WO2013141132A1 - 加熱硬化性溶液組成物、それを用いた硬化物、プリプレグ及び繊維強化複合材料 - Google Patents
加熱硬化性溶液組成物、それを用いた硬化物、プリプレグ及び繊維強化複合材料 Download PDFInfo
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
-
- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- 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
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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
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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
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
-
- 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
- C08J2349/00—Characterised by the use of homopolymers or copolymers of compounds having one or more carbon-to-carbon triple bonds; Derivatives of such polymers
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
-
- 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 thermosetting solution composition that gives an imide oligomer having an addition-reactive functional group at its terminal by heating and a cured product thereof, a cured product using the same, a prepreg, and a fiber-reinforced composite material.
- Oligomers in which both ends of polyimide are sealed with addition-reactive functional groups are conventionally known as matrix resins for molded products and fiber-reinforced composite materials because their cured products have excellent heat resistance.
- an imide oligomer whose terminal is sealed with 4- (2-phenylethynyl) phthalic anhydride is considered to have an excellent balance of moldability, heat resistance, and mechanical properties.
- Patent Document 1 discloses curing.
- An object of the present invention is to provide a terminal-modified imide oligomer having excellent heat resistance and mechanical properties and a highly practical product, and a cured product thereof, and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride,
- a terminal-modified imide oligomer obtained by reacting an aromatic diamine compound with 4- (2-phenylethynyl) phthalic anhydride and having a logarithmic viscosity of 0.05-1 and a cured product thereof are disclosed.
- Patent Document 2 discloses a thermosetting solution composition that does not use a high-boiling solvent such as N-methyl-2-pyrrolidone or N, N-dimethylacetamide in order to facilitate removal of the solvent in the process of forming a cured product.
- a high-boiling solvent such as N-methyl-2-pyrrolidone or N, N-dimethylacetamide
- thermosetting solution composition dissolved in an organic solvent containing alcohol as a main component and an uncured resin composite using the same are disclosed.
- thermosetting solution composition that provides a cured product having excellent oxidation resistance and a high glass transition temperature (Tg).
- Tg glass transition temperature
- Another object of the present invention is to provide a thermosetting solution composition suitable for use in the production of a fiber-reinforced composite material, in which no reaction failure is observed during curing.
- Still another object of the present invention is to provide a cured product, a prepreg, and a fiber-reinforced composite material using the above-mentioned thermosetting solution composition.
- the present inventors have intensively studied. As a result, by using a specific aromatic diamine having no oxygen atom in the molecule as an aromatic diamine component, the present invention has excellent oxidation resistance and a glass transition.
- a thermosetting solution composition that can give a cured product having a high temperature (Tg) and that does not exhibit a reaction failure during curing and is suitable for use in the production of a fiber-reinforced composite material, and a cured product using the same
- Tg high temperature
- the present inventors have found that a prepreg and a fiber-reinforced composite material can be obtained, and have reached the present invention.
- an aromatic tetracarboxylic acid component containing 20 mol% or more of 2,3,3 ′, 4′-biphenyltetracarboxylic acid compound (B) two derived from an amino group Two carbon-nitrogen bond axes are located on the same straight line, the aromatic diamine having no oxygen atom in the molecule, and the two carbon-nitrogen bond axes derived from amino groups are not located on the same straight line. And an aromatic diamine component having no oxygen atom in the molecule, and (C) a terminal blocking agent having a phenylethynyl group.
- a thermosetting solution composition is provided.
- aromatic diamines having two carbon-nitrogen bond axes derived from the amino group (B) on the same straight line and having no oxygen atom in the molecule -Diaminobenzene, an aromatic diamine in which the two carbon-nitrogen bond axes derived from the amino group are not located on the same straight line and have no oxygen atom in the molecule can be 1,3-diaminobenzene .
- the component (A) can further contain a 3,3 ′, 4,4′-biphenyltetracarboxylic acid compound.
- the end-capping agent having a phenylethynyl group (C) can be a 4- (2-phenylethynyl) phthalic acid compound.
- thermosetting solution composition obtained by heat curing the thermosetting solution composition.
- thermosetting solution composition characterized by impregnating a fibrous reinforcing material with the thermosetting solution composition.
- a fiber-reinforced composite material obtained by heating and curing the prepreg.
- thermosetting solution composition suitable for use in the present invention, a cured product using the composition, a prepreg, and a fiber-reinforced composite material can be provided.
- the heat-curable solution composition of this embodiment is a solution composition that gives an imide oligomer having an addition-reactive functional group at the terminal and a cured product thereof by heating.
- the imide oligomer has an aromatic tetracarboxylic acid component containing 20 mol% or more of a 2,3,3 ′, 4′-biphenyltetracarboxylic acid compound, and two carbon-nitrogen bond axes derived from an amino group.
- An aromatic diamine that is located on a line and does not have an oxygen atom in the molecule and an aromatic diamine that does not have two carbon-nitrogen bond axes derived from an amino group on the same straight line and has no oxygen atom in the molecule Including an aromatic diamine component having no oxygen atom in the molecule and having a phenylethynyl group as an addition-reactive functional group at the terminal.
- the aromatic tetracarboxylic acid component which is the component (A) of the thermosetting solution composition according to the present embodiment contains a 2,3,3 ′, 4′-biphenyltetracarboxylic acid compound, It is preferable that it is 20 mol% or more in (A) component, and it is preferable to contain especially 30 mol% or more. If the content of the 2,3,3 ', 4'-biphenyltetracarboxylic acid compound is low, the glass transition temperature (Tg) of the resulting cured product will be low, and the toughness may not be sufficient.
- the aromatic tetracarboxylic acid component may contain other biphenyltetracarboxylic acid compounds.
- Examples of other biphenyltetracarboxylic acid compounds include 3,3 ′, 4,4′-biphenyltetracarboxylic acid compounds, Examples include 2,2 ′, 3,3′-biphenyltetracarboxylic acid compounds.
- 2,3,3 ′, 4′-biphenyltetracarboxylic acid compounds include 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (A-BPDA), an ester or salt of 2,3,3 ′, 4′-biphenyltetracarboxylic acid.
- Dianhydrides (s-BPDA), esters or salts of 3,3 ′, 4,4′-biphenyltetracarboxylic acid, and 2,2 ′, 3,3′-biphenyltetracarboxylic acid compounds include 2 , 2 ', 3,3'-biphenyltetracarboxylic acid, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, ester or salt of 2,2 ', 3,3'-biphenyltetracarboxylic acid Is included.
