[go: up one dir, main page]

WO2017179359A1 - Agent durcisseur de résine époxy, composition de résine époxy et matériau composite renforcé par des fibres de carbone - Google Patents

Agent durcisseur de résine époxy, composition de résine époxy et matériau composite renforcé par des fibres de carbone Download PDF

Info

Publication number
WO2017179359A1
WO2017179359A1 PCT/JP2017/010411 JP2017010411W WO2017179359A1 WO 2017179359 A1 WO2017179359 A1 WO 2017179359A1 JP 2017010411 W JP2017010411 W JP 2017010411W WO 2017179359 A1 WO2017179359 A1 WO 2017179359A1
Authority
WO
WIPO (PCT)
Prior art keywords
epoxy resin
curing agent
resin composition
compound
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/010411
Other languages
English (en)
Japanese (ja)
Inventor
唯我 浅井
友孝 和田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Gas Chemical Co Inc
Original Assignee
Mitsubishi Gas Chemical Co Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Gas Chemical Co Inc filed Critical Mitsubishi Gas Chemical Co Inc
Priority to JP2018511938A priority Critical patent/JP7074053B2/ja
Priority to CN201780021820.0A priority patent/CN108884211B/zh
Publication of WO2017179359A1 publication Critical patent/WO2017179359A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/14—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of indefinite length
    • B29C39/18—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of indefinite length incorporating preformed parts or layers, e.g. casting around inserts or for coating articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
    • C08G59/184—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 using pre-adducts of epoxy compounds with curing agents with amines

