represented by General Formula (1) is basically a 1,2,4,5-benzenetetracarboxylic acid diester, a 3,3',4,4'-biphenyltetracarboxylic acid diester, a combination of them, a 1,2,4,5-benzenetetracarboxylic acid diester that is partially replaced with a diester of bis(3,4-carboxyphenyl) ether, or a 3,3',4,4'-biphenyltetracarboxylic acid diester that is partially replaced with a diester of bis(3,4-carboxyphenyl) ether.
  • a 1,2,4,5-benzenetetracarboxylic acid diester, a 3,3',4,4'-biphenyltetracarboxylic acid diester, or a diester of bis(3,4-carboxyphenyl) ether may be partially replaced with an additional aromatic tetracarboxylic acid as long as the advantageous effects of the invention are achieved.
  • Examples of the additional aromatic tetracarboxylic acid include 3, 3', 4,4'- benzophenonetetracarboxylic dianhydride (BTDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a- BPDA), 2,2',3,3'-biphenyltetracarboxylic dianhydride (i-BPDA), 2,2-bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-carboxyphenyl) ether dianhydride, and 1,2,3,4-benzenetetracarboxylic dianhydride.
  • the additional aromatic tetracarboxylic acids may be used singly or in combination of two or more of them.
  • the aromatic tetracarboxylic acid diester represented by Formula (1) includes 1,2,4,5- benzenetetracarboxylic acid dimethyl ester, 1,2,4,5-benzenetetracarboxylic acid diethyl ester, 1,2,4,5- benzenetetracarboxylic acid dipropyl ester, 1,2,4,5-benzenetetracarboxylic acid diisopropyl ester, 1,2,4,5- benzenetetracarboxylic acid dibutyl ester, and other isomers of these compounds in terms of two ester groups, but is not necessarily limited to them. Two ester groups are not necessarily the same.
  • 1,2,4,5-benzenetetracarboxylic acid dimethyl ester and 1,2,4,5- benzenetetracarboxylic acid diethyl ester are preferred because a resin after thermal curing can achieve a high glass transition temperature.
  • Component (BZ) is preferred because a resin after thermal curing can achieve a high glass transition temperature.
  • 2-phenyl-4,4'-diaminodiphenyl ether is used as a component of the varnish of the present invention.
  • the use of the component allows the terminally modified imide oligomer represented by General Formula (3) to have the skeleton derived from the 2-phenyl-4,4'-diaminodiphenyl ether in the molecule.
  • the 2-phenyl-4,4'-diaminodiphenyl ether may be partially replaced with an additional aromatic diamine.
  • Examples of the additional aromatic diamine include 1,4-diaminobenzene, 1,3- diaminobenzene, 1,2-diaminobenzene, 2, 6-diethyl- 1,3-diaminobenzene, 4,6-diethyl-2-methyl-l,3- diaminobenzene, 3, 5-diethyltoluene-2, 6-diamine, 4,4'-diaminodiphenyl ether (4,4'-ODA), 3,4'- diaminodiphenyl ether (3,4'-ODA), 3,3'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 4,4'- diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis(2,6-diethyl-4- aminophenyl)methane, 4,4'-methylene-
  • the aromatic diamine compound is particularly preferably 9,9-bis(4-aminophenyl/fluorene, 9,9-bis(4-(4-aminophenoxy/phenyl/fluorene, or 1,3- diaminobenzene.
  • the aromatic diamine compounds are preferably copolymerized, and the copolymer is used in an amount of 0 to 50% by mole, preferably 0 to 25% by mole, and more preferably 0 to 10% by mole relative to the total amount of diamines.
  • the diamine for copolymerization is particularly preferably 9,9-bis(4-aminophenyl/fluorene.
  • the 4-(2-phenylethynyl/phthalic acid monoester represented by General Formula (2/ is used as a component of the varnish of the present invention.
  • the 4-(2-phenylethynyl/phthalic acid monoester represented by General Formula (2/ is a component that reacts with the components (A) and (B) to form a part of the skeleton of the imide resin composition represented by General Formula (3/ described later.
  • General Formula (2/ is preferably an organic group having 1 to 12 carbon atoms, more preferably an organic group having 1 to 9 carbon atoms, and even more preferably an organic group having 1 to 6 carbon atoms because an alcohol component that is generated and eliminated by amic acid formation reaction with a diamine by heat preferably has a low boiling point in order to be immediately volatilized and removed during production of the imide resin composition or molding of the composite material.
  • Formula (2) include, but are not necessarily limited to, 4-(2-phenylethynyl)phthalic acid monoethyl ester, 4-(2-phenylethynyl)phthalic acid monomethyl ester, 4-(2-phenylethynyl)phthalic acid monopropyl ester, 4-(2-phenylethynyl)phthalic acid monoisopropyl ester, and 4-(2-phenylethynyl)phthalic acid monobutyl ester.
  • the organic solvent used for the preparation of the varnish is a solvent having a boiling point of 150°C or less at 1 atmosphere and is preferably a solvent having a boiling point of 100°C or less in order to be immediately volatilized and removed during synthesis of the imide oligomer by heat.
  • the boiling point is 90°C or less.
  • the boiling point is 80°C or less.
  • the boiling point is 70°C or less.
  • the organic solvent include methanol having a boiling point of about 65°C, ethanol having a boiling point of about 78°C, 2-propanol having a boiling point of about 82°C, and 1 -propanol having a boiling point of about 97°C. These organic solvents may be used singly or as a mixture of two or more of them.
  • the amount of the aromatic tetracarboxylic acid diester represented by General Formula (1) included in the varnish is 1 to 500 parts by weight, preferably 20 to 280 parts by weight, and more preferably 40 to 200 parts by weight relative to 100 parts by weight of the organic solvent.
  • the amount of the 2-phenyl-4,4'-diaminodiphenyl ether is 1 to 450 parts by weight, preferably 40 to 400 parts by weight, and more preferably 40 to 280 parts by weight relative to 100 parts by weight of the organic solvent.
