KR101805677B1 - Epoxy resin composition for aramid-fiber-reinforced composite material, prepreg, and fiber-reinforced composite material - Google Patents

Abstract

The present invention relates to an epoxy resin composition for an aramid fiber reinforced composite material, a prepreg and a fiber-reinforced composite material. The present invention is an epoxy resin composition comprising at least the following components [A], [B] Wherein the ratio of the epoxy resin composition to the epoxy resin composition is 1 to 30 parts by weight of TPAE [B] and 3 to 10 parts by weight of a curing agent [C] in 100 parts by weight of the epoxy resin [A] Composition can be provided.
It is also possible to provide a fiber reinforced composite material obtained by curing a prepreg obtained by impregnating an epoxy resin composition for an aramid fiber reinforced composite material with a reinforcing fiber and a prepreg.

Description

EPOXY RESIN COMPOSITION FOR ARAMID-FIBER-REINFORCED COMPOSITE MATERIAL, PREPREG, AND FIBER-REINFORCED COMPOSITE MATERIAL BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition,

The present invention relates to an epoxy resin composition, a prepreg and a fiber-reinforced composite material for an aramid fiber reinforced composite material. More particularly, the present invention relates to an epoxy resin composition for an aramid fiber reinforced composite material, Compositions, prepregs and fiber reinforced composites.

The fiber reinforced composite material is produced by impregnating a reinforcing material such as carbon fiber or aramid fiber with a resin such as epoxy, which is a known material. Fiber reinforced composites have high nose strength and inelasticity. For this reason, it is used as an industrial structural material for aircraft and automobiles. It is also used as a material for everyday products such as sports goods such as tennis rackets, golf shafts and fishing rods.

Of these composite materials, prepreg which is a sheet-shaped intermediate material impregnated with a partially hardened resin is a mainstream in reinforcing fibers as a reinforcing material.

The prepreg can be applied not only to a sheet shape but also to a tape shape and a chip shape, and can be easily processed into various shapes. In addition, it can be applied to a wide variety of fields because it can be applied variously to reinforced fibers and resins according to purposes. For this reason, demand for prepregs is increasing recently.

As the reinforcing fiber used for the composite material, carbon fiber, aramid fiber, glass fiber and kebola fiber are commonly used. Among them, protective equipment such as bulletproof vests, bulletproof helmets, hockey sticks, golf shafts, etc., should be used to mitigate the impact. Composite intermediate materials using aramid fibers are used as such materials. It is also used as an internal aggregate for aircraft such as Boeing 747 and as a reinforcing material for civil engineering cement.

The aramid fiber is an aromatic polyamide fiber. An aramid bond - CONH bonds an aromatic ring such as a benzene ring to form a polymer polyamide. The aramid fiber has a meta system represented by poly (m-phenylene isophthalamide) and a para system represented by poly (p-phenylene telptamide). Para-aramid fibers having properties such as high strength, high elasticity and high damping are generally used as materials. In addition, the aramid fiber is not broken much better than the carbon fiber and the glass fiber, and is advantageous as a shock absorbing material because of its light weight and toughness. Aramid fiber does not burn well and has excellent heat resistance and flame retardancy to carbonize when it is over 500 degrees Celsius. Also, no matter how much force is applied, it is considered to be the best plastic reinforcing material among reinforced fibers. The aramid fiber had the strength to lift about two tons of automobiles even with a small diameter of about 5mm. The aramid fiber is three times stronger than nylon and five times stronger than steel of the same weight.

Epoxy resin is commonly used as a matrix material for a composite material using such an aramid fiber. However, the epoxy resin used in the conventional aramid composite material has a disadvantage in that it is broken by impact, and the adhesion between the phenolic resin and the aramid fiber is low due to the structural difference between the molecules. In this respect, studies on epoxy resins that are resistant to impact and structurally adherent to molecules in aramid fibers are being actively pursued.

Aramid fiber is a material with chemically inert properties. In addition, it is known that the fiber surface is very slippery and the adhesion property with the matrix is poor when the composite material is manufactured. In order to solve the above-mentioned problems, methods for improving the adhesiveness through surface treatment of fibers have been made. In the present invention, the adhesion between the aramid fiber and the matrix is improved by a method different from the above method. TPAE, a new additive for aramid composite resin, can be used to increase the bond strength between resin and fiber.

In the prior art, an invention such as Korean Patent Laid-Open Publication No. 10-2007-0001180 (name of the invention: carbon fiber and its manufacturing method, prepreg and golf shaft) has been proposed.

The present invention provides an epoxy resin composition, a prepreg and a fiber reinforced composite material for an aramid fiber reinforced composite material having high adhesiveness with an aramid fiber by adding a polyamide thermoplastic polymer to the polyimide thermoplastic polymer I have to.

In order to solve the above problems, the present invention provides an epoxy resin composition comprising at least the following components [A], [B] and [C], wherein the ratio of the epoxy resin composition is 100 parts by weight of the epoxy resin [A] 1 to 30 parts by weight of TPAE [B], and 3 to 10 parts by weight of a curing agent [C]. The epoxy resin composition for an aramid fiber-reinforced composite material according to claim 1,

[A]: Epoxy resin

[B]: TPAE (Thermoplastic Polyamide Elastomers)

[C]: Curing agent

The epoxy resin [A] preferably contains at least two glycidyl groups per molecule and is selected from the group consisting of bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, glycidyl ether type resin, glycidyl ester A phenol novolak epoxy resin, a cresol novolak epoxy resin, a bisphenol epoxy resin, an isocyanate-modified epoxy resin, and a mixture thereof may be used as the epoxy resin .

The TPAE [B] may have a structure represented by the following general formula (1).

≪ Formula 1 >

(Where PA is Polyamide and PE is Polyether)

Also, the curing agent [C] includes at least two amine hydroxyl groups per molecule, and may be selected from the group consisting of dicyandiamide, 4-4-diaminodiphenylsulfone, 3-3-diaminodiphenylsulfone, 4-4- A mixture thereof, and a mixture thereof.

Further, it may further comprise a curing accelerator [D].

Further, it may further contain an inorganic filler [E].

Further, it may further include a coupling agent [F].

It may further comprise sodium dodecylbenzene sulfonate functionalized Graphene Oxide [G].

It may further comprise a diluent [H].

In the present invention, the epoxy resin composition for an aramid fiber reinforced composite material may be impregnated into the reinforcing fiber.

Further, the reinforcing fiber may be an aramid fiber.