Definitions

  • the present invention relates to an epoxy resin curing agent, an epoxy resin composition containing the epoxy resin curing agent and an epoxy resin, a cured product of the epoxy resin composition, and a carbon fiber reinforced composite material including carbon fibers.
  • CFRP Carbon Fiber Reinforced Plastics
  • CFRP molding methods are different for automobile structural material applications, wind power generation blade applications, pressure vessel applications, and aerospace applications, the required characteristics for the matrix resin for CFRP also differ depending on the applications.
  • wind power blades have been molded by infusion molding, Va-RTM method (Vacuum Assist Resin Transfer Molding) or Light-RTM method.
  • reinforcing fibers are arranged in advance in a mold composed of an upper mold using a film or FRP and a lower mold, and the mold is evacuated to obtain an epoxy resin composition serving as a matrix resin. It is filled with normal pressure and impregnated into reinforcing fibers, and then the epoxy resin is cured and molded.
  • an epoxy resin composition in which an epoxy resin and an epoxy resin curing agent are mixed is usually filled into a mold. Takes tens of minutes. Therefore, the epoxy resin composition used in these molding methods is required to have a low viscosity and a long pot life.
  • an epoxy resin curing agent isophorone diamine, a polyamine compound having a polyether skeleton, and the like are used.
  • the filament winding method is a method in which the outer surface of a liner is coated with a reinforcing fiber yarn obtained by impregnating a reinforcing fiber yarn with a matrix resin such as an epoxy resin composition, and then the matrix resin is cured.
  • a matrix resin such as an epoxy resin composition
  • CFRP for automotive structural materials is molded by the high cycle RTM method.
  • the conventional RTM method is one of sealed molds using a pair of upper and lower molds. A fiber reinforced preform is placed in the mold, the mold is clamped and sealed, and then epoxy resin is injected from the injection hole. In this method, a resin such as a composition is poured into a mold and impregnated into a fiber reinforced preform, and then the resin is cured and then released.
  • the conventional RTM method requires several hours for molding time (preform placement, resin impregnation, resin curing, and mold release). Therefore, in the production of CFRP for automotive structural materials, higher productivity and higher cycle The RTM method is used.
  • the molding technology using the high-cycle RTM method has greatly reduced all of the fiber-reinforced preform placement time, resin impregnation time, resin curing time, and mold release time, and has shortened the total molding time to about 10 minutes. Is.
  • the high cycle RTM method in the process from resin impregnation to curing, for example, in the high pressure RTM method, which is a kind of high cycle RTM method, the reinforcing fibers are arranged in a pair of upper and lower molds and sealed, and the inside of the mold is sealed. Reduce pressure.
  • the epoxy resin that is the main component of the epoxy resin composition and the epoxy resin curing agent are pumped in a mist state from separate tanks to the mixing head, and after impingement mixing, they are immediately injected into the mold and impregnated into carbon fibers. And cure the epoxy resin.
  • the epoxy resin composition after the impingement mixing is injected at a high pressure from a plurality of injection holes in order to increase the filling speed into the mold and the impregnation speed into the carbon fiber.
  • the pot life of the epoxy resin composition which is a mixture of the epoxy resin and the epoxy resin curing agent, is required so much. And not.
  • the impregnation into the reinforcing fiber, the filling rate into the mold is high, and the curing is fast, so that the epoxy resin composition used in the high cycle RTM method has a low It must be viscous and fast-curing.
  • Patent Documents 1 to 3 disclose an epoxy resin curing agent containing a modified product of a polyamine compound such as bis (aminomethyl) cyclohexane or xylylenediamine.
  • an epoxy resin curing agent used for molding by a high cycle RTM method or the like and an epoxy resin composition containing the curing agent and an epoxy resin, it is necessary to achieve both fast curability and low viscosity.
  • conventional epoxy resin curing agents and epoxy resin compositions have not been satisfactory in achieving both fast curability and low viscosity.
  • a method of adding a large amount of a curing accelerator is also conceivable.
  • the pot life of the epoxy resin composition is shortened, which may not be suitable for molding a large member.
  • An object of the present invention is an epoxy resin curing agent and an epoxy resin composition, which are fast-curing and low-viscosity, and are suitably used for molding by a high cycle RTM method, etc., and a cured product and carbon of the epoxy resin composition It is providing the carbon fiber reinforced composite material containing a fiber.
  • an epoxy resin curing agent containing an addition reaction product of an amine compound having a specific structure and a predetermined amount of an epoxy compound.
  • the present invention relates to the following [1] to [13].
  • An epoxy resin curing agent containing a reacted addition reaction product H 2 N—H 2 C—A—CH 2 —NH 2 (1) (In Formula (1), A is a cyclohexylene group or a phenylene group.)
  • R 11 to R 14 are each independently an alkyl group having 1 to 6 carbon atoms, and a, b, c and d are each independently an integer of 0 to 4.
  • a plurality of R 11 The plurality of R 12 , the plurality of R 13 , and the plurality of R 14 may be the same or different from each other, and X 1 and X 2 are each independently a single bond, —CH 2 —, —CH (CH 3 ) —, or —C (CH 3 ) 2 —, R 15 is —CH 2 CH (OH) —, or —CH (OH) CH 2 —, n represents the average number of repeating units, and 0 A number of ⁇ 1.0.
  • the epoxy resin curing agent according to any one of [1] to [4], further including a curing accelerator.
  • An epoxy resin composition comprising the epoxy resin curing agent according to any one of [1] to [5] above and an epoxy resin.
  • the epoxy resin composition according to [6] wherein the epoxy resin is an epoxy resin containing an aromatic ring or an alicyclic structure in the molecule.
  • R 21 to R 24 are each independently an alkyl group having 1 to 6 carbon atoms, and p, q, r, and s are each independently an integer of 0 to 4.
  • 21 , the plurality of R 22 , the plurality of R 23 , and the plurality of R 24 may be the same or different from each other, and Y 1 and Y 2 are each independently a single bond, —CH 2 —, —CH ( CH 3 ) —, or —C (CH 3 ) 2 —, R 25 is —CH 2 CH (OH) —, or —CH (OH) CH 2 —, m represents the average number of repeating units, It is a number from 0 to 0.2.) [9] The epoxy resin composition according to any one of [6] to [8] above, wherein the viscosity at a temperature of 40 ° C.
  • a carbon fiber reinforced composite material comprising a cured product of the epoxy resin composition according to any one of [6] to [10] above and carbon fiber.
  • the carbon fiber reinforced composite material according to [11] which is a structural material for automobiles.
  • an epoxy resin curing agent and an epoxy resin composition that are fast-curing and low-viscosity capable of producing CFRP such as automobile structural materials and building materials with high productivity by a high cycle RTM method or the like. it can.
  • the epoxy resin composition is used as a CFRP matrix resin, it has excellent carbon fiber impregnation properties and is fast-curing, so that it takes only a short time to release from the mold, and CFRP production. Can be improved.
  • the amount of the compound (B) having at least one epoxy group in the molecule exceeds 0.100 mol per mol of the amine compound (A) represented by the following general formula (1). It is characterized by containing an addition reaction product reacted at a ratio of less than 200 mol. H 2 N—H 2 C—A—CH 2 —NH 2 (1) (In Formula (1), A is a cyclohexylene group or a phenylene group.) By making the amine compound (A) an addition reaction product modified by the addition reaction with the compound (B), curability when used as an epoxy resin curing agent can be improved.
  • an epoxy resin curing agent and an epoxy resin composition that achieve both fast curability and low viscosity are obtained by setting the addition amount of the compound (B) to the amine compound (A) within the predetermined range. It is a thing.
  • the amine compound (A) is a compound represented by the general formula (1).
  • A is a cyclohexylene group or a phenylene group, and a cyclohexylene group is preferable.
