JP2003020410A - Resin composition for fiber-reinforced composite material and fiber-reinforced composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide both a resin composition for a fiber-reinforced composite material having excellent ignition resistance, flame retardance and moldability and the fiber-reinforced composite material. SOLUTION: This resin composition for the fiber-reinforced composite material comprises a thermosetting resin and has a processible viscosity within the temperature range of 25-90 deg.C and <=400 kW/m<2> maximum exothermic rate of a cured product obtained by curing the resin composition during combustion. The fiber-reinforced composite material comprises the cured product of the resin composition and reinforcing fibers.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for a fiber-reinforced composite material having excellent flame retardancy and a fiber-reinforced composite material. More specifically, structural materials for aircraft,
Starting with structural materials for railway vehicles, golf shafts,
The present invention relates to a resin composition for fiber-reinforced composite material and a fiber-reinforced composite material, which can be suitably applied to sports applications such as fishing rods and other general industrial applications.

[0002]

2. Description of the Related Art In the industry, there is a demand for lighter, tougher and more heat-resistant composite materials that can substitute for the currently used composite materials. For example, much research has been done in the aerospace industry on the use of structural composite materials to replace metals. Structural composite material mainly composed of thermoplastic or thermosetting resin and glass or carbon fiber has a specific strength,
Since it is excellent in mechanical strength such as specific elastic modulus, it has been widely used from the past to the present in sports applications such as golf shafts and fishing rods, structural materials for aircraft, etc., and good results have been obtained.

A thermosetting resin having excellent fluidity and heat resistance is often used as a resin constituting such a composite material. The thermosetting resin has excellent adhesiveness to reinforcing fibers and moldability. It is required to exhibit excellent mechanical strength and to exhibit high mechanical strength even in a high temperature and wet environment. In order to develop a high degree of mechanical strength, a resin having a high elastic modulus is desired because it depends not only on the carbon fiber but also on the elastic modulus of the resin. Therefore, as the thermosetting resin, a phenol resin, a melamine resin, a bismaleimide resin, an unsaturated polyester resin, a cyanate ester resin, an epoxy resin, a benzoxazine resin or the like is used depending on the application.

In many applications represented by railway vehicle structures, materials having higher heat resistance and flame retardancy than those used so far are required. In particular, it is important not to ignite the railway vehicle structure first, and in Japan, there is a notice on measures against fire accidents in trains (May 1969).
On March 15, Tekkoun No. 81), the criteria for determining the ignition resistance are set, and the ignition resistance of the material is required.

As a method for improving the flame retardancy of the thermosetting resin, a method of incorporating a flame retardant is generally used. The most common flame retardant for thermosetting resins is a halogen compound such as a bromine compound, which has a high flame retardant effect. However, it is well known that a resin composition containing a halogen compound has a high possibility of generating a toxic gas such as dioxin to the human body during combustion. From the viewpoint of preventing secondary disasters such as delay in escape due to smoke and toxic gas generated when materials burn, and in recent years, due to safety to the human body and impact on the environment, dioxin-free and halogen-free orientation has become stronger. However, it has become necessary to improve flame retardancy without containing halogen compounds.

As a method for improving flame retardancy without containing a halogen compound, JP-A No. 11-147965 discloses that a metal oxide is mixed with an epoxy resin containing no halogen compound to improve the flame retardancy. Although a method has been proposed, in order to obtain sufficient flame retardancy, it is necessary to add a large amount of metal oxide, which increases the viscosity of the resin. If resin viscosity is high, resin transfer
When molding a fiber-reinforced composite material using a molding method (hereinafter referred to as RTM method) or the like, the resin does not sufficiently impregnate the reinforcing fiber, defects such as voids occur, and a molded product with excellent quality cannot be obtained. Such a problem may occur.

[0007]

SUMMARY OF THE INVENTION In view of such background of the prior art, the present invention provides a resin composition for fiber reinforced composite material excellent in ignition resistance, flame retardancy and moldability, and fiber reinforced using the same. The purpose is to provide a composite material.

[0008]

The present invention has the following constitution in order to solve the above problems. That is, a resin composition comprising a thermosetting resin, having a processable viscosity in the temperature range of 25 to 90 ° C., and having a maximum heat release rate at the time of combustion of a cured product obtained by curing the resin composition. Of 400 kW / m ² or less is a resin composition for a fiber-reinforced composite material.

Further, the present invention has the following configuration. That is, it is a fiber-reinforced composite material comprising a cured product of the resin composition for a fiber-reinforced composite material and reinforcing fibers.

[0010]

DISCLOSURE OF THE INVENTION In view of the above problems, the present inventors have made earnest studies, and as a result, have found that a resin composition having a specific function can solve all of these problems at once. . That is, the resin composition has a processable viscosity at any temperature of 25 to 90 ° C., and a cured product obtained by curing the resin composition has a maximum heat generation rate of 400 kW / m ² upon combustion. It has been clarified that the following resin composition can provide a fiber-reinforced composite material having excellent ignition resistance and flame retardancy.

The resin composition for a fiber-reinforced composite material of the present invention comprises a thermosetting resin. As the thermosetting resin, those having high resin elastic modulus, heat resistance and flame retardancy are preferable, and for example, phenol resin, cyanate ester resin, epoxy resin, benzoxazine resin and the like are preferably used.

Of these, the phenol resin is a reaction product obtained by a condensation reaction of phenols and formaldehyde, and examples thereof include a resol type phenol resin.
Of these, water-based resol-type phenolic resins are preferably used from the viewpoint of workability and work environment. The phenol resin is preferably used in combination with a curing agent in order to improve the curability. As the curing agent for the phenol resin, aromatic sulfonic acids such as toluenesulfonic acid, phenolsulfonic acid and xylenesulfonic acid, phosphoric acid esters such as ethylene glycol phosphate, phosphoric acid and organic acids are preferably used.

The cyanate ester resin which can be preferably used in the present invention is a compound represented by the formula (I).