Further, the fiber reinforced composite material can be obtained by curing the prepreg.

The present invention increases the number of nitrogen and oxygen atoms in the epoxy resin composition and increases the hydrogen bonding power with the aramid fiber having an amide group, thereby improving the adhesion between the epoxy resin composition and the aramid fiber.

Further, the present invention can provide an epoxy resin having superior brittleness and lower impact strength than general epoxy resin because of the toughness characteristic of TPAE resin itself.

Further, since the polyamide-based polymer containing TPAE is mixed and the vulcanizing agent and the vulcanization accelerator are not required, the present invention can simplify the kneading process.

Further, when the epoxy resin composition of the present invention is applied to the aramid prepreg, the interfacial adhesion between the fiber and the resin is improved rather than that of the conventional aramid prepreg, so that it is possible to produce a composite molding having high strength and rigidity.

In addition, when the aramid fiber composite material of the present invention is applied to a robot hand for a bulletproof helmet or an LCD, an aramid fiber composite material having a vibration damping ratio of at least 2 times higher than that of a carbon fiber composite material can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view for explaining a configuration of an aramid prepreg in which an epoxy resin composition according to an embodiment of the present invention is used; FIG.

Hereinafter, the description of the present invention with reference to the drawings is not limited to a specific embodiment, and various transformations can be applied and various embodiments can be made. It is to be understood that the following description covers all changes, equivalents, and alternatives falling within the spirit and scope of the present invention.

In the following description, the terms first, second, and the like are used to describe various components and are not limited to their own meaning, and are used only for the purpose of distinguishing one component from another component.

Like reference numerals used throughout the specification denote like elements.

As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. It is also to be understood that the terms " comprising, "" comprising, "or" having ", and the like are intended to designate the presence of stated features, integers, And should not be construed to preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Hereinafter, an epoxy resin composition, a prepreg and a fiber-reinforced composite material for an aramid fiber-reinforced composite material of the present invention will be described in detail with reference to FIG. 1 for explaining an embodiment of the present invention.

The epoxy resin composition of the present invention may contain an epoxy resin [A], a TPAE [B], and a curing agent [C].

The epoxy resin [A] contained in the epoxy resin composition of the present invention may contain two or more glycidyl groups in the molecule. By containing at least two glycidyl groups in the epoxy resin, the content of the inorganic fine particles in the resin composition as a whole can be greatly improved when the compounds are mixed. The specific properties attributable to the inorganic fine particles can be sufficiently exhibited, and the thermal expansion rate can be significantly lowered. Therefore, the insulating property and thermal shock resistance can be improved.

100 parts by weight of the epoxy resin [A] in the epoxy resin composition may be used.

An epoxy resin is a thermosetting resin produced by polymerization of a dendritic substance having two or more epoxy groups in a molecule and an epoxy group. The epoxy resin is excellent in mechanical properties such as bending strength and hardness, and does not cause generation of volatile substances and shrinkage in volume during curing, and has a large adhesive force in terms of material. Based on these properties, it is used to adhere almost everything such as ceramics, glass and metal plate adhesion. It is also excellent in chemical resistance and used for paints and the like.

Epoxy resins are synthesized by condensation polymerization of bisphenol A and epichlorohydrin. By controlling the ratio of bisphenol A to epichlorohydrin, epoxy resins having various molecular weights can be prepared. Epoxy resins have epoxy groups in the molecule. This epoxy group reacts with the curing agent to form a three-dimensional polymer structure crosslinked.

The epoxy resin [A] used in the present invention is not particularly limited as long as it is a compound having two or more epoxy groups in the compound. Examples of the epoxy resin include bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol S type epoxy resin, brominated epoxy resin, hydrogenated bisphenol-A type epoxy resin A novolac type epoxy resin, a phenol epoxy resin, an epoxy modified polyol, a dimer acid modified epoxy resin, a rubber modified epoxy resin, a urethane modified epoxy resin , Naphthalene type epoxy resin, epoxy resin having fluorene skeleton, epoxy resin made of a copolymer of phenolic compound and dicyclopentadiene, diglycidylglycerinol, tetrakis (glycidyloxyphenyl) ethane, Glycidyl ether type epoxy resin compositions such as tris (glycidyloxyphenyl) methane, tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, triglycidylaminok It may be a sol, tetraglycidyl xylene diamine and a glycidyl amine type, such as an epoxy resin, a biphenyl type epoxy resin, an isocyanate modified epoxy resin, mixtures thereof and the epoxy resin having in the 2 or more epoxy groups such molecules.

The epoxy resin [A] used in the present invention can be used alone or in combination with the above-mentioned kinds of resins. Particularly, when it is applied to a composite material having excellent heat resistance and mechanical properties, a polyfunctional epoxy resin and a bifunctional epoxy resin can be used in combination. For example, a polyfunctional epoxy resin is used in combination with a phenol novolak type epoxy resin, a bifunctional epoxy resin A bisphenol A type epoxy resin or a bisphenol F type epoxy resin can be used in combination.

Further, an epoxy resin and a thermosetting resin can be copolymerized and used. Examples of the thermosetting resin that can be used in this case include an unsaturated polyester resin, a vinyl ester resin, an epoxy resin, a benzoxazine resin, a phenol resin, a urea resin, a melamine resin and a polyimide resin.

For reference, co-polymerization means co-polymerization of two or more monomers (monomers). Structures according to the type of copolymerization include alternating copolymers, random (random) copolymers, block copolymers and branched copolymers. Through this copolymerization, completely different thermal and mechanical properties can be imparted.

An epoxy resin having a defect-free nanostructure can be used by a self-assembly control of a block copolymer by a copolymer method of an epoxy resin which can be used in the present invention. In this case, the heat treatment time for crosslinking can be shortened.

Also, a polymer blend method in which different polymers are physically mixed can be used as a method of modifying physical properties of the polymer. This method can realize much more various properties than copolymerization.

In addition, the solid bisphenol A type epoxy resin provides a structure with a low cross-linking density as compared with the liquid bisphenol A type epoxy resin. Therefore, although the heat resistance is low, a structure having high toughness can be obtained. For this reason, the glycidylamine type epoxy resin or the liquid bisphenol A type epoxy resin is preferably used in combination with the bisphenol F type epoxy resin.

In addition, the epoxy resin having a naphthalene skeleton has characteristics of low water absorption and high heat resistance.

In addition, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, phenol aralkyl type epoxy resin and diphenyl fluorene type epoxy resin have a low water absorption property.