  • A is 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group, 1,2-phenylene group, 1,3-phenylene group, and 1,4-cyclohexyl group.
  • cyclohexylene group in this specification includes both cis and trans forms.
  • the amine compound (A) examples include 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, o-xylylenediamine, m-xylylenediamine (MXDA) and p-xylylenediamine (PXDA).
  • the amine compound (A) includes 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (amino) from the viewpoint of heat resistance and weather resistance, and performance of a cured product of the resulting epoxy resin composition.
  • An amine compound (A) can be used individually by 1 type or in combination of 2 or more types.
  • the compound (B) used in the present invention may be a compound having at least one epoxy group in the molecule, and has two or more epoxy groups in the molecule from the viewpoint of reactivity with the amine compound (A).
  • the compound which has is more preferable.
  • diglycidyl ether compounds are preferable, and in terms of heat resistance and the performance of the cured product of the resulting epoxy resin composition, an aromatic ring or alicyclic structure is present in the molecule.
  • the diglycidyl ether compound containing is more preferable, and the diglycidyl ether compound containing an aromatic ring in the molecule is more preferable.
  • the compound shown by following General formula (2) is preferable.
  • R 11 to R 14 are each independently an alkyl group having 1 to 6 carbon atoms, and a, b, c and d are each independently an integer of 0 to 4.
  • a plurality of R 11 , a plurality of R 12, all of the plurality of R 13, and a plurality of R 14 may be the same, independently each good .
  • X 1 and X 2 be different from each other, a single bond, -CH 2 -, - CH ( CH 3 ) —, or —C (CH 3 ) 2 —,
  • R 15 is —CH 2 CH (OH) —, or —CH (OH) CH 2 —
  • n represents the average number of repeating units, and 0
  • R 11 to R 14 are preferably an alkyl group having 1 to 4 carbon atoms, and more preferably at least one selected from the group consisting of a methyl group, an ethyl group, an isopropyl group, and a t
  • a, b, c, and d are each preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
  • X 1 and X 2 are preferably —CH 2 — or —C (CH 3 ) 2 —, and more preferably —C (CH 3 ) 2 —.
  • n is preferably 0 to 0.7, more preferably 0 to 0.5, and preferably 0 to 0.3. More preferably, it is more preferably 0.01 to 0.2.
  • Specific examples of the compound (B) used in the present invention other than the compound represented by the general formula (2) include butyl glycidyl ether, phenyl glycidyl ether, m-cresyl glycidyl ether, p-cresyl. Glycidyl ether, o-cresyl glycidyl ether, neodecanoic acid glycidyl ester, neopentyl glycol diglycidyl ether, 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl Examples include ether.
  • the said compound (B) can be used individually by 1 type or in combination of 2 or more types.
  • the said compound (B) may be the same compound as the epoxy resin used as a main ingredient of the epoxy resin composition of this invention mentioned later, and may differ.
  • the compound (B) was reacted at a ratio of more than 0.100 mol and less than 0.200 mol with respect to 1 mol of the amine compound (A). It is an addition reaction product.
  • the reaction ratio of the compound (B) is 0.100 mol or less with respect to 1 mol of the amine compound (A)
  • the effect of improving the curing rate of the resulting epoxy resin curing agent containing the addition reaction product is not sufficient.
  • the reaction ratio of the compound (B) is 0.200 mol or more with respect to 1 mol of the amine compound (A)
  • the resulting epoxy resin curing agent and epoxy resin composition containing the addition reaction product have high viscosity.
  • the reaction ratio of the compound (B) to 1 mol of the amine compound (A) is preferably 0.110 mol or more, more preferably 0.115 mol or more, preferably less than 0.180 mol, more preferably Is 0.170 mol or less, more preferably 0.160 mol or less, still more preferably 0.150 mol or less, and still more preferably 0.140 mol or less.
  • Examples of the addition reaction product of the amine compound (A) and the compound (B) when a compound having two epoxy groups in the molecule is used as the compound (B) include the following structures (a) to Although what has (d) is mentioned, it is not limited to these. In the following structural formulas (a) to (d), A represents a residue of the amine compound (A), and B represents a residue of the compound (B).
  • the production method of the addition reaction product of the amine compound (A) and the compound (B) is not particularly limited, and a conventionally known method can be used.
  • a method may be mentioned in which an amine compound (A) is charged into a reactor, and a predetermined amount of the compound (B) is added at once, or added in portions by dropping or the like, followed by heating and reaction.
  • the addition reaction is preferably performed in an inert atmosphere such as nitrogen gas.
  • the temperature and reaction time during the addition reaction can be appropriately selected according to the type of the compound (B) used. From the viewpoint of preventing the reaction rate and productivity and the decomposition of the raw materials, the temperature during the addition reaction is preferably 50 to 150 ° C, more preferably 70 to 120 ° C.
  • the reaction time is preferably 0.5 to 12 hours, more preferably 1 to 6 hours after the addition of the compound (B) is completed.
  • the epoxy resin curing agent of the present invention may further contain a curing accelerator.
  • the curing accelerator does not react with the addition reaction product and has a function of increasing the reactivity of the epoxy group in the epoxy resin. Therefore, when a curing accelerator is added to the epoxy resin curing agent of the present invention, the curing rate can be further improved.
  • the curing accelerator is not particularly limited. For example, phenolic compounds, organic acids, organic acid salts, tertiary amines, quaternary ammonium salts, imidazoles, organic phosphorus compounds, quaternary phosphonium salts, diazabicyclo Alkenes, organometallic salt compounds, boron compounds, metal halides and the like can be mentioned. Among these, from the viewpoint of achieving both fast curability and low viscosity, one or more selected from the group consisting of phenol compounds, organic acids and organic acid salts are preferred.
  • any compound having at least one phenolic hydroxyl group in the molecule can be used without particular limitation.
  • a phenol compound having a molecular weight of less than 1,000 is preferable from the viewpoint of exerting an effect even when the blending amount is small, and miscibility with the addition reaction product and the epoxy resin described later, and is represented by the following general formula (3). Compounds are more preferred.
  • R 1 and R 2 are each independently an OH group or an alkyl group having 1 to 4 carbon atoms. J and k are each independently an integer of 0 to 5 and j + k is 1)
  • the plurality of R 1 and the plurality of R 2 may be the same or different from each other, but at least one of them is an OH group, Z is a single bond, an alkylene group having 1 to 6 carbon atoms.
  • R 1 and R 2 are preferably OH groups, j and k are each independently an integer of 0 to 2, and j + k is preferably 1 to 3.
  • examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group, and an alkylene group having 1 to 3 carbon atoms is preferable.
  • examples of the alkylidene group having 2 to 6 carbon atoms include an ethylidene group (—CH (CH 3 ) —), a propylidene group (—C (CH 3 ) 2 —), and an alkylidene group having 2 to 3 carbon atoms is preferable. .
  • Examples of the cycloalkylene group having 5 to 10 carbon atoms include a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group.
  • Examples of the cycloalkylidene group having 5 to 10 carbon atoms include a cyclohexylidene group and a 3,5,5-trimethylcyclohexylidene group.
  • Examples of the aryl moiety of the aryl alkylene group having 7 to 15 carbon atoms and the arylalkylidene group having 7 to 15 carbon atoms include aryl groups having 6 to 14 ring carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group. Is mentioned.
  • Z is preferably at least one selected from the group consisting of a single bond, an alkylene group having 1 to 3 carbon atoms, and an alkylidene group having 2 to 3 carbon atoms, and is a single bond, methylene group, ethylidene group, or propylidene. It is preferably a group, more preferably a methylene group, an ethylidene group, or a propylidene group.
