WO2019111607A1 - Epoxy resin curing agent, epoxy resin composition and cured product of same, and fiber-reinforced composite material - Google Patents

Epoxy resin curing agent, epoxy resin composition and cured product of same, and fiber-reinforced composite material Download PDF

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Publication number
WO2019111607A1
WO2019111607A1 PCT/JP2018/040831 JP2018040831W WO2019111607A1 WO 2019111607 A1 WO2019111607 A1 WO 2019111607A1 JP 2018040831 W JP2018040831 W JP 2018040831W WO 2019111607 A1 WO2019111607 A1 WO 2019111607A1
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WO
WIPO (PCT)
Prior art keywords
epoxy resin
curing agent
resin composition
fiber
resin curing
Prior art date
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PCT/JP2018/040831
Other languages
French (fr)
Japanese (ja)
Inventor
唯我 浅井
孝介 池内
Original Assignee
三菱瓦斯化学株式会社
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Publication date
Application filed by 三菱瓦斯化学株式会社 filed Critical 三菱瓦斯化学株式会社
Priority to CN201880073511.2A priority Critical patent/CN111417667B/en
Priority to JP2019558078A priority patent/JP7322709B2/en
Publication of WO2019111607A1 publication Critical patent/WO2019111607A1/en

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Classifications

    • 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
    • C08G59/40—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
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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

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 thereof, and a fiber-reinforced composite comprising a cured product of the epoxy resin composition and a reinforcing fiber. It relates to the material.
  • CFRP Carbon Fiber Reinforced Plastics
  • CFRP since the molding method of CFRP is different in automobile structural material application, wind power generation blade application, pressure vessel application, and aerospace application, the required characteristics for the matrix resin for CFRP also differ depending on the application.
  • wind power generation blades have come to be molded by injection molding, vacuum assisted resin transfer molding (Va-RTM) or light-RTM.
  • Va-RTM vacuum assisted resin transfer molding
  • reinforcing fibers are arranged in advance in a mold consisting of an upper mold and a lower mold using a film or FRP, and the inside of the mold is evacuated to form an epoxy resin composition as a matrix resin. It is filled at normal pressure to impregnate into reinforcing fibers and then the epoxy resin is cured and shaped.
  • an epoxy resin composition in which an epoxy resin and an epoxy resin curing agent are mixed is usually filled into a mold due to the characteristics of the molding method. It takes several tens of minutes. Therefore, it is required that the epoxy resin composition used in these molding methods 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 in which a reinforcing fiber yarn is impregnated 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 automobile structural materials is molded by the high cycle RTM method.
  • the conventional RTM method is one of closed mold molding using a pair of upper and lower molds, a fiber reinforced preform is disposed in the mold, and after clamping and sealing the mold, epoxy resin is injected from the injection hole A resin such as a composition is injected 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), and therefore, in the production of CFRP for automotive structural material applications, a higher productivity high cycle is achieved.
  • the RTM method is used.
  • the molding technology by the high cycle RTM method significantly reduced all of the placement time of the fiber reinforced preform, the impregnation time of the resin, the curing time of the resin, and the mold release time, and reduced the total molding time to about 10 minutes. It is a thing.
  • the high cycle RTM method in the process from resin impregnation to curing, for example, in the high pressure RTM method, which is a type of high cycle RTM method, reinforcing fibers are placed in a pair of upper and lower molds and sealed to seal the inside of the molds. Reduce pressure.
  • the epoxy resin which is the main component of the epoxy resin composition
  • the epoxy resin curing agent are pumped from separate tanks to the mixing head in the form of mist and injected immediately into the mold after collision mixing to impregnate the carbon fiber. And cure the epoxy resin.
  • the epoxy resin composition is injected at 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.
  • AEP N-aminoethyl piperazine
  • IPDA isophorone diamine
  • An object of the present invention is to provide a pot life of an epoxy resin composition obtained which contains N-aminoethyl piperazine and / or isophorone diamine which is widely used as an epoxy resin curing agent component, which is rapidly curable and has a low viscosity.
  • An epoxy resin curing agent capable of improving the heat resistance of a cured product, an epoxy resin composition containing the same and a cured product thereof, and a fiber reinforced composite material comprising the cured product of the epoxy resin composition and reinforcing fibers It is.
  • an epoxy resin curing agent containing at least one compound selected from the group consisting of N-aminoethyl piperazine and isophorone diamine and bis (aminomethyl) cyclohexane Found that the above problems can be solved.
  • the present invention relates to the following [1] to [9].
  • An epoxy resin curing agent containing at least one compound (A) selected from the group consisting of N-aminoethyl piperazine and isophorone diamine and bis (aminomethyl) cyclohexane (B).
  • A selected from the group consisting of N-aminoethyl piperazine and isophorone diamine and bis (aminomethyl) cyclohexane
  • B bis (aminomethyl) cyclohexane
  • the epoxy resin cured as described in the above [1], wherein the mass ratio of the (A) component to the (B) component satisfies 0.575 ⁇ (A) / [(A) + (B)] ⁇ 1.
  • Agent [3] The epoxy resin curing agent according to the above [1] or [2], wherein the component (A) is N-aminoethyl piperazine.
  • the epoxy resin curing agent of the present invention comprises at least one compound (A) selected from the group consisting of N-aminoethyl piperazine (AEP) and isophorone diamine (IPDA), and bis (aminomethyl) cyclohexane (B) contains.
  • AEP N-aminoethyl piperazine
  • IPDA isophorone diamine
  • B bis (aminomethyl) cyclohexane
  • the present invention improves various characteristics derived from AEP and IPDA by blending bis (aminomethyl) cyclohexane in an epoxy resin curing agent containing AEP and IPDA which are widely used as an epoxy resin curing agent component, It has been found that the rapid curing property, low viscosity and long pot life of the obtained epoxy resin composition can be achieved, and the heat resistance of the cured product can be improved.
  • the epoxy resin curing agent of the present invention contains, as component (A), at least one compound selected from the group consisting of N-aminoethyl piperazine (AEP) and isophorone diamine (IPDA). These compounds are widely used as epoxy resin curing agent components and are excellent in economy.
  • AEP has the advantages of rapid curing and low viscosity, and improved toughness of the cured product of the resulting epoxy resin composition.
  • IPDA also has the advantage that the pot life of the resulting epoxy resin composition is extended and the heat resistance of the cured product is increased.
  • At least one compound selected from the group consisting of AEP and IPDA can be appropriately selected as the component (A) used in the present invention, according to the desired performance and application.
  • AEP and IPDA are used in combination, the content ratio thereof is not particularly limited.
  • AEP and IPDA may be used at a mass ratio of 1/99 to 99/1, preferably 5/95 to 95/5.
  • the component (A) is N-aminoethyl piperazine or N-amino ethyl piperazine and isophorone from the viewpoint of rapid curing and low viscosity. It is preferably a mixture of diamines, more preferably N-aminoethyl piperazine.
  • the epoxy resin curing agent of the present invention contains a predetermined amount of bis (aminomethyl) cyclohexane as the component (B).
  • the epoxy resin composition containing the epoxy resin curing agent containing the said (A) component rapid curability, low viscosity, long pot life can be achieved, and the heat resistance of the cured product can also be improved.
  • methyl) cyclohexane include 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane and 1,4-bis (aminomethyl) cyclohexane, and one of these may be used alone. Or two or more kinds can be used in combination.
  • 1,3-bis (aminomethyl) cyclohexane is preferable.
  • Bis (aminomethyl) cyclohexane may be in cis form, trans form or a mixture thereof.
  • the molar ratio of cis form / trans form is preferably 5/95 to 95/5, more preferably 10/90 to 90/10. .
  • the epoxy resin curing agent of the present invention preferably satisfies a mass ratio of component (A) to component (B) of 0.575 ⁇ (A) / [(A) + (B)] ⁇ 1.
  • a mass ratio of component (A) to component (B) 0.575 ⁇ (A) / [(A) + (B)] ⁇ 1.
  • the mass ratio (A) / [(A) + (B)] is 1, ie, the component (B) is not contained, the rapid curing property, low viscosity, long pot life or cured product of the resulting epoxy resin composition
  • One of the high heat resistance of can not be achieved.
  • the mass ratio (A) / [(A) + (B)] exceeds 0.575, the proportion of AEP or IPDA in the epoxy resin curing agent is high, which is excellent in economics.
  • various properties derived from AEP or IPDA can be easily expressed.
  • the mass ratio (A) / [(A) + (A) of the epoxy resin curing agent of the present invention is obtained.
  • B) is preferably 0.95 or less, more preferably 0.90 or less, still more preferably 0.85 or less, and from the viewpoint of expressing various properties derived from AEP or IPDA, more preferably 0. 60 or more, more preferably 0.65 or more, still more preferably 0.70 or more, and still more preferably 0.75 or more.
  • the epoxy resin curing agent of the present invention may contain a known curing agent other than the component (A) and the component (B), a known curing accelerator, an additive, a solvent, and the like.
  • curing agents other than the components (A) and (B) include polyamine compounds having two or more amino groups in the molecule other than the components (A) and (B), or modified products thereof.
  • polyamine compound examples include linear aliphatic polyamine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, 2-methylpentamethylenediamine and trimethylhexamethylenediamine; o Aromatic ring-containing aliphatic polyamine compounds such as xylylenediamine, m-xylylenediamine, p-xylylenediamine; mensene diamine, norbornane diamine, tricyclodecane diamine, adamantane diamine, diaminocyclohexane, 1,4-diamino- 2-Methylcyclohexane, 1,4-diamino-3,6-diethylcyclohexane, diaminodiethylmethylcyclohexane, 3,3'-dimethyl-4,4'-diaminodi Polyamine compounds
  • the content thereof is preferably 50% by mass or less, more preferably 30% by mass, based on the total amount of the epoxy resin curing agent of the present invention, from the viewpoint of efficiently expressing the effects of the present invention.
  • the following content is more preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably 10% by mass or less, still more preferably 5% by mass or less, still more preferably 1% by mass or less.
  • a minimum is 0 mass%.
  • curing accelerators examples include phenol compounds such as bisphenol A and styrenated phenol and salts thereof; sulfonic acid compounds such as p-toluenesulfonic acid and methanesulfonic acid and salts or esters thereof; salicylic acid and benzoic acid Carboxylic acid compounds and salts thereof; mercaptan-terminated polysulfide compounds; guanidine compounds; alkanolamine compounds and the like. These can be used singly or in combination of two or more.
  • the content thereof is preferably 50% by mass or less, more preferably 30% by mass, based on the total amount of the epoxy resin curing agent of the present invention, from the viewpoint of efficiently expressing the effects of the present invention. % Or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably 10% by mass or less, still more preferably 5% by mass or less, still more preferably 1% by mass or less, still more preferably Is 0.5 mass% or less. Moreover, a minimum is 0 mass%.
  • the content of the curing accelerator in the epoxy resin curing agent may be in the above range, and the concentration of the curing accelerator may be appropriately varied during preparation or use of the epoxy resin curing agent.
  • the compounding ratio of the curing accelerator to the epoxy resin curing agent may be constant during molding of the epoxy resin composition containing the curing agent, or the curing accelerator is supplied while forming a concentration gradient during molding. For example, it may be varied.
  • the total content of the components (A) and (B) is preferably 50% by mass or more based on the total amount of the epoxy resin curing agent of the present invention. More preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 85% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, particularly preferably 99% by mass or more (The upper limit is 100% by mass).
  • the epoxy resin curing agent of the present invention preferably has a viscosity at a temperature of 25 ° C. of 150 mPa ⁇ s or less, more preferably 100 mPa ⁇ s or less, still more preferably 60 mPa ⁇ s or less.
  • the lower limit value of the viscosity of the epoxy resin curing agent at a temperature of 25 ° C. is not particularly limited, but is preferably 10 mPa ⁇ s or more from the viewpoint of miscibility with the epoxy resin.
  • the viscosity of the epoxy resin curing agent can be measured using an E-type viscometer.
  • a use apparatus the kind of compounding components, a mixture ratio, etc., it can select suitably.
  • component (A), component (B) and, if necessary, other compounding components may be brought into contact simultaneously and mixed, or some components constituting the epoxy resin curing agent may be supplied while giving a concentration gradient. , May be mixed.
  • each component contained in the epoxy resin curing agent and the epoxy resin may be simultaneously mixed and prepared. From the viewpoint of preventing gelation from progressing before use, it is preferable that the components contained in the epoxy resin curing agent be brought into contact and mixed immediately before use.
  • the temperature at which each component contained in the epoxy resin curing agent is mixed is preferably 5 to 30 ° C., more preferably 10 to 25 ° C., from the viewpoint of suppressing the increase in viscosity. It is.
  • the mixing time is preferably in the range of 0.1 to 15 minutes, more preferably 0.2 to 10 minutes, and still more preferably 0.5 to 5 minutes.
  • the epoxy resin composition of the present invention contains the epoxy resin curing agent of the present invention and an epoxy resin.
  • the epoxy resin any epoxy resin having a glycidyl group that reacts with active amine hydrogen in the epoxy resin curing agent of the present invention can be used, but from the viewpoint of excellent mechanical strength of the cured product
  • an epoxy resin containing an aromatic ring or an alicyclic structure in the molecule more preferably at least one member selected from the group consisting of bisphenol A epoxy resin and bisphenol F epoxy resin, and bisphenol A epoxy resin Is more preferred.
  • an epoxy resin represented by the following general formula (1) is particularly preferable in view of low viscosity and sufficient mechanical strength of a cured product.
  • R 11 to R 14 each independently represent an alkyl group having 1 to 6 carbon atoms, and p, q, r, and s each independently represent an integer of 0 to 4.
  • a plurality of R 12 , a plurality of R 13 and a plurality of R 14 may be all the same as or different from each other Y 1 and Y 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 —
  • m represents the average number of repeating units, It is a number between 0 and 0.2.
  • R 11 to R 14 are preferably an alkyl group having 1 to 4 carbon atoms, and at least one selected from the group consisting of a methyl group, an ethyl group, an isopropyl group and a t-butyl group is more preferable.
  • Each of p, q, r and s is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably all 0s.
  • Y 1 and Y 2 are preferably —CH 2 — or —C (CH 3 ) 2 —, more preferably —C (CH 3 ) 2 —.
  • m is preferably 0 to 0.15, and more preferably 0.01 to 0.1.
  • the epoxy equivalent of the epoxy resin is preferably 300 g / equivalent or less, more preferably 220 g / equivalent or less, still more preferably 200 g / equivalent or less, from the viewpoint of achieving both the low viscosity and fast curing of the epoxy resin composition. Still 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 control components such as thixotropic agents, pigments, leveling agents, tackifiers, and fine particles of elastomers. 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 / the 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, further preferably 1/1. is there.
  • the ratio may finally be in the above range, and may be constant during molding of the epoxy resin composition or may be varied during molding.
  • the viscosity at a temperature of 40 ° C. of the epoxy resin composition of the present invention is preferably 400 mPa ⁇ s or less, more preferably 350 mPa ⁇ s or less, and still more preferably 300 mPa ⁇ s or less.
  • productivity is improved when used for FRP applications.
