WO2015064551A1 - Matrix composition for fiber-reinforced composite material, fiber-reinforced composite material, and method for producing fiber-reinforced composite material - Google Patents

Abstract

The purpose of the present invention is to provide: a matrix composition which can be used suitably for a fiber-reinforced composite material having excellent heat resistance and toughness; a fiber-reinforced composite material which comprises a cured product of the matrix composition and a fibrous material; and a method for producing the fiber-reinforced composite material. The matrix composition for a fiber-reinforced composite material according to the present invention is characterized by containing an epoxy resin represented by general formula (1). [In general formula (1), A represents a bivalent organic group containing a cyclic ether structure.]

Description

MATRIX COMPOSITION FOR FIBER-REINFORCED COMPOSITE MATERIAL, FIBER-REINFORCED COMPOSITE AND METHOD FOR PRODUCING FIBER-REINFORCED COMPOSITE

The present invention relates to a matrix composition for a fiber reinforced composite material containing an epoxy resin, a fiber reinforced composite material comprising a cured product of the matrix composition and a fibrous material, and a method for producing the fiber reinforced composite material.

Conventionally, a fiber reinforced composite material composed of a reinforced fiber such as carbon fiber and a matrix is known to have excellent mechanical properties while being lightweight, and is used in a wide range of fields such as aircraft, automobiles, and leisure goods. Yes. As the matrix of the fiber reinforced composite material, a thermosetting resin, in particular, an epoxy resin is used. Among them, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (hereinafter also referred to as TGDDM) is heat resistant. It is widely used because it is particularly excellent. However, the fiber reinforced composite material obtained by using the matrix composition containing TGDDM has a problem of low toughness while exhibiting excellent heat resistance.

As a method for improving the toughness of such a fiber reinforced composite material, Patent Documents 1 and 2 describe a method of adding a core-shell polymer to a matrix composition. However, the matrix composition containing the core-shell polymer may have problems such as high viscosity and poor adhesion to carbon fibers. Patent Document 2 also describes a method of adding an aliphatic epoxy resin having excellent toughness as another method. However, when such an aliphatic epoxy resin is added, although the toughness of the matrix composition is improved, there is a problem that the heat resistance is remarkably lowered.

As described above, when TGDDM having excellent heat resistance is used as the matrix of the fiber reinforced composite material, the conventional toughness improvement method has a problem that physical properties other than toughness are remarkably lowered in response to the demand for improvement in toughness. Therefore, it has been difficult to improve toughness without deteriorating physical properties such as heat resistance and adhesion to carbon fibers. In particular, it has been extremely difficult to obtain a matrix composition that is a fiber-reinforced composite material excellent in both heat resistance and toughness.

JP 2013-159618 A JP 2010-126702 A

The present invention is a matrix composition that can be suitably used for a fiber-reinforced composite material having excellent heat resistance and toughness, a fiber-reinforced composite material comprising a cured product of the matrix composition and a fibrous material, and It aims at providing the manufacturing method of a fiber reinforced composite material.

As a result of intensive studies, the present inventors have found that a matrix composition containing an epoxy resin having a specific chemical structure can provide a fiber-reinforced composite material having excellent heat resistance and toughness, and completed the present invention.

That is, this invention relates to the matrix composition for fiber reinforced composite materials characterized by including the epoxy resin represented by following General formula (1).

[In General Formula (1), A is a divalent organic group containing a cyclic ether structure;
X represents a divalent organic group containing any one structure selected from the group consisting of the following general formulas (2) to (6) and (9);

{In General Formula (2), R ¹ represents a single bond, a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and some of the carbon atoms are heteroatoms) May be substituted, and some or all of the hydrogen atoms on the carbon chain may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring is monocyclic, condensed or It may be a spiro ring, may have both a condensed ring and a spiro ring, a part of carbon atoms may be substituted with a heteroatom, or a part or all of hydrogen on the ring may be substituted Good). };

{In General Formula (3), R ² represents a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and some of the carbon atoms are substituted with heteroatoms) Or a part or all of hydrogens on the carbon chain may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring) And may have both a condensed ring and a spiro ring, a part of carbon atoms may be substituted with a heteroatom, and a part or all of hydrogen on the ring may be substituted). Show. };

{In General Formula (4), R ³ represents a single bond, a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and a part of the carbon atoms are heteroatoms) May be substituted, and some or all of the hydrogen atoms on the carbon chain may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring is monocyclic, condensed or It may be a spiro ring, may have both a condensed ring and a spiro ring, a part of carbon atoms may be substituted with a heteroatom, or a part or all of hydrogen on the ring may be substituted Good). };

{In General Formula (5), R ⁴ represents a single bond, a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and a part of the carbon atoms are heteroatoms) May be substituted, and some or all of the hydrogen atoms on the carbon chain may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring is monocyclic, condensed or It may be a spiro ring, may have both a condensed ring and a spiro ring, a part of carbon atoms may be substituted with a heteroatom, or a part or all of hydrogen on the ring may be substituted Good). };

{In General Formula (6), R ⁵ represents a single bond, a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and some of the carbon atoms are heteroatoms) May be substituted, and some or all of the hydrogen atoms on the carbon chain may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring is monocyclic, condensed or It may be a spiro ring, may have both a condensed ring and a spiro ring, a part of carbon atoms may be substituted with a heteroatom, or a part or all of hydrogen on the ring may be substituted Good)
Z ¹ and Z ² are each independently hydrogen or a structure represented by the following general formula (7) or the following general formula (8) (wherein at least one of Z ¹ and Z ² has the following general formula ( 7) or a structure represented by the following general formula (8). ;

(In the general formula (7), V is hydrogen, a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and some of the carbon atoms are substituted with hetero atoms) Or a part or all of hydrogens on the carbon chain may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring) And may have both a condensed ring and a spiro ring, a part of carbon atoms may be substituted with a heteroatom, and a part or all of hydrogen on the ring may be substituted). Show
U is hydrogen, a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, part of the carbon atoms may be substituted with a heteroatom, A part or all of hydrogens may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring, and a condensed ring and a spiro ring) And a part of the carbon atom may be substituted with a heteroatom, or part or all of the hydrogen on the ring may be substituted).
Y is a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be linear or branched, a part of carbon atoms may be substituted with a heteroatom, A part or all of which may be substituted), a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring, and has both a condensed ring and a spiro ring) Or a part of the carbon atoms may be substituted with a heteroatom, or part or all of the hydrogen atoms on the ring may be substituted), or a chain carbonization having 1 to 20 carbon atoms. A group in which a carbonyl group is introduced into a hydrogen group or the above cyclic hydrocarbon group having 3 to 20 carbon atoms is shown. );

