JP2014114368A - Thermosetting bismaleimide-based resin composition and prepreg, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a prepreg which can manufacture a fiber reinforced composite material having high heat resistance and high fracture toughness, and has superior handleability and molding processability, and to provide a resin composition used for manufacturing the prepreg.SOLUTION: A prepreg is produced by impregnating a reinforcing fiber base material with a thermosetting bismaleimide-based resin composition including component (a), a bismaleimide compound; component (b), an alkenylphenol and/or an alkenylphenol ether compound; and component (c), an amine terminated acrylonitrile-butadiene copolymer as essential components, where the content of the component (c) is 3-30 mass%.

Description

  The present invention relates to a thermosetting bismaleimide resin composition used for producing a fiber-reinforced composite material and a method for producing the same. The present invention also relates to a prepreg obtained by impregnating a reinforcing fiber substrate with this thermosetting bismaleimide resin composition and a method for producing the same.

  Fiber reinforced composite materials are widely used in aerospace products and the like because of their excellent specific strength and specific elasticity. As the use of fiber reinforced composite materials expands, the demand for fiber reinforced composite materials having heat resistance that can withstand high temperatures of 200 ° C. or higher and excellent fracture toughness is increasing. Accordingly, there is a need for a prepreg capable of producing a fiber-reinforced composite material having high heat resistance and high fracture toughness.

  The prepreg is composed of a reinforcing fiber base material and a matrix resin impregnated in the reinforcing fiber base material. Conventionally, polyimide resins and bismaleimide resins have been used as matrix resins with high heat resistance. However, prepregs using a polyimide resin as a matrix resin are delayed in practical use because of poor molding processability. A prepreg using a bismaleimide resin as a matrix resin has poor handleability and molding processability compared to a case where an epoxy resin is used as a matrix resin. In addition, since the bismaleimide resin has poor toughness, the fiber-reinforced composite material using the bismaleimide resin as the matrix resin has low fracture toughness.

  As a method to increase the toughness of bismaleimide resin, a method of dispersing a carboxyl group-terminated rubber compound in the matrix resin and a method of dissolving a thermoplastic resin such as polyimide compatible with the bismaleimide resin in the matrix resin are studied. Has been. However, in the conventionally proposed method, the toughness is not sufficiently increased and other physical properties are greatly deteriorated.

  Patent Document 1 discloses a prepreg composed of an aromatic bismaleimide compound, an alkenylphenol or alkenylphenoxy group-containing comonomer, and a soluble thermoplastic polyimide resin. The fiber reinforced composite material produced using this prepreg has high fracture toughness, but has insufficient heat resistance and solvent resistance such as solvent cracking due to methyl ethyl ketone (MEK).

  Patent Document 2 includes a polyfunctional maleimide compound in which 50% by mass or more exists in a solid form, an alkenylphenol or an alkenylphenol ether compound, and a thermoplastic resin, and the thermoplastic resin does not dissolve in the matrix resin. Discloses a prepreg localized on the surface of the prepreg. The fiber reinforced composite material produced using this prepreg has high fracture toughness but is not sufficient in heat resistance and heat oxidation resistance.

  Patent Document 3 discloses a prepreg containing polyphenylmethane maleimide, 1,6-bismaleimide (2,2,4-trimethyl) hexane, and diallyl bisphenol A as essential components. This prepreg is excellent in handleability such as tackiness and draping properties of the prepreg because crystals of phenylmethanemaleimide oligomer dissolved in diallyl bisphenol A are difficult to precipitate in the resin composition. However, the fracture toughness is low.

  Therefore, there is a demand for a prepreg that can produce a fiber-reinforced composite material that is excellent in handleability and moldability, and that has high heat resistance and high fracture toughness.

Japanese Patent Laid-Open No. 3-197559 JP-A-8-127663 JP 2011-102345 A

  An object of the present invention is to provide a prepreg that can produce a fiber-reinforced composite material having high heat resistance and high fracture toughness, and that has high handleability and moldability, and a resin composition that is used for manufacturing the prepreg. There is to do.

  The present inventors impregnate a reinforcing fiber substrate with a resin composition comprising a bismaleimide compound, an alkenylphenol and / or alkenylphenol ether compound, and an acrylonitrile-butadiene copolymer having an amine end group. The found prepreg was found to be excellent in handleability and molding processability. And the fiber reinforced composite material produced using this prepreg discovered that heat resistance and fracture toughness were high, and came to complete this invention.

  The present invention for solving the above problems is as follows.

[1] The following components (a) to (c) (a) component: bismaleimide compound,
(B) component: alkenylphenol and / or alkenylphenol ether compound,
(C) component: an acrylonitrile-butadiene copolymer having amine end groups,
As an essential component,
(C) Content of component is 3-30 mass%, The thermosetting bismaleimide-type resin composition characterized by the above-mentioned.

  [2] The thermosetting bismaleimide resin composition according to [1], wherein a ratio of a solid phase component in the thermosetting bismaleimide resin composition is 5 to 50% by mass.

  [3] The thermosetting bismaleimide resin composition according to [1] or [2], wherein the component (a) comprises an aromatic bismaleimide compound and an aliphatic bismaleimide compound.

  [4] The thermosetting bismaleimide resin composition according to any one of [1] to [3], wherein the amine end group is a secondary amine end group.

  [5] The thermosetting bismaleimide resin composition according to any one of [1] to [4], which contains 0.1 to 15% by mass of a thermoplastic resin.