  • the viscosity of the epoxy resin composition can be measured using an E-type viscometer, specifically by the method described in the examples.
  • the epoxy resin composition of the present invention preferably has a gelation time at a temperature of 80 ° C. of 30 minutes or less, more preferably 25 minutes or less, still more preferably 20 minutes or less, still more preferably 15 from the viewpoint of rapid curing. It is less than a minute.
  • the gelation time is preferably 0.5 minutes or more, more preferably 1.0 minutes or more.
  • the gelation time at a temperature of 120 ° C. is preferably 10 minutes or less, more preferably 8.0 minutes or less, still more preferably 5.0 minutes or less, and still more preferably 3.0 minutes or less. Further, from the viewpoint of workability, the gelation time is preferably 0.2 minutes or more, more preferably 0.5 minutes or more.
  • the gelation time can be measured using a rheometer by the method described in the examples. Specifically, storage modulus G ′ and loss modulus G ′ ′ of the epoxy resin composition are measured at a temperature of 80 ° C. (or 120 ° C.), a frequency of 1 Hz, and a plate distance of 0.5 mm using a rheometer The point at which G ′ and G ′ ′ intersect is the gelation time.
  • curing agent, an epoxy resin, and the other component as needed can be mixed and manufactured using a well-known method and apparatus.
  • the temperature at the time of mixing each component contained in an epoxy resin composition can be suitably adjusted according to the viscosity of an epoxy resin, from a viewpoint of suppressing a viscosity rise, Preferably it is 120 degrees C or less, More preferably, it is 100 degrees C or less It is preferably 30 ° C. or more, more preferably 50 ° C. or more from the viewpoint of the miscibility of the epoxy resin.
  • the mixing time is preferably in the range of 0.1 to 15 minutes, more preferably 0.2 to 10 minutes, and still more preferably 0.5 to 5 minutes.
  • molding methods mentioned later, for example can be used.
  • the cured product of the epoxy resin composition of the present invention (hereinafter, also simply referred to as "the cured product of the present invention") is obtained by curing the above-described epoxy resin composition of the present invention by a known method.
  • the curing conditions of the epoxy resin composition are appropriately selected according to the application and the form, and are not particularly limited.
  • the form of the cured product of the present invention is also not particularly limited, and can be selected according to the application.
  • the application of the epoxy resin composition is a paint
  • the cured product of the composition is usually in the form of a film.
  • the cured product of the present invention is preferably a matrix resin of a fiber-reinforced composite material described later.
  • the epoxy resin composition of the present invention has a high glass transition temperature (Tg) of a cured product from the viewpoint of improving the productivity of a molded product when used for a fiber reinforced composite material etc. and from the viewpoint of the heat resistance of the molded product. Is preferred.
  • Tg glass transition temperature
  • the mold cycle can be shortened because mold release is possible without cooling the mold to a low temperature when used for a fiber reinforced composite material or the like.
  • the heat resistance of the molded article is also improved.
  • a differential scanning calorimeter is used to make a difference from 30.degree. C.
  • the Tg determined by performing scanning thermal analysis is preferably 100 ° C. or more, more preferably 110 ° C. or more, still more preferably 120 ° C. or more, and still more preferably 123 ° C. or more.
  • the Tg of the cured product can be measured specifically by the method described in the examples.
  • the epoxy resin composition containing the epoxy resin curing agent according to the present invention is characterized by rapid curing, low viscosity, long pot life, and high heat resistance of the cured product. It is preferable that it is especially for carbon fiber reinforced composites (CFRP).
  • a fiber reinforced composite material includes a cured product of the epoxy resin composition and a reinforcing fiber, and is obtained by impregnating the reinforcing resin with the epoxy resin composition and then curing the composition. it can.
  • the FRP may further contain a foam in addition to the cured product of the epoxy resin composition and the reinforcing fibers.
  • the reinforcing fibers include glass fibers, carbon fibers, boron fibers, aramid fibers, cellulose fibers, nanocellulose fibers and metal fibers.
  • the reinforcing fibers may be used alone or in combination of two or more.
  • carbon fiber is preferable from the viewpoint of strength and lightness of the obtained composite material.
  • the carbon fiber used for CFRP may be manufactured using rayon, polyacrylonitrile (PAN) or the like as a raw material, or may be manufactured by spinning using a pitch of petroleum or coal as a raw material.
  • PAN polyacrylonitrile
  • the fiber length is preferably 1 mm or more, more preferably 3 mm or more, still more preferably 6 mm or more, as the average fiber length of the non-continuous fiber to be used from the viewpoint of the strength of the obtained FRP. Preferably it is 10 mm or more.
  • the upper limit of the average fiber length of the non-continuous fiber to be used is preferably 500 cm or less, more preferably 300 cm or less, and still more preferably 100 cm or less, from the viewpoint of formability.
  • the average fiber length can be measured by visual observation, observation by an optical microscope, a scanning electron microscope (SEM) or the like. 100 fibers can be randomly selected to measure the length, and the average fiber length of number average can be calculated.
  • the average fiber diameter of the reinforcing fibers is preferably 1 to 100 ⁇ m, more preferably 3 to 50 ⁇ m, and still more preferably 4 to 20 ⁇ m. When the average fiber diameter is in this range, processing is easy, and the elastic modulus and strength of the obtained FRP are excellent.
  • the average fiber diameter can be measured by observation with a scanning electron microscope (SEM) or the like. The length can be measured by randomly selecting 50 or more fibers, and the average fiber diameter of number average can be calculated.
  • the fineness of the reinforcing fiber is preferably 20 to 4,500 tex, and more preferably 50 to 4,000 tex. When the fineness is in this range, the impregnation of the epoxy resin composition is easy, and the elastic modulus and the strength of the obtained FRP are excellent.
  • the fineness can be determined by determining the weight of long fibers of an arbitrary length and converting it to the weight per 1,000 m.
  • the number of filaments is usually about 500 to about 60,000, and a reinforcing fiber can be preferably used.
  • Examples of the form of the reinforcing fiber include various forms such as a monofilament or a multifilament simply arranged to cross in one direction or alternately, a fabric such as a woven fabric, a non-woven fabric or a mat.
  • a fabric such as a woven fabric, a non-woven fabric or a mat.
  • the form of a monofilament, a fabric, a nonwoven fabric or a mat is preferable, and the form of a fabric is more preferable.
  • the foam material is not particularly limited, but examples thereof include foam materials composed of resin materials such as polyvinyl chloride resin, polyurethane resin, polystyrene resin, polyolefin resin, acrylic resin, phenol resin, polymethacrylimide resin, epoxy resin, etc.
  • resin materials such as polyvinyl chloride resin, polyurethane resin, polystyrene resin, polyolefin resin, acrylic resin, phenol resin, polymethacrylimide resin, epoxy resin, etc.
  • the epoxy resin curing agent and epoxy resin composition of the present invention are quick-curing, the epoxy resin curing agent and the epoxy resin are mixed immediately before molding. After that, it is preferable to carry out the impregnation and curing of the reinforcing fiber, preferably within 10 minutes, more preferably within 5 minutes.
  • methods for producing fiber reinforced composite materials include low pressure RTM method, medium pressure RTM method, high pressure RTM method, compression RTM method, liquid compression molding method, liquid laydown method, liquid laydown method, spray laydown method, surface RTM method, prepreg compression molding It is preferable to have a step of forming by a method or a wet compression molding (WCM) method, and a Dynamic Fluid Compression Molding method.
  • WCM wet compression molding
  • the low pressure RTM method, the medium pressure RTM method, or the high pressure RTM method is preferable from the viewpoint of application to the high cycle RTM method, the medium pressure RTM method or the high pressure RTM method is more preferable. Is more preferably a high pressure RTM method.
  • low pressure in the low pressure RTM method means that the pressure at the time of pumping when the epoxy resin which is the main agent of the epoxy resin composition and the epoxy resin curing agent are pumped and mixed is less than 0.5 MPa Say that.
  • the "medium pressure” in the medium pressure RTM method refers to a pressure of 0.5 MPa or more and less than 7 MPa
  • the "high pressure” in the high pressure RTM method refers to a pressure of 7 MPa or more and 20 MPa or less. Since the epoxy resin composition of the present invention is rapidly curable and has a low viscosity, it can be filled quickly into the mold and impregnated into the reinforcing fiber quickly and rapidly, so that the molding time can be significantly shortened.
  • the epoxy resin curing agent and the epoxy resin composition of the present invention are particularly suitable for the above molding method.
  • medium to large-sized FRPs for automobile structural materials and building materials can be produced with high productivity by applying the epoxy resin curing agent and epoxy resin composition of the present invention. .
  • a collision mixing mixer as an apparatus for mixing an epoxy resin which is a main component of an epoxy resin composition, and an epoxy resin curing agent.
  • reinforcing fibers are placed in a pair of upper and lower molds and sealed, and the inside of the mold is depressurized.
  • the epoxy resin, which is the main component of the epoxy resin composition, and the epoxy resin curing agent are filled in separate tanks, and each is discharged at a high speed from very small holes (orifices) in the mixing chamber of the collision mixing mixer. Make collision mixing.
  • the epoxy resin composition thus prepared is injected at high pressure into a mold to impregnate the reinforcing fibers, and then the epoxy resin is cured.
  • a dynamic mixer as an apparatus for mixing an epoxy resin, which is a main component of an epoxy resin composition, and an epoxy resin curing agent.
  • the dynamic mixer is provided with a cylindrical high-speed rotating body having irregularities on the surface.
  • an epoxy resin which is a main component of an epoxy resin composition and an epoxy resin curing agent are filled in separate tanks, each is sent to a dynamic mixer, and the two components of the main agent and the curing agent are mixed by the rotating body. .
  • the epoxy resin composition thus prepared is poured into a mold to impregnate the reinforcing fibers and then the epoxy resin is cured.
  • the low pressure RTM method is advantageous in the case where the compounding ratio of the epoxy resin and the epoxy resin curing agent is largely different, in view of the device cost and the space saving of the device.
  • a static mixer is a tubular reactor incorporating one or more static mixers consisting of a large number of mixing elements. For example, an epoxy resin which is a main component of an epoxy resin composition and an 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 to impregnate the reinforcing fibers and then the epoxy resin is cured.
  • the medium pressure RTM method is advantageous in that the epoxy resin composition can be pumped into the mold and in terms of equipment cost.
  • the reinforced fiber and the foamed material may be disposed in the mold to produce the FRP in the same manner as described above. it can.
  • the epoxy resin curing agent and epoxy resin composition of the present invention can be suitably used for the liquid compression molding (LCM) method, liquid laydown method, and wet compression molding (WCM) method.
  • LCM liquid compression molding
  • WCM wet compression molding
  • the epoxy resin composition is cast on a reinforcing fiber (on the reinforcing fiber and the foam when the FRP further includes a foam), and then heat compression is applied to strengthen The epoxy resin is cured while being impregnated into the fibers.
  • the Dynamic Fluid Compression Molding method is an improvement method of the LCM method, the liquid laydown method, and the WCM method, and is characterized in that the pressure in the mold is reduced during heat compression.
  • the temperature at which the epoxy resin composition is injected into a mold or impregnated into reinforcing fibers 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 which the epoxy resin curing agent is mixed 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 of the epoxy resin can be appropriately adjusted according to the viscosity of the epoxy resin, but it is preferably 30 to 120 ° C., more preferably 50 to 100 ° C.
  • the temperature may be constant during molding or may be varied during molding.
  • the impregnation time of the epoxy resin composition to the reinforcing fiber is preferably 0.1 to 15 minutes, more preferably 0.2 to 10 minutes, still more preferably 0.5 to 5 minutes, from the viewpoint of moldability and productivity. It is.
  • the discharge rate at the time of injecting the epoxy resin composition into the mold is preferably 5 to 400 g per second, more preferably 10 to 100 g per second, still more preferably 20 to 60 g per second from the viewpoint of moldability and productivity. .
  • the speed may be constant during molding or may be varied during molding.
  • 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 temperature may be constant during molding or may be varied during molding.
  • the curing time of the epoxy resin composition is preferably 0.1 to 15 minutes, more preferably 0.2 to 10 minutes, and still more preferably 0.5 to 5 minutes, from the viewpoint of moldability and productivity.
  • the fiber-reinforced composite material of the present invention is preferably a structural material for automobiles and a building material, particularly a structural material for automobiles.
  • Structural materials for automobiles include bumpers, spoilers, cowlings, front grills, garnishes, bonnets, trunk lids, fender panels, door panels, roof panels, instrument panels, door trims, quarter trims, roof linings, pillar garnishes, deck trims, and tonoboards.
  • the viscosity of the epoxy resin composition was measured at 40 ° C. and 80 ° C., respectively, using an E-type viscometer “TVE-22H type viscometer cone plate type” (manufactured by Toki Sangyo Co., Ltd.). In the measurement at 80 ° C., the measurement was started immediately after preparing the epoxy resin composition by mixing the epoxy resin and the epoxy resin curing agent, and the measured value was read every 30 seconds to confirm the temporal change of the viscosity. The lower the viscosity at 40 ° C. and the viscosity after 80 ° C. for 30 seconds, the lower the initial viscosity, the higher the filling properties at the time of molding, and the better the moldability. In addition, the change in viscosity with time in measurement at 80 ° C. is small, and the lower the viscosity is maintained, the longer the pot life is.
  • Tg Glass transition temperature
  • Examples 1 to 7 and Comparative Examples 1 to 3 (Preparation of Epoxy Resin Curing Agent and Epoxy Resin Composition)
  • Component (A) N-aminoethyl piperazine (AEP, manufactured by Tosoh Corp.) and isophorone diamine (IPDA, manufactured by EVONIK), and component (B) 1,3-bis (aminomethyl) cyclohexane (1,1) 3-BAC, manufactured by Mitsubishi Gas Chemical Co., Ltd., cis / trans ratio 77/23) was blended by mass parts shown in Table 1 and mixed to obtain an epoxy resin curing agent.
  • AEP N-aminoethyl piperazine
  • IPDA isophorone diamine
  • the epoxy resin curing agent and the main component bisphenol A liquid epoxy resin (“jER 825", manufactured by Mitsubishi Chemical Corporation), the number of active amine hydrogens in the epoxy resin curing agent, and the epoxy resin as the main component
  • the epoxy resin composition was prepared by blending and mixing so that the number of epoxy groups in the composition is equimolar.
  • the obtained epoxy resin curing agent and epoxy resin composition were evaluated by the above-mentioned method. The results are shown in Table 1.
  • R 15 is —CH 2 CH (OH) — or —CH (OH) CH 2 —.
  • the epoxy resin compositions of Examples 1 to 3 maintain quick curing property. However, the viscosity was lowered, the pot life was extended, and the heat resistance of the cured product was further improved. Moreover, compared with the epoxy resin composition of Comparative Example 2 using only IPDA which is the component (A) as the epoxy resin curing agent, the epoxy resin compositions of Examples 4 to 6 have low pot life while maintaining low pot life. The viscosity was improved, and the curing speed and the heat resistance of the cured product were improved. As compared with the epoxy resin composition of Comparative Example 3, the epoxy resin composition of Example 7 was improved in the viscosity, the pot life, the curing rate and the heat resistance of the cured product.