(In the general formula (8), W represents a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and a part of the carbon atoms may be substituted with a hetero atom) Or a part or all of hydrogen on the carbon chain may be substituted), a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring, And a spiro ring, a part of the carbon atom may be substituted with a heteroatom, or a part or all of hydrogen on the ring may be substituted), or the carbon A group in which a carbonyl group is introduced into a chain hydrocarbon group having 1 to 20 carbon atoms or a cyclic hydrocarbon group having 3 to 20 carbon atoms;
T is a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be linear or branched, a part of the carbon atom may be substituted with a hetero atom, A part or all of them may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring, and both a condensed ring and a spiro ring) Or a part of the carbon atom may be substituted with a heteroatom, and a part or all of the hydrogen on the ring may be substituted). )};

{In General Formula (9), R ⁶ represents a single bond, a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and a part of the carbon atoms are heteroatoms) May be substituted, and some or all of the hydrogen atoms on the carbon chain may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring is monocyclic, condensed or It may be a spiro ring, may have both a condensed ring and a spiro ring, a part of carbon atoms may be substituted with a heteroatom, or a part or all of hydrogen on the ring may be substituted Good)
Z ³ represents a structure represented by the following general formula (7) or the following general formula (8). ;

(In the general formula (7), V is hydrogen, a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and some of the carbon atoms are substituted with hetero atoms) Or a part or all of hydrogens on the carbon chain may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring) And may have both a condensed ring and a spiro ring, a part of carbon atoms may be substituted with a heteroatom, and a part or all of hydrogen on the ring may be substituted). Show
U is hydrogen, a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, part of the carbon atoms may be substituted with a heteroatom, A part or all of hydrogens may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring, and a condensed ring and a spiro ring) And a part of the carbon atom may be substituted with a heteroatom, or part or all of the hydrogen on the ring may be substituted).
Y is a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be linear or branched, a part of carbon atoms may be substituted with a heteroatom, A part or all of which may be substituted), a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring, and has both a condensed ring and a spiro ring) Or a part of the carbon atoms may be substituted with a heteroatom, or part or all of the hydrogen atoms on the ring may be substituted), or a chain carbonization having 1 to 20 carbon atoms. A group in which a carbonyl group is introduced into a hydrogen group or the above cyclic hydrocarbon group having 3 to 20 carbon atoms is shown. );

(In the general formula (8), W represents a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and a part of the carbon atoms may be substituted with a hetero atom) Or a part or all of hydrogen on the carbon chain may be substituted), a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring, And a spiro ring, part of the carbon atom may be substituted with a heteroatom, or part or all of the hydrogen on the ring may be substituted), or the carbon A group in which a carbonyl group is introduced into a chain hydrocarbon group having 1 to 20 carbon atoms or a cyclic hydrocarbon group having 3 to 20 carbon atoms;
T is a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be linear or branched, a part of the carbon atom may be substituted with a hetero atom, A part or all of them may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring, and both a condensed ring and a spiro ring) Or a part of the carbon atom may be substituted with a heteroatom, and a part or all of the hydrogen on the ring may be substituted). )};
n represents 0 to 200. ]

In the matrix composition of the present invention, the content of the epoxy resin is preferably 45 to 99% by weight in the total solid content.

In the matrix composition of the present invention, the fiber reinforced composite material is preferably a carbon fiber reinforced composite material.

In the matrix composition of the present invention, the epoxy resin preferably has a number average molecular weight of 250 to 100,000.

The fiber-reinforced composite material of the present invention is characterized by comprising a cured product of the matrix composition of the present invention and a fibrous material.

The manufacturing method of the fiber reinforced composite material of this invention is characterized by including the following processes.
(I) a step of impregnating the fibrous material with the matrix composition of the present invention; and (ii) a step of heat-treating the fibrous material impregnated with the matrix composition in the step (i).

In the method for producing a fiber-reinforced composite material of the present invention, the fibrous material is preferably carbon fiber.

Since the matrix composition of this invention contains the epoxy resin which has a specific structure, it can provide the fiber reinforced composite material excellent in heat resistance and toughness. Moreover, since the fiber reinforced composite material of this invention consists of the hardened | cured material and fibrous material of the matrix composition of this invention, it is excellent in heat resistance and toughness. Furthermore, according to the manufacturing method of the fiber reinforced composite material of the present invention, the fiber reinforced composite material of the present invention can be preferably manufactured.

<< Matrix composition >>
First, the matrix composition of the present invention will be described.
The matrix composition for fiber-reinforced composite materials according to the present invention includes an epoxy resin represented by the following general formula (1).

<Epoxy resin>
The said epoxy resin is contained as a hardening component in the matrix composition of this invention, and is represented by following General formula (1).

In the general formula (1), A represents a divalent organic group containing a cyclic ether structure. The divalent organic group containing a cyclic ether structure is not particularly limited, and examples thereof include divalent organic groups containing a cyclic ether structure represented by the following formulas (10) to (13), furan, tetrahydrofuran, and tetrahydropyran. , Divalent organic groups containing cyclic ether structures derived from dioxane, benzopyran, xanthene, oxazole-based compounds and the like. Here, the “organic group” in the “divalent organic group containing a cyclic ether structure” means a group composed of hydrogen, carbon, and oxygen, and preferably has 2 to 20 carbon atoms, more preferably 2 carbon atoms. ~ 10.

(In formula (10), some or all of the hydrogen atoms on the ring may be substituted.)

(In Formula (11), a part or all of hydrogen on the ring and the carbon chain may be independently substituted.)

(In Formula (12), a part or all of hydrogen on the ring and carbon chain may be independently substituted.)

(In Formula (13), a part or all of hydrogen on the ring and the carbon chain may be independently substituted.)

In the epoxy resin, A in the general formula (1) is preferably a divalent organic group including a cyclic ether structure represented by any one of the formulas (10) to (13). Since these cyclic ether structures have two or more heterocycles in close proximity, when used in a matrix composition, a fiber-reinforced composite material with exceptional heat resistance and toughness can be obtained.

