JP2000344870A - Epoxy resin composition, prepreg, and fiber-reinforced composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition which can be a matrix resin excellent in heat resistance and adhesive properties and can make compression strength and impact resistance compatible even at high temperature and humidity by compounding an epoxy resin with an aromatic polyamine and a compound which has a specific partial chemical structure and a functional group reactive with the epoxy resin or the aromatic polyamin. SOLUTION: This resin composition contains an epoxy resin, an aromatic polyamine, and a compound which has at least one kind of partial structure selected from among those represented by formulas I, II, III, and IV and has at least one functional group reactive with the epoxy resin or the aromatic polyamine, that is, a functional group selected from among carboxyl, phenolic hydroxyl, amino, sec-amino, and mercapto groups and a double bond in conjugation with a carbonyl group. The amount of the compound compounded is 0.5-30 pts.wt. based on 100 pts.wt. epoxy resin. Preferably, the composition gives a cured item having a glass transition point of 160-250 deg.C, a tensile elongation of 8% or higher, and a flexural modulus of 3.2 GPa or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition for producing a fiber-reinforced composite material, a prepreg obtained by impregnating a reinforcing fiber with the epoxy resin composition, and an epoxy resin composition and a reinforcing fiber. The present invention relates to a fiber-reinforced composite material.

More specifically, when a fiber-reinforced composite material is produced, an epoxy resin composition having mainly excellent compressive strength and impact resistance, and particularly having favorable characteristics as a structural material for aircraft, ships, vehicles and the like, and the epoxy resin It relates to a prepreg in which the composition is used.

[0003]

2. Description of the Related Art Fiber-reinforced composite materials comprising a reinforcing fiber and a resin are widely used in aerospace applications, general industrial applications, and sports applications because of their light weight and excellent mechanical strength. Various methods are employed for producing a fiber-reinforced composite material, and in many cases, a prepreg, which is a sheet-like intermediate substrate in which a reinforcing fiber is impregnated with a resin, is used. In this case, a composite material can be obtained by laminating a plurality of prepregs and then heating them.

In this case, a thermosetting resin represented by an epoxy resin or a thermoplastic resin is used as the resin.
An epoxy resin that exhibits excellent mechanical strength when used as a fiber-reinforced composite material is often used.

On the other hand, carbon fibers, aramid fibers, and glass fibers are mainly used as the reinforcing fibers. Above all, carbon fibers that are excellent in specific strength and specific elastic modulus and can provide a high-performance composite material are often used.

A fiber-reinforced composite material generally has high strength in the same direction as the orientation of the fiber because it reflects the physical properties of the reinforcing fiber, but strength in other directions, especially shear strength, is not always excellent. There are many disadvantages of reinforced composite materials. Strength in the direction in which the fiber is not oriented,
Above all, to increase the shear strength, it is effective to improve the adhesiveness (hereinafter simply referred to as adhesiveness) between the reinforcing fiber and the resin.

In recent years, fiber-reinforced composite materials have been applied not only to aircraft but also to structural materials for automobiles, railway vehicles, ships, and the like.

When a fiber-reinforced composite material is applied to such a structural material, a plurality of unidirectional prepregs, in which fibers are aligned in a certain direction, are often laminated with regularity and used. Various stresses (tensile stress,
The method of breaking when compressive stress, torsional stress, impact stress, etc.) is applied is complicated, and the strength in the direction perpendicular to the fiber (hereinafter abbreviated as 90 ° direction) governs the strength of the whole material. Many. Therefore, to improve the mechanical strength of the structural material, it is effective to improve the adhesiveness.

[0009] Impact resistance is an important property for such structural materials, and particularly, compressive strength after receiving a sudden impact force is important. For example, the composite material receives an impact force due to a drop of tools or collision with pebbles or the like, and peeling occurs between layers of the composite material, so that the compressive strength is reduced and the composite material cannot be used as a structural material.

In order to increase the compressive strength, efforts have been made to improve the strength of reinforcing fibers, particularly carbon fibers, and to improve the toughness and elongation of resins. According to the analysis, the strength of the carbon fiber itself and the improvement of the toughness and elongation of the resin do not necessarily contribute to increasing the compressive strength, but rather the strength contribution in the 90 ° direction is rather large. It has become clear.

It is important that the compressive strength does not deteriorate even under high temperature and high humidity. In addition, in the above-mentioned applications, when used in the form of a plate material, holes for bolts are often drilled and used, and the compressive strength of a plate-like material having holes drilled (hereinafter abbreviated as a perforated plate material), particularly Compressive strength under high temperature and high humidity is important.

The compressive strength depends on the elastic modulus and adhesiveness of the resin, and can be increased as the elastic modulus and adhesiveness are higher. In order to maintain a high elastic modulus even under high temperature and high humidity, it is required that the resin has heat resistance and adhesiveness under high temperature and high humidity.

In order to improve such adhesiveness, surface treatment of reinforcing fibers has been studied. For example, in the case of glass fibers, surface treatment with a silane coupling agent, and in the case of carbon fibers, surface treatment such as electrolytic oxidation. There is. However, there is a limit to the effect of enhancing the adhesiveness only by treating the reinforcing fiber, and in order to satisfy the recent demand for further improvement in the properties of composite materials, a method of improving the adhesiveness by modifying the resin should be taken. It is. At present, although there is a finding that it is effective to mix a certain type of thermoplastic resin with respect to an epoxy resin that is often used as a resin of a fiber-reinforced composite material, according to this, the adhesiveness is still insufficient. There is the present situation.

[0014]

DISCLOSURE OF THE INVENTION In view of the above problems, the present invention provides a cured product of a resin which becomes a matrix resin having excellent heat resistance and adhesiveness, and in particular, achieves both compressive strength and impact resistance even under high temperature and high humidity. And a fiber reinforced composite material suitable for use in structural members such as aircraft, vehicles and ships, an epoxy resin composition capable of producing the composite material, and a prepreg obtained by impregnating reinforcing fibers with such an epoxy resin composition. It is something you want to do.

[0015]

The present invention has the following arrangement to achieve the above object. That is, it is an epoxy resin composition containing the following components [A] and [B]. [A] Aromatic polyamine [B] One molecule having at least one partial structure selected from the following formulas (1) to (4) in the molecule and capable of reacting with an epoxy resin or an aromatic polyamine Compound having

[0016]

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[0017]

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[0018]

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[0019]

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Further, the present invention has the following configuration to achieve the above object. That is, it is a prepreg obtained by impregnating reinforcing fibers with the epoxy resin composition.

Further, the present invention has the following configuration to achieve the above object. That is, it is a fiber-reinforced composite material comprising a reinforcing fiber and a cured product of the epoxy resin composition.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors diligently studied the above-mentioned problems, and in an epoxy resin composition containing an epoxy resin and an aromatic polyamine, having a specific partial structure in the molecule, In addition, the inventor has found that when a specified compound having one functional group capable of reacting with an epoxy resin or an aromatic polyamine as a curing agent for the epoxy resin is compounded, such a problem can be solved at once.

In the present invention, the epoxy resin used has two or more epoxy groups in the molecule.

The epoxy resin having two or more epoxy groups in the molecule includes a bifunctional epoxy resin having two epoxy groups and a trifunctional or more epoxy resin having three or more epoxy groups.

In the present invention, as the bifunctional epoxy resin, bifunctional glycidyl ether, difunctional glycidylamine, and difunctional glycidyl ester can be used.

Specific examples of the glycidyl ether include a bisphenol A epoxy resin obtained from bisphenol A, a tetrabromobisphenol A epoxy resin obtained from tetrabromobisphenol A, a bisphenol F epoxy resin obtained from bisphenol F,
Bisphenol type epoxy resins such as bisphenol S type epoxy resin obtained from bisphenol S, resorcin diglycidyl ether, hydroquinone diglycidyl ether, diglycidyl of 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethylbiphenyl Ether, diglycidyl ether of 9,9-bis (4-hydroxyphenyl) fluorene,
Diglycidyl ether of 1,6-dihydroxynaphthalene,
Bifunctional oxazolidone-type epoxy resins are exemplified. Here, the bifunctional oxazolidone type epoxy resin is an epoxy resin obtained by reacting a bifunctional epoxy resin with diisocyanate, and has an oxazolidone ring in the structure. Here, bisphenol A type epoxy resin is used as a bifunctional epoxy resin as a raw material,
Bisphenol F type epoxy resin, bisphenol S type epoxy resin and the like are used, and as the diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and the like are used.