  • Example 8 (manufacture of CFRP)
  • the epoxy resin composition of Example 1 was hand lay-up molded at room temperature to obtain a carbon fiber fabric ("CO6343" manufactured by Toray Industries, Inc., T300 plain weave cloth, 3 K, 198 g / m 2 , 0.25 mm thickness, 4 ply) To make a CFRP base material. Subsequently, the CFRP base material was placed on an aluminum upper and lower mold preheated to 120 ° C. in an oven, the mold was immediately closed, and heating was performed for 3 minutes to cure the epoxy resin composition to obtain CFRP. The obtained CFRP can be easily released from the aluminum upper and lower molds, and it has been confirmed that the curing of the epoxy resin composition has progressed in a short time. In addition, the appearance was good without any defect due to the infiltration of the epoxy resin composition into the carbon fiber being low.
  • CO6343 manufactured by Toray Industries, Inc., T300 plain weave cloth, 3 K, 198 g / m 2 , 0.25 mm

Abstract

An epoxy resin curing agent which contains (A) at least one compound selected from the group consisting of N-aminoethyl piperazine and isophorone diamine and (B) a bis(aminomethyl)cyclohexane; an epoxy resin composition which contains this epoxy resin curing agent and an epoxy resin; a cured product of this epoxy resin composition; and a fiber-reinforced composite material which contains a cured product of this epoxy resin composition and reinforcing fibers.

Description

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Epoxy resin curing agent, epoxy resin composition and cured product thereof, and fiber reinforced composite material
　本発明は、エポキシ樹脂硬化剤、該エポキシ樹脂硬化剤とエポキシ樹脂とを含有するエポキシ樹脂組成物及びその硬化物、並びに、該エポキシ樹脂組成物の硬化物と、強化繊維とを含む繊維強化複合材に関する。 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 thereof, and a fiber-reinforced composite comprising a cured product of the epoxy resin composition and a reinforcing fiber. It relates to the material.
　炭素繊維強化複合材（以下「ＣＦＲＰ（Ｃａｒｂｏｎ Ｆｉｂｅｒ Ｒｅｉｎｆｏｒｃｅｄ Ｐｌａｓｔｉｃｓ）」ともいう）は、非常に高い弾性率、強度を有し、かつ軽量であることから金属代替材料として注目されている。ＣＦＲＰは特に自動車構造材用途、風力発電ブレード用途、圧力容器用途、航空宇宙用途への需要が加速することが見込まれており、ＣＦＲＰに用いられる炭素繊維と、エポキシ樹脂等のマトリクス樹脂の需要も近年増大している。 Carbon fiber reinforced composites (hereinafter also referred to as "CFRP (Carbon Fiber Reinforced Plastics)") have attracted attention as metal substitutes because they have very high elastic modulus, strength, and light weight. In particular, CFRP is expected to accelerate demand for automotive structural material applications, wind power generation blade applications, pressure vessel applications, and aerospace applications, and demand for carbon fibers used for CFRP and matrix resins such as epoxy resins is also expected. It has been increasing in recent years.
　ところで、自動車構造材用途、風力発電ブレード用途、圧力容器用途、航空宇宙用途それぞれにおいてＣＦＲＰの成形方法が異なることから、ＣＦＲＰ用のマトリクス樹脂に対する要求特性も用途によって異なっている。
　例えば風力発電ブレードは、インフュージョン成形、Ｖａ－ＲＴＭ法（Ｖａｃｕｕｍ　Ａｓｓｉｓｔ　Ｒｅｓｉｎ　Ｔｒａｎｓｆｅｒ　Ｍｏｌｄｉｎｇ）又はＬｉｇｈｔ－ＲＴＭ法にて成形されるようになってきた。これらの方法では、例えば、フィルムやＦＲＰを使用した上型と、下型とからなる型内に予め強化繊維を配置し、この金型内を真空引きし、マトリクス樹脂となるエポキシ樹脂組成物を常圧で充填して強化繊維へ含浸させ、次いで、該エポキシ樹脂を硬化させて成形する。
　インフュージョン成形やＶａ－ＲＴＭ法、Ｌｉｇｈｔ－ＲＴＭ法による成形では、その成形法の特徴上、エポキシ樹脂とエポキシ樹脂硬化剤とを混合したエポキシ樹脂組成物を金型内へ充填するのに、通常は数十分程度かかる。そのため、これらの成形法に使用されるエポキシ樹脂組成物には低粘度でかつポットライフが長いことが要求される。エポキシ樹脂硬化剤としては、イソホロンジアミン、ポリエーテル骨格のポリアミン化合物等が使用されている。 By the way, since the molding method of CFRP is different in automobile structural material application, wind power generation blade application, pressure vessel application, and aerospace application, the required characteristics for the matrix resin for CFRP also differ depending on the application.
For example, wind power generation blades have come to be molded by injection molding, vacuum assisted resin transfer molding (Va-RTM) or light-RTM. In these methods, for example, reinforcing fibers are arranged in advance in a mold consisting of an upper mold and a lower mold using a film or FRP, and the inside of the mold is evacuated to form an epoxy resin composition as a matrix resin. It is filled at normal pressure to impregnate into reinforcing fibers and then the epoxy resin is cured and shaped.
In molding by injection molding, Va-RTM method, or Light-RTM method, an epoxy resin composition in which an epoxy resin and an epoxy resin curing agent are mixed is usually filled into a mold due to the characteristics of the molding method. It takes several tens of minutes. Therefore, it is required that the epoxy resin composition used in these molding methods have a low viscosity and a long pot life. As an epoxy resin curing agent, isophorone diamine, a polyamine compound having a polyether skeleton, and the like are used.
　また、圧力容器用途のＣＦＲＰにおいては、フィラメントワインディング法による成形が用いられる。フィラメントワインディング法は、強化繊維糸にエポキシ樹脂組成物などのマトリクス樹脂を含浸させた強化繊維糸を用いてライナーの外表面を被覆した後、該マトリクス樹脂を硬化させる方法である。この方法に用いるエポキシ樹脂組成物は、ポットライフが短く速硬化性であると、成形前の段階でエポキシ樹脂が硬化してしまう。したがってフィラメントワインディング法には速硬化性のエポキシ樹脂組成物は適用できない。 Further, in CFRP for pressure vessel use, molding by a filament winding method is used. The filament winding method is a method in which the outer surface of a liner is coated with a reinforcing fiber yarn in which a reinforcing fiber yarn is impregnated with a matrix resin such as an epoxy resin composition, and then the matrix resin is cured. In the epoxy resin composition used in this method, if the pot life is short and quick curing, the epoxy resin is cured at a stage before molding. Therefore, a rapid curing epoxy resin composition can not be applied to the filament winding method.
　これに対し自動車構造材用途のＣＦＲＰは、ハイサイクルＲＴＭ法にて成形されている。これは従来のＲＴＭ法を改良したものである。
　従来のＲＴＭ法は上下一対の金型を使用した密閉型成形の一つであり、該金型内に繊維強化プリフォームを配置し、金型をクランプして密閉した後、注入孔からエポキシ樹脂組成物等の樹脂を金型内に注入して繊維強化プリフォームに含浸させ、次いで該樹脂を硬化させた後、離型するという方法である。しかしながら従来のＲＴＭ法では、成形時間（プリフォームの配置、樹脂含浸、樹脂硬化、及び離型まで）に数時間を要するため、自動車構造材用途のＣＦＲＰの製造では、より生産性の高いハイサイクルＲＴＭ法が用いられている。 On the other hand, CFRP for automobile structural materials is molded by the high cycle RTM method. This is an improvement of the conventional RTM method.
The conventional RTM method is one of closed mold molding using a pair of upper and lower molds, a fiber reinforced preform is disposed in the mold, and after clamping and sealing the mold, epoxy resin is injected from the injection hole A resin such as a composition is injected into a mold and impregnated into a fiber reinforced preform, and then the resin is cured and then released. However, the conventional RTM method requires several hours for molding time (preform placement, resin impregnation, resin curing, and mold release), and therefore, in the production of CFRP for automotive structural material applications, a higher productivity high cycle is achieved. The RTM method is used.
　ハイサイクルＲＴＭ法による成形技術は、繊維強化プリフォームの配置時間、樹脂の含浸時間、樹脂の硬化時間、及び離型時間のすべてを大幅に短縮し、トータルの成形時間を１０分程度まで短縮したものである。ハイサイクルＲＴＭ法において、樹脂の含浸から硬化までの工程では、例えばハイサイクルＲＴＭ法の一種である高圧ＲＴＭ法において、上下一対の金型内に強化繊維を配置して密閉し、金型内を減圧にする。次いで、エポキシ樹脂組成物の主剤であるエポキシ樹脂と、エポキシ樹脂硬化剤とを、別々のタンクからミキシングヘッドへミスト状態で圧送し、衝突混合後に速やかに金型内に注入して炭素繊維に含浸させ、エポキシ樹脂を硬化させる。衝突混合後のエポキシ樹脂組成物は、金型内への充填速度及び炭素繊維への含浸速度を高めるため、複数の注入孔から高圧注入される。 The molding technology by the high cycle RTM method significantly reduced all of the placement time of the fiber reinforced preform, the impregnation time of the resin, the curing time of the resin, and the mold release time, and reduced the total molding time to about 10 minutes. It is a thing. In the high cycle RTM method, in the process from resin impregnation to curing, for example, in the high pressure RTM method, which is a type of high cycle RTM method, reinforcing fibers are placed in a pair of upper and lower molds and sealed to seal the inside of the molds. Reduce pressure. Next, the epoxy resin, which is the main component of the epoxy resin composition, and the epoxy resin curing agent are pumped from separate tanks to the mixing head in the form of mist and injected immediately into the mold after collision mixing to impregnate the carbon fiber. And cure the epoxy resin. After impact mixing, the epoxy resin composition is injected at 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.
　従来のＲＴＭ法向けのエポキシ樹脂組成物に用いるエポキシ樹脂硬化剤として、汎用品であるＮ－アミノエチルピペラジン（ＡＥＰ）、イソホロンジアミン（ＩＰＤＡ）、又はこれらの混合物を用いることが知られている（例えば、特許文献１及び非特許文献１を参照）。 It is known to use N-aminoethyl piperazine (AEP), isophorone diamine (IPDA), which is a general-purpose product, or a mixture thereof as an epoxy resin curing agent used for an epoxy resin composition for the conventional RTM method ( See, for example, Patent Document 1 and Non-Patent Document 1).
特表平９－５０７２６２号公報Japanese Patent Publication No. 9-507262
　ハイサイクルＲＴＭ法などによる成形に用いられるエポキシ樹脂硬化剤、及び該硬化剤とエポキシ樹脂とを含有するエポキシ樹脂組成物においては、速硬化性でかつ低粘度であること、ポットライフが長いこと、及び、硬化物のガラス転移温度（Ｔｇ）が高く耐熱性が良好であることが望まれる。
　しかしながら、ＡＥＰは速硬化性であり初期粘度が低い一方で、ポットライフが短く、得られるエポキシ樹脂組成物の硬化物のＴｇが低くなるという問題がある。またＩＰＤＡはポットライフが長く、得られるエポキシ樹脂組成物の硬化物のＴｇは比較的高くなるが、硬化速度が遅く初期粘度が高いという問題があった。ＡＥＰとＩＰＤＡのそれぞれの欠点を改善すべくこれらを混合したとしても、ハイサイクルＲＴＭ法などによる成形に用いられるエポキシ樹脂硬化剤としては十分満足のいく性能は得られなかった。 In the epoxy resin curing agent used for molding by the high cycle RTM method and the like, and in the epoxy resin composition containing the curing agent and the epoxy resin, rapid curing and low viscosity, long pot life, And, it is desirable that the glass transition temperature (Tg) of the cured product be high and the heat resistance be good.
However, while AEP is rapidly curable and has a low initial viscosity, there is a problem that the pot life is short and the Tg of the cured product of the resulting epoxy resin composition is low. In addition, IPDA has a long pot life, and the Tg of the cured product of the obtained epoxy resin composition is relatively high, but there is a problem that the curing speed is slow and the initial viscosity is high. Even if these were mixed in order to improve each defect of AEP and IPDA, a sufficiently satisfactory performance could not be obtained as an epoxy resin curing agent used for molding by the high cycle RTM method or the like.
　本発明の課題は、エポキシ樹脂硬化剤成分として汎用されているＮ－アミノエチルピペラジン及び／又はイソホロンジアミンを含有し、速硬化性でかつ低粘度であり、得られるエポキシ樹脂組成物のポットライフ及び硬化物の耐熱性を改善し得るエポキシ樹脂硬化剤、これを含有するエポキシ樹脂組成物及びその硬化物、並びに、該エポキシ樹脂組成物の硬化物と強化繊維とを含む繊維強化複合材を提供することにある。 An object of the present invention is to provide a pot life of an epoxy resin composition obtained which contains N-aminoethyl piperazine and / or isophorone diamine which is widely used as an epoxy resin curing agent component, which is rapidly curable and has a low viscosity. An epoxy resin curing agent capable of improving the heat resistance of a cured product, an epoxy resin composition containing the same and a cured product thereof, and a fiber reinforced composite material comprising the cured product of the epoxy resin composition and reinforcing fibers It is.
　本発明者は上記課題を解決するため鋭意検討した結果、Ｎ－アミノエチルピペラジン及びイソホロンジアミンからなる群から選ばれる少なくとも１種の化合物と、ビス（アミノメチル）シクロヘキサンとを含有するエポキシ樹脂硬化剤により、上記課題を解決できることを見出した。 The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, an epoxy resin curing agent containing at least one compound selected from the group consisting of N-aminoethyl piperazine and isophorone diamine and bis (aminomethyl) cyclohexane. Found that the above problems can be solved.
　すなわち、本発明は下記［１］～［９］に関する。
［１］Ｎ－アミノエチルピペラジン及びイソホロンジアミンからなる群から選ばれる少なくとも１種の化合物（Ａ）と、ビス（アミノメチル）シクロヘキサン（Ｂ）とを含有するエポキシ樹脂硬化剤。
［２］前記（Ａ）成分と（Ｂ）成分との質量比が０．５７５＜（Ａ）／［（Ａ）＋（Ｂ）］＜１を満たす、上記［１］に記載のエポキシ樹脂硬化剤。
［３］前記（Ａ）成分がＮ－アミノエチルピペラジンである、上記［１］又は［２］に記載のエポキシ樹脂硬化剤。
［４］前記（Ｂ）成分が１，３－ビス（アミノメチル）シクロヘキサンである、上記［１］～［３］のいずれか１項に記載のエポキシ樹脂硬化剤。
［５］前記（Ａ）成分及び（Ｂ）成分の合計含有量が５０質量％以上である、上記［１］～［４］のいずれか１項に記載のエポキシ樹脂硬化剤。
［６］上記［１］～［５］のいずれか１項に記載のエポキシ樹脂硬化剤と、エポキシ樹脂とを含有するエポキシ樹脂組成物。
［７］上記［６］に記載のエポキシ樹脂組成物の硬化物。
［８］上記［６］に記載のエポキシ樹脂組成物の硬化物と、強化繊維とを含む繊維強化複合材。
［９］前記強化繊維が炭素繊維である、上記［８］に記載の繊維強化複合材。 That is, the present invention relates to the following [1] to [9].