[6] Components (a) to (c) below (a) Component: Bismaleimide compound,
(B) component: alkenylphenol and / or alkenylphenol ether compound,
(C) component: an acrylonitrile-butadiene copolymer having amine end groups,
Are mixed at a temperature of 60 to 140 ° C., The method for producing a thermosetting bismaleimide resin composition according to [1].

  This invention contains the prepreg of the following [7]-[9] manufactured using the said thermosetting bismaleimide-type resin composition.

[7] a reinforcing fiber base;
The thermosetting bismaleimide resin composition according to [1] impregnated in the reinforcing fiber base;
A prepreg consisting of
The ratio of the said thermosetting bismaleimide-type resin composition in the said prepreg is 20-60 mass%, The prepreg characterized by the above-mentioned.

  [8] The prepreg according to [7], wherein the reinforcing fiber base is a reinforcing fiber base composed of carbon fibers.

  [9] The method for producing a prepreg according to [7] or [8], wherein the reinforcing fiber substrate is impregnated with the thermosetting bismaleimide resin composition according to [1] at a temperature of 70 to 160 ° C.

  The prepreg produced using the thermosetting bismaleimide resin composition of the present invention has little change with time in tackiness and drapeability and high storage stability. Therefore, even if it is a prepreg after long-term storage, the handleability is good.

  The resin obtained by curing the thermosetting bismaleimide resin composition of the present invention has a high glass transition temperature. Therefore, the fiber reinforced composite material produced using the prepreg of the present invention has high heat resistance.

  The fiber-reinforced composite material produced using the prepreg of the present invention has high fracture toughness because rubber particles that absorb impact are dispersed in the matrix resin.

  Hereinafter, the details of the thermosetting bismaleimide resin composition of the present invention and the prepreg of the present invention constituted by using the thermosetting bismaleimide resin composition will be described.

(1) Thermosetting Bismaleimide Resin Composition The thermosetting bismaleimide resin composition of the present invention (hereinafter also referred to as “the resin composition”)
(A) component: a bismaleimide compound;
(B) component: an alkenylphenol and / or an alkenylphenol ether compound;
(C) component: an acrylonitrile-butadiene copolymer having amine end groups;
Is contained as an essential component. Moreover, it is preferable that a thermoplastic resin is included as an arbitrary component.

  In the present resin composition, the component (a) and the component (b) react and cure during heating, and the amine end group of the component (c) reacts with the component (a) to form a maleimide structure. Accordingly, the component (c) in the present resin composition has a high molecular weight during the curing reaction, phase-separates, and precipitates as particles in the matrix resin. Particles precipitated by this phase separation (hereinafter also referred to as “rubber particles”) have a main chain of rubber and are firmly bonded in the matrix resin. This rubber particle absorbs the impact from the outside with respect to a fiber reinforced composite material, and suppresses crack propagation. As a result, the fiber reinforced composite material finally obtained using this resin composition has high fracture toughness.

(1-1) Bismaleimide Compound As the bismaleimide compound (hereinafter also referred to as BMI) blended in the resin composition, a conventionally known bismaleimide compound can be used. For example, the bismaleimide compound represented by following formula (1) is mentioned.

[In Formula (1), R _{1 to} R ₄ each independently include —H, —CH ₃ , —C ₂ H ₅ , —C ₃ H ₇ , —F, —Cl, —Br, and —I. Represents a group selected from the group; X will be described later. ]
In the present invention, the bismaleimide compound is preferably a combination of a bismaleimide compound containing an aromatic ring structure and a bismaleimide compound not containing an aromatic ring structure. By using these together, the handleability of the obtained prepreg can be improved.

(1-1-1) Aromatic Bismaleimide Compound When the bismaleimide compound contains an aromatic ring structure (hereinafter also referred to as “aromatic bismaleimide compound”), X in formula (1) is the following formula (2 ) To (8) are preferred.

Wherein _{(5), R} 5 _{is, -CH 2 -, - C (} CH 3) 2 -, - O -, - SO 2 - represents a. ]

Wherein (6), _{R 5 is, -CH 2 -, - C (} CH 3) 2 -, - O -, - SO 2 - represents a. R _{6 to} R ₉ are each independently a group selected from the group consisting of —H, —CH ₃ , —C ₂ H ₅ , —C ₃ H ₇ , —F, —Cl, —Br and —I. Represents. ]

Wherein (7), _{R 5 is, -CH 2 -, - C (} CH 3) 2 -, - O -, - SO 2 - represents a. ]

Wherein _{(8), R} 10 ~R ₁₁ are each _{independently, -CH 2 -, - C (} CH 3) 2 -, - O -, - SO 2 - represents a. In formula (8), n is 0-0.5. ]

  Examples of such aromatic bismaleimide compounds include N, N′-4,4′-diphenylmethane bismaleimide, N, N′-4,4′-diphenyl ether bismaleimide, N, N′-m-phenylene bismaleimide, N, N′-p-phenylene bismaleimide, N, N′-m-toluylene bismaleimide, N, N′-4,4′-biphenylene bismaleimide, N, N′-4,4 ′-(3 3′-dimethylbiphenylene) bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, N, N′-4,4′-diphenylsulfone bismaleimide, N, N′-4,4′-benzoph Examples include enone bismaleimide.