The details of the reaction for obtaining a bifunctional oxazolidone type epoxy resin from a bifunctional epoxy resin and diisocyanate are described in US Pat. No. 3,331,374, US Pat. No. 3,334,110, and US Pat.
No. 39, U.S. Pat. No. 3,721,650, U.S. Pat. No. 3,737,406, JP-A-48-103
570, JP-A-49-37999, JP-A-49-94798, JP-A-49-93491, JP-A-50-136398, and JP-A-50-1
It is disclosed in many publications such as 17771.

Specific examples of glycidylamine include diglycidylaniline, diglycidyl-o-toluidine and the like.

Specific examples of glycidyl esters include diglycidyl phthalate, diglycidyl terephthalate, diglycidyl dimer, and the like.

In the present invention, as the trifunctional or higher functional epoxy resin, trifunctional or higher functional glycidyl ether and trifunctional or higher functional glycidylamine can be used.

Specific examples of the glycidyl ether include phenol derivatives such as phenol, alkylphenol and halogenated phenol; novolak epoxy resins which are glycidyl ethers of novolak obtained from naphthol derivatives such as naphthol, alkylnaphthol and halogenated naphthol; Examples thereof include an epoxy resin starting from a derivative or a copolymer of a naphthol derivative and dicyclopentadiene, triglycidyl ether of tris (p-hydroxyphenyl) methane, and tetraglycidyl ether of tetrakis (p-hydroxyphenyl) ethane.

Specific examples of glycidylamine include tetraglycidyldiaminodiphenylmethane, tetraglycidyl m-xylylenediamine and the like. Examples of epoxy resins having both structures of glycidyl ether and glycidylamine include triglycidyl-m-aminophenol, triglycidyl-p-aminophenol, and triglycidylaminocresol.

In the present invention, these epoxy resins are
They can be used alone or as a mixture of two or more. When a bifunctional epoxy resin and a trifunctional or higher epoxy resin are used in combination, the flexural modulus,
It is preferable because a cured product of a resin having high tensile elongation and high heat resistance can be obtained. In this case, in 100 parts by weight of the epoxy resin,
60 to 95 parts by weight, preferably 8 parts by weight of the bifunctional epoxy resin
It is preferable to use 0 to 95 parts by weight and the other to be a trifunctional or higher epoxy resin since a cured product having sufficient flexural modulus, tensile elongation and heat resistance can be easily obtained. If the amount of the bifunctional epoxy resin is less than 60 parts by weight, the heat resistance and the elastic modulus may decrease, and if it exceeds 95 parts by weight, the tensile elongation may decrease.

In the present invention, as the bifunctional epoxy resin,
Tetrabromobisphenol A type epoxy resin, bisphenol S type epoxy resin, 4,4'-dihydroxy-3,3 ',
Using diglycidyl ether of 5,5'-tetramethylbiphenyl, diglycidyl ether of 9,9-bis (4-hydroxyphenyl) fluorene, diglycidyl ether of 1,6-dihydroxynaphthalene, and bifunctional oxazolidone type epoxy resin It is preferable because a cured product having higher heat resistance, elastic modulus and tensile elongation can be obtained.

The trifunctional or higher functional epoxy resin includes tetraglycidyl diaminodiphenylmethane, tetraglycidyl m-xylylenediamine, triglycidyl-m
-Aminophenol, triglycidyl-p-aminophenol, and triglycidylaminocresol are preferably used, and tetraglycidyldiaminodiphenylmethane is more preferable because a cured product having higher heat resistance and higher elastic modulus can be obtained.

In the present invention, the constituent element [A] is an aromatic polyamine. The aromatic polyamine is blended as a curing agent for the epoxy resin. The aromatic polyamine is a compound having an aromatic ring and having two or more amino groups.
The aromatic polyamine represented by the following formula (5) is preferably used when it is mixed with an epoxy resin as a curing agent, because it gives a cured product having particularly excellent heat resistance.

[0037]

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(Wherein, m _{1 to} m ₃ and n _{1 to} n ₃ are 0 or 1,
D ^{1 to} D ¹⁶ are at least one selected from a hydrogen atom, a halogen atom, and an alkyl group, and E ^{1 to} E ³ are —SO ₂ —, an alkylene group, an oxygen atom, a sulfur atom, —CO—, and —COO.
And represents at least one selected from -Q-OCO- (Q is an alkylene group having 1 to 5 carbon atoms). As the aromatic polyamine represented by the above formula (5), specifically, the following types (I) to (V) can be used. (I) m ₁ = m ₂ = m ₃ = 0, n ₁ = n ₂ = n ₃ = 0 Specific examples include m-phenylenediamine, p-phenylenediamine, diethyltoluenediamine and the like. (II) m ₁ = 1, m ₂ = m ₃ = 0, n ₁ = 1, n ₂ = n ₃ = 0 As specific examples, 4,4′-diaminodiphenyl sulfone,
3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-
Methylenebis (2,5-diethylaniline), 4,4'-methylenebis (2,6-diisopropylaniline), 4,4 '-(2-ethyl-6-methylaniline), 4,4'-methylenebis (2- Isopropyl-6-methylaniline), 4,4'-methylenebis (3-chloro-2,6-diethylaniline), trimethylenebis (4-
Aminobenzoate), hexamethylenebis (4-aminobenzoate), neopentylenebis (4-aminobenzoate) and the like. (III) m ₁ = m ₂ = 1, m ₃ = 0, n ₁ = n ₂ = 1, n ₃ =
0 Specific examples include 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene,
Bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene and the like can be mentioned. (IV) m ₁ = m ₂ = m ₃ = 1, n ₁ = 1, n ₂ = 0, n ₃ = 1 Specific examples include 4,4′-bis (4-aminophenoxy) biphenyl. (V) m ₁ = m ₂ = m ₃ = 1, n ₁ = n ₂ = n ₃ = 1 As specific examples, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3- Aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and 2,2-bis [4- (3-aminophenoxy) phenyl] propane.

In the present invention, in addition to these, 1,8-diaminonaphthalene, 9,9-bis (4-aminophenyl) fluorene and the like can be used as the constituent element [A].

As the aromatic polyamine represented by the above formula (5) and the above (I) and (II), there is a liquid at room temperature of 25 ° C. such as diethyltoluenediamine, and these are liquid composite molding described later. It is preferably used when producing a composite material by a method or the like. Further, 4,4′-diaminodiphenylsulfone and 3,3′-diaminodiphenylsulfone, which are aromatic polyamines represented by the formulas (5) and (II), are obtained by mixing an epoxy resin and an aromatic polyamine. It is preferably used for prepregs because of its excellent storage stability after being adjusted to a solution state.

In the present invention, the constituent element [B] has at least one kind of partial structure (hereinafter simply referred to as partial structure A) selected from the following formulas (1) to (4) in the molecule; It is a compound having one functional group capable of reacting with an epoxy resin or an aromatic polyamine (hereinafter, abbreviated as a reactive functional group).

[0042]

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[0043]

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[0044]

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[0045]

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The partial structure A interacts with the reinforcing fibers to enhance the adhesiveness between the reinforcing fibers and the matrix resin (hereinafter simply referred to as adhesiveness). Effective interactions are roughly classified into the following two.

First, there is a hydrogen bond. This is effective when a functional group such as -OH or -NH exists on the surface of the reinforcing fiber.

Next, there is an electric attraction between the reinforcing fiber and the dipole contained in the resin. Here, substructure A acts as a strong permanent dipole. An induced dipole is generated by such a permanent dipole, and an electric attractive force is generated between the reinforcing fiber and the matrix resin, that is, a cured product of the resin. Such an electric attraction is particularly effective in a reinforcing fiber having a small number of surface functional groups, such as carbon fiber, and for which there has been no effective method for improving adhesiveness.

