WO2023219007A1 - Composition de résine thermodurcissable, article moulé, matériau de moulage pour matériau composite renforcé par des fibres, et matériau composite renforcé par des fibres - Google Patents

Composition de résine thermodurcissable, article moulé, matériau de moulage pour matériau composite renforcé par des fibres, et matériau composite renforcé par des fibres Download PDF

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WO2023219007A1
WO2023219007A1 PCT/JP2023/016826 JP2023016826W WO2023219007A1 WO 2023219007 A1 WO2023219007 A1 WO 2023219007A1 JP 2023016826 W JP2023016826 W JP 2023016826W WO 2023219007 A1 WO2023219007 A1 WO 2023219007A1
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resin composition
thermosetting resin
component
registered trademark
composition according
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Japanese (ja)
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真琴 鈴木
大典 小西
紘也 土田
啓之 平野
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東レ株式会社
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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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/58—Epoxy resins
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43—Compounds containing sulfur bound to nitrogen
    • C08K5/435—Sulfonamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • the present invention relates to a thermosetting resin composition preferably used for aerospace components and general industrial applications, and molded articles using the same, molding materials for fiber-reinforced composite materials, and fiber-reinforced composite materials.
  • thermosetting resins made from isocyanate compounds have excellent heat resistance, fracture toughness, and adhesive properties, and are used in various fields such as paints, adhesives, foams, and elastomer materials.
  • thermosetting resins composed of isocyanate compounds and epoxy resins produce rigid oxazolidone rings through thermosetting, and in addition to the above properties, they also have excellent moist heat resistance, so they are expected to be applied to structural material applications. ing.
  • isocyanate compounds have the disadvantage of high reactivity and short pot life, and are therefore not suitable for use in structural material applications such as fiber-reinforced composite materials, especially injection molding methods such as resin transfer molding (RTM method). It was difficult to apply it to
  • Patent Document 1 discloses a method for improving the pot life at room temperature of a thermosetting resin composition by using an imidazolium catalyst as a catalyst for a resin composition consisting of an epoxy resin and a polyisocyanate. There is.
  • Patent Document 2 describes a technique of adding a carboxamide compound to a urethane prepolymer and an isocyanate to obtain a urethane polyisocyanate resin composition that achieves both curing speed and pot life.
  • Patent Document 3 discloses a method of heating and reacting an epoxy resin and a polyisocyanate in the presence of an alkali halide catalyst to obtain a polymer having a polyoxazolidinone structure with excellent heat resistance.
  • thermosetting resin composition described in Patent Document 1 can be handled relatively stably at room temperature, but the viscosity stability during high temperature injection was insufficient. Further, although the heat resistance of the cured product obtained from the thermosetting resin composition is excellent, there is no mention of the elastic modulus under wet heat and the fracture toughness value.
  • thermosetting resin composition described in Patent Document 2 exhibits a long pot life, but the deformability and fracture toughness of the cured product were insufficient.
  • An object of the present invention is to provide a thermosetting resin composition, a molded article, and a fiber-reinforced composite material using the same, which improve the drawbacks of the prior art.
  • thermosetting resin composition having the following structure, and completed the present invention.
  • the present invention and its preferred embodiments consist of the following configurations.
  • [1] A thermosetting resin composition containing the following components [A], [B], [C] and [D].
  • R 1 represents a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl or aryl ring.
  • R 2 represents hydrogen or a substituted or unsubstituted cycloalkyl or aryl ring. Represents a substituted linear or branched alkyl group having 1 to 10 carbon atoms.
  • R 1 in formula (I) is a tolyl group, a phenyl group, or a chlorophenyl group.
  • the value (Mh/Me) obtained by dividing the number of moles of isocyanate groups (Mh) contained in component [B] by the total number of moles of epoxy groups (Me) contained in component [A] is 0.7 to 2.0, the thermosetting resin composition according to any one of [1] to [3].
  • Component [C] The thermosetting resin composition according to any one of [1] to [4], wherein the catalyst is a quaternary onium salt.
  • Component [C] The thermosetting resin composition according to [6], containing component [E].
  • E] A compound having a structure represented by formula (II) in its molecule.
  • n represents an integer of 1 to 6
  • m represents an integer of 4 to 1,000.
  • R 1 ' and R 2 ' are independently a hydrogen atom, an alkyl group, a hydroxyl group, or an aryl group.
  • R 1 and R 2 independently represent a hydrogen atom, an alkyl group, a hydroxyl group, or an aryl group.
  • X represents O, NH, S, or COO.
  • COO represents OCO.
  • Component [A] The thermosetting resin composition according to any one of [1] to [8], which contains an aliphatic epoxy resin as the epoxy resin.
  • Component [A] The thermosetting resin composition according to [9], which contains 10% by mass or more and 80% by mass or less of an aliphatic epoxy resin in 100% by mass of the epoxy resin.
  • Component [F] The thermosetting resin composition according to any one of [1] to [10], which contains a toughening agent.
  • a molding material for a fiber-reinforced composite material comprising the thermosetting resin composition according to any one of [1] to [12] and reinforcing fibers.
  • a fiber-reinforced composite material comprising a molded article obtained by heat-curing the thermosetting resin composition according to [12] and reinforcing fibers.
  • a fiber-reinforced composite material obtained by heating and curing the molding material for fiber-reinforced composite material according to [13].
  • thermosetting resin composition that has excellent fracture toughness and heat resistance of a cured resin product, as well as excellent elastic modulus in a moist heat environment.
  • thermosetting resin composition of the present invention can control the flow time and curing time of the resin in the injection process, and can provide the above performance, so it can be used for fiber reinforced composite materials by injection molding. It can be suitably used as a thermosetting resin composition suitable for manufacturing.
  • thermosetting resin composition of the present invention includes [A] an epoxy resin, [B] an isocyanate compound, [C] a catalyst, and [D] a sulfonamide compound represented by formula (I) as essential components. First, these components will be explained.