  • the amount of the 4-(2-phenylethynyl)phthalic acid monoester represented by General Formula (2) is 1 to 400 parts by weight, preferably 5 to 100 parts by weight, and more preferably 10 to 80 parts by weight relative to 100 parts by weight of the organic solvent.
  • Formula (1), the 2-phenyl-4,4'-diaminodiphenyl ether, and the 4-(2-phenylethynyl)phthalic acid monoester represented by General Formula (2) is in a dissolved state in the organic solvent.
  • the dissolved state means the condition in which each component is substantially uniformly dissolved in an organic solvent to such an extent that each component is not visually observed and the components are present without reacting with each other.
  • the condition in which each component is present can be observed by the method described in Example 1.
  • the varnish of the present invention can be obtained by mixing the aromatic tetracarboxylic acid diester represented by General Formula (1), the aromatic diamine including 2- phenyl-4,4'-diaminodiphenyl ether, and the 4-(2-phenylethynyl)phthalic acid monoester represented by General Formula (2) in the organic solvent in such a manner that the total amount of ester groups is substantially the same as the total amount of primary amino groups while the amount of each component is adjusted within the above parts by weight.
  • the aromatic tetracarboxylic acid diester represented by General Formula (1) the aromatic diamine including 2- phenyl-4,4'-diaminodiphenyl ether
  • the 4-(2-phenylethynyl)phthalic acid monoester represented by General Formula (2) in the organic solvent in such a manner that the total amount of ester groups is substantially the same as the total amount of primary amino groups while the amount of each component is adjusted within the above parts by weight.
  • the aromatic tetracarboxylic acid diester represented by General Formula (1) the aromatic diamine including 2-phenyl-4,4'-diaminodiphenyl ether, and the 4-(2-phenylethynyl)phthalic acid monoester represented by General Formula (2) are preferably uniformly dissolved in the organic solvent in the varnish in a total solid content concentration of greater than 65% by weight or more at 25°C, and more preferably 70 % by weight or more, and even more preferably 80 % by weight or more.
  • the total solid content concentration is between 70% and 95% by weight. In some embodiments, the total solid concentration is between 70% and 90% by weight. In some embodiments, the total solid concentration is between 70% and 85% by weight. In some embodiments, the total solid concentration is between 70% and 80% by weight. In some embodiments, the total solid concentration is between 75% and 90% by weight. In some embodiments, the total solid concentration is between 75% and 85% by weight. In some embodiments, the total solid concentration is between 75% and 80% by weight.
  • the varnish of the present invention can be produced by using the components in such a manner that the total molar amount of ester groups of one or two or more of the aromatic tetracarboxylic acid diester compounds and the 4-(2-phenylethynyl)phthalic acid monoester is substantially the same as the total molar amount of amino groups of the aromatic diamine including 2- phenyl-4,4'-diaminodiphenyl ether, and stirring the components in the organic solvent preferably at a temperature of 75 °C or more and particularly preferably 85 °C or more to uniformly dissolve the components.
  • the varnish of the present invention can also be obtained through successive steps including a step of using an dianhydride of an aromatic tetracarboxylic acid or anhydride of 4-(2- phenylethynyl )phthalic acid or the mixtures as the starting materials and carrying out esterification using an alcohol as the reaction solution.
  • one or two or more of the aromatic tetracarboxylic anhydrides or 4-(2-phenylethynyl)phthalic anhydride or the mixture are heated, refluxed, and stirred in an alcohol solvent at a temperature of 100°C or less, particularly 80°C or less, for 3 hours or more, particularly preferably 6 hours and more and the fully esterified aromatic tetracarboxylic acid diester represented by General Formula (1) or fully esterified 4-(2-phenylethynyl)phthalic acid monoester by General Formula (2) or the mixture are synthesized.
  • the solvent is removed, and the aromatic tetracarboxylic acid diester represented by General Formula (1) or 4-(2-phenylethynyl)phthalic acid monoester by General Formula (2) or the mixture are isolated.
  • the aromatic diamines including 2- phenyl-4,4'-diaminodiphenyl ether are used in such a manner that the total molar amount of ester groups of all the components is substantially the same as the total molar amount of amino groups, and the components are stirred in an organic solvent preferably at a temperature of 90 °C or less, particularly preferably 80 °C or less, to be uniformly dissolved, yielding the varnish.
  • the varnish prepared as above may be concentrated by partially volatilizing the organic solvent used or may be diluted by freshly adding the organic solvent, if the solid content concentration is required to be adjusted. Alternatively, by completely volatilizing the organic solvent used, a solid material composition of the varnish in which the components are uniformly mixed may be isolated. The isolated material composition can be dissolved in an organic solvent to give the varnish once again, as needed. The varnish or the solid material composition undergoes no reaction of forming a terminally modified amic acid oligomer“having an amide-acid bond” (also called amic acid oligomer) when stored at room temperature or a temperature equal to or lower than the room temperature, and can be stably stored for a long period of time.
  • a terminally modified amic acid oligomer“having an amide-acid bond” also called amic acid oligomer
  • a preferred method for producing the varnish of the present invention is exemplified by a method including a step of synthesizing an aromatic tetracarboxylic acid diester (A) represented by General Formula (1) and a 4-(2-phenylethynyl)phthalic acid monoester (C) represented by General Formula (2) and a step of preparing a varnish by adding an aromatic diamine (B) including 2 -phenyl-4, 4'- diaminodiphenyl ether.
  • A aromatic tetracarboxylic acid diester
  • C 4-(2-phenylethynyl)phthalic acid monoester
  • B aromatic diamine
  • the aromatic diamine (B) including 2 -phenyl-4, 4'- diaminodiphenyl ether is added to the solution in the alcohol solution above, and the resulting solution in the alcohol solvent is stirred at a reaction temperature of about 70 to 85°C for about 30 to 360 minutes, yielding a solution (varnish) in the alcohol solvent in which all the components are uniformly dissolved.