The urethane-modified epoxy resin and the isocyanate-modified epoxy resin also have high fracture toughness and elongation.

The TPAE [B] used in the present invention is a polyamide thermoplastic elastomer. The blending amount of TPAE [B] is preferably 1 to 30 parts by weight based on 100 parts by weight of the epoxy resin [A]. If the blending amount of TPAE [B] is less than 1 part by weight, the adhesiveness of the aramid fiber-reinforced composite material may be little. When the blending amount of TPAE [B] is more than 30 parts by weight, compatibility with epoxy resin may be poor and phase separation may occur, and viscosity may be increased, which may make it difficult to prepare prepreg.

The polyamide-based thermoplastic elastomer is a representative engineering TPE in the form of a multiblock copolymer in which the crystalline polyamide forms a hard segment and the rubber phase polyether or polyester having a low glass transition temperature forms a soft segment.

The hard segment polyamides include aliphatic nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, and aromatic-containing nylon 2.T, nylon 4.T, and nylon 6.T.

As the soft segment, polyethers such as poly (tetramethylene oxide) (PTMO, PTMG or PTHF), poly (ethylene oxide) (PEO, PEG) and poly (propylene oxide) Is used. Also, polyesters, polycarbonates, polybutadienes, polydimethylsiloxanes, and mixtures thereof may be used.

In addition, a biomass-based TPAE using nylon 11 as a hard segment, which can be produced based on castor oil, may be used. These TPAEs have a high limit on the use temperature of TPE materials due to the polyamide that forms the hard segment. In addition, it has excellent endothelial destruction properties, abrasion resistance, and chemical resistance. For this reason, it can be applied to sports goods, automobile fuel hoses, hydraulic and pneumatic devices, and medical tubes.

TPAE can be synthesized by solution polymerization and melt polymerization in bulk, among which the bulk melt polymerization method is used industrially.

In general, a solution polymerization method using a solvent is used in cases where it is difficult to carry out the polymerization in a bulk condition and the polyamide block and the polyether block do not have sufficient compatibility, because the melting temperature of the polymer and the synthesized polymer is too high.

For example, TPAE can be synthesized by reacting α, ω-polyoxyethlene dicarboxylic acid, which is a polyether having -COOH groups at both ends, with a dibasic acid and a diisocyanate on a polar solvent such as tetramethylene sulfone.

TPAE using this method can be prepared by dissolving PTMG, PEG, or a mixture thereof such that 4,4'-methylene bis (phenylisocyanate) (MDI), adipic acid, isophthalic acid, azelaic acid and polyamide are dissolved in a solvent. ≪ / RTI >

On the other hand, the polyamide and the polyether segment are incompatible and phase separation occurs, and the reaction between the reactive chain ends can occur only at the interface. This reaction can be promoted by using an acid halide with good reactivity as a terminal functional group.

For example, an α, ω-dihydroxy polyether having a -OH group at both ends is reacted with diacid chloride in bulk at 60-90 ° C. to prepare a polyether having acid chloride at both ends, Can be mixed with an aqueous solution of diamine and NaOH to synthesize TPAE.

Alternatively, bulk polymerization without the use of an organic solvent may be used. The polyamide-b-ether copolymer can be synthesized by inducing a bond between a polyether and a polyamide oligomer having an amine terminal group by using 4,4'-disubstituted bisoxazolones as a chain coupling agent without using a solvent.

Such a polymerization method can be carried out in a short time at a relatively low temperature without applying a vacuum. It is also advantageous that the quantitative molar ratio between the chain coupling agent and the amine end reactant should be matched and there is no constraint to precisely match the quantitative molar ratio between polyamide and polyether.

In order to improve the mechanical properties and thermal stability of TPAE, it is possible to synthesize poly (ether-b-amide) with imide bond by multi-block copolymerization of monomers and diaminopolyether with trimellitic anhydride have. At this time, naphthalene-1,2,5-tricarboxylic aicd can also be used as a monomer for such polymerization.

In addition, polyamide and polyether can be transesterified. The condensation reaction of a less reactive diol with a diester can occur more effectively than a reaction with a dibasic acid. In addition, the esters of dibasic acids have a low melting temperature, so that mixing between the reactants can be made easier.

For example, a multi-block copolymer composed of PA66-PTMO can be synthesized by changing a polyamide block having a carboxyl group end to a hydroxybutyrate or butanoate end and then reacting the polyamide block with a polyether polyol by an ester exchange reaction. At this time, 1,4-butane diol or n- butanol may be produced as a by-product by the transesterification reaction.

Since the polyamide oligomer and the polyol are very incompatible with each other, the initial polymerization system is inevitably made up of two phases, and the polymerization reaction occurs at the interface thereof, so that the polymerization reaction rate is very low at the initial stage of the reaction. However, since the block copolymer obtained from the polymerization acts as a compatibilizing agent between two oligomers, the reaction proceeds faster over time.

In addition, rapid stirring is necessary for the esterification reaction between oligomers to take place effectively. When the stirring speed is increased, the viscosity of the polymer is lowered by the shear thinning of the polymer, so that the diffusion of the reactant is facilitated and the mixing can be performed well. However, the increase in shear rate may be accompanied by the Weisenbeg effect. Therefore, it is possible to add additives that increase the viscosity of the mixture to prevent the Weisenbeg effect.

Since TPAE has a multi-block copolymer structure, properties of each segment are determined by what degree to which they are bonded.

For example, when comparing the use of nylon 6 with nylon 12 as a hard segment, the use of nylon 6 is more absorbent than nylon 12, reflecting the properties of nylon 6 homopolymer.

The use of hydrophilic PEG as a soft segment significantly improves the antistatic properties compared to the use of relatively hydrophobic PPG.

In addition, all physical properties are determined by the ratio of the hard segment to the soft segment. When the content of the soft segment is increased, the flexibility is increased, but the mechanical properties such as the melting temperature and the tensile strength are lowered.

And, the higher the polyamide content, the hard segment, the better the overall chemical resistance.

TPAE has a small specific gravity among TPE, easy molding processability, excellent hydrolysis resistance, thermal stability and chemical resistance.

Polyester TPE is somewhat less formable and less specific than TPAE.

Urethane TPE is excellent in adhesion and abrasion resistance but is not suitable for use in other performance aspects.

TPAE is advantageous in that it has good thermal stability during processing, short cycle time, easy coloring of pigments and dyes, good dimensional stability after molding, rapid crystallization speed and short injection molding cycle. This advantage has the effect of reducing the production cost.