  • Component [A] in the present invention is an epoxy resin.
  • Such epoxy resin is not particularly limited as long as it is a compound having an epoxy group in its molecule. Examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, amine type epoxy resin, aliphatic epoxy resin, and the like.
  • the epoxy resins may be used alone or in combination of multiple types.
  • Examples of commercially available bisphenol A epoxy resins include “jER (registered trademark)” 825, “jER (registered trademark)” 828 (manufactured by Mitsubishi Chemical Corporation), and “Epotote (registered trademark)” YD-128. , “Epotote (registered trademark)” YD-8125, (all manufactured by Nippon Steel Chemical & Materials Co., Ltd.), “DER (registered trademark)” 331, “DER (registered trademark)” 332 (all manufactured by Dow Chemical Co., Ltd.) ) etc. can be used.
  • bisphenol F-type epoxy resins include, for example, "jER (registered trademark)” 806, “jER (registered trademark)” 807, “jER (registered trademark)” 4004P (manufactured by Mitsubishi Chemical Corporation), “EPICLON (registered trademark)” 830 (manufactured by DIC Corporation), “Epototh (registered trademark)” YD-170, “Epototh (registered trademark)” YDF-8170C, (manufactured by Nippon Steel Chemical & Materials Co., Ltd.) ) etc. can be used.
  • Examples of the amine-type epoxy resin used in the present invention include tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, diglycidylaniline, and the like. Specific examples of such epoxy resins include the following.
  • Examples of commercially available tetraglycidyldiaminodiphenylmethane include "Sumi Epoxy (registered trademark)” ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), YH434L (manufactured by Nippon Steel Chemical & Materials Co., Ltd.), and “jER (registered trademark)” 604 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.). Mitsubishi Chemical Corporation), “Araldite (registered trademark)” MY720, “Araldite (registered trademark)” MY721 (manufactured by Huntsman Advanced Materials), etc. can be used.
  • Examples of commercially available triglycidylaminophenols include "Sumiepoxy (registered trademark)” ELM100, “Sumiepoxy (registered trademark)” ELM120 (manufactured by Sumitomo Chemical Co., Ltd.), “Araldite (registered trademark)” MY0500, and “Araldite”. (registered trademark)” MY0510, “Araldite (registered trademark)” MY0600 (manufactured by Huntsman Advanced Materials), “jER (registered trademark)” 630 (manufactured by Mitsubishi Chemical Corporation), etc. can.
  • GAN N,N-diglycidylaniline
  • GOT N,N-diglycidyl-o-toluidine
  • TOREP registered trademark
  • )''A-204E diglycidyl-p-phenoxyaniline
  • Examples of the aliphatic epoxy resin used in the present invention include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,6-hexanediol diglycidyl ether.
  • Examples include glycidyl ether, hydrogenated bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and the like.
  • Examples of commercially available aliphatic epoxy resins include "Denacol (registered trademark)” EX-810, “Denacol (registered trademark)” EX-841, “Denacol (registered trademark)” EX-211, and “Denacol (registered trademark)”.
  • thermosetting resin composition of the present invention preferably contains at least one type of aliphatic epoxy resin as component [A].
  • the thermosetting resin composition of the present invention can achieve both high levels of heat resistance and fracture toughness, which are usually a trade-off. This effect of improving heat resistance and fracture toughness is not seen when other epoxy resin curing agents such as amine compounds or acid anhydride compounds are used, but when component [B]: isocyanate compound is used as a curing agent. This is a specific effect that occurs only in
  • the thermosetting resin composition of the present invention preferably contains an aliphatic epoxy resin in 10% by mass or more and 80% by mass or less, and preferably 30% by mass or more and 70% by mass or less in 100% by mass of component [A]. More preferably, the content is 30% by mass or more and 50% by mass or less. When the content of the aliphatic epoxy resin is within this range, the balance between heat resistance and fracture toughness is better, so the thermosetting resin composition of the present invention is more suitable as a matrix resin for fiber-reinforced composite materials. It can be suitably used.
  • Component [B] in the present invention is an isocyanate compound.
  • Such an isocyanate compound is not particularly limited as long as it has an isocyanate group in its molecule.
  • the isocyanate group reacts with the epoxy group of component [A] by heat curing to form a rigid oxazolidone ring structure, whereby the molded product exhibits excellent moist heat resistance and toughness.
  • isocyanate compounds include aromatic isocyanates, aliphatic isocyanates, alicyclic isocyanates, and the like.
  • aromatic isocyanates containing aromatics in their molecular skeletons are preferably used because they exhibit excellent curing reactivity and excellent heat resistance.
  • Isocyanate compounds preferably used in the present invention include, for example, aliphatic isocyanates such as hexamethylene diisocyanate and 1,2,3,4-tetraisocyanate butane, p-phenylene diisocyanate, tolylene diisocyanate, and diphenyl-4,4-diisocyanate.
  • aromatic isocyanates such as benzene-1,2,4-triisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate (MDI), diphenylpropane diisocyanate, tetramethylene xylene diisocyanate, polymethylene polyphenyl polyisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, lysine Examples include alicyclic isocyanates such as diisocyanate, methylene bis(4-cyclohexyl isocyanate), and isopropylidene dicyclohexyl diisocyanate. Note that these isocyanate compounds and the like may be used alone or in combination of two or more.
  • aliphatic isocyanates for example, HDI (manufactured by Tosoh Corporation), “Duranate (registered trademark)” D101, “Duranate (registered trademark)” D201 (all manufactured by Asahi Kasei Corporation), etc. can be used. I can do it.
  • aromatic isocyanates examples include “Lupranate (registered trademark)” MS, “Lupranate (registered trademark)” MI, “Lupranate (registered trademark)” M20S, “Lupranate (registered trademark)” M11S, and “Lupranate (registered trademark)”.