In the formulas (10) to (13), examples of the substituent that can be substituted with hydrogen on the carbon chain or hydrogen on the ring include an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, butyl group, C _1-20 alkyl group such as s-butyl group and t-butyl group), cycloalkyl group (C _3-10 cycloalkyl group such as cyclopentyl group, cyclohexyl group, etc.), cycloalkenyl group (cyclopentyl group, cyclohexyl group, etc.) C _3-10 cycloalkenyl group such as cell group), heterocyclic group (C _2-10 heterocyclic group containing a hetero atom such as oxygen atom, nitrogen atom and sulfur atom), aryl group [phenyl group, alkylphenyl group _{C 6-10} aryl groups such as (methylphenyl group (tolyl group), a dimethylphenyl group (xylyl) or the like), etc.], an aralkyl group (benzyl group, phenethyl _{C 6-10} aryl _{-C 1-4} alkyl group, etc.) etc., a methylene group, a vinyl group, a hydrocarbon group such as an allyl group, and _{a C 1-4} alkoxy group such as an alkoxy group (methoxy group), a hydroxyl group, Hydroxy (poly) alkyleneoxy group (hydroxy (poly) C _2-4 alkyleneoxy group etc.), acyl group (C _1-6 acyl group such as acetyl group), oxy group, thioxy group, phosphino group, halogeno group ( Fluoro group, chloro group, etc.), amino group, imino group, N-oxide group, nitro group, cyano group and the like. In addition, the hydrogen on the carbon chain or the hydrogen on the ring may be partially substituted, or all may be substituted.

X in the general formula (1) represents a divalent organic group including any one structure selected from the group consisting of the following general formulas (2) to (6) and (9).

In the general formulas (2) to (6) and (9), R ¹ to R ⁶ are each a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be linear or branched, Some of the atoms may be substituted with heteroatoms, and some or all of the hydrogens on the carbon chain may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein The ring may be a single ring, a condensed ring or a spiro ring, may have both a condensed ring and a spiro ring, a part of carbon atoms may be substituted with a heteroatom, and a part of hydrogen on the ring Or all of them may be substituted), and R ¹ and R ³ to R ⁶ may be a single bond.

Here, examples of the hetero atom that can be substituted with a part of the carbon atom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a boron atom, a selenium atom, and a tellurium atom.
Examples of the substituent that can replace hydrogen on the carbon chain or hydrogen on the ring include, for example, alkyl groups (methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group). _{C 1-20} alkyl group), a cycloalkyl group (cyclopentyl etc., such as _{C 3-10} cycloalkyl groups such as cyclohexyl group), a cycloalkenyl group (cyclo Pentel group, _{C 3-10} cycloalkyl such as cyclohexylene cell group Alkenyl groups, etc.), heterocyclic groups (C _2-10 heterocyclic groups containing heteroatoms such as oxygen, nitrogen and sulfur atoms), aryl groups [phenyl groups, alkylphenyl groups (methylphenyl groups (tolyl groups), dimethylphenyl group _{C 6-10} aryl group (xylyl) or the like), etc.], an aralkyl group (benzyl group, _{C 6-10} aryl such as phenethyl group - _1-4 alkyl group), a methylene group, a vinyl group, a hydrocarbon group such as an allyl group, and a C _1-4 alkoxy group such as an alkoxy group (methoxy group), a hydroxyl group, a hydroxy (poly) alkyleneoxy group (hydroxy (Poly) C _2-4 alkyleneoxy group, etc.), acyl group (C _1-6 acyl group such as acetyl group), oxy group, thioxy group, phosphino group, halogeno group (fluoro group, chloro group etc.), amino group Group, imino group, N-oxide group, nitro group, cyano group and the like. In addition, the hydrogen on the carbon chain or the hydrogen on the ring may be partially substituted, or all may be substituted.

Z ¹ , Z ² and Z ³ in the general formulas (6) and (9) are structures represented by the following general formula (7) or the following general formula (8), respectively. Furthermore, ^{Z 1} and ^{Z 2,} which may be ^hydrogen, at least one of the Z 1, ^{Z 2} is a structure represented by the following general formula (7) or the following general formula (8).

V, U, Y, W and T in the general formulas (7) and (8) are each a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, Is optionally substituted with a heteroatom, and part or all of the hydrogen on the carbon chain may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein The ring may be a single ring, a condensed ring or a spiro ring, may have both a condensed ring and a spiro ring, may have a carbon atom partially substituted with a heteroatom, and may be a hydrogen atom on the ring. Part or all may be substituted), U and V may be hydrogen, and Y and W may be a chain hydrocarbon group having 1 to 20 carbon atoms or a chain hydrocarbon group having 3 to 20 carbon atoms. It may be a group in which a carbonyl group is introduced into a cyclic hydrocarbon group.

Here, examples of the hetero atom that can be substituted with a part of the carbon atom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a boron atom, a selenium atom, and a tellurium atom.
Examples of the substituent that can replace hydrogen on the carbon chain or hydrogen on the ring include, for example, alkyl groups (methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group). _{C 1-20} alkyl group), a cycloalkyl group (cyclopentyl etc., such as _{C 3-10} cycloalkyl groups such as cyclohexyl group), a cycloalkenyl group (cyclo Pentel group, _{C 3-10} cycloalkyl such as cyclohexylene cell group Alkenyl groups, etc.), heterocyclic groups (C _2-10 heterocyclic groups containing heteroatoms such as oxygen, nitrogen and sulfur atoms), aryl groups [phenyl groups, alkylphenyl groups (methylphenyl groups (tolyl groups), dimethylphenyl group _{C 6-10} aryl group (xylyl) or the like), etc.], an aralkyl group (benzyl group, _{C 6-10} aryl such as phenethyl group - _1-4 alkyl group), a methylene group, a vinyl group, a hydrocarbon group such as an allyl group, and a C _1-4 alkoxy group such as an alkoxy group (methoxy group), a hydroxyl group, a hydroxy (poly) alkyleneoxy group (hydroxy (Poly) C _2-4 alkyleneoxy group, etc.), acyl group (C _1-6 acyl group such as acetyl group), oxy group, thioxy group, phosphino group, halogeno group (fluoro group, chloro group etc.), amino group Group, imino group, N-oxide group, nitro group, cyano group and the like. In addition, the hydrogen on the carbon chain or the hydrogen on the ring may be partially substituted, or all may be substituted.

In the general formula (1), n (degree of polymerization) is 0 to 200. n is preferably 0 to 20, and more preferably 0 to 10.
In the epoxy resin represented by the general formula (1), n is an average value of the entire resin.

In the matrix composition of this invention, as an epoxy resin represented by General formula (1), only 1 type may be used independently and 2 or more types may be used together.

The number average molecular weight of the epoxy resin represented by the general formula (1) used as a raw material in the matrix composition of the present invention is not particularly limited, but is preferably 250 to 100,000, more preferably 300 to 15,000. Preferably, it is 300 to 1500. If the number average molecular weight is less than 250, the crosslinking density may be too high when cured, and if it exceeds 100,000, a sufficient crosslinking density cannot be obtained when cured. Physical properties such as hardness and chemical resistance may be insufficient.