  From the viewpoint of heat resistance of the fiber-reinforced composite material after heat curing, N, N′-4,4′-diphenylmethane bismaleimide, N, N′-4,4′-diphenyl ether bismaleimide, N, N′-m -Toluylene bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 4-methyl-1,3-phenylenebismaleimide, N, N'-4,4'-diphenylsulfon bismaleimide N, N′-4,4′-benzophenone bismaleimide, N, N′-4,4′-diphenylmethane bismaleimide, N, N′-4,4′-diphenyl ether bismaleimide, N, N′— m-toluylene bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 4-methyl-1,3-phenylene Sumareimido is particularly preferred. These aromatic bismaleimide compounds may be used alone or in combination of two or more.

  The content of the aromatic bismaleimide compound in the resin composition is preferably 20 to 80% by mass, more preferably 35 to 65% by mass, more preferably 35 to 65% by mass with respect to the total mass of the resin composition. It is especially preferable that it is 50 mass%. When the content of the aromatic bismaleimide compound is less than 20% by mass, the heat resistance of the fiber-reinforced composite material obtained using the resin composition tends to be low. When the content of the aromatic bismaleimide compound exceeds 80% by mass, the fracture toughness of the fiber-reinforced composite material finally obtained using the resin composition tends to decrease.

(1-1-2) Aliphatic bismaleimide compound When the bismaleimide compound does not contain an aromatic ring structure (hereinafter, also referred to as “aliphatic bismaleimide compound”), X in formula (1) represents the following formula ( The structure described in 9) to (11) is preferable.

  [In Formula (9), n is an integer of 10 or less, and 1, 2, 3, 4, 6 are preferable. ]

  Examples of such aliphatic bismaleimide compounds include 1,6′-bismaleimide- (2,2,4-trimethyl) hexane, hexamethylenediamine bismaleimide, N, N′-1,2-ethylenebismaleimide, N , N′-1,3-propylene bismaleimide and N, N′-1,4-tetramethylene bismaleimide. 1,6'-bismaleimide- (2,2,4-trimethyl) hexane and hexamethylenediamine bismaleimide are particularly preferred. The aliphatic bismaleimide compound may be used alone or in combination of two or more.

  The content of the aliphatic bismaleimide compound in the resin composition is preferably 3 to 30% by mass, more preferably 5 to 20% by mass, and more preferably 7 to 15% with respect to the total mass of the resin composition. It is particularly preferable that the content is% by mass. When the blending amount of the aliphatic bismaleimide compound is less than 3% by mass, the toughness of the fiber-reinforced composite material finally obtained using the resin composition is poor, and the fracture toughness tends to be lowered. When content of an aliphatic bismaleimide compound exceeds 30 mass%, there exists a tendency for the heat resistance of the fiber reinforced composite material finally obtained using this resin composition to fall easily.

(1-2) Alkenylphenol and / or alkenylphenol ether compound The alkenylphenol ether compounded in the present resin composition is obtained by the reaction of a phenolic compound and an alkenyl halide. Phenol is obtained (Japanese Patent Laid-Open No. 52-994). In the present invention, the transition structure may be contained in the alkenylphenol and / or alkenylphenol ether compound.

  As the alkenylphenol and / or alkenylphenol ether, allylphenol, methallylphenol or an ether thereof is preferable. More preferably, the alkenylphenol or alkenylphenol ether is a compound of the following formulas (12) to (16).

[In Formula (12), R < ₁₂ >, R < ₁₃ >, R < ₁₄ > is respectively independently hydrogen or a C2-C10 alkenyl group, Preferably they are an allyl group or a propenyl group. However, at least one of R ₁₂ , R ₁₃ , and R ₁₄ is an alkenyl group having 2 to 10 carbon atoms. ]

[In the formula (13), R ₁₅ represents a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO— or —SO ₂ —. R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are each independently hydrogen or an alkenyl group having 2 to 10 carbon atoms, preferably an allyl group or a propenyl group. However, at least one of R ₁₆ , R ₁₇ , R ₁₈ , and R ₁₉ is an alkenyl group having 2 to 10 carbon atoms. ]

  Of the formula (13), compounds of the following formula (14) are particularly preferred.

[In the formula (14), R ₁₅ represents a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO— or —SO ₂ —. ]

[In the formula (15), R ₂₀ and R ₂₁ are a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO— or —SO ₂ —. R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, preferably an allyl group Or it is a propenyl group. However, at least one of R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ is an alkenyl group having 2 to 10 carbon atoms. P is an integer of 0-10. ]

[In the formula (16), R ₁₅ represents a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO— or —SO ₂ —. R ₂₈ and R ₂₉ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and preferably an allyl group or a propenyl group. However, at least one of R ₂₈ and R ₂₉ is an alkenyl group having 2 to 10 carbon atoms. ]

  Examples of the alkenylphenol or alkenylphenol ether compound include O, O′-diallylbisphenol A, 4,4′-dihydroxy-3,3′-diallyldiphenyl, bis (4-hydroxy-3-allylphenyl) methane, 2,2′-bis (4-hydroxy-3,5-diallylphenyl) propane, 2,2′-diallylbisphenol F, 4,4′-dihydroxy-3,3′-diallyldiphenyl ether, 4,4′-bis -O-propenylphenoxy-benzophenone and the like can be mentioned. Among these, since the glass transition point of the resin after heat curing is high, O, O′-diallylbisphenol A, 2,2′-bis (4-hydroxy-3,5-diallylphenyl) propane, 2,2 ′ -Diallyl bisphenol F etc. are preferable. O, O'-diallylbisphenol A is particularly preferred because it lowers the viscosity of the resin composition. In the present resin composition, alkenylphenol and / or alkenylphenol ether may be used alone or in combination of two or more.