[1] An epoxy resin curing agent containing at least one compound (A) selected from the group consisting of N-aminoethyl piperazine and isophorone diamine and bis (aminomethyl) cyclohexane (B).
[2] The epoxy resin cured as described in the above [1], wherein the mass ratio of the (A) component to the (B) component satisfies 0.575 <(A) / [(A) + (B)] <1. Agent.
[3] The epoxy resin curing agent according to the above [1] or [2], wherein the component (A) is N-aminoethyl piperazine.
[4] The epoxy resin curing agent according to any one of the above [1] to [3], wherein the component (B) is 1,3-bis (aminomethyl) cyclohexane.
[5] The epoxy resin curing agent according to any one of the above [1] to [4], wherein the total content of the components (A) and (B) is 50% by mass or more.
[6] An epoxy resin composition comprising the epoxy resin curing agent according to any one of the above [1] to [5] and an epoxy resin.
[7] A cured product of the epoxy resin composition as described in the above [6].
[8] A fiber reinforced composite material comprising a cured product of the epoxy resin composition as described in the above [6] and a reinforcing fiber.
[9] The fiber-reinforced composite material according to the above [8], wherein the reinforcing fiber is a carbon fiber.
　本発明によれば、エポキシ樹脂硬化剤成分として汎用されているＮ－アミノエチルピペラジンやイソホロンジアミンをエポキシ樹脂硬化剤として用いながら、ハイサイクルＲＴＭ法などによって自動車用構造材や建材などのＣＦＲＰを生産性よく製造できるエポキシ樹脂硬化剤及びエポキシ樹脂組成物を提供することができる。
　当該エポキシ樹脂組成物はポットライフが長いため作業性が良好である。また、ＣＦＲＰをはじめとするＦＲＰのマトリクス樹脂として用いると、強化繊維への含浸性に優れ、速硬化性であることから金型からの離型が可能になるまでの時間も短く、ＦＲＰの生産性を向上させることができる。さらに、得られるＦＲＰの耐熱性も良好になる。 According to the present invention, while using N-aminoethyl piperazine and isophorone diamine which are generally used as epoxy resin curing agent components as epoxy resin curing agents, high cycle RTM method etc. are used to produce CFRPs such as automotive structural materials and building materials It is possible to provide an epoxy resin curing agent and an epoxy resin composition which can be produced with good quality.
Since the said epoxy resin composition has a long pot life, its workability is good. In addition, when used as a matrix resin of FRP, including CFRP, it is excellent in the ability to impregnate reinforcing fibers and has a quick curing property, so that the time until mold release from molds becomes possible is short, and FRP production It is possible to improve the quality. Furthermore, the heat resistance of the obtained FRP is also improved.
［エポキシ樹脂硬化剤］
　本発明のエポキシ樹脂硬化剤は、Ｎ－アミノエチルピペラジン（ＡＥＰ）及びイソホロンジアミン（ＩＰＤＡ）からなる群から選ばれる少なくとも１種の化合物（Ａ）と、ビス（アミノメチル）シクロヘキサン（Ｂ）とを含有する。
　本発明は、エポキシ樹脂硬化剤成分として汎用されているＡＥＰやＩＰＤＡを含有するエポキシ樹脂硬化剤において、ビス（アミノメチル）シクロヘキサンを配合することにより、ＡＥＰとＩＰＤＡに由来する諸特性を改善し、得られるエポキシ樹脂組成物の速硬化性、低粘度、ロングポットライフを達成し、硬化物の耐熱性も向上できることを見出したものである。 [Epoxy resin curing agent]
The epoxy resin curing agent of the present invention comprises at least one compound (A) selected from the group consisting of N-aminoethyl piperazine (AEP) and isophorone diamine (IPDA), and bis (aminomethyl) cyclohexane (B) contains.
The present invention improves various characteristics derived from AEP and IPDA by blending bis (aminomethyl) cyclohexane in an epoxy resin curing agent containing AEP and IPDA which are widely used as an epoxy resin curing agent component, It has been found that the rapid curing property, low viscosity and long pot life of the obtained epoxy resin composition can be achieved, and the heat resistance of the cured product can be improved.
＜（Ａ）成分＞
　本発明のエポキシ樹脂硬化剤は、（Ａ）成分として、Ｎ－アミノエチルピペラジン（ＡＥＰ）及びイソホロンジアミン（ＩＰＤＡ）からなる群から選ばれる少なくとも１種の化合物を含有する。これらの化合物はエポキシ樹脂硬化剤成分として汎用されており経済性に優れる。
　エポキシ樹脂硬化剤の性能として、ＡＥＰは速硬化性かつ低粘度であり、得られるエポキシ樹脂組成物の硬化物の靭性が向上するという利点を有する。またＩＰＤＡは、得られるエポキシ樹脂組成物のポットライフが長くなり、かつ硬化物の耐熱性が高くなるという利点を有する。これらの特性を考慮し、所望する性能及び用途に応じて、本発明に用いる（Ａ）成分としてＡＥＰ及びＩＰＤＡからなる群から選ばれる少なくとも１種の化合物を適宜選択することができる。
　ＡＥＰとＩＰＤＡを併用する場合、その含有量比にも特に制限はなく、例えば、ＡＥＰとＩＰＤＡを質量比で１／９９～９９／１、好ましくは５／９５～９５／５の割合で用いることができる。
　ハイサイクルＲＴＭ法などによる成形に用いられるエポキシ樹脂硬化剤である場合、速硬化性でかつ低粘度であるという点から、（Ａ）成分はＮ－アミノエチルピペラジン、又はＮ－アミノエチルピペラジンとイソホロンジアミンの混合物であることが好ましく、Ｎ－アミノエチルピペラジンであることがより好ましい。 <(A) component>
The epoxy resin curing agent of the present invention contains, as component (A), at least one compound selected from the group consisting of N-aminoethyl piperazine (AEP) and isophorone diamine (IPDA). These compounds are widely used as epoxy resin curing agent components and are excellent in economy.
As the performance of the epoxy resin curing agent, AEP has the advantages of rapid curing and low viscosity, and improved toughness of the cured product of the resulting epoxy resin composition. IPDA also has the advantage that the pot life of the resulting epoxy resin composition is extended and the heat resistance of the cured product is increased. In consideration of these properties, at least one compound selected from the group consisting of AEP and IPDA can be appropriately selected as the component (A) used in the present invention, according to the desired performance and application.
When AEP and IPDA are used in combination, the content ratio thereof is not particularly limited. For example, AEP and IPDA may be used at a mass ratio of 1/99 to 99/1, preferably 5/95 to 95/5. Can.
When it is an epoxy resin curing agent used for molding by the high cycle RTM method or the like, the component (A) is N-aminoethyl piperazine or N-amino ethyl piperazine and isophorone from the viewpoint of rapid curing and low viscosity. It is preferably a mixture of diamines, more preferably N-aminoethyl piperazine.
＜（Ｂ）成分＞
　本発明のエポキシ樹脂硬化剤は、（Ｂ）成分として所定量のビス（アミノメチル）シクロヘキサンを含有する。これにより、前記（Ａ）成分を含有するエポキシ樹脂硬化剤を含むエポキシ樹脂組成物において速硬化性、低粘度、ロングポットライフを達成し、硬化物の耐熱性も向上させることができる
　ビス（アミノメチル）シクロヘキサンとしては、１，２－ビス（アミノメチル）シクロヘキサン、１，３－ビス（アミノメチル）シクロヘキサン、１，４－ビス（アミノメチル）シクロヘキサンが挙げられ、これらのうち１種を単独で、又は２種以上を組み合わせて用いることができる。これらの中でも１，３－ビス（アミノメチル）シクロヘキサンが好ましい。
　なおビス（アミノメチル）シクロヘキサンは、シス体、トランス体、又はこれらの混合物のいずれであってもよい。ビス（アミノメチル）シクロヘキサンがシス体とトランス体の混合物である場合、シス体／トランス体のモル比は、好ましくは５／９５～９５／５、より好ましくは１０／９０～９０／１０である。 <(B) component>
The epoxy resin curing agent of the present invention contains a predetermined amount of bis (aminomethyl) cyclohexane as the component (B). Thereby, in the epoxy resin composition containing the epoxy resin curing agent containing the said (A) component, rapid curability, low viscosity, long pot life can be achieved, and the heat resistance of the cured product can also be improved. Examples of methyl) cyclohexane include 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane and 1,4-bis (aminomethyl) cyclohexane, and one of these may be used alone. Or two or more kinds can be used in combination. Among these, 1,3-bis (aminomethyl) cyclohexane is preferable.
Bis (aminomethyl) cyclohexane may be in cis form, trans form or a mixture thereof. When bis (aminomethyl) cyclohexane is a mixture of cis form and trans form, the molar ratio of cis form / trans form is preferably 5/95 to 95/5, more preferably 10/90 to 90/10. .
　本発明のエポキシ樹脂硬化剤は、（Ａ）成分と（Ｂ）成分との質量比が０．５７５＜（Ａ）／［（Ａ）＋（Ｂ）］＜１を満たすことが好ましい。質量比（Ａ）／［（Ａ）＋（Ｂ）］が１、すなわち（Ｂ）成分を含有しない場合は、得られるエポキシ樹脂組成物の速硬化性、低粘度、ロングポットライフ、又は硬化物の高耐熱性のいずれかが達成できなくなる。また、質量比（Ａ）／［（Ａ）＋（Ｂ）］が０．５７５を超える場合は、エポキシ樹脂硬化剤中のＡＥＰ又はＩＰＤＡの割合が高くなるため経済性に優れる。また、ＡＥＰ又はＩＰＤＡに由来する諸特性を発現し易くなる。
　得られるエポキシ樹脂組成物において速硬化性、低粘度、ロングポットライフ、及び硬化物の高耐熱性を得る観点から、本発明のエポキシ樹脂硬化剤における質量比（Ａ）／［（Ａ）＋（Ｂ）］は、好ましくは０．９５以下、より好ましくは０．９０以下、さらに好ましくは０．８５以下であり、ＡＥＰ又はＩＰＤＡに由来する諸特性を発現する観点からは、より好ましくは０．６０以上、さらに好ましくは０．６５以上、よりさらに好ましくは０．７０以上、よりさらに好ましくは０．７５以上である。 The epoxy resin curing agent of the present invention preferably satisfies a mass ratio of component (A) to component (B) of 0.575 <(A) / [(A) + (B)] <1. When the mass ratio (A) / [(A) + (B)] is 1, ie, the component (B) is not contained, the rapid curing property, low viscosity, long pot life or cured product of the resulting epoxy resin composition One of the high heat resistance of can not be achieved. When the mass ratio (A) / [(A) + (B)] exceeds 0.575, the proportion of AEP or IPDA in the epoxy resin curing agent is high, which is excellent in economics. In addition, various properties derived from AEP or IPDA can be easily expressed.
From the viewpoint of obtaining fast curing, low viscosity, long pot life and high heat resistance of the cured product in the obtained epoxy resin composition, the mass ratio (A) / [(A) + (A) of the epoxy resin curing agent of the present invention is obtained. B) is preferably 0.95 or less, more preferably 0.90 or less, still more preferably 0.85 or less, and from the viewpoint of expressing various properties derived from AEP or IPDA, more preferably 0. 60 or more, more preferably 0.65 or more, still more preferably 0.70 or more, and still more preferably 0.75 or more.
　本発明のエポキシ樹脂硬化剤は、前記（Ａ）成分及び（Ｂ）成分以外の公知の硬化剤や、公知の硬化促進剤、添加剤、及び溶剤等を含有していてもよい。
　前記（Ａ）成分及び（Ｂ）成分以外の硬化剤としては、前記（Ａ）成分及び（Ｂ）成分以外の、分子内に２つ以上のアミノ基を有するポリアミン化合物又はその変性体などが挙げられる。当該ポリアミン化合物としては、例えば、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ヘキサメチレンジアミン、２－メチルペンタメチレンジアミン、トリメチルヘキサメチレンジアミン等の鎖状脂肪族ポリアミン化合物；ｏ－キシリレンジアミン、ｍ－キシリレンジアミン、ｐ－キシリレンジアミン等の芳香環含有脂肪族ポリアミン化合物；メンセンジアミン、ノルボルナンジアミン、トリシクロデカンジアミン、アダマンタンジアミン、ジアミノシクロヘキサン、１，４－ジアミノ－２－メチルシクロヘキサン、１，４－ジアミノ－３，６－ジエチルシクロヘキサン、ジアミノジエチルメチルシクロヘキサン、３，３’－ジメチル－４，４’－ジアミノジシクロヘキシルメタン、３，３’，５，５’－テトラメチル－４，４’－ジアミノジシクロヘキシルメタン、４，４’－ジアミノジシクロヘキシルメタン等の脂環式構造を有するポリアミン化合物；フェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン、ジエチルトルエンジアミン、２，２’－ジエチル－４，４’－メチレンジアニリン等の芳香族ポリアミン化合物；Ｎ，Ｎ’－ビス（アミノエチル）ピペラジン等の複素環式構造を有するポリアミン化合物；ポリエーテルポリアミン化合物等が挙げられる。また、当該ポリアミン化合物の変性体としては、上記化合物のマンニッヒ変性物、エポキシ変性物、マイケル付加物、マイケル付加・重縮合物、スチレン変性物、ポリアミド変性物等が挙げられる。これらは１種を単独で、又は２種以上を組み合わせて用いることができる。
　本発明の効果を効率的に発現する観点から、当該硬化剤を含有する場合、その含有量は、本発明のエポキシ樹脂硬化剤全量に対して好ましくは５０質量％以下、より好ましくは３０質量％以下、さらに好ましくは２０質量％以下、よりさらに好ましくは１５質量％以下、よりさらに好ましくは１０質量％以下、よりさらに好ましくは５質量％以下、よりさらに好ましくは１質量％以下である。また、下限は０質量％である。 The epoxy resin curing agent of the present invention may contain a known curing agent other than the component (A) and the component (B), a known curing accelerator, an additive, a solvent, and the like.
Examples of curing agents other than the components (A) and (B) include polyamine compounds having two or more amino groups in the molecule other than the components (A) and (B), or modified products thereof. Be Examples of the polyamine compound include linear aliphatic polyamine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, 2-methylpentamethylenediamine and trimethylhexamethylenediamine; o Aromatic ring-containing aliphatic polyamine compounds such as xylylenediamine, m-xylylenediamine, p-xylylenediamine; mensene diamine, norbornane diamine, tricyclodecane diamine, adamantane diamine, diaminocyclohexane, 1,4-diamino- 2-Methylcyclohexane, 1,4-diamino-3,6-diethylcyclohexane, diaminodiethylmethylcyclohexane, 3,3'-dimethyl-4,4'-diaminodi Polyamine compounds having an alicyclic structure such as chlorohexylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane; phenylenediamine, diaminodiphenylmethane , Aromatic polyamine compounds such as diaminodiphenyl sulfone, diethyltoluenediamine, 2,2'-diethyl-4,4'-methylenedianiline; and heterocyclic structures such as N, N'-bis (aminoethyl) piperazine Polyamine compounds; polyether polyamine compounds and the like can be mentioned. In addition, as modified products of the polyamine compound, Mannich modified products, epoxy modified products, Michael adducts, Michael addition / polycondensates, styrene modified products, polyamide modified products etc. of the above compounds can be mentioned. These can be used singly or in combination of two or more.