In the present specification, the number average molecular weight means a value calculated by gel permeation chromatography (hereinafter also referred to as GPC) measurement.

The epoxy equivalent of the epoxy resin represented by the general formula (1) is not particularly limited, but is preferably 125 to 50000 g / eq, and more preferably 150 to 7500 g / eq. If the epoxy equivalent is less than 125 g / eq, it may become brittle even if the crosslinking density becomes excessively high when cured, and if it exceeds 50000 g / eq, a sufficient crosslinking density is obtained when cured. This is because the physical properties such as surface hardness and chemical resistance may be insufficient. The epoxy equivalent is calculated according to JIS K7236.

In the matrix composition of the present invention, the content of the epoxy resin represented by the general formula (1) is not particularly limited, but is preferably 45 to 99% by weight in the total solid content in the matrix composition, More preferably, it is 50 to 97% by weight. If it is less than 45% by weight, it may become brittle when cured due to excessively high crosslink density, and if it exceeds 99% by weight, sufficient crosslink density cannot be obtained when cured, and surface hardness , Physical properties such as chemical resistance tend to be insufficient.

<Optional component>
The matrix composition of the present invention may contain other optional components in addition to the epoxy resin represented by the general formula (1). Examples of other optional components include a curing agent, a curing catalyst, a solvent, a filler, a modifier, a flame retardant, and the like.

In this specification, a hardening | curing agent means what crosslinks itself when a matrix composition hardens | cures. In the present specification, the curing catalyst refers to a catalyst that promotes a crosslinking reaction, although the matrix composition does not crosslink itself when it is cured.

The curing agent is not particularly limited, and examples thereof include phenol novolak resins, amine compounds (for example, 4,4-diaminodiphenyl sulfone), modified polyamines, amino resins, polyaminoamide resins, imidazole compounds, carboxylic acids, acid anhydrides. Compounds, phenols, quaternary ammonium salts, methylol group-containing compounds, blocked isocyanates, mercaptans, triflic acid salts, boron trifluoride ether complex compounds, boron trifluoride, light or heat Examples thereof include diazonium salts, sulfonium salts, iodonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts that generate an acid. These curing agents may be used alone or in combination of two or more.

When the curing agent is contained, the equivalent ratio of the functional group in the curing agent to the epoxy group in the epoxy resin represented by the general formula (1) is not particularly limited, but in the range of 0.5 to 2.0. Preferably, it is in the range of 0.8 to 1.5. When the equivalence ratio is outside the range of 0.5 to 2.0, unreacted epoxy groups or functional groups remain in the cured product even after curing, resulting in poor curing, reduced physical properties, reduced reliability of the cured product (for example, , Deterioration over time).

The curing catalyst is not particularly limited. For example, tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, triphenylphosphine, trioctylphosphine, tricyclohexylphosphine, tris (2 , 6-dimethoxyphenyl) phosphine, etc., ethyltriphenylphosphonium bromide, phosphonium salts such as tetraphenylphosphonium / tetraphenylborate, phosphine complexes such as triphenylphosphine / triphenylborane, 2-methylimidazole, 2- Examples thereof include imidazoles such as ethyl-4-methylimidazole and boron trifluoride complexes. These curing catalysts may be used independently and may use 2 or more types together.

When the curing catalyst is contained, the content is not particularly limited, but is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin represented by the general formula (1), 0.5 to More preferably, it is 2 parts by weight. If the content of the curing catalyst is less than 0.1 parts by weight, curing may be poor. If the content exceeds 5 parts by weight, the self-polymerization reaction of the epoxy group proceeds or the curing catalyst functions as a curing agent. This is because a cured product having desired physical properties may not be obtained.

In addition, some of the curing agents described above may function as a curing catalyst depending on the content thereof, and some of the curing catalysts described above may serve as curing agents depending on the content. Although there are those which can function, since the curing agent or the curing catalyst is an optional component in the matrix composition of the present invention, the curing agent which can function as a curing catalyst or the curing catalyst which can function as a curing agent Even if is used, the content is not particularly limited.

The solvent is not particularly limited. For example, alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Glycol ethers such as monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol monobutyl ether, and alkylene glycols such as methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol methyl ether acetate, and 3-methoxybutyl-1-acetate Cole monoalkyl ether acetates, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone, 2-hydroxypropion Ethyl acetate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, Examples thereof include esters such as ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate. These solvents may be used alone or in combination of two or more.

When the solvent is contained, its content is not particularly limited, but it is preferably 0 to 70% by weight in the matrix composition.

Although it does not specifically limit as a filler, For example, Conductive fillers, such as metals, such as silicas, such as crystalline silica and amorphous silica, powder, flakes, or fibers, carbon black, carbon fiber, carbon nanotube, and graphene , Antimony oxide, magnesium hydroxide, aluminum hydroxide, zinc borate, molybdate compound, tin oxide compound, phosphorus filler, zirconium filler, iron oxide, cuprous oxide, flame retardant filler such as layered clay, titanium Examples thereof include conductive fillers such as barium oxide and lead zirconate titanate, and heat resistance improving fillers such as organic-inorganic hybrids by an alkoxide sol-gel method.
These fillers may be used independently and may use 2 or more types together.

When the filler is contained, its content is not particularly limited, but it is preferably 0.005 to 50% by weight in the matrix composition.

The modifier is not particularly limited, and examples thereof include acrylonitrile-butadiene rubber and silicone powder. These modifiers may be used alone or in combination of two or more.

When the modifier is contained, its content is not particularly limited, but is preferably 0.005 to 50% by weight in the matrix composition.

Although it does not specifically limit as a flame retardant, For example, a halogen compound, a phosphorus compound, an inorganic compound etc. are mentioned. These flame retardants may be used alone or in combination of two or more.

When the flame retardant is contained, the content thereof is not particularly limited, but is preferably 0.005 to 50% by weight in the matrix composition.

<Application>
The matrix composition of the present invention is used as a base material (matrix) of a fiber reinforced composite material, and includes an epoxy resin having a specific structure, and thus is suitable for a fiber reinforced composite material having excellent heat resistance and toughness. Can be used.

<< Fiber-reinforced composite >>
Next, the fiber reinforced composite material of the present invention will be described.
The fiber reinforced composite material of the present invention is a fiber reinforced composite material comprising a cured product of the matrix composition of the present invention and a fibrous material.

