JP2010163504A - Epoxy resin composition, fiber reinforced composite material, and process for producing fiber reinforced composite material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: an epoxy resin composition which has a low viscosity, a high Tg, a high modulus, and excellent toughness; and a fiber-reinforced composite material which has superior thermal properties, compression strength, impact resistance, fatigue resistance, and tensile strength in the 0° direction with the application of the epoxy resin for fiber reinforced composite materials, and is most suitable as an aircraft member or the like. <P>SOLUTION: The epoxy resin composition comprises at least a specific tetrafunctional epoxy resin of constitutional element [A] and a specific aromatic diamine curing agent of constitutional element [B] which has a total carbon atoms of not less than 6. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition used as a matrix resin of a fiber-reinforced composite material suitably used for aircraft members, spacecraft members, automobile members, ship members and the like. More specifically, the present invention relates to an epoxy resin composition having a low viscosity, a high glass transition temperature (Tg), a high elastic modulus, and excellent toughness. The present invention also relates to a fiber reinforced composite material produced using such an epoxy resin composition and a method for producing such a fiber reinforced composite material.

  Fiber reinforced composites composed of reinforced fibers such as glass fibers, carbon fibers, and aramid fibers, and cured products of thermosetting resins such as unsaturated polyester resins, vinyl ester resins, epoxy resins, phenol resins, cyanate ester resins, and bismaleimide resins. Since the material is lightweight, it has excellent mechanical properties such as strength and elastic modulus, and therefore, it is used in many fields such as aircraft members, spacecraft members, automobile members, ship members, civil engineering and building materials, and sports equipment. In particular, for applications that require high performance, fiber reinforced composite materials using continuous fibers are used. Carbon fibers with excellent specific strength and specific elastic modulus are used as reinforcing fibers, and carbon fibers are bonded to carbon fibers as matrix resins. Many epoxy resins having excellent properties are used.

  In particular, when a fiber reinforced composite material is used for an aircraft member or a spacecraft member, an epoxy resin cured product obtained by curing an epoxy resin composition has a high glass transition temperature (Tg), a high elastic modulus, and toughness. It is necessary to be excellent.

  In order to obtain such a cured epoxy resin, an epoxy resin obtained by combining tetraglycidyldiaminodiphenylmethane (hereinafter sometimes abbreviated as TGDDM) and diaminodiphenylsulfone (hereinafter sometimes abbreviated as DDS). A method of adding a thermoplastic resin such as polyethersulfone or polyetherimide to the composition has been studied (see, for example, Patent Documents 1 to 4). According to this method, an epoxy resin having a high Tg and a high elastic modulus and excellent in toughness is considered possible.

  On the other hand, in recent years, in the resin transfer molding (hereinafter sometimes abbreviated as RTM) method in which a reinforcing fiber substrate is directly impregnated with a liquid thermosetting resin and cured, molding cost reduction is achieved. Therefore, the application to aircraft members and spacecraft members has been expanded.

  In the RTM method, when the thermosetting resin is injected into the reinforcing fiber base, there is a restriction on the resin design that it must be a low-viscosity liquid, high Tg, high elastic modulus, and excellent toughness. Furthermore, it is required that the epoxy resin composition has a low viscosity. However, the methods described in Patent Documents 1 to 4 cannot be applied to the RTM method because the viscosity increases remarkably.

  To solve this problem, a method of combining TGDDM or p-aminophenol type epoxy resin and a specific alkyl-substituted diaminodiphenylmethane as a curing agent has been studied (see Patent Documents 5 and 6).

  However, the method of combining TGDDM and a specific alkyl-substituted diaminodiphenylmethane still has a problem that the improvement in toughness is still insufficient and the viscosity of the epoxy resin composition is still significantly high and insufficient. Further, the method of combining the p-aminophenol type epoxy resin and the specific alkyl-substituted diaminodiphenylmethane still has a problem that it is very brittle and has insufficient toughness.

European Published Patent No. 0366979 European Published Patent No. 0495518 Japanese Patent Laid-Open No. 01-320146 Japanese Patent Laid-Open No. 05-287091 US Published Patent No. 6379799 JP-A-1-254730

  In view of the background of such conventional technology, an object of the present invention is an epoxy resin composition having low viscosity, high Tg, high elastic modulus and excellent toughness, and excellent thermal performance by applying such an epoxy resin composition. An object of the present invention is to provide a fiber reinforced composite material having characteristics, compressive strength, impact resistance, fatigue resistance, and 0 ° direction tensile strength, and being optimal as an aircraft member.

The present invention employs the following means in order to solve such problems. That is, the epoxy resin composition includes at least the following constituent elements [A] and [B], and the total carbon number of R ^{9 to} R ¹² of the constituent element [B] is 6 or more. Is.
[A] A tetrafunctional epoxy resin represented by any one of the following formulas (I) and (II)

(In the above chemical formula, R ^{1 to} R ⁸ are each a substituent selected from hydrogen, halogen, and an alkyl group having 1 to 4 carbon atoms.)
[B] Aromatic diamine curing agent represented by the following formula (III)

(In the above chemical formula, R ^{9 to} R ¹² are each a substituent selected from hydrogen, halogen, and an alkyl group having 1 to 8 carbon atoms.)
In a preferred embodiment of the epoxy resin composition of the present invention, the compounding amount of the component [A] is 30 parts by mass or more with respect to 100 parts by mass of the total epoxy resin, and further includes the following component [C]. Is preferred.
[C] Tetrafunctional epoxy resin represented by the following formula (IV)

(In the chemical formula, R ^{13 to} R ¹⁶ are each a substituent selected from hydrogen, halogen, and an alkyl group having 1 to 4 carbon atoms.)
In addition, the constituent element [A] of the present invention is preferably such that two groups represented by the following formula (V) are bonded to the 1,3-positions of the aromatic ring or cyclohexane ring.

Further, the curing agent contains at least two or more types of aromatic diamine curing agents, at least one of which is an aromatic diamine curing agent represented by the component [B], and further, the curing agent is 25 ° C. It is preferably composed of a solid aromatic diamine curing agent and an aromatic diamine curing agent which is liquid at 25 ° C. At this time, the substituent of R _{18 to} R ₂₁ of the constituent element [B] is any one of an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Is preferred.

  Furthermore, it is preferable to use an alkyl-substituted diaminodiphenylmethane represented by the component [B] and an aromatic diamine represented by any one of the following formulas (VI), (VII), and (VIII).

(In the chemical formula, R ^{17 to} R ²⁸ are each a substituent selected from hydrogen, halogen, and an alkyl group having 1 to 4 carbon atoms.)
A preferred embodiment of the fiber reinforced composite material of the present invention is composed of at least a cured product of the above epoxy resin composition and carbon fibers. Further, the reinforcing fiber base material having carbon fibers is orthogonal to the warp made of strands of the carbon fibers and the auxiliary warps of fiber bundles made of glass fibers or chemical fibers arranged in parallel therewith. A non-crimp woven fabric comprising a weft made of glass fibers or chemical fibers arranged in a cross-section, wherein the auxiliary warp and the weft cross each other to hold the carbon fiber strands together to form a woven fabric Is.

  Further, a preferred embodiment of the method for producing a fiber-reinforced composite material of the present invention is that a warp composed of carbon fiber strands and an auxiliary warp composed of fiber bundles composed of glass fibers or chemical fibers arranged in parallel therewith are orthogonal to these. A non-crimped woven fabric comprising a weft of glass fibers or chemical fibers arranged in such a manner that the auxiliary warp and the weft intersect each other to form a woven fabric in which carbon fiber strands are held together. It arrange | positions in a type | mold, inject | pours and impregnates the said epoxy resin composition, Then, it heat-hardens. Furthermore, the injection of the epoxy resin composition is preferably performed by vacuum suction in the mold.

  According to the present invention, low viscosity, excellent impregnation into reinforcing fibers, excellent Tg, which is important for developing heat resistance of fiber reinforced composite materials, impact resistance, fatigue resistance, 0 ° direction of fiber reinforced composite materials An epoxy resin composition having excellent toughness necessary for developing the tensile strength can be obtained. And at least, the fiber reinforced composite material composed of the cured product of the epoxy resin composition and the carbon fiber is excellent in heat resistance, compressive strength, impact resistance, fatigue resistance, and tensile strength. It can be suitably used for machine members, automobile members, ship members and the like.

1 is a schematic perspective view of a non-crimp fabric related to a practical form as a carbon fiber composite material of the present invention.

  As a result of intensive studies on an epoxy resin composition having a low viscosity, a high Tg, a high elastic modulus, and excellent toughness, the present inventors have found that a tetrafunctional epoxy resin having a specific structure and an aromatic diamine having a specific structure are cured. It has been found that when combined with an agent, all these properties are satisfied.