  The alkenylphenol and / or alkenylphenol ether compound functions as a curing agent for the bismaleimide compound. The blending amount in the resin composition is preferably 10 to 70% by mass, more preferably 20 to 50% by mass, and particularly preferably 25 to 40% by mass. The resin composition can contain alkenylphenol and / or alkenylphenol ether compound as appropriate within the above predetermined range, thereby adjusting the viscosity and obtaining good moldability. Moreover, the present resin composition can be sufficiently impregnated into the reinforcing fiber base material and can be sufficiently adhered to the reinforcing fiber base material.

  In the present resin composition, part or all of the aromatic bismaleimide compound and / or the aliphatic bismaleimide compound may be dissolved in the alkenylphenol and / or alkenylphenol ether compound. The present resin composition preferably contains a liquid phase component and a solid phase component, and the ratio of the solid phase component in the resin composition is preferably 5 to 50% by mass, and preferably 15 to 45% by mass. It is more preferable that the content is 25 to 40% by mass. In addition, in this invention, a solid-phase component means the component which exists in solid form in the resin composition of temperature 80 degreeC. Among the solid phase components, the bismaleimide resin is dissolved in the resin composition at a temperature equal to or lower than the molding temperature of the prepreg formed using the resin composition. The liquid phase component refers to a component that exists in a liquid state in a resin composition at a temperature of 80 ° C.

  When the ratio of the solid phase component in the resin composition exceeds 50% by mass, the viscosity of the resin composition may be remarkably increased. As a result, the handleability may be significantly deteriorated in the resin composition manufacturing process and the prepreg manufacturing process. When the ratio of the solid phase component in the resin composition is less than 5% by mass, the bismaleimide compound is dissolved in the alkenylphenol and / or alkenylphenol ether compound. And when a hardening reaction advances simultaneously by the heating at the time of melt | dissolution, a resin composition may become high molecular weight and a viscosity may become high. As a result, the handleability in the manufacturing process of the resin composition and the manufacturing process of the prepreg may be significantly deteriorated.

(1-3) Acrylonitrile-butadiene copolymer having amine end groups An acrylonitrile-butadiene copolymer (hereinafter also referred to as “ATBN”) having amine end groups is blended in the resin composition. As this ATBN, known ATBN can be used. Among them, ATBN in which amino groups are introduced at both ends of a nitrile-butadiene rubber (NBR) molecule is preferable. ATBN represented by the following formula (17) is particularly preferred.

  [In Formula (17), m is 70-95 and n is 5-30. ]

  As such ATBN, commercially available products such as “HYPRO ATBN 1300X16 (registered trademark)” and “HYPRO ATBN 1300X45 (registered trademark)” (both manufactured by Emerald Performance Materials) can be preferably used.

  The content of ATBN in the resin composition is 3 to 30% by mass, preferably 5 to 25% by mass, and particularly preferably 10 to 20% by mass. When the content of ATBN is 3% by mass or more, the rubber particles formed from ATBN can efficiently absorb the impact received by the fiber reinforced composite material. Therefore, the fracture toughness of the fiber reinforced composite material is increased. When the content of ATBN is 30% by mass or less, the viscosity of the resin composition does not become too high, and the handleability in the resin composition manufacturing process and the prepreg manufacturing process is excellent. The fiber reinforced composite material in which the rubber particles formed from the predetermined amount of ATBN are uniformly dispersed in the matrix resin suppresses crack propagation to impact. That is, fracture toughness is high.

  A maleimide-terminated rubber obtained by reacting ATBN and a bismaleimide compound in advance can also be blended with the resin composition. The maleimide-terminated rubber can be obtained by stirring ATBN having an amino group at both ends and a bismaleimide compound at room temperature to 80 ° C. for 30 minutes. Alternatively, ATBN having an amino group at both ends and a bismaleimide compound can be obtained by stirring in a solvent at room temperature to 80 ° C. for 30 minutes, and then removing the solvent. Examples of the solvent to be used include methyl ethyl ketone (MEK) and acetone.

  The maleimide-terminated rubber thus obtained has a rubber main chain and has a large molecular weight. Therefore, the toughness of the resin obtained after curing of the resin composition is high, and the mechanical properties and heat resistance are excellent. In addition, the reactivity of both ends of the molecule at room temperature is low. Therefore, room temperature storage stability is high. That is, a particularly preferable property is imparted as a resin composition for producing a prepreg.

(1-4) Thermoplastic Resin The resin composition preferably contains a thermoplastic resin. A known thermoplastic resin can be used as the thermoplastic resin. Thermoplastic resins soluble in alkenylphenol and / or alkenylphenol ether compounds (hereinafter also referred to as “soluble thermoplastic resins”), thermoplastic resins insoluble in alkenylphenol and / or alkenylphenol ether compounds (hereinafter referred to as “insoluble heat”). Any of the “plastic resin” can be used.

(1-4-1) Soluble thermoplastic resin In the present invention, “soluble in alkenylphenol and / or alkenylphenol ether compound” means alkenylphenol and / or alkenyl under the temperature conditions for molding a fiber-reinforced composite material. It means that a part or all of the phenol ether compound is dissolved. In the molding process of the fiber reinforced composite material, the soluble thermoplastic resin dissolves in the resin composition when the resin composition is heated, and increases the viscosity of the resin composition. Thereby, the flow of the resin composition during molding can be prevented.