When the curing agent is contained, the content thereof is preferably 50% by mass or less, more preferably 30% by mass, based on the total amount of the epoxy resin curing agent of the present invention, from the viewpoint of efficiently expressing the effects of the present invention. The following content is more preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably 10% by mass or less, still more preferably 5% by mass or less, still more preferably 1% by mass or less. Moreover, a minimum is 0 mass%.
　公知の硬化促進剤としては、ビスフェノールＡ、スチレン化フェノール等のフェノール系化合物及びその塩；ｐ－トルエンスルホン酸、メタンスルホン酸等のスルホン酸系化合物及びその塩あるいはエステル化物；サリチル酸、安息香酸等のカルボン酸系化合物及びその塩；メルカプタン末端ポリサルファイド化合物；グアニジン系化合物；アルカノールアミン系化合物等が挙げられる。これらは１種を単独で、又は２種以上を組み合わせて用いることができる。
　本発明の効果を効率的に発現する観点から、当該硬化促進剤を含有する場合、その含有量は、本発明のエポキシ樹脂硬化剤全量に対して好ましくは５０質量％以下、より好ましくは３０質量％以下、さらに好ましくは２０質量％以下、よりさらに好ましくは１５質量％以下、よりさらに好ましくは１０質量％以下、よりさらに好ましくは５質量％以下、よりさらに好ましくは１質量％以下、よりさらに好ましくは０．５質量％以下である。また、下限は０質量％である。
　エポキシ樹脂硬化剤中の硬化促進剤の含有量は最終的に上記範囲となればよく、エポキシ樹脂硬化剤の調製時又は使用時に硬化促進剤の濃度を適宜変動させてもよい。例えば、硬化促進剤のエポキシ樹脂硬化剤に対する配合割合は該硬化剤を含有するエポキシ樹脂組成物の成形中、一定であってもよいし、成形中に硬化促進剤を濃度勾配をつけながら供給するなどして変動させてもよい。 Examples of known curing accelerators include phenol compounds such as bisphenol A and styrenated phenol and salts thereof; sulfonic acid compounds such as p-toluenesulfonic acid and methanesulfonic acid and salts or esters thereof; salicylic acid and benzoic acid Carboxylic acid compounds and salts thereof; mercaptan-terminated polysulfide compounds; guanidine compounds; alkanolamine compounds and the like. These can be used singly or in combination of two or more.
When the curing accelerator is contained, the content thereof is preferably 50% by mass or less, more preferably 30% by mass, based on the total amount of the epoxy resin curing agent of the present invention, from the viewpoint of efficiently expressing the effects of the present invention. % Or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably 10% by mass or less, still more preferably 5% by mass or less, still more preferably 1% by mass or less, still more preferably Is 0.5 mass% or less. Moreover, a minimum is 0 mass%.
The content of the curing accelerator in the epoxy resin curing agent may be in the above range, and the concentration of the curing accelerator may be appropriately varied during preparation or use of the epoxy resin curing agent. For example, the compounding ratio of the curing accelerator to the epoxy resin curing agent may be constant during molding of the epoxy resin composition containing the curing agent, or the curing accelerator is supplied while forming a concentration gradient during molding. For example, it may be varied.
　但し、本発明の効果を効率的に発現する観点からは、前記（Ａ）成分及び（Ｂ）成分の合計含有量を、本発明のエポキシ樹脂硬化剤全量に対して好ましくは５０質量％以上、より好ましくは７０質量％以上、さらに好ましくは８０質量％以上、よりさらに好ましくは８５質量％以上、よりさらに好ましくは９０質量％以上、よりさらに好ましくは９５質量％以上、特に好ましくは９９質量％以上（上限は１００質量％）となるようにする。 However, from the viewpoint of efficiently expressing the effects of the present invention, the total content of the components (A) and (B) is preferably 50% by mass or more based on the total amount of the epoxy resin curing agent of the present invention. More preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 85% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, particularly preferably 99% by mass or more (The upper limit is 100% by mass).
　本発明のエポキシ樹脂硬化剤は、温度２５℃における粘度が好ましくは１５０ｍＰａ・ｓ以下、より好ましくは１００ｍＰａ・ｓ以下、さらに好ましくは６０ｍＰａ・ｓ以下である。温度２５℃における粘度が１５０ｍＰａ・ｓ以下であると、エポキシ樹脂との混和が容易であり、ＦＲＰ用途に用いた際には生産性が向上する。エポキシ樹脂硬化剤の温度２５℃における粘度の下限値には特に制限はないが、エポキシ樹脂との混和性の点から、好ましくは１０ｍＰａ・ｓ以上である。エポキシ樹脂硬化剤の粘度は、Ｅ型粘度計を用いて測定できる。 The epoxy resin curing agent of the present invention preferably has a viscosity at a temperature of 25 ° C. of 150 mPa · s or less, more preferably 100 mPa · s or less, still more preferably 60 mPa · s or less. When the viscosity at a temperature of 25 ° C. is 150 mPa · s or less, mixing with an epoxy resin is easy, and productivity is improved when used for FRP applications. The lower limit value of the viscosity of the epoxy resin curing agent at a temperature of 25 ° C. is not particularly limited, but is preferably 10 mPa · s or more from the viewpoint of miscibility with the epoxy resin. The viscosity of the epoxy resin curing agent can be measured using an E-type viscometer.
　本発明のエポキシ樹脂硬化剤の製造方法には特に制限はなく、使用形態や使用装置、配合成分の種類及び配合割合等に応じて適宜選択することができる。例えば（Ａ）成分、（Ｂ）成分、及び必要に応じその他の配合成分を同時に接触させて混合してもよいし、エポキシ樹脂硬化剤を構成する一部の成分を濃度勾配をつけながら供給し、混合してもよい。また後述するように、エポキシ樹脂組成物の調製時に、エポキシ樹脂硬化剤に含まれる各成分とエポキシ樹脂とを同時に混合して調製してもよい。
　使用前にゲル化が進行するのを避ける観点から、エポキシ樹脂硬化剤に含まれる各成分は使用直前に接触させて混合することが好ましい。エポキシ樹脂硬化剤を単独で調製する場合、エポキシ樹脂硬化剤に含まれる各成分を混合する際の温度は、粘度上昇を抑制する観点から、好ましくは５～３０℃、より好ましくは１０～２５℃である。また、混合時間は好ましくは０．１～１５分、より好ましくは０．２～１０分、さらに好ましくは０．５～５分の範囲である。 There is no restriction | limiting in particular in the manufacturing method of the epoxy resin hardening agent of this invention, According to a use form, a use apparatus, the kind of compounding components, a mixture ratio, etc., it can select suitably. For example, component (A), component (B) and, if necessary, other compounding components may be brought into contact simultaneously and mixed, or some components constituting the epoxy resin curing agent may be supplied while giving a concentration gradient. , May be mixed. Also, as described later, when preparing the epoxy resin composition, each component contained in the epoxy resin curing agent and the epoxy resin may be simultaneously mixed and prepared.
From the viewpoint of preventing gelation from progressing before use, it is preferable that the components contained in the epoxy resin curing agent be brought into contact and mixed immediately before use. When preparing the epoxy resin curing agent alone, the temperature at which each component contained in the epoxy resin curing agent is mixed is preferably 5 to 30 ° C., more preferably 10 to 25 ° C., from the viewpoint of suppressing the increase in viscosity. It is. The mixing time is preferably in the range of 0.1 to 15 minutes, more preferably 0.2 to 10 minutes, and still more preferably 0.5 to 5 minutes.
［エポキシ樹脂組成物］
　本発明のエポキシ樹脂組成物は、前記本発明のエポキシ樹脂硬化剤とエポキシ樹脂とを含有するものである。該エポキシ樹脂としては、本発明のエポキシ樹脂硬化剤中の活性アミン水素と反応するグリシジル基を持つエポキシ樹脂であればいずれも使用することができるが、硬化物の機械的強度に優れる観点からは、分子内に芳香環又は脂環式構造を含むエポキシ樹脂であることが好ましく、ビスフェノールＡ型エポキシ樹脂及びビスフェノールＦ型エポキシ樹脂からなる群から選ばれる１種以上がより好ましく、ビスフェノールＡ型エポキシ樹脂がさらに好ましい。中でも、低粘度でかつ硬化物の機械的強度を確保できる観点から下記一般式（１）で示されるエポキシ樹脂が特に好ましい。 [Epoxy resin composition]
The epoxy resin composition of the present invention contains the epoxy resin curing agent of the present invention and an epoxy resin. As the epoxy resin, any epoxy resin having a glycidyl group that reacts with active amine hydrogen in the epoxy resin curing agent of the present invention can be used, but from the viewpoint of excellent mechanical strength of the cured product And an epoxy resin containing an aromatic ring or an alicyclic structure in the molecule, more preferably at least one member selected from the group consisting of bisphenol A epoxy resin and bisphenol F epoxy resin, and bisphenol A epoxy resin Is more preferred. Among them, an epoxy resin represented by the following general formula (1) is particularly preferable in view of low viscosity and sufficient mechanical strength of a cured product.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
（式（１）中、Ｒ１１～Ｒ１４はそれぞれ独立に炭素数１～６のアルキル基であり、ｐ、ｑ、ｒ、及びｓはそれぞれ独立に０～４の整数である。複数のＲ１１、複数のＲ１２、複数のＲ１３、及び複数のＲ１４はすべて同一でもよく、互いに異なってもよい。Ｙ１及びＹ２はそれぞれ独立に、単結合、－ＣＨ２－、－ＣＨ（ＣＨ３）－、又は－Ｃ（ＣＨ３）２－である。Ｒ１５は－ＣＨ２ＣＨ（ＯＨ）－、又は－ＣＨ（ＯＨ）ＣＨ２－である。ｍは平均繰り返し単位数を示し、０～０．２の数である。）
　Ｒ１１～Ｒ１４は炭素数１～４のアルキル基であることが好ましく、メチル基、エチル基、イソプロピル基、及びｔ－ブチル基からなる群から選ばれる少なくとも１種がより好ましい。
　ｐ、ｑ、ｒ、及びｓはいずれも０～２の整数であることが好ましく、０又は１であることがより好ましく、すべて０であることがさらに好ましい。
　Ｙ１及びＹ２は－ＣＨ２－、又は－Ｃ（ＣＨ３）２－であることが好ましく、－Ｃ（ＣＨ３）２－であることがより好ましい。
　また、低粘度でかつ硬化物の機械的強度を確保できる観点から、ｍは０～０．１５であることが好ましく、０．０１～０．１であることがより好ましい。 In the formula (1), R 11 to R 14 each independently represent an alkyl group having 1 to 6 carbon atoms, and p, q, r, and s each independently represent an integer of 0 to 4. 11 , a plurality of R 12 , a plurality of R 13 and a plurality of R 14 may be all the same as or different from each other Y 1 and Y 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 — m represents the average number of repeating units, It is a number between 0 and 0.2.)
R 11 to R 14 are preferably an alkyl group having 1 to 4 carbon atoms, and at least one selected from the group consisting of a methyl group, an ethyl group, an isopropyl group and a t-butyl group is more preferable.
Each of p, q, r and s is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably all 0s.
Y 1 and Y 2 are preferably —CH 2 — or —C (CH 3 ) 2 —, more preferably —C (CH 3 ) 2 —.
Further, in view of low viscosity and sufficient mechanical strength of the cured product, m is preferably 0 to 0.15, and more preferably 0.01 to 0.1.
　また、エポキシ樹脂のエポキシ当量は、エポキシ樹脂組成物の低粘度性及び速硬化性を両立する観点から、好ましくは３００ｇ／当量以下、より好ましくは２２０ｇ／当量以下、さらに好ましくは２００ｇ／当量以下、よりさらに好ましくは１８０ｇ／当量以下である。
　エポキシ樹脂は、１種を単独で使用してもよいし、２種以上を併用してもよい。 Further, the epoxy equivalent of the epoxy resin is preferably 300 g / equivalent or less, more preferably 220 g / equivalent or less, still more preferably 200 g / equivalent or less, from the viewpoint of achieving both the low viscosity and fast curing of the epoxy resin composition. Still 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.
　本発明のエポキシ樹脂組成物には、さらに、充填材、可塑剤などの改質成分、揺変剤などの流動調整成分、顔料、レベリング剤、粘着付与剤、エラストマー微粒子などのその他の成分を用途に応じて含有させてもよい。 The epoxy resin composition of the present invention further uses other components such as fillers, modifying components such as plasticizers, flow control components such as thixotropic agents, pigments, leveling agents, tackifiers, and fine particles of elastomers. You may make it contain according to.
　本発明のエポキシ樹脂組成物中の前記エポキシ樹脂硬化剤の含有量は、エポキシ樹脂中のエポキシ基の数に対するエポキシ樹脂硬化剤中の活性アミン水素数の比（エポキシ樹脂硬化剤中の活性アミン水素数／エポキシ樹脂中のエポキシ基数）が、好ましくは１／０．８～１／１．２、より好ましくは１／０．９～１／１．１、さらに好ましくは１／１となる量である。当該比は最終的に上記範囲となればよく、エポキシ樹脂組成物の成形中一定であってもよいし、成形中に変動させてもよい。 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 / the 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, further preferably 1/1. is there. The ratio may finally be in the above range, and may be constant during molding of the epoxy resin composition or may be varied during molding.
　本発明のエポキシ樹脂組成物の温度４０℃における粘度は、好ましくは４００ｍＰａ・ｓ以下、より好ましくは３５０ｍＰａ・ｓ以下、さらに好ましくは３００ｍＰａ・ｓ以下である。温度４０℃における粘度が４００ｍＰａ・ｓ以下であると、ＦＲＰ用途に用いた際には生産性が向上する。エポキシ樹脂組成物の温度４０℃における粘度の下限値には特に制限はないが、ＦＲＰの成形において、レイノルズ数の上昇により金型内で乱流が生じて強化繊維に乱れが生じることを抑制する点から、好ましくは１５０ｍＰａ・ｓ以上である。エポキシ樹脂組成物の粘度は、Ｅ型粘度計を用いて、具体的には実施例に記載の方法で測定できる。 The viscosity at a temperature of 40 ° C. of the epoxy resin composition of the present invention is preferably 400 mPa · s or less, more preferably 350 mPa · s or less, and still more preferably 300 mPa · s or less. When the viscosity at a temperature of 40 ° C. is 400 mPa · s or less, productivity is improved when used for FRP applications. The lower limit of the viscosity of the epoxy resin composition at a temperature of 40 ° C. is not particularly limited, but in FRP molding, turbulence is generated in the mold due to an increase in Reynolds number to suppress turbulence in the reinforcing fiber From the point of view, it is preferably 150 mPa · s or more. The viscosity of the epoxy resin composition can be measured using an E-type viscometer, specifically by the method described in the examples.