- a biphenyltetracarboxylic acid compound other than 2,3,3 ′, 4′-biphenyltetracarboxylic acid compound is used as the aromatic tetracarboxylic acid component
- 3,3 ′, 4,4′-biphenyl is used. It is preferable to use a tetracarboxylic acid compound.
- the 3,3 ′, 4,4′-biphenyltetracarboxylic acid compound is preferably used in the range of 20 to 80 mol% in the component (A), particularly in the range of 30 to 70 mol%. Is preferred.
- the resulting cured product may not have sufficient oxidation resistance, and if the content is high, the resulting thermosetting solution composition The stability of the product and the toughness of the cured product may not be sufficient.
- the two carbon-nitrogen bond axes derived from the amino group are located on the same straight line.
- having no oxygen atom in the molecule means having no ether bond, carbonyl group or the like in the molecule.
- aromatic diamines in which two carbon-nitrogen bond axes derived from an amino group are located on the same straight line and have no oxygen atom in the molecule, 1,4-diaminobenzene (PPD), 2,5-diaminotoluene, 2,2'-bis (trifluoromethyl) benzidine, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 3,3 ', 5,5'-tetramethylbenzidine, 4,4-diaminooctafluoro Biphenyl and the like can be mentioned. These may be used alone or in combination.
- 1,3-diaminobenzene MPD
- 2,4- Diaminotoluene 2,6-diaminotoluene
- 3,3'-diaminodiphenylmethane 4,4'-diaminodiphenylmethane
- 2,2-bis (3-aminophenyl) propane 2,2-bis (4-aminophenyl)
- propane and 9,9′-bis (4-aminophenyl) fluorene may be used alone or in combination.
- 1,4-diaminobenzene paraphenylenediamine, PPD
- 1,3-diaminobenzene metalaphenylenediamine, MPD
- PPD paraphenylenediamine
- MPD metalaphenylenediamine
- the ratio of PPD is preferably in the range of 10 to 90 mol% in the component (B), particularly preferably in the range of 20 to 80 mol%. Outside this range, the oxidation resistance and toughness of the cured product may not be sufficient.
- an end-capping agent used for introducing an addition-reactive functional group at the end which is the component (C) of the thermosetting solution composition according to this embodiment one having an ethynyl group is preferable, and in particular, phenylethynyl. Those having a group are preferred.
- the end to be sealed may be either an amine end or a carboxylic acid end, but those that react with the amine end to form an imide group are preferred.
- An example of such a terminal blocking agent is 4- (2-phenylethynyl) phthalic acid compound.
- the 4- (2-phenylethynyl) phthalic acid compound includes 4- (2-phenylethynyl) phthalic anhydride, ester or salt of 4- (2-phenylethynyl) phthalic acid.
- thermosetting solution composition of this embodiment may contain a component having an action of promoting imidization reaction.
- the content is preferably in the range of 0.01 to 3% by mass with respect to the amount of all components.
- an imidazole compound has an action of promoting dissolution when preparing a solution composition, and can shorten the dissolution time. Furthermore, it has the effect of accelerating curing when an uncured molded body is heated under pressure to produce a cured product (cured molded body), and a cured molded body with excellent characteristics can be easily obtained. become.
- imidazole compounds include known compounds as imidization catalysts for polyimides such as 2-methylimidazole and 1,2-dimethylimidazole.
- the aromatic diamine component is preferably used in a stoichiometric excess molar amount with respect to the aromatic tetracarboxylic acid component.
- the amount of the aromatic diamine component to be used is appropriately adjusted so that the resulting imide oligomer has a desired molecular weight, but the aromatic diamine component is used in an amount of 1.05 to 2 with respect to 1 mol of the aromatic tetracarboxylic acid component. It is preferably used in an amount in the range of 0 mol, and particularly preferably in an amount in the range of 1.10 to 1.25 mol.
- the terminal blocking agent is 1.8 to 2.2 times the molar amount corresponding to the difference between the molar amount of the aromatic diamine component and the molar amount of the aromatic tetracarboxylic acid component, preferably 1.95 to It is preferable to use a 2.0 times molar amount.
- imide oligomers having different molecular weights produced individually can be mixed and used.
- the heat curable solution composition of the present embodiment can be obtained by mixing the aromatic tetracarboxylic acid component, the aromatic diamine component and the terminal blocking agent by a known method.
- aromatic tetracarboxylic dianhydride, aromatic diamine and 4- (2-phenylethynyl) phthalic anhydride are substantially equal in the total amount of acid anhydride groups and the total amount of amino groups.
- solvent used in the above method examples include N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide, N, N-dimethylacetamide (DMAc), N, N-diethylacetamide, N-methylcaprolactam, ⁇ -Butyrolactone (GBL), cyclohexanone and the like. These solvents may be used alone or in combination of two or more. With respect to the selection of these solvents, a known technique of a polyimide precursor solution composition can be applied.
- the obtained solution can be used as it is or after being appropriately concentrated or diluted. Further, if necessary, this solution is poured into water or the like and isolated as a powder product, and the powder product is appropriately dissolved in a solvent and used as the thermosetting solution composition of this embodiment. it can.
- thermosetting solution composition of the present embodiment includes, for example, as a second method, aromatic tetracarboxylic dianhydride and 4- (2-phenylethynyl) phthalic anhydride, and lower aliphatic alcohol. It can also be prepared by adding to the containing solution, converting the resulting suspension to a partially lower aliphatic alkyl ester by heating and dissolving it, and then adding an aromatic diamine to the solution. The obtained solution can be used as it is or after being appropriately concentrated or diluted.
- Examples of the solution used in the above method include an organic solvent containing a lower aliphatic alcohol (a monovalent aliphatic alcohol having 1 to 6 carbon atoms) as a main component.
- the lower aliphatic alcohol is preferably methanol or ethanol.
- a mixture of lower aliphatic alcohols may be used, but the mixture preferably contains 50% by volume or more of methanol or ethanol, and particularly preferably contains 80% by volume or more of methanol or ethanol.
- a low-boiling solvent other than the lower aliphatic alcohol eg, ketone
- the amount of the low-boiling solvent other than the lower aliphatic alcohol in that case is 30% by volume or less. desirable.
- Methanol is particularly preferable as the lower aliphatic alcohol used for obtaining the partial lower aliphatic alkyl ester.
- methyl ester is used as the lower aliphatic alkyl ester, excellent shape maintainability is exhibited when a cured product is produced using the heat curable solution composition.