  • the varnish of the present invention may have any solution viscosity as long as the advantageous effects of the invention are achieved, but the solution viscosity is preferably 500 centi poise or more, more preferably 1000 centipoise or more, and even more preferably 3,000 centi poise or more, at 25°C.
  • the solution viscosity is determined by the method described in examples.
  • the varnish is heated to react the component (A), the component (B), and the component
  • the dehydration and cyclization method of the amic acid oligomer is exemplified by a method of adding an imidizing agent at a temperature of about 0 to 140°C and a method of heating the oligomer at a temperature of 140 to 275°C.
  • the thermally reactive substituent at each terminal do not cause polymerization reaction.
  • the obtained imide resin composition may be in a varnish form in which the composition is dissolved in an organic solvent, a semidried paste form, or a completely dried solid form.
  • the completely dried solid form can have excellent melt flowability at high temperature and excellent molding processability.
  • R 6 and R 7 are a hydrogen atom or a phenyl group; one of R 6 and R 7 is a phenyl group; R 8 and R 9 are the same or different and are a divalent aromatic diamine residue; Ri 0 and Ri i are the same or different and are a tetravalent aromatic tetracarboxylic acid residue; m and n satisfy relations of m > 1, n > 0, 1 ⁇ m + n ⁇ 10, and 0.05 ⁇ m/(m + n) ⁇ 1; and repeating units are optionally arranged in a block sequence or a random sequence.
  • the aromatic diamine residue represented by R 8 and R 9 in General Formula (3) means a divalent aromatic organic group formed by removing two amino groups from an aromatic diamine.
  • the aromatic tetracarboxylic acid residue means a tetravalent aromatic organic group formed by removing four carboxyl groups from an aromatic tetracarboxylic acid.
  • the aromatic organic group is an organic group having an aromatic ring.
  • the aromatic organic group is preferably an organic group having 4 to 40 carbon atoms, more preferably an organic group having 4 to 30 carbon atoms, and even more preferably an organic group having 4 to 20 carbon atoms.
  • the aromatic tetracarboxylic acid constituting the tetravalent aromatic tetracarboxylic acid residue represented by Ri 0 and Rn in General Formula (3) is preferably a 1, 2,4,5- benzenetetracarboxylic acid, a 3,3',4,4'-biphenyltetracarboxylic acid, or a bis(3,4-carboxyphenyl) ether, and specifically preferably 1,2,4,5-benzenetetracarboxylic dianhydride and 3, 3', 4,4'- biphenyltetracarboxylic dianhydride.
  • the“m” pieces of R j0 and the“n” pieces of Rn in General Formula (3) be a tetravalent residue of a 1,2,4,5-benzenetetracarboxylic acid, and the remainder of them be a tetravalent residue of a 3,3',4,4'-biphenyltetracarboxylic acid.
  • the tetravalent aromatic tetracarboxylic acid residue represented by Ri 0 and Rn be a tetravalent residue of a 1,2,4,5-benzenetetracarboxylic acid
  • the terminally modified imide oligomer be the compound represented by General Formula (4).
  • R 6 and R 7 are a hydrogen atom or a phenyl group; one of R 6 and R 7 is a phenyl group; R 8 and R 9 are the same or different and are a divalent aromatic diamine residue; m and n satisfy relations of m > 1, n > 0, 1 ⁇ m + n ⁇ 10, and 0.05 ⁇ m/(m + n) ⁇ 1; and repeating units are optionally arranged in a block sequence or a random sequence.
  • the tetravalent aromatic tetracarboxylic acid residue represented by Ri 0 and Rn be a tetravalent residue of a 3,3',4,4'-biphenyltetracarboxylic acid, and the terminally modified imide oligomer be the compound represented by General Formula (5).
  • R 6 and R 7 are a hydrogen atom or a phenyl group; one of R 6 and R 7 is a phenyl group; R 8 and R 9 are the same or different and are a divalent aromatic diamine residue; m and n satisfy relations of m > 1, n > 0, 1 ⁇ m + n ⁇ 10, and 0.05 ⁇ m/(m + n) ⁇ 1; and repeating units are optionally arranged in a block sequence or a random sequence.
  • the varnish is stirred and reacted at a reaction temperature of 30 to 150°C for about 1 to 180 minutes to give the terminally modified amic acid oligomer.
  • the reaction solution is then further stirred at 140 to 275°C for 5 minutes to 24 hours to give the terminally modified imide oligomer and to remove the organic solvent in the reaction solution. If necessary, the reaction solution is cooled to around room temperature, and the terminally modified imide oligomer is crystallized. The crystal is subjected to solid-liquid separation by filtration, for example, giving a solid imide resin composition.
  • the solid imide resin composition preferably has a minimum melt viscosity of 10,000
  • the terminally modified imide oligomer included in the imide resin composition of the present invention has substantially no possibility of undergoing hydrolysis, thus causing no viscosity reduction or other deteriorations as compared with amic acid oligomers, and can be stably stored for a long period of time without additives.
  • the terminally modified imide oligomer may be mixed with other oligomers having different molecular weights or with thermoplastic polyimides.
  • thermoplastic polyimide is a polyimide that becomes soft by heat, and specifically may be any commercial product without any limitation in terms of type and the like.
  • the solid imide resin composition can be further heated in a molten state to give a molded article of an imide resin composition, having a higher molecular weight.
  • the molded article can be produced by melting the solid imide resin composition at a temperature of 200 to 280°C and thermally curing the molten composition at 280 to 500°C for about 10 minutes to 40 hours.
  • the molded article can also be produced by a single step of heating a varnish applied onto a support at 280 to 500°C for about 10 minutes to 40 hours.
  • the molded article preferably has a Tg of 300°C or more, more preferably 330°C or more, and even more preferably 350°C or more, for example, when used as high temperature members around the engines of aircraft.