  That is, the group represented by (IX) below is bonded to an aromatic ring or a cyclohexane ring, but since the nitrogen atom is bonded to such a ring via a methylene group, the degree of freedom is high. It was found that when combined with the prepared diaminodiphenylmethane, it has a low viscosity, a high Tg, a high elastic modulus, and a high toughness of the cured product, and solves such problems all at once.

  In the present invention, the epoxy resin refers to a compound having an epoxy group in the molecule. The epoxy resin composition refers to an uncured composition containing an epoxy resin, an amine curing agent, and a curing accelerator that is added as necessary, and the cured epoxy resin or cured product refers to the epoxy resin composition. It refers to a cured product obtained by curing.

  The epoxy resin of the component [A] of the present invention is a tetrafunctional aromatic epoxy resin having a specific structure obtained by glycidylation of xylylenediamine represented by the above formula (I), or represented by the above formula (II). A tetrafunctional aromatic epoxy resin having a specific structure obtained by glycidylation of di (aminomethyl) cyclohexane obtained by hydrogenating an aromatic ring (hereinafter sometimes abbreviated as hydrogenation).

R ^{1 to} R ⁴ of the epoxy resin represented by the above formula (I) of the component [A] of the present invention are each a substituent selected from hydrogen, halogen, and an alkyl group having 1 to 4 carbon atoms. From the viewpoint of obtaining a cured product having a high Tg, R ^{1 to} R ⁵ are preferably hydrogen and an alkyl group having 1 to 4 carbon atoms. Further, it is preferable that at least one halogen R ¹ to R ⁴ in terms of being able to impart flame retardancy.

  In the epoxy resin represented by the above formula (I) of the component [A] of the present invention, two groups represented by (V) bonded to the aromatic ring are bonded to the 1,3-position or 1,4-position. It is preferable to do. That is, when the group represented by (V) bonded to the aromatic ring is bonded to the 1,3-position, a cured product having higher toughness than that bonded to the 1,4-position or the 1,2-position is obtained. , 1, 3 position, or 1 and 4 position, when it couple | bonds, the hardened | cured material of high Tg can be obtained. In addition, among the constituents [A], the epoxy resin having two groups (V) bonded to the aromatic ring of the epoxy resin represented by the above formula (I) and the constituents [ B], when combined with the specific aromatic diamine curing agent represented by the above formula (III), it is possible to obtain an epoxy resin composition having a very excellent toughness while having a high Tg and a high elastic modulus by a synergistic effect. I can do it.

  Specific examples of the epoxy resin represented by the above formula (I) of the component [A] of the present invention include N, N, N ′, N′-tetraglycidyl-1,3-xylylenediamine, N, N, N ′, N′-tetraglycidyl-1,4-xylylenediamine, N, N, N ′, N′-tetraglycidyl-1,2-xylylenediamine, N, N, N ′, N′-tetraglycidyl -5-isopropyl-1,3-xylylenediamine, N, N, N ', N'-tetraglycidyl-5-methyl-1,3-xylylenediamine, N, N, N', N'-tetraglycidyl -5-ethyl-1,3-xylylenediamine, N, N, N ', N'-tetraglycidyl-5-isopropyl-1,3-xylylenediamine, N, N, N', N'-tetraglycidyl -5-tert-butyl-1,3-xylyl Diamine, N, N, N ′, N′-tetraglycidyl-5-chloro-1,3-xylylenediamine, N, N, N ′, N′-tetraglycidyl-5-bromo-1,3-xylylenediamine Amine, N, N, N ′, N′-tetraglycidyl-4,6-dimethyl-1,3-xylylenediamine, N, N, N ′, N′-tetraglycidyl-4,6-diethyl-1, 3-xylylenediamine, N, N, N ′, N′-tetraglycidyl-4,6-diisopropyl-1,3-xylylenediamine, N, N, N ′, N′-tetraglycidyl-4,6- Di-t-butyl-1,3-xylylenediamine, N, N, N ′, N′-tetraglycidyl-4-methyl-6-ethyl-1,3-xylylenediamine, N, N, N ′, N'-tetraglycidyl-2,4,6-trimethi -1,3-xylylenediamine, N, N, N ′, N′-tetraglycidyl-2,4,5,6-tetramethyl-1,3-xylylenediamine, N, N, N ′, N ′ -Tetraglycidyl-1,4-xylylenediamine, N, N, N ', N'-tetraglycidyl-1,4-xylylenediamine, N, N, N', N'-tetraglycidyl-2,3- Dimethyl-1,4-xylylenediamine, N, N, N ′, N′-tetraglycidyl-2,3-diethyl-1,4-xylylenediamine, N, N, N ′, N′-tetraglycidyl- 2,3-diisopropyl-1,4-xylylenediamine, N, N, N ′, N′-tetraglycidyl-2,3-di-t-butyl-1,4-xylylenediamine, N, N, N ', N'-tetraglycidyl-2,3-dimethyl-5, 6-diethyl-1,4-xylylenediamine, N, N, N ′, N′-tetraglycidyl-2,3-dimethyl-5,6-diisopropyl-1,4-xylylenediamine, N, N, N ', N'-tetraglycidyl-2,3,5,6-tetramethyl-1,4-xylylenediamine, N, N, N', N'-tetraglycidyl-1,2-xylylenediamine, N, N, N ′, N′-tetraglycidyl-4,5-dimethyl-1,2-xylylenediamine, N, N, N ′, N′-tetraglycidyl-4,5-diethyl-1,2-xylylenediamine Examples thereof include amines, N, N, N ′, N′-tetraglycidyl-3,4,5,6-tetraethyl-1,2-xylylenediamine and the like.

R ^{5 to} R ⁸ of the epoxy resin represented by the above formula of the component [A] are each a substituent selected from hydrogen, halogen, and an alkyl group having 1 to 4 carbon atoms. From the viewpoint of obtaining a cured product having a high Tg, R ^{5 to} R ⁸ are preferably hydrogen and an alkyl group having 1 to 4 carbon atoms. Further, it is preferable that at least one halogen R ⁵ to R ⁸ in terms of being able to impart flame retardancy.

  In the epoxy resin represented by the above formula (II) of the constituent element [A] of the present invention, two groups represented by (V) bonded to a hydrogenated aromatic ring are in the 1,3-position or 1,4. It is preferable to bond to the position. That is, when the group represented by (V) that is bonded to the hydrogenated aromatic ring is bonded to the 1,3-position, the cured product is superior in toughness compared to bonding to the 1,4-position or the 1,2-position. Can be obtained, and a cured product having a high Tg can be obtained when bonded to the 1,3-position or 1,4-position. Among them, the epoxy resin in which two groups represented by (V) bonded to the hydrogenated aromatic ring of the epoxy resin represented by the above formula (II) of the component [A] are bonded to the 1,3-positions; When the specific aromatic diamine curing agent represented by the above formula (III) of the component [B] is combined, an epoxy resin composition having a high Tg and a high elastic modulus due to a synergistic effect, and having an extremely excellent toughness. Can be obtained.

  Specific examples of the epoxy resin represented by the formula (II) include 1,3-bis (diglycidylaminomethyl) cyclohexane, 1,2-bis (diglycidylaminomethyl) cyclohexane, 1,4-bis (diglycidylamino). Methyl) cyclohexane, 1,3-bis (diglycidylaminomethyl) -5-methyl-cyclohexane, 1,3-bis (diglycidylaminomethyl) -5-ethyl-cyclohexane, 1,3-bis (diglycidylaminomethyl) ) -5-isopropyl-cyclohexane, 1,3-bis (diglycidylaminomethyl) -5-tert-butyl-cyclohexane, 1,3-bis (diglycidylaminomethyl) -5-chloro-cyclohexane, 1,3- Bis (diglycidylaminomethyl) -5-bromo-cyclohexane, 1,3-bis (diglycol Dilaminomethyl) -4,6-dimethyl-cyclohexane, 1,3-bis (diglycidylaminomethyl) -4,6-diethyl-cyclohexane, 1,3-bis (diglycidylaminomethyl) -4,6-diisopropyl Cyclohexane, 1,3-bis (diglycidylaminomethyl) -4,6-di-t-butyl-cyclohexane, 1,3-bis (diglycidylaminomethyl) -2,4,6-triethyl-cyclohexane, 1 , 3-bis (diglycidylaminomethyl) -2,4,5,6-tetraethyl-cyclohexane, 1,4-bis (diglycidylaminomethyl) -2,3-dimethyl-cyclohexane, 1,4-bis (di-) Glycidylaminomethyl) -2,3-diethyl-cyclohexane, 1,4-bis (diglycidylaminomethyl) -2,3- Diisopropyl-cyclohexane, 1,4-bis (diglycidylaminomethyl) -2,3-di-t-butyl-cyclohexane, 1,4-bis (diglycidylaminomethyl) -2,3-dimethyl-5,6- Diethyl-cyclohexane, 1,4-bis (diglycidylaminomethyl) -2,3-dimethyl-5,6-diisopropyl-cyclohexane, 1,4-bis (diglycidylaminomethyl) -2,3-diethyl-5 6-diisopropyl-cyclohexane, 1,4-bis (diglycidylaminomethyl) -2,3,5,6-tetraethyl-cyclohexane, 1,4-bis (diglycidylaminomethyl) -2,3,5,6- Tetramethyl-cyclohexane, 1,4-bis (diglycidylaminomethyl) -2,3,5,6-tetraisopropyl-cycl Hexane, 1,2-bis (diglycidylaminomethyl) -3,4,5,6-tetramethyl-cyclohexane, 1,2-bis (diglycidylaminomethyl) -3,4,5,6-tetraethyl-cyclohexane Is mentioned.