[0014]

[Chemical 1]

(In the formula, n is an integer of 1 or more, and A is an n-valent organic group.) Specific examples of the cyanate ester resin represented by the structural formula (I) are 1,3- or 1, 4-dicyanate benzene, 4,4′-dicyanate biphenyl, ortho-substituted dicyanate ester represented by the following structural formula (II),

[0016]

[Chemical 2]

(In the above formula, the R _{1 to} R ₄ groups represent a hydrogen atom or a methyl group and may be the same or different, and X is a divalent group, preferably having 1 to 4 carbon atoms. An alkylene group, oxygen (-O-), or divalent sulfur (-S-), a sulfonyl group (-SO2-), or a carbonyl group (-CO-) is represented.) As represented by the following structural formula (III) Polyphenylene oxide cyanate ester,

[0018]

[Chemical 3]

(Where, h is an integer satisfying h ≧ 0, i
Is an integer satisfying i ≧ 1, R _{5 to} R ₁₂ groups represent a hydrogen atom or a methyl group and may be the same or different, and X is a divalent group, preferably having 1 to 4 carbon atoms. It represents an alkylene group, oxygen (-O-), divalent sulfur (-S-), sulfonyl group (-SO2-), or carbonyl group (-CO-). ) A tricyanate ester represented by the following structural formula (IV):

[0020]

[Chemical 4]

(In the above formula, R _{13 to} R ₁₇ groups represent a hydrogen atom or a methyl group and may be the same or different from each other.) Polycyanate ester represented by the following structural formula (V),

[0022]

[Chemical 5]

(In the above formula, k is an integer of 1 or more, R _{18 to} R
Group ₂₀ represents a hydrogen atom or a methyl group, which may be the same or different from each other, X is a divalent group, preferably an alkylene group having 1 to 4 carbon atoms, oxygen (-O
-), or divalent sulfur (-S-), a sulfonyl group (-SO ₂ -), a carbonyl group (-CO-). )
Is preferably used.

Of these cyanate ester resins, bis (4-cyanatephenyl) methane, bis (4-cyanatephenyl) ethane and 2,2-bis (4-cyanatephenyl) propane are preferred from the viewpoint of moldability and heat resistance. Bis (4-cyanatephenyl) can be used because of its low viscosity and excellent moldability.
Ethane is more preferably used.

The cyanate ester resin may be composed of only a monomer, or may be a resin in which several molecules are polymerized into an oligomer state.

A curing agent can be added to the cyanate ester resin in order to improve the curability.
As the curing agent for cyanate ester resin, a metal coordination type curing agent or an active hydrogen type curing agent is preferably used.

Examples of the metal coordination type curing agent to be added to the cyanate ester resin include copper acetylacetonate, zinc octylate, tin octylate, zinc naphthenate,
It is possible to use cobalt naphthenate, tin stearate, zinc stearate and chelates of iron, cobalt, zinc, copper, manganese and titanium with a bidentate ligand such as catechol, and to improve curability and moldability. From the viewpoint, copper acetylacetonate can be preferably used. The amount of the metal coordination type curing agent to be blended is preferably 0.001 to 10 parts by weight based on 100 parts by weight of the cyanate ester resin from the viewpoint of compatibility between curability and stability of the resin composition. , 0.01 to 3 parts by weight are more preferable.

As the active hydrogen type curing agent to be added to the cyanate ester resin, it is preferable to add phenols. Examples of the phenols include 1 to 10 carbon atoms having one phenolic hydroxyl group.
Alkylphenol having an alkyl group contained therein, bisphenol A having two phenolic hydroxyl groups, bisphenol F, bisphenol AD, bisphenol S, bisphenol Z, dihydroxybiphenyl, dihydroxynaphthalene, dihydroxybenzophenone, (phenylene diisopropylidene) bisphenol , And halogen-substituted or alkyl-substituted compounds thereof, and polyphenols having three or more phenolic hydroxyl groups are preferably used. Of these,
It is preferable to use a compound having two or more phenolic hydroxyl groups because the curability of the resin composition is more excellent. The blending amount of these phenols is preferably 0.01 to 30 parts by weight, and more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the cyanate ester resin.

As the benzoxazine resin which can be preferably used in the present invention, a compound having one or more structural units VI represented by the structural formula (VI) in the molecule can be used.

[0030]

[Chemical 6]

(In the formula, R ₂₁ is a chain alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group or a substituted phenyl group, and the aromatic ring has an oxygen atom. Hydrogen is bonded to at least one carbon atom of the ortho position and the para position of the bonded carbon atom.) Such a benzoxazine resin is an intramolecular compound from the viewpoint of further improving the moisture-heat resistance property of the obtained composite material. Next structural formula (VII)

[0032]

[Chemical 7]

A structural unit VII which does not have the structural unit VII represented by the following formula or which satisfies the following formula (1)
It is preferable that at least one of those having

X1 ≧ X2 (1) X1: the number of structural units VII represented by the following structural formula (VIII) present in the molecule X2: present by the following structural formula (VIII) present in the molecule Number of structural units VII that are not

[0035]

[Chemical 8]

(In the formula, R ₂₂ is a chain alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, or a substituted phenyl group.) In the present invention, a benzoxazine resin Is synthesized from a corresponding phenol, a primary amine and formaldehyde or a derivative thereof according to the method described in Japanese Patent No. 2595437 or Japanese Patent Publication No. 9-502452, according to the reaction route represented by the following reaction formula (2). can do.

[0037]

[Chemical 9]

(In the formula, R ₂₃ is a chain alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, or a substituted phenyl group.) In the present invention, a benzoxazine resin Examples of the compound include at least one selected from the group consisting of compounds represented by the following structural formula (IX).

[0039]

[Chemical 10]

The benzoxazine resin may be composed of only a monomer, or may be polymerized in a few molecules to be in an oligomer state.

The benzoxazine resin preferably contains a curing agent for the benzoxazine resin, a curing aid for curing the resin, and / or a curing catalyst. This allows
The handleability and curability of the resulting composite material intermediate are improved, and a fiber-reinforced composite material having excellent mechanical properties can be obtained. As the curing agent for the benzoxazine resin, an acid such as a phenol compound or a carboxylic acid, or an amine can be preferably used.

The epoxy resin which can be preferably used in the present invention is a resin having an average of two or more epoxy groups per molecule, and particularly amines, phenols and compounds having a carbon-carbon double bond are precursors. The epoxy resin of is preferably used.

Specifically, various isomers of tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, and triglycidylaminocresol as glycidylamine type epoxy resins using amines as precursors. The body.

Tetraglycidylaminodiphenylmethane is preferable as a resin for composite materials as aircraft structural materials because it has excellent heat resistance.