  • Specific examples of the compound represented by the general formula (3) include bisphenol A [4,4 ′-(propane-2,2-diyl) diphenol], bisphenol F [bis (4-hydroxyphenyl) methane], Bisphenol AP [1,1-bis (4-hydroxyphenyl) -1-phenylethane], bisphenol AF [2,2-bis (4-hydroxyphenyl) hexafluoropropane], bisphenol B [2,2-bis (4 -Hydroxyphenyl) butane], bisphenol BP [bis (4-hydroxyphenyl) diphenylmethane], bisphenol S [bis (4-hydroxyphenyl) sulfone], bisphenol E [1,1-bis (4-hydroxyphenyl) ethane], Styrenated phenol, hydroxybiphenyl, dihydroxybifu Alkylsulfonyl and the like.
  • bisphenol A 4,4 ′-(propane-2,2-diyl) diphenol
  • bisphenol F bis (4-hydroxyphenyl) methane
  • bisphenol E are considered from the viewpoint of solubility in a curing agent.
  • At least one selected from the group consisting of [1,1-bis (4-hydroxyphenyl) ethane] and styrenated phenols is preferred, and bisphenol A [4,4 from the viewpoint of exerting an effect even when the blending amount is small.
  • the styrenated phenol is preferably a 1: 1 adduct of styrene and phenol, and is a compound represented by the following formula (3-1).
  • the main component of the styrenated phenol is preferably a compound represented by the following formula (3-1), but multiple additions such as a 2: 1 adduct of styrene and phenol, a 3: 1 adduct of styrene and phenol, etc.
  • the body may be contained.
  • the “main component” means that the content is 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more (upper limit is 100%) when all the constituents are 100% by mass. Mass%).
  • Examples of commercially available styrenated phenols include “Kumanox-3110”, “Kumanox-3111”, “Kumanox-3114”, “Kumanox-3120”, “Kumanox-SP” manufactured by Kumho Petrochemical, and the like.
  • phenol compounds other than the compound represented by the general formula (3) include phenol, cresol, hydroquinone, 1-naphthol, 2-naphthol, resorcin, phenol novolak resin, p-isopropylphenol, p-tert-butylphenol, nonylphenol, and the like. Is mentioned.
  • Examples of the organic acids used as the curing accelerator include carboxylic acid compounds and sulfonic acid compounds.
  • carboxylic acid compounds include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butanoic acid, 2-ethylhexanoic acid and benzoic acid; hydroxymonocarboxylic acids such as lactic acid and salicylic acid; oxalic acid, malonic acid, maleic acid, And polyvalent carboxylic acids such as itaconic acid, fumaric acid, adipic acid, sebacic acid, isophthalic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid and hexahydrophthalic acid.
  • Examples of the sulfonic acid compounds include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid and the like.
  • organic acids sulfonic acid compounds are preferable, and p-toluenesulfonic acid is more preferable.
  • organic acid salts include salts of the above organic acids.
  • DBU diazabicycloundecene
  • DBN diazabicyclooctane
  • tetraethylammonium salt tetrabutylammonium salt.
  • Examples of the curing accelerator other than the above include tertiary ethylenes such as triethylenediamine, triethanolamine, benzyldimethylamine, dimethylcyclohexylamine, and 2- (dimethylaminomethyl) phenol.
  • Examples of quaternary ammonium salts include tetraethylammonium bromide and tetrabutylammonium bromide.
  • Examples of imidazoles include 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole Etc.
  • Examples of organic phosphorus compounds include triphenylphosphine, diphenylphosphine, tributylphosphine, and triphenyl phosphite.
  • Examples of quaternary phosphonium salts include tetraphenylphosphonium bromide and tetra-n-butylphosphonium bromide.
  • Examples of the diazabicycloalkenes include 1,8-diazabicyclo [5.4.0] undecene-7.
  • Examples of the organic metal salt compound include zinc octylate and tin octylate.
  • Examples of the boron compound include boron trifluoride and triphenyl borate.
  • Examples of the metal halide include zinc chloride and stannic chloride.
  • a hardening accelerator can be used individually by 1 type or in combination of 2 or more types.
  • the content of the curing accelerator in the epoxy resin curing agent is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the addition reaction product.
  • the content of the curing accelerator with respect to 100 parts by mass of the addition reaction product is 1 part by mass or more, an effect of improving curability is obtained.
  • the epoxy resin curing agent and the epoxy resin composition containing the epoxy resin composition do not have high viscosity, and are particularly suitable for CFRP molded by the high cycle RTM method. The mechanical strength and heat resistance are not lowered.
  • the content of the curing accelerator in the epoxy resin curing agent is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, more preferably 15 parts by mass with respect to 100 parts by mass of the addition reaction product. It is 10 parts by mass or less, more preferably 10 parts by mass or less.
  • the epoxy resin curing agent of the present invention may contain a known curing agent other than the addition reaction product, a known additive, a solvent, and the like.
  • the curing agent other than the addition reaction product include polyamine compounds other than the component (A) or modified products thereof.
  • polyamine compound examples include chain aliphatic polyamine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, 2-methylpentamethylenediamine, and trimethylhexamethylenediamine; Sendiamine, isophoronediamine, norbornanediamine, tricyclodecanediamine, adamantanediamine, diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-3,6-diethylcyclohexane, diaminodiethylmethylcyclohexane, 3 , 3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane and the like having an alicyclic structure Aromatic compounds such as phenylenediamine,
  • the content of the addition reaction product is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total amount of the epoxy resin curing agent of the present invention. More preferably, it is 80% by mass or more, more preferably 85% by mass or more, and still more preferably 90% by mass or more (the upper limit is 100% by mass).
  • the epoxy resin curing agent of the present invention has a viscosity at a temperature of 25 ° C. of preferably 10,000 mPa ⁇ s or less, more preferably 8,000 mPa ⁇ s or less, further preferably 5,000 mPa ⁇ s or less, and still more preferably 3, 000 mPa ⁇ s or less, more preferably 2,000 mPa ⁇ s or less, even more preferably 1,000 mPa ⁇ s or less, still more preferably 800 mPa ⁇ s or less, and even more preferably 500 mPa ⁇ s or less.
  • the lower limit of the viscosity of the epoxy resin curing agent at 25 ° C. is not particularly limited, but is preferably 10 mPa ⁇ s or more, more preferably 50 mPa ⁇ s or more, and still more preferably 100 mPas, from the viewpoint of miscibility with the epoxy resin.
  • -It is more than s.
  • the epoxy resin composition of the present invention contains the epoxy resin curing agent of the present invention and an epoxy resin.
  • Any epoxy resin having a glycidyl group that reacts with the active amine hydrogen in the epoxy resin curing agent of the present invention can be used as the epoxy resin, but from the viewpoint of excellent mechanical strength of the cured product.
  • An epoxy resin containing an aromatic ring or alicyclic structure in the molecule is preferred, and an epoxy resin containing an aromatic ring in the molecule is more preferred.
  • an epoxy resin represented by the following general formula (4) is particularly preferred from the viewpoint of low viscosity and ensuring the mechanical strength of the cured product.
  • R 21 to R 24 are each independently an alkyl group having 1 to 6 carbon atoms, and p, q, r, and s are each independently an integer of 0 to 4.) 21 , the plurality of R 22 , the plurality of R 23 , and the plurality of R 24 may be the same or different from each other, and Y 1 and Y 2 are each independently a single bond, —CH 2 —, —CH ( CH 3 ) —, or —C (CH 3 ) 2 —, R 25 is —CH 2 CH (OH) —, or —CH (OH) CH 2 —, m represents the average number of repeating units, It is a number from 0 to 0.2.) R 21 to R 24 are preferably alkyl groups having 1 to 4 carbon atoms, more preferably at least one selected from the group consisting of a methyl group, an ethyl group, an isopropyl group, and a t-butyl group.
  • p, q, r, and s are each preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
  • Y 1 and Y 2 are preferably —CH 2 — or —C (CH 3 ) 2 —, and more preferably —C (CH 3 ) 2 —.
  • m is preferably 0 to 0.15, more preferably 0.01 to 0.1, from the viewpoint of low viscosity and ensuring the mechanical strength of the cured product.
  • the epoxy equivalent of the epoxy resin is preferably 300 g / equivalent or less, more preferably 220 g / equivalent or less, and still more preferably 200 g / equivalent or less, from the viewpoint of achieving both low viscosity and fast curability of the epoxy resin composition. More preferably, it is 180 g / equivalent or less.