- thermosetting solution composition When it is desired to avoid environmental pollution caused by methanol generated when evaporating and removing a solvent from an uncured body using the above-mentioned heat curable solution composition and heating at a high temperature to obtain a subsequent cured body, After manufacturing a thermosetting solution composition using methanol, the solution composition is once dried to obtain a thermosetting powder composition, and this powder composition is dissolved in a solvent with low environmental impact such as ethanol. Then, a method of preparing a heat-curable solution composition again and preparing an uncured body using the composition can be used.
- the temperature at which the solvent is removed by evaporation in order to obtain a heat-curable powder composition is preferably 60 ° C. or lower.
- a small amount of solvent may remain in the heat curable powder composition, but the volatile component composed of the remaining solvent or alcohol generated when heated at a high temperature to obtain a cured product is in the range of 18 to 25%.
- the range of 20 to 22% is more preferable.
- the heat curable solution composition obtained as described above is a cured product obtained by heating in the presence or absence of a curing catalyst, either alone or as a composite material obtained by impregnating a fibrous reinforcing material. It can be.
- a film can be obtained by applying a heat-curable solution composition to a support and heat-curing at 260 to 500 ° C. for 5 to 200 minutes.
- the above thermosetting powder composition is filled in a mold, and a preform is formed by compression molding at 1 to 1000 kg / cm 2 at 10 to 260 ° C. for about 1 to 240 minutes.
- the molded body can be produced by heating at 260 to 500 ° C. for 10 minutes to 40 hours at normal pressure without applying pressure.
- a cured product (imide group-containing molded product) in which Tg cannot be confirmed at Tg of 340 ° C. or higher or 340 ° C. or lower can be obtained.
- a sheet-like matrix material of high-strength fibers is impregnated with the heat curable solution composition and, if necessary, a solvent.
- An uncured fiber reinforced composite material (prepreg) is prepared by evaporating and removing a part of the material by heating or the like.
- the prepreg has an appropriate volatile content for ensuring good handleability (drapability and tackiness) when producing a fiber-reinforced composite material by heating under pressure, and an obtained fiber-reinforced composite material.
- an appropriate adhesion amount of the component forming the resin is required.
- a high-strength fiber sheet-like matrix material is impregnated with a thermosetting solution composition containing a component that forms an appropriate amount of resin by a method such as a dipping method or a casting method, and then in a hot air oven or the like. It is preferable to evaporate and remove excess volatile components by heating and drying.
- a high-strength fiber sheet-like matrix material is impregnated with a predetermined amount of a thermosetting solution composition, and is heated and dried. Temperature range: 40 to 150 ° C., time range: 0.5 to 30 minutes
- a prepreg having a preferable resin content (Rc) of 30 to 50% by mass and a volatile content (Vc) of 10 to 30% by mass can be suitably prepared.
- high-strength fibers As the sheet-like matrix material made of high-strength fibers used for producing the prepreg, those made of known high-strength fibers used for producing fiber-reinforced composite materials can be suitably used.
- Preferred high-strength fibers are carbon fibers, aramid fibers, glass fibers, and ceramic fibers such as Tyranno fibers (titanium dioxide fibers).
- the obtained prepreg is preferably stored and transported in a state where each of both surfaces thereof is covered with a resin sheet such as polyethylene terephthalate (PET) or a covering sheet such as paper.
- a resin sheet such as polyethylene terephthalate (PET) or a covering sheet such as paper.
- PET polyethylene terephthalate
- the prepreg in such a covering state is Usually, it is stored and transported in a roll state.
- a known method may be applied. For example, after cutting a roll-shaped prepreg to a desired size and laminating a plurality of cut uncured fiber reinforced composite material pieces (from several to 100 or more), using a heating press or an autoclave, 140 After drying and imidization by heating at ⁇ 310 ° C. under normal pressure or reduced pressure for 5 to 270 minutes, at a temperature of 250 to 500 ° C. under normal pressure or a pressure of 0.1 to 20 MPa for 1 second to 240 minutes. By heating to a certain extent, a fiber reinforced composite material is obtained.
- a fiber reinforced composite material obtained by heat curing an uncured fiber reinforced composite material (prepreg) in which a fibrous reinforcing material is impregnated with the heat curable solution composition of the present embodiment is excellent in mechanical properties and the like. It is suitable for applications such as space industry equipment.
- each measured value is based on the following method.
- Examples 7 to 15 and Comparative Examples 6 to 8 A differential scanning calorimeter Q100 series manufactured by TA Instruments Japan Co., Ltd. with respect to a resin film having a thickness of about 0.12 mm obtained by the method described in the examples.
- the DSC curve was measured while raising the temperature at 20 ° C./min in a nitrogen atmosphere (20 ml / min).
- the temperature at the intersection of tangents at the inflection point of the DSC curve was defined as the glass transition temperature.
- Examples 16 and 17 and Comparative Example 9 For the CFRP plate obtained by the method described in the examples, the measurement mode is the three-point bending mode and the temperature increase rate is 10 ° C./min. Thus, the glass transition temperature was measured.
- Viscosity The viscosity was measured at 30 ° C. using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.).
- SBS Interlaminar shear strength Measured according to ASTM D2344. A universal testing machine (model number 5582) manufactured by Instron was used for the measurement.
- Vf carbon fiber content
- Vv porosity
- Carbon fiber content (Vf) and porosity (Vv) were measured by the sulfuric acid decomposition method according to ASTM D3171.
- each monomer component was shown by the following display.
- a-BPDA 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride
- s-BPDA 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride
- PPD 1,4-diaminobenzene (Paraphenylenediamine)
- MPD 1,3-diaminobenzene (metaphenylenediamine)
- PEPA 4- (phenylethynyl) phthalic anhydride
- TPE-R 1,3-bis (4-aminophenoxy) benzene
- ODA 4,4'-diaminodiphenyl ether
- 34-ODA 3,4'-diaminodiphenyl ether
- NMP N-methylpyrrolidone 2-Mz: 2-methylimidazole
- Example 1 A polyethylene lidded container was charged with 2.896 g (0.02678 mol) of PPD as a diamine component, 1.241 g (0.01148 mol) of MPD and 36.863 g of NMP as a solvent, and stirred to obtain a uniform solution. .
- 10.00 g (0.03399 mol) of a-BPDA as an acid component and 2.109 g (0.00850 mol) of PEPA were added while stirring to obtain a uniform solution (thermosetting solution composition).
- This homogeneous solution was cast on the surface of a glass plate and treated on a hot plate at 80 ° C. for 3 minutes. Further, the solution was cast on the hot plate at 80 ° C.
- Example 2 S-BPDA 4.285 (0.01456 mol), a-BPDA 9.999 g (0.03399 mol) and PEPA 3.014 g (0.01214 mol) as the acid component, and PPD 4.138 g (0.03826 mol) as the diamine component
- a thermosetting solution composition and a film were obtained using 1.773 g (0.01640 mol) of MPD and 47.585 g of NMP. The characteristics of the film are shown in Table 1.