  • Examples of commercially available alicyclic isocyanates include "Takenate (registered trademark)” 600 (manufactured by Mitsui Chemicals, Inc.) and “Fortimo (registered trademark)” 1,4-H6XDI (manufactured by Mitsui Chemicals, Inc.). Can be mentioned.
  • the thermosetting resin composition of the present invention has a value (Mh) obtained by dividing the number of moles of isocyanate groups (Mh) contained in component [B] by the total number of moles of epoxy groups (Me) contained in component [A].
  • /Me) is preferably in the range of 0.7 to 2.0, more preferably in the range of 1.0 to 1.5.
  • Me (mass of epoxy resin A/epoxy equivalent of epoxy resin A)+(mass of epoxy resin B/epoxy equivalent of epoxy resin B)+...+(mass of epoxy resin W/epoxy equivalent of epoxy resin W) ).
  • the glass transition temperature (Tg) of the cured resin product of the thermosetting resin composition of the present invention is determined by the storage modulus and temperature obtained by temperature-rising measurement of DMA measurement (dynamic viscoelasticity measurement). It can be calculated from a scatter diagram.
  • the glass transition temperature is the temperature at the intersection of the tangent line drawn to the glass region and the tangent line drawn to the glass transition region in the above scatter diagram.
  • Component [C] in the present invention is a catalyst.
  • the catalyst promotes the curing reaction between the epoxy group of component [A] and the isocyanate group of component [B].
  • the oxazolidone cyclization reaction proceeds preferentially, and a fiber-reinforced composite material with excellent fracture toughness, deformation ability, and moist heat resistance of the cured product is obtained.
  • catalysts preferably used in the present invention include imidazole compounds, tertiary amine compounds, heterocyclic amine compounds, imidazolium salts, quaternary onium salts, and inorganic salts. These catalysts may be used alone or in combination of two or more. Among these, quaternary onium salts represented by quaternary ammonium salts and quaternary phosphonium salts can be preferably used because they exhibit high heat resistance and mechanical properties.
  • imidazole compounds include, for example, “Curezol (registered trademark)” 2E4MZ, “Curezol (registered trademark)” 2PZ, “Curezol (registered trademark)” 2P4MZ, “Cureduct (registered trademark)” P-0505 (the above, (manufactured by Shikoku Kasei Co., Ltd.), 1-methylimidazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and the like can be used.
  • tertiary amine compounds examples include triethylamine, tributylamine, triphenylamine, and N,N-dimethylbenzylamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.).
  • heterocyclic amine compounds include, for example, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]-5-nonene, and 7-methyl.
  • 1,8-diazabicyclo[5.4.0]undec-7-ene 1,5-diazabicyclo[4.3.0]-5-nonene
  • 7-methyl 1,8-diazabicyclo[4.4.0]dec-5-ene
  • 1,5,7-triazabicyclo[4.4.0]dec-5-ene 1,4-diazabicyclo [2.2.2]
  • Octane 4-dimethylaminopyridine, 4-aminopyridine (all manufactured by Tokyo Chemical Industry Co., Ltd.), etc. can be used.
  • imidazolium salts examples include 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium chloride, and 1-ethyl-3-methyl Imidazolium iodide, 1-hexyl-3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and the like can be used.
  • quaternary ammonium salts include, for example, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrapropylammonium bromide, tetrapropylammonium chloride, and tetrapropylammonium.
  • Iodide manufactured by Tokyo Kasei Kogyo Co., Ltd.
  • Iodide manufactured by Tokyo Kasei Kogyo Co., Ltd.
  • Examples of commercially available quaternary phosphonium salts include “TBP-BB (registered trademark),” “TPP-PB (registered trademark),” “TPP-MB (registered trademark),” and “TPP-EB (registered trademark).” , “TPP-IPI (registered trademark)” (all manufactured by Hokuko Sangyo Co., Ltd.), (2-hydroxy-5-methylphenyl)triphenylphosphonium bromide, 1-ethyl-3-methylimidazolium bromide (all manufactured by Tokyo (manufactured by Kasei Kogyo Co., Ltd.), etc. can be used.
  • inorganic salts include alkali metal salts, alkaline earth metal salts, first transition metal salts, and the like.
  • Commercial products of such inorganic salts include calcium chloride, calcium bromide, calcium iodide, magnesium chloride, magnesium bromide, magnesium iodide, potassium chloride, potassium bromide, potassium iodide, sodium chloride, sodium bromide, and iodine.
  • Sodium chloride, lithium chloride, lithium bromide, lithium iodide (all manufactured by Tokyo Kasei Kogyo Co., Ltd.), etc. can be used.
  • Component [D] in the present invention is a sulfonamide compound represented by the following formula (I).
  • R 1 represents a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl or aryl ring.
  • R 2 represents hydrogen or a substituted or unsubstituted cycloalkyl or aryl ring. represents a substituted straight-chain or branched alkyl group having 1 to 10 carbon atoms).
  • the thermosetting resin composition of the present invention exhibits excellent latent properties that cannot be achieved with component [A], component [B], and component [C] alone. Specifically, in the temperature range from room temperature to which it is exposed in the resin injection step, the thermosetting resin composition exhibits a certain period (hereinafter referred to as induction time) in which the reaction does not proceed. In addition, it exhibits fast curing properties in which the reaction rapidly progresses after the induction time has elapsed. Generally, there is a trade-off relationship between latent and fast curing properties, and it is difficult to have both at the same time, but the thermosetting resin composition of the present invention can simultaneously achieve the above characteristics.
  • component [D] inhibits for a certain period of time the reaction between epoxy groups and isocyanate groups promoted by component [C], and the multimerization reaction between isocyanate groups that occurs at room temperature. .
  • component [C] inhibits for a certain period of time the reaction between epoxy groups and isocyanate groups promoted by component [C], and the multimerization reaction between isocyanate groups that occurs at room temperature. .