In order for the partial structure A to effectively interact with the reinforcing fibers, it is necessary to contact the surface of the reinforcing fibers, so that the component [B] needs to have one reactive functional group. is there. When having two or more reactive functional groups,
The partial structure A is taken into the inside of the network structure, making it substantially difficult to contact the surface of the reinforcing fiber,
It becomes difficult to effectively interact with the reinforcing fiber (see FIG. 1A), but when it has one reactive functional group, the partial structure A is not restricted by the network and easily contacts the reinforcing fiber surface. (See FIG. 1B).

The reactive functional group preferably has a relatively slow reactivity to the reaction between the epoxy resin and its curing agent. In this case, for the main curing reaction,
In the initial stage, the reaction progress amount of the reactive functional group is small, and the reaction proceeds later, and as a result,
This is because a large amount of the partial structure A is present at the terminal portion of the internal network structure, and even when the amount of the component [B] is small, the partial structure A is sufficient for achieving the effects of the present invention.

The component [B] not only increases the adhesiveness but also has the function of increasing the flexural modulus of the matrix resin. It is presumed that the cause of this action is that the partial structure A and the functional groups such as -OH and -NH present in the cured product form hydrogen bonds and restrict the molecular motion of the matrix resin.

Specific examples of the reactive functional group include at least one selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, an amino group, a secondary amine structure, a mercapto group, an epoxy group, and a double bond conjugated with a carbonyl group. One type is mentioned. Examples of the compound having one reactive functional group include a compound represented by the following formula (6) or (8).

[0053]

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(Where X is

[0055]

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And R ⁴ is an alkyl group or an aryl group.

Y is either —O— or —NR ⁵ —, R ⁵ is an alkyl group or an aryl group, and n is 0 or 1.

R ¹ is a divalent group derived from a hydrocarbon, and m is 0 or 1.

Z is a carboxyl group, a phenolic hydroxyl group, an amino group, a mercapto group, a group represented by the following general formula (7),

[0060]

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Wherein R ⁶ , R ⁷ , R ⁸ and R ⁹ are any of hydrogen, an alkyl group and an aryl group. R ²
Is any of hydrogen, an alkyl group, and an aryl group;
³ is hydrogen, an alkyl group, an aryl group, -WR ¹⁰ , -W-
OR ¹¹ , -W-NR ¹² R ¹³ , and R ¹⁰ , R
¹¹ is an alkyl group or an aryl group; R ¹² and R ¹³ are any of hydrogen, an alkyl group and an aryl group;
CO- or -SO ₂ - is.

The above alkyl group, aryl group and R¹
Represents an alkyl group, an aryl group, a halogen, an alkoxy group
It may have a substituent selected from the following. Further, R¹,
R^Two, R ^Three, R^Five, R⁶Any two may form a ring
No. )

[0063]

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(Where X is

[0065]

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Wherein R ¹⁷ is an alkyl group or an aryl group. R ¹⁵ is an alkyl group or an aryl group, R ¹⁶ is any of hydrogen, an alkyl group, an aryl group, and an acyl group, and n is 0 or 1.

R ¹⁴ is a divalent group derived from a hydrocarbon, and m is 0 or 1.

Z is a carboxyl group, a phenolic hydroxyl group, an amino group, a mercapto group, a group represented by the following general formula (9),

[0069]

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R ¹⁸ , R ¹⁹ , R ²⁰ , R
²¹ is any of hydrogen, an alkyl group, an aryl group, and an acyl group.

The above alkyl group, aryl group and R¹⁴
Is an alkyl, aryl, halogen, or alkoxy group
It may have a selected substituent. Further, R¹⁴,
R¹⁵, R ¹⁶, R¹⁸Any two may form a ring
No.

A compound having one carboxyl group and having the general formula (6)
Specific examples of the compound represented by include oxamic acid, succinamic acid, 2- (phenylcarbamoyloxy) propionic acid, 5-hydantoin acetic acid, and the like.

A compound having one carboxyl group and having the general formula (8)
Specific examples of the compound represented by, N-acetylglycine, N-acetylalanine, 4-acetamidobenzoic acid, N-
Examples include acetylanthranilic acid, 4-acetamidobutyric acid, 6-acetamidohexanoic acid, hippuric acid, pyroglutamic acid, N-tosylglycine, and N-dimethylphosphinoylglycine.

Specific examples of the compound having one phenolic hydroxyl group and represented by the general formula (6) include salicylamide, 4-hydroxybenzamide, 4-hydroxyphenylacetamide and the like.

Specific examples of the compound having one phenolic hydroxyl group and represented by the general formula (8) include 4-hydroxyacetanilide, 3-hydroxyacetanilide, N-acetyltyramine and the like.

Specific examples of the compound having one amino group and represented by the general formula (6) include 4-aminobenzamide,
3-aminobenzamide, 4-aminobutylamide, 6-aminohexaneamide, 3-aminophthalimide, 4-aminophthalimide, sulfanilamide, 1-butyl-3-sulfanylurea, ashram, Fast Red ITR base, FGL base, 2 -Amino-N-ethyl-N-phenylbenzenesulfonamide and the like.

Specific examples of the compound having one amino group and represented by the general formula (8) include 4′-aminoacetanilide, 4′-amino-N-methylacetanilide, 3′-aminopropionanilide, And the like.

Having one secondary amine structure and having the general formula (6)
Specific examples of the compound represented by, nipecotamide, N,
N-diethylnipecotamide, isonipecotamide and the like.

A compound having one secondary amine structure and having the general formula (8)
Specific examples of the compound represented by include 1-acetylpiperazine, 1-tosylpiperazine and the like.

Specific examples of the compound having one mercapto group and represented by the general formula (8) include 4-acetamidothiophenol, N- (2-mercaptoethyl) acetamide and the like.

Specific examples of the compound having one epoxy group and represented by the general formula (6) include glycidamide, N-phenylglycidamide, N, N-diethylglycidamide, N-methoxymethylglycidamide, N-hydroxymethylglycidamide, 2,3-epoxy-3-methylbutyramide, 2,3-epoxy-2-methylpropionamide, 9,10-epoxystearamide and the like.

Specific examples of the compound having one epoxy group and represented by the general formula (8) include N-glycidyl phthalimide.

In addition to the compound represented by formula (6) or (8), hydrazides such as acetohydrazide, benzohydrazide, 3-aminorhodanine, Benzenesulfohydrazide and the like can be mentioned.

The functional group capable of reacting with the aromatic polyamine further includes a double bond conjugated to a carbonyl group. The double bond conjugated with the carbonyl group performs a Michael-type addition reaction with the amino group of the aromatic polyamine.

The compound having one double bond conjugated to a carbonyl group is represented by the following general formula (10) or (11)
Can be used.

[0086]

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(Where X is

[0088]

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And R ²⁸ is an alkyl group or an aryl group.

Y is either —O— or —NR ²⁹ —, R ²⁹ is an alkyl group or an aryl group, and n is 0 or 1.

R ²² is a divalent group derived from a hydrocarbon.

R ²³ , R ²⁴ and R ²⁵ represent hydrogen, an alkyl group,
Any of aryl groups.

R ²⁶ is any of hydrogen, an alkyl group and an aryl group, and R ²⁷ is a hydrogen, an alkyl group, an aryl group,
-WR ³⁰ , -W-OR ³¹ , or -W-NR ³² R ³³ , wherein R ³⁰ and R ³¹ are an alkyl group or an aryl group, and R ³² and R ³³ are a hydrogen, an alkyl group, or an aryl group And W is —CO— or —SO ₂ —.

The above alkyl group, aryl group and R¹⁸
Is an alkyl, aryl, halogen, or alkoxy group
It may have a substituent selected from the following. Further, R^{twenty two},
R^{twenty three}, R ^{twenty four}, R^{twenty five}, R²⁶, R²⁷, R²⁹Any two of
A ring may be formed. )

[0095]

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(Where X is

[0097]

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Wherein R ⁴⁰ is an alkyl group or an aryl group, and n is 0 or 1.