- thermosetting solution composition and a film were obtained in the same manner as in Example 1 except that NMP83.273 g was used. However, the molded body collapsed during the heat treatment, and a resin film could not be produced. .
- thermosetting solution composition and a film were obtained in the same manner as in Comparative Example 1 except that 6.709 g (0.02295 mol) of TPE-R and 76.487 g of NMP were used.
- the properties of the film are shown in Table 2. The obtained film was inferior in both Tg and TOS.
- thermosetting solution composition and a film were obtained in the same manner as in Comparative Example 1 except that 3.445 g (0.0721 mol) of ODA and 53.658 g of NMP were used.
- the properties of the film are shown in Table 2. The obtained film was inferior in both Tg and TOS.
- Example 3 6.499 g (0.02209 mol) of s-BPDA as an acid component, 6.500 g (0.02209 mol) of a-BPDA and 2.741 g (0.01104 mol) of PEPA as a diamine component, 2.687 g (0.02485 mol) of PPD as a diamine component
- a thermosetting solution composition and a film were obtained using 2.686 g (0.02484 mol) of MPD and 43.305 g of NMP. The characteristics of the film are shown in Table 1.
- thermosetting solution composition Without using a-BPDA as the acid component, 12.001 g (0.04079 mol) of s-BPDA and 2.530 g (0.01019 mol) of PEPA and 2.481 g (0.02294 mol) of PPD and 2.482 g of MPD as the diamine component ( 0.02295 mol), and a thermosetting solution composition was obtained in the same manner as in Example 1 except that 39.972 g of NMP was used. However, the molded body collapsed during the heat treatment, and a film could be produced. There wasn't.
- Example 4 S-BPDA 8.998 g (0.03058 mol), a-BPDA 3.857 g (0.01311 mol) and PEPA 2.711 g (0.01092 mol) as the acid component and 1.063 g (0.00983 mol) PPD as the diamine component
- a thermosetting solution composition and a film were obtained using 4.253 g (0.03932 mol) of MPD and 42.821 g of NMP. The characteristics of the film are shown in Table 1.
- Example 5 9.000 g (0.03059 mol) of s-BPDA, 3.856 g (0.01311 mol) of a-BPDA and 2.711 g (0.01092 mol) of PEPA as the acid component, and 4.252 g (0.03932 mol) of PPD as the diamine component
- a thermosetting solution composition and a film were obtained using 1.064 g (0.00984 mol) of MPD and 42.825 g of NMP.
- the characteristics of the film are shown in Table 1.
- Example 6 9.000 g (0.03059 mol) of s-BPDA, 5.399 g (0.01835 mol) of a-BPDA and 3.037 g (0.01223 mol) of PEPA as an acid component, and 1.323 g (0.01223 mol) of PPD as a diamine component
- MPD 4.631 g (0.04282 mol) and NMP 47.965 g were used in the same manner as in Example 1 to obtain a thermosetting solution composition and film. The characteristics of the film are shown in Table 1.
- Example 7 A separable flask was charged with 47.10 g (0.1601 mol) of a-BPDA as an acid component, 9.93 g (0.0400 mol) of PEPA and 63.50 g of methanol as a solvent, and 2-Mz0. 1528 g was added and stirred under reflux conditions to dissolve uniformly. After cooling the solution to room temperature, 13.63 g (0.1260 mol) of PPD which is a diamine component and 5.84 g (0.0540 mol) of MPD were added and stirred to obtain a uniform thermosetting solution composition. This solution was placed in a container made of polyimide film and placed in an oven maintained at 80 ° C. The oven was heated to 260 ° C.
- thermosetting powder composition is sandwiched between polyimide films, pressed with a press machine heated to 290 ° C., then heated to 370 ° C. in about 20 minutes, heat-treated at 370 ° C. for 60 minutes, and the thickness is about 0 A 12 mm resin film was obtained.
- the properties of the film are shown in Table 3.
- Example 8 47.05 g (0.1599 mol) of a-BPDA as an acid component and 9.94 g (0.0400 mol) of PEPA, 63.50 g of methanol as a solvent, 0.1529 g of 2-Mz as a catalyst, and 9.73 g of PPD as a diamine (0 0.0900 mol) and 9.73 g (0.0900 mol) of MPD were used in the same manner as in Example 7 to obtain a thermosetting solution composition and a resin film. The properties of the film are shown in Table 3.
- Example 9 47.10 g (0.1601 mol) of a-BPDA as an acid component and 9.94 g (0.0400 mol) of PEPA, 63.50 g of methanol as a solvent, 0.1510 g of 2-Mz as a catalyst, and 3.91 g of PPD as a diamine (0 0.0362 mol) and MPD 15.60 g (0.1443 mol) were used in the same manner as in Example 7 to obtain a thermosetting solution composition and a resin film. The properties of the film are shown in Table 3.
- Example 10 As an acid component, 14.11 g (0.0480 mol) of s-BPDA, 32.96 g (0.1120 mol) of a-BPDA, 9.95 g (0.0400 mol) of PEPA, 63.50 g of methanol as a solvent, A thermosetting solution composition and a resin film were obtained in the same manner as in Example 7 except that 0.153 g of Mz was used and 13.63 g (0.1260 mol) of PPD and 5.84 g (0.0540 mol) of MPD were used as diamine components. It was. Table 4 shows the characteristics of the film.
- Example 11 14.10 g (0.0479 mol) of s-BPDA as an acid component, 32.94 g (0.1120 mol) of a-BPDA and 9.93 g (0.0400 mol) of PEPA, 63.14 g of methanol as a solvent, A thermosetting solution composition and a resin film were obtained in the same manner as in Example 7 except that 0.1528 g of Mz was used and 9.73 g (0.0900 mol) of PPD and 0.73 g (0.0400 mol) of MPD were used as diamines. . Table 4 shows the characteristics of the film.
- Example 12 14.13 g (0.0480 mol) of s-BPDA as an acid component, 32.96 g (0.1120 mol) of a-BPDA and 9.93 g (0.0400 mol) of PEPA, 63.50 g of methanol as a solvent, A thermosetting solution composition and a resin film were obtained in the same manner as in Example 7 except that 0.153 g of Mz was used and 3.89 g (0.0360 mol) of PPD and 15.57 g (0.1440 mol) of MPD were used as diamines. . Table 4 shows the characteristics of the film.