  • this is a remarkable effect that can only be achieved with the sulfonamide compound represented by formula (I), and it is necessary that at least one hydrogen atom is covalently bonded to the nitrogen atom in the sulfonamide bond.
  • the induction time and curing time are the values obtained by dividing the curing time (Tc) measured by the induction time (Ti) when the thermosetting resin composition is exposed to a predetermined temperature, that is, Tc/Ti can be evaluated using the value as an index.
  • the curing time is defined as the time from the time of exposure to a predetermined temperature until the curing is completed, and includes the induction time. Therefore, since the value of Tc will never be greater than the value of Ti, the value of Tc/Ti will never be less than 1. In the thermosetting resin composition of the present invention, it is preferable that 1 ⁇ Tc/Ti ⁇ 9.
  • Tc/Ti When Tc/Ti is 9 or less, it is possible to optimize the fluidity retention time during the thermosetting process without prolonging the curing time, that is, the molding cycle time, so it is suitable for resin injection and impregnation processes. It can be suitably used.
  • the value of Tc/Ti more preferably satisfies 1 ⁇ Tc/Ti ⁇ 5, further preferably satisfies 1 ⁇ Tc/Ti ⁇ 3, and particularly preferably satisfies 1 ⁇ Tc/Ti ⁇ 2. .
  • the thermosetting resin composition of the present invention preferably contains an inorganic salt as component [C].
  • An inorganic salt is a salt composed of a cation made of an inorganic substance such as a metal element and an anion derived from a base.
  • an inorganic salt as component [C]
  • the curing time can be shortened without significantly shortening the induction time. That is, the value of Tc/Ti becomes smaller, and the balance between latent and fast curing properties becomes better.
  • it is preferable to include an alkali metal halide as component [C] since the thermosetting epoxy resin composition can be cured in a wide temperature range from 50°C to 200°C.
  • thermosetting resin composition of the present invention simultaneously contains a quaternary onium salt and an inorganic salt as component [C].
  • a quaternary onium salt and an inorganic salt By simultaneously containing a quaternary onium salt and an inorganic salt, rapid curing properties that cannot be achieved with an inorganic salt alone are exhibited. It is speculated that this effect is due to the catalyst activation effect of the inorganic salt being promoted by the quaternary onium salt.
  • the induction time (Ti) in the present invention can be evaluated from the complex viscosity ⁇ * measured for the thermosetting epoxy resin composition of the present invention at a predetermined temperature.
  • Ti is the time required for ⁇ * measured at a predetermined temperature using a dynamic viscoelasticity measuring device to reach four times the value from the measurement start point.
  • the curing time (Tc) in the present invention can be determined by observing the change over time in the complex viscosity ⁇ * at a predetermined temperature, and obtaining the time at which ⁇ * reaches saturation as Tc.
  • thermosetting resin composition of the present invention Furthermore, by including the component [D] in the thermosetting resin composition of the present invention, the deformability and fracture toughness of the cured resin become extremely excellent. In addition, since it is possible to suppress the deterioration of physical properties when water is absorbed, the elastic modulus under wet heat and the heat resistance after wetting are also excellent, so it is suitably used as a fiber reinforced composite material for structural materials.
  • the thermosetting resin composition of the present invention has a value obtained by dividing the flexural modulus of a cured resin product obtained by curing the resin composition (moist heat 82 degrees) by the flexural modulus (23 degrees Celsius, 50% RH), That is, it has a characteristic that E 82 /E 23 is larger than 0.70.
  • E 82 /E 23 is larger than 0.70, the mechanical properties of the fiber-reinforced composite material made of the thermosetting resin composition when used in high temperature and high humidity conditions, especially the compressive strength under moist heat, become difficult to decrease. Therefore, it can be widely applied to structural materials.
  • the upper limit of E 82 /E 23 is 1 because the flexural modulus (moist heat 82° C.) is never higher than the flexural modulus (23° C., 50% RH).
  • the bending elastic modulus (82° C. in wet heat) and the bending elastic modulus (23° C., 50% RH) can be evaluated by a three-point bending test according to JIS K7171 (1994).
  • the bending elastic modulus (moist heat 82°C) can be evaluated by, for example, performing a three-point bending test on a cured resin material that has been immersed in boiling water for two days in a constant temperature bath set at 82°C.
  • R 2 is preferably hydrogen.
  • the induction time can be more effectively expressed, so the Tc/Ti value is small, that is, it has excellent latent and fast curing properties, so it is suitable for the resin injection process. Can be used.
  • R 1 is preferably selected from a tolyl group, a phenyl group, or a chlorophenyl group.
  • R 1 is the above-mentioned substituent, the water absorption rate is lowered, so that the cured resin has an excellent elastic modulus under wet heat.
  • R 1 is a tolyl group or a chlorophenyl group, the deformation ability of the cured resin material is simultaneously increased, so that the fatigue properties of the fiber-reinforced composite material are improved.
  • R 2 is other than hydrogen in formula (I)
  • commercially available compounds in which R 2 is other than hydrogen in formula (I) include, for example, N-methylmethanesulfonamide, N-ethylmethanesulfonamide, N-cyclohexylmethanesulfonamide, N- Methylbenzenesulfonamide, N-ethylbenzenesulfonamide, N-methyl-p-toluenesulfonamide, N-methyl-p-chlorobenzenesulfonamide, N-ethyl-p-chlorobenzenesulfonamide, N-methylphenylmethanesulfonamide, N - Ethyl phenyl methanesulfonamide, N-methylcyclohexane sulfonamide, N-ethylcyclohexane sulfonamide (manufactured by Tokyo Kasei Kogyo Co., Ltd.
  • R 2 is hydrogen in formula (I)
  • compounds in which R 2 is hydrogen in formula (I) include methanesulfonamide, benzenesulfonamide, m-toluenesulfonamide, p-chlorobenzenesulfonamide, and phenylmethanesulfonamide.