As the epoxy resin containing phenol as a precursor, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin or other bisphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, etc. Novolak type epoxy resin and resorcinol type epoxy resin. Examples of the epoxy resin containing a compound having a carbon-carbon double bond as a precursor pair include alicyclic epoxy resins and the like. Further, a phosphorus-containing epoxy resin containing a phosphorus atom in these epoxy resins is also used. Further, these epoxy resins may be used alone, may be appropriately mixed and used, and may contain a monoepoxy compound. A combination of a glycidyl amine type epoxy resin and a glycidyl ether type epoxy resin is preferable because it has both heat resistance, water resistance and workability.

These epoxy resins are preferably used in combination with a curing agent. As a curing agent used in these epoxy resin compositions, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine,
Such as dimer acid ester of aromatic amine having active hydrogen such as m-xylylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, bis (aminomethyl) norbornane, bis (4-aminocyclohexyl) methane, polyethyleneimine Aliphatic amines having active hydrogen, epoxy compounds, acrylonitrile, phenol and formaldehyde, modified amines obtained by reacting these active hydrogen amines with compounds such as thiourea, dimethylaniline, dimethylbenzylamine, 2,4, 6-tris (dimethylaminomethyl)
Tertiary amines having no active hydrogen such as phenol and 1-substituted imidazole, dicyandiamide, tetramethylguanidine, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride Such as carboxylic acid anhydrides, polycarboxylic acid hydrazides such as adipic hydrazide and naphthalene dicarboxylic acid hydrazide, polyphenol compounds such as novolac resins, polymercaptans such as esters of thioglycolic acid and polyols, boron trifluoride ethylamine complex Lewis acid complexes such as
Examples include aromatic sulfonium salts.

These hardening agents may be combined with a suitable hardening aid to enhance the hardening activity. A preferred example is dicyandiamide containing 3-phenyl-1,
1-dimethylurea, 3- (3,4-dichlorophenyl) -1,
1-dimethylurea (DCMU), 3- (3-chloro-4-
Examples of combining urea derivatives such as methylphenyl) -1,1-dimethylurea, 2,4-bis (3,3-dimethylureido) toluene as a curing aid, carboxylic acid anhydrides and novolac resins with tertiary amines. Examples of combining the above as a curing aid are given.

In the present invention, a thermoplastic resin may be included in the resin composition. In particular, a thermoplastic resin such as a nylon resin, a polyester resin, a polyetherketone resin, a polyphenylene sulfide resin, a polysulfone resin, a polyethersulfone resin, or a thermoplastic polyimide is preferably used. Of these, polyetherimide resins and polyethersulfone resins are more preferably used.

Further, in the present invention, a flame retardant may be blended with the resin. As the flame retardant, an organic flame retardant or an inorganic flame retardant can be used. Particularly, a flame retardant containing no halogen is preferably used.
As the organic flame retardant, red phosphorus, phosphoric acid ester, boric acid ester, boric anhydride, polymerizable phosphorus compound monomer and the like are preferably used. As the inorganic flame retardant, ammonium salt, metal hydroxide and the like are preferably used.

Among the phosphates which can be used in the present invention, specific examples of the phosphate having one phosphorus atom in the molecule include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate and tributoxyethyl phosphate. , An aliphatic phosphate such as octyldiphenyl phosphate, and an aromatic phosphate represented by the following structural formula (X).

[0051]

[Chemical 11]

(Wherein a, b and c are integers selected from 1 to 5, R _{24 to} R ₂₆ are hydrogen or a hydrocarbon group having 1 to 4 carbon atoms) of the phosphoric acid ester which can be used in the present invention. Among them, as a specific example of a phosphoric acid ester compound having two phosphorus atoms in a molecule represented by the following structural formula (XI), an aromatic phosphoric acid ester represented by the following structural formula (XII) is Can be mentioned.

[0053]

[Chemical 12]

[0054]

[Chemical 13]

(In the formula, B1 is represented by the following general formulas (XIII) to (X
R _{24 to} R _{26 each} are a divalent organic group represented by any one of V) to hydrogen or a hydrocarbon group having 1 to 4 carbon atoms.

[0056]

[Chemical 14]

[0057]

[Chemical 15]

[0058]

[Chemical 16]

In the formula, R _{36 to} R ₅₁ are a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms and may be the same or different. X represents an alkylene group having 1 to 4 carbon atoms. ) Among these phosphate ester compounds, the obtained cured product has a high resin elastic modulus, high flame retardancy, and good moldability. Therefore, triphenyl phosphate, tricresyl phosphate, trikisyl phosphate Silenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, resorcinol bisdiphenyl phosphate, bisphenol A bisdiphenyl phosphate and the like are preferably used.

As the boric acid ester which can be used in the present invention, those containing a higher proportion of boron are preferable, and specifically, polyborates such as viborate and boric anhydride are preferably used. These boric acid esters not only reduce the volatility of boron contained in the boron compound when the resin composition is exposed to fire and improve the flame retardancy, but also increase the boron-oxygen bond in the composition. Therefore, the degree of glass formation is increased, and by forming a glass film on the surface, a large flame retardancy is exerted.

The borate such as borate has a wide decomposition temperature distribution when heated. That is, they tend to decompose over a wide temperature range and at elevated temperatures. As a result, the glass forming action is improved, and by forming a glass film on the surface, great flame retardancy is imparted. Such decomposition temperature distribution can be easily determined by thermogravimetric analysis.

This is a butyl borate or boroborate having a very narrow decomposition distribution, indicating that it tends to decompose or volatilize substantially completely over a narrow temperature range, resulting in a reduced tendency to form borate gas. It is markedly different from the decomposition distribution of monoborate such as phenyl acid.

The boric acid ester is preferably 5 to 20% by weight, more preferably 5 to 20% by weight in the molecule.
The one containing 8% by weight of boron is preferable. A boron concentration of 5% by weight or more is preferable because it improves the glass forming action during heating and reduces the total amount of borate ester added to the resin composition.

Among these boric acid esters, boric acid trialkyl esters represented by the following structural formula (XVI) are preferably used.

[0065]

[Chemical 17]

(In the formula, R _{52 to} R ₅₄ are groups having 1 to 18, preferably 1 to 8 carbon atoms.) Among such boric acid esters, R _{52 to} R ₅₄ are 6 to 18 Those which are secondary or tertiary alkyl groups or aryl groups having carbon atoms of are preferably used. One such preferred borate ester is borester 5 (tri-n
Octyl boric acid, containing 2.7% by weight of boron).