  The compounding amount of the epoxy resin of the component [A] is preferably 30 parts by mass or more, more preferably 60 parts by mass, and further 80 parts by mass with respect to 100 parts by mass of the total epoxy resin. preferable. Within this range, the Tg, elastic modulus, and toughness of the cured epoxy resin are particularly excellent. That is, when the blending amount is 30 parts by mass or more, a cured product having further excellent elasticity and toughness is obtained, and when the blending amount is 60 parts by mass or less, a cured product of a cured product having further excellent toughness is obtained.

Moreover, in order to obtain a cured product having a high Tg, the epoxy resin composition of the present invention contains the component [C], which is a tetrafunctional aromatic epoxy resin represented by the formula (III), in 100 parts by mass of the total epoxy resin. It is preferable to mix | blend 40 mass parts or more with respect to it, It is more preferable to mix | blend 40-80 mass parts, Furthermore, it is preferable to mix | blend 50-70 mass parts. That is, when the blending amount is 40 parts by mass or more, a cured product having a higher Tg is obtained, and when the blending amount is 80 parts by mass or less, a cured product having further excellent toughness is obtained. Here, from the viewpoint that a cured product having a high Tg is obtained, R ^{13 to} R ¹⁶ are preferably hydrogen and an alkyl group having 1 to 4 carbon atoms. Moreover, it is preferable that at least one of R < ¹³ > -R < ¹⁶ > is a halogen from a viewpoint that a flame retardance can be provided.

  Examples of the tetrafunctional aromatic epoxy resin of the constituent element [C] include N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl. −3,3′-dimethyl-4,4′-diaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl-3,3′-diethyl-4,4′-diaminodiphenylmethane, N, N, N ′ , N′-tetraglycidyl-3,3′-diisopropyl-4,4′-diaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl-3,3′-di-t-butyl-4,4 ′ -Diaminodiphenylmethane, N, N, N ', N'-tetraglycidyl-3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, N, N, N', N'-tetraglyci -3,3′-diisopropyl-5,5′-diethyl-4,4′-diaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl-3,3′-diisopropyl-5,5′-dimethyl -4,4'-diaminodiphenylmethane, N, N, N ', N'-tetraglycidyl-3,3'-di-t-butyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl-3,3′-di-t-butyl-5,5′-dimethyl-4,4′-diaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl- 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl-3,3 ′, 5,5′-tetraethyl-4,4 ′ -Diaminodiphenylmethane, N N, N ′, N′-tetraglycidyl-3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl-3,3 ′, 5,5′-tetra-t-butyl-4,4′-diaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl-3,3′-dichloro-4,4′-diaminodiphenylmethane, N, N , N ′, N′-Tetraglycidyl-3,3′-dibromo-4,4′-diaminodiphenylmethane, and other glycidylamine-type epoxy resins are excellent in the balance of Tg and elastic modulus of the resulting cured product preferable.

  The epoxy resin composition of the present invention can contain an epoxy resin other than the constituent elements [A] and [C]. The epoxy resin used in the present invention preferably has two or more epoxy groups in one molecule from the viewpoint that a cured product having a high Tg and a high elastic modulus can be obtained. Examples of such epoxy resins include bifunctional or higher glycidyl ether type epoxy resins. For example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, tetrabromobisphenol A diglycidyl ether, bisphenol AD diglycidyl ether, 2,2 ′, 6,6′-tetramethyl-4,4′-biphenol diglycidyl ether N, N, O-triglycidyl-m-aminophenol, N, N, O-triglycidyl-p-aminophenol, N, N, O-triglycidyl-4-amino-3-methylphenol, N, N Diglycidylaniline, N, N-diglycidyl-o-toluidine, diglycidyl ether of 9,9-bis (4-hydroxyphenyl) fluorene, triglycidyl ether of tris (p-hydroxyphenyl) methane, tetrakis (p-hydroxy) Phenyl) ethane tet Glycidyl ether, phenol novolak glycidyl ether, cresol novolac glycidyl ether, glycidyl ether of phenol and dicyclopentadiene condensate, glycidyl ether of phenol aralkyl resin, triglycidyl isocyanurate, N-glycidyl phthalimide, 5-ethyl-1,3- Examples thereof include diglycidyl-5-methylhydantoin, oxazolidone type epoxy resin and phenol aralkyl type epoxy resin obtained by addition of bisphenol A diglycidyl ether and tolylene isocyanate. In addition, an epoxy resin having a dicyclopentadiene skeleton, an epoxy resin having a biphenylaralkyl skeleton, and triglycidyl isocyanurate can be given. Moreover, an aliphatic epoxy resin and an alicyclic epoxy resin can be mix | blended in the range which does not cause a remarkable fall of Tg.

The component [B] of the present invention is an aromatic diamine curing agent represented by the following formula (IV). Here, R ^{9 to} R ¹² in the chemical formula are each a substituent selected from hydrogen, halogen, and an alkyl group having 1 to 4 carbon atoms. Furthermore, the total carbon number of R ^{9 to} R ¹² of the constituent element [B] needs to be 6 or more, and more preferably 8 or more. When the total number of carbon atoms is 6 or more, a cured epoxy resin having excellent toughness can be obtained, and as a result, a fiber-reinforced composite material having excellent impact resistance, fatigue resistance, and 0 ° tensile strength can be obtained. The aromatic diamine curing agent means a compound having an aromatic ring in the molecule, further having two amine nitrogen atoms in the molecule, and having a plurality of active hydrogens. Moreover, the active hydrogen here means a hydrogen atom bonded to an aminic nitrogen atom.

  Examples of the aromatic diamine curing agent of the component [B] include 3,3′-diisopropyl-4,4′-diaminodiphenylmethane, 3,3′-di-t-butyl-4,4′-diaminodiphenylmethane, 3,3′-diethyl-5,5′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-diisopropyl-5,5′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-di -T-butyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5 '-Diethyl-4,4'-diaminodiphenylmethane, 3,3'-di-t-butyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5 '-Tetraisopropyl-4,4'-diaminodiphenylmethane, 3,3'-di-t-butyl-5,5'-diisopropyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetra -T-butyl-4,4'-diaminodiphenylmethane and the like.

Especially, the substituent of R < ⁹ > -R < ¹² > of component [B] is either n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. Is preferred. When the substituents of R ^{9 to} R ¹² are an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group, the Tg, elastic modulus, and toughness of the cured epoxy resin Both of these are particularly excellent. Furthermore, even if it is solid, once it is heated, the curing agent remains in a liquid state for a long time, so that the epoxy resin composition is injected into a reinforcing fiber base material and impregnated, and then cured by heating. It can use suitably for the manufacturing method of fiber reinforced composite materials, such as a molding (RTM) method.

  In the present invention, the curing agent includes at least two or more types of aromatic diamine curing agents, and at least one of the aromatic diamine curing agents is preferably the aromatic diamine curing agent of the component [B]. . By combining two or more kinds of aromatic diamine curing agents, the curing agent retains the liquid state for a longer period of time, so that it can be suitably used in a method for producing a fiber-reinforced composite material such as the RTM method. Furthermore, it is preferable that at least two kinds of aromatic diamine curing agents of the component [B] are included. In this case, since the curing agent is kept in a liquid state for a longer time, it can be more suitably used in a method for producing a fiber-reinforced composite material such as the RTM method, and further, a toughened epoxy resin cured product can be obtained.

  In the present invention, the curing agent preferably contains an aromatic diamine curing agent that is solid at 25 ° C. and an aromatic diamine curing agent that is liquid at 25 ° C. In this case, since the curing agent is kept in a liquid state for a longer time, it can be suitably used in a method for producing a fiber-reinforced composite material such as the RTM method. Furthermore, any of Tg, elastic modulus, and toughness of the cured epoxy resin can be used. Thigh is particularly excellent.