  • cyclohexylsulfonamide manufactured by Tokyo Kasei Kogyo Co., Ltd.
  • Top Sizer registered trademark
  • No. 1 S p-toluenesulfonamide
  • orthoamide o-toluenesulfonamide
  • the value (Mc/Ms) obtained by dividing the number of moles (Mc) of component [C] by the number of moles (Ms) of component [D] is in the range of 0.1 to 10. It is preferable that the Within this range, the induction time (Ti) can be arbitrarily controlled without impairing fast curing properties. That is, in the injection or impregnation process, it is possible to design the induction time depending on the molding temperature and time.
  • component [E] When the thermosetting resin composition of the present invention contains an inorganic salt as component [C], component [E] preferably contains a compound having a structure represented by the following formula (II) in the molecule.
  • n represents an integer of 1 to 6
  • m represents an integer of 4 to 1,000.
  • R 1 ' and R 2 ' are independently a hydrogen atom, an alkyl group, a hydroxyl group, or Represents an aryl group.
  • R 1 and R 2 independently represent a hydrogen atom, an alkyl group, a hydroxyl group, or an aryl group.
  • X represents O, NH, S, or COO.
  • COO represents OCO (including the chemical structure of).
  • thermosetting resin composition of the present invention When an inorganic salt is included as component [C], by simultaneously including component [E], the compatibility of the inorganic salt with the resin composition increases, and the fast curing properties of the thermosetting resin composition of the present invention are more excellent. It becomes something. Further, since the homogeneity of the thermosetting resin composition is improved, the mechanical properties of a molded article obtained by heating and curing the thermosetting resin composition of the present invention are also excellent.
  • thermosetting resin composition of the present invention simultaneously contains a quaternary onium salt and an inorganic salt as component [C], and also contains component [E].
  • R 1 ', R 2 ', R 1 and R 2 of component [E] is an alkyl group
  • the number of carbon atoms contained in the alkyl group is preferably 1 to 5.
  • the compatibility between component [C] and the epoxy resin increases, and the curing properties and mechanical properties of the cured resin product tend to be even better.
  • alkyl groups having 1 to 5 carbon atoms include methyl, ethyl, propyl, butyl, isopropyl, pentyl, and the like.
  • the thermosetting resin composition of the present invention may include component [F]: a toughening agent.
  • the toughening agent is an additive that improves the toughness of a molded article obtained by heating and curing the thermosetting resin composition of the present invention, and includes component [A], component [B], component [C], and component [ By simultaneously containing component [F] in the thermosetting resin composition containing [D], the fracture toughness value of the molded article obtained by heating and curing the thermosetting resin composition is specifically improved.
  • component [F] examples include crosslinked rubber particles such as core-shell rubber particles, thermoplastic elastomers such as block copolymers, carboxyl group-terminated butadiene nitrile rubber (hereinafter sometimes referred to as CTBN), and the like.
  • CTBN carboxyl group-terminated butadiene nitrile rubber
  • crosslinked rubber particles include, for example, "Kane Ace (registered trademark)” MX-153, “Kane Ace (registered trademark)” MX-154, “Kane Ace (registered trademark)” MX-257, and “Kane Ace (registered trademark)”.
  • MX-416 manufactured by Kaneka Co., Ltd. or the like can be used.
  • thermoplastic elastomers examples include “NanoStrength (registered trademark)” M52N, “Nanostrength (registered trademark)” M22N, “Nanostrength (registered trademark)” E21, and “Nanostrength (registered trademark)” M41 ( As mentioned above, products such as those manufactured by Arkema Co., Ltd. can be used.
  • CTBN Commercial products of CTBN include, for example, “Hypro (registered trademark)” 1300X31, “Hypro (registered trademark)” 1300X13, “Hypro (registered trademark)” 1300X13NA, “Hypro (registered trademark)” 1300 (manufactured by) etc. can be used.
  • the thermosetting resin composition of the present invention may include component [G]: an internal mold release agent.
  • internal mold release agent refers to a compound that, when added, prevents a molded article obtained by heating and curing a thermosetting resin composition from coming into too close contact with a mold.
  • component [G] for example, general internal mold release agents such as metal salts such as zinc stearate, ester compounds, silicone compounds, and fluorine-containing compounds can be used. Among these, ester compounds that do not generate heat of reaction with component (B) are preferred.
  • the heat generation chart obtained by this measurement represents the reactivity at that temperature. Therefore, the calorific value per unit mass in the chart can be used as an index of reactivity, and if it is 15 J/g or less, the reaction heat is negligible and it can be judged that no reaction heat is generated. can.
  • ester compounds include ester compounds of organic fatty acids and alcohols, ester compounds of carboxylic acids and alcohols, and the like.
  • mold release agents include, for example, "MOLD WIZ (registered trademark)" INT-1846, INT-1836, INT-1850, INT-1854, INT-1888LE (hereinafter referred to as AXEL PLASTICS RESEARCH LABORATORIES).
  • thermosetting resin composition of the present invention may be kneaded using a machine such as a kneader, a planetary mixer, a three-roll extruder, or a twin-screw extruder, or, if uniform kneading is possible, You can also mix by hand using a beaker and spatula.
  • a machine such as a kneader, a planetary mixer, a three-roll extruder, or a twin-screw extruder, or, if uniform kneading is possible, You can also mix by hand using a beaker and spatula.
  • thermosetting resin composition of the present invention can be used as a fiber-reinforced composite material that is integrated with a reinforcing fiber base material.
  • the epoxy resin composition prepared by the above method and the reinforcing fiber base material are integrated into a composite and thermally cured to produce a fiber-reinforced composite material using the cured product of the thermosetting resin composition of the present invention as a matrix resin.