- Example 13 As an acid component, 28.26 g (0.0961 mol) of s-BPDA, 18.82 g (0.0640 mol) of a-BPDA and 9.93 g (0.0400 mol) of PEPA, 63.50 g of methanol as a solvent, A thermosetting solution composition and a resin film were obtained in the same manner as in Example 7 except that 0.163 g of Mz was used and 13.63 g (0.1260 mol) of PPD and 5.85 g (0.0541 mol) of MPD were used as diamines. . Table 4 shows the characteristics of the film.
- Example 14 As the acid component, 28.25 g (0.0960 mol) of s-BPDA, 18.82 g (0.0640 mol) of a-BPDA and 9.93 g (0.0400 mol) of PEPA, 63.50 g of methanol as the solvent, and 2- A thermosetting solution composition and a resin film were obtained in the same manner as in Example 7 except that 0.153 g of Mz was used and 9.73 g (0.0900 mol) of MPD and 9.73 g (0.0900 mol) of MPD were used as diamines. . Table 4 shows the characteristics of the film.
- Example 15 As an acid component, 28.25 g (0.0960 mol) of s-BPDA, 18.85 g (0.0641 mol) of a-BPDA, 9.93 g (0.04000 mol) of PEPA, 63.50 g of methanol as a solvent, and 2- A thermosetting solution composition and a resin film were obtained in the same manner as in Example 7 except that 0.190 g of Mz was used and 3.90 g (0.0361 mol) of PPD and 15.57 g (0.1440 mol) of MPD were used as diamines. . Table 4 shows the characteristics of the film.
- thermosetting solution composition and a resin film were obtained in the same manner as in Example 7 except that 13.729 g of PPD (13.63 g, 0.1260 mol) and TPE-R 15.79 g (0.0540 mol) were used as diamines. It was. Table 5 shows the characteristics of the film. The obtained film was inferior in both Tg and TOS.
- thermosetting solution composition having a solid content concentration of 40 to 60% by weight was prepared in the same manner as in Example 1 with the composition shown in Table 6.
- This heat curable solution composition was impregnated into a carbon fiber fabric (HTS 40 3K, weight per unit area: 200 g / m 2 ) manufactured by Toho Tenax Co., Ltd. and dried in an oven at 80 to 100 ° C. for 10 to 30 minutes to obtain a prepreg. .
- the drying conditions were adjusted so that the volatile content after drying was about 15% by weight.
- the volatile content was calculated from the weight loss after heating at 250 ° C. for 1 hour.
- the obtained prepreg was cut into 100 ⁇ 150 mm, stacked in 12 sheets, placed in an autoclave molding machine, heated at 370 ° C. for 1 hour under a pressure of 1.38 MPa, and a 2.72 mm thick carbon fiber reinforced plastic (CFRP ) Obtained a board.
- CFRP plate was found to be a non-defective product from which no voids were observed, based on an ultrasonic flaw detection test and cross-sectional observation using a stereomicroscope. Table 6 shows the properties of the obtained CFRP plate.
- Example 17 A CFRP plate was obtained in the same manner as in Example 16 except that a thermosetting solution composition was prepared with the composition shown in Table 6. Table 6 shows the properties of the obtained CFRP plate.
- Example 9 A CFRP plate was obtained in the same manner as in Example 16 except that a thermosetting solution composition was prepared with the composition shown in Table 6. Table 6 shows the properties of the obtained CFRP plate. The obtained CFRP plate was inferior in both Tg and TOS.
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Abstract
Description
本発明の目的は、耐酸化性に優れ、ガラス転移温度(Tg)の高い硬化物を与える加熱硬化性溶液組成物を提供することにある。
本発明の他の目的は、硬化時に反応不良が認められず、繊維強化複合材料の製造に用いるのに適した加熱硬化性溶液組成物を提供することにある。