In the present invention, R ⁹ and R ¹¹ of the constituent element [B] are the same substituent, the substituents of R ¹⁰ and R ¹² are the same, and R ⁹ , R ¹¹ and R ¹⁰ , R ^{12 are the same.} It is preferable that the combinations of the substituents in are different. In this case, an epoxy resin cured product having a higher Tg and a higher elastic modulus can be obtained. Examples of the aromatic diamine curing agent of the component [B] include 3,3′-diisopropyl-4,4′-diaminodiphenylmethane and 3,3′-di-t-butyl-4,4′-diaminodiphenylmethane. 3,3′-diethyl-5,5′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-diisopropyl-5,5′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′- Di-t-butyl-5,5′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-diisopropyl-5,5′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-di- Examples thereof include t-butyl-5,5′-diethyl-4,4′-diaminodiphenylmethane and 3,3′-di-t-butyl-5,5′-diisopropyl-4,4′-diaminodiphenylmethane.

  Moreover, it is preferable that the compounding quantity of the aromatic diamine hardening | curing agent of structural element [B] is 20 mass parts or more with respect to 100 mass parts of all the hardening | curing agents, and it is more preferable that it is 40 mass parts or more. That is, when the blending amount is 20 parts by mass or more, an epoxy resin cured product that is further excellent in high Tg, high elastic modulus, and toughness can be obtained.

  The epoxy resin composition of the present invention may contain a diamine curing agent other than the aromatic diamine curing agent of the component [B]. Examples of the diamine curing agent include aliphatic diamine curing agents such as hexamethylene diamine, 1,3-pentane diamine, and 2-methylpentamethylene diamine, isophorone diamine, 4,4′-methylene biscyclohexyl amine, 4, Examples include alicyclic diamine curing agents such as 4′-methylenebis (2-methylcyclohexylamine), bis (aminomethyl) norbornane, 1,2-cyclohexanediamine, and 1,3-bisaminomethylcyclohexane. Furthermore, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 2,2′-diethyldiaminodiphenylmethane, 4,4′-methylenebis (N-methylaniline) Aromatic diamine curing such as 4,4′-methylenebis (N-ethylaniline), 4,4′-methylenebis (N-sec-butylaniline), N, N′-di-sec-butyl-p-phenylenediamine Agents. These liquid diamine curing agents may be used alone or in combination. Among these, it is preferable to use an aromatic diamine curing agent in order to obtain a cured product having a high Tg and a high elastic modulus.

Furthermore, it is preferable to use an aromatic diamine curing agent represented by any one of the above formulas (V) to (VII) or a mixture thereof because of its low viscosity and excellent impregnation into reinforcing fibers. Here, from the viewpoint of obtaining a cured product having a high Tg, R ^{17 to} R ²⁸ are preferably hydrogen and an alkyl group having 1 to 4 carbon atoms. Moreover, it is preferable that at least one of R < ¹⁷ > -R < ²⁸ > is a halogen from a viewpoint that a flame retardance can be provided.

  Of these, diethyltoluenediamine such as 2,4-diethyl-6-methyl-m-phenylenediamine, 4,6-diethyl-2-methyl-m-phenylenediamine, and 4,6-diethyl-m-phenylenediamine are used. It is preferable. In this case, an epoxy resin cured product having a high Tg and a high elastic modulus can be obtained. As such an aromatic diamine curing agent, “jER Cure (registered trademark)” W manufactured by Japan Epoxy Resin Co., Ltd. can be used.

  In addition, the epoxy resin composition of the present invention includes a curing accelerator, a plasticizer, a dye, a pigment, an inorganic filler, an antioxidant, an ultraviolet absorber, a coupling agent, a surfactant and the like as other components as necessary. Can be included. Moreover, high toughening agents such as core-shell polymer particles can be included.

  The epoxy resin composition of the present invention can be cured by mixing an epoxy resin and an amine curing agent at a predetermined ratio. The mixing ratio of the epoxy resin and the amine curing agent is determined by the type of epoxy resin and amine curing agent used. Specifically, the ratio of the number of epoxy groups contained in the epoxy resin in the epoxy resin composition to the number of active hydrogens contained in the amine curing agent is preferably 0.7 to 1.3, more preferably 0.8. Mix so that 8-1.2. That is, by setting the ratio in the range of 0.7 to 1.3, a cured product having a higher Tg and a higher elastic modulus can be obtained.

  The initial viscosity at 70 ° C. of the epoxy resin composition of the present invention is preferably 250 mPa · s or less, more preferably 150 mPa · s or less, and further preferably 100 mPa · s or less. The viscosity was measured in accordance with JIS Z8803 (1991) "Viscosity measurement method using a conical-flat plate viscometer" E type viscometer (Tokimec Co., Ltd.) equipped with a standard cone rotor (1 ° 34 '× R24). Using a TVE-30H, manufactured at a rotational speed of 50 rpm. The initial viscosity is measured after adjusting the epoxy resin composition and holding it at 70 ° C. for 5 minutes. By setting the initial viscosity at 70 ° C. to 250 mPa · s or less, a fiber-reinforced composite material having further excellent impregnation into reinforcing fibers and excellent quality can be obtained.

  The resin tensile elongation at 25 ° C. of the cured product of the epoxy resin composition of the present invention is preferably 4.0%, more preferably 5.0%, and even more preferably 6.0%. preferable. The resin tensile elongation is measured at 25 ° C. according to JIS K7113 using a cured product obtained by curing the epoxy resin composition at 180 ° C. for 2 hours. When the resin tensile elongation is 4.0% or more, a fiber-reinforced composite material having further excellent impact resistance, fatigue resistance, and 0 ° direction tensile strength can be obtained.

  The flexural modulus at 25 ° C. of the cured product of the epoxy resin composition of the present invention is preferably in the range of 2.6 to 4.5 GPa, more preferably in the range of 3.0 to 4.5 GPa. Is preferably in the range of 3.4 to 4.5 GPa. In addition, the measurement of a bending elastic modulus is performed at 25 degreeC according to JISK7171-1994 using the hardened | cured material which hardened | cured the epoxy resin composition at 180 degreeC for 2 hours. When the flexural modulus is 2.6 GPa or more, a fiber-reinforced composite material having higher compressive strength is obtained. When the flexural modulus is 4.5 GPa or less, a fiber-reinforced composite material having further excellent impact resistance and fatigue resistance is obtained.

  Examples of the reinforcing fiber in the present invention include glass fiber, carbon fiber, and aramid fiber. Among these, carbon fiber is preferably used from the viewpoint of obtaining a fiber-reinforced composite material that is particularly lightweight and excellent in mechanical properties such as strength and elastic modulus.

  Examples of the carbon fiber in the present invention include acrylic, pitch, and rayon carbon fibers. Among them, acrylic carbon fibers having high tensile strength are preferably used.

  As the carbon fiber in the present invention, the tensile elastic modulus is preferably 200 or more, more preferably 250 or more from the viewpoint that a fiber-reinforced composite material that is lightweight and excellent in elastic modulus can be obtained. It is preferable that it is 280 or more. By setting the tensile elastic modulus to 200 GPa or more, a fiber-reinforced composite material having a higher elastic modulus and an excellent lightening effect can be obtained.

  Further, as the carbon fiber in the present invention, as described in the specification of Japanese Patent No. 2955145, a flatness having a fineness of 3000 to 20000 denier, a yarn width of 4 to 16 mm, and a yarn width / yarn thickness ratio of 30 or more. It is preferable to use a thread. By using such a flat yarn, a reinforced fiber base material in which the bending of the carbon fiber strand is small is obtained, and a fiber reinforced composite material having excellent mechanical properties such as compressive strength is obtained.

  The reinforcing fiber in the present invention can be used as a reinforcing fiber base material alone or in combination with a plurality of kinds of the reinforcing fibers, or in combination with other chemical fibers. Such a reinforcing fiber substrate preferably has at least carbon fiber. As the reinforcing fiber base of the present invention, those in which reinforcing fibers are aligned in substantially the same direction, woven fabric, knit, braid, mat and the like can be used. Among these, from the viewpoint that a fiber-reinforced composite material having a high fiber volume content can be obtained, a so-called unidirectional woven fabric in which reinforcing fibers arranged in almost one direction are fixed with glass fibers or chemical fibers is preferably used.