  • the method of composite integration of the thermosetting resin composition and the fiber-reinforced base material is not particularly limited, but examples include RTM method, liquid composite molding method, filament winding method, hand lay-up method, pultrusion method, and prepreg method. Laws etc.
  • thermosetting resin composition of the present invention maintains the resin at a low viscosity for an arbitrary period of time by controlling the Mc/Ms ratio described above at a temperature range from room temperature to thermosetting temperature, for example, 23°C to 180°C. Therefore, the impregnation characteristics of the reinforcing fiber base material can be optimized depending on the molding process.
  • it since it can be cured at high speed at the thermosetting temperature, it is particularly suitable for use in the RTM method.
  • a reinforcing fiber base material or preform is placed in a mold, a liquid matrix resin is injected into the mold to impregnate the reinforcing fibers, and then heated to release the thermosetting resin composition. This is a method of curing a material to obtain a fiber-reinforced composite material, which is a molded product.
  • thermosetting resin composition in the method for producing a fiber reinforced composite material by injection molding using the thermosetting resin composition of the present invention is not particularly limited, but is maintained at 23°C to 180°C. It is preferable to place a reinforcing fiber base material in a mold and inject the thermosetting resin composition of the present invention. Note that the thermosetting temperature does not need to be the same as the temperature at the time of injection, and the time required for thermosetting may be shortened by increasing the temperature as appropriate.
  • the mold used in the RTM method may be a closed mold made of a rigid material, or an open mold made of a rigid material and a flexible film (bag).
  • the reinforcing fiber substrate can be placed between an open mold of rigid material and a flexible film.
  • the rigid material various existing materials such as metal such as steel and aluminum, fiber reinforced plastic (FRP), wood, and plaster are used.
  • FRP fiber reinforced plastic
  • Polyamide, polyimide, polyester, fluororesin, silicone resin, etc. are used as the material for the flexible film.
  • the reinforcing fibers used in the reinforcing fiber base material used in the fiber-reinforced composite material of the present invention are not particularly limited, and examples include glass fibers, carbon fibers, aramid fibers, boron fibers, alumina fibers, silicon carbide fibers, etc. can be used. Two or more of these fibers may be used in combination. From the viewpoint of obtaining a lightweight and highly rigid fiber-reinforced composite material, it is preferable to use carbon fiber.
  • the fiber-reinforced composite material of the present invention has excellent mechanical properties, compressive strength under wet heat, and impact resistance, so it can be used in aircraft parts such as fuselages, main wings, tails, rotor blades, fairings, cowls, doors, seats, interior materials, etc.
  • Spacecraft parts such as motor cases and main wings, artificial satellite parts such as structures and antennas, automobile parts such as outer panels, chassis, aerodynamic parts, and seats, railway vehicle parts such as structures and seats, ship parts such as hulls and seats, etc. It can be preferably used for many structural materials.
  • ⁇ Other additives substitutes for component [D]
  • N,N'-diethyl-p-toluenesulfonamide manufactured by Tokyo Chemical Industry Co., Ltd.
  • Benzamide manufactured by Tokyo Kasei Kogyo Co., Ltd.
  • N-methylbenzamide manufactured by Tokyo Kasei Kogyo Co., Ltd.
  • component [E] component [C] and component [E] were made compatible in advance and then mixed with component [B] to obtain a curing agent liquid.
  • thermosetting resin composition was obtained by mixing a predetermined amount of an epoxy base liquid and a curing agent liquid or another epoxy resin curing agent and kneading the mixture for 3 minutes using a planetary mixer.
  • the resin compositions are as shown in Tables 1 to 9.
  • ⁇ Measurement of viscosity of resin composition> Using a dynamic viscoelasticity measuring device (ARES-G2: manufactured by TA Instruments), using a parallel plate with a diameter of 40 mm, under the measurement conditions of a frequency of 1 Hz and a gap of 1.0 mm, the above ⁇ Method for Preparing a Resin Composition> The complex viscosity ( ⁇ * ) of the resin composition prepared according to the following was measured. At this time, the resin composition was placed on a parallel plate set at the measurement temperature listed in Tables 1 to 9, and ⁇ * obtained 10 seconds later was defined as the viscosity ( ⁇ 0 ) of the resin composition.
  • RATS-G2 dynamic viscoelasticity measuring device
  • Tc Measurement of curing time (Tc)> Changes over time in the dynamic viscoelasticity of the resin composition prepared according to the above ⁇ Preparation of the resin composition> using a polymer curing measuring device (ATD-1000: manufactured by Alpha Technologies) at a frequency of 1 Hz and a strain amount of 1%. was measured at the measurement temperatures listed in Tables 1 to 9, and the time when the complex viscosity ⁇ * reached 1,000,000 Pa ⁇ s was defined as the curing time (Tc).
  • ATTD-1000 manufactured by Alpha Technologies
  • a test piece with a width of 12.7 mm and a length of 45 mm was cut out from this cured resin product, and the test piece was set in a solid twisting jig using a dynamic viscoelasticity measuring device (ARES-G2, manufactured by TA Instruments). Measurements were conducted over a temperature range of 40 to 260°C at a temperature increase rate of 5°C/min, a frequency of 1Hz, and a strain of 0.08%. At this time, the glass transition temperature (dry Tg) was defined as the temperature at the intersection of the tangent line drawn to the glass state and the tangent line drawn to the glass transition temperature region in the obtained storage modulus versus temperature graph.
  • Example 1 Component [A]: As an epoxy resin [A]-1: 100 parts by mass of “jER (registered trademark)” 828, Component [B]: As an isocyanate compound [B]-2: “Lupranate (registered trademark)” MI 66 parts by mass, component [C]: as a catalyst [C]-1: 2.8 parts by mass of tetrabutylammonium bromide, [D]: as a sulfonamide compound represented by formula (I) [D]-2: " A thermosetting resin composition was prepared using 2.1 parts by mass of Topsizer (registered trademark) No. 3 according to the above ⁇ Method for Preparing a Resin Composition>.