本発明のさらに他の目的は、上記加熱硬化性溶液組成物を用いた硬化物、プリプレグ及び繊維強化複合材料を提供することにある。
本発明の第1の態様によると、(A)2,3,3’,4’-ビフェニルテトラカルボン酸化合物を20モル%以上含む芳香族テトラカルボン酸成分、(B)アミノ基に由来する二つの炭素-窒素結合軸が同一直線上に位置し、分子内に酸素原子を有しない芳香族ジアミンと、アミノ基に由来する二つの炭素-窒素結合軸が同一直線上に位置せず、分子内に酸素原子を有しない芳香族ジアミンとを含む、分子内に酸素原子を有しない芳香族ジアミン成分、及び(C)フェニルエチニル基を有する末端封止剤を混合して得られたことを特徴とする加熱硬化性溶液組成物が提供される。
また、前記(A)成分として、さらに、3,3’,4,4’-ビフェニルテトラカルボン酸化合物を含むことができる。
また、前記(C)のフェニルエチニル基を有する末端封止剤を、4-(2-フェニルエチニル)フタル酸化合物とすることができる。
本実施形態の加熱硬化性溶液組成物は、加熱により末端に付加反応性官能基を有するイミドオリゴマーおよびその硬化物を与える溶液組成物である。そのイミドオリゴマーは、2,3,3’,4’-ビフェニルテトラカルボン酸化合物を20モル%以上含む芳香族テトラカルボン酸成分、および、アミノ基に由来する二つの炭素-窒素結合軸が同一直線上に位置し、分子内に酸素原子を有しない芳香族ジアミンと、アミノ基に由来する二つの炭素-窒素結合軸が同一直線上に位置せず、分子内に酸素原子を有しない芳香族ジアミンとを含む、分子内に酸素原子を有しない芳香族ジアミン成分で構成され、末端に付加反応性官能基であるフェニルエチニル基を有するものである。
同様に、3,3’,4,4’-ビフェニルテトラカルボン酸化合物には、3,3’,4,4’-ビフェニルテトラカルボン酸、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(s-BPDA)、3,3’,4,4’-ビフェニルテトラカルボン酸のエステルまたは塩が含まれ、2,2’,3,3’-ビフェニルテトラカルボン酸化合物には、2,2’,3,3’-ビフェニルテトラカルボン酸、2,2’,3,3’-ビフェニルテトラカルボン酸二無水物、2,2’,3,3’-ビフェニルテトラカルボン酸のエステルまたは塩が含まれる。
アミノ基に由来する二つの炭素-窒素結合軸が同一直線上に位置し、分子内に酸素原子を有しない芳香族ジアミンとして、1,4-ジアミノベンゼン(PPD)、2,5-ジアミノトルエン、2,2’-ビス(トリフルオロメチル)ベンジジン、2,2’-ジメチルベンジジン、3,3’-ジメチルベンジジン、3,3’,5,5’-テトラメチルベンジジン、4,4-ジアミノオクタフルオロビフェニルなどを挙げることができる。これらは、単独で用いても良いし、複数を混合して用いても良い。
また、アミノ基に由来する二つの炭素-窒素結合軸が同一直線上に位置せず、分子内に酸素原子を有しない芳香族ジアミンとして、1,3-ジアミノベンゼン(MPD)、2,4-ジアミノトルエン、2,6-ジアミノトルエン、3,3’-ジアミノジフェニルメタン、4,4’-ジアミノジフェニルメタン、2,2-ビス(3-アミノフェニル)プロパン、2,2-ビス(4-アミノフェニル)プロパン、9,9’-ビス(4-アミノフェニル)フルオレンなどを挙げることができる。これらは、単独で用いても良いし、複数を混合して用いても良い。
実施例記載の方法により得られた厚み約0.05mm(実施例1~6および比較例1~5)または約0.12mm(実施例7~15および比較例6~8)の樹脂フィルムについて、270℃で4時間乾燥後の重量を基準とし、イナートガスオーブンINH-21CD-S(光洋サーモシステム株式会社)を用いて350℃で100時間流動空気に露呈した後の重量減少を、基準の重量に対する重量パーセントで表した。測定は3つのサンプルについて同時に行い、これらの平均値をTOS値とした。
実施例16、17および比較例9のCFRP板については、274℃、3000時間の条件とした以外は、上記と同様にしてTOS値を算出した。
実施例1~6および比較例1~5:実施例記載の方法により得られた厚み約0.05mmの樹脂フィルムについて、ティー・エイ・インスツルメント・ジャパン社製の固体粘弾性アナライザーRSAIIIを用い、窒素中、周波数10Hz、3℃/分で昇温しながら引張モードで粘弾性を測定した。温度に対して貯蔵弾性係数をプロットしたグラフの変曲点について接線を引き、その交点の温度をガラス転移温度とした。また、tanδのピークトップの温度から求めたTgは、Tg(tanδ)とした。
実施例7~15および比較例6~8:実施例記載の方法により得られた厚み約0.12mmの樹脂フィルムについて、ティー・エイ・インスツルメント・ジャパン社製の示差走査熱量測定装置Q100シリーズを用い、窒素雰囲気下(20ml/min)、20℃/minで昇温しながらDSC曲線を測定した。DSC曲線の変曲点における、接線の交点の温度をガラス転移温度とした。
実施例16、17および比較例9:実施例記載の方法により得られたCFRP板について、測定モードが3点曲げモードであり昇温速度が10℃/分であること以外は実施例1と同様にしてガラス転移温度を測定した。
E型粘時計(東京計器株式会社製)を用いて30℃で測定した。
(4)層間せん断強度(SBS)
ASTM D2344に従い測定した。測定にはインストロン社製の万能試験機(型番5582)を用いた。
(5)炭素繊維含有率(Vf)及び空隙率(Vv)測定
ASTM D3171に従い硫酸分解法により、炭素繊維含有率(Vf)及び空隙率(Vv)を測定した。
a-BPDA:2,3,3’,4’-ビフェニルテトラカルボン酸二無水物
s-BPDA:3,3’,4,4’-ビフェニルテトラカルボン酸二無水物
PPD:1,4-ジアミノベンゼン(パラフェニレンジアミン)
MPD:1,3-ジアミノベンゼン(メタフェニレンジアミン)
PEPA:4-(フェニルエチニル)無水フタル酸
TPE-R:1,3-ビス(4-アミノフェノキシ)ベンゼン
ODA:4,4’-ジアミノジフェニルエーテル
3,4-ODA:3,4’-ジアミノジフェニルエーテル
NMP:N―メチルピロリドン
2-Mz:2-メチルイミダゾール
ポリエチレン製の蓋付き容器に、ジアミン成分であるPPD2.896g(0.02678モル)とMPD1.241g(0.01148モル)そして溶媒であるNMP36.863gを投入し、撹拌して均一溶液を得た。次いで、撹拌しながら酸成分であるa-BPDA10.000g(0.03399モル)とPEPA2.109g(0.00850モル)を投入し、均一溶液(加熱硬化性溶液組成物)を得た。この均一溶液をガラス板の表面に流延し、ホットプレート上にて80℃で3分処理した。その上に更に溶液を流延してホットプレート上にて80℃で20分、オーブンに入れて150℃で10分加熱処理した。その後、電気炉にて200℃から370℃に約28分で昇温し、370℃で60分加熱処理して、厚みが約0.05mmの樹脂フィルムを得た。フィルムの特性を表1に示す。
酸成分としてs-BPDA4.285(0.01456モル)とa-BPDA9.999g(0.03399モル)とPEPA3.014g(0.01214モル)を、ジアミン成分としてPPD4.138g(0.03826モル)とMPD1.773g(0.01640モル)を、そしてNMP47.585gを用いて、実施例1と同様にして加熱硬化性溶液組成物およびフィルムを得た。フィルムの特性を表1に示した。
酸成分としてs-BPDAを用いず、a-BPDA25.000g(0.08497モル)とPEPA5.275g(0.02125モル)を、ジアミン成分としてMPDを用いず、PPD10.338g(0.09560モル)を、そしてNMP83.273gを用いた以外は実施例1と同様にして加熱硬化性溶液組成物およびフィルムを得たが、熱処理中に成形体が崩壊し、樹脂フィルムを作製することができなかった。