R ³⁴ is a divalent group derived from a hydrocarbon.

R ³⁵ , R ³⁶ and R ^{37 each} represent hydrogen, an alkyl group,
Any of aryl groups.

R ³⁸ is an alkyl group or an aryl group, and R ³⁹ is hydrogen, an alkyl group, an aryl group, or an acyl group.

The above alkyl group, aryl group and R ³⁴
May have a substituent selected from an alkyl group, an aryl group, a halogen, and an alkoxy group. Further, R ³⁴ , R
Any two of ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , and R ³⁹ may form a ring. Further, in the compound having one double bond conjugated to a carbonyl group, the carbonyl group conjugated to the double bond may be the same as the carbonyl group represented by the formula (1).
That is, it may have a partial structure B represented by the following formula (12).

[0103]

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As the compound having the partial structure B represented by the above formula (12), a compound represented by the following general formula (13) can be used.

[0105]

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(Where R ⁴¹ , R ⁴² and R ⁴³ are hydrogen, an alkyl group or an aryl group. R ⁴⁴ is a hydrogen, an alkyl group or an aryl group, R ⁴⁵ is a hydrogen,
Alkyl group, aryl group, -WR ⁴⁶ , -W-OR ⁴⁷ ,-
Are either ^{W-NR 48 R 49, R} 46, R 47 is an alkyl group or an aryl group, R ^48, R ⁴⁹ represents hydrogen, an alkyl group, or a aryl group, W is -CO- Or —SO ₂ —.

The above-mentioned alkyl group and aryl group may have a substituent selected from an alkyl group, an aryl group, a halogen and an alkoxy group. Further, R ⁴¹ , R ⁴² , R ⁴³ ,
Any two of R ⁴⁴ and R ⁴⁵ may form a ring. As the compound having the partial structure B represented by the general formula (12), a maleimide and a maleimide derivative further having an alkyl group or an aryl group as a substituent can be used.

Specific examples of the compound represented by the general formula (10) include 2- (phenylcarbamoyloxy) ethyl methacrylate, 2- (methacryloyloxy) propionamide, 2- (phenylureido) ethyl methacrylate,
Lactamide acrylate, lactamide methacrylate,
2- (dimethylthiocarbamoyloxy) ethyl methacrylate, 2- (tosylcarbamoyloxy) ethyl methacrylate and the like can be mentioned.

Specific examples of the compound represented by the general formula (11) include 2- (methoxycarbonylamino) ethyl methacrylate, 2- (phenoxycarbonylamino) ethyl methacrylate and the like.

Specific examples of the compound represented by the general formula (13) include acrylamide, methacrylamide, crotonamide, cinnamamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dibutylacrylamide, N, N-dibenzylacrylamide, N-tert-butylacrylamide, N-isopropylacrylamide,
N-butylacrylamide, Nt-butylacrylamide,
Nt-octylacrylamide, N-hydroxymethylacrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, diacetoneacrylamide, 1-acryloylmorpholine, 1,2,3,6-tetrahydrophthalimide, Nadimide and the like.

Examples of the maleimide derivative having an alkyl group or an aryl group as a substituent include N-ethylmaleimide, N-isopropylmaleimide, N-phenylmaleimide and the like.

The partial structure A may be a part of a larger structure. For example, as the compound having an amide bond represented by the formula (1), there is a carboxylic acid amide. In addition, a compound having an amide bond in a part of the ring may be used.
In this case, it is particularly preferable because the adhesion is greatly improved. The partial structure A may be a part of a larger structure such as an imide, urethane, urea, biuret, hydantoin, carboxylic hydrazide, hydroxamic acid, semicarbazide, or semicarbazone.

The constituent element [B] may be used alone or in combination. The constituent element [B] is an epoxy resin 10
It is preferable to mix 0.5 to 30 parts by weight with respect to 0 part by weight, more preferably 0.5 to 20 parts by weight, further preferably 0.5 to 10 parts by weight. If the amount is less than 0.5 part by weight, the adhesiveness cannot be sufficiently improved, and if it exceeds 30 parts by weight, the heat resistance of the cured product may decrease.

The component [B] may be liquid or solid at room temperature of 25 ° C. When a solid material is used, it may be dissolved by heating and stirring after being mixed with the epoxy resin composition, or may be left undissolved. When compounded in a non-dissolved state, it is preferable to use one that has been pulverized to a particle size of 10 μm or less.

In the present invention, the amount of each component is preferably adjusted in the epoxy resin composition in the following two cases (a) and (b). (A) In the case where the reactive functional group is a functional group capable of reacting with the epoxy resin, the constituent element [B] has the following ratio of Nresin to Nab (Nresi
n: Nab) is 1: 0.4 to 1: 1.2, preferably 1:
It is better to mix in the range of 0.6 to 1: 1.1. When Nab is less than 0.4, curing may be insufficient,
Exceeds 1.2, the strength of the resulting composite material may decrease. Nresin: the number of epoxy groups in the epoxy resin Nab: the sum of the number of active hydrogens in component [A] and the number of active hydrogens in component [B] (b) a reactive functional group capable of reacting with an aromatic polyamine In some cases, the component [B] is a ratio of the following Nb and Na (Nb: Na)
Is 1: 0.4 to 1: 1.2, preferably 1: 0.6 to
It is better to mix them in the range of 1: 1.1. If Na is less than 0.4, curing may be insufficient, and Na may be less than 1.2.
If the ratio exceeds, the strength of the obtained composite material may be reduced. Nb: number of epoxy groups of epoxy resin and component [B]
Na: the number of active hydrogens in component [A] In the present invention, a certain curing catalyst is used in component [A]
By using together with, the curing time can be further shortened,
The curing temperature can be lowered. As such a curing catalyst, specifically, a boron trifluoride amine complex, a sulfonium salt, a phosphonium salt, or the like can be used.

In the present invention, a high molecular compound, organic particles, inorganic particles and other components can be blended in the epoxy resin composition as a modifier.

As the polymer compound, a thermoplastic resin is preferably used. By blending a thermoplastic resin, effects such as viscosity control at the time of impregnating the resin, handleability at the time of forming a prepreg, and improvement of adhesiveness can be enhanced.

As the thermoplastic resin, it is preferable to use a thermoplastic resin having a hydrogen-bonding functional group for which a synergistic effect can be expected in order to improve the adhesiveness. Specific examples of the hydrogen-bonding functional group include an alcoholic hydroxyl group, an amide bond, and a sulfonyl group.

Examples of the thermoplastic resin having an alcoholic hydroxyl group include polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, and polyvinyl alcohol and phenoxy resins. Examples of the thermoplastic resin having an amide bond include sulfonyl groups such as polyamide and polyimide. Examples of the thermoplastic resin include polysulfone. Polyamide, polyimide and polysulfone may have a functional group such as an ether bond or a carbonyl group in the main chain. The polyamide may have a substituent at the nitrogen atom of the amide group.

Examples of the thermoplastic resin which is soluble in an epoxy resin and has a hydrogen-bonding functional group include polyvinylacetal resin, vinylex (registered trademark, manufactured by Chisso Corporation),
Phenoxy resin UCARPKHP (trade name, manufactured by Union Carbide Co.), Macromelt (registered trademark, manufactured by Henkel Hakusui Co., Ltd.) as a polyamide resin, Amilan C
M4000 (registered trademark, manufactured by Toray Industries, Inc.), Ultem (registered trademark, manufactured by General Electric Co., Ltd.), Matrimid 5218 (registered trademark, manufactured by Ciba), and Victrex (registered trademark, as a polysulfone)
Mitsui Toatsu Chemical Co., Ltd.) and UDEL (registered trademark, manufactured by Union Carbide Co.) can be used.

The thermoplastic resin is used in an amount of 1 to 20 with respect to 100% by weight of the total epoxy resin in order to give the epoxy resin an appropriate viscoelasticity and obtain good mechanical properties in the obtained composite material.
% By weight, preferably 2 to 10% by weight.