  • Topsizer registered trademark
  • thermosetting resin composition the Tc/Ti measured at 100°C was 7.8 according to the above ⁇ Measurement of induction time (Ti)> and ⁇ Measurement of curing time (Tc)>, and the latent and rapid Curability was good.
  • thermosetting resin composition the above ⁇ Evaluation method for flexural modulus of cured resin product (23°C, 50% RH): E 23 > and ⁇ Bending elastic modulus of cured resin product (humid heat 82°C): E 82
  • the E 23 was 3.6 GPa
  • the E 82 was 2.9 GPa
  • the E 82 /E 23 was 0.81, showing an excellent moist heat elastic modulus.
  • the amount of bending strain was 4.0%, which was good.
  • thermosetting resin composition and a cured resin product were produced in the same manner as in Example 1, except that the resin composition was changed as shown in Tables 1 to 7.
  • thermosetting resin composition of each example was 1.2 to 8.8, and had an excellent balance between latent and fast curing properties. Furthermore, when E 82 and E 23 , wet and dry Tg, water absorption, and fracture toughness values were evaluated, good physical properties were obtained at all levels. Furthermore, when the epoxy resin compositions of each example were evaluated for viscosity at the measurement temperatures listed in Tables 1 to 7, the viscosity was 10 to 336 mPa ⁇ s, indicating a viscosity suitable for injection molding. In addition, in Examples 44 to 46, the surface was smooth and the cured resin product did not deform or warp during demolding, demonstrating good demoldability.
  • thermosetting resin composition was produced in the same manner as in Example 1 except that the resin composition shown in Table 8 was used. Since the resin composition does not contain component [D], the Tc/Ti measured at 100°C according to the above ⁇ Measurement of induction time (Ti)> and ⁇ Measurement of curing time (Tc)> is insufficient at 70. Met.
  • thermosetting resin composition the above ⁇ Evaluation method for flexural modulus of cured resin product (23°C, 50% RH): E 23 > and ⁇ Bending elastic modulus of cured resin product (humid heat 82°C): E 82
  • the E 23 was high at 4.6 GPa, but the E 82 was extremely low at 1.5 GPa, and the E 82 /E 23 was 0.33. Further, the amount of bending strain was 0.5%, and the deformation ability was extremely low.
  • Heat resistance was evaluated according to the above ⁇ Method for evaluating the glass transition temperature (dry Tg) of cured resin products> and ⁇ Method for evaluating the glass transition temperature (wet Tg) of cured resin products>, and the dry Tg was 92°C, wet Tg. Tg was 75°C, which was insufficient. Note that the water absorption rate was 8.0%. Further, when the fracture toughness value was evaluated according to the above ⁇ Method for evaluating fracture toughness value of cured resin product>, the cured resin product was extremely brittle and could not be evaluated.
  • thermosetting resin composition was prepared in the same manner as in Example 1, except that the corresponding resin composition listed in Table 8 was used, and Tc/Ti, E82 and E23 , wet and dry Tg, water absorption, and fracture The toughness value was evaluated.
  • thermosetting resin composition of Comparative Example 2 contains a sulfonamide compound (N,N'-diethyl-p-toluenesulfonamide) in which hydrogen is not covalently bonded to the nitrogen atom, instead of component [D].
  • Ti was short and unstable at 0.5 minutes.
  • component [D] was not included, the water absorption rate was as high as 8.7%, and the wet heat elastic modulus was extremely low, with E 82 of 2.0 GPa and E 82 /E 23 of 0.47. Further, the amount of bending strain was as low as 1.0%, and the fracture toughness value was so low that it could not be evaluated.
  • thermosetting resin composition of Comparative Example 3 contained benzamide instead of component [D], but the Ti was short at 1.5 minutes and was unstable. Further, the water absorption rate was as high as 8.3%, the E 82 was 1.8 GPa, and the E 82 /E 23 was 0.41, which resulted in a significantly low wet heat elastic modulus. Further, the amount of bending strain was as low as 0.8%, and the fracture toughness value was so low that it could not be evaluated.
  • thermosetting resin composition of Comparative Example 4 contained N-methylbenzamide instead of component [D], but the Ti was short at 1.5 minutes and was unstable. Furthermore, the water absorption rate was as high as 8.2%, the E 82 was 1.9 GPa, and the E 82 /E 23 was 0.41, which resulted in a significantly low wet heat elastic modulus. Further, the amount of bending strain was as low as 0.5%, and the fracture toughness value was so low that it could not be evaluated.
  • thermosetting resin composition of Comparative Example 5 did not contain component [B], component [C], and component [D], but contained "jER Cure (registered trademark)" W as a curing agent for the epoxy resin. .
  • Ti was stable for 50 minutes, but Tc was long at 610 minutes, resulting in insufficient fast curing properties. Further, the fracture toughness value was 0.70 MPa ⁇ m 0.5 , which was insufficient.
  • thermosetting resin composition of Comparative Example 6 did not contain component [B], component [C], and component [D], but contained “Lonzacure (registered trademark)” M-MIPA as a curing agent for the epoxy resin. did. Ti was stable at 85 minutes, but Tc was long at 800 minutes, resulting in insufficient fast curing properties. Furthermore, the fracture toughness value was 0.80 MPa ⁇ m 0.5 , which was insufficient.
  • thermosetting resin composition of Comparative Example 7 did not contain component [B], component [C], and component [D], but "RIKACID (registered trademark)" HH was blended as a curing agent for the epoxy resin.
  • Tc showed quick curing properties of 25 minutes, but Ti had a short curing time of 1.0 minutes and was unstable. Further, the fracture toughness value was 0.70 MPa ⁇ m 0.5 , which was insufficient.