  • Polymerization of the imide resin composition can be observed by the method described in examples.
  • the degree of high molecular weight is not limited specifically.
  • the molded article can be molded into a desired shape by a known method.
  • the shape is exemplified by a film shape, a sheet shape, shapes molded into three dimensional shapes such as a rectangular solid shape and a rod-like shape, but is not limited to particular shapes.
  • a molded article molded into a film preferably has a tensile elongation at break of 10% or more, more preferably 15% or more, and even more preferably 20% or more in order to absorb the energy of external impact to reduce damage when the molded article is used as a cured resin molded article or a fiber- reinforced composite material.
  • Tg and the tensile elongation at break are determined by the methods described in examples.
  • the molded article of the imide resin composition is preferably colored transparent from the viewpoint of the uniformity of curing reaction and reaction completion.
  • the prepreg of the present invention is produced by infiltrating the varnish into fibers.
  • the prepreg of the present invention can be obtained as follows, for example.
  • the material compositions (A), (B), and (C) are uniformly dissolved at a high concentration of a total amount of greater than 65% by weight or more to give a varnish. If necessary, the varnish is appropriately concentrated or diluted, and then is impregnated into fibers arranged in one direction in a planer shape or a fiber fabric, yielding a wet prepreg.
  • the wet prepreg may be dried by a known method, giving a dry prepreg.
  • the prepreg of the present invention includes the wet prepreg and the dry prepreg.
  • the amount of the terminally modified imide oligomer represented by General Formula (3) attached to the fibers is preferably 10 to 60% by weight, more preferably 20 to 50% by weight, and even more preferably 30 to 50% by weight, relative to the total weight of the prepreg.
  • the amount of the organic solvent attached to fibers is preferably 1 to 30% by weight, more preferably 5 to 25% by weight, and even more preferably 5 to 20% by weight relative to the total weight of the prepreg.
  • Examples of the fibers used in the present invention include inorganic fibers such as carbon fibers, glass fibers, metal fibers, and ceramic fibers; and synthetic organic fibers such as polyamide fibers, polyester fibers, polyolefin fibers, and novoloid fibers. These fibers may be used as a single type or a combination of two or more types. In particular, in order to achieve excellent mechanical characteristics, carbon fibers are desirable.
  • any type of carbon fibers can be used without any limitation, and examples of the carbon fibers include polyacrylonitrile (PAN)-based carbon fibers, rayon-based carbon fibers, lignin-based carbon fibers, and pitch-based carbon fibers.
  • PAN polyacrylonitrile
  • carbon fibers such as PAN-based carbon fibers and pitch-based carbon fibers are preferred because they are generally used and inexpensive and have high strength.
  • the carbon fibers have been subjected to sizing treatment. Such fibers may be used without any treatment or may be washed with an organic solvent or the like to remove the sizing agent, as necessary. It is preferable that fiber bundles be opened with air, rollers, or other means in advance and the resin or a resin solution be impregnated between single yams of the carbon fibers.
  • the imide prepreg of the present invention is produced by further heating the prepreg.
  • the imide prepreg of the present invention can be obtained as follows, for example.
  • a solution of the wet prepreg or the dry prepreg in an organic solvent is heated at 140 to
  • the amount of the terminally modified imide oligomer attached to the fibers in the imide wet prepreg is preferably 5 to 50% by weight, more preferably 20 to 50% by weight, and even more preferably 30 to 50% by weight relative to the total weight of the prepreg.
  • the amount of the organic solvent attached to the fibers is preferably 1 to 30% by weight, more preferably 5 to 25% by weight, and even more preferably 5 to 20% by weight relative to the total weight of the prepreg.
  • the amount of the terminally modified imide oligomer attached to the fibers in the imide dry prepreg is preferably 20 to 80% by weight, more preferably 20 to 60% by weight, and even more preferably 30 to 50% by weight relative to the total weight of the prepreg.
  • the fibers used in the imide prepreg of the present invention may be the same as the fibers used in the above described prepreg.
  • the fiber material constituting the imide prepreg has a structure of a continuous fiber form such as UD (unidirectional) forms, weave forms (plain weave, satin weave, for example), and knit forms, and is not limited to particular forms.
  • the form can be appropriately selected depending on the purpose.
  • the forms may be used singly or in combination of two or more of them.
  • the fiber-reinforced composite material of the present invention can be obtained as follows, for example.
  • a predetermined number of the prepregs are stacked and thermally cured with an autoclave, a hot press, or a similar apparatus at a temperature of 80 to 500°C at a pressure of 1 to 1,000 kg/cm 2 for about 10 minutes to 40 hours, giving a fiber-reinforced composite material.
  • the imide wet prepregs or the imide dry prepregs may be stacked and thermally cured in the same manner as the above, giving a fiber-reinforced composite material.
  • the fiber-reinforced composite material of the present invention obtained as above preferably has a glass transition temperature (Tg) of 300°C or more.
  • Tg glass transition temperature
  • the present invention also provides a fiber-reinforced composite material showing no generation of microcracks inside and maintain greater than about 70%, preferably about more than 80%, and even more preferably more than 90% initial interlaminar shear strength (ILSS) or short beam shear (SBS) strength measured at room temperature, and about 200 °C to about 250 °C, preferably about 232 °C after thermal cycling in the temperature range between about -60 °C and about 250°C, preferably between about -54 °C and about 232 °C preferably for 500 cycles or more, and more preferably 1000 cycles or more and even more preferably 2000 cycles or more.
  • ILSS interlaminar shear strength
  • SBS short beam shear
  • the film-like molded article of the imide resin composition or the imide prepreg may be inserted between a fiber-reinforced composite material and a different material, and the whole may be heated and melted to be integrated, giving a fiber-reinforced composite material structure.
  • the different material is not limited to particular materials and may be any material commonly used in the field. Examples of the material include honeycomb metal materials and sponge-like core materials.