<Fibrous material>
The fibrous material is used as a reinforcing material in the fiber-reinforced composite material of the present invention.
Although it does not specifically limit as a fibrous material, For example, synthetic resin fibers, such as carbon fiber, glass fiber, and an aromatic polyamide-type resin fiber, etc. can be used. These fibrous materials may be used alone or in combination of two or more. In these, it is preferable to use carbon fiber. The reason is that the fiber-reinforced composite material can remarkably enjoy the effect that it has excellent heat resistance and toughness, and the carbon fiber is lighter than other fibrous materials. It is because it can use suitably for various uses, such as these.

The property of the fibrous material is not particularly limited. For example, woven fabric, knitted fabric, unidirectional fiber substrate (substrate in which fiber bundles are aligned in parallel in one direction), stitch substrate (multiple layers of fiber substrate) And a sheet-like base material such as a base material in the form of stitched together.

The content of the fibrous material in the fiber-reinforced composite material of the present invention is not particularly limited, but is preferably 10 to 70% by volume, and more preferably 30 to 60% by volume. When the content is less than 10% by volume, the surface of the fiber reinforced composite material tends to be uneven, and warping and undulation tend to increase. When the content exceeds 70% by volume, the matrix composition is sufficiently added to the fibrous material. Impregnation may not be possible.

The fiber-reinforced composite material of the present invention can be manufactured, for example, by the method for manufacturing the fiber-reinforced composite material of the present invention described later.

Since the fiber-reinforced composite material of the present invention is composed of the matrix composition of the present invention and a fibrous material, it is excellent in heat resistance and toughness.

<Application>
Although it does not specifically limit as a use of the fiber reinforced composite material of this invention, For example, leisure goods, such as an aircraft, a motor vehicle, a fishing tackle, etc. are mentioned.

<< Production Method of Fiber Reinforced Composite >>
Next, the manufacturing method of the fiber reinforced composite material of this invention is demonstrated.
The manufacturing method of the fiber reinforced composite material of this invention is characterized by including the following processes.
(I) a step of impregnating the fibrous material with the matrix composition of the present invention; and (ii) a step of heat-treating the fibrous material impregnated with the matrix composition in step (i).

In the step (i), the method for impregnating the fibrous material with the matrix composition of the present invention is not particularly limited. For example, the fibrous material is contacted with the matrix composition of the present invention coated on a release paper or the like. A method of impregnating a fibrous material with the matrix composition of the present invention, placing a fiber base material or preform made of a fibrous material in a mold, and injecting the matrix composition into the mold The method of impregnating a fibrous material with the matrix composition of the present invention can be mentioned.

In step (ii), the fibrous material impregnated with the matrix composition in step (i) is heat-treated.
In the step (ii), the fibrous material impregnated with the matrix composition in the step (i) may be semi-cured by a drying treatment to form a prepreg, and then completely cured by a heat treatment. Alternatively, it may be completely cured by a single heat treatment.
The conditions for the drying treatment are not particularly limited. For example, conditions for drying treatment at 50 to 200 ° C. for 0.5 to 10 hours can be employed.
The conditions for the heat treatment are not particularly limited. For example, conditions for heat treatment at 150 to 230 ° C. for 0.5 to 10 hours can be employed.

In the method for producing a fiber-reinforced composite material of the present invention, the fibrous material is preferably carbon fiber. This is because a fiber-reinforced composite material that is particularly excellent in heat resistance and toughness can be produced.

According to the method for producing a fiber reinforced composite material of the present invention, the fiber reinforced composite material of the present invention can be suitably produced.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

<Manufacture of epoxy resin>
Production Example 1 Production of Isosorbide Diglycidyl Ether Epichlorohydrin (760 g) and isosorbide (100 g) were charged at room temperature into a 1 L separable flask. While stirring the mixture vigorously, solid sodium hydroxide (60 g) was added at 50 ° C. over 1 hour, and then stirred at the same temperature for 3 hours. After the reaction, water was added to dissolve the by-produced salt, thereby separating the organic layer and the aqueous layer. The organic layer was washed 3 times with pure water (100 g), and then excess epichlorohydrin was removed under reduced pressure. The obtained residue was filtered to obtain 168 g of isosorbide diglycidyl ether (in general formula (1), n = 0 epoxy resin).
As for the analytical value of the obtained isosorbide diglycidyl ether, the epoxy equivalent was 163 g / eq, and the number average molecular weight Mn was 310 based on the analysis by GPC.
Here, the epoxy equivalent was measured according to JIS K7236. The molecular weight measurement by GPC was performed using high performance liquid chromatography (HPLC) (Waters 2695, manufactured by Waters). As the column, a column in which Waters styrene (registered trademark) HR 1 THF and Waters stratagel (registered trademark) HR 0.5 THF manufactured by Waters were connected in series one by one was used. Tetrahydrofuran was used as the mobile phase, and the mobile phase speed was 1.00 mL / min. The column temperature was 40 ° C., the detector was a differential refractometer, and the molecular weight was determined as the molecular weight in terms of polystyrene. In addition, the measurement of the epoxy equivalent in the following manufacture example and the molecular weight measurement by GPC were also performed on the same conditions.

Production Example 2 Production of Isosorbide Polyester Resin A A 1 L separable flask was charged with isosorbide diglycidyl ether (400 g), cis-4-cyclohexene-1,2-dicarboxylic acid (124 g) and tetramethylammonium chloride (3 g) at room temperature. The mixture was charged below and the mixture was stirred at 80 ° C. for 3 hours. The reaction mixture was filtered to obtain 490 g of a mixture of isosorbide polyester resin A.
As for the analytical value of the entire mixture of the obtained isosorbide polyester resin A, the epoxy equivalent was 460 g / eq, and the number average molecular weight Mn was 1172 from the analysis by GPC.

Production Example 3 Production of Isosorbide Polyester Resin B In a 1 L separable flask, isosorbide diglycidyl ether (400 g), cis-4-cyclohexene-1,2-dicarboxylic acid (66 g) and tetramethylammonium chloride (3 g) were added at room temperature. The mixture was charged below and the mixture was stirred at 80 ° C. for 3 hours. The reaction mixture was filtered to obtain 436 g of a mixture of isosorbide polyester resin B.
As for the analytical value of the whole mixture of the obtained isosorbide polyester resin B, the epoxy equivalent was 292 g / eq, and the number average molecular weight Mn was 409 from the analysis by GPC.

(Production Example 4) Production of isosorbide polyether resin A A 1 L separable flask was charged with isosorbide diglycidyl ether (400 g), bisphenol F (123 g) and tetramethylammonium chloride (3 g) at room temperature, and this mixture was heated to 80 ° C. Stir for 3 hours. The reaction mixture was filtered to obtain 489 g of a mixture of isosorbide polyether resin A.
As for the analytical value of the entire mixture of the obtained isosorbide polyether resin A, the epoxy equivalent was 450 g / eq, and the number average molecular weight Mn was 1209 from the analysis by GPC.