酸成分としてs-BPDAを用いずa-BPDA19.999g(0.06797モル)とPEPA4.221g(0.01700モル)を、ジアミン成分としてMPDを用いず、PPD5.790g(0.05354モル)とTPE-R6.709g(0.02295モル)を、そしてNMP76.487gを用いた以外は比較例1と同様にして加熱硬化性溶液組成物およびフィルムを得た。フィルムの特性を表2に示した。得られたフィルムは、Tg、TOSともに劣っていた。
酸成分としてs-BPDAを用いず、a-BPDA15.000g(0.05098モル)とPEPA3.163g(0.01274モル)を、ジアミン成分としてMPDを用いず、PPD4.341g(0.04014g)とODA3.445g(0.01721モル)を、そしてNMP53.658gを用いた以外は比較例1と同様にして加熱硬化性溶液組成物およびフィルムを得た。フィルムの特性を表2に示した。得られたフィルムは、Tg、TOSともに劣っていた。
酸成分としてs-BPDA6.499g(0.02209モル)とa-BPDA6.500g(0.02209モル)とPEPA2.741g(0.01104モル)を、ジアミン成分としてPPD2.687g(0.02485モル)とMPD2.686g(0.02484モル)を、そしてNMP43.305gを用いて、実施例1と同様にして加熱硬化性溶液組成物およびフィルムを得た。フィルムの特性を表1に示した。
酸成分としてs-BPDA10.000g(0.03399モル)とa-BPDA10.001g(0.03399モル)とPEPA4.219g(0.01700モル)を、ジアミン成分としてPPDを用いず、MPD8.272g(0.07649モル)を、そしてNMP66.621gを用いた以外は実施例2と同様にして加熱硬化性溶液組成物およびフィルムを得た。フィルムの特性を表2に示した。得られたフィルムは、Tgが劣っていた。
酸成分としてa-BPDAを用いず、s-BPDA12.001g(0.04079モル)とPEPA2.530g(0.01019モル)を、ジアミン成分としてPPD2.481g(0.02294モル)とMPD2.482g(0.02295モル)を、そしてNMP39.972gを用いた以外は実施例1と同様にして加熱硬化性溶液組成物を得たが、熱処理中に成形体が崩壊し、フィルムを作製することができなかった。
酸成分としてs-BPDA8.998g(0.03058モル)とa-BPDA3.857g(0.01311モル)とPEPA2.711g(0.01092モル)を、ジアミン成分としてPPD1.063g(0.00983モル)とMPD4.253g(0.03932モル)を、そしてNMP42.821gを用いて、実施例1と同様にして加熱硬化性溶液組成物およびフィルムを得た。フィルムの特性を表1に示した。
酸成分としてs-BPDA9.000g(0.03059モル)とa-BPDA3.856g(0.01311モル)とPEPA2.711g(0.01092モル)を、ジアミン成分としてPPD4.252g(0.03932モル)とMPD1.064g(0.00984モル)を、そしてNMP42.825gを用いて、実施例1と同様にして加熱硬化性溶液組成物およびフィルムを得た。フィルムの特性を表1に示した。
酸成分としてs-BPDA9.000g(0.03059モル)とa-BPDA5.399g(0.01835モル)とPEPA3.037g(0.01223モル)を、ジアミン成分としてPPD1.323g(0.01223モル)とMPD4.631g(0.04282モル)を、そしてNMP47.965gを用いて、実施例1と同様にして加熱硬化性溶液組成物およびフィルムを得た。フィルムの特性を表1に示した。
セパラブルフラスコに、酸成分であるa-BPDA47.10g(0.1601モル)とPEPA9.93g(0.0400モル)、そして溶媒であるメタノール63.50gを投入し、触媒である2-Mz0.1528gを加えて還流条件下で撹拌し均一に溶解させた。溶液を室温に冷却後、ジアミン成分であるPPD13.63g(0.1260モル)とMPD5.84g(0.0540モル)を入れて攪拌し、均一な加熱硬化性溶液組成物を得た。この溶液をポリイミドフィルムで作った容器に入れて、80℃に保ったオーブンに入れた。オーブンを2℃/分で260度まで昇温して3時間保持し、得られた固形分を粉砕して加熱硬化性粉末組成物を得た。この加熱硬化性粉末組成物をポリイミドフィルムで挟み、290℃に加熱したプレス機でプレスし、その後370℃まで約20分で昇温し、370℃で60分加熱処理して、厚みが約0.12mmの樹脂フィルムを得た。フィルムの特性を表3に示す。
酸成分としてa-BPDA47.05g(0.1599モル)とPEPA9.94g(0.0400モル)を、溶媒としてメタノール63.50gを、触媒として2-Mz0.1529gを、ジアミンとしてPPD9.73g(0.0900モル)とMPD9.73g(0.0900モル)を用いた以外は実施例7と同様にして加熱硬化性溶液組成物および樹脂フィルムを得た。フィルムの特性を表3に示す。
酸成分としてa-BPDA47.10g(0.1601モル)とPEPA9.94g(0.0400モル)を、溶媒としてメタノール63.50gを、触媒として2-Mz0.1510gを、ジアミンとしてPPD3.91g(0.0362モル)とMPD15.60g(0.1443モル)を用いた以外は実施例7と同様にして加熱硬化性溶液組成物および樹脂フィルムを得た。フィルムの特性を表3に示す。
酸成分としてs-BPDA14.11g(0.0480モル)とa-BPDA32.96g(0.1120モル)とPEPA9.95g(0.0400モル)を、溶媒としてメタノール63.50gを、触媒として2-Mz0.1530gを、ジアミン成分としてPPD13.63g(0.1260モル)とMPD5.84g(0.0540モル)を用いた以外は実施例7と同様にして加熱硬化性溶液組成物および樹脂フィルムを得た。フィルムの特性を表4に示す。
酸成分としてs-BPDA14.10g(0.0479モル)とa-BPDA32.94g(0.1120モル)とPEPA9.93g(0.0400モル)を、溶媒としてメタノール63.14gを、触媒として2-Mz0.1528gを、ジアミンとしてPPD9.73g(0.0900モル)とMPD0.73g(0.0400モル)を用いた以外は実施例7と同様にして加熱硬化性溶液組成物および樹脂フィルムを得た。フィルムの特性を表4に示す。
酸成分としてs-BPDA14.13g(0.0480モル)とa-BPDA32.96g(0.1120モル)とPEPA9.93g(0.0400モル)を、溶媒としてメタノール63.50gを、触媒として2-Mz0.1530gを、ジアミンとしてPPD3.89g(0.0360モル)とMPD15.57g(0.1440モル)を用いた以外は実施例7と同様にして加熱硬化性溶液組成物および樹脂フィルムを得た。フィルムの特性を表4に示す。
酸成分としてs-BPDA28.26g(0.0961モル)とa-BPDA18.82g(0.0640モル)とPEPA9.93g(0.0400モル)を、溶媒としてメタノール63.50gを、触媒として2-Mz0.1529gを、ジアミンとしてPPD13.63g(0.1260モル)とMPD5.85g(0.0541モル)を用いた以外は実施例7と同様にして加熱硬化性溶液組成物および樹脂フィルムを得た。フィルムの特性を表4に示す。
酸成分としてs-BPDA28.25g(0.0960モル)とa-BPDA18.82g(0.0640モル)とPEPA9.93g(0.0400モル)を、溶媒としてメタノール63.50gを、触媒として2-Mz0.1530gを、ジアミンとしてPPD9.73g(0.0900モル)とMPD9.73g(0.0900モル)を用いた以外は実施例7と同様にして加熱硬化性溶液組成物および樹脂フィルムを得た。フィルムの特性を表4に示す。