  • DSC differential scanning calorimeter
  • a dynamic viscoelasticity analyzer (DMA, model: DMA-Q-800, manufactured by TA Instruments) was used for measurement in a cantilever manner at a strain of 0.1% at a frequency of 1 Hz under a nitrogen stream at a temperature increase rate of 3°C/min. The intersection of two tangent lines before and after the drop of a storage elastic modulus curve was regarded as the glass transition temperature.
  • a rheometer (model: AR2000, manufactured by TA Instruments) was used for measurement with a 25-mm parallel plate at a temperature increase rate of 4°C/min.
  • thermogravimetric analyzer (TGA, model: SDT-2960, manufactured by TA
  • a tensilon versatile testing machine (trade name: TENSIFON/UTM-II-20, manufactured by ORIENTEC Co., Ftd.) was used for measurement at room temperature at a tensile speed of 3 mm/min.
  • the test pieces had a film-like shape having a length of 20 mm, a width of 3 mm, and a thickness of 80 to 120 mhi. Measurement of infrared absorption spectrum
  • a FT/IR-230S spectrometer manufactured by JASCO Corporation was used for infrared absorption spectrum measurement at room temperature in a measurement range of 400 cm 1 to 4,000 cm 1 at an accumulation number of 32.
  • a measuring microscope STM-MJS manufactured by Olympus Corporation, was used for measurement at a magnification of 50 to 500.
  • Composite specimens are placed in a thermal cycling chamber. The composites were thermally cycled between -54 °C and 232 °C with a 15-minute hold at 232 °C and a 10-minute hold at - 54°C. Up to 2000 thermal cycles were performed. Samples were taken out every 400 cycles for microcrack inspection using optical microscope and interlaminar shear strength test.
  • the varnish was placed in a glass petri dish. By heating the varnish in a circulation air oven at an internal temperature of 60° C for 3 hours and further heating the varnish at 250 ° C for 1 hour, amic acid bond formation reaction and imide bond formation reaction were carried out while ethanol was removed, yielding a terminal-modified imide oligomer.
  • the powdery terminal-modified imide oligomer before curing had a Tg of 210°C from
  • IR spectrum measurement of some of the film-like imide resin composition showed the disappearance of the absorption around 2,210 cm 1 assigned to the stretching vibration of the triple bond in the phenylethynyl moiety as the terminal group of the terminally modified imide oligomer, and this indicated that the pressurized thermoforming allowed the terminally modified imide oligomer component in the film-like imide resin composition to undergo thermal addition reaction and to be polymerized.
  • the film-like cured product had a Tg of 337°C by DSC measurement, a Tg of 336°C by DMA measurement, and a 5% weight loss temperature of 538°C by TGA.
  • the film-like cured product had an elastic modulus of 3.1 GPa, a breaking strength of 143 MPa, and a breaking elongation of 31%.
  • a varnish having a solid content concentration of about 75 % by weight in which the raw material composition of the terminally modified polyimide resin was uniformly dissolved in an ethanol solvent was prepared in a same manner with Example 1 other than changing the amount of ethanol initially added to 695.93 g (15106 mmol).
  • a varnish having a solid content concentration of about 80 % by weight in which the raw material composition of the terminally modified polyimide resin was uniformly dissolved in an ethanol solvent was prepared in a same manner with Example 1 other than changing the amount of ethanol initially added to 574.36 g (12467 mmol).
  • a varnish having a solid content concentration of about 85 % by weight in which the raw material composition of the terminally modified polyimide resin was uniformly dissolved in an ethanol solvent was prepared in a same manner with Example 1 other than changing the amount of ethanol initially added to 467.45 g (10147 mmol).
  • the varnish was placed in a glass petri dish. By heating the varnish in a circulation air oven at an internal temperature of 60°C for 3 hours and further heating the varnish at 250 °C for 1 hour, amic acid bond formation reaction and imide bond formation reaction were carried out while methanol was removed, yielding a terminally modified imide oligomer.
  • the powdery terminal-modified imide oligomer before curing had a Tg of 221°C from
  • IR spectrum measurement of some of the film-like imide resin composition showed the disappearance of the absorption around 2,210 cm 1 assigned to the stretching vibration of the triple bond in the phenylethynyl moiety as the terminal group of the terminally modified imide oligomer, and this indicated that the pressurized thermoforming allowed the terminally modified imide oligomer component in the film-like imide resin composition to undergo thermal addition reaction and to be polymerized.
  • the film-like cured product had a Tg of 355°C from DSC measurement result, a Tg of 357°C from DMA measurement result, and a 5% weight loss temperature of 537°C by TGA.
  • the film-like cured product had an elastic modulus of 3.2 GPa, a breaking strength of 137 MPa, and a breaking elongation of 20%.
  • the varnish obtained above was dried under vacuum at room temperature, giving a powdered raw material composition of the terminally modified polyimide resin.
  • the powder was smoothly dissolved in MeOH-d 4 and was subjected to H-NMR measurement in the same manner as in Example 1.
  • the result revealed that all the components included in the raw material composition of the terminally modified polyimide resin formed ion complexes (salts) in the varnish in the methanol solution prepared in the example.
  • the varnish was placed in a glass petri dish. By heating the varnish in a circulation air oven at an internal temperature of 60°C for 3 hours and further heating the varnish at 250 °C for 1 hour, amic acid bond formation reaction and imide bond formation reaction were carried out while methanol was removed, yielding a terminally modified imide oligomer.
  • the varnish was placed in a glass petri dish. By heating the varnish in a circulation air oven at an internal temperature of 60°C for 3 hours and further heating the varnish at 250°C for 1 hour, amic acid bond formation reaction and imide bond formation reaction were carried out while ethanol was removed, yielding a terminal-modified imide oligomer.