Other preferred borate esters are those derived from diols and boric acid which tend to have high boron contents. A particularly preferred borate ester is a polyalkylenebiborate in which the alkylene group has 2 to 8 carbon atoms, such as borester 35, i.e. tri (1,3-).
Butanediol) biborate (containing 7.1% by weight boron), Borester 7, i.e. tri (2-methyl-2,4-pentanediol) biborate (containing 5.9% by weight boron). ), And Borester) 1
5, i.e. trioctylene glycol diborate (4.
It contains 76% by weight of boron).

A preferred boric anhydride is, for example, Borester 33, hexylene glycol boric anhydride (7.5
It contains boron by weight).

Polyvinyl alcohol borate ester is also preferably used as the borate ester.

The above-mentioned "BORESTER" is a trademark, and the boron ester compounds referred to in the present invention are
Commercially available from Rhodia.

These boric acid esters and boric anhydride are preferably blended in an amount of 0.1 to 30 parts by weight with respect to 100 parts by weight of the thermosetting resin. If the amount of boric acid ester or boric anhydride is less than 0.1 part by weight, the resulting cured product is not sufficiently flame-retardant, which is not preferable. Also, the compounding amount is 3
If it exceeds 0 part by weight, the heat resistance may be remarkably lowered, such as the glass transition temperature being lowered. From the viewpoint of achieving both flame retardancy and heat resistance of the resulting cured product, these boric acid esters and boric anhydride are 1 to 100 parts by weight of the thermosetting resin.
It is more preferable to add 20 parts by weight.

As the polymerizable phosphorus compound monomer which can be used in the present invention, polyphosphonate, allylphosphonate, polyphosphate, phosphonate type polyol and the like can be used.

Examples of ammonium salts usable in the present invention include ammonium borate, ammonium sulfamate, ammonium phosphate, ammonium molybdate, and ammonium polyphosphate.

The metal hydroxides usable in the present invention include aluminum hydroxide, magnesium hydroxide, tin hydroxide, zirconium hydroxide, dawsonite, calcium aluminate, barium metaborate, zinc borate, borax, Examples thereof include kaolin clay and calcium carbonate.

Further, in the present invention, an elastomer may be used as another additive as long as flame retardancy is not impaired.

The resin composition for a fiber reinforced composite material of the present invention is characterized by having a processable viscosity at 25 ° C to 90 ° C. Here, the processable viscosity means a hand lay-up method, a filament winding method (hereinafter referred to as FW method), a pull-through method, R
In a method for producing a fiber-reinforced composite material such as a TM method and a resin film infusion method (hereinafter referred to as RFI method), it means a viscosity at which a reinforcing fiber can be impregnated with a resin composition, and preferably 1 mPa.・ S〜
It has a viscosity in the range of 1500 mPa · s.
If the processable viscosity of the resin composition is less than 1 mPa · s, a resin-impregnated portion may be generated in the obtained fiber-reinforced composite material, which is not preferable. Also, 150
When the viscosity exceeds 0 mPa · s, the reinforcing fiber may not be impregnated with the resin composition, which is not preferable. When the viscosity of the resin composition is high, the viscosity of the resin composition can be reduced by increasing the temperature at which the reinforcing fiber is impregnated with the resin composition, but in this case, while impregnating the reinforcing fiber with the resin composition, It is not preferable because it may be gelled or cured and molding may not be possible. Processable viscosity is 1m
More preferably, Pa · s to 1000 mPa · s,
More preferably, it is 10 mPa · s to 500 mPa · s.

It is preferable because hot water can be used as a heat source when the reinforcing fiber is impregnated with the resin composition of the present invention having the above-mentioned processable viscosity.

In the present invention, the maximum heat generation rate at the time of combustion of the cured product obtained by curing the resin composition is 400 kW / m ²
It must be: Maximum heat generation rate is 350k
W / m ² or less is preferable, smaller is more preferable, and 0 is more preferable, but 0 has not been realized yet. The maximum heat generation rate during combustion reflects the ease with which the fire spreads after ignition, and it can be said that the smaller the maximum heat generation rate, the higher the flame retardancy. The maximum heat release rate of the cured product obtained by curing the resin composition is 40
If it exceeds 0 kW / m ² , it may not be possible to obtain a fiber-reinforced composite material having sufficient ignition resistance and flame retardancy, which is not preferable.

In the present invention, the smoke concentration of the cured product obtained by curing the resin composition upon combustion is preferably 150 m ^-1 or less. Further, it is more preferably 120 m ^-1 or less. The smoke concentration at the time of combustion reflects the amount of smoke generated after ignition, and it can be said that the smaller the smoke concentration, the higher the flame retardancy. If the smoke concentration of the cured product obtained by curing the resin composition upon combustion exceeds 150 m ^-1 , it may not be possible to obtain a fiber-reinforced composite material having sufficient ignition resistance and flame retardancy, which is not preferable. .

A fiber-reinforced composite material can be obtained by blending a cured product obtained by curing the resin composition for a fiber-reinforced composite material of the present invention and a reinforcing fiber. At that time, as the reinforcing fiber,
Glass fibers, carbon fibers, aramid fibers, boron fibers, alumina fibers, nylon fibers, silicon carbide fibers and the like can be used. In order to obtain higher mechanical properties, glass fiber and carbon fiber are preferably used, and carbon fiber is more preferably used.

When carbon fiber is used as the reinforcing fiber, the tensile modulus of the carbon fiber is 200 to 700 G in order to achieve both impact resistance and rigidity of the obtained fiber reinforced composite material.
Pa is preferable. If it is less than 200 GPa, the specific strength of the obtained fiber reinforced composite material is lowered and the resulting weight is increased, which is not preferable. 700
If it exceeds GPa, the obtained fiber-reinforced composite material becomes brittle, which is not preferable. Among such carbon fibers,
It is preferable to use carbon fibers having a tensile elongation of 1.5% or more in a strand tensile test because a fiber-reinforced composite material having more excellent impact resistance can be obtained, and the tensile elongation is 1.7.
It is more preferable to use carbon fiber of at least%.

The tensile strength of the carbon fiber is preferably 3000 MPa or more, more preferably 4000 MPa or more, and further preferably 4500 MPa or more. If it is less than 3000 MPa, the tensile strength of the obtained composite material becomes insufficient, and it may be difficult to apply it to aircraft structural materials, railway vehicle structural materials, etc. that require high mechanical strength, which is not preferable. .