  Examples of the soluble thermoplastic resin include polyethersulfone, polysulfone, polyetherimide, and polyimide.

  The content of the soluble thermoplastic resin is preferably 0.1 to 15% by mass, and more preferably 1 to 10% by mass. When the content of the soluble thermoplastic resin is less than 0.1% by mass, the viscosity of the resin composition is not sufficiently increased, and the resin composition may be flowed. When the content of the soluble thermoplastic resin exceeds 15% by mass, the viscosity of the resin composition increases, and the handleability may be significantly deteriorated.

(1-4-2) Insoluble thermoplastic resin An insoluble thermoplastic resin is contained in the resin composition of this invention as needed. In the present invention, the term “thermoplastic resin insoluble in alkenylphenol and / or alkenylphenol ether compound” means a thermoplastic that does not dissolve in alkenylphenol and / or alkenylphenol ether compound at least under the temperature conditions for molding the fiber-reinforced composite material. Refers to resin. An example of the insoluble thermoplastic resin is a polyimide resin.

  The content of the insoluble thermoplastic resin is preferably 0.1 to 15% by mass, and more preferably 1 to 10% by mass. When the content of the insoluble thermoplastic resin is less than 0.1% by mass, the viscosity of the resin composition is not sufficiently increased, and the flow of the resin composition may be caused. When the content of the insoluble thermoplastic resin exceeds 15% by mass, the viscosity of the resin composition becomes high, and the handleability may be significantly deteriorated. Although the particle diameter of an insoluble thermoplastic resin is not specifically limited, It is preferable that it is 0.1-100 micrometers, and it is more preferable that it is 1-50 micrometers.

(1-5) Other components The present resin composition may contain other components as long as the heat resistance, molding processability and toughness are not impaired. Examples of other components include polymerization inhibitors, conductive particles, conductive fillers, inorganic fillers, rubbery components, toughness imparting agents, stabilizers, mold release agents, and colorants.

(2) Manufacturing method of thermosetting bismaleimide resin composition To manufacture this resin composition, (a) to (c) components as essential components and thermoplastic resin and other components as optional components are mixed. And a method in which the composition is uniformly dissolved and / or dispersed, and the method is not particularly limited. These components may be mixed at room temperature, but it is preferable to mix by heating in order to produce economically. In this case, heating temperature is 30-180 degreeC normally, 50-150 degreeC is preferable and 60-140 degreeC is more preferable. When the temperature exceeds 180 ° C., the polymerization reaction is accelerated, and the resin composition may be cured during mixing.

  When kneading this resin composition, it is preferable to blend a part or all of the component (a) as a solid phase component. That is, it is preferable not to dissolve part or all of the component (a) in the component (b). When the component (a) and the component (b) are completely dissolved by heating, the handleability and storage stability may deteriorate as a result of the progress of the curing reaction. (B) Component (c) and other components are heated and dissolved in component (b), then the temperature is lowered and then component (a) is added to suppress the curing reaction between component (a) and component (b). it can.

  Kneading may be performed in one stage or in multiple stages. Moreover, although the mixing order of each component of a resin composition is not limited, It is preferable to add the component mix | blended as a solid-phase component after the other component in a resin composition melt | dissolves. This facilitates uniform dispersion of the solid phase component in the resin composition. The kneading time varies depending on the temperature, but is preferably 10 to 180 minutes.

  The soluble thermoplastic resin is preferably dissolved in the alkenylphenol and / or alkenylphenol ether compound at a dissolution temperature of 80 to 130 ° C. before kneading with the bismaleimide compound.

  When blending an insoluble thermoplastic resin, the powder is supplied into the resin composition and mixed as dispersed particles.

  As the kneading machine apparatus, conventionally known apparatuses such as a roll mill, a planetary mixer, a kneader, an extruder, and a Banbury mixer can be used.

(3) Prepreg The prepreg of the present invention (hereinafter also referred to as “present prepreg”) is a prepreg in which the reinforcing fiber base material is impregnated with the above-mentioned thermosetting bismaleimide resin composition.

  In the production of this prepreg, the reinforcing fibers constituting the reinforcing fiber substrate include carbon fibers, glass fibers, aramid fibers, silicon carbide fibers, polyester fibers, ceramic fibers, alumina fibers, boron fibers, metal fibers, mineral fibers, rocks. Examples thereof include fibers and slug fibers. Among these reinforcing fibers, carbon fibers, glass fibers, and aramid fibers are preferable, carbon fibers from which specific strength, specific elastic modulus is good, and a lightweight and high-strength fiber-reinforced composite material is more preferable, among carbon fibers, Polyacrylonitrile (PAN) -based carbon fibers having excellent tensile strength are particularly preferred.

When PAN-based carbon fiber is used as the reinforcing fiber, the tensile elastic modulus is preferably 170 to 600 GPa, and particularly preferably 220 to 450 GPa. The tensile strength is preferably 3920 MPa (400 kgf / mm ² ) or more. By using such carbon fibers, the mechanical properties of the fiber-reinforced composite material can be improved.

The shape of the reinforcing fiber base is not limited, but is preferably a sheet-like material from the viewpoint of workability. As the reinforcing fiber sheet, for example, a sheet-like material in which a large number of reinforcing fibers are aligned in one direction, bi-directional woven fabrics such as plain weave and twill weave, multiaxial woven fabric, non-woven fabric, mat, knit, braid, and reinforcing fiber And the like. The thickness of the reinforcing fiber sheet is preferably 0.01 to 3 mm, and more preferably 0.1 to 1.5 mm. Also, the basis weight of the reinforcing fiber sheet is preferably ^{70~400g / m 2, 100~300g / m} 2 is more preferable.