  • An epoxy resin may be used individually by 1 type, and may use 2 or more types together.
  • the epoxy resin composition of the present invention further uses other components such as fillers, modifying components such as plasticizers, flow adjusting components such as thixotropic agents, pigments, leveling agents, tackifiers, and elastomer fine particles. You may make it contain according to.
  • the content of the epoxy resin curing agent in the epoxy resin composition of the present invention is the ratio of the number of active amine hydrogens in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin (active amine hydrogen in the epoxy resin curing agent).
  • Number / number of epoxy groups in the epoxy resin) is preferably 1 / 0.8 to 1 / 1.2, more preferably 1 / 0.9 to 1 / 1.1, and still more preferably 1/1. is there.
  • the viscosity at a temperature of 40 ° C. is 5,000 mPa ⁇ s or less, more preferably 2,000 mPa ⁇ s or less, further preferably 1,500 mPa ⁇ s or less, and still more preferably 1, It is 200 mPa ⁇ s or less, more preferably 1,000 mPa ⁇ s or less, still more preferably 800 mPa ⁇ s or less, and still more preferably 750 mPa ⁇ s or less.
  • productivity is improved when used for CFRP.
  • the turbulence in the carbon fiber due to a turbulent flow in the mold due to an increase in the Reynolds number in CFRP molding. From the viewpoint, it is preferably 150 mPa ⁇ s or more, more preferably 300 mPa ⁇ s or more.
  • the gelation time at a temperature of 80 ° C. is preferably 12 minutes or less, more preferably 10 minutes or less, and even more preferably 9.0 minutes or less, from the viewpoint of fast curing. From the viewpoint of workability, the gelation time is preferably 0.5 minutes or more, more preferably 1.0 minutes or more.
  • the gelation time can be measured by a method described in Examples using a rheometer. Specifically, using a rheometer, the storage elastic modulus G ′ and loss elastic modulus G ′′ of the epoxy resin composition are measured at a temperature of 80 ° C., a frequency of 1 Hz, and a distance between plates of 0.5 mm, and G ′ and G ′. The point at which 'intersects is the gel time.
  • the production method of the epoxy resin composition of the present invention is not particularly limited, and can be produced by mixing an epoxy resin curing agent, an epoxy resin, and other components as necessary using a known method and apparatus. There is no restriction
  • the epoxy resin curing agent and the epoxy resin composition containing the epoxy resin curing agent of the present invention are preferably used for fiber-reinforced composite materials because they have the characteristics of being fast-curing and having a low viscosity. It is preferable for a composite material.
  • a fiber reinforced composite material includes a cured product of the epoxy resin composition and reinforcing fibers, and after impregnating the epoxy resin composition with reinforcing fibers, the composition is cured. Obtainable.
  • the FRP may further contain a foam material in addition to the cured product of the epoxy resin composition and the reinforcing fiber. Examples of the reinforcing fiber include glass fiber, carbon fiber, boron fiber, and metal fiber.
  • Reinforcing fibers may be used alone or in combination of two or more.
  • carbon fiber is preferable from the viewpoint of the strength and light weight of the composite material to be obtained.
  • a foam material the foam material comprised from resin materials, such as a polyvinyl chloride resin, a polyurethane resin, a polystyrene resin, polyolefin resin, an acrylic resin, a phenol resin, a polymethacrylimide resin, an epoxy resin, is mentioned It is done.
  • the carbon fiber reinforced composite material including the cured product of the epoxy resin composition and carbon fibers will be described.
  • the carbon fiber reinforced composite material (CFRP) of the present invention includes a cured product of the epoxy resin composition and carbon fibers. After impregnating the epoxy resin composition into carbon fibers, the composition is It can be obtained by curing. In addition to the cured product of the epoxy resin composition and the carbon fiber, the CFRP may further contain a reinforcing fiber other than the carbon fiber and the foamed material.
  • the carbon fiber used in the CFRP of the present invention may be manufactured using rayon, polyacrylonitrile (PAN) or the like as a raw material, or manufactured by spinning a pitch such as petroleum or coal as a raw material. Also good.
  • Examples of the form of the carbon fiber include various forms such as monofilaments or multifilaments arranged so as to cross one direction or alternately, a fabric such as a knitted fabric, a nonwoven fabric, or a mat. Of these, monofilaments, fabrics, non-woven fabrics or mats are preferred, and fabrics are more preferred.
  • a recycled product obtained by reusing carbon fiber scraps, or a recycled product obtained by removing resin from CFRP can be used.
  • the average fiber diameter of the carbon fibers is preferably 1 to 100 ⁇ m, more preferably 3 to 50 ⁇ m, and even more preferably 4 to 20 ⁇ m. When the average fiber diameter is within this range, processing is easy and the resulting CFRP has excellent elastic modulus and strength.
  • the average fiber diameter can be measured by observation with a scanning electron microscope (SEM) or the like. More than 50 fibers can be selected at random, the length can be measured, and the average fiber diameter of the number average can be calculated.
  • the fineness of the carbon fiber is preferably 20 to 4,500 tex, more preferably 50 to 4,000 tex. When the fineness is within this range, the epoxy resin composition can be easily impregnated, and the resulting composite material has excellent elastic modulus and strength.
  • the fineness can be obtained by obtaining the weight of long fibers having an arbitrary length and converting it to the weight per 1,000 m. Usually, carbon fibers having a filament number of about 500 to 60,000 can be preferably used.
  • the method for producing the carbon fiber reinforced composite material of the present invention includes a low pressure RTM method, a medium pressure RTM method, a high pressure RTM method, a compression RTM method, a liquid compression molding method, a liquid laydown method, a spray laydown method, and a surface RTM method. It is preferable to have a step of molding by a prepreg compression molding method or a liquid cast molding method.
  • the medium pressure RTM method or the high pressure RTM method is more preferable, and from the viewpoint of molding speed. Is more preferably the high pressure RTM method.
  • low pressure in the low pressure RTM method means that the pressure at the time of pumping and mixing the epoxy resin that is the main component of the epoxy resin composition and the epoxy resin curing agent is less than 0.5 MPa. It means that.
  • intermediate pressure in the medium pressure RTM method means that the pressure is 0.5 MPa or more and less than 7 MPa
  • high pressure in the high pressure RTM method means that the pressure is 7 MPa or more and 20 MPa or less.
  • the epoxy resin composition is fast-curing and has a low viscosity, filling into the mold and impregnation into the carbon fiber is fast and cures quickly, so that the molding time can be greatly shortened. Therefore, the epoxy resin curing agent and the epoxy resin composition of the present invention are particularly suitable for the molding method. In addition, by using the above molding method, it is possible to produce medium to large CFRP for automobile structural materials and building materials with high productivity by applying the epoxy resin curing agent and the epoxy resin composition of the present invention. .
  • a collision mixing mixer as an apparatus for mixing an epoxy resin, which is the main component of the epoxy resin composition, and an epoxy resin curing agent.
  • an epoxy resin which is the main component of the epoxy resin composition
  • an epoxy resin curing agent For example, carbon fibers are placed in a pair of upper and lower molds and sealed, and the inside of the mold is decompressed.
  • the epoxy resin, which is the main component of the epoxy resin composition, and the epoxy resin curing agent are filled in separate tanks, each of which is discharged from a very small hole (orifice) at high speed, and inside the mixing chamber of the collision mixing mixer. Crash mixing.
  • the epoxy resin composition thus prepared is injected into the mold at high pressure to impregnate the carbon fiber, and then the epoxy resin is cured.
  • a dynamic mixer as an apparatus for mixing an epoxy resin that is a main component of the epoxy resin composition and an epoxy resin curing agent.