As the organic particles to be added to the epoxy resin composition of the present invention, rubber particles and thermoplastic resin particles are preferable. These particles have the effect of improving the toughness of the matrix resin of the fiber-reinforced composite material and the impact resistance of the fiber-reinforced composite material.

Rubber particles and thermoplastic resin particles are used as the organic particles. These particles have the effect of improving the toughness of the resin and the impact resistance of the fiber-reinforced composite material.
It is preferably from 30 to 30 parts by weight. As rubber particles,
Crosslinked rubber particles, and core-shell rubber particles obtained by graft-polymerizing a heterogeneous polymer on the surface of the crosslinked rubber particles are preferably used. As the crosslinked rubber particles, acrylic rubber fine particles such as a crosslinked product of a carboxyl-modified butadiene-acrylonitrile copolymer can be used. As the core-shell rubber particles, a butadiene / alkyl methacrylate / styrene copolymer, an acrylate / methacrylate copolymer, a butyl acrylate / methyl methacrylate copolymer, or the like can be used. As the thermoplastic resin particles, polyamide or polyimide particles are preferably used.

As the inorganic particles, silica, alumina, synthetic mica and the like can be blended. The inorganic particles are 0.5 to 30 parts by weight based on 100 parts by weight of the epoxy resin,
Preferably, 0.5 to 10 parts by weight is blended.

The organic particles and the inorganic particles are sometimes blended for the purpose of coloring the matrix resin.

When the epoxy resin composition according to the present invention is used for a prepreg, the viscosity of the resin composition is a complex viscosity obtained by measuring dynamic viscoelasticity at room temperature of 25 ° C. and 0.5 Hz. 10,000-300,000 Pa ・
s, preferably 50,000 to 300,000 Pa · s. If it is less than 10,000 Pa · s, it may be difficult to maintain the shape of the prepreg,
If the value exceeds a · s, the prepreg may not be able to be provided with an appropriate tackiness, or the prepreg may be hardened and have poor drapability.

In the obtained fiber-reinforced composite material, the compressive strength of the perforated plate material (hereinafter abbreviated as “perforated plate compressive strength”) as an index of the compressive strength, particularly, the compressive strength of the perforated plate at high temperature and high humidity, In order to increase the compressive strength after a sudden impact force, which is an indicator of impact resistance (hereinafter abbreviated as compressive strength after impact), the matrix resin must have high heat resistance in addition to high adhesiveness. It is preferable that both the flexural modulus and the tensile elongation are high.

The glass transition temperature of the matrix resin is from 160 to 250 ° C., preferably from 160 to 250 ° C., in order to obtain a fiber reinforced composite material having high heat resistance, and particularly to obtain a fiber reinforced composite material which gives high compression properties even under high temperature and high humidity. The matrix resin has a flexural modulus at room temperature of 25 ° C. of 3.2 GPa or more, preferably 3.5 to 5 Ga.
It is good. The tensile elongation of the matrix resin at a room temperature of 25 ° C. is preferably 8% or more, and more preferably 10 to 30%.

The flexural modulus of the matrix resin under high temperature and high humidity, specifically, a cured resin having a thickness of 2 mm
A test piece cut out to a width of 10 mm and a length of 60 mm
After being immersed in warm water of 20 ° C. for 20 hours, the test piece measured at 82 ° C. has a flexural modulus of 2.6 GPa or more, preferably 2.8 GPa or more. A matrix resin having such physical properties can be obtained by blending the components [A] and [B] as described above to prepare and cure the epoxy resin composition. The curing temperature depends on the type of the component [A] and the type of the curing catalyst used in combination, but is preferably from 130 to 200 ° C, preferably from 150 to 200 ° C.
° C, more preferably 170-190 ° C,
The curing time is 1 to 12 hours, preferably 1.5 to 4 hours.

In the present invention, glass fibers, carbon fibers, aramid fibers, boron fibers, alumina fibers, silicon carbide fibers and the like can be used as the reinforcing fibers.
These fibers can be used as a mixture of two or more kinds, but carbon fibers are preferably used in order to obtain a lightweight and highly durable composite material. With a smaller amount of use,
In order to sufficiently exhibit the rigidity of the composite material, it is preferable to use carbon fibers having a high elastic modulus. Elastic modulus is 20
It is good to be 0 GPa or more, preferably 210 to 800 GPa.

The prepreg according to the present invention is obtained by impregnating reinforcing fibers with the epoxy resin composition as described above.

The prepreg is prepared by dissolving the resin composition in a solvent such as methyl ethyl ketone or methanol to reduce the viscosity.
It is manufactured by a wet method of impregnation or a hot melt method of lowering the viscosity by heating to impregnate.

The wet method is a method in which a reinforcing fiber is immersed in a solution containing an epoxy resin, then pulled up, and the solvent is evaporated using an oven or the like to obtain a prepreg.

The hot melt method is a method of directly impregnating a reinforcing fiber with an epoxy resin whose viscosity has been reduced by heating, or a method in which a film in which an epoxy resin is once coated on a release paper or the like is first prepared, and then a film is formed on both sides of the reinforcing fiber. This is a method for producing a prepreg impregnated with a resin by laminating the films from one side and applying heat and pressure. The hot melt method is preferable because there is no solvent remaining in the prepreg.

The form and arrangement of the reinforcing fibers used in the prepreg are not particularly limited, and for example, long fibers aligned in one direction, a single tow, a woven fabric, a mat, a knit, a braid, and the like are used.

A fiber-reinforced composite material using a prepreg is
After laminating the prepreg, it can be produced by a method of heating and curing while applying pressure to the laminate.

A typical method of applying heat and pressure is an autoclave molding method. In the autoclave molding method, a prepreg is laminated on a mold, covered with a bag film, the inside is evacuated, and the prepregs are brought into close contact with each other, and then heated and pressed in an autoclave to obtain a composite material. A high-quality composite material can be obtained.

The prepreg according to the present invention can be used for aerospace applications such as primary wings, tails, floor beams, etc., primary structural materials for aircraft, flaps, ailerons, cowls, fairings, interior materials, etc., rocket motor cases,
In general industrial applications such as satellite structural materials, it is particularly suitable for manufacturing structural materials for mobile bodies such as automobiles, ships, and railway vehicles.

Examples of the prepreg molding method other than the autoclave molding method include a press molding method, a bag molding method, a wrapping tape method, and an internal pressure molding method.

Further, as a method of directly impregnating a reinforcing fiber with an epoxy resin without using a prepreg, followed by heat curing, a liquid composite molding method, a filament winding method, a hand lay-up method, a pultrusion method, etc. Is mentioned. In these, a method of preparing an epoxy resin composition by mixing two liquids of an epoxy resin main agent and an aromatic amine immediately before use is generally used.

The liquid composite molding method is a so-called preform made of reinforcing fibers, that is, a woven fabric having a sheet shape or a three-dimensional curved surface, which is preformed to a point approximately similar to the shape of the final molded product.
This is a method of injecting a liquid epoxy resin composition into a mat or the like and then curing the epoxy resin composition to obtain a fiber-reinforced composite material. This production method is a molding method that is frequently used because a member having a complicated shape can be molded and the productivity is good. This production method includes RTM (Resin Transfer Mol
ding) method, SRIM (Structural Reaction Injection)
Molding) method, VaRTM (Vacuum-assisted Resin Tra)
nsfer Molding) method, SCRIMP (Seeman's Composite)
e Resin Infusion Molding) method.

The filament winding method is a method in which a reinforcing fiber is impregnated with an epoxy resin composition, wound around a cored bar, and then the epoxy resin composition is cured to obtain a fiber-reinforced composite material. This production method is a molding method that is frequently used because a cylindrical member can be easily molded and the productivity is good.

The hand lay-up method is to impregnate a preform made of reinforcing fibers by impregnating a necessary and sufficient amount of an epoxy resin composition with a roller, and then curing the epoxy resin composition to obtain a fiber reinforced fiber. The pultrusion method, which is a method of forming a composite material, refers to a method in which a reinforcing fiber bundle is impregnated with an epoxy resin composition, and then the epoxy resin composition is cured through the reinforcing fiber bundle in a heating mold. This is a method in which a molded body is pulled out using the method to obtain a fiber-reinforced composite material. Since the pultrusion method uses continuous reinforcing fibers, a fiber-reinforced composite material having high strength and high rigidity can be obtained.