  The unidirectional woven fabric in the present invention is composed of, for example, a warp made of carbon fiber strands, and a weft made of glass fiber or chemical fiber orthogonal thereto, and the warp and the weft intersect with each other to form a plain weave structure. Things. Moreover, the warp (1 of FIG. 1) which consists of a strand of carbon fiber shown in FIG. 1, the auxiliary warp (2 of FIG. 1) of the fiber bundle which consists of a glass fiber or a chemical fiber arrange | positioned in parallel with this, orthogonal to these Nonwoven fabrics having a non-crimp structure in which carbon fiber strands are integrally held by the auxiliary warp and the weft intersecting each other are mentioned. Among these, non-crimp fabrics are preferably used from the viewpoints of excellent straightness of carbon fibers and excellent compressive strength of the fiber-reinforced composite material. Among them, the fiber reinforced composite material comprising the cured product of the epoxy resin composition of the present invention and a non-crimp fabric is excellent in the straightness of carbon fiber, and the synergistic effect of the cured product of the epoxy resin composition having a high elastic modulus. Thus, the compressive strength of the fiber reinforced composite material is particularly excellent. Furthermore, the impact resistance and fatigue resistance are particularly excellent.

  In the unidirectional woven fabric of the present invention, the fineness of the auxiliary warp is preferably 20% or less, more preferably 10% or less, and even more preferably 5% or less of the fineness of the warp composed of carbon fiber strands. It is preferable. By setting such a range, warp auxiliary yarns are more easily deformed than carbon fiber strands, a unidirectional woven fabric with a small bend in carbon fiber strands is obtained, and a fiber-reinforced composite material having further excellent mechanical properties such as compressive strength is obtained. It is done.

  In the unidirectional fabric of the present invention, the fineness of the weft is preferably 20% or less, more preferably 10% or less, and further preferably 5% or less of the fineness of the warp made of carbon fiber strands. Preferably there is. By setting this range, a unidirectional woven fabric in which the bending of the carbon fiber strand generated around the weft is small can be obtained, and a fiber-reinforced composite material having further excellent mechanical properties such as compressive strength can be obtained.

  A binder is appropriately attached to the reinforcing fiber base material in the present invention for the purpose of preventing the orientation deviation of the reinforcing fibers, temporarily adhering the reinforcing fiber base materials, and improving the impact resistance of the resulting fiber reinforced composite material. I can keep it. There are no particular restrictions on the composition of the binder, and existing ones can be used. However, those containing a thermoplastic resin as the main component can be preferably used because they have little change in physical properties during storage in addition to the above-mentioned purpose.

  When the fiber-reinforced composite material of the present invention is used as an aircraft structural member, excellent heat resistance is required, and therefore an engineering plastic having a high glass transition temperature is preferable as the thermoplastic resin used for the binder. In particular, polysulfone, polyethersulfone, polyimide, polyetherimide and the like can be suitably used.

  It is preferable that a binder composition comprising a thermoplastic resin is mixed with an appropriate plasticizer component to adjust the glass transition temperature as a binder to an appropriate range, specifically 50 to 70 ° C. Here, for the plasticizer component, it is preferable to select a compound that can react with the epoxy resin composition. As such a plasticizer component, an epoxy resin is particularly preferable. The epoxy resin used as the plasticizer component is not particularly limited. For example, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetrabromobisphenol A, phenol novolac, cresol novolac, hydroquinone, resorcinol, 4,4′-dihydroxy-3 , 3 ′, 5,5′-tetramethylbiphenyl, 1,6-dihydroxynaphthalene, 9,9-bis (4-hydroxyphenyl) fluorene, tris (p-hydroxyphenyl) methane, tetrakis (p-hydroxyphenyl) ethane And glycidyl ether type epoxy resin obtained by the reaction of epichlorohydrin. In addition, an epoxy resin having a dicyclopentadiene skeleton, an epoxy resin having a biphenylaralkyl skeleton, and triglycidyl isocyanurate can be given. Also, for example, N, N, O-triglycidyl-m-aminophenol, N, N, O-triglycidyl-p-aminophenol, N, N, O-triglycidyl-4-amino-3-methylphenol, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl-4,4′-diamino-3,3′-diethyldiphenylmethane, N , N, N ′, N′-tetraglycidyl-m-xylylenediamine and the like glycidylamine type epoxy resins. Moreover, for example, polyphenol, polyamine, polycarboxylic acid, polycarboxylic anhydride, polyacrylate, sulfonamide and the like can be mentioned.

  In the fiber reinforced composite material in the present invention, the fiber volume content of the reinforcing fibers is preferably in the range of 45 to 70%, more preferably in the range of 50 to 65%, and further 55 to 60%. It is preferable to be within the range. When the fiber volume content is 45% or more, a fiber-reinforced composite material having a higher elastic modulus and excellent weight reduction effect can be obtained. When the fiber volume content is 70% or less, there is no decrease in strength due to abrasion between the reinforcing fibers, and the tensile strength. Thus, a fiber-reinforced composite material having excellent mechanical properties can be obtained.

  As a preferable molding method of the fiber-reinforced composite material in the present invention, from the viewpoint of efficiently obtaining a fiber-reinforced composite material, a method of obtaining a fiber-reinforced composite material by impregnating and curing a liquid epoxy resin composition in a reinforcing fiber, For example, a hand lay-up method, a filament winding method, a pultrusion method, an RTM method and the like can be mentioned. Among these, it is preferable to use the RTM method from the viewpoint that a complex-shaped fiber-reinforced composite material can be obtained efficiently. Here, the RTM method means a method of obtaining a fiber-reinforced composite material by impregnating and curing a liquid epoxy resin composition on a reinforcing fiber base disposed in a mold.

  In the present invention, the mold used for the RTM method may be a closed mold made of a rigid material, or an open mold of a rigid material and a flexible film (bag) can be used. In the latter case, the reinforcing fiber substrate can be placed between an open mold of rigid material and a flexible film. As the rigid material, various existing materials such as metals such as steel and aluminum, fiber reinforced plastic (FRP), wood, and plaster are used. As the flexible film material, polyamide, polyimide, polyester, fluororesin, silicone resin, or the like is used.

  In the RTM method of the present invention, when a closed mold of a rigid material is used, it is usually performed by pressurizing and clamping, and pressurizing and injecting the fiber reinforced composite material epoxy resin composition. At this time, it is also possible to provide a suction port separately from the injection port and connect it to a vacuum pump for suction. It is also possible to perform the suction and inject the epoxy resin composition only at atmospheric pressure without using any special pressurizing means. This method can be suitably used because a large member can be manufactured by providing a plurality of suction ports.

  In the RTM method of the present invention, when an open mold of a rigid material and a flexible film are used, suction is usually performed and the epoxy resin is injected only at atmospheric pressure without using a special pressurizing means. In order to achieve good impregnation by injection only at atmospheric pressure, it is effective to use a resin diffusion medium. Furthermore, it is preferable to apply a gel coat to the surface of the rigid material prior to installation of the fiber base material or preform made of reinforcing fibers.

  When a rigid material closed mold is used as the mold, the inside of the mold means a cavity formed by the closed mold, and when a rigid material open mold and a flexible film are used, The term “in the space surrounded by the open mold and the flexible film” means.

  In the RTM method of the present invention, the reinforcing fiber substrate is impregnated with the epoxy resin composition, and then heat-cured. The mold temperature at the time of heat curing is usually selected to be higher than the mold temperature at the time of injection of the epoxy resin composition. The mold temperature during heat curing is preferably 80 to 200 ° C. The heat curing time is preferably 1 to 20 hours. After the heat curing is completed, the mold is removed and the fiber reinforced composite material is taken out. Thereafter, post-curing may be performed by heating the obtained fiber-reinforced composite material at a higher temperature. The post-curing temperature is preferably 150 to 200 ° C., and the time is preferably 1 to 4 hours.

  In the present invention, a resin supply tank described in, for example, a VaRTM (Vacuum-assisted Resin Transfer Molding) method, a SCRIMP (Seeman's Composite Resin Infusion Molding Process) method, and a special table 2005-527410, which are derivatives of the RTM method. CAPRI (Controlled Atmospheric Pressure Resin Infusion) method for controlling the resin injection process, particularly VaRTM method more appropriately, by exhausting to a pressure lower than atmospheric pressure, using cyclic compression, and controlling the net molding pressure Can be suitably used.

  When manufacturing a fiber reinforced composite material by such an RTM method, it is preferable to use the above-mentioned unidirectional woven fabric and further a non-crimped woven fabric as the reinforcing fiber substrate. In a non-crimp fabric, the gap between the warp made of carbon fiber strands (1 in FIG. 1) and the auxiliary warp of fiber bundles made of glass fibers or chemical fibers (2 in FIG. 1) arranged in parallel with this is resin. Since it functions as a flow path, a fiber-reinforced composite material can be efficiently obtained by using a non-crimp fabric. Furthermore, since the epoxy resin of the present invention has a low viscosity, a fiber-reinforced composite material can be obtained more efficiently. Further, the obtained fiber reinforced composite material has particularly excellent compressive strength, and particularly excellent impact resistance and fatigue resistance.