  • the dynamic mixer includes a cylindrical high-speed rotating body having irregularities on the surface.
  • the epoxy resin that is the main ingredient of the epoxy resin composition and the epoxy resin curing agent are filled in separate tanks, each of which is fed to a dynamic mixer, and the two liquids of the main ingredient and the curing agent are mixed by the rotating body. .
  • the epoxy resin composition thus prepared is poured into a mold and impregnated in carbon fibers, and then the epoxy resin is cured.
  • the low-pressure RTM method is advantageous when the blending ratio of the epoxy resin and the epoxy resin curing agent is greatly different, or from the viewpoint of equipment cost and space saving of the equipment.
  • a static mixer is a tubular reactor incorporating one or more static mixers composed of a large number of mixing elements.
  • the epoxy resin that is the main component of the epoxy resin composition and the epoxy resin curing agent are filled in separate tanks, and each is sent to a static mixer.
  • the epoxy resin composition thus prepared is poured into a mold and impregnated in carbon fibers, and then the epoxy resin is cured.
  • the medium pressure RTM method is advantageous from the viewpoints of being able to pump the epoxy resin composition into the mold and apparatus cost.
  • the CFRP further includes a foam material in addition to the cured product of the epoxy resin composition and the carbon fiber
  • the carbon fiber and the foam material may be disposed in the mold and the CFRP may be manufactured in the same manner as described above. it can.
  • the epoxy resin curing agent and the epoxy resin composition of the present invention can also be suitably used for the liquid compression molding (LCM) method and the liquid laydown method.
  • LCM liquid compression molding
  • an epoxy resin composition is cast and impregnated on carbon fiber (on the carbon fiber and foam material when CFRP further includes a foam material), and then heated and compressed to form an epoxy resin. Is cured.
  • the temperature at which the epoxy resin composition is injected into the mold or impregnated into the carbon fiber is preferably 30 to 120 ° C., more preferably 50 to 100 ° C.
  • the temperature at the time of mixing the epoxy resin curing agent and the epoxy resin can also be set individually.
  • the temperature at the time of mixing the epoxy resin curing agent is preferably 5 to 30 ° C., more preferably 10 to 25 ° C. from the viewpoint of suppressing an increase in viscosity.
  • the temperature at the time of mixing the epoxy resin can be appropriately adjusted according to the viscosity of the epoxy resin, but is preferably 30 to 120 ° C, more preferably 50 to 100 ° C.
  • the impregnation time of the epoxy resin composition into the carbon fiber is preferably 0.1 to 15 minutes, more preferably 0.2 to 10 minutes, and further preferably 0.5 to 5 minutes from the viewpoint of moldability and productivity. It is.
  • the curing temperature of the epoxy resin composition is preferably 50 to 200 ° C, more preferably 80 to 150 ° C, and still more preferably 100 to 150 ° C.
  • the curing time of the epoxy resin composition is preferably 0.1 to 15 minutes, more preferably 0.2 to 10 minutes, and further preferably 0.5 to 5 minutes from the viewpoint of moldability and productivity.
  • CFRP can be produced with high productivity by the above molding method.
  • the carbon fiber reinforced composite material of the present invention is preferably an automotive structural material or a building material, particularly an automotive structural material.
  • Automotive structural materials include bumpers, spoilers, cowlings, front grilles, garnishes, bonnets, trunk lids, fender panels, door panels, roof panels, instrument panels, door trims, quarter trims, roof linings, pillar garnishes, deck trims, tonneau boards.
  • viscosity The viscosity of the epoxy resin curing agent and the epoxy resin composition was measured using an E type viscometer “TVE-22H type viscometer cone plate type” (manufactured by Toki Sangyo Co., Ltd.). The epoxy resin curing agent was measured at 25 ° C., and the epoxy resin composition was measured at 40 ° C. The lower the viscosity, the higher the filling property during molding and the better the molding property.
  • R 15 is —CH 2 CH (OH) — or —CH (OH) CH 2 —.
  • the addition reaction product obtained as described above was used as an epoxy resin curing agent.
  • This epoxy resin curing agent and the main agent bisphenol A type liquid epoxy resin ("jER825", manufactured by Mitsubishi Chemical Corporation), the number of active amine hydrogens in the epoxy resin curing agent, and the epoxy resin epoxy as the main agent
  • the epoxy resin composition was prepared by blending and mixing so that the number of radicals was equimolar.
  • curing agent and epoxy resin composition it evaluated by the above-mentioned method. The results are shown in Table 1.
  • R 25 represents —CH 2 CH (OH) — or —CH (OH) CH 2 —.
  • Example 2 10 g of bisphenol A (4,4 ′-(propane-2,2-diyl) diphenol, manufactured by Kanto Chemical Co., Inc.) as a curing accelerator was added to 100 g of the addition reaction product obtained in Example 1 above. And mixed to obtain an epoxy resin curing agent.
  • This epoxy resin curing agent and the main agent bisphenol A type liquid epoxy resin ("jER825", manufactured by Mitsubishi Chemical Corporation), the number of active amine hydrogen of the epoxy resin curing agent and the epoxy in the epoxy resin as the main agent
  • the epoxy resin composition was prepared by blending and mixing so that the number of radicals was equimolar. About the obtained epoxy resin hardening
  • Example 1 an addition reaction product was obtained in the same manner as in Example 1 except that the amount (addition amount) of jER828 as compound (B) was changed as shown in Table 1. Moreover, the epoxy resin composition was prepared by the same method as Example 1 using this addition reaction thing as an epoxy resin hardening
  • Example 5 In Example 1, addition was performed in the same manner as in Example 1 except that metaxylylenediamine (MXDA, manufactured by Mitsubishi Gas Chemical Co., Inc.) was used instead of 1,3-BAC as the amine compound (A). A reaction product was obtained. Moreover, the epoxy resin composition was prepared by the same method as Example 1 using this addition reaction thing as an epoxy resin hardening
  • MXDA metaxylylenediamine
  • Example 1 the above-described bisphenol A type liquid epoxy resin “jER825” (manufactured by Mitsubishi Chemical Corporation) was used as the compound (B) instead of jER828, and the amount used (addition amount) thereof was as shown in Table 1. Except that, an addition reaction product was obtained in the same manner as in Example 1. Moreover, the epoxy resin composition was prepared by the same method as Example 1 using this addition reaction thing as an epoxy resin hardening
  • Example 8 To 100 g of the addition reaction product obtained in Example 6, 3 g of p-toluenesulfonic acid monohydrate was blended and mixed as a curing accelerator to obtain an epoxy resin curing agent.
  • the epoxy resin composition was prepared by blending and mixing so that the number of epoxy groups was equimolar. About the obtained epoxy resin hardening
  • Example 1 an addition reaction product was obtained in the same manner as in Example 1 except that the amount (addition amount) of jER828 as compound (B) was changed as shown in Table 1. Moreover, the epoxy resin composition was prepared by the same method as Example 1 using this addition reaction thing as an epoxy resin hardening
  • Table 1 shows that the epoxy resin curing agent and the epoxy resin composition of the present invention are fast-curing and have a relatively low viscosity. Therefore, it is suitable for manufacturing various molded articles using a molding method such as a high cycle RTM method. On the other hand, it was difficult for the epoxy resin curing agents and epoxy resin compositions of Comparative Examples 1 to 4 to achieve both fast curability and low viscosity.
  • an epoxy resin curing agent and an epoxy resin composition that are fast-curing and low-viscosity capable of producing CFRP such as automobile structural materials and building materials with high productivity by a high cycle RTM method or the like. it can.
  • the epoxy resin composition is used as a CFRP matrix resin, it has excellent carbon fiber impregnation properties and is fast-curing, so that it takes only a short time to release from the mold, and CFRP production. Can be improved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Reinforced Plastic Materials (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Moulding By Coating Moulds (AREA)