A plurality of reinforcing fibers can be used in combination as the reinforcing fibers.

A sizing agent may be attached to the reinforcing fibers, and the amount of the sizing agent attached is preferably 0.01% by weight to 5% by weight, and 0.1% by weight to
More preferably, it is 3% by weight. If the amount of the sizing agent is less than 0.1% by weight, the handleability is deteriorated, which is not preferable. Further, if the amount of the sizing agent to be attached exceeds 5% by weight, the ignitability and flame retardancy may be lowered, which is not preferable.

As the sizing agent to be attached to the reinforcing fiber, for example, those described in Japanese Patent No. 3003513 can be used. Of these, epoxy compounds such as bisphenol A type epoxy resin, urethane modified epoxy resin, polyethylene glycol diglycidyl ether, glycerol triglycidyl ether, acrylic acid adduct of bisphenol A type epoxy resin, methacrylic acid addition of bisphenol A type epoxy resin Compounds, compounds having unsaturated bonds such as unsaturated polyester, and polyethylene glycol, polypropylene glycol, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, polyvinyl formal, polytetramethylene adipate, butane ethylene oxide / polyethylene Oxide adducts and urethane compounds are preferably used.

The form and arrangement of the reinforcing fibers are not particularly limited and can be appropriately selected from woven fabrics, nonwoven fabrics, mats, knits, braids, unidirectional strands, rovings, chopped fabrics, etc., but they are at a higher level of lightness and durability. In order to obtain a fiber-reinforced composite material, the reinforcing fibers may be in the form of continuous fibers such as woven fabrics, unidirectional strands and rovings. Here, as the woven fabric, a conventionally known woven fabric can be applied. Further, as the woven structure, a unidirectional woven fabric using a reinforcing fiber as a warp yarn and a glass fiber or an organic fiber as a weft yarn for preventing misalignment, a plain weave, a twill weave, a entangled weave, and a satin weave can be used. It should be noted that the surface of the woven fabric is preferably a woven fabric made of carbon fiber, since the woven fabric is provided with aesthetics such as color and luster.

A preform can be applied as the form of the reinforcing fiber. Here, the preform usually means a laminate of woven fabrics made of long-fiber reinforcing fibers, or a product obtained by stitching and integrating them with a stitch thread, or a fiber structure such as a three-dimensional fabric or braid. .

The fiber-reinforced composite material obtained by blending the resin composition for a fiber-reinforced composite material of the present invention and the reinforcing fiber preferably has a fiber volume fraction of 1 with respect to the fiber-reinforced composite material.
It is preferably 0 to 85%, more preferably 30 to 70%. If it is less than 10%, the weight of the obtained composite material becomes excessively large, and the advantage of the fiber-reinforced composite material excellent in specific strength and specific elastic modulus may be impaired.
If it exceeds%, poor resin impregnation occurs, the resulting composite material is likely to have many voids, and the mechanical strength thereof may be greatly reduced, such being undesirable.

The fiber-reinforced composite material obtained by blending the cured product obtained by curing the resin composition for fiber-reinforced composite material of the present invention and the reinforcing fiber is the hand lay-up method, FW method, pull-through method, RTM method, It can be manufactured by a method such as the RFI method.

The hand layup method is a method in which a reinforcing fiber is impregnated with a resin and a predetermined number of layers are laminated to obtain an intermediate. The FW method is a method in which a fiber bundle in which a mandrel or the like is impregnated with a resin is wound in a predetermined direction to obtain an intermediate.
The plutotrusion method is a method in which a resin is immersed in reinforcing fibers and then impregnated in a mold to obtain an intermediate. The RTM method is
In this method, reinforcing fibers are arranged in advance in a mold, and then a resin is injected to obtain an intermediate. The RFI method is a method of arranging a preform in which a resin is attached to reinforcing fibers in advance.

Thus, the fiber-reinforced composite material can be obtained by heating and curing the intermediate body having a predetermined shape.

A fiber reinforced composite material comprising a cured product of the resin composition for a fiber reinforced composite material of the present invention and a reinforced fiber can be used in the form of a sheet, ribbon, cloth, tape or the like in which reinforced fibers are aligned in one direction. An intermediate obtained by impregnating an uncured fiber-reinforced composite material resin composition, after obtaining an intermediate for forming a composite material as a so-called prepreg, heating,
It can also be obtained by curing.

The prepreg is prepared by dissolving a resin in a solvent to lower the viscosity and impregnating it with a wet method, and by coating the resin on a release paper, aligning the reinforcing fibers on the release paper, and heating or melting the resin to roll or doctor blade. It can be manufactured by a hot-melt method (dry method) in which pressure impregnation is carried out with the like, and then the mixture is allowed to cool. The wet method can be suitably used for a prepreg made of a glass fiber woven fabric.

These manufacturing methods are appropriately used depending on the production amount, scale, shape, etc. of the target composite material.
For example, the RTM method is suitable for mass-producing a complex material having a relatively complicated shape in a short time.

Further, each of these production methods has a more preferable processable viscosity, for example, 10 to 1000 mPa · s is preferable in the RTM method and 10 to 500 mPa · s is preferable in the pultrusion method. The viscosity of the resin can be adjusted by blending additives and diluents and controlling the impregnation temperature.

For example, when manufacturing a fiber reinforced composite material by the RTM method, in order to ensure the impregnating property of the resin composition into the reinforcing fiber, the injection temperature of the molding die when the resin composition is injected is increased. Although it is advantageous to reduce the viscosity, if the injection temperature is too high, the curing reaction of the resin composition may progress during injection, resulting in thickening or gelation, and the cost of molding dies and heating equipment. Rises and economic efficiency deteriorates. From this viewpoint, the injection temperature is preferably 25 to 90 ° C, and more preferably 25 to 50 ° C. If the temperature is lower than 25 ° C, the viscosity of the resin composition is high, and it may be difficult to inject the resin composition into the molding die. If the temperature is higher than 90 ° C, the viscosity of the resin composition increases excessively. It is not preferable because gelation may progress over time and molding may become difficult.