TPAE also exhibits excellent flexibility at low temperatures compared to TPU or TPEE.

TPAE has characteristics such as low specific gravity, excellent flexural fatigue resistance, low hysteresis, and excellent low temperature characteristics.

Such excellent formability and abrasion resistance are used in industrial products such as automobile gears and belts, medical supplies such as catheters and dental flossing.

In addition, TPAE having a low polyamide content and good phase separation has excellent transparency and printability, and thus can be used as a decoration film for high-end sporting goods.

In addition, since TPAE has excellent drug-carrying function and releasing function, it can also be used as a carrier of fragrance, pesticide, medicine and the like.

Commercially available products of TPAE [B] used in the present invention include TPAE (Thermoplastic Polyamide elastomer) series (manufactured by Toka, Japan).

In the epoxy resin composition for a fiber-reinforced composite material of the present invention, the components (components) other than the curing agent [C] are uniformly heated and kneaded at a temperature of about 150 to 170 캜 and then cooled to a temperature of about 60 캜 , Followed by kneading by adding a curing agent [C]. The mixing method of each component is not particularly limited to this method.

In the present invention, thermoplastic resin particles can be blended into the epoxy resin composition. When the aramid fiber-reinforced composite material is produced by blending the thermoplastic resin particles, the toughness of the matrix resin can be improved and the impact resistance can be improved.

For this reason, a thermoplastic resin can be mixed or dissolved in the epoxy resin composition of the present invention.

Such a thermoplastic resin is generally selected from the group consisting of a carbon-carbon bond, an amide bond, an imide bond, an ester bond, an ether bond, a carbonate bond, a urethane bond, a thioether bond, a sulfone bond and a carbonyl bond to a main chain May be a thermoplastic resin having a selected bond.

Further, the thermoplastic resin may have a partially crosslinked structure. It may also be crystalline or amorphous.

Particularly, a polyimide having a polyimide, polycarbonate, polyacetal, polyphenylene oxide, polyphenylene sulfide, polyarylate, polyester, polyamide imide, polyimide, polyetherimide, At least one resin selected from the group consisting of polyether sulfone, polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, polyaramid, polyether nitrile and polybenzimidazole may be mixed or dissolved in the epoxy resin composition.

In order to obtain excellent heat resistance of the epoxy resin composition, a thermoplastic resin having a glass transition temperature (Tg) of at least 150 캜 and at least 170 캜 of a thermoplastic resin is preferable. If the glass transition temperature of the thermoplastic resin to be blended is less than 150 캜, it may be easily deformed by heat when used as a molded article.

As the terminal functional group of the thermoplastic resin, a hydroxyl group, a carboxyl group, a thiol group, an acid anhydride and the like can be reacted with the cationic polymerizable compound and used.

The thermoplastic resin can compensate for the weakness of the epoxy resin. In addition, the instability of the thermoplastic resin in molding can be stabilized by the epoxy resin. Therefore, a mixture of an epoxy resin and a thermoplastic resin can obtain better physical properties than those obtained by using them alone.

As the material of the thermoplastic resin particles used in the present invention, a thermoplastic resin that can be used by mixing or dissolving in the epoxy resin composition can be used.

Among them, polyamide can be used. Of the polyamides, nylon 12, nylon 11 and nylon 6/12 copolymers have excellent thermosetting properties and can improve the bonding strength with resins.

The shape of the thermoplastic resin particles may be spherical particles, non-spherical particles, or porous particles. However, spherical particles do not deteriorate the flow characteristics of the resin, so they are excellent in viscoelasticity and have no origin of stress concentration , And can provide high impact resistance.

The epoxy resin composition for a fiber-reinforced composite material of the present invention can be used by blending a curing agent [C]. The curing agent [C] used in the present invention is a compound having an active group capable of reacting with an epoxy group.

The blending amount of the curing agent [C] is preferably 3 to 10 parts by weight based on 100 parts by weight of the epoxy resin [A]. If the blending amount of the curing agent [C] is less than 3 parts by weight, the epoxy resin composition may not be cured properly. If the blending amount of the curing agent [C] is more than 10 parts by weight, the unreacted dicyandiamide curing agent may remain and the heat resistance and mechanical properties of the epoxy resin composition may be deteriorated.

The curing agent [C] used in the present invention contains two or more amino groups per molecule and is selected from the group consisting of dicyandiamide, 4-4'-Diaminodiphenylsulfone, 3-3'iaminodiphenylsulfone, 4-4'Methylenedianiline, ≪ / RTI >

The curing agent [C] may be at least one selected from the group consisting of aromatic polyamines, aminobenzoic acid esters, various acid anhydrides, phenol novolak resins, cresol novolak resins, polyphenol compounds, imidazole derivatives, aliphatic amines, tetramethylguanidine, Carboxylic acid anhydrides such as hexahydrophthalic anhydride, Lewis acid complexes such as carboxylic acid hydrazide, carboxylic acid amide, polymercaptan and boron trifluoride ethylamine complex, and the like can be used.

Also included is at least one of a polyamide resin, amide amine resin, polyamide Adduct resin, modified aliphatic amine curing resin, modified alicyclic amine curing resin, modified aromatic amine curing resin, water soluble curing resin and acid anhydride curing resin Can be used.

As examples of dicyandiamide and urea compounds, a combination of 3,4-dichlorophenyl-1,1-dimethylurea or imidazoles can be used as a curing agent. As a result, a high heat resistance water resistance can be obtained while curing at a relatively low temperature.

When the epoxy resin is cured using an acid anhydride, a cured product having a lower water absorption rate than the amine compound curing can be used.

By using the curing agent as described, an epoxy resin composition having excellent heat resistance can be obtained. The optimum value of the amount of the curing agent added may vary depending on the type of the epoxy resin and the curing agent.

The epoxy resin composition for a fiber-reinforced composite material of the present invention can be used by blending a curing accelerator [D]. The curing accelerator [D] curing activity used in the present invention can be enhanced.

The blending amount of the curing accelerator [D] is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the epoxy resin [A]. If the blending amount of the curing accelerator [D] is less than 0.1 part by weight, the curing acceleration reaction rate of the curing agent may be slowed down. When the blending amount of the curing accelerator [D] is more than 10 parts by weight, the viscosity of the epoxy resin composition may increase and the mechanical properties of the cured product may be deteriorated.

 Examples of the curing accelerator [D] used in the present invention include 3-phenyl-1,1-dimethyl urea, 3- (3,4-dichlorophenyl) -1,1-dimethyl urea (DCMU) , Urea derivatives such as 3- (3-chloro-4-methylphenyl) -1,1-dimethyl urea and 2,4-bis (3,3-dimethylureido) toluene or imidazole derivatives as a curing accelerator .