Abstract

L'invention concerne : un agent durcisseur de résine époxy contenant un produit de réaction d'addition obtenu lorsque plus de 0,100 mole et moins de 0,200 mole d'un composé (B) est amené à réagir avec 1 mole d'un composé amine (A) représenté par la formule générale (1), ledit composé (B) ayant au moins un groupe époxy par molécule ; une composition de résine époxy comprenant ce dernier ; et un matériau composite renforcé par des fibres de carbone comprenant un produit durci de ladite composition de résine époxy et des fibres de carbone. H2N-H2C-A-CH2-NH2 (1) (Dans la formule (1), A représente un groupe cyclohexylène ou un groupe phénylène.)
PCT/JP2017/010411 2016-04-12 2017-03-15 Agent durcisseur de résine époxy, composition de résine époxy et matériau composite renforcé par des fibres de carbone Ceased WO2017179359A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2018511938A JP7074053B2 (ja) 2016-04-12 2017-03-15 エポキシ樹脂硬化剤、エポキシ樹脂組成物、炭素繊維強化複合材
CN201780021820.0A CN108884211B (zh) 2016-04-12 2017-03-15 环氧树脂固化剂、环氧树脂组合物、碳纤维增强复合材料

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-079549 2016-04-12
JP2016079549 2016-04-12

Publications (1)

Publication Number Publication Date
WO2017179359A1 true WO2017179359A1 (fr) 2017-10-19

Family

ID=60041710

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/010411 Ceased WO2017179359A1 (fr) 2016-04-12 2017-03-15 Agent durcisseur de résine époxy, composition de résine époxy et matériau composite renforcé par des fibres de carbone

Country Status (4)

Country Link
JP (1) JP7074053B2 (fr)
CN (1) CN108884211B (fr)
TW (1) TWI729088B (fr)
WO (1) WO2017179359A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021029170A1 (fr) * 2019-08-14 2021-02-18 三菱瓦斯化学株式会社 Composition de résine époxy, film barrière aux gaz et stratifié
WO2025063171A1 (fr) * 2023-09-19 2025-03-27 旭化成株式会社 Composition de résine époxy, matériau d'étanchéité, matériau d'étanchéité de semi-conducteur, adhésif, module de caméra, boîtier de semi-conducteur et appareil électronique