  20-60 mass% is preferable with respect to the total mass of a reinforced fiber base material and this resin composition, and, as for content of this resin composition in this prepreg, 30-50 mass% is more preferable. When the content of the resin composition is less than 20% by mass, voids or the like may be generated inside the fiber reinforced composite material produced using this prepreg. When content of this resin composition exceeds 60 mass%, content of a reinforced fiber runs short and the intensity | strength of the fiber reinforced composite material obtained falls easily.

  The water absorption of the present prepreg is preferably 2 to 40%, more preferably 4 to 25%. In the present invention, the water absorption rate is an index indicating the porosity in the prepreg. The higher the water absorption rate, the higher the porosity in the prepreg. When the water absorption rate is high, there are many voids in the prepreg, and the handleability during molding deteriorates. Moreover, since voids are likely to remain in the manufactured fiber-reinforced composite material, the mechanical properties may be adversely affected. When the water absorption is low, there are few voids in the prepreg, so that the drapability is low. Therefore, good moldability (shape followability) cannot be obtained. In addition, the measuring method of a water absorption rate is mentioned later.

(4) Manufacturing method of prepreg This prepreg can be manufactured by impregnating this resin composition in a reinforced fiber base material. As a method for impregnating the resin composition into the reinforcing fiber base, a known wet method or dry method can be used. Since the wet method uses an organic solvent, it is necessary to remove the organic solvent after impregnating the resin composition. Therefore, it is preferable to use a hot melt method which is a dry method in which there is no possibility that the organic solvent remains.

  In the hot melt method, the resin composition and the reinforced fiber base material stacked are heated under pressure to reduce the viscosity of the resin composition and impregnate the reinforced fiber base material with the resin composition. . When the reinforcing fiber base is a sheet, it is preferable to stack the resin composition formed into a film on the reinforcing fiber base.

  This resin composition can be formed into a film by a known method. For example, the resin composition can be formed into a film by casting on a support such as release paper or release film using a die coater, applicator, reverse roll coater, comma coater, knife coater, etc. it can. The temperature which manufactures a film is suitably set according to the viscosity of this resin composition. Usually, the temperature is preferably 60 to 130 ° C, more preferably 80 to 110 ° C.

  The thickness of the resin composition film is preferably about 8 to 350 μm, more preferably 10 to 200 μm.

  The pressurizing condition for impregnating the reinforcing fiber substrate with the resin composition is appropriately adjusted according to the composition and viscosity of the resin composition. Usually, the linear pressure is 0.98 to 245 N / cm, more preferably 19.6 to 147 N / cm. When the linear pressure is less than 0.98 N / cm, it is difficult to sufficiently impregnate the reinforcing fiber sheet with the resin composition. The pressurization may be performed once or may be performed in a plurality of times.

  The heating temperature for impregnating the reinforcing fiber substrate with the resin composition is appropriately adjusted according to the viscosity of the resin composition. Usually, it is 70-160 degreeC and 80-120 degreeC is preferable. When heating temperature is less than 70 degreeC, the viscosity of this resin composition does not become low, and this resin composition cannot fully be impregnated in a reinforced fiber base material. When the heating temperature exceeds 160 ° C., the curing reaction of the component (a) and the component (b) in the resin composition proceeds, and the prepreg begins to cure. For this reason, tackiness and drapeability are likely to deteriorate.

  The industrial production rate of the prepreg is not particularly limited. However, in consideration of productivity and economy, in the case of continuous production, it is preferably 0.1 m / min or more, more preferably 1 to 50 m / min. 5 to 20 m / min is particularly preferable.

(5) Method of using the present prepreg The present prepreg can be made into a fiber-reinforced composite material by curing by a known method. As a method for producing a fiber-reinforced composite material using the present prepreg, conventionally known methods such as manual layup, automatic tape layup (ATL), automatic fiber placement, vacuum bagging, autoclave curing, curing other than autoclave, Examples include fluid assisted processing, pressure assisted processes, match mold processes, simple press curing, press clave curing, or methods using continuous band presses.

  For example, the formed fiber reinforced composite material can be produced by laminating the present prepreg, pressurizing to 0.2 to 1 MPa in an autoclave, and heating at 150 to 204 ° C. for 1 to 8 hours. Heat treatment can be further improved by performing the treatment for 2 to 20 hours while increasing the temperature stepwise in the temperature range of 180 to 280 ° C. as post-cure.

  This prepreg uses a highly heat-resistant resin composition. Therefore, the fiber reinforced composite material produced using this prepreg has a heat resistance of at least 200 ° C. or more.

  In the curing process of the resin composition, the product obtained by the reaction of ATBN and the bismaleide compound is phase-separated in the matrix resin and precipitated as rubber particles. The rubber particles are uniformly dispersed in the matrix resin and are firmly bonded to the matrix resin. Therefore, the rubber particles absorb external impacts and suppress the propagation of cracks in the fiber reinforced composite material. Therefore, the fiber reinforced composite material produced using this prepreg has high fracture toughness.

The delamination strength (GIc) of the fiber reinforced composite material produced using this prepreg is preferably 175 to 800 J / m ² , more preferably 300 to 600 J / m ² .