[0097]

EXAMPLES The present invention will be described in more detail below with reference to examples. The evaluation methods and the like used in the examples were carried out by the following methods. (1) Measurement of physical properties of uncured resin A. Viscosity measurement The viscosity of the uncured resin composition at 25 ° C was measured.
For the viscometer, cone-plate type rotary viscometer TVE-30H
(Manufactured by Toki Sangyo Co., Ltd.) was used. 1 ° 3 for rotor
4'x R24 was used. (2) Measurement of physical properties of cured resin A. Measurement of heat generation rate The resin composition was poured into a mold and cured under a curing condition suitable for each resin in a hot air dryer to prepare a resin cured plate having a thickness of 3 mm. Next, a test piece having a width of 50 mm and a length of 50 mm was cut out and a corn calorimeter (manufactured by Toyo Seiki Seisakusho Co., Ltd., “Corn Calorimeter III”) was used in accordance with ISO-5660-1. B. Measurement of Smoke Density The resin composition was poured into a mold and cured under a curing condition suitable for each resin in a hot air dryer to prepare a resin cured plate having a thickness of 3 mm. Next, a test piece having a width of 50 mm and a length of 50 mm was cut out and subjected to ISO-5660-1 using a corn calorimeter (“Corn Calorimeter III” manufactured by Toyo Seiki Seisaku-sho, Ltd.). (3) Manufacturing method of fiber reinforced composite material Mold 300 mm in length, 300 mm in width, 1 m in height
m having a rectangular parallelepiped cavity, consisting of an upper mold and a lower mold, a resin injection port provided at the center of the upper mold, and resin injection ports at the four corners of the lower mold Was used.

The following were used as preforms. Tensile strength is 3530 MPa, tensile elastic modulus is 230
GPA, elongation 1.3%, density 1.96 g, carbon fiber having 3000 filaments with bisphenol A type epoxy resin attached as a 1.2% sizing agent, carbon fiber basis weight 198 g / m ² A plain weave carbon fiber woven fabric having a basis weight was prepared, which was cut in such a manner that each side was perpendicular or parallel to the reinforcing fiber, and five square layers each having a side of 280 mm were stacked and used.

This preform was set in a molding die and clamped, and then the resin composition was decompressed in vacuum under a reduced pressure and injected into the molding die.

This was cured under curing conditions suitable for each resin composition to obtain a fiber reinforced composite material. (4) Notification of fire accident countermeasures for combustion test trains (May 1, 1969)
5th Tetsu Un 81, hereinafter referred to as Tetsu No 81)
A combustion test was conducted. The thickness of the sample was 2 mm 2. The ignition test specified in Tetsuun 81 consists of the following contents.
The sample of B5 size was held at an angle of 45 ° and held vertically below the center of the lower surface of the sample. Place the fuel container on the cradle so that the center of the container is at 4 mm, and use ethyl alcohol 0
． Ignite with 5 cc and leave until the fuel is burned out. The flammability is determined during and after the alcohol is burned, and the ignition, flame, smoke, and flame are observed during burning, and after burning, afterflame, dust, carbonization, and deformation are examined. The observation result is, for example, "ignition" and "flame".
Yes, "Smoke" normal, "Fire" flame does not exceed the upper end of the test piece, "No residual flame", "No dust", "Carbonated" reaches the upper end of the test piece, "Deformation" reaches the edge ・If it is local penetration, the determination result is "flame retardant". Also, no "ignition", no "ignition", little "smoke", and "carbonization" 100
Discoloration of mm or less, “deformation” If the surface deformation is 100 mm or less, it is “noncombustible”. In addition, the iron luck 81
English book "Plastic flame retardancy-Low smoke emission and measures against harmful combustion gas" Nikkan Kogyo Shimbun (1978) and Nishizawa "Enlarged version of new polymer flame retardant-its science and practical technology" Taiseisha (1
992).

<Example 1> As a phenol resin, an aqueous resol type phenol resin (BRL manufactured by Showa Highpolymer Co., Ltd.) was used.
-240) 100 parts by weight, FRH-50 as a curing catalyst
A resin composition was obtained by uniformly mixing 10 parts by weight (manufactured by Showa Highpolymer Co., Ltd.). This resin composition was poured into a mold and dried in a hot air drier at 120 ° C. for 30 minutes, then 15 minutes.
Heat at 0 ° C for 50 minutes and then at 180 ° C for 2 hours, then add 1 more
The resin cured plate having a thickness of 3 mm was prepared by heating at 00 ° C. for 86 hours, and the heat generation rate and smoke density were measured. The measurement results are shown in Table 1. The viscosity of the uncured resin is 2 using the above resin composition.
The viscosity at 5 ° C was measured. The measurement results are shown in Table 1. Further, the production of the fiber-reinforced composite material using the above resin composition was performed as follows. Molding die has a length of 30
It has a rectangular parallelepiped cavity of 0 mm, width 300 mm, and height 1 mm. It consists of an upper mold and a lower mold. A resin injection port is provided in the center of the upper mold, and four corners of the lower mold. The one having a resin spout was used.

The preform has a tensile strength of 35.
30 MPa, tensile modulus of 230 GPa, elongation of 1.3
%, A density of 1.96 g, a number of 3000 filaments of bisphenol A type epoxy resin adhered as a 1.2% sizing agent to a plain weave carbon fiber fabric having a carbon fiber areal weight of 198 g / m ² Five square layers each having a side of 280 mm, which was prepared and cut so that each side thereof was perpendicular or parallel to the reinforcing fiber, were used.

This preform was set in a molding die and clamped, and then the above resin composition was decompressed in vacuum and injected into the molding die under vacuum decompression.

This was heated in a hot air dryer at 120 ° C. for 30 minutes, then at 150 ° C. for 50 minutes, then at 180 ° C. for 2 minutes.
It was heated for an hour and further heated at 100 ° C. for 86 hours to obtain a fiber reinforced composite material.

Using this fiber reinforced composite material, a combustion test was conducted according to the method described above. Maximum heat generation rate is 400
It has a flame retardancy of less than kW / m ² and a smoke density of less than 150 m ⁻¹ . Further, the viscosity of the resin composition at 25 ° C. showed a processable viscosity and the moldability was good. Furthermore, it was "non-combustible" in the specification of the combustion test according to Iron Transport No. 81.