  • the powdery terminal-modified imide oligomer before curing had a Tg of 245°C from
  • IR spectrum measurement of some of the film-like imide resin composition showed the disappearance of the absorption around 2,210 cm 1 assigned to the stretching vibration of the triple bond in PEPA as the terminal group of the terminally modified imide oligomer, and this indicated that the pressurized thermoforming allowed the terminally modified imide oligomer component in the film-like imide resin composition to undergo thermal addition reaction and to be polymerized.
  • the film-like cured product had a Tg of 334°C by DSC measurement, a Tg of 335°C by DMA measurement, and a 5% weight loss temperature of 538°C by TGA.
  • the film-like cured product had an elastic modulus of 3.1 GPa, a breaking strength of 141 MPa, and a breaking elongation of 35%.
  • a varnish having a solid content concentration of about 75 % by weight in which the raw material composition of the terminally modified polyimide resin was uniformly dissolved in an ethanol solvent was prepared in a same manner with Example 6 other than changing the amount of ethanol initially added to 622.87 g (13520 mmol).
  • a varnish having a solid content concentration of about 80 % by weight in which the raw material composition of the terminally modified polyimide resin was uniformly dissolved in an ethanol solvent was prepared in a same manner with Example 6 other than changing the amount of ethanol initially added to 515.54 g (11190 mmol).
  • a varnish having a solid content concentration of about 85 % by weight in which the raw material composition of the terminally modified polyimide resin was uniformly dissolved in an ethanol solvent was prepared in a same manner with Example 6 other than changing the amount of ethanol initially added to 419.72 g (9110 mmol).
  • a varnish having a solid content concentration of about 85 % by weight in which the raw material composition of the terminally modified polyimide resin was uniformly dissolved in an methanol solvent was prepared in a same manner with Example 6 other than changing the solvent initially added to methanol.
  • the mixture was polymerized at room temperature for 2.5 hours, then at 60°C for 1.5 hours, and at room temperature for 1 hour, giving an amic acid oligomer.
  • 0.9929 g (4 mmol) of 4-(2-phenylethynyl)phthalic anhydride was added to the reaction solution.
  • the mixture was reacted at room temperature for 12 hours to undergo terminal modification, and subsequently was stirred at 195°C for 5 hours to undergo imide bond formation.
  • the reaction solution was poured into 900 mL of ion-exchanged water, and precipitated powder was collected by filtration.
  • the powder was washed with 80 mL of methanol for 30 minutes, and the powder obtained by filtration was dried under reduced pressure at 130°C for a day, giving a product.
  • the powdery terminal-modified imide oligomer before curing had a Tg of 213°C from
  • IR spectrum measurement of some of the film-like imide resin composition showed the disappearance of the absorption around 2,210 cm 1 assigned to the stretching vibration of the triple bond in the phenylethynyl moiety as the terminal group of the terminally modified imide oligomer, and this indicated that the pressurized thermoforming allowed the terminally modified imide oligomer component in the film-like imide resin composition to undergo thermal addition reaction and to be polymerized.
  • the obtained film-like cured product had a Tg of 346°C by DSC measurement, a Tg of 343°C by DMA measurement, and a 5% weight loss temperature of 538°C by TGA.
  • the film-like cured product had an elastic modulus of 3.2 GPa, a breaking strength of 132 MPa, and a breaking elongation of 16%.
  • the powdery terminal-modified imide oligomer before curing had a Tg of 217°C from
  • IR spectrum measurement of some of the film-like imide resin composition showed the disappearance of the absorption around 2,210 cm 1 assigned to the stretching vibration of the triple bond in the phenylethynyl moiety as the terminal group of the terminally modified imide oligomer, and this indicated that the pressurized thermoforming allowed the terminally modified imide oligomer component in the film-like imide resin composition to undergo thermal addition reaction and to be polymerized.
  • the film-like cured product had a Tg of 336°C by DSC measurement, a Tg of 346°C by DMA measurement, and a 5% weight loss temperature of 538°C by TGA.
  • the film-like cured product had an elastic modulus of 2.8 GPa, a breaking strength of 128 MPa, and a breaking elongation of 18%.
  • reaction solution was poured into 900 mL of ion-exchanged water, and precipitated powder was collected by filtration.
  • the powder was washed with 80 mL of methanol for 30 minutes, and the powder obtained by filtration was dried under reduced pressure at 130°C for a day, giving a product.
  • the powdery terminal-modified imide oligomer before curing had a Tg of 213°C from
  • IR spectrum measurement of some of the film-like imide resin composition showed the disappearance of the absorption around 2,210 cm 1 assigned to the stretching vibration of the triple bond in the phenylethynyl moiety as the terminal group of the terminally modified imide oligomer, and this indicated that the pressurized thermoforming allowed the terminally modified imide oligomer component in the film-like imide resin composition to undergo thermal addition reaction and to be polymerized.
  • the obtained film- like cured product had a Tg of 356°C by DSC measurement, a Tg of 356°C by DMA measurement, and a 5% weight loss temperature of 538°C by TGA.
  • the film- like cured product had an elastic modulus of 3.2 GPa, a breaking strength of 132 MPa, and a breaking elongation of 15%.
  • Each vacuum-dried product of the varnishes obtained in Examples 1 to 10 had excellent solubility in organic solvents such as methanol and ethanol.
  • Examples 1 to 10 had a minimum melt viscosity of higher than 300°C, which indicates excellent melt flowability at high temperature and excellent molding processability.
  • Each film-like molded article obtained by heating the solid imide resin compositions obtained in Examples 1 to 10 in a molten state to be polymerized had a Tg of higher than 300°C and underwent almost no thermal decomposition even at a high temperature of higher than 500°C. This result reveals that the cured resin moldings have extremely high heat resistance and also have high breaking strength and breaking elongation.
  • the varnishes obtained in Examples 1 to 10 included organic solvents having lower boiling points than those included in the varnishes obtained in Comparative Examples 1 to 3. It is thus obvious that such organic solvents can be readily removed out of the system for a short period of time, and a polyimide powder having excellent thermal properties can be simply obtained without any special purification operation (reprecipitation).