　本発明のエポキシ樹脂組成物は、速硬化性の観点から、温度８０℃におけるゲル化時間が、好ましくは３０分以下、より好ましくは２５分以下、さらに好ましくは２０分以下、よりさらに好ましくは１５分以下である。また、作業性の観点からは、当該ゲル化時間は、好ましくは０．５分以上、より好ましくは１．０分以上である。
　また、温度１２０℃におけるゲル化時間は、好ましくは１０分以下、より好ましくは８．０分以下、さらに好ましくは５．０分以下、よりさらに好ましくは３．０分以下である。また、作業性の観点からは、当該ゲル化時間は、好ましくは０．２分以上、より好ましくは０．５分以上である。
　上記ゲル化時間はレオメーターを用いて、実施例に記載の方法で測定できる。具体的には、レオメーターを用いて温度８０℃（又は１２０℃）、周波数１Ｈｚ、プレート間距離０．５ｍｍでエポキシ樹脂組成物の貯蔵弾性率Ｇ’、損失弾性率Ｇ’’を測定し、Ｇ’とＧ’’とが交差する点をゲル化時間とする。 The epoxy resin composition of the present invention preferably has a gelation time at a temperature of 80 ° C. of 30 minutes or less, more preferably 25 minutes or less, still more preferably 20 minutes or less, still more preferably 15 from the viewpoint of rapid curing. It is less than a minute. Moreover, 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 at a temperature of 120 ° C. is preferably 10 minutes or less, more preferably 8.0 minutes or less, still more preferably 5.0 minutes or less, and still more preferably 3.0 minutes or less. Further, from the viewpoint of workability, the gelation time is preferably 0.2 minutes or more, more preferably 0.5 minutes or more.
The gelation time can be measured using a rheometer by the method described in the examples. Specifically, storage modulus G ′ and loss modulus G ′ ′ of the epoxy resin composition are measured at a temperature of 80 ° C. (or 120 ° C.), a frequency of 1 Hz, and a plate distance of 0.5 mm using a rheometer The point at which G ′ and G ′ ′ intersect is the gelation time.
　本発明のエポキシ樹脂組成物の製造方法には特に制限はなく、エポキシ樹脂硬化剤、エポキシ樹脂、及び必要に応じ他の成分を公知の方法及び装置を用いて混合し、製造することができる。エポキシ樹脂組成物に含まれる各成分の混合順序にも特に制限はなく、前記エポキシ樹脂硬化剤を調製した後、これをエポキシ樹脂と混合してもよく、エポキシ樹脂硬化剤を構成する各成分及びエポキシ樹脂を同時に混合してもよい。
　使用前にゲル化が進行するのを避ける観点から、エポキシ樹脂組成物に含まれる各成分は使用直前に接触させて混合することが好ましい。エポキシ樹脂組成物に含まれる各成分を混合する際の温度は、エポキシ樹脂の粘度に応じて適宜調整できるが、粘度上昇を抑制する観点から、好ましくは１２０℃以下、より好ましくは１００℃以下であり、エポキシ樹脂の混和性の観点から、好ましくは３０℃以上、より好ましくは５０℃以上である。また、混合時間は好ましくは０．１～１５分、より好ましくは０．２～１０分、さらに好ましくは０．５～５分の範囲である。装置としては、例えば後述する各種成形方法において例示される装置を用いることができる。 There is no restriction | limiting in particular in the manufacturing method of the epoxy resin composition of this invention, An epoxy resin hardening | curing agent, an epoxy resin, and the other component as needed can be mixed and manufactured using a well-known method and apparatus. There is no particular limitation on the order of mixing of the components contained in the epoxy resin composition, and after preparing the epoxy resin curing agent, it may be mixed with the epoxy resin, and each component constituting the epoxy resin curing agent and The epoxy resin may be mixed simultaneously.
It is preferable to contact and mix each component contained in an epoxy resin composition immediately before use from a viewpoint of avoiding that gelatinization progresses before use. Although the temperature at the time of mixing each component contained in an epoxy resin composition can be suitably adjusted according to the viscosity of an epoxy resin, from a viewpoint of suppressing a viscosity rise, Preferably it is 120 degrees C or less, More preferably, it is 100 degrees C or less It is preferably 30 ° C. or more, more preferably 50 ° C. or more from the viewpoint of the miscibility of the epoxy resin. The mixing time is preferably in the range of 0.1 to 15 minutes, more preferably 0.2 to 10 minutes, and still more preferably 0.5 to 5 minutes. As an apparatus, the apparatus illustrated in the various shaping | molding methods mentioned later, for example can be used.
［硬化物］
　本発明のエポキシ樹脂組成物の硬化物（以下、単に「本発明の硬化物」ともいう）は、上述した本発明のエポキシ樹脂組成物を公知の方法で硬化させたものである。エポキシ樹脂組成物の硬化条件は用途、形態に応じて適宜選択され、特に限定されない。
　本発明の硬化物の形態も特に限定されず、用途に応じて選択することができる。例えばエポキシ樹脂組成物の用途が塗料である場合、当該組成物の硬化物は通常、膜状である。なお本発明の効果を有効に発揮する観点からは、本発明の硬化物は後述する繊維強化複合材のマトリックス樹脂であることが好ましい。 [Cured product]
The cured product of the epoxy resin composition of the present invention (hereinafter, also simply referred to as "the cured product of the present invention") is obtained by curing the above-described epoxy resin composition of the present invention by a known method. The curing conditions of the epoxy resin composition are appropriately selected according to the application and the form, and are not particularly limited.
The form of the cured product of the present invention is also not particularly limited, and can be selected according to the application. For example, when the application of the epoxy resin composition is a paint, the cured product of the composition is usually in the form of a film. From the viewpoint of effectively exhibiting the effects of the present invention, the cured product of the present invention is preferably a matrix resin of a fiber-reinforced composite material described later.
　本発明のエポキシ樹脂組成物は、繊維強化複合材などに用いた際の成形品の生産性を向上させる観点、及び成形品の耐熱性の観点から、硬化物のガラス転移温度（Ｔｇ）が高い方が好ましい。エポキシ樹脂組成物の硬化物のＴｇが高いと、繊維強化複合材などに用いた際に金型を低い温度まで冷却しなくても離型可能であるため、成形サイクルを短縮できる。また、成形品の耐熱性も良好になる。
　例えば本発明のエポキシ樹脂組成物は、温度１２０℃で１５分硬化させて得られた硬化物について、示差走査熱量計を用いて、昇温速度５℃／分の条件で３０～２５０℃まで示差走査熱分析を行うことにより求められるＴｇが好ましくは１００℃以上、より好ましくは１１０℃以上、さらに好ましくは１２０℃以上、よりさらに好ましくは１２３℃以上である。硬化物のＴｇは、具体的には実施例に記載の方法で測定できる。 The epoxy resin composition of the present invention has a high glass transition temperature (Tg) of a cured product from the viewpoint of improving the productivity of a molded product when used for a fiber reinforced composite material etc. and from the viewpoint of the heat resistance of the molded product. Is preferred. When the Tg of the cured product of the epoxy resin composition is high, the mold cycle can be shortened because mold release is possible without cooling the mold to a low temperature when used for a fiber reinforced composite material or the like. In addition, the heat resistance of the molded article is also improved.
For example, for the cured product obtained by curing the epoxy resin composition of the present invention at a temperature of 120.degree. C. for 15 minutes, a differential scanning calorimeter is used to make a difference from 30.degree. C. to 250.degree. The Tg determined by performing scanning thermal analysis is preferably 100 ° C. or more, more preferably 110 ° C. or more, still more preferably 120 ° C. or more, and still more preferably 123 ° C. or more. The Tg of the cured product can be measured specifically by the method described in the examples.
［繊維強化複合材（ＦＲＰ）］
　本発明のエポキシ樹脂硬化剤を含有するエポキシ樹脂組成物は、速硬化性、低粘度、ロングポットライフであり、及び硬化物が高耐熱性であるという特徴を有することから、繊維強化複合材用であることが好ましく、特に、炭素繊維強化複合材（ＣＦＲＰ）用であることが好ましい。
　繊維強化複合材は、前記エポキシ樹脂組成物の硬化物と、強化繊維とを含むものであり、強化繊維に前記エポキシ樹脂組成物を含浸させた後、該組成物を硬化させることにより得ることができる。ＦＲＰは、前記エポキシ樹脂組成物の硬化物と強化繊維の他に、さらに発泡材を含んでもよい。 [Fiber-Reinforced Composite (FRP)]
The epoxy resin composition containing the epoxy resin curing agent according to the present invention is characterized by rapid curing, low viscosity, long pot life, and high heat resistance of the cured product. It is preferable that it is especially for carbon fiber reinforced composites (CFRP).
A fiber reinforced composite material includes a cured product of the epoxy resin composition and a reinforcing fiber, and is obtained by impregnating the reinforcing resin with the epoxy resin composition and then curing the composition. it can. The FRP may further contain a foam in addition to the cured product of the epoxy resin composition and the reinforcing fibers.
　強化繊維としては、例えば、ガラス繊維、炭素繊維、ボロン繊維、アラミド繊維、セルロース繊維、ナノセルロース繊維及び金属繊維などが挙げられる。強化繊維は１種を単独で使用してもよいし、２種以上を併用してもよい。これらの中でも、得られる複合材の強度及び軽量性の観点からは炭素繊維が好ましい。
　ＣＦＲＰに用いられる炭素繊維は、レーヨンやポリアクリロニトリル（ＰＡＮ）などを原料として製造したものであってもよいし、石油や石炭などのピッチを原料として紡糸して製造したものであってもよい。また、炭素繊維の端材を再利用した再生品や、ＣＦＲＰから樹脂を除去した再生品の炭素繊維を用いることもできる。 Examples of the reinforcing fibers include glass fibers, carbon fibers, boron fibers, aramid fibers, cellulose fibers, nanocellulose fibers and metal fibers. The reinforcing fibers may be used alone or in combination of two or more. Among these, carbon fiber is preferable from the viewpoint of strength and lightness of the obtained composite material.
The carbon fiber used for CFRP may be manufactured using rayon, polyacrylonitrile (PAN) or the like as a raw material, or may be manufactured by spinning using a pitch of petroleum or coal as a raw material. In addition, it is also possible to use recycled carbon fibers of recycled carbon fiber scraps and recycled products obtained by removing resin from CFRP.
　強化繊維は、連続繊維と非連続繊維のいずれを用いることもできる。非連続繊維を用いる場合、その繊維長は、得られるＦＲＰの強度の観点から、使用する非連続繊維の平均繊維長として好ましくは１ｍｍ以上、より好ましくは３ｍｍ以上、さらに好ましくは６ｍｍ以上、よりさらに好ましくは１０ｍｍ以上である。また、使用する非連続繊維の平均繊維長の上限は、賦型性の観点から、好ましくは５００ｃｍ以下、より好ましくは３００ｃｍ以下、さらに好ましくは１００ｃｍ以下である。なお、平均繊維長は、目視、光学顕微鏡、走査型電子顕微鏡（ＳＥＭ）などによる観察によって測定することが可能である。１００本の繊維を無作為に選んで長さを測定し、個数平均の平均繊維長を算出することができる。 As the reinforcing fibers, either continuous fibers or non-continuous fibers can be used. When using a non-continuous fiber, the fiber length is preferably 1 mm or more, more preferably 3 mm or more, still more preferably 6 mm or more, as the average fiber length of the non-continuous fiber to be used from the viewpoint of the strength of the obtained FRP. Preferably it is 10 mm or more. The upper limit of the average fiber length of the non-continuous fiber to be used is preferably 500 cm or less, more preferably 300 cm or less, and still more preferably 100 cm or less, from the viewpoint of formability. The average fiber length can be measured by visual observation, observation by an optical microscope, a scanning electron microscope (SEM) or the like. 100 fibers can be randomly selected to measure the length, and the average fiber length of number average can be calculated.
　強化繊維の平均繊維径は、１～１００μｍであることが好ましく、３～５０μｍがより好ましく、４～２０μｍであることがさらに好ましい。平均繊維径がこの範囲であると、加工が容易であり、得られるＦＲＰの弾性率及び強度が優れたものとなる。なお、平均繊維径は走査型電子顕微鏡（ＳＥＭ）などによる観察によって測定することが可能である。５０本以上の繊維を無作為に選んで長さを測定し、個数平均の平均繊維径を算出することができる。 The average fiber diameter of the reinforcing fibers is preferably 1 to 100 μm, more preferably 3 to 50 μm, and still more preferably 4 to 20 μm. When the average fiber diameter is in this range, processing is easy, and the elastic modulus and strength of the obtained FRP are excellent. The average fiber diameter can be measured by observation with a scanning electron microscope (SEM) or the like. The length can be measured by randomly selecting 50 or more fibers, and the average fiber diameter of number average can be calculated.
　強化繊維の繊度は、２０～４，５００ｔｅｘが好ましく、５０～４，０００ｔｅｘがより好ましい。繊度がこの範囲であると、エポキシ樹脂組成物の含浸が容易であり、得られるＦＲＰの弾性率及び強度が優れたものとなる。なお、繊度は任意の長さの長繊維の重量を求めて、１，０００ｍ当たりの重量に換算して求めることができる。フィラメント数は通常、５００～６０，０００程度の強化繊維を好ましく用いることができる。 The fineness of the reinforcing fiber is preferably 20 to 4,500 tex, and more preferably 50 to 4,000 tex. When the fineness is in this range, the impregnation of the epoxy resin composition is easy, and the elastic modulus and the strength of the obtained FRP are excellent. The fineness can be determined by determining the weight of long fibers of an arbitrary length and converting it to the weight per 1,000 m. The number of filaments is usually about 500 to about 60,000, and a reinforcing fiber can be preferably used.
　強化繊維の形態としては、例えば単にモノフィラメント又はマルチフィラメントを一方向又は交互に交差するように並べたもの、編織物等の布帛、不織布あるいはマット等の種々の形態が挙げられる。これらのうち、モノフィラメント、布帛、不織布あるいはマットの形態が好ましく、布帛の形態がより好ましい。 Examples of the form of the reinforcing fiber include various forms such as a monofilament or a multifilament simply arranged to cross in one direction or alternately, a fabric such as a woven fabric, a non-woven fabric or a mat. Among these, the form of a monofilament, a fabric, a nonwoven fabric or a mat is preferable, and the form of a fabric is more preferable.