[0144]

The present invention will be described in more detail with reference to the following examples. All parts in the examples represent parts by weight. All measurements of mechanical properties were performed at room temperature unless otherwise specified.
C. and an environment of 50% relative humidity. (1) Dynamic viscoelasticity of resin composition The complex viscosity η ^* at a frequency of 0.5 Hz and a temperature of 25 ° C. is determined using a viscoelasticity measuring device ARES manufactured by Rheometric Scientific Co., Ltd. It was an index of dynamic viscoelasticity. (2) Physical properties of cured resin (plate material) Tensile elongation The epoxy resin composition is heated to 130 ° C, the curing agent and the thermoplastic resin are uniformly dissolved in the epoxy resin, then degassed in a vacuum, poured into a mold, and heat-cured in a 180 ° C oven for 2 hours. Then, a cured resin (plate material) having a thickness of 2 mm was produced. Next, a small (1/2) type test piece was cut out from the cured resin (plate material) according to JIS K7113, and the tensile elongation was determined. B. Flexural modulus From resin cured product (plate material) prepared in accordance with item A above, width 10
A test piece having a length of 60 mm and a length of 60 mm was cut out, and the test speed was 2.
A three-point bending test was performed at 5 mm / min and a fulcrum distance of 32 mm to determine the flexural modulus. After immersing this test piece in hot water at 71 ° C. for 2 weeks,
The flexural modulus under high temperature and high humidity was determined. C. Glass transition temperature According to JIS K7112, the glass transition temperature of the cured resin and the fiber-reinforced composite material was determined by the DSC method. Here, the measurement device includes a METTLER DSC-T30
00 system (manufactured by Mettler), and the heating rate was 40
° C / min. (2) Preparation of one-way prepreg The epoxy resin composition was applied on release paper using a reverse roll coater to prepare a resin film. Next, carbon fibers (12,000 filaments, tensile strength 5500 MPa, tensile modulus 3
00 GPa, elongation 1.9%, resin strand weight 450
g / 1000 m, density 1.8 g / cm ³ ), and the resin composition is impregnated by heating and pressing the two resin films on both sides of the carbon fiber to obtain a carbon fiber weight of 19
A unidirectional prepreg with 0 g / m ² and a carbon fiber weight fraction of 65% was produced. (3) Preparation of laminated board (composite material) The unidirectional prepreg prepared according to the above item (2) is (0 °)
₁₃ , (+ 45/0 / -45 / 90 °) _3S and (+ 45 /
0 / -45 / 90 °) The layers were laminated in a _2S configuration, heated in an autoclave at a temperature of 180 ° C. and a pressure of 0.59 MPa for 2 hours, and cured to obtain a laminate. (4) Physical properties of laminate (composite material) 90 ° tensile strength The unidirectional prepreg prepared according to the above item (2) is (0 °)
_According to ASTM D3039, a width of 25.4 mm was obtained from a laminate obtained by laminating in the same manner as in the above item (3).
A test piece having a length of 38.1 mm was cut out and subjected to a tensile test to determine a 90 ° tensile strength. B. Compression strength after impact The unidirectional prepreg prepared according to (2) above was
/ 0 / -45 / 90 °) Laminated in a _3S configuration, as described in (3) above
According to ASTM D3039, a 0 ° direction was 152.4 mm and a 90 ° direction was 10
A 1.6 mm test piece was cut out, a drop weight impact of 30.5 N · m was applied to the center of the test piece, and the compressive strength after the impact was measured using an Instron 1128 tester. C. Perforated plate compressive strength The unidirectional prepreg prepared according to the above item (2) is
/ 0 / -45 / 90 °) Laminated in a _2S configuration, as described in (3) above
From the laminate obtained in the same manner as above, the direction of 0 ° is 304.8 m.
A test piece having an m, 90 ° direction of 38.1 mm was cut out, and a circular hole having a diameter of 6.35 mm was formed in the center of the test piece to form a perforated plate material, and the perforated plate compression strength was determined.

After immersing this test piece in hot water at 71 ° C. for 2 weeks, the compressive strength of the perforated plate at high temperature and high humidity in a constant temperature bath at a temperature of 82 ° C. was determined. Example 1 The following materials were kneaded using a kneader to obtain a resin composition.

Oxazolidone type epoxy resin 70 parts (XAC4152, trade name, reaction product of bisphenol A type epoxy resin and tolylene diisocyanate, manufactured by Asahi Ciba Co., Ltd.) Bisphenol F type epoxy resin 20 parts (Epiclon 830, registered trademark, Dainippon Japan) Ink Chemical Industry Co., Ltd.) Tetraglycidyldiaminodiphenylmethane 10 parts (Sumiepoxy ELM434, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) N, N-dimethylacrylamide 5 parts (Kojin Co., Ltd.) 3,3'- 28 parts of diaminodiphenyl sulfone (manufactured by Wakayama Seika Co., Ltd.) 5 parts of polysulfone (“Victrex” PES5003P, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) Using this resin composition, a cured resin ( Sheet material) and laminates, and their physical properties were measured. The measurement results are shown in Table 1. Example 2 The following materials were kneaded using a kneader to obtain a resin composition.

Oxazolidone type epoxy resin 70 parts (XAC4152, trade name, reaction product of bisphenol A type epoxy resin and tolylene diisocyanate, manufactured by Asahi Ciba Co., Ltd.) Bisphenol F type epoxy resin 20 parts (Epiclon 830, registered trademark, Dainippon Japan) Ink Chemical Industry Co., Ltd.) Tetraglycidyl diaminodiphenylmethane 10 parts (Sumiepoxy ELM434, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) Nn-butoxyacrylamide 5 parts (Kasano Kosan Co., Ltd.) 3,3'- Diaminodiphenyl sulfone 27 parts (manufactured by Wakayama Seika Co., Ltd.) Polysulfone 5 parts ("Victrex" PES5003P, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) Using this resin composition, a cured resin ( Plate materials) and laminates, and measure their physical properties It was. The measurement results are shown in Table 1. Example 3 The following raw materials were kneaded using a kneader to obtain a resin composition.

Oxazolidone type epoxy resin 70 parts (XAC4152, trade name, reaction product of bisphenol A type epoxy resin and tolylene diisocyanate, manufactured by Asahi Ciba Co., Ltd.) Bisphenol F type epoxy resin 20 parts (Epiclon 830, registered trademark, Dainippon Japan) Ink Chemical Industry Co., Ltd.) Tetraglycidyl diaminodiphenylmethane 10 parts (Sumiepoxy ELM434, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) Salicylamide 5 parts (Yoshitomi Fine Chemical Co., Ltd.) 3,3'-diaminodiphenylsulfone 23 Part (manufactured by Wakayama Seika Co., Ltd.) Polysulfone 5 parts (“Victrex” PES5003P, registered trademark, manufactured by Mitsui Chemicals, Inc.) Using this resin composition, according to the method described above, a cured resin (plate material), laminated Plates were made and their physical properties were measured The measurement results are shown in Table 1. Comparative Example 1 The following raw materials were kneaded using a kneader to obtain a resin composition.

Oxazolidone type epoxy resin 70 parts (XAC4152, trade name, reaction product of bisphenol A type epoxy resin and tolylene diisocyanate, manufactured by Asahi Ciba Co., Ltd.) Bisphenol F type epoxy resin 20 parts (Epiclon 830, registered trademark, Dainippon Japan) Ink Chemical Industry Co., Ltd.) Tetraglycidyldiaminodiphenylmethane 10 parts (Sumiepoxy ELM434, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) 3,3'-Diaminodiphenylsulfone 25 parts (Wakayama Seika Co., Ltd.) Polysulfone 5 Part (“Victrex” PES5003P, registered trademark, manufactured by Mitsui Chemicals, Inc.) Using this resin composition, a cured resin (plate material) and a laminate were prepared according to the method described above, and their physical properties were measured. The measurement results are shown in Table 1. Example 4 The following raw materials were kneaded using a kneader to obtain a resin composition.