  • thermosetting resin composition was prepared in the same manner as in Example 1, except that the corresponding resin composition listed in Table 9 was used, and Tc/Ti, E82 and E23 , wet and dry Tg, water absorption, and fracture The toughness value was evaluated.
  • thermosetting resin compositions of Comparative Examples 8 to 10 were prepared by adding component [F] to the epoxy resin compositions of Comparative Examples 5 to 7, respectively.
  • component [F] the fracture toughness value of all compositions improved, but compared to the examples, at least among component [A], component [B], component [C], and component [D] Since it did not contain one, the improvement effect was general.
  • thermosetting resin composition was prepared in the same manner as in Example 1, except that the corresponding resin composition listed in Table 9 was used, and Tc/Ti, E82 and E23 , wet and dry Tg, water absorption, and fracture The toughness value was evaluated.
  • thermosetting resin composition of Comparative Example 11 contains an aliphatic epoxy resin as component [A], but does not contain component [B], component [C], and component [D].
  • "jER Cure (registered trademark)" W was blended as a curing agent for the epoxy resin.
  • the bending strain was 12.1%
  • the fracture toughness value was 1.01 MPa ⁇ m 0.5 , which were excellent values, but the wet and dry Tg were decreased, and the heat resistance was It was not possible to achieve both fracture toughness and fracture toughness.
  • thermosetting resin composition of Comparative Example 12 contains an aliphatic epoxy resin as component [A], but does not contain component [B], component [C], and component [D].
  • “Rikacid (registered trademark)” HH was blended as a curing agent for the epoxy resin.
  • the bending strain was 8.3% and the fracture toughness value was 0.97 MPa ⁇ m 0.5 , which were excellent values, but the wet and dry Tg were decreased, and the heat resistance was It was not possible to achieve both fracture toughness and fracture toughness.
  • thermosetting resin composition of the present invention can control the resin flow time and curing speed, and can provide a cured resin that has high fracture toughness and high elastic modulus under moist heat.
  • the fiber-reinforced composite material made of the epoxy resin composition has excellent compressive properties and impact resistance under wet heat, so it can be suitably used for aerospace parts and structural members for general industry.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention a pour but de procurer : une composition de résine thermodurcissable permettant de réguler le temps d'écoulement de la résine et la vitesse de durcissement et présentant une résistance à la rupture et un module d'élasticité élevés lorsqu'elle est soumise à une chaleur humide ; et un matériau composite renforcé par des fibres constitué de la composition de résine époxy.　La présente invention concerne une composition de résine thermodurcissable contenant des composants [A], [B], [C] et [D]. [A] Une résine époxy. [B] Un composé isocyanate. [C] Un catalyseur. [D] Un composé sulfone-amide de formule (I) (dans la formule (I), R1 représente un groupe alkyle linéaire ou ramifié qui présente de 1 à 10 atomes de carbone et qui est substitué ou non substitué, ou un anneau cycloalkyle ou aryle substitué ou non substitué ; R2 représente l'hydrogène ou un groupe alkyle linéaire ou ramifié qui présente de 1 à 10 atomes de carbone et qui est substitué ou non substitué).
PCT/JP2023/016826 2022-05-09 2023-04-28 Composition de résine thermodurcissable, article moulé, matériau de moulage pour matériau composite renforcé par des fibres, et matériau composite renforcé par des fibres WO2023219007A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02289609A (ja) * 1987-04-09 1990-11-29 Ashland Oil Inc 一成分型硬化性エポキシ樹脂組成物
JP2006241187A (ja) * 2005-02-28 2006-09-14 Asahi Kasei Corp 新規エポキシ硬化促進剤及びそれを含有する硬化性組成物
CN108841286A (zh) * 2018-05-21 2018-11-20 三江学院 一种耐磨耐腐蚀表面涂层材料及其制备方法
CN112662090A (zh) * 2020-12-21 2021-04-16 淄博科信腾达信息科技有限公司 一种改性硬质聚氯乙烯泡沫及其制备方法
WO2022102467A1 (fr) * 2020-11-16 2022-05-19 東レ株式会社 Composition de résine époxy thermodurcissable, article moulé à base de celle-ci, matériau composite renforcé de fibres, matériau de moulage pour matériaux composites renforcés de fibres et procédé de production d'un matériau composite renforcé de fibres
WO2022124191A1 (fr) * 2020-12-08 2022-06-16 東レ株式会社 Composition de résine époxyde thermodurcissable, article moulé à partir de résine époxyde thermodurcissable, matériau de moulage pour matériau composite renforcé par des fibres, matériau composite renforcé par des fibres et procédé de production de matériau composite renforcé par des fibres

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02289609A (ja) * 1987-04-09 1990-11-29 Ashland Oil Inc 一成分型硬化性エポキシ樹脂組成物
JP2006241187A (ja) * 2005-02-28 2006-09-14 Asahi Kasei Corp 新規エポキシ硬化促進剤及びそれを含有する硬化性組成物
CN108841286A (zh) * 2018-05-21 2018-11-20 三江学院 一种耐磨耐腐蚀表面涂层材料及其制备方法
WO2022102467A1 (fr) * 2020-11-16 2022-05-19 東レ株式会社 Composition de résine époxy thermodurcissable, article moulé à base de celle-ci, matériau composite renforcé de fibres, matériau de moulage pour matériaux composites renforcés de fibres et procédé de production d'un matériau composite renforcé de fibres
WO2022124191A1 (fr) * 2020-12-08 2022-06-16 東レ株式会社 Composition de résine époxyde thermodurcissable, article moulé à partir de résine époxyde thermodurcissable, matériau de moulage pour matériau composite renforcé par des fibres, matériau composite renforcé par des fibres et procédé de production de matériau composite renforcé par des fibres
CN112662090A (zh) * 2020-12-21 2021-04-16 淄博科信腾达信息科技有限公司 一种改性硬质聚氯乙烯泡沫及其制备方法

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