Example 2 100 parts by weight of bis (4-cyanatephenyl) ethane (Arocy L-10 manufactured by Asahi Ciba Co., Ltd.) as a cyanate ester resin, and copper acetylacetonate (Tokyo Chemical Industry Co., Ltd. as an organometallic compound). )) 0.1 part by weight and bisphenol A (manufactured by Nacalai Tesque) as an active hydrogen type catalyst, and then stirred using a stirrer HM-500 manufactured by Keyence, and further, as a phosphoric acid ester, cresyl diphenyl phosphate (large). 20 parts by weight of Hachi Chemical Industry Co., Ltd. was added and stirred to obtain a resin composition. Using this resin composition, a resin cured product was produced according to the method described in Example 1 except for the curing temperature and the curing time. The curing temperature here was 180 ° C., and the curing time was 2 hours. The heat generation rate and smoke density were measured. The viscosity of the uncured resin is 25 using the above resin composition.
Viscosity at ° C was measured according to the method described in Example 1. The fiber-reinforced composite material using the above resin composition was produced according to the method described in Example 1 except for the curing temperature and the curing time. The curing temperature here is 180 ° C,
The curing time was 2 hours. Using this fiber-reinforced composite material, a combustion test was conducted according to the method described above. The measurement results are shown in Table 1. The maximum heat generation rate was less than 400 kW / m ² , and the smoke density was less than 150 m ^-1 , indicating high flame retardancy. Further, the viscosity of the resin composition at 25 ° C. showed a processable viscosity and the moldability was good. Furthermore, it was "non-combustible" in the specification of the combustion test according to Iron Transport No. 81. <Example 3> Bisphenol F-type glycidyl ether-type epoxy resin (Ep807, manufactured by Yuka Shell Co., Ltd.) 10
To 0 parts by weight, 49.6 parts by weight of diaminodiphenylmethane (manufactured by Wako Pure Chemical Industries, Ltd.) was melt-kneaded. To this, 30 parts by weight of cresyl diphenyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd.) as a phosphoric acid ester was added and stirred to obtain a resin composition. Using this resin composition, a resin cured product was produced according to the method described in Example 1 except for the curing temperature and the curing time. The curing temperature here was 180 ° C., and the curing time was 2 hours. The heat generation rate and smoke density were measured. The viscosity of the uncured resin is 70 using the above resin composition.
Viscosity at ° C was measured according to the method described in Example 1.

Further, the fiber-reinforced composite material using the above resin composition was produced in the same manner as in Example 1 except for the curing temperature and the curing time.
It was performed according to the method described in. The curing temperature here is 18
The curing time was 0 ° C. and the curing time was 2 hours. Using this fiber-reinforced composite material, a combustion test was conducted according to the method described above. The measurement results are shown in Table 1. Maximum heat generation rate is 400kW / m
^The flame retardancy was less than ² , and the smoke density was less than 150 m ^-1 , indicating high flame retardancy. The viscosity of the resin composition at 70 ° C. was a processable viscosity and the moldability was good.
Further, it was "non-combustible" in the standard of the combustion test according to Tetsuun 81. <Example 4> 228 was added to bisphenol A without using a solvent.
1 part by weight, 186 parts by weight of aniline, and 120 parts by weight of paraformaldehyde were placed in a flask, respectively, immersed in an oil bath and stirred by a mechanical stirrer at 110 to 120 ° C for 20 minutes to dissolve, and then at 130 to 140 ° C for 20 minutes. Then, the flask is cooled in an ice bath and the following structural formula (XVII)
A benzoxazine compound represented by

[0108]

[Chemical 18]

Next, 30 parts by weight of a bisphenol F type glycidyl ether type epoxy resin (Ep807, manufactured by Yuka Shell Co., Ltd.) was added to 70 parts by weight of this benzoxazine compound, and cresyl diphenyl phosphate (Dahachi Co., Ltd.) was used as a phosphoric ester. 23 parts by weight of Chemical Industry Co., Ltd. was added and stirred to obtain a resin composition. Using this resin composition, a resin cured product was produced according to the method described in Example 1 except for the curing temperature and the curing time. The curing temperature here is 20
The curing time was 0 ° C. and the curing time was 2 hours. The heat generation rate and smoke density were measured. The viscosity of the uncured resin was measured using the above resin composition at 70 ° C. according to the method described in Example 1.

Further, the production of the fiber reinforced composite material using the above resin composition was carried out in the same manner as in Example 1 except for the curing temperature and the curing time.
It was performed according to the method described in. The curing temperature here is 20
The curing time was 0 ° C. and the curing time was 2 hours. Using this fiber-reinforced composite material, a combustion test was conducted according to the method described above. The measurement results are shown in Table 1. Maximum heat generation rate is 400kW / m
^The flame retardancy was less than ² , and the smoke density was less than 150 m ^-1 , indicating high flame retardancy. Further, the viscosity of the resin composition at 70 ° C. showed a processable viscosity and the moldability was good.
Further, it was "non-combustible" in the standard of the combustion test according to Tetsuun 81. <Comparative Example 1> As a phenol resin, 80 parts by weight of an aqueous resol-type phenol resin (BRL-240 manufactured by Showa Highpolymer Co., Ltd.) and 20 parts by weight of polyethylene glycol (PEG 4000, manufactured by Wako Pure Chemical Industries, Ltd.) are KEYENCE. The mixture was uniformly mixed using a stirrer HM-500, and 10 parts by weight of FRH-50 (manufactured by Showa Highpolymer Co., Ltd.) as a curing catalyst was added and stirred to obtain a resin composition.
Using this resin composition, a resin cured product was prepared according to the method described in Example 1. The heat generation rate and smoke density were measured. The viscosity of the uncured resin was measured at 25 ° C. according to the method described in Example 1 using the above resin composition. The maximum heat generation rate is greater than 400 kW / m ² and the smoke density is also greater than 150 m ^−1.
The flame retardancy was lower than that of

The fiber-reinforced composite material using the above resin composition was prepared according to the method described in Example 1. Since the viscosity of the resin composition is high and molding is difficult, it was tried to raise the temperature of the resin composition to reduce the viscosity,
It was not possible to obtain a fiber-reinforced composite material because the resin gelled during molding. Moreover, subsequent measurements could not be performed. Comparative Example 2 Bis (4
-Cyanate phenyl) ethane (Aro manufactured by Asahi Chiba Co., Ltd.
Cy L-10) 100 parts by weight, and copper acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.) as an organometallic compound.
After mixing 1 part by weight, bisphenol A (manufactured by Nacalai Tesque) as an active hydrogen type catalyst was mixed and then stirred using a stirrer HM-500 manufactured by KEYENCE to obtain a resin composition. Using this resin composition, a resin cured product was produced according to the method described in Example 1 except for the curing temperature and the curing time. The curing temperature here was 180 ° C., and the curing time was 2 hours. The heat generation rate and smoke density were measured. The viscosity of the uncured resin was measured at 25 ° C. according to the method described in Example 1 using the above resin composition.