Oxazolidone type epoxy resin 70 parts (XAC4152, trade name, reaction product of bisphenol A type epoxy resin and tolylene diisocyanate, manufactured by Asahi Ciba Co., Ltd.) Bisphenol F type epoxy resin 20 parts (Epiclon 830, registered trademark, Dainippon Japan) Ink Chemical Industry Co., Ltd.) Tetraglycidyl diaminodiphenylmethane 10 parts (Sumiepoxy ELM434, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) N, N-dimethylacrylamide 5 parts (Kojin Co., Ltd.) 4,4'- 28 parts of diaminodiphenyl sulfone (Sumicure S, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) 5 parts of polysulfone ("Victrex" PES5003P, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) Using this resin composition, , Resin cured product (plate material), laminated board, It was measured for these properties. The measurement results are shown in Table 2. (Example 5) The following raw materials were kneaded using a kneader to obtain a resin composition.

Oxazolidone type epoxy resin 70 parts (XAC4152, trade name, reaction product of bisphenol A type epoxy resin and tolylene diisocyanate, manufactured by Asahi Ciba Co., Ltd.) Bisphenol F type epoxy resin 20 parts (Epiclon 830, registered trademark, Dainippon Japan) Ink Chemical Industry Co., Ltd.) Tetraglycidyldiaminodiphenylmethane 10 parts (Sumiepoxy ELM434, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) N, N-dimethylacrylamide 7 parts (Kojin Co., Ltd.) 4,4'- 29 parts of diaminodiphenyl sulfone (Sumicure S, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) 5 parts of polysulfone (“Victrex” PES5003P, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) Using this resin composition, , Resin cured product (plate material), laminated board, It was measured for these properties. The measurement results are shown in Table 2. Comparative Example 2 The following materials were kneaded using a kneader to obtain a resin composition.

Oxazolidone type epoxy resin 70 parts (XAC4152, trade name, reaction product of bisphenol A type epoxy resin and tolylene diisocyanate, manufactured by Asahi Ciba Co., Ltd.) Bisphenol F type epoxy resin 20 parts (Epiclon 830, registered trademark, Dainippon Japan) Ink Chemical Industry Co., Ltd.) Tetraglycidyldiaminodiphenylmethane 10 parts (Sumiepoxy ELM434, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) 4,4'-diaminodiphenylsulfone 25 parts (Sumicure S, registered trademark, Sumitomo Chemical Co., Ltd.) )) Polysulfone 5 parts (“Victrex” PES5003P, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) Using this resin composition, according to the method described above, a resin cured product (plate material) and a laminated board are prepared, Physical properties were measured. The measurement results are shown in Table 2. Example 6 The following materials were kneaded using a kneader to obtain a resin composition.

Oxazolidone type epoxy resin 70 parts (XAC4152, trade name, reaction product of bisphenol A type epoxy resin with tolylene diisocyanate, manufactured by Asahi Ciba Co., Ltd.) Bisphenol F type epoxy resin 20 parts (Epiclon 830, registered trademark, Dainippon Japan) Ink Chemical Industry Co., Ltd.) Tetraglycidyldiaminodiphenylmethane 10 parts (Sumiepoxy ELM434, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) N, N-dimethylacrylamide 5 parts (Kojin Co., Ltd.) Trimethylene bis (p -Aminobenzoate) 36 parts (CUA-4, trade name, manufactured by Ihara Chemical Co., Ltd.) 5 parts of polysulfone ("Victrex" PES5003P, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) Using this resin composition, According to the method, cured resin (plate material), laminated board To prepare, to determine their physical properties. The measurement results are shown in Table 2. Comparative Example 3 The following materials were kneaded using a kneader to obtain a resin composition.

Oxazolidone type epoxy resin 70 parts (XAC4152, trade name, reaction product of bisphenol A type epoxy resin and tolylene diisocyanate, manufactured by Asahi Ciba Co., Ltd.) Bisphenol F type epoxy resin 20 parts (Epiclon 830, registered trademark, Dainippon Japan) Ink Chemical Industry Co., Ltd.) Tetraglycidyl diaminodiphenylmethane 10 parts (Sumiepoxy ELM434, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) Trimethylene bis (p-aminobenzoate) 32 parts (CUA-4, trade name, Ihara Chemical Co., Ltd.) 5 parts of polysulfone (“Victrex” PES5003P, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) Using this resin composition, according to the method described above, a resin cured product (plate material) and a laminate were prepared. Their physical properties were measured. The measurement results are shown in Table 2. (Example 7) The following materials were kneaded using a kneader to obtain a resin composition.

Biphenyl type epoxy resin 60 parts (Epicoat YX4000H, registered trademark, diglycidyl ether of 4,4-dihydroxy-3,3,5,5-tetramethylbiphenyl) Bisphenol F type epoxy resin 30 parts (Epiclon 830, registered Trademark, manufactured by Dainippon Ink and Chemicals, Inc.) Tetraglycidyl diaminodiphenylmethane 10 parts (Sumiepoxy ELM434, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) N, N-dimethylacrylamide 5 parts (manufactured by Kojin) 3 38 parts of 3'-diaminodiphenyl sulfone (manufactured by Wakayama Seika Co., Ltd.) 5 parts of polysulfone (“Victrex” PES5003P, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) Using this resin composition, A resin cured product (plate material) and a laminate were prepared, and their physical properties were measured. Table 3 shows the measurement results. Comparative Example 4 The following materials were kneaded using a kneader to obtain a resin composition.

Biphenyl type epoxy resin 60 parts (Epicoat YX4000H, registered trademark, diglycidyl ether of 4,4-dihydroxy-3,3,5,5-tetramethylbiphenyl) Bisphenol F type epoxy resin 30 parts (Epiclon 830, registered Trademark, manufactured by Dainippon Ink and Chemicals, Inc.) Tetraglycidyl diaminodiphenylmethane 10 parts (Sumiepoxy ELM434, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) N, N-dimethylacrylamide 5 parts (manufactured by Kojin) 3 , 3'-diaminodiphenyl sulfone 35 parts (Wakayama Seika Co., Ltd.) Polysulfone 5 parts ("Victrex" PES5003P, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) Using this resin composition, A resin cured product (plate material) and a laminate were prepared, and their physical properties were measured. Table 3 shows the measurement results. Example 8 The following materials were kneaded using a kneader to obtain a resin composition.

35 parts of biphenyl type epoxy resin (Epicoat YX4000H, registered trademark, diglycidyl ether of 4,4-dihydroxy-3,3,5,5-tetramethylbiphenyl) 35 parts of tetrabromobisphenol A type epoxy resin (Epiclon 152) (Registered trademark, manufactured by Dainippon Ink and Chemicals, Inc.) Bisphenol F type epoxy resin 20 parts (Epiclon 830, registered trademark, manufactured by Dainippon Ink and Chemicals, Inc.) Tetraglycidyl diaminodiphenylmethane 10 parts (Sumiepoxy ELM434, registered trademark) 5 parts of N, N-dimethylacrylamide (produced by Kojin Co., Ltd.) 33 parts of 3,3'-diaminodiphenylsulfone (produced by Wakayama Seika Co., Ltd.) 5 parts of polysulfone (“Victrex "PES5003P, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) Using this resin composition, a cured resin (plate material) and a laminated board were prepared according to the above-described method, and the physical properties thereof were measured. Table 3 shows the measurement results. Comparative Example 5 The following materials were kneaded using a kneader to obtain a resin composition.

35 parts of biphenyl type epoxy resin (Epicoat YX4000H, registered trademark, diglycidyl ether of 4,4-dihydroxy-3,3,5,5-tetramethylbiphenyl) 35 parts of tetrabromobisphenol A type epoxy resin (Epiclon 152) (Registered trademark, manufactured by Dainippon Ink and Chemicals, Inc.) Bisphenol F type epoxy resin 20 parts (Epiclon 830, registered trademark, manufactured by Dainippon Ink and Chemicals, Inc.) Tetraglycidyl diaminodiphenylmethane 10 parts (Sumiepoxy ELM434, registered trademark) 29 parts of 3,3'-diaminodiphenyl sulfone (manufactured by Wakayama Seika Co., Ltd.) 5 parts of polysulfone (“Victrex” PES5003P, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) This resin composition Using the product, cure the resin according to the method described above. A product (plate material) and a laminate were prepared, and their physical properties were measured. Table 3 shows the measurement results. Example 9 The following raw materials were kneaded using a kneader to obtain a resin composition.