When dicyandiamide alone is used, a temperature of about 170 to 180 DEG C is required for curing. However, the resin composition using such a combination can be cured at about 80 to 150 ° C.

In particular, a combination of dicyandiamide and a compound having two or more urea bonds per molecule may be used. As the compound having two or more urea bonds in one molecule, 1,1'-4 (methyl-m-phenylene) bis (3,3-dimethylurea) or 4,4'-methylene bis (phenyldimethylurea) is used . When these compounds are used, curing may be possible at a temperature of 150 to 160 ° C for 2 to 10 minutes.

In addition, when applied to a thin plate, the flame retardancy of the epoxy resin composition is improved and can be used for electric / electronic materials applications.

 Further, the boron trifluoride ethylamine complex may be combined with the aromatic amine as a curing accelerator.

In a field requiring low-temperature curability, a latent curing agent may be used so that the curing agent can be activated at a reaction initiation temperature of 70 to 125 캜.

Such reaction initiation temperature (hereinafter referred to as activation temperature) can be obtained by differential scanning calorimetry (DSC). Specifically, the epoxy resin composition to which 10 parts by weight of the curing agent to be evaluated is added to 100 parts by weight of a bisphenol A type epoxy resin having an epoxy equivalent of about 184 to 194 is subjected to differential scanning calorimetry Can be obtained from the tangent line intersection. If the activation temperature is lower than 70 deg. C, the stability may not be sufficient. If the activation temperature is higher than 125 deg. C, sufficient curability may not be obtained.

Examples of the latent curing agent that activates at 70 to 125 占 폚 include a curing agent such as an amine curing type latent curing agent, a microcapsulated latent curing agent, an amine imide, a block isocyanate, and a carbamic acid ester in an epoxy group to form an oxazolidinone ring A vinyl ether block carboxylic acid, a salt of an imidazole and a carboxylic acid, a carbamine salt of an amine, an onium salt and the like can be used.

For reference, the amide duct type latent curing agent means a compound having primary, secondary and tertiary amino groups, and various imidazole compounds reacted with these compounds to have a high molecular weight and insolubilization at a storage temperature .

In addition, a microcapsulated latent curing agent may be used. For reference, the microcapsule type latent curing agent is prepared by coating a high molecular material such as an epoxy resin, a polyurethane resin, a polystyrene type, a polyimide, and a cyclodextrin as a shell with a curing agent as a nucleus to make contact between the epoxy resin and the curing agent Respectively.

Further, when a specific curing agent is combined with a latent curing agent which is activated at 70 to 125 ° C by a curing agent, rapid curing can be performed at a low temperature. For example, a curing agent system in which a latent curing agent such as "Amicure" PN-23 is combined with an organic acid dihydrazide such as valine dihydrazide, or a curing agent system in which a latent curing agent is combined with a curing accelerator such as DCMU can be used. By using the epoxy resin composition, the epoxy resin composition can be cured at about 110 DEG C for about 10 minutes.

The epoxy resin composition for a fiber-reinforced composite material of the present invention can be used by mixing an inorganic filler [E]. The inorganic filler [E] used in the present invention can improve heat resistance, durability and strength. The inorganic filler [E] improves the thermal stability of the epoxy resin composition by lowering the thermal expansion coefficient.

The blending amount of the inorganic filler [E] is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the epoxy resin [A]. When the amount of the inorganic filler [E] is less than 0.1, the heat resistance of the epoxy resin composition may be deteriorated. When the blend amount of the inorganic filler [E] is more than 5 parts by weight, the resin is less denaturalized and the adhesion with the aramid fiber can be remarkably lowered.

Examples of the inorganic filler [E] include aluminum nitride, silicon carbide, talc, calcium carbonate, diatomaceous earth, vermiculite, boron nitride, fumed silica, silicon oxide, aluminum oxide, titanium oxide, magnesium oxide, . ≪ / RTI >

The epoxy resin composition for a fiber-reinforced composite material of the present invention can be used by mixing a coupling agent [F]. The coupling agent [F] used in the present invention is intended to increase the adhesion between an organic epoxy resin and an inorganic material.

The mixing amount of the coupling agent [F] is preferably 1 to 10 parts by weight based on 100 parts by weight of the epoxy resin [A]. When the amount of the coupling agent [F] is less than 1 part by weight, the effect of improving the adhesion between the organic resin and the inorganic filler, which are components of the epoxy resin composition, may be insignificant. When the amount of the coupling agent [F] is more than 10 parts by weight, there is a problem that the glass transition temperature (Tg) is lowered.

Examples of the coupling agent [F] include 3-glycidoxypropyl trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (2- (3, Siloxane coupling agents such as 4-epoxycyclohexyl ethyl trimethoxysilane and 3-glycidyloxypropyl methyldiethoxysilane, and di (dioctylphosphato) ethylene titanate Titanate-based coupling agents such as di (cumyl) phenyl oxoethylene titanate, isopropyltri (dioctyl pyrophosphate) titanate, and the like can be used have.

The epoxy resin composition for a fiber-reinforced composite material of the present invention may be blended with sodium dodecylbenzene sulfonate functionalized Graphene Oxide [G]. The sodium dodecylbenzene sulfonate functionalized Graphene Oxide [G] used in the present invention can greatly improve heat resistance, abrasion resistance and mechanical strength. Sodium dodecylbenzene sulfonate functionalized Graphene Oxide [G] has a two-dimensional single sheet structure, has a large surface area, has flexibility and transparency, and can improve the physical properties of the epoxy resin composition.

The blending amount of sodium dodecylbenzene sulfonate functionalized Graphene Oxide [G] is 0.1 to 10 parts by weight based on 100 parts by weight of the epoxy resin [A]. When the amount of the sodium dodecylbenzene sulfonate functionalized Graphene Oxide [G] is less than 0.1 part by weight, the effect of improving the physical properties of the epoxy resin composition may be insignificant. Also, when the amount of the sodium dodecylbenzene sulfonate functionalized Graphene Oxide [G] is more than 10 parts by weight, there is a possibility that the adhesion of the resin to the aramid fibers may be lowered due to lowering the moisture requirement.

The epoxy resin composition for a fiber-reinforced composite material of the present invention can be used by blending a diluent [H]. The diluent [H] used in the present invention can be used for controlling the solubility, viscosity and specific gravity of the epoxy resin composition.