(Production Example 5) Production of isosorbide polyether resin B A 1 L separable flask was charged with isosorbide diglycidyl ether (400 g), bisphenol F (74 g) and tetramethylammonium chloride (3 g) at room temperature, and this mixture was heated to 80 ° C. Stir for 3 hours. The reaction mixture was filtered to obtain 444 g of a mixture of isosorbide polyether resin B.
As for the analytical value of the whole mixture of the obtained isosorbide polyether resin B, the epoxy equivalent was 307 g / eq, and the number average molecular weight Mn was 472 from the analysis by GPC.

Production Example 6 Production of Isosorbide Polyurethane Resin A A 1 L separable flask was charged with diphenylmethane diisocyanate (200 g), tetrahydrofuran (400 g) and isosorbide (58 g) at room temperature and stirred until the isosorbide was dissolved. Tetrakis (2,4-pentanedionato) zirconium (IV) (4 g) was charged at the same temperature, and after stirring for 3 hours, glycidol (118 g) was charged. The resulting mixture was transferred to a Buchner funnel lined with filter paper and filtered. The obtained solid was washed with water (100 g) and methanol (300 g) in this order. The solid was transferred to a flask and dried at 80 ° C. for 1 hour on a rotary evaporator to obtain 314 g of a mixture of isosorbide polyurethane resin A.
As for the analytical value of the entire mixture of the obtained isosorbide polyurethane resin A, the epoxy equivalent was 325 g / eq, and the number average molecular weight Mn was 1770 from the analysis by GPC.

(Production Example 7) Production of isosorbide polyurethane resin B A 1 L separable flask was charged with diphenylmethane diisocyanate (200 g), tetrahydrofuran (358 g) and isosorbide (35 g) at room temperature and stirred until the isosorbide was dissolved. Tetrakis (2,4-pentanedionato) zirconium (IV) (4 g) was charged at the same temperature, and after stirring for 3 hours, glycidol (118 g) was charged. The resulting mixture was transferred to a Buchner funnel lined with filter paper and filtered. The obtained solid was washed with water (100 g) and methanol (300 g) in this order. The solid material was transferred to a flask and dried on a rotary evaporator at 80 ° C. for 1 hour to obtain 293 g of a mixture of isosorbide polyurethane resin B.
As for the analytical value of the whole mixture of the obtained isosorbide polyurethane resin B, the epoxy equivalent was 207 g / eq, and the number average molecular weight Mn was 406 from the analysis by GPC.

Production Example 8 Production of Isosorbide Polyester Polyether Resin A 1 L separable flask was charged with isosorbide diglycidyl ether (400 g), salicylic acid (89 g) and tetramethylammonium chloride (3 g) at room temperature, and the mixture was heated at 80 ° C. Stir for 3 hours. The reaction mixture was filtered to obtain 492 g of a mixture of isosorbide polyester polyether resin.
As for the analytical value of the entire mixture of the obtained isosorbide polyester polyether resin, the epoxy equivalent was 340 g / eq, and the number average molecular weight Mn was 442 from the analysis by GPC.

Production Example 9 Production of Isosorbide Modified Polyester Resin A A 1 L separable flask was charged with butyl vinyl ether (136 g), cis-4-cyclohexene-1,2-dicarboxylic acid (110 g) and p-toluenesulfonic acid (2 g) at room temperature. The mixture was charged below and the mixture was stirred at 60 ° C. for 2 hours. Isosorbide diglycidyl ether (400 g) and tetramethylammonium chloride (3 g) were added to the reaction mixture at room temperature, and the mixture was stirred at 100 ° C. for 6 hours. The reaction mixture was filtered to obtain 651 g of a mixture of isosorbide-modified polyester resin A.
As for the analytical value of the whole mixture of the obtained isosorbide-modified polyester resin A, the epoxy equivalent was 461 g / eq, and the number average molecular weight Mn was 1130 from the analysis by GPC.

Production Example 10 Production of Isosorbide Modified Polyester Resin B Into a 1 L separable flask, butyl vinyl ether (68 g), 3,4-dihydro-2H-pyran (57 g), cis-4-cyclohexene-1,2-dicarboxylic acid ( 110 g) and p-toluenesulfonic acid (2 g) were charged at room temperature, and the mixture was stirred at 60 ° C. for 2 hours. Isosorbide diglycidyl ether (400 g) and tetramethylammonium chloride (3 g) were added to the reaction mixture at room temperature, and the mixture was stirred at 100 ° C. for 6 hours. The reaction mixture was filtered to obtain 640 g of a mixture of isosorbide-modified polyester resin B.
As for the analytical value of the entire mixture of the obtained isosorbide-modified polyester resin B, the epoxy equivalent was 482 g / eq, and the number average molecular weight Mn was 1014 from the analysis by GPC.

Production Example 11 Production of Isosorbide Modified Polyester Resin C Into a 1 L separable flask, 3,4-dihydro-2H-pyran (114 g), cis-4-cyclohexene-1,2-dicarboxylic acid (110 g) and p-toluene were added. Sulfonic acid (2 g) was charged at room temperature, and the mixture was stirred at 60 ° C. for 2 hours. Isosorbide diglycidyl ether (400 g) and tetramethylammonium chloride (3 g) were added to the reaction mixture at room temperature, and the mixture was stirred at 100 ° C. for 6 hours. The reaction mixture was filtered to obtain 598 g of a mixture of isosorbide-modified polyester resin C.
As for the analytical value of the entire mixture of the obtained isosorbide-modified polyester resin C, the epoxy equivalent was 434 g / eq, and the number average molecular weight Mn was 852 from the analysis by GPC.

Production Example 12 Production of Isosorbide Modified Polyester Polyether Resin A A 1 L separable flask was charged with butyl vinyl ether (68 g), salicylic acid (89 g) and p-toluenesulfonic acid (2 g) at room temperature, and this mixture was heated to 60 ° C. And stirred for 2 hours. Isosorbide diglycidyl ether (400 g) and tetramethylammonium chloride (3 g) were added to the reaction mixture at room temperature, and the mixture was stirred at 100 ° C. for 6 hours. The reaction mixture was filtered to obtain 630 g of a mixture of isosorbide-modified polyester polyether resin A.
As for the analytical value of the entire mixture of the obtained isosorbide-modified polyester polyether resin A, the epoxy equivalent was 440 g / eq, and the number average molecular weight Mn was 880 from the analysis by GPC.