  • a polyimide film was placed as a release film, and two set of the stacked wet prepregs of the raw material composition of the terminally modified polyimide resin produced in Example 11 were prepared on the film with lay-up sequences of [0] x and [0/+45/-45/90] s , respectively.
  • the lay-up sequence [0] x indicates a stack of 8 wet prepregs, where the orientation of the fibers between each successive wet prepreg in the stack is in the same direction.
  • the lay-up sequence of [0/+45/-45/90] s is also a stack of 8 wet prepregs; however, in this sequence the first wet prepreg has fiber orientation defined at 0 degrees, the second wet prepreg has fiber orientation at +45 degrees relative to that of the first wet prepreg, the third wet prepreg has a fiber orientation of -45 degrees relative to that of the first wet prepreg, and the fourth wet prepreg has fiber orientation of 90 degrees relative to that of the first wet prepreg, and then the fifth through eighth wet prepregs have a symmetrically mirrored sequence to the first through fourth, i.e, the fifth through eighth wet prepregs have fiber orientations of 90, -45, +45, and 0, respectively.
  • a polyimide film and a stainless steel plate were further stacked.
  • the whole was heated on a hot press at a temperature increase rate of about 5 °C/min from room temperature to 250 °C and heated at 250 °C for 1 hour.
  • the whole was further heated at a temperature increase rate of about 5°C/min from 250°C to 320°C and heated at 320°C for 10 minutes.
  • the whole was heated under a pressure condition of 1.3 MPa at a temperature increase rate of about 5°C/min to 370°C and was heated under the same pressure condition at 370°C for 1 hour.
  • the appearance observation revealed the production of a good fiber-reinforced composite material laminate having very smooth surfaces and containing the resin that was uniformly infiltrated into the fibers.
  • the obtained laminate had a glass transition temperature (DSC) of 345 °C, a fiber volume fraction (Vf) of 0.55.
  • the obtained fiber-reinforced composite material laminate had a glass transition temperature of higher than 300°C, which indicates excellent heat resistance, and had an short beam shear (SBS) strength of about 73 MPa determined by short beam shear test at room temperature in a three-point bending manner, which indicates excellent mechanical characteristics, as illustrated in FIG. 3 for both the [0]g and [0/+45/-45/90] s lay-up sequences.
  • SBS short beam shear
  • the obtained fiber-reinforced composite material laminates were exposed in a thermal cycling condition in the temperature range between -54 °C and 232 °C up to 2000 cycles.
  • the obtained fiber-reinforced composite material laminates showed no generation of microcracks, cracks and delaminations inside after thermal cycles by microscope observation as shown in FIGS. 4A-4B for the [0] 8 and [0/+45/-45/90] s lay-up sequences, respectively, between 0 to 2000 thermal cycles in increments of 400 cycles.
  • the varnish was placed in a glass petri dish. By heating the varnish in a circulation air oven at an internal temperature of 60°C for 3 hours and further heating the varnish at 200°C for 1 hour, amic acid bond formation reaction and imide bond formation reaction were carried out while methanol was removed, yielding a terminally modified imide oligomer.
  • the varnish was placed in a glass petri dish. By heating the varnish in a circulation air oven at an internal temperature of 60°C for 3 hours and further heating the varnish at 200°C for 1 hour, amic acid bond formation reaction and imide bond formation reaction were carried out while methanol was removed, yielding a terminally modified imide oligomer.
  • the present invention can provide a varnish having excellent solubility in organic solvents having low boiling points, such as alcohols, and excellent solution storage stability.
  • the terminally modified imide oligomer produced by using the varnish exhibits excellent moldability, and thermal curing of the oligomer enables the production of a cured product having high heat resistance, toughness, and mechanical characteristics.
  • components (A), (B), and (C) are present in the varnish at a solid content of more than 65 %, wherein the component (A) is an aromatic tetracarboxylic acid diester represented by General Formula (1) below and is present in an amount of 1 to 500 parts by weight, based on the total weight of the varnish; wherein the component (B) is 2-phenyl-4,4'-diaminodiphenyl ether and is present in an amount of 1 to 450 parts by weight, based on the total weight of the varnish, wherein the component (C) is a 4-(2-phenylethynyl)phthalic acid monoester represented by General Formula (2) and is present in an amount of 1 to 400 parts by weight, based on the total weight of the varnish, and wherein the component (D) is an organic solvent having a boiling point of 150°C or less at 1 atmosphere or a mixture of two or more of the organic solvents which includes methanol, ethanol, 1 -propanol, and 2-propano
  • R 2 and R 3 are the same or different, and are an aliphatic organic group or an aromatic organic group, and R 2 and R 3 are located in a cis configuration or a trans configuration, and
  • R4 and R 5 are a hydrogen atom, an aliphatic organic group, or an aromatic organic group
  • R4 and R 5 are aliphatic organic groups or an aromatic organic group; and/or wherein the aliphatic organic group represented by R 2 and R 3 in General Formula (1) is an organic group having an aliphatic chain, and wherein the aromatic organic group is an organic group having an aromatic ring; and/or
  • aromatic tetracarboxylic acid diester residue represented by R j in General Formula (1) is a tetravalent aromatic organic group formed by removing four carboxyl groups from an aromatic tetracarboxylic acid;
  • aromatic tetracarboxylic acid diester residue represented by Ri is a tetravalent residue of a 1,2,4,5-benzenetetracarboxylic acid or a tetravalent residue of a 3, 3’, 4,4’- biphenyltetracarboxylic acid;
  • Ri in General Formula (1) is a combination of two or more selected from the group consisting of a tetravalent aromatic tetracarboxylic acid diester represented by a tetravalent residue of a 1,2,4,5-benzenetetracarboxylic acid, an aromatic tetracarboxylic acid diester represented by a tetravalent residue of a 3,3',4,4'-biphenyltetracarboxylic acid, and an aromatic tetracarboxylic acid diester represented by a tetravalent residue of a bis(3,4-carboxyphenyl) ether; and/or
  • aliphatic organic group represented by R4 or R 5 in General Formula (2) is an organic group having an aliphatic chain, and wherein the aromatic organic group is an organic group having an aromatic ring;
  • component (B) further comprises one or more additional aromatic diamines.