The diluent [H] is for lowering the viscosity of the epoxy resin composition.

The blending amount of the diluent [H] is 50 to 200 parts by weight per 100 parts by weight of the epoxy resin [A]. When the blending amount of the diluent [H] is less than 50 parts by weight, the effect of lowering the viscosity of the epoxy resin composition may be insignificant. If the amount of the diluent [H] is more than 200 parts by weight, the glass transition temperature (Tg) and mechanical properties of the cured product may be deteriorated.

Examples of the diluent [H] include alkyl monoglycidyl ethers containing at least one glycidyl group per molecule, phenol monoglycidyl ether, alkylphenol monoglycidyl ether, polyglycol diglycidyl ether , Alkyl diglycidyl ether, and the like.

 Specific examples of the reactive diluent include a coenzyme type reactive diluent having one epoxy group, a bifunctional reactive diluent having two epoxy groups, and a multifunctional reactive diluent having three or more epoxy groups.

The epoxy resin composition for an aramid fiber-reinforced composite material of the present invention may contain a latent curing accelerator, an antioxidant, a defoaming agent, a defoaming agent, a dispersing agent, a pigment, a dye and other components, if necessary, in addition to the above essential components.

Further, the components and additives may be dispersively mixed and vacuum-mixed using an universal mixer or the like.

The method for producing the epoxy resin composition for an aramid fiber-reinforced composite material of the present invention is as follows. 1 to 30 parts by weight of a TPAE additive and 50 to 100 parts by weight of MEK (Methy Ethyl Ketone) are first mixed for 3 hours to 5 hours at a temperature of 60 to 80 degrees with a stirrer based on 100 parts by weight of an epoxy resin.

Next, the primary mixed mixture and the epoxy resin and the inorganic filler, the coupling agent, the defoamer, the pigment, the fuel, the curing accelerator, and the latent curing accelerator are secondarily mixed using a stirrer for 1 to 2 hours.

Next, 3 to 10 parts by weight of a curing agent is mixed with the secondarily mixed result by means of a stirrer for 10 to 30 minutes.

The epoxy resin composition for an aramid fiber reinforced composite material can be manufactured through the above-described manufacturing process.

For reference, the epoxy reacts primarily with the active hydrogen of the curing agent, but the curing reaction may also be caused by the cured tertiary amine. Therefore, it can generally be used less than the calculation amount.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view for explaining a configuration of an aramid prepreg in which an epoxy resin composition according to an embodiment of the present invention is used. FIG.

Referring to FIG. 1, an aramid prepreg 10 according to an embodiment of the present invention includes an epoxy resin composition 100 and an aramid fiber 200.

The epoxy resin composition (100) of the present invention can be produced using the materials and methods as described above. The thus prepared epoxy resin composition 100 is impregnated with the aramid fiber 200 and cured to obtain the aramid prepreg 10.

Examples of the reinforcing fiber used in the prepreg of the present invention include aramid fiber, carbon fiber, carbon nanotube fiber, glass fiber, boron fiber, kebola fiber, poly-phenylene benzobisoxazole fiber, spectra fiber, high tensile polyethylene fiber, alumina Fiber and silicon carbide fiber, metal fiber, silicon carbide inorganic fiber and silicon nitride inorganic fiber. In addition, two or more of these fibers may be used in combination. The shape and arrangement of the reinforcing fibers are not limited. Thus, the shape and arrangement of the reinforcing fibers can be made in various forms, such as one-sided or cross-over.

Regarding the shape and arrangement of the aramid fibers, they can be selected from long fibers and fabrics aligned in one direction according to the needs of the user.

In order to obtain a light and durable aramid fiber reinforced composite material, a continuous fiber form such as a long fiber (fiber bundle) or a fabric in which the aramid fiber is aligned in one direction may be used. Further, unidirectional prepreg and fabric prepreg can be mixed and formed.

The unidirectional prepregs are aligned in the direction of the reinforcing fibers. Therefore, the flexural strength of the fiber is high because the flexure of the fiber is small.

Further, when a plurality of prepregs are laminated in an appropriate lamination structure and then molded, there is an advantage that the modulus of elasticity and strength in each direction of the aramid fiber reinforced composite material can be easily controlled.

Particularly, in applications where light weight or high strength of the material is required, it is preferable to use aramid fibers having excellent non-elasticity and non-elasticity.

The aramid fiber used in the present invention may be an aramid fiber having a tensile modulus of at least 450 Gpa in terms of impact resistance. Further, in order to obtain a composite material having high rigidity and mechanical strength, aramid fibers having a tensile strength of 4.5 to 7 Gpa may be used. It is also preferable that the tensile elongation is 1.5 to 3% high strength, high elongation aramid fiber.

Further, in order to obtain a composite material having high rigidity and mechanical strength, an aramid having a tensile strength of 20 cN / dtex or more can be used.

It is also preferred that the fiber has an elastic modulus of from 350 to 700 cN / dtex.

Further, the elongation at break is preferably an aramid fiber having a high strength of 2.5 to 5%.

The prepreg of the present invention is obtained by impregnating an aramid fiber with an epoxy resin composition for a fiber-reinforced composite material.

The content of the epoxy resin composition in the prepreg may be 20 to 60 parts by weight based on 100 parts by weight of the aramid fiber. If the epoxy resin composition is lower than 20 parts by weight, impregnation of the resin composition is not sufficient, and voids may be formed inside the composite material to be produced. As a result, the physical properties of the composite material can be remarkably lowered. If the epoxy resin composition is more than 60 parts by weight, the weight of the resulting composite material becomes excessive, and the physical properties of the fiber-reinforced composite material having excellent non-rigidity and inelasticity may be deteriorated.

About 0.5 to 15 m per minute can be produced based on the length of the aramid fiber in the step of impregnating the prepreg with the epoxy resin composition. In this case, impregnation and compression can proceed at the same time.

A method of applying thermoplastic resin particles in the form of particles to the surface of the primary prepreg made of the aramid fiber and the epoxy resin as the matrix resin of the present invention can be used.

It is also possible to adjust the mixture in which the particles are uniformly mixed in the epoxy resin as the matrix resin and block the intrusion of these particles with the reinforcing fiber in the process of impregnating the aramid fiber with the mixture to localize the particles on the surface portion of the prepreg Method can be used.

It is also possible to prepare the primary prepreg by impregnating an aramid fiber with an epoxy resin in advance, and applying a film of a thermosetting resin containing a large amount of these particles to the surface of the primary prepreg.