Further, the production of the fiber-reinforced composite material using the above resin composition was carried out in the same manner as in Example 1 except for the curing temperature and curing time.
It was performed according to the method described in. The curing temperature here is 18
The curing time was 0 ° C. and the curing time was 2 hours. Using this fiber-reinforced composite material, a combustion test was conducted according to the method described above. The measurement results are shown in Table 1. Maximum heat generation rate is 400kW / m
^The flame retardancy was lower than that of Examples 1 to 4, and the smoke density was higher than 150 m ^-1 . In addition, it was "extremely flame-retardant" in the standard of the combustion test according to Iron Transport No. 81. <Comparative Example 3> Bisphenol F glycidyl ether type epoxy resin (Ep807, manufactured by Yuka Shell Co., Ltd.) 10
49.6 parts by weight of diaminodiphenylmethane (manufactured by Wako Pure Chemical Industries, Ltd.) was melt-kneaded with 0 parts by weight to obtain a resin composition. Using this resin composition, a resin cured product was produced according to the method described in Example 1 except for the curing temperature and the curing time. The curing temperature here was 180 ° C., and the curing time was 2 hours. The heat generation rate and smoke density were measured. The viscosity of the uncured resin was measured using the above resin composition at 70 ° C. according to the method described in Example 1.

Further, the production of the fiber reinforced composite material using the above resin composition was conducted in the same manner as in Example 1 except for the curing temperature and the curing time.
It was performed according to the method described in. The curing temperature here is 18
The curing time was 0 ° C. and the curing time was 2 hours. Using this fiber-reinforced composite material, a combustion test was conducted according to the method described above. The measurement results are shown in Table 1. Maximum heat generation rate is 400kW / m
² and the smoke density were considerably higher than 150 m ^-1 , and the flame retardance was lower than that of Examples 1 to 4. Further, it was "flame retardant" in the standard of the combustion test according to Tetsuun 81. <Comparative Example 4> Bisphenol A was added to 228 without using a solvent.
Parts by weight, 186 parts by weight of aniline and 120 parts by weight of paraformaldehyde were placed in a flask, respectively, immersed in an oil bath and stirred by a mechanical stirrer at 110 to 120 ° C for 20 minutes to dissolve, and then at 130 to 140 ° C for 20 minutes. Then, the flask is cooled in an ice bath and the following structural formula (XVII)
A benzoxazine compound represented by

[0114]

[Chemical 19]

Next, 30 parts by weight of a bisphenol F glycidyl ether type epoxy resin (Ep807, manufactured by Yuka Shell Co., Ltd.) was added to 70 parts by weight of this benzoxazine compound, and the mixture was stirred to obtain a resin composition. Using this resin composition, a resin cured product was produced according to the method described in Example 1 except for the curing temperature and the curing time. The curing temperature here was 200 ° C., and the curing time was 2 hours. The heat generation rate and smoke density were measured. The viscosity of the uncured resin was measured using the above resin composition at 70 ° C. according to the method described in Example 1.

Further, the production of the fiber-reinforced composite material using the above resin composition was carried out in the same manner as in Example 1 except for the curing temperature and curing time.
It was performed according to the method described in. The curing temperature here is 20
The curing time was 0 ° C. and the curing time was 2 hours. Using this fiber-reinforced composite material, a combustion test was conducted according to the method described above. The measurement results are shown in Table 1. Maximum heat generation rate is 400kW / m
^The flame retardancy was lower than that of Examples 1 to 4, and the smoke density was higher than 150 m ^-1 . In addition, it was "extremely flame-retardant" in the standard of the combustion test according to Iron Transport No. 81.
The above measurement results are shown in Table 1.

[0117]

[Table 1]

[0118]

According to the present invention, it is possible to provide a resin composition for a fiber-reinforced composite material and a fiber-reinforced composite material which are excellent in ignition resistance and flame retardancy.

The fiber-reinforced composite material obtained by blending the cured product of the resin composition for fiber-reinforced composite material of the present invention and the reinforcing fiber is required to have a high degree of moisture-heat resistance, specific strength and specific elastic modulus. It can be used particularly suitably as an application of structural materials for aircraft, structural materials for satellites, structural materials for railway vehicles, and sports equipment.

Continued front page    F term (reference) 4F072 AA04 AA07 AB10 AB34 AC05                       AD11 AD13 AD23 AE07 AF01                       AF02 AF06 AF11 AF17 AK05                       AL01 AL02 AL05                 4J002 AA021 CC031 CD001 CM001                       DA016 DA057 DE077 DE097                       DE147 DE237 DG007 DH047                       DH057 DJ037 DK007 EW047                       EY017 FA046 FD016 FD137                       GC00 GN00

Claims (9)

[Claims] 1. A resin composition comprising a thermosetting resin, which has a processable viscosity in the temperature range of 25 to 90 ° C. and which is obtained by curing the resin composition during combustion. A resin composition for a fiber-reinforced composite material, which has a maximum heat generation rate of 400 kW / m ² or less. 2. The resin composition for a fiber-reinforced composite material according to claim 1, wherein the cured product obtained by curing the resin composition has a smoke concentration of 150 m ⁻¹ or less when burned. 3. The thermosetting resin composition contains at least one selected from a phenol resin, a cyanate ester resin, an epoxy resin, and a benzoxazine resin. The resin composition for fiber-reinforced composite material. 4. The resin composition for a fiber-reinforced composite material according to claim 1, wherein the resin composition contains a flame retardant. 5. A fiber-reinforced composite material comprising a cured product of the resin composition for a fiber-reinforced composite material according to any one of claims 1 to 4 and a reinforcing fiber. 6. The fiber-reinforced composite material according to claim 5, wherein the fiber volume fraction of the fiber-reinforced composite material is 10 to 85%. 7. The fiber-reinforced composite material according to claim 5, wherein the reinforcing fibers are carbon fibers. 8. A carbon fiber having a tensile modulus of 200 to 700 G.
It is Pa, The fiber reinforced composite material of Claim 7 characterized by the above-mentioned. 9. The reinforcing fiber contains 0.01% by weight of a sizing agent.
The fiber-reinforced composite material according to claim 5, wherein the fiber-reinforced composite material is deposited in an amount of -5% by weight.