Production Example 13 Production of Isosorbide-Modified Polyester Polyether Resin B Into a 1 L separable flask, butyl vinyl ether (31 g), 3,4-dihydro-2H-pyran (27 g), salicylic acid (89 g) and p-toluenesulfonic acid ( 2 g) was charged at room temperature and the mixture was stirred at 60 ° C. for 2 hours. Isosorbide diglycidyl ether (400 g) and tetramethylammonium chloride (3 g) were added to the reaction mixture at room temperature, and the mixture was stirred at 100 ° C. for 6 hours. The reaction mixture was filtered to obtain 556 g of a mixture of isosorbide-modified polyester polyether resin B.
As for the analytical value of the entire mixture of the obtained isosorbide-modified polyester polyether resin B, the epoxy equivalent was 418 g / eq, and the number average molecular weight Mn was 824 from the analysis by GPC.

(Production Example 14) Production of isosorbide-modified polyester polyether resin C To a 1 L separable flask, 3,4-dihydro-2H-pyran (53 g), salicylic acid (89 g) and p-toluenesulfonic acid (2 g) were added at room temperature. The mixture was stirred and the mixture was stirred at 60 ° C. for 2 hours. Isosorbide diglycidyl ether (400 g) and tetramethylammonium chloride (3 g) were added to the reaction mixture at room temperature, and the mixture was stirred at 100 ° C. for 6 hours. The reaction mixture was filtered to obtain 520 g of a mixture of isosorbide-modified polyester polyether resin C.
As for the analytical value of the whole mixture of the obtained isosorbide-modified polyester polyether resin C, the epoxy equivalent was 432 g / eq, and the number average molecular weight Mn was 910 from the analysis by GPC.

Production Example 15 Production of N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane Epichlorohydrin (750 g) and diaminodiphenylmethane (80 g) were charged at room temperature into a 1 L separable flask. While stirring this mixture vigorously, solid sodium hydroxide (70 g) was added at 50 ° C. over 1 hour, and then stirred at the same temperature for 3 hours. After the reaction, water was added to dissolve the by-produced salt, thereby separating the organic layer and the aqueous layer. The organic layer was washed 3 times with pure water (100 g), and then excess epichlorohydrin was removed under reduced pressure. The obtained residue was filtered to obtain 172 g of N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane.
As for the analytical value of the obtained N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane, the epoxy equivalent was 110 g / eq, and the number average molecular weight Mn was 453 from the analysis by GPC.

<Evaluation of physical properties of fiber reinforced composites>
In Examples 1 to 14 and Comparative Examples 1 and 2 below, 4,4′-diaminodiphenylsulfone (manufactured by Mitsui Chemicals Fine Co., Ltd.) was used as the curing agent.
As the fiber material, carbon fiber (manufactured by Toho Tenax Co., Ltd., Besfight IM600-24K) was used.

(Examples 1 to 14, Comparative Examples 1 and 2)
The epoxy resin or 1,6-hexanediol diglycidyl ether (manufactured by Nagase ChemteX Corporation, Denacol EX-212) manufactured in Production Examples 1 to 15 and a curing agent were mixed at a weight ratio shown in Table 1 below. A matrix composition was obtained.
The obtained matrix composition was heated at 120 ° C. to obtain a uniform liquid, and then applied onto release paper. The carbon fiber was impregnated with the matrix composition by covering the coated matrix composition with carbon fibers that were aligned in one direction from above. The volume content of carbon fiber was adjusted to 50 ± 1%. The carbon fiber impregnated with the matrix composition was dried at 150 ° C. for 2 hours using a hot air dryer to obtain a unidirectional prepreg. The obtained prepreg was heat-treated at 200 ° C. for 1 hour using a hot air dryer to obtain a fiber-reinforced composite material. Using the obtained fiber reinforced composite material, physical properties were evaluated by the method described later. The results are shown in Table 1.

<Method for evaluating physical properties>
In Examples 1 to 14 and Comparative Examples 1 and 2, the physical properties of the fiber reinforced composite materials were evaluated by the following methods.
1. Glass transition temperature (Tg)
The fiber reinforced composite materials obtained in Examples 1 to 14 and Comparative Examples 1 and 2 were cut into a size of 50 mm in length, 10 mm in width, and 2 mm in thickness to obtain a test piece, in accordance with JIS K7244. It was measured.
2. The fiber-reinforced composite materials obtained in the flexural modulus examples 1 to 14 and comparative examples 1 and 2 were cut into a size of 100 mm in length, 15 mm in width, and 2 mm in thickness to obtain a test piece, which was applied to JIS K7074. Measured in conformity.

3. Bending strength The fiber reinforced composite materials obtained in Examples 1 to 14 and Comparative Examples 1 and 2 were cut into a length of 100 mm, a width of 15 mm, and a thickness of 2 mm to obtain a test piece, which was compliant with JIS K7074. And measured.

4). Relative strain rate For Examples 1 to 14 and Comparative Examples 1 and 2, the bending strain (ε) was calculated as ε = 600 sh / L ² (s: deflection, h: thickness of test piece, L: distance between fulcrums). The deflection value was determined by measuring the displacement when the test piece broke when measuring the bending strength. The bending strain when the test piece did not break was defined as “no break”. Based on the distortion rate of Comparative Example 1, the relative distortion rates of Examples 1 to 14 and Comparative Example 2 were calculated. For example, in the case of Comparative Example 2, calculation was performed as (relative strain rate (%) of Comparative Example 2 = bending strain of Comparative Example 2 / bending strain of Comparative Example 1 × 100).

Claims (7)

1. A matrix composition for a fiber-reinforced composite material, comprising an epoxy resin represented by the following general formula (1).
   

   

   [In General Formula (1), A is a divalent organic group containing a cyclic ether structure;
   X represents a divalent organic group containing any one structure selected from the group consisting of the following general formulas (2) to (6) and (9);
   

   

   {In General Formula (2), R ¹ represents a single bond, a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and some of the carbon atoms are heteroatoms) May be substituted, and some or all of the hydrogen atoms on the carbon chain may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring is monocyclic, condensed or It may be a spiro ring, may have both a condensed ring and a spiro ring, a part of carbon atoms may be substituted with a heteroatom, or a part or all of hydrogen on the ring may be substituted Good). };
   

   

   {In General Formula (3), R ² represents a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and some of the carbon atoms are substituted with heteroatoms) Or a part or all of hydrogens on the carbon chain may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring) And may have both a condensed ring and a spiro ring, a part of carbon atoms may be substituted with a heteroatom, and a part or all of hydrogen on the ring may be substituted). Show. };
   

   