  The present prepreg is excellent in storage stability, and maintains the moldability immediately after production even after at least 10 days have passed since the production of the present prepreg. Therefore, a fiber-reinforced composite material having high heat resistance and high fracture toughness can be produced even after a predetermined time has elapsed.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples described below.

  The following were used as raw materials for the resin composition and prepreg.

[(A) component]
[Aromatic bismaleimide compounds]
・ Matrimid 5292 A (trade name) (N, N′-4,4′-diphenylmethane bismaleimide, manufactured by Huntsman Advanced Materials)
・ BMI-1100H (trade name) (N, N′-4,4′-diphenylmethane bismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd.)
・ BMI-2300 (trade name) (Phenylmethane maleimide oligomer, manufactured by Daiwa Kasei Kogyo Co., Ltd.)
・ BMI-80 (trade name) (2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane, manufactured by KAI Kasei Co., Ltd.)
・ BMI-7000H (trade name) (4-methyl-1,3-phenylenebismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd.)
[Aliphatic bismaleimide compounds]
・ BMI-TMH (trade name) (1,6′-bismaleimide- (2,2,4-trimethyl) hexane, manufactured by Daiwa Kasei Kogyo Co., Ltd.)
GP-207-R (trade name) (1,6′-hexamethylenediamine bismaleimide (HMDA-BMI), manufactured by Cymer)

[Component (b)]
・ Matrimid 5292 B (trade name) (O, O′-diallylbisphenol A, manufactured by Huntsman Advanced Materials)
DABPA (trade name) (2,2'-diallylbisphenol A, manufactured by Daiwa Kasei Kogyo Co., Ltd.)

[Component (c)]
・ HYPRO ATBN 1300X16 (registered trademark) (manufactured by Emerald Performance Materials)

[Acrylonitrile-butadiene copolymer having carboxyl group terminal]
・ HYCAR CTBN 1300X13 (registered trademark) (manufactured by BF Goodrich)

[Soluble thermoplastic resin]
-Ultem 1000-1000 (trade name) pulverized product (polyetherimide, manufactured by SABIC Innovative Plastics, average particle size 15 μm)
・ Sumika Excel 5003P (trade name) pulverized product (polyethersulfone, manufactured by Sumitomo Chemical Co., Ltd., average particle size: 15 μm)
The above polyetherimide and polyethersulfone are soluble in the component (b).

[Insoluble thermoplastic resin]
・ AURUM PD450M (trade name) pulverized product (polyimide resin, manufactured by Mitsui Chemicals, Inc., average particle size 14 μm)
・ P84 (trade name) (polyimide resin, manufactured by HP Polymers, average particle size: 15 μm)
The polyimide resin is insoluble in alkenylphenol or alkenylphenol ether compound.

[Carbon fiber substrate]
IMS 65 E 23 24K 830 tex (carbon fiber strand, manufactured by Toho Tenax Co., Ltd., tensile strength: 5800 MPa, tensile elastic modulus: 290 GPa)

  The physical properties of the resin composition, prepreg and fiber reinforced composite material were measured by the following methods.

[Average particle size]
Various particle sizes were measured using a laser diffraction / scattering particle size analyzer (Microtrack method) MT3300 manufactured by Nikkiso Co., Ltd., and D50 was defined as the average particle size.

[Water absorption rate]
The prepreg was cut into a square having a side of 100 mm, and the mass (W1) was measured. Thereafter, the prepreg was submerged in a desiccator. After reducing the pressure inside the desiccator to 10 kPa or less, the air and water inside the prepreg were replaced by returning to normal pressure. The prepreg was taken out of the water, the surface water was wiped off, and the mass (W2) of the prepreg was measured. From these measured values, the following formula: water absorption (%) = [(W2-W1) / W1] × 100
W1: Mass of prepreg (g)
W2: Mass of prepreg after water absorption (g)
Was used to calculate the water absorption rate.

[Room temperature storage stability]
The prepreg was stored at a temperature of 26.7 ° C. and a humidity of 65% for 10 days, then cut into a square having a side of 100 mm, and laminated so as to cover a bent portion of a mold described later. The mold surface shape was a shape in which the metal plate was bent at an angle of 90 degrees at the center with a curvature r = 12.7 mm, and the bent portion protruded upward. The lamination state of the prepreg mold was evaluated. The evaluation results were represented by the following criteria (◯, Δ, ×).
○: The surface shape of the mold is sufficiently followed, and the handleability is almost the same as that immediately after production.
(Triangle | delta): Although the hardening reaction of a prepreg progresses and tack property and drape property are falling, it follows a metal mold | die surface shape and can be used without a problem.
X: The curing reaction of the prepreg has progressed, the tackiness and draping properties have been remarkably lowered, and do not follow the surface shape of the mold.

[Tackiness]
The tackiness of the prepreg was measured by the following tack probe test using a tacking test apparatus TAC-II (RHESCA CO., LTD.). Set the prepreg on the test stage held at 27 ° C, apply the initial load of 100 gf with a φ5 tack probe held at 27 ° C, and pull it out at the test speed of 10 mm / sec. Pull-out load) was determined. A tack probe test was performed on each of the prepregs immediately after production and the prepregs stored at a temperature of 26.7 ° C. and a humidity of 65% for 10 days. The maximum pulling load of the prepreg stored for 10 days relative to the maximum pulling load of the prepreg immediately after production was defined as the tack retention. The evaluation results of tackiness were represented by the following criteria (◯, Δ, ×).
○: The maximum pulling load immediately after production is 100 gf or more, and the tack retention after storage for 10 days is 100 to 50%.
Δ: The maximum pull-out load immediately after production is 100 gf or more, and the tack retention after storage for 10 days is 50 to 25%.
X: The maximum pull-out load immediately after production is 100 gf or more, and the tack retention after storage for 10 days is 25 to 0%.