  • a prepreg including a fiber impregnated by the varnish comprising components (A) to (D); and/or
  • aliphatic organic group represented by R 2 and R 3 in General Formula (1) is an organic group having an aliphatic chain, and wherein the aromatic organic group is an organic group having an aromatic ring;
  • aromatic tetracarboxylic acid diester residue represented by Ri in General Formula (1) is a tetravalent aromatic organic group formed by removing four carboxyl groups from an aromatic tetracarboxylic acid;
  • aromatic tetracarboxylic acid diester residue represented by Ri is a tetravalent residue of a 1,2,4,5-benzenetetracarboxylic acid or a tetravalent residue of a 3, 3’, 4,4’- biphenyltetracarboxylic acid;
  • Ri in General Formula (1) is a combination of two or more selected from the group consisting of a tetravalent aromatic tetracarboxylic acid diester represented by a tetravalent residue of a 1,2,4,5-benzenetetracarboxylic acid, an aromatic tetracarboxylic acid diester represented by a tetravalent residue of a 3,3',4,4'-biphenyltetracarboxylic acid, and an aromatic tetracarboxylic acid diester represented by a tetravalent residue of a bis(3,4-carboxyphenyl) ether; and/or
  • aliphatic organic group represented by R 4 or R 5 in General Formula (2) is an organic group having an aliphatic chain, and wherein the aromatic organic group is an organic group having an aromatic ring;
  • component (B) further comprises one or more additional aromatic diamines.
  • an imide prepreg prepared by heating the prepreg;
  • R 6 and R 7 are each a hydrogen atom or a phenyl group
  • R 6 and R 7 are a phenyl group
  • R 8 and R 9 are the same or different, and are each a divalent aromatic diamine residue
  • R 10 and R n are the same or different, and are each a tetravalent aromatic tetracarboxylic acid residue
  • m and n satisfy relations of m > 1, n > 0, 1 ⁇ m + n ⁇ 10, and 0.05 ⁇ m/(m + n) ⁇ 1, and wherein repeating units of the m-unit and n-unit in General Formula (3) are optionally arranged in a block sequence or a random sequence.
  • a fiber-reinforced composite material prepared by stacking at least one of a plurality of prepregs, a plurality of imide prepregs, or a combination of prepregs and imide prepregs, and thermally curing the stack, wherein a prepreg including a fiber impregnated by the varnish comprising components (A) to (D), and wherein an imide prepreg is prepared by heating a prepreg; and/or
  • the fiber-reinforced composite material has a Tg of 300°C or more;
  • R 6 and R 7 are each a hydrogen atom or a phenyl group
  • R 6 and R 7 are a phenyl group
  • R 8 and R 9 are the same or different, and are each a divalent aromatic diamine residue, wherein Ri 0 and Rn are the same or different, and are each a tetravalent aromatic tetracarboxylic acid residue,
  • m and n satisfy relations of m > 1, n > 0, 1 ⁇ m + n ⁇ 10, and 0.05 ⁇ m/(m + n) ⁇ 1, and wherein repeating units of the m-unit and n-unit in General Formula (3) are optionally arranged in a block sequence or a random sequence.
  • Solid imide resin composition prepared by heating the varnish comprising components (A) to (D) to remove the component (D), where the solid imide resin composition is represented by General Formula (3),
  • R 6 and R 7 are each a hydrogen atom or a phenyl group
  • R 6 and R 7 are a phenyl group
  • R 8 and R 9 are the same or different, and are each a divalent aromatic diamine residue, wherein Ri 0 and Rn are the same or different, and are each a tetravalent aromatic tetracarboxylic acid residue.
  • m and n satisfy relations of m > 1, n > 0, 1 ⁇ m + n ⁇ 10, and 0.05 ⁇ m/(m + n) ⁇ 1, and wherein repeating units of the m-unit and n-unit in General Formula (3) are optionally arranged in a block sequence or a random sequence.
  • a molded article of a polymerized imide resin composition prepared by heating the solid imide resin composition in a molten state;
  • the polymerized imide resin composition has a glass transition temperature (Tg) of 300°C or more;
  • the polymerized imide resin composition has a glass transition temperature (Tg) of 330°C or more; and/or
  • the polymerized imide resin composition has a glass transition temperature (Tg) of 350°C or more;
  • the molded article is in the shape of a film, the film having a tensile elongation at break of 10% or more;
  • the film having a tensile elongation at break of 15% or more;
  • the film having a tensile elongation at break of 20% or more.

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Abstract

L'invention concerne un vernis et une composition de résine de polyimide, un préimprégné et un stratifié renforcé par des fibres préparé à partir de ce dernier. Selon un mode de réalisation, le vernis comprend des constituants (A) à (D), les constituants (A), (B) et (C) étant présents à une teneur en extrait sec supérieure à 65 %. Le constituant (A) est un diester d'acide tétracarboxylique aromatique représenté par la formule générale (1) ci-dessous et est présent en une quantité de 1 à 500 parties en poids, le constituant (B) est le 2-phényl-4,4'-diaminodiphényl éther et est présent en une quantité de 1 à 450 parties en poids, le constituant (C) est un monoester d'acide 4-(2-phényléthynyl)phtalique représenté par la formule générale (2) et est présent en une quantité de 1 à 400 parties en poids, et le constituant (D) est un solvant organique présent en une quantité de 100 parties en poids, par rapport au poids total du vernis.
PCT/US2019/033300 2018-05-21 2019-05-21 Vernis de polyimide présentant une résistance élevée à la chaleur et une excellente résistance mécanique Ceased WO2019226641A1 (fr)

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