　発泡材としては特に制限はないが、例えばポリ塩化ビニル樹脂、ポリウレタン樹脂、ポリスチレン樹脂、ポリオレフィン樹脂、アクリル樹脂、フェノール樹脂、ポリメタクリルイミド樹脂、エポキシ樹脂等の樹脂材料から構成される発泡材が挙げられる。 The foam material is not particularly limited, but examples thereof include foam materials composed of resin materials such as polyvinyl chloride resin, polyurethane resin, polystyrene resin, polyolefin resin, acrylic resin, phenol resin, polymethacrylimide resin, epoxy resin, etc. Be
　繊維強化複合材の製造方法には特に制限はないが、本発明のエポキシ樹脂硬化剤及びエポキシ樹脂組成物は速硬化性であるため、エポキシ樹脂硬化剤と、エポキシ樹脂とを成形の直前に混合した後、好ましくは１０分以内、より好ましくは５分以内に、強化繊維への含浸及び硬化を行うことが好ましい。
　この観点から、繊維強化複合材の製造方法は、低圧ＲＴＭ法、中圧ＲＴＭ法、高圧ＲＴＭ法、コンプレッションＲＴＭ法、リキッドコンプレッションモールディング法、リキッドレイダウン法、スプレーレイダウン法、サーフェイスＲＴＭ法、プリプレグコンプレッションモールディング法又はウェットコンプレッションモールディング（ＷＣＭ）法、及びＤｙｎａｍｉｃ　Ｆｌｕｉｄ　Ｃｏｍｐｒｅｓｓｉｏｎ　Ｍｏｌｄｉｎｇ法により成形する工程を有することが好ましい。これらの成形法の中でも、ハイサイクルＲＴＭ法に適用する観点から、低圧ＲＴＭ法、中圧ＲＴＭ法、又は高圧ＲＴＭ法が好ましく、中圧ＲＴＭ法又は高圧ＲＴＭ法がより好ましく、成形速度の観点からは高圧ＲＴＭ法がさらに好ましい。
　なお本明細書において、低圧ＲＴＭ法における「低圧」とは、エポキシ樹脂組成物の主剤であるエポキシ樹脂と、エポキシ樹脂硬化剤とを圧送して混合する際の圧送時の圧力が０．５ＭＰａ未満であることをいう。同様に、中圧ＲＴＭ法における「中圧」とは上記圧力が０．５ＭＰａ以上、７ＭＰａ未満、高圧ＲＴＭ法における「高圧」とは上記圧力が７ＭＰａ以上、２０ＭＰａ以下であるものを指す。
　本発明のエポキシ樹脂組成物は速硬化性でかつ低粘度であるため、金型内への充填及び強化繊維への含浸が速く、速やかに硬化するため、成形時間を大幅に短縮できる。したがって本発明のエポキシ樹脂硬化剤及びエポキシ樹脂組成物は、上記成形法に特に好適である。また、上記成形法を用いることにより、本発明のエポキシ樹脂硬化剤及びエポキシ樹脂組成物を適用して、自動車用構造材や建材用などの中～大型のＦＲＰを生産性よく製造することができる。 There is no particular limitation on the method of producing the fiber-reinforced composite material, but since the epoxy resin curing agent and epoxy resin composition of the present invention are quick-curing, the epoxy resin curing agent and the epoxy resin are mixed immediately before molding. After that, it is preferable to carry out the impregnation and curing of the reinforcing fiber, preferably within 10 minutes, more preferably within 5 minutes.
From this point of view, methods for producing fiber reinforced composite materials include low pressure RTM method, medium pressure RTM method, high pressure RTM method, compression RTM method, liquid compression molding method, liquid laydown method, liquid laydown method, spray laydown method, surface RTM method, prepreg compression molding It is preferable to have a step of forming by a method or a wet compression molding (WCM) method, and a Dynamic Fluid Compression Molding method. Among these molding methods, the low pressure RTM method, the medium pressure RTM method, or the high pressure RTM method is preferable from the viewpoint of application to the high cycle RTM method, the medium pressure RTM method or the high pressure RTM method is more preferable. Is more preferably a high pressure RTM method.
In the present specification, “low pressure” in the low pressure RTM method means that the pressure at the time of pumping when the epoxy resin which is the main agent of the epoxy resin composition and the epoxy resin curing agent are pumped and mixed is less than 0.5 MPa Say that. Similarly, the "medium pressure" in the medium pressure RTM method refers to a pressure of 0.5 MPa or more and less than 7 MPa, and the "high pressure" in the high pressure RTM method refers to a pressure of 7 MPa or more and 20 MPa or less.
Since the epoxy resin composition of the present invention is rapidly curable and has a low viscosity, it can be filled quickly into the mold and impregnated into the reinforcing fiber quickly and rapidly, so that the molding time can be significantly shortened. Therefore, the epoxy resin curing agent and the epoxy resin composition of the present invention are particularly suitable for the above molding method. In addition, by using the above-described molding method, medium to large-sized FRPs for automobile structural materials and building materials can be produced with high productivity by applying the epoxy resin curing agent and epoxy resin composition of the present invention. .
　高圧ＲＴＭ法では、エポキシ樹脂組成物の主剤であるエポキシ樹脂と、エポキシ樹脂硬化剤とを混合する装置として衝突混合ミキサーを使用することが好ましい。例えば、上下一対の金型内に強化繊維を配置して密閉し、金型内を減圧にする。次いで、エポキシ樹脂組成物の主剤であるエポキシ樹脂と、エポキシ樹脂硬化剤とを別々のタンクに充填し、それぞれを非常に小さい穴（オリフィス）から高速で吐出し、衝突混合ミキサーのミキシングチャンバー内で衝突混合させる。このようにして調製したエポキシ樹脂組成物を金型内に高圧注入して強化繊維に含浸させ、次いで、エポキシ樹脂を硬化させる。 In the high pressure RTM method, it is preferable to use a collision mixing mixer as an apparatus for mixing an epoxy resin which is a main component of an epoxy resin composition, and an epoxy resin curing agent. For example, reinforcing fibers are placed in a pair of upper and lower molds and sealed, and the inside of the mold is depressurized. Next, the epoxy resin, which is the main component of the epoxy resin composition, and the epoxy resin curing agent are filled in separate tanks, and each is discharged at a high speed from very small holes (orifices) in the mixing chamber of the collision mixing mixer. Make collision mixing. The epoxy resin composition thus prepared is injected at high pressure into a mold to impregnate the reinforcing fibers, and then the epoxy resin is cured.
　低圧ＲＴＭ法では、エポキシ樹脂組成物の主剤であるエポキシ樹脂と、エポキシ樹脂硬化剤とを混合する装置としてダイナミックミキサーを使用することが好ましい。ダイナミックミキサーは、表面に凹凸を有する筒状の高速回転体を備えている。例えば、エポキシ樹脂組成物の主剤であるエポキシ樹脂と、エポキシ樹脂硬化剤とを別々のタンクに充填し、それぞれをダイナミックミキサーに送液して前記回転体により主剤と硬化剤の２液を混合する。このようにして調製したエポキシ樹脂組成物を金型内に注入して強化繊維に含浸させ、次いで、エポキシ樹脂を硬化させる。低圧ＲＴＭ法は、エポキシ樹脂とエポキシ樹脂硬化剤との配合比が大きく異なる場合や、装置コスト、装置の省スペース化の観点で有利である。
　中圧ＲＴＭ法では、エポキシ樹脂組成物の主剤であるエポキシ樹脂と、エポキシ樹脂硬化剤とを混合する装置としてスタティックミキサーを使用することが好ましい。スタティックミキサーは、多数のミキシングエレメントからなる静止型混合器を１個以上組み込んだ管型反応器である。例えば、エポキシ樹脂組成物の主剤であるエポキシ樹脂と、エポキシ樹脂硬化剤とを別々のタンクに充填し、それぞれをスタティックミキサーに送液する。スタティックミキサーのねじれたエレメントに主剤と硬化剤の２液を通すことで、分割・転換・反転等の作用より２液が混合される。このようにして調製したエポキシ樹脂組成物を金型内に注入して強化繊維に含浸させ、次いで、エポキシ樹脂を硬化させる。中圧ＲＴＭ法は、金型内にエポキシ樹脂組成物を圧送できること、及び、装置コストの観点で有利である。 In the low pressure RTM method, it is preferable to use a dynamic mixer as an apparatus for mixing an epoxy resin, which is a main component of an epoxy resin composition, and an epoxy resin curing agent. The dynamic mixer is provided with a cylindrical high-speed rotating body having irregularities on the surface. For example, an epoxy resin which is a main component of an epoxy resin composition and an epoxy resin curing agent are filled in separate tanks, each is sent to a dynamic mixer, and the two components of the main agent and the curing agent are mixed by the rotating body. . The epoxy resin composition thus prepared is poured into a mold to impregnate the reinforcing fibers and then the epoxy resin is cured. The low pressure RTM method is advantageous in the case where the compounding ratio of the epoxy resin and the epoxy resin curing agent is largely different, in view of the device cost and the space saving of the device.
In the medium pressure RTM method, it is preferable to use a static mixer as an apparatus for mixing an epoxy resin, which is a main component of an epoxy resin composition, and an epoxy resin curing agent. A static mixer is a tubular reactor incorporating one or more static mixers consisting of a large number of mixing elements. For example, an epoxy resin which is a main component of an epoxy resin composition and an epoxy resin curing agent are filled in separate tanks, and each is sent to a static mixer. By passing the two components of the main agent and the curing agent through the twisted element of the static mixer, the two components are mixed by the action of division, conversion, inversion and the like. The epoxy resin composition thus prepared is poured into a mold to impregnate the reinforcing fibers and then the epoxy resin is cured. The medium pressure RTM method is advantageous in that the epoxy resin composition can be pumped into the mold and in terms of equipment cost.
　ＦＲＰが前記エポキシ樹脂組成物の硬化物と強化繊維の他にさらに発泡材を含む場合は、前記金型内に強化繊維及び発泡材を配置して、前記と同様にＦＲＰの製造を行うことができる。 When the FRP further contains a foamed material in addition to the cured product of the epoxy resin composition and the reinforced fiber, the reinforced fiber and the foamed material may be disposed in the mold to produce the FRP in the same manner as described above. it can.
　リキッドコンプレッションモールディング（ＬＣＭ）法、リキッドレイダウン法、及びウェットコンプレッションモールディング（ＷＣＭ）法にも本発明のエポキシ樹脂硬化剤及びエポキシ樹脂組成物を好適に用いることができる。ＬＣＭ法、リキッドレイダウン法、及びＷＣＭ法では、強化繊維上（ＦＲＰがさらに発泡材を含む場合は、強化繊維及び発泡材上）にエポキシ樹脂組成物を流延させた後、加熱圧縮して強化繊維へ含浸させながらエポキシ樹脂を硬化させる。Ｄｙｎａｍｉｃ　Ｆｌｕｉｄ　Ｃｏｍｐｒｅｓｓｉｏｎ　Ｍｏｌｄｉｎｇ法は、ＬＣＭ法、リキッドレイダウン法、及びＷＣＭ法の改良方法であり、加熱圧縮の際に金型内を減圧することが特徴である。 The epoxy resin curing agent and epoxy resin composition of the present invention can be suitably used for the liquid compression molding (LCM) method, liquid laydown method, and wet compression molding (WCM) method. In the LCM method, liquid lay-down method, and WCM method, the epoxy resin composition is cast on a reinforcing fiber (on the reinforcing fiber and the foam when the FRP further includes a foam), and then heat compression is applied to strengthen The epoxy resin is cured while being impregnated into the fibers. The Dynamic Fluid Compression Molding method is an improvement method of the LCM method, the liquid laydown method, and the WCM method, and is characterized in that the pressure in the mold is reduced during heat compression.
　ＦＲＰの成形において、エポキシ樹脂組成物を金型内に注入、又は強化繊維に含浸させる際の温度は、好ましくは３０～１２０℃、より好ましくは５０～１００℃である。エポキシ樹脂硬化剤とエポキシ樹脂とを別々のタンクから供給して成形直前に混合する場合、エポキシ樹脂硬化剤とエポキシ樹脂との混合時の温度は、個別に設定することもできる。エポキシ樹脂硬化剤の混合時の温度は、粘度上昇を抑制する観点から、好ましくは５～３０℃、より好ましくは１０～２５℃である。またエポキシ樹脂の混合時の温度は、エポキシ樹脂の粘度に応じて適宜調整できるが、好ましくは３０～１２０℃、より好ましくは５０～１００℃である。上記温度は成形中一定であってもよいし、成形中に変動させてもよい。
　エポキシ樹脂組成物の強化繊維への含浸時間は、成形性及び生産性の観点から、好ましくは０．１～１５分、より好ましくは０．２～１０分、さらに好ましくは０．５～５分である。
　エポキシ樹脂組成物を金型内に注入する際の吐出速度は、成形性及び生産性の観点から、好ましくは毎秒５～４００ｇ、より好ましくは毎秒１０～１００ｇ、さらに好ましくは毎秒２０～６０ｇである。上記速度は成形中一定であってもよいし、成形中に変動させてもよい。 In FRP molding, the temperature at which the epoxy resin composition is injected into a mold or impregnated into reinforcing fibers is preferably 30 to 120 ° C., more preferably 50 to 100 ° C. When the epoxy resin curing agent and the epoxy resin are supplied from separate tanks and mixed immediately before molding, the temperature at the time of mixing the epoxy resin curing agent and the epoxy resin can also be set individually. The temperature at which the epoxy resin curing agent is mixed is preferably 5 to 30 ° C., more preferably 10 to 25 ° C., from the viewpoint of suppressing an increase in viscosity. Further, the temperature at the time of mixing of the epoxy resin can be appropriately adjusted according to the viscosity of the epoxy resin, but it is preferably 30 to 120 ° C., more preferably 50 to 100 ° C. The temperature may be constant during molding or may be varied during molding.
The impregnation time of the epoxy resin composition to the reinforcing fiber is preferably 0.1 to 15 minutes, more preferably 0.2 to 10 minutes, still more preferably 0.5 to 5 minutes, from the viewpoint of moldability and productivity. It is.
The discharge rate at the time of injecting the epoxy resin composition into the mold is preferably 5 to 400 g per second, more preferably 10 to 100 g per second, still more preferably 20 to 60 g per second from the viewpoint of moldability and productivity. . The speed may be constant during molding or may be varied during molding.
　エポキシ樹脂組成物の硬化温度は、好ましくは５０～２００℃、より好ましくは８０～１５０℃、さらに好ましくは１００～１５０℃である。硬化温度は成形中一定であってもよいし、成形中に変動させてもよい。硬化温度が５０℃以上であれば、エポキシ樹脂の硬化が十分に進み、得られるＦＲＰの機械的特性が優れたものとなる。また、２００℃以下であれば、金型温度調整にかかるコストが低く済む。エポキシ樹脂組成物の硬化時間は、成形性及び生産性の観点から、好ましくは０．１～１５分、より好ましくは０．２～１０分、さらに好ましくは０．５～５分である。 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 temperature may be constant during molding or may be varied during molding. When the curing temperature is 50 ° C. or more, curing of the epoxy resin proceeds sufficiently, and the mechanical properties of the obtained FRP become excellent. Moreover, if it is 200 degrees C or less, the cost concerning mold temperature adjustment will be low. The curing time of the epoxy resin composition is preferably 0.1 to 15 minutes, more preferably 0.2 to 10 minutes, and still more preferably 0.5 to 5 minutes, from the viewpoint of moldability and productivity.