As a result, the thermoplastic resin particles uniformly exist in the depth range of 20% of the thickness of the prepreg, so that a prepreg for a fiber composite material having high impact resistance can be obtained.

In another embodiment, the aramid reinforcing fibers may be impregnated into the epoxy resin composition.

The prepreg of the present invention can be produced by a wet method in which an epoxy resin composition is dissolved in a solvent such as methyl ethyl ketone (MEK) or acetone, and the viscosity is adjusted to impregnate the reinforcing fiber.

The wet method is a method in which a reinforcing fiber is dipped in a solution of an epoxy resin composition, then is purged, and heated to evaporate the solvent to obtain a prepreg.

In addition, the prepreg of the present invention can be produced by a hot melt method in which the epoxy resin composition is heated to lower the viscosity to impregnate the reinforcing fiber.

The hot melt method is a method in which an epoxy resin composition whose viscosity is lowered by heating is directly impregnated into the reinforcing fiber, or a resin film in which an epoxy resin composition is coated on the surface of a release paper or the like is prepared and the resin film is laminated on both sides or one side of the reinforcing fiber And the epoxy resin composition is impregnated with the epoxy resin composition by heating and pressing to obtain a prepreg. This method has the effect of preventing deterioration of the physical properties because there is substantially no solvent remaining in the prepared prepreg.

When the hot melt method is used, the heating temperature in the production of the resin composition may be 30 to 80 degrees. If it is less than 30 degrees, the viscosity may become high and the resin may be in an unstable state. On the other hand, if it exceeds 80 DEG C, the curing of the resin may proceed during coating and the viscosity may increase significantly.

A hot melt type prepreg is produced by applying heat at a high temperature and pressure within a range that hardening does not occur with the reinforcing fiber due to the fact that the volatile matter in the resin is very small by applying heat to generate the flow of the thermosetting resin. .

For thermoplastics, Film Casting, Powder Deposition, Film Stacking, and Commingled Yarn Impregnation methods can be used.

In the case of the prepreg of the present invention, the solvent type may be manufactured by passing a fabric through a tube containing a low viscosity resin, removing the solvent by applying heat, and packaging the release film and the release paper.

The fiber-reinforced composite material of the present invention is obtained by laminating a plurality of prepregs prepared by a wet method, a hot-melt method and a solvent type, and then applying a high heat and a high pressure to a plurality of laminated prepregs to heat the epoxy resin Curing method, and the like.

For reference, as a method of imparting high temperature and high pressure, a press molding method, a bugging molding method, an autoclave molding method, a lapping tape method, an internal pressure forming method, or the like can be used.

The aramid fiber-reinforced composite material of the present invention can also be produced by a method that does not use a prepreg using an epoxy resin composition.

A hand lay-up method, a filament winding method, a pearl truing method, a resin / injection / molding method, and a resin / transfer / molding method can be used as methods for directly curing the epoxy resin composition by impregnating the epoxy resin composition .

The aramid fiber reinforced composite material of the present invention can be used for aviation, wind power, automobile parts, electronic products, everyday products, and the like.

A product to which an aramid prepreg implemented through the present invention is applied, for example, a robot hand for transferring an LCD. Recently, the screen size of TV in the display industry is getting bigger. In addition, the size of glass substrates for displays has been increasing in order to increase productivity in LCD manufacturing plants. Accordingly, the size of the robot hand is also increasing. As the length of the robot hand becomes longer, there is a need for a highly rigid material capable of supporting the control of the glass substrate fixing capability of the display and the deflection amount of the hand during transportation. The glass substrate, which is larger than in the past, causes a phenomenon that vibration of the robot hand is increased during transportation, and the robot hand frequently stops during operation. There is a problem that the waiting time until the restarting after the stop is lengthened, thereby deteriorating the productivity of the panel. Therefore, it is possible to apply to a robot hand using a composite material having high strength, high rigidity and excellent vibration damping ability by improving the adhesion between the aramid fiber and the resin interface.

The use of the prepreg resin composition and the aramid prepreg and the fiber reinforced composite material applied thereto according to the present invention can provide a robotic hand for transferring an LCD having a higher performance as compared with the conventional transfer robot hand.

Hereinafter, the epoxy resin composition, prepreg and fiber-reinforced composite material for an aramid fiber-reinforced composite material of the present invention will be described in more detail with reference to Examples and Comparative Examples. The material of the epoxy resin composition used in the examples, the prepreg, the method for producing the fiber-reinforced composite material, and the shearing strength evaluation method are shown below. However, the present invention is not limited to the embodiments described below.

[Reference]

35 parts by weight of a liquid epoxy resin (liquid BPA resin YD-128, Kukdo Chemical), 65 parts by weight of a solid epoxy resin (solid phase BPA resin YD-011, Kukdo Chemical) and 50 parts by weight of MEK (methyl ethyl ketone, And the mixture was first mixed for about 4 hours at a temperature of 70 degrees using an agitator. Three parts by weight of a curing accelerator (DCMU, Air Product) was added to the primary mixed resultant, and the mixture was further mixed for about one hour using a stirrer. 6 parts by weight of a hardening agent (DICY, Air Product) was added to the secondary mixed resultant and mixed for about 30 minutes by a stirrer. The mixed epoxy resin composition was impregnated with 100 parts by weight of aramid fiber (Hera Krone HF 300 yarn, Kolon) to prepare a prepreg.

[Example 1] EZR -CV07

35 parts by weight of a liquid epoxy resin (liquid BPA resin YD-128, Kukdo Chemical), 65 parts by weight of a solid epoxy resin (solid phase BPA resin YD-011, National Kagaku KK), 50 parts by weight of MEK (methyl ethyl ketone, And 6 parts by weight of Thermoplastic Polyamide Elastomer (TPAE-32, TOKA) were put into a mixer and mixed for about 4 hours at a temperature of 70 degrees using a stirrer. Three parts by weight of a curing accelerator (DCMU, Air Product) was added to the primary mixed resultant, and the mixture was further mixed for about one hour using a stirrer. 6 parts by weight of a hardening agent (DICY, Air Product) was added to the secondary mixed resultant and mixed for about 30 minutes by a stirrer. The mixed epoxy resin composition was impregnated with 100 parts by weight of aramid fiber (Hera Krone HF 300 yarn, Kolon) to prepare a prepreg.