Bisphenol S-type epoxy resin 70 parts (Epiclon EXA1514, registered trademark, manufactured by Dainippon Ink and Chemicals, Inc.) Bisphenol F-type epoxy resin 20 parts (Epiclon 830, registered trademark, manufactured by Dainippon Ink and Chemicals, Inc.) 10 parts of tetraglycidyldiaminodiphenylmethane (Sumiepoxy ELM434, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) 5 parts of N, N-dimethylacrylamide (manufactured by Kojin Co., Ltd.) 29 parts of 3,3'-diaminodiphenylsulfone (Wakayama) 5 parts of polysulfone ("Victrex" PES5003P, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) Using this resin composition, a resin cured product (plate material) and a laminated board are produced according to the method described above. And their physical properties were measured. The measurement results are shown in Table 4. Comparative Example 6 The following raw materials were kneaded using a kneader to obtain a resin composition.

Bisphenol S-type epoxy resin 70 parts (Epiclon EXA1514, registered trademark, manufactured by Dainippon Ink and Chemicals, Inc.) Bisphenol F-type epoxy resin 20 parts (Epiclon 830, registered trademark, manufactured by Dainippon Ink and Chemicals, Inc.) 10 parts of tetraglycidyldiaminodiphenylmethane (Sumiepoxy ELM434, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) 26 parts of 3,3′-diaminodiphenylsulfone (manufactured by Wakayama Seika Co., Ltd.) 5 parts of polysulfone (“Victrex” PES5003P, (Registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) Using this resin composition, a cured resin (plate material) and a laminated board were prepared according to the method described above, and the physical properties thereof were measured. The measurement results are shown in Table 4. Example 10 The following materials were kneaded using a kneader to obtain a resin composition.

Bisphenol S-type epoxy resin 35 parts (Epiclon EXA1514, registered trademark, manufactured by Dainippon Ink and Chemicals, Inc.) Biphenyl-type epoxy resin 35 parts (Epicoat YX4000H, registered trademark, 4,4-dihydroxy-3,3,3 Diglycidyl ether of 5,5-tetramethylbiphenyl) Bisphenol F type epoxy resin 20 parts (Epiclon 830, registered trademark, manufactured by Dainippon Ink & Chemicals, Inc.) Tetraglycidyl diaminodiphenylmethane 10 parts (Sumiepoxy ELM434, registered trademark, Sumitomo 5 parts of N, N-dimethylacrylamide (produced by Kojin Co., Ltd.) 33 parts of 3,3'-diaminodiphenylsulfone (produced by Wakayama Seika Co., Ltd.) 5 parts of polysulfone (“Victrex” PES5003P (Registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) Using the resin composition, a cured resin (plate material) and a laminate were prepared according to the above-described method, and the physical properties thereof were measured. The measurement results are shown in Table 4. Comparative Example 7 The following materials were kneaded using a kneader to obtain a resin composition.

Bisphenol S-type epoxy resin 35 parts (Epiclon EXA1514, registered trademark, manufactured by Dainippon Ink and Chemicals, Inc.) Biphenyl-type epoxy resin 35 parts (Epicoat YX4000H, registered trademark, 4,4-dihydroxy-3,3,3 Diglycidyl ether of 5,5-tetramethylbiphenyl) Bisphenol F type epoxy resin 20 parts (Epiclon 830, registered trademark, manufactured by Dainippon Ink & Chemicals, Inc.) Tetraglycidyl diaminodiphenylmethane 10 parts (Sumiepoxy ELM434, registered trademark, Sumitomo 33 parts of 3,3′-diaminodiphenylsulfone (manufactured by Wakayama Seika Co., Ltd.) 5 parts of polysulfone (“Victrex” PES5003P, registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) In accordance with the method described above, the cured resin ( Plate material) and a laminated plate, and their physical properties were measured. The measurement results are shown in Table 4.

[0163]

[Table 1]

[0164]

[Table 2]

[0165]

[Table 3]

[0166]

[Table 4]

[0167]

According to the present invention, a resin composition having excellent adhesion between the reinforcing fibers and the matrix resin, and excellent flexural modulus, tensile elongation and heat resistance of the matrix resin can be obtained.
From this resin composition and a reinforcing fiber represented by a carbon fiber, a fiber-reinforced composite material excellent in various strength properties can be stably and inexpensively manufactured even under high temperature and high humidity.

The fiber-reinforced composite material according to the present invention has excellent compressive strength, particularly, the compressive strength of a perforated plate. Also, it has high compressive strength of a perforated plate material even under high temperature and high humidity conditions. This effect is remarkable when the matrix resin has a high flexural modulus. This is presumed to be because a matrix resin having a high flexural modulus has an effect of preventing Euler buckling of the reinforcing fibers.

The fiber reinforced composite material according to the present invention has excellent impact resistance represented by compressive strength after impact.

The fiber reinforced composite material according to the present invention has excellent 90 ° tensile strength, 90 ° bending strength, torsional strength, crushing strength, in-plane shear strength, and mode II interlayer toughness measured by the End Notched Flexure method. Become. This is remarkable when the tensile elongation of the matrix resin is high. It is presumed that this is because a matrix resin having a high tensile elongation has the effect of preventing the propagation of microcracks due to local fiber breakage and the prevention of separation between the reinforcing fibers and the matrix resin.

In the aerospace application, the fiber-reinforced composite material according to the present invention is used for primary structural materials of aircraft such as wings, tail fins, floor beams, etc., and for secondary structural materials such as flaps, ailerons, cowls, fairings, and interior materials. It is suitably used for rocket motor cases and structural materials for artificial satellites.
In general industrial applications, structural materials for vehicles such as automobiles, ships, and railway vehicles, drive shafts, leaf springs, windmill blades, pressure vessels, flywheels, papermaking rollers,
Civil engineering for roofing materials, cables, reinforcing bars, repair reinforcement materials, etc.
It is suitably used for building materials. Further, in sports applications, it is suitably used for rackets such as golf shafts, fishing rods, tennis, badminton, and squash, for sticks such as hockey, and for ski poles.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of a polymer network.

[Explanation of symbols]

1: a functional group capable of reacting with an epoxy resin or an aromatic polyamine 2: a partial structure selected from formulas (1) to (4) 3: a polymer network structure

Claims (7)

[Claims] 1. An epoxy resin composition comprising the following components [A] and [B]. [A] Aromatic polyamine [B] One molecule having at least one partial structure selected from the following formulas (1) to (4) in the molecule and capable of reacting with an epoxy resin or an aromatic polyamine Compound having Embedded image Embedded image Embedded image 2. The epoxy resin composition according to claim 1, wherein the amount of the component [B] is 0.5 to 30 parts by weight based on 100 parts by weight of the epoxy resin. 3. The functional group capable of reacting with an epoxy resin or an aromatic polyamine in the component [B] is a carboxyl group, a phenolic hydroxyl group, an amino group, a secondary amine structure, a mercapto group, an epoxy group, or a carbonyl group. The epoxy resin composition according to claim 1, which is at least one member selected from the group consisting of a double bond conjugated with the above. 4. The cured product has a glass transition temperature of 160 to
The epoxy resin composition according to any one of claims 1 to 3, which is at 250C. 5. The cured product has a tensile elongation of 8% or more and a flexural modulus of 3.2 GPa or more.
The epoxy resin composition according to any one of items 1 to 4, 6. A prepreg obtained by impregnating reinforcing fibers with the epoxy resin composition according to any one of claims 1 to 5. 7. A fiber-reinforced composite material comprising a reinforcing fiber and a cured product of the epoxy resin composition according to claim 1.