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120682597A (zh) * 2019-03-06 2025-09-23 三菱瓦斯化学株式会社 环氧树脂组合物和其固化物、以及纤维增强复合材料

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4999198A (fr) * 1973-01-18 1974-09-19
JPH05310890A (ja) * 1992-05-12 1993-11-22 Mitsubishi Rayon Co Ltd エポキシ樹脂組成物及びそれからの複合材料用プリプレグ
JPH083282A (ja) * 1994-06-22 1996-01-09 Mitsubishi Gas Chem Co Inc エポキシ樹脂硬化剤
JP2006070125A (ja) * 2004-09-01 2006-03-16 Asahi Denka Kogyo Kk エポキシ樹脂用硬化剤組成物
JP2007186693A (ja) * 2005-12-16 2007-07-26 Mitsubishi Gas Chem Co Inc エポキシ樹脂用硬化剤組成物及びエポキシ樹脂組成物
WO2013081895A2 (fr) * 2011-12-01 2013-06-06 Dow Global Tecnologies LLC Composition d'accélérateur liquide pour durcisseurs

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4859081B2 (ja) * 2000-04-21 2012-01-18 三菱レイヨン株式会社 複合材料の製造方法
US8431653B2 (en) * 2005-12-16 2013-04-30 Mitsubishi Electric Company, Inc. Curing agent composition for epoxy resins and epoxy resin composition
KR20150020532A (ko) * 2012-05-16 2015-02-26 주식회사 다이셀 경화성 수지 조성물 및 그의 경화물, 프리프레그, 및 섬유 강화 복합 재료
CN103214792B (zh) * 2013-04-11 2015-12-02 奇瑞汽车股份有限公司 一种碳纤维/环氧树脂复合材料及其制备方法
JP6452335B2 (ja) * 2013-08-09 2019-01-16 日鉄ケミカル＆マテリアル株式会社 エポキシ樹脂組成物及びその硬化物
JP6648438B2 (ja) * 2014-08-27 2020-02-14 Jnc株式会社 液晶性化合物、液晶組成物およびその重合体

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4999198A (fr) * 1973-01-18 1974-09-19
JPH05310890A (ja) * 1992-05-12 1993-11-22 Mitsubishi Rayon Co Ltd エポキシ樹脂組成物及びそれからの複合材料用プリプレグ
JPH083282A (ja) * 1994-06-22 1996-01-09 Mitsubishi Gas Chem Co Inc エポキシ樹脂硬化剤
JP2006070125A (ja) * 2004-09-01 2006-03-16 Asahi Denka Kogyo Kk エポキシ樹脂用硬化剤組成物
JP2007186693A (ja) * 2005-12-16 2007-07-26 Mitsubishi Gas Chem Co Inc エポキシ樹脂用硬化剤組成物及びエポキシ樹脂組成物
WO2013081895A2 (fr) * 2011-12-01 2013-06-06 Dow Global Tecnologies LLC Composition d'accélérateur liquide pour durcisseurs

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021029170A1 (fr) * 2019-08-14 2021-02-18 三菱瓦斯化学株式会社 Composition de résine époxy, film barrière aux gaz et stratifié
JPWO2021029170A1 (ja) * 2019-08-14 2021-09-13 三菱瓦斯化学株式会社 エポキシ樹脂組成物、ガスバリア性フィルム及び積層体
US12281195B2 (en) 2019-08-14 2025-04-22 Mitsubishi Gas Chemical Company, Inc. Epoxy resin composition, gas barrier film, and laminate
WO2025063171A1 (fr) * 2023-09-19 2025-03-27 旭化成株式会社 Composition de résine époxy, matériau d'étanchéité, matériau d'étanchéité de semi-conducteur, adhésif, module de caméra, boîtier de semi-conducteur et appareil électronique

Also Published As

Publication number Publication date
JPWO2017179359A1 (ja) 2019-02-21
TW201736427A (zh) 2017-10-16
CN108884211A (zh) 2018-11-23
JP7074053B2 (ja) 2022-05-24
CN108884211B (zh) 2021-04-06
TWI729088B (zh) 2021-06-01

Similar Documents

Publication Publication Date Title
JP6256666B1 (ja) エポキシ樹脂硬化剤、エポキシ樹脂組成物、炭素繊維強化複合材
EP1266921B1 (fr) Composition de r sine poxy pour mati re composite renforc e par des fibres
TWI649372B (zh) 纖維強化複合材料
KR20140041718A (ko) 경화성 수지 조성물 및 그것을 사용한 경화물의 제조 방법
CN111434704A (zh) 用于环氧配制剂的单烷基化二胺：用于环氧体系的新固化剂
JP7322709B2 (ja) エポキシ樹脂硬化剤、エポキシ樹脂組成物及びその硬化物、並びに繊維強化複合材
JP7074053B2 (ja) エポキシ樹脂硬化剤、エポキシ樹脂組成物、炭素繊維強化複合材
JP6878944B2 (ja) エポキシ樹脂硬化剤、エポキシ樹脂組成物、繊維強化複合材
AU2019233463B2 (en) Epoxy resin composition, prepreg, fiber-reinforced composite material, and production methods therefor
JP7459861B2 (ja) エポキシ樹脂組成物及びその硬化物、並びに繊維強化複合材
JP2017505367A (ja) 速硬化性で高ガラス転移温度のエポキシ樹脂系
WO2020246144A1 (fr) Agent de durcissement de résine époxy, composition de résine époxy et produit durci de celui-ci, et matériau composite renforcé par des fibres
JP7072465B2 (ja) エポキシ化合物、エポキシ樹脂、エポキシ樹脂組成物、樹脂硬化物、プリプレグ、繊維強化複合材料、及びこれらの製造方法
JP7334484B2 (ja) エポキシ樹脂硬化剤、エポキシ樹脂組成物及びその硬化物、並びに繊維強化複合材
JP7072466B2 (ja) エポキシ化合物、エポキシ樹脂、エポキシ樹脂組成物、樹脂硬化物、プリプレグ、繊維強化複合材料、及びこれらの製造方法
JP2003238658A (ja) 繊維強化複合材料用エポキシ樹脂組成物および繊維強化複合材料の製造方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018511938

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17782177

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 17782177

Country of ref document: EP

Kind code of ref document: A1