  Furthermore, when manufacturing a fiber reinforced composite material by such an RTM method, the above-mentioned unidirectional woven fabric, or a non-crimped woven fabric is used as the reinforcing fiber base, and the inside of the mold is used by using a vacuum pump or the like. It is preferable to impregnate the epoxy resin composition by vacuum suction. In a non-crimp fabric, the gap between the warp made of carbon fiber strands (1 in FIG. 1) and the auxiliary warp of fiber bundles made of glass fibers or chemical fibers (2 in FIG. 1) arranged in parallel with this is resin. A large fiber-reinforced composite material can be efficiently obtained by functioning as a flow path and vacuum suction inside the mold. Furthermore, since the epoxy resin of the present invention has a low viscosity, a large fiber-reinforced composite material can be obtained more efficiently. Further, the obtained fiber reinforced composite material has particularly excellent compressive strength, and particularly excellent impact resistance and fatigue resistance. Since the fiber-reinforced composite material of the present invention has excellent thermal properties, compressive strength, impact resistance, and 0 ° direction tensile strength, the fuselage, main wing, tail wing, moving blade, fairing, cowl, door, seat, interior material Aircraft parts such as motor parts, spacecraft parts such as motor cases and main wings, structures, artificial satellite parts such as antennas, outer panels, chassis, aerodynamic members, automobile parts such as seats, structures, railway vehicle parts such as seats, hulls, seats It can be preferably used for many structural materials such as ship members.

  Hereinafter, the present invention will be described specifically by way of examples. The resin raw materials used in the examples, the adjustment method of the epoxy resin composition, the preparation method of the cured product, and the measurement methods of the respective characteristics are shown below.

<Resin raw material>
The following commercially available products were used for adjusting the epoxy resin composition.

(1) Epoxy resin (a) Epoxy resin of component [A] “TETRAD (registered trademark)” X (N, N, N ′, N′-tetraglycidyl-1,3-xylylenediamine, epoxy equivalent: 99g / mol, manufactured by Mitsubishi Gas Chemical Co., Ltd.)
"TETRAD (registered trademark)" C (1,3-bis (diglycidylaminomethyl) cyclohexane, epoxy equivalent: 105 g / mol, manufactured by Mitsubishi Gas Chemical Co., Ltd.)
(B) Epoxy resin of component [C] “Araldite (registered trademark)” MY721 (N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, epoxy equivalent: 113 g / mol, Huntsman・ Advanced Materials
“Araldite®” MY722 (N, N, N ′, N′-tetraglycidyl-3,3′-diethyl-4,4′-diaminodiphenylmethane, epoxy equivalent: 125 g / mol, Huntsman Advanced Materials (Made by company)
(C) Other epoxy resin “jER (registered trademark)” 630 (N, N, O-triglycidyl-p-aminophenol, epoxy equivalent: 98 g / mol, manufactured by Japan Epoxy Resins Co., Ltd.).

  "JER (registered trademark)" 825 (bisphenol A type diglycidyl ether, epoxy equivalent: 175 g / mol, manufactured by Japan Epoxy Resin Co., Ltd.).

(2) Amine curing agent (a) Aromatic diamine curing agent of component [B] “Lonza Cure (registered trademark)” M-MIPA (3,3′-diisopropyl-5,5′-dimethyl-4,4 ′ - diaminodiphenylmethane, active hydrogen equivalent: 78 g / ^mol, and the total number of carbon atoms in ^R 9 ~R ^12: 8, solid (mp: 72 ° C.), manufactured by Lonza)
“Lonza Cure (registered trademark)” M-DEA (3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenylmethane, active hydrogen equivalent: 78 g / mol, total carbon number of R ^{9 to} R ¹² : 8. Solid (Melting point: 88 ° C., manufactured by Lonza)
“Lonza Cure (registered trademark)” M-DIPA (3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminodiphenylmethane, active hydrogen equivalent: 93 g / mol, total carbon number of R ^{9 to} R ¹² : 12, solid (melting point: 30 ° C.), manufactured by Lonza).

(B) Other diamine curing agent • 3,3′-DAS (3,3′-diaminodiphenylsulfone, active hydrogen equivalent: 45 g / mol, solid (melting point: 171 ° C.), manufactured by Mitsui Chemicals Fine 62 Co., Ltd.)
"Ancamine (registered trademark)" 2049 (4,4'-methylenebis (2-methylcyclohexylamine) [cycloaliphatic diamine curing agent], active hydrogen equivalent: 60 g / mol, manufactured by Air Products)
“Kayahard (registered trademark)” AA (2,2′-diethyl-4,4′-diaminodiphenylmethane [aromatic diamine curing agent represented by formula (IV), total carbon number of R ^{9 to} R ¹² 4), active hydrogen equivalent: 64 g / mol, liquid (viscosity at 25 ° C .: 2000 to 3000 mPa · s), manufactured by Nippon Kayaku Co., Ltd.).

<Adjustment of epoxy resin composition>
The epoxy resin composition shown to Tables 1-3 was adjusted with the following procedure. A predetermined amount of the epoxy resin heated to 70 ° C. was weighed into a 300 ml stainless beaker and stirred with a spatula until uniform to obtain a main agent. A predetermined amount of the diamine curing agent was weighed into a 300 ml stainless beaker, heated to 120 ° C. to 180 ° C., and stirred with a spatula until the solid was dissolved to obtain a curing agent. Next, the main agent and the curing agent heated to 70 ° C. were mixed and stirred with a spatula until uniform to obtain an epoxy resin composition.

<Measurement of liquid retention time of curing agent>
40 ml of the curing agent obtained by the above method was weighed into a glass bottle containing 50 ml, stored in a temperature environment at 25 ° C., and 0.3 g was sampled every predetermined time to confirm the presence or absence of crystal precipitation. The sampled curing agent was sandwiched between two glass plates, and the presence or absence of crystal precipitation was confirmed using a laser microscope VK-9510 manufactured by Keyence Corporation at a magnification of 50 times. In this measurement, the time until the crystals were precipitated was defined as the liquid retention time of the curing agent.

<Measurement of initial viscosity of epoxy resin composition at 70 ° C.>
The initial viscosity at 70 ° C. of the epoxy resin composition obtained by the above method was determined using a standard cone rotor (1 ° 34 ′ × R24) according to “Conemeter-Viscosity Measurement Method Using a Flat Plate Viscometer” in JIS Z8803 (1991). Using an attached E-type viscometer (TVE-30H, manufactured by Tokimec Co., Ltd.), the measurement was performed at a rotational speed of 50 revolutions / minute. The initial viscosity was measured after adjusting the epoxy resin composition and holding it at 70 ° C. for 5 minutes.

<Method for producing cured epoxy resin>
The epoxy resin composition obtained by the above method was poured into a mold having a plate cavity having a thickness of 2 mm and 6 mm, and cured by heating in an oven under the following conditions to obtain a cured resin plate.
(1) The temperature is raised from 30 ° C. to 180 ° C. at a rate of 1.5 ° C./min.
(2) Hold at 180 ° C. for 2 hours.
(3) The temperature is lowered from 180 ° C. to 30 ° C. at a rate of 2.5 ° C./min.

<Measurement of glass transition temperature (Tg) of cured epoxy resin>
A test piece having a length of 55 mm and a width of 12.7 mm was cut out from the cured resin plate having a thickness of 2 mm obtained by the above method, and Tg was measured by the DMA method according to SACMA SRM18R-94. The apparatus used was ARES manufactured by Rheometrics. The heating rate was 5 ° C./min, and the measurement frequency was 1 Hz. The intersection temperature value of the tangent in the glass state and the tangent in the transition state in the obtained temperature-storage modulus G ′ curve was defined as Tg.

<Measurement of flexural modulus of cured epoxy resin>
A test piece having a length of 60 mm and a width of 10 mm was cut out from the cured resin plate having a thickness of 2 mm obtained by the above method, and a three-point bending test was performed at a test speed of 2.5 mm / min and a distance between fulcrums of 32 mm. JIS K7171- The flexural modulus was measured according to 1994. The measurement temperature was 25 ° C.

<Resin tensile elongation measurement of cured epoxy resin>
Based on JISK7113, a small 1 (1/2) test piece was produced from the cured resin plate obtained by the above method, and the tensile elongation was measured. The apparatus used was 4201 type Tensilon manufactured by Instron. Here, the crosshead speed was 2.5 mm / min, and the measurement temperature was 25 ° C.