　本発明のエポキシ樹脂硬化剤又はエポキシ樹脂組成物を用いて、上記の成形法によりＦＲＰを生産性よく製造することができる。本発明の繊維強化複合材は、自動車用構造材や建材、特に自動車用構造材であることが好ましい。自動車用構造材としては、バンパー、スポイラー、カウリング、フロントグリル、ガーニッシュ、ボンネット、トランクリッド、フェンダーパネル、ドアパネル、ルーフパネル、インストルメントパネル、ドアトリム、クオータートリム、ルーフライニング、ピラーガーニッシュ、デッキトリム、トノボード、パッケージトレイ、ダッシュボード、コンソールボックス、キッキングプレート、スイッチベース、シートバックボード、シートフレーム、アームレスト、サンバイザ、インテークマニホールド、エンジンヘッドカバー、エンジンアンダーカバー、オイルフィルターハウジング等が挙げられる。 Using the epoxy resin curing agent or epoxy resin composition of the present invention, FRP can be produced with high productivity by the above-mentioned molding method. The fiber-reinforced composite material of the present invention is preferably a structural material for automobiles and a building material, particularly a structural material for automobiles. Structural materials for automobiles include bumpers, spoilers, cowlings, front grills, garnishes, bonnets, trunk lids, fender panels, door panels, roof panels, instrument panels, door trims, quarter trims, roof linings, pillar garnishes, deck trims, and tonoboards. Package trays, dashboards, console boxes, kicking plates, switch bases, seat backboards, seat frames, armrests, sun visors, intake manifolds, engine head covers, engine under covers, oil filter housings, etc.
　以下に実施例及び比較例を挙げて本発明を詳細に説明するが、本発明は下記実施例に限定されるものではない。なお、各種測定及び評価は以下の方法に従って行った。 EXAMPLES The present invention will be described in detail by way of examples and comparative examples below, but the present invention is not limited to the following examples. In addition, various measurements and evaluations were performed according to the following methods.
（粘度）
　Ｅ型粘度計「ＴＶＥ－２２Ｈ型粘度計　コーンプレートタイプ」（東機産業（株）製）を用いて、４０℃及び８０℃にてそれぞれエポキシ樹脂組成物の粘度を測定した。８０℃での測定においては、エポキシ樹脂及びエポキシ樹脂硬化剤を混合してエポキシ樹脂組成物を調製した直後に測定を開始し、３０秒ごとに測定値を読み取って粘度の経時変化を確認した。
　４０℃における粘度、及び８０℃３０秒経過後における粘度が低いほど、初期粘度が低く、成形時の充填性が高くなり成形性が良好であることを示す。また、８０℃での測定における粘度の経時変化が少なく、低粘度を維持しているほどポットライフが長いことを示す。 (viscosity)
The viscosity of the epoxy resin composition was measured at 40 ° C. and 80 ° C., respectively, using an E-type viscometer “TVE-22H type viscometer cone plate type” (manufactured by Toki Sangyo Co., Ltd.). In the measurement at 80 ° C., the measurement was started immediately after preparing the epoxy resin composition by mixing the epoxy resin and the epoxy resin curing agent, and the measured value was read every 30 seconds to confirm the temporal change of the viscosity.
The lower the viscosity at 40 ° C. and the viscosity after 80 ° C. for 30 seconds, the lower the initial viscosity, the higher the filling properties at the time of molding, and the better the moldability. In addition, the change in viscosity with time in measurement at 80 ° C. is small, and the lower the viscosity is maintained, the longer the pot life is.
（ゲル化時間）
　レオメーター「ＡＲＥＳ－Ｇ２」（ＴＡインスツルメント製）を用いて、８０℃及び１２０℃で測定を行った。８０℃（又は１２０℃）に加温したアルミプレート間にエポキシ樹脂組成物を充填し、温度８０℃（又は１２０℃）、周波数１Ｈｚ、プレート間距離０．５ｍｍで貯蔵弾性率Ｇ’、損失弾性率Ｇ’’を測定して、Ｇ’とＧ’’とが交差する点をゲル化時間とした。ゲル化時間が短いほど速硬化性であることを示す。 (Gelation time)
The measurement was performed at 80 ° C. and 120 ° C. using a rheometer “ARES-G2” (manufactured by TA Instruments). The epoxy resin composition is filled between aluminum plates heated to 80 ° C. (or 120 ° C.), storage modulus G 'at a temperature of 80 ° C. (or 120 ° C.), frequency 1 Hz, plate distance 0.5 mm, loss elasticity The rate G ′ ′ was measured, and the point at which G ′ and G ′ ′ intersected was taken as the gelation time. The shorter the gelation time, the faster the curing.
（ガラス転移温度（Ｔｇ））
　エポキシ樹脂組成物の硬化物のＴｇは、１２０℃で１５分加熱して硬化させたエポキシ樹脂組成物について、示差走査熱量計「ＤＳＣ　６２００」（セイコーインスツル（株）製）を用いて、昇温速度５℃／分の条件で３０～２５０℃まで示差走査熱分析を行うことにより求めた。 (Glass transition temperature (Tg))
The Tg of the cured product of the epoxy resin composition is raised using a differential scanning calorimeter “DSC 6200” (manufactured by Seiko Instruments Inc.) for the epoxy resin composition cured by heating at 120 ° C. for 15 minutes. It was determined by performing differential scanning calorimetry up to 30 to 250 ° C. at a temperature rate of 5 ° C./min.
実施例１～７及び比較例１～３（エポキシ樹脂硬化剤及びエポキシ樹脂組成物の調製）
　（Ａ）成分であるＮ－アミノエチルピペラジン（ＡＥＰ、東ソー（株）製）及びイソホロンジアミン（ＩＰＤＡ、ＥＶＯＮＩＫ製）、並びに成分（Ｂ）である１，３－ビス（アミノメチル）シクロヘキサン（１，３－ＢＡＣ、三菱瓦斯化学（株）製、シス／トランス比＝７７／２３）を、表１に示す質量部で配合して混合し、エポキシ樹脂硬化剤を得た。
　さらに、このエポキシ樹脂硬化剤と、主剤であるビスフェノールＡ型液状エポキシ樹脂（「ｊＥＲ８２５」、三菱化学（株）製）とを、エポキシ樹脂硬化剤中の活性アミン水素数と、主剤であるエポキシ樹脂中のエポキシ基数とが等モルとなるよう配合して混合し、エポキシ樹脂組成物を調製した。
　得られたエポキシ樹脂硬化剤及びエポキシ樹脂組成物について、前述の方法で評価を行った。結果を表１に示す。なお、エポキシ樹脂ｊＥＲ８２５は下記構造式で示され、エポキシ当量は１７５ｇ／当量、ｍ＝０．０３５である。 Examples 1 to 7 and Comparative Examples 1 to 3 (Preparation of Epoxy Resin Curing Agent and Epoxy Resin Composition)
Component (A) N-aminoethyl piperazine (AEP, manufactured by Tosoh Corp.) and isophorone diamine (IPDA, manufactured by EVONIK), and component (B) 1,3-bis (aminomethyl) cyclohexane (1,1) 3-BAC, manufactured by Mitsubishi Gas Chemical Co., Ltd., cis / trans ratio = 77/23) was blended by mass parts shown in Table 1 and mixed to obtain an epoxy resin curing agent.
Furthermore, the epoxy resin curing agent and the main component bisphenol A liquid epoxy resin ("jER 825", manufactured by Mitsubishi Chemical Corporation), the number of active amine hydrogens in the epoxy resin curing agent, and the epoxy resin as the main component The epoxy resin composition was prepared by blending and mixing so that the number of epoxy groups in the composition is equimolar.
The obtained epoxy resin curing agent and epoxy resin composition were evaluated by the above-mentioned method. The results are shown in Table 1. The epoxy resin jER 825 is represented by the following structural formula, and has an epoxy equivalent of 175 g / equivalent, m = 0.035.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　上記式中、Ｒ１５は－ＣＨ２ＣＨ（ＯＨ）－、又は－ＣＨ（ＯＨ）ＣＨ２－である。 In the above formulae, R 15 is —CH 2 CH (OH) — or —CH (OH) CH 2 —.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表１より、エポキシ樹脂硬化剤として（Ａ）成分であるＡＥＰのみを用いた比較例１のエポキシ樹脂組成物と比較して、実施例１～３のエポキシ樹脂組成物は速硬化性を維持しつつ、低粘度化され、ポットライフが長くなり、さらに硬化物の耐熱性が向上した。また、エポキシ樹脂硬化剤として（Ａ）成分であるＩＰＤＡのみを用いた比較例２のエポキシ樹脂組成物と比較して、実施例４～６のエポキシ樹脂組成物はポットライフを維持しつつ、低粘度化され、硬化速度及び硬化物の耐熱性が向上した。
　比較例３のエポキシ樹脂組成物と比較して、実施例７のエポキシ樹脂組成物は粘度、ポットライフ、硬化速度及び硬化物の耐熱性がいずれも改善された。 From Table 1, compared with the epoxy resin composition of Comparative Example 1 using only AEP which is the component (A) as the epoxy resin curing agent, the epoxy resin compositions of Examples 1 to 3 maintain quick curing property. However, the viscosity was lowered, the pot life was extended, and the heat resistance of the cured product was further improved. Moreover, compared with the epoxy resin composition of Comparative Example 2 using only IPDA which is the component (A) as the epoxy resin curing agent, the epoxy resin compositions of Examples 4 to 6 have low pot life while maintaining low pot life. The viscosity was improved, and the curing speed and the heat resistance of the cured product were improved.
As compared with the epoxy resin composition of Comparative Example 3, the epoxy resin composition of Example 7 was improved in the viscosity, the pot life, the curing rate and the heat resistance of the cured product.
実施例８（ＣＦＲＰの製造）
　実施例１のエポキシ樹脂組成物を、室温でのハンドレイアップ成形により、炭素繊維織物（東レ（株）製「ＣＯ６３４３」、Ｔ３００平織りクロス、３Ｋ、１９８ｇ／ｍ２、０．２５ｍｍ厚、４ｐｌｙ）に含浸させてＣＦＲＰ基材を作製した。続いて、オーブン内で予め１２０℃に加熱したアルミ上下型にＣＦＲＰ基材を載せ、速やかに型を閉じ、３分加熱してエポキシ樹脂組成物を硬化させてＣＦＲＰを得た。得られたＣＦＲＰはアルミ上下型から容易に離型することができ、エポキシ樹脂組成物の硬化が短時間で進行していることが確認できた。またエポキシ樹脂組成物の炭素繊維への含浸性が低いことなどによる欠陥もなく、外観が良好であった。 Example 8 (manufacture of CFRP)
The epoxy resin composition of Example 1 was hand lay-up molded at room temperature to obtain a carbon fiber fabric ("CO6343" manufactured by Toray Industries, Inc., T300 plain weave cloth, 3 K, 198 g / m 2 , 0.25 mm thickness, 4 ply) To make a CFRP base material. Subsequently, the CFRP base material was placed on an aluminum upper and lower mold preheated to 120 ° C. in an oven, the mold was immediately closed, and heating was performed for 3 minutes to cure the epoxy resin composition to obtain CFRP. The obtained CFRP can be easily released from the aluminum upper and lower molds, and it has been confirmed that the curing of the epoxy resin composition has progressed in a short time. In addition, the appearance was good without any defect due to the infiltration of the epoxy resin composition into the carbon fiber being low.
　本発明によれば、エポキシ樹脂硬化剤成分として汎用されているＮ－アミノエチルピペラジンやイソホロンジアミンをエポキシ樹脂硬化剤として用いながら、ハイサイクルＲＴＭ法などによって自動車用構造材や建材などのＣＦＲＰを生産性よく製造できるエポキシ樹脂硬化剤及びエポキシ樹脂組成物を提供することができる。
　当該エポキシ樹脂組成物はポットライフが長いため作業性が良好である。また、ＣＦＲＰをはじめとするＦＲＰのマトリクス樹脂として用いると、強化繊維への含浸性に優れ、速硬化性であることから金型からの離型が可能になるまでの時間も短く、ＦＲＰの生産性を向上させることができる。さらに、得られるＦＲＰの耐熱性も良好になる。
  According to the present invention, while using N-aminoethyl piperazine and isophorone diamine which are generally used as epoxy resin curing agent components as epoxy resin curing agents, high cycle RTM method etc. are used to produce CFRPs such as automotive structural materials and building materials It is possible to provide an epoxy resin curing agent and an epoxy resin composition which can be produced with good quality.
Since the said epoxy resin composition has a long pot life, its workability is good. In addition, when used as a matrix resin of FRP, including CFRP, it is excellent in the ability to impregnate reinforcing fibers and has a quick curing property, so that the time until mold release from molds becomes possible is short, and FRP production It is possible to improve the quality. Furthermore, the heat resistance of the obtained FRP is also improved.

Claims (9)

  1. 　Ｎ－アミノエチルピペラジン及びイソホロンジアミンからなる群から選ばれる少なくとも１種の化合物（Ａ）と、ビス（アミノメチル）シクロヘキサン（Ｂ）とを含有するエポキシ樹脂硬化剤。 An epoxy resin curing agent containing at least one compound (A) selected from the group consisting of N-aminoethyl piperazine and isophorone diamine and bis (aminomethyl) cyclohexane (B).
  2. 　前記（Ａ）成分と（Ｂ）成分との質量比が０．５７５＜（Ａ）／［（Ａ）＋（Ｂ）］＜１を満たす、請求項１に記載のエポキシ樹脂硬化剤。 The epoxy resin curing agent according to claim 1, wherein a mass ratio of the component (A) to the component (B) satisfies 0.575 <(A) / [(A) + (B)] <1.
  3. 　前記（Ａ）成分がＮ－アミノエチルピペラジンである、請求項１又は２に記載のエポキシ樹脂硬化剤。 The epoxy resin curing agent according to claim 1 or 2, wherein the component (A) is N-aminoethyl piperazine.
  4. 　前記（Ｂ）成分が１，３－ビス（アミノメチル）シクロヘキサンである、請求項１～３のいずれか１項に記載のエポキシ樹脂硬化剤。 The epoxy resin curing agent according to any one of claims 1 to 3, wherein the component (B) is 1,3-bis (aminomethyl) cyclohexane.
  5. 　前記（Ａ）成分及び（Ｂ）成分の合計含有量が５０質量％以上である、請求項１～４のいずれか１項に記載のエポキシ樹脂硬化剤。 The epoxy resin curing agent according to any one of claims 1 to 4, wherein the total content of the components (A) and (B) is 50% by mass or more.
  6. 　請求項１～５のいずれか１項に記載のエポキシ樹脂硬化剤と、エポキシ樹脂とを含有するエポキシ樹脂組成物。 An epoxy resin composition comprising the epoxy resin curing agent according to any one of claims 1 to 5 and an epoxy resin.
  7. 　請求項６に記載のエポキシ樹脂組成物の硬化物。 A cured product of the epoxy resin composition according to claim 6.
  8. 　請求項６に記載のエポキシ樹脂組成物の硬化物と、強化繊維とを含む繊維強化複合材。 The fiber reinforced composite material containing the hardened | cured material of the epoxy resin composition of Claim 6, and a reinforced fiber.
  9. 　前記強化繊維が炭素繊維である、請求項８に記載の繊維強化複合材。
          The fiber reinforced composite according to claim 8, wherein the reinforcing fiber is a carbon fiber.
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