[Comparative Example 1]

35 parts by weight of a liquid epoxy resin (liquid BPA resin YD-128, Kukdo Chemical), 65 parts by weight of a solid epoxy resin (solid phase BPA resin YD-011, National Kagaku KK), 50 parts by weight of MEK (methyl ethyl ketone, And 6 parts by weight of Polyvinylfomal (PVF-K, SIGMA-ALDRICH) were put into a mixer and mixed for about 4 hours at a temperature of 70 degrees using a stirrer. Three parts by weight of a curing accelerator (DCMU, Air Product) was added to the primary mixed resultant, and the mixture was further mixed for about one hour using a stirrer. 6 parts by weight of a hardening agent (DICY, Air Product) was added to the secondary mixed resultant and mixed for about 30 minutes by a stirrer. The mixed epoxy resin composition was impregnated with 100 parts by weight of aramid fiber (Hera Krone HF 300 yarn, Kolon) to prepare a prepreg.

[Comparative Example 2]

35 parts by weight of a liquid epoxy resin (liquid BPA resin YD-128, Kukdo Chemical), 65 parts by weight of a solid epoxy resin (solid phase BPA resin YD-011, National Kagaku KK), 50 parts by weight of MEK (methyl ethyl ketone, And 6 parts by weight of phenoxy (YP-50, Kukdo Chemical) were put into a mixer, and the mixture was first mixed for about 4 hours at a temperature of 70 degrees using a stirrer. Three parts by weight of a curing accelerator (DCMU, Air Product) was added to the primary mixed resultant, and the mixture was further mixed for about one hour using a stirrer. 6 parts by weight of a hardening agent (DICY, Air Product) was added to the secondary mixed resultant and mixed for about 30 minutes by a stirrer. The mixed epoxy resin composition was impregnated with 100 parts by weight of aramid fiber (Hera Krone HF 300 yarn, Kolon) to prepare a prepreg.

[Evaluation of physical properties of aramid prepreg using epoxy resin composition]

The shear strength of the aramid prepreg prepared in Reference Example 1, Comparative Example 1 and Comparative Example 2 (Universal Testing Machine, INSTRON 3382) was evaluated, and the results are shown in Table 1.

The shear strength test of the aramid fiber prepreg was carried out using a universal material testing machine according to the test standard of ASTM-D3165.

For reference, when the shear adhesive strength of the aramid prepreg is measured, breakage occurs at the interface between the aramid fiber and the resin. Therefore, evaluating the shear bond strength of the aramid prepreg can be considered as a useful measurement method for evaluating the adhesion between the aramid fiber and the resin.

Table 1

From Table 1, it can be seen that Example 1 using Thermoplastic Polyamide Elastomer (TPAE-32, TOKA) is superior to Reference and Comparative Examples 1 and 2 in shear strength. In Example 1 of the present invention, the shear strength was increased by about 14% based on the reference.

In Comparative Example 1 using polyvinylfomal (PVF-K), which is typically used as a resin additive for prepreg, the shear strength increased by about 3.5%. On the other hand, in Comparative Example 2 using Phenoxy (YP-50), the shear strength was reduced by about 3%.

Thus, it can be seen that the shear strength of the aramid prepreg using the thermoplastic polyamide elastomer (TPAE-32, TOKA) of Example 1 of the present invention is improved compared with the conventional method.

Further, it can be concluded from this result that the adhesion between the aramid prepreg and the resin is increased. This means that the mechanical properties of the aramid fiber prepreg are improved.

The present invention can provide an effect of improving the adhesive strength between the epoxy resin and the aramid fiber which is a problem of the conventional aramid prepreg.

As described above, the epoxy resin composition, prepreg and fiber reinforced composite material for aramid fiber reinforced composite according to the present invention have improved adhesion and shear strength. Such high rigidity, high strength and vibration damping characteristics can be applied to various industrial fields.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be clear to the person.

10: Aramid prepreg
100: Epoxy resin composition
200: aramid fiber

Claims (12)

The epoxy resin composition comprising at least the following components [A], [B] and [C], wherein the proportion of the epoxy resin composition is from 1 to 30 parts by weight of TPAE [B] relative to 100 parts by weight of the epoxy resin [A] And 3 to 10 parts by weight of a curing agent [C]
[A]: Epoxy resin
[B]: TPAE (Thermoplastic Polyamide Elastomers)
[C]: Curing agent
The epoxy resin [A]
Wherein at least two glycidyl groups per molecule are contained, and at least one of a bisphenol-A epoxy resin, a bisphenol-F epoxy resin, a bisphenol S epoxy resin, a hydrosene bisphenol-A epoxy resin, Selected from the group consisting of ether type epoxy resins, glycidyl ester type resins, glycidylamine type epoxy resins, biphenyl epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, isocyanate modified epoxy resins, and mixtures thereof Or an epoxy resin and a thermosetting resin,
The thermosetting resin
An unsaturated polyester resin, a vinyl ester resin, an epoxy resin, a benzoxazine resin, a phenol resin, a urea resin, a melamine resin and a polyimide resin,
0.1 to 10 parts by weight of a curing accelerator [D]
The curing accelerator [D]
(Methyl-m-phenylene) bis (3,3-dimethylurea) or 4,4'-methylene bis (phenyldimethylurea) which is a compound having two or more urea bonds in one molecule,
0.1 to 5 parts by weight of an inorganic filler [E], 1 to 10 parts by weight of a coupling agent [F], 0.1 to 10 parts by weight of sodium dodecylbenzene sulfonate functionalized Graphene Oxide [G] and 50 to 200 parts by weight of a diluent [H]
In the epoxy resin composition,
Further comprising a thermoplastic resin,
The thermoplastic resin
Wherein the glass transition temperature (Tg) is 150 to 170 占 폚, and the particles have a spherical shape.
delete The method according to claim 1,
Wherein the TPAE [B] has a structure represented by the following formula (1).
≪ Formula 1 >

(Where PA is Polyamide, PE is Polyether, and n is 7.26).
The method according to claim 1,
The curing agent [C] comprises two or more amino groups per molecule, and is composed of dicyandiamide, 4-4'-Diaminodiphenylsulfone, 3-3'-Diaminodiphenylsulfone, 4-4'-Methylenedianiline, Lt; RTI ID = 0.0 > 1, < / RTI >
delete delete delete delete delete A prepreg comprising the reinforcing fiber impregnated with an epoxy resin composition for an aramid fiber reinforced composite material according to any one of claims 1, 3 and 4.
11. The method of claim 10,
Wherein the reinforcing fiber is an aramid fiber.
A fiber-reinforced composite material obtained by curing the prepreg according to claim 11.

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