<Preparation of Reinforcing Fiber Substrate 1 Having Carbon Fiber>
Reinforcing fiber substrate 1 having carbon fibers used in Examples 13 and 14 and Comparative Examples 7 and 8 was produced as follows. PAN-based untwisted carbon fiber bundle “Treca (registered trademark)” T800S-24K-10C (Toray Industries, Inc., 24000 filaments) is used as a warp yarn, and it is aligned at a density of 1.8 yarns / cm and is unidirectional A sheet-like reinforcing fiber bundle group was formed. Glass fibers ECE225 1/0 1Z (manufactured by Nittobo Co., Ltd.) are used as wefts, arranged at a density of 3 strands / cm in a direction perpendicular to the unidirectional sheet-like reinforcing fiber bundle group, and using a loom A woven fabric having a plain weave structure in which the warp and the weft are woven so as to cross each other and carbon fibers are substantially arranged in one direction was produced, and used as a reinforcing fiber substrate. The carbon fiber basis weight of the obtained reinforcing fiber base was 190 g / m ² . Furthermore, 60 parts by mass of “Sumika Excel (registered trademark)” 5003P (manufactured by Sumitomo Chemical Co., Ltd.), which is a polyethersulfone, and “jER (registered trademark)” 806, which is a glycidyl ether of bisphenol F, are used as the reinforcing fiber base material. 23.5 parts by mass (manufactured by Japan Epoxy Resin Co., Ltd.), 12.5 parts by mass of NC-3000 (manufactured by Nippon Kayaku Co., Ltd.) which is an epoxy resin having a biphenylaralkyl skeleton, and TEPIC- which is triglycidyl isocyanurate 4 parts by mass of P (manufactured by Nissan Chemical Industries, Ltd.) was melt-kneaded at 210 ° C. with a twin screw extruder, and the resulting resin composition was classified after freezing and pulverization to obtain a volume average particle diameter of 100 μm and a glass transition temperature. Binder particles at 73 ° C. were obtained. The obtained binder particles are spontaneously dropped onto one surface of the reinforcing fiber substrate while being measured with an embossing roll and a doctor blade, and uniformly dispersed through a vibration net, so that the binder particle weight is 25 g / m ^2. Sprayed on. Thereafter, a far-infrared heater was passed under conditions of 200 ° C. and 0.3 m / min, and the binder particles were fused to the entire surface of one side of the reinforcing fiber substrate to obtain a reinforcing fiber substrate 1 with binder particles.

<Preparation of Reinforcing Fiber Substrate 2 Having Carbon Fiber>
The reinforcing fiber substrate 2 having the carbon fibers used in Example 15 was produced as follows. PAN-based untwisted carbon fiber bundle “Torayca (registered trademark)” T800S-24K-10C (manufactured by Toray Industries, Inc., 24000 filaments) is used as a warp and aligned at a density of 1.8 yarns / cm and parallel to this. In addition, glass fiber bundles ECE225 1/0 1Z (manufactured by Nittobo Co., Ltd., 200 filaments) are arranged at a density of 1.8 fibers / cm as auxiliary warp yarns arranged alternately. Groups were formed. Polyamide fiber bundles (polyamide 66, 7 filaments) are used as wefts, arranged at a density of 3 strands / cm in a direction perpendicular to the unidirectional sheet-like reinforcing fiber bundle group, and the auxiliary warp and weft yarns using a loom. Were woven so as to cross each other, and a unidirectional woven fabric having a non-crimp structure as shown in FIG. The carbon fiber basis weight of the obtained reinforcing fiber base was 190 g / m ² . Furthermore, by the same method as that for the reinforcing fiber base 1, the binder particles were fused to the entire surface of one side of the reinforcing fiber base to obtain a reinforcing fiber base 2 with binder particles.

<Glass Transition Temperature (Tg) Measurement, Fabrication of Fiber Reinforced Composite Material for 0 ° Direction Tensile Test, 0 ° Direction Compression Test>
The fiber reinforced composite materials for Tg measurement and the 0 ° tensile test used in Examples 13 to 15 and Comparative Examples 7 and 8 were produced by the RTM method as follows. The reinforcing fiber substrate with binder particles cut out to 395 mm × 395 mm in a mold having a plate-like cavity of 400 mm × 400 mm × 1.14 mm is aligned in the same direction with the fiber direction of the carbon fiber being 0 °. Six preforms were stacked to produce a preform and clamped. Subsequently, after the mold was heated to a temperature of 70 ° C., an epoxy resin composition previously heated to a temperature of 70 ° C. was injected into the mold at an injection pressure of 0.2 MPa using a resin injection device, A reinforcing fiber substrate was impregnated. After impregnation, the mold was heated to a temperature of 130 ° C. at a rate of 1.5 ° C./min, held at a temperature of 130 ° C. for 2 hours, then cooled to a temperature of 30 ° C. and demolded. After demolding, post-curing was performed in an oven under the following conditions to obtain a fiber-reinforced composite material.
(1) The temperature is raised from 30 ° C. to 180 ° C. at a rate of 1.5 ° C./min.
(2) Hold at a temperature of 180 ° C. for 2 hours.
(3) The temperature is decreased from 180 ° C. to 30 ° C. at a rate of 2.5 ° C./min.

<Preparation of Tg measurement specimen of fiber reinforced composite material>
Using the fiber-reinforced composite material obtained by the above method, a rectangular test piece having a length of 55 mm and a width of 12.7 mm was cut out with the 90 ° direction as the length direction of the test piece.

<Tg measurement of fiber reinforced composite material>
Using the test piece for Tg measurement obtained by the above method, Tg was measured by the DMA method according to SACMA SRM18R-94. The apparatus used was ARES manufactured by Rheometrics. The heating rate was 5 ° C./min, and the measurement frequency was 1 Hz. The intersection temperature value of the tangent in the glass state and the tangent in the transition state in the obtained temperature-storage modulus G ′ curve was defined as Tg.

<Preparation of 0 ° direction tensile test piece of fiber reinforced composite material>
Using the fiber reinforced composite material obtained by the above method, in accordance with ASTM D3039-00, after bonding the tab, a rectangular test having a length of 254 mm and a width of 12.7 mm with the 0 ° direction as the length direction of the test piece A piece was cut out.
<0 ° direction tensile test of fiber reinforced composite material>
Using the 0 ° direction compression test piece obtained by the above method, a tensile test was performed at a test speed of 1.27 mm / min in accordance with ASTM D3039-00 in a 23 ° C. environment. The number of samples was 5, and the average value was used.

<Preparation of 0 ° direction compression test piece of fiber reinforced composite material>
Using the fiber-reinforced composite material obtained by the above method and adhering the tab in accordance with SACMA-SRM 1R-94, the 0 ° direction is the length direction of the test piece, the length is 80.0 mm, and the width is 15. A 0 mm rectangular test piece was cut out.

<0 ° direction compression test of fiber reinforced composite material>
A compression test was performed at a test speed of 1.0 mm / min in accordance with SACMA-SRM 1R-94 in a 23 ° C. environment using the 0 ° direction compression test piece obtained by the above method. The number of samples was 5, and the average value was used.

<Examples 1 and 2>
An epoxy resin composition was prepared using the resin raw materials shown in Table 1, and the initial viscosity at 70 ° C. was measured. As a result, all had sufficiently low viscosity. Next, a cured product was prepared, and Tg, flexural modulus, and tensile elongation were measured. As a result, it was found that all of Tg, elastic modulus and fracture toughness were high and excellent. In particular, Example 2 was found to have a very high tensile elongation and was particularly excellent.

<Examples 3 to 5>
An epoxy resin composition was prepared using the resin raw materials shown in Table 1, and the initial viscosity at 70 ° C. was measured. As a result, all had sufficiently low viscosity. Next, a cured product was prepared, and Tg, flexural modulus, and tensile elongation were measured. As a result, it was found that all of Tg, elastic modulus and tensile elongation were high and excellent.

<Examples 6 and 7>
An epoxy resin composition was prepared using the resin raw materials shown in Table 2, and the initial viscosity at 70 ° C. was measured. As a result, all had sufficiently low viscosity. Next, a cured product was prepared, and Tg, flexural modulus, and tensile elongation were measured. As a result, it was found that all of Tg, elastic modulus and tensile elongation were high and excellent. Furthermore, it was found that Example 6 has a very high elastic modulus and is particularly excellent.

<Examples 8 and 9>
An epoxy resin composition was prepared using the resin raw materials shown in Table 2, and the initial viscosity at 70 ° C. was measured. As a result, all had sufficiently low viscosity. Next, a cured product was prepared, and Tg, flexural modulus, and tensile elongation were measured. As a result, it was found that all of Tg, elastic modulus and tensile elongation were high and excellent. Furthermore, Example 9 was found to have a very low viscosity and was particularly excellent.