   {In General Formula (4), R ³ represents a single bond, a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and a part of the carbon atoms are heteroatoms) May be substituted, and some or all of the hydrogen atoms on the carbon chain may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring is monocyclic, condensed or It may be a spiro ring, may have both a condensed ring and a spiro ring, a part of carbon atoms may be substituted with a heteroatom, or a part or all of hydrogen on the ring may be substituted Good). };
   

   

   {In General Formula (5), R ⁴ represents a single bond, a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and a part of the carbon atoms are heteroatoms) May be substituted, and some or all of the hydrogen atoms on the carbon chain may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring is monocyclic, condensed or It may be a spiro ring, may have both a condensed ring and a spiro ring, a part of carbon atoms may be substituted with a heteroatom, or a part or all of hydrogen on the ring may be substituted Good). };
   

   

   {In General Formula (6), R ⁵ represents a single bond, a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and some of the carbon atoms are heteroatoms) May be substituted, and some or all of the hydrogen atoms on the carbon chain may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring is monocyclic, condensed or It may be a spiro ring, may have both a condensed ring and a spiro ring, a part of carbon atoms may be substituted with a heteroatom, or a part or all of hydrogen on the ring may be substituted Good)
   Z ¹ and Z ² are each independently hydrogen or a structure represented by the following general formula (7) or the following general formula (8) (wherein at least one of Z ¹ and Z ² has the following general formula ( 7) or a structure represented by the following general formula (8). ;
   

   

   (In the general formula (7), V is hydrogen, a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and some of the carbon atoms are substituted with hetero atoms) Or a part or all of hydrogens on the carbon chain may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring) And may have both a condensed ring and a spiro ring, a part of carbon atoms may be substituted with a heteroatom, and a part or all of hydrogen on the ring may be substituted). Show
   U is hydrogen, a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, part of the carbon atoms may be substituted with a heteroatom, A part or all of hydrogens may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring, and a condensed ring and a spiro ring) And a part of the carbon atom may be substituted with a heteroatom, or part or all of the hydrogen on the ring may be substituted).
   Y is a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be linear or branched, a part of carbon atoms may be substituted with a heteroatom, A part or all of which may be substituted), a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring, and has both a condensed ring and a spiro ring) Or a part of the carbon atoms may be substituted with a heteroatom, or part or all of the hydrogen atoms on the ring may be substituted), or the chain carbonization having 1 to 20 carbon atoms A group in which a carbonyl group is introduced into a hydrogen group or the cyclic hydrocarbon group having 3 to 20 carbon atoms is shown. );
   

   

   (In the general formula (8), W represents a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and a part of the carbon atoms may be substituted with a hetero atom) Or a part or all of hydrogen on the carbon chain may be substituted), a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring, And a spiro ring, part of the carbon atom may be substituted with a heteroatom, or part or all of the hydrogen on the ring may be substituted), or the carbon A group in which a carbonyl group is introduced into a chain hydrocarbon group having 1 to 20 carbon atoms or a cyclic hydrocarbon group having 3 to 20 carbon atoms;
   T is a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be linear or branched, a part of the carbon atom may be substituted with a hetero atom, A part or all of them may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring, and both a condensed ring and a spiro ring) Or a part of the carbon atom may be substituted with a heteroatom, and a part or all of the hydrogen on the ring may be substituted). )};
   

   

   {In General Formula (9), R ⁶ represents a single bond, a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and a part of the carbon atoms are heteroatoms) May be substituted, and some or all of the hydrogen atoms on the carbon chain may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring is monocyclic, condensed or It may be a spiro ring, may have both a condensed ring and a spiro ring, a part of carbon atoms may be substituted with a heteroatom, or a part or all of hydrogen on the ring may be substituted Good)
   Z ³ represents a structure represented by the following general formula (7) or the following general formula (8). ;
   

   

   (In the general formula (7), V is hydrogen, a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and some of the carbon atoms are substituted with hetero atoms) Or a part or all of hydrogens on the carbon chain may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring) And may have both a condensed ring and a spiro ring, a part of carbon atoms may be substituted with a heteroatom, and a part or all of hydrogen on the ring may be substituted). Show
   U is hydrogen, a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, part of the carbon atoms may be substituted with a heteroatom, A part or all of hydrogens may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring, and a condensed ring and a spiro ring) And a part of the carbon atom may be substituted with a heteroatom, or part or all of the hydrogen on the ring may be substituted).
   Y is a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be linear or branched, a part of carbon atoms may be substituted with a heteroatom, A part or all of which may be substituted), a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring, and has both a condensed ring and a spiro ring) Or a part of the carbon atoms may be substituted with a heteroatom, or part or all of the hydrogen atoms on the ring may be substituted), or the chain carbonization having 1 to 20 carbon atoms A group in which a carbonyl group is introduced into a hydrogen group or the cyclic hydrocarbon group having 3 to 20 carbon atoms is shown. );
   

   

   (In the general formula (8), W represents a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be a straight chain or a branched chain, and a part of the carbon atoms may be substituted with a hetero atom) Or a part or all of hydrogen on the carbon chain may be substituted), a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring, And a spiro ring, a part of the carbon atom may be substituted with a heteroatom, or part or all of the hydrogen on the ring may be substituted), or the carbon A group in which a carbonyl group is introduced into a chain hydrocarbon group having 1 to 20 carbon atoms or a cyclic hydrocarbon group having 3 to 20 carbon atoms;
   T is a chain hydrocarbon group having 1 to 20 carbon atoms (wherein the carbon chain may be linear or branched, a part of the carbon atom may be substituted with a hetero atom, A part or all of them may be substituted), or a cyclic hydrocarbon group having 3 to 20 carbon atoms (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring, and both a condensed ring and a spiro ring) Or a part of the carbon atom may be substituted with a heteroatom, and a part or all of the hydrogen on the ring may be substituted). )};
   n represents 0 to 200. ]
2. The matrix composition according to claim 1, wherein the content of the epoxy resin is 45 to 99% by weight in the total solid content.
3. The matrix composition according to claim 1, wherein the fiber reinforced composite material is a carbon fiber reinforced composite material.
4. The matrix composition according to any one of claims 1 to 3, wherein the epoxy resin has a number average molecular weight of 250 to 100,000.
5. A fiber-reinforced composite material comprising a cured product of the matrix composition according to any one of claims 1 to 4 and a fibrous material.
6. A method for producing a fiber reinforced composite material comprising the following steps:
   (I) a step of impregnating the fibrous material with the matrix composition according to any one of claims 1 to 4; and (ii) a heat treatment of the fibrous material impregnated with the matrix composition in the step (i). Process.
7. The method for producing a fiber-reinforced composite material according to claim 6, wherein the fibrous material is carbon fiber.