酸成分としてs-BPDA28.25g(0.0960モル)とa-BPDA18.85g(0.0641モル)とPEPA9.93g(0.04000モル)を、溶媒としてメタノール63.50gを、触媒として2-Mz0.1530gを、ジアミンとしてPPD3.90g(0.0361モル)とMPD15.57g(0.1440モル)を用いた以外は実施例7と同様にして加熱硬化性溶液組成物および樹脂フィルムを得た。フィルムの特性を表4に示す。
酸成分としてa-BPDA18.83g(0.0640モル)とPEPA9.93g(0.0400モル)を、溶媒としてメタノール73.44gを、触媒として2-Mz0.1729gを、ジアミンとしてPPD13.63g(0.1260モル)とTPE-R15.79g(0.0540モル)を用いた以外は実施例7と同様にして加熱硬化性溶液組成物および樹脂フィルムを得た。フィルムの特性を表5に示す。得られたフィルムは、TOSが劣っていた。
酸成分としてa-BPDA18.83g(0.0640モル)とPEPA9.93g(0.0400モル)を、溶媒としてメタノール68.47gを、触媒として2-Mz0.1629gを、ジアミンとしてPPD13.63g(0.1260モル)と3,4‘-ODA10.80g(0.0539モル)を用いた以外は実施例7と同様にして加熱硬化性溶液組成物および樹脂フィルムを得た。フィルムの特性を表5に示す。得られたフィルムは、TOSが劣っていた。
酸成分としてs-BPDA28.25g(0.0960モル)a-BPDA18.82g(0.0640モル)とPEPA9.92g(0.0400モル)を、溶媒としてメタノール73.44gを、触媒として2-Mz0.1729gを、ジアミンとしてPPD13.63g(0.1260モル)とTPE-R15.79g(0.0540モル)を用いた以外は実施例7と同様にして加熱硬化性溶液組成物および樹脂フィルムを得た。フィルムの特性を表5に示す。得られたフィルムは、Tg、TOSともに劣っていた。
表6に示した組成で実施例1と同様な方法で固形分濃度40~60重量%の加熱硬化性溶液組成物を調製した。この加熱硬化性溶液組成物を、東邦テナックス社製の炭素繊維織物(HTS40 3K、目付重量200g/m2)に含浸させ、80~100℃のオーブンで10~30分乾燥してプリプレグを得た。乾燥条件は乾燥後の揮発分が約15重量%となるように調整した。なお、揮発分は、250℃、1時間加熱後の重量減少から算出した。得られたプリプレグを100×150mmにカットして12枚重ね、オートクレーブ成形機に入れて1.38MPaの加圧下、370℃で1時間加熱処理して厚さ2.72mmの炭素繊維強化プラスチック(CFRP)板を得た。得られたCFRP板は、超音波探傷試験および実体顕微鏡による断面観察から、ボイドが見られない良品であることがわかった。得られたCFRP板の特性を表6に示す。
表6に示した組成で加熱硬化性溶液組成物を調製したこと以外は実施例16と同様にしてCFRP板を得た。得られたCFRP板の特性を表6に示す。
表6に示した組成で加熱硬化性溶液組成物を調製したこと以外は実施例16と同様にしてCFRP板を得た。得られたCFRP板の特性を表6に示す。得られたCFRP板は、Tg、TOSともに劣っていた。
Claims (7)
- (A)2,3,3’,4’-ビフェニルテトラカルボン酸化合物を20モル%以上含む芳香族テトラカルボン酸成分、(B)アミノ基に由来する二つの炭素-窒素結合軸が同一直線上に位置し、分子内に酸素原子を有しない芳香族ジアミンと、アミノ基に由来する二つの炭素-窒素結合軸が同一直線上に位置せず、分子内に酸素原子を有しない芳香族ジアミンとを含む、分子内に酸素原子を有しない芳香族ジアミン成分、及び(C)フェニルエチニル基を有する末端封止剤を混合して得られたことを特徴とする加熱硬化性溶液組成物。
- 前記(B)のアミノ基に由来する二つの炭素-窒素結合軸が同一直線上に位置し、分子内に酸素原子を有しない芳香族ジアミンが、1,4-ジアミノベンゼンであり、アミノ基に由来する二つの炭素-窒素結合軸が同一直線上に位置せず、分子内に酸素原子を有しない芳香族ジアミンが、1,3-ジアミノベンゼンであることを特徴とする請求項1記載の加熱硬化性溶液組成物。
- 前記(A)成分として、さらに、3,3’,4,4’-ビフェニルテトラカルボン酸化合物を含むことを特徴とする請求項1または2記載の加熱硬化性溶液組成物。
- 前記(C)のフェニルエチニル基を有する末端封止剤が、4-(2-フェニルエチニル)フタル酸化合物であることを特徴とする請求項1~3いずれか記載の加熱硬化性溶液組成物。
- 請求項1~4いずれか記載の加熱硬化性溶液組成物を加熱硬化して得られたことを特徴とする硬化物。
- 請求項1~4いずれか記載の加熱硬化性溶液組成物を繊維状補強材に含浸させたことを特徴とするプリプレグ。
- 請求項6記載のプリプレグを加熱硬化して得られたことを特徴とする繊維強化複合材料。
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CN105625041A (zh) * | 2015-12-25 | 2016-06-01 | 广东生益科技股份有限公司 | 一种聚酰亚胺定型布及其制作方法 |
US10047246B2 (en) | 2014-05-12 | 2018-08-14 | Kaneka Corporation | Varnish including 2-phenyl-4,4′-diaminodiphenyl ether, imide resin composition having excellent moldability, cured resin molded article having excellent breaking elongation, prepreg thereof, imide prepreg thereof, and fiber-reinforced material thereof having high heat resistance and excellent mechanical strength |
JP2020117690A (ja) * | 2019-01-18 | 2020-08-06 | 株式会社カネカ | イミドオリゴマー、ワニス、それらの硬化物、並びにそれらを用いたプリプレグ及び繊維強化複合材料 |
WO2021199898A1 (ja) | 2020-03-30 | 2021-10-07 | 株式会社カネカ | 特定の組成を有するポリアミド酸、ワニス、硬化物、複合材料 |
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US10047246B2 (en) | 2014-05-12 | 2018-08-14 | Kaneka Corporation | Varnish including 2-phenyl-4,4′-diaminodiphenyl ether, imide resin composition having excellent moldability, cured resin molded article having excellent breaking elongation, prepreg thereof, imide prepreg thereof, and fiber-reinforced material thereof having high heat resistance and excellent mechanical strength |
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WO2021199898A1 (ja) | 2020-03-30 | 2021-10-07 | 株式会社カネカ | 特定の組成を有するポリアミド酸、ワニス、硬化物、複合材料 |
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