<Examples 10 to 12>
An epoxy resin composition was prepared using the resin raw materials shown in Table 2, and the initial viscosity at 70 ° C. was measured. As a result, all had sufficiently low viscosity. Next, a cured product was prepared, and Tg, flexural modulus, and tensile elongation were measured. As a result, it was found that all of Tg, elastic modulus and tensile elongation were high and excellent. Furthermore, Example 9 was found to have a very low viscosity and was particularly excellent. Furthermore, it turned out that Examples 10-12 are especially excellent also in the storage stability of a hardening | curing agent. Moreover, it turned out that the liquid retention time of the hardening | curing agent of Example 10 is long, and the liquid retention time of the hardening | curing agent of Examples 11 and 12 is very long.

<Comparative Example 1>
An epoxy resin composition was prepared using the resin raw materials shown in Table 3, and the initial viscosity at 70 ° C. was measured. As a result, the viscosity was sufficiently low. Next, a cured product was prepared, and Tg, flexural modulus, and tensile elongation were measured. As a result, it was found that the elastic modulus and tensile elongation were significantly low and insufficient. The epoxy resin composition used here did not contain the constituent element [A].

<Comparative example 2>
An epoxy resin composition was prepared using the resin raw materials shown in Table 3, and the initial viscosity at 70 ° C. was measured. As a result, the viscosity was very high and insufficient. Next, a cured product was prepared, and Tg, flexural modulus, and tensile elongation were measured. As a result, it was found that the tensile elongation was low and insufficient. The epoxy resin composition used here did not contain the constituent element [A].

<Comparative Example 3>
An epoxy resin composition was prepared using the resin raw materials shown in Table 3, and the initial viscosity at 70 ° C. was measured. As a result, the viscosity was sufficiently low. Next, a cured product was prepared, and Tg, flexural modulus, and tensile elongation were measured. As a result, it was found that the tensile elongation was significantly low and insufficient. The epoxy resin composition used here did not contain the constituent element [A].

<Comparative example 4>
An epoxy resin composition was prepared using the resin raw materials shown in Table 3, and the initial viscosity at 70 ° C. was measured. As a result, the curing agent in the epoxy resin composition was precipitated as a solid content, and the viscosity measurement could not be performed.

<Comparative Example 5>
An epoxy resin composition was prepared using the resin raw materials shown in Table 3, and the initial viscosity at 70 ° C. was measured. As a result, the viscosity was sufficiently low. Next, a cured product was prepared, and Tg, flexural modulus, and tensile elongation were measured. As a result, it was found that the tensile elongation was low and insufficient. The curing agent used here was an alicyclic diamine curing agent containing no aromatic ring.

<Comparative Example 6>
An epoxy resin composition was prepared using the resin raw materials shown in Table 3, and the initial viscosity at 70 ° C. was measured. As a result, the viscosity was sufficiently low. Next, a cured product was prepared, and Tg, flexural modulus, and tensile elongation were measured. As a result, it was found that the tensile elongation was low and insufficient. The curing agent used here is an aromatic diamine curing agent represented by the formula (III), but the total carbon number of R _{18 to} R ₂₁ is four.

<Examples 13 and 14>
As a result of producing a fiber reinforced composite material by the RTM method using the epoxy resin compositions of Examples 2 and 7 and the reinforcing fiber base material 1 with binder particles, the carbon fiber was used when any epoxy resin composition was used. A good-quality molded article having a volume content of 56% was obtained. As a result of measuring Tg, 0 ° compressive strength, and 0 ° direction tensile strength of these fiber-reinforced composite materials, it was found that all were excellent. In particular, it was found that when the epoxy resin composition of Example 13 was used, the 0 ° tensile strength was particularly excellent.

<Example 15>
As a result of producing a fiber-reinforced composite material by the RTM method using the epoxy resin composition of Example 7 and the reinforcing fiber substrate 2 with binder particles, a high-quality molded article having a carbon fiber volume content of 56% was obtained. Obtained. As a result of measuring Tg, 0 ° compressive strength, and 0 ° direction tensile strength of this fiber reinforced composite material, it was found that all were particularly excellent.

<Comparative Example 7>
As a result of producing a fiber reinforced composite material by the RTM method using the epoxy resin composition of Comparative Example 6 and the reinforcing fiber base material 1 with binder particles, a molded article with good quality having a volume content of carbon fiber of 56% is obtained. Obtained. As a result of measuring Tg, 0 ° compressive strength, and 0 ° direction tensile strength of this fiber reinforced composite material, it was found that the 0 ° direction tensile strength was significantly low and insufficient.

<Comparative Example 8>
As a result of producing a fiber reinforced composite material by the RTM method using the epoxy resin composition of Comparative Example 1 and the reinforcing fiber base material 1 with binder particles, a high-quality molded article having a carbon fiber volume content of 56% is obtained. Obtained. As a result of measuring the Tg, 0 ° compressive strength, and 0 ° direction tensile strength of this fiber reinforced composite material, it was found that the 0 ° compressive strength was significantly low and insufficient.

1: Warp 2: Auxiliary warp 3: Weft

Claims (14)

An epoxy resin composition comprising at least the following constituent elements [A] and [B], wherein the total carbon number of R ^{9 to} R ¹² of the constituent element [B] is 6 or more Composition.
[A] A tetrafunctional epoxy resin represented by any one of the following formulas (I) and (II)

(In the above chemical formula, R ^{1 to} R ⁸ are each a substituent selected from hydrogen, halogen, and an alkyl group having 1 to 4 carbon atoms.)
[B] Aromatic diamine curing agent represented by the following formula (III)

(In the above chemical formula, R ^{9 to} R ¹² are each a substituent selected from hydrogen, halogen, and an alkyl group having 1 to 4 carbon atoms.) The curing agent contains at least two kinds of aromatic diamine curing agents, and at least one of the aromatic diamine curing agents is an aromatic diamine curing agent represented by the constituent element [B]. The epoxy resin composition as described. The epoxy resin composition according to claim 1, comprising at least two kinds of aromatic diamine curing agents represented by the constituent element [B] as the curing agent. The epoxy resin composition according to any one of claims 1 to 3, comprising an aromatic diamine curing agent that is solid at 25 ° C and an aromatic diamine curing agent that is liquid at 25 ° C as the curing agent. R ^{9 to} R ¹² of the component [B] are any substituents selected from an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group. Item 5. The epoxy resin composition according to any one of Items 1 to 4. The epoxy resin composition in any one of Claims 1-5 whose compounding quantity of component [A] is 30 mass parts or more with respect to 100 mass parts of all the epoxy resins. Furthermore, the epoxy resin composition in any one of Claims 1-6 containing the following structural element [C].
[C] Tetrafunctional epoxy resin represented by the following formula (IV)

(In the chemical formula, R ^{13 to} R ¹⁶ are each a substituent selected from hydrogen, halogen, and an alkyl group having 1 to 4 carbon atoms.) The constituent element [A] is formed by bonding two groups represented by the following formula (V) to the 1,3-positions of an aromatic ring or a cyclohexane ring. Epoxy resin composition.

Furthermore, the epoxy resin composition in any one of Claims 1-8 containing the aromatic diamine hardening | curing agent shown by either of following Formula, (VI), (VII), (VIII).

(In the chemical formula, R ^{17 to} R ²⁸ are each a substituent selected from hydrogen, halogen, and an alkyl group having 1 to 4 carbon atoms.) A fiber-reinforced composite material comprising at least a cured product of the epoxy resin composition according to any one of claims 1 to 9 and a reinforcing fiber substrate having carbon fibers. The reinforcing fiber substrate having the carbon fiber is orthogonal to the warp made of the carbon fiber strand and the auxiliary warp of the fiber bundle made of glass fiber or chemical fiber arranged in parallel to the warp. It is a woven fabric having a non-crimp structure, which is composed of a weft made of glass fibers or chemical fibers that are arranged, and the auxiliary warp and the weft intersect each other, whereby the strands of carbon fibers are held together to form a woven fabric. The fiber-reinforced composite material according to claim 10. A method for producing a fiber-reinforced composite material, wherein a reinforcing fiber substrate having carbon fibers is placed in a mold, and the epoxy resin composition according to any one of claims 1 to 9 is injected and impregnated, followed by heat curing. . The reinforcing fiber substrate having the carbon fiber is orthogonal to the warp made of the carbon fiber strand and the auxiliary warp of the fiber bundle made of glass fiber or chemical fiber arranged in parallel to the warp. It is a woven fabric having a non-crimp structure, which is composed of a weft made of glass fibers or chemical fibers that are arranged, and the auxiliary warp and the weft intersect each other, whereby the strands of carbon fibers are held together to form a woven fabric. The manufacturing method of the fiber reinforced composite material of Claim 11. The method for producing a fiber-reinforced composite material according to claim 13, wherein the injection of the epoxy resin composition is performed by vacuum suction in the mold.

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