[Drapability]
The prepreg drapeability was evaluated by the following test in accordance with ASTM D1388. The prepreg was cut in a 90 ° direction with respect to the 0 ° fiber direction, and the drape property (flexural rigidity, mg * cm) with respect to the inclination at an inclination angle of 41.5 ° was evaluated. This evaluation was performed immediately after manufacturing the prepreg and after storage for a predetermined period at a temperature of 26.7 ° C. and a humidity of 65%. The evaluation results were represented by the following criteria (◯, Δ, ×).
○: Even after 20 days, the drapeability is the same as that immediately after production.
(Triangle | delta): Even after 10-day progress, drape property does not change from immediately after manufacture (after 10 days, a slight fall was seen in drape property).
X: After 10 days, the drapeability was lower than that immediately after the production, which was a problem level for use.

[Glass-transition temperature]
The prepreg was cut into a square with a side of 100 mm, and _{two of them} were laminated to obtain a laminate having a laminate configuration [0] ₂ . Using a normal vacuum autoclave molding method, molding was performed at 180 ° C. for 6 hours under a pressure of 0.59 MPa. The obtained molded product was taken out and post-cured on a free stand for 12 hours at 200 ° C. using a hot air circulating dryer.

  The obtained molded product was cut into dimensions of 2.54 mm wide × 10.2 mm long, and Tg of the carbon fiber reinforced composite material was measured by a bending mode using TMA (thermomechanical analyzer, manufactured by Bruker). The measurement was performed in a nitrogen atmosphere by raising the temperature to 400 ° C. at a rate of temperature increase of 10 ° C./min.

[Interlaminar fracture toughness mode I (GIc)]
The obtained prepreg was cut into a square having a side of 360 mm, then laminated, and two laminates were produced in which 10 layers were laminated in the 0 ° direction. In order to generate an initial crack, a release film was sandwiched between two laminates, and both were combined to obtain a prepreg laminate having a laminate configuration [0] ₂₀ . Using a normal vacuum autoclave molding method, molding was performed for 6 hours under the condition of 180 ° C. under a pressure of 0.59 MPa. Thereafter, using a hot air circulating oven, post-cure was performed for 12 hours on a free stand at a temperature of 200 ° C. to obtain a molded product. The obtained molded product (carbon fiber reinforced composite material) was cut into dimensions of 12.7 mm width × 304.8 mm length to obtain a specimen having an interlaminar fracture toughness mode I (GIc).

  A test that uses the double cantilever interlaminar fracture toughness test method (DCB method) as a test method for GIc, and after the pre-crack (initial crack) of 12.7 mm is generated from the tip of the release film, the test further advances the crack. Went. The test was terminated when the crack growth length reached 127 mm from the tip of the pre-crack. The crosshead speed of the test piece tensile tester was 12.7 mm / min, and measurement was performed at n = 5. The crack growth length was measured from both end faces of the test piece using a microscope, and GIc was calculated by measuring the load and crack opening displacement.

[Example 1]
BMI-2300, TMH-BMI, and Matrimid 5292B were stirred at 100 ° C. for 30 minutes using a stirrer at the ratio shown in Table 1, and completely dissolved. Then, it cooled to 80 degreeC, Matrimid 5292A, BMI-7000H, and HYPRO ATBN 1300X16 were added, and it stirred for 30 minutes, and prepared the thermosetting bismaleimide-type resin composition.

This thermosetting bismaleimide resin composition was applied on a release film with a single-sided resin film basis weight shown in Table 1 using a film coater to obtain a resin sheet. Next, carbon fiber strands (IMS 65 E 23 24K 830 tex) are supplied between two resin sheets and uniformly arranged in one direction [weight per unit area (190 g / m ² )]. And was pressed and heated at 110 ° C. using a roller to obtain a prepreg. The content rate of the thermosetting bismaleimide resin composition with respect to the whole prepreg was 35 mass%. Table 1 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg.

[Examples 2 to 4]
A prepreg was obtained in the same manner as in Example 1 except that the amount of HYPRO ATBN 1300X16 was changed. Table 1 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg.

[Comparative Example 1]
A resin composition and a prepreg were obtained in the same manner as in Example 1 except that HYPRO ATBN 1300X16 was not added. Table 1 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg.

  In Comparative Example 1 in which HYPRO ATBN 1300X16 was not added to the resin composition, the prepreg had good room temperature storage stability, tack retention, and draping properties. A carbon fiber reinforced composite material produced using this prepreg The interlaminar fracture toughness mode I was a low value as compared with Examples 1-4.

[Comparative Examples 2 and 3]
A resin composition and a prepreg were obtained in the same manner as in Example 1 except that HYPRO ATBN 1300X16 was changed to HYCAR CTBN 1300X13. Table 1 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg.

  Although the room temperature storage stability, tack retention, and draping property of the prepreg were good, the interlaminar fracture toughness mode I of the carbon fiber reinforced composite material produced using this prepreg was low as compared with Examples 1-4. Value.

[Example 5]
DABPA and Ultem 1000-1000 were stirred at 120 ° C. for 30 minutes using a stirrer at the ratio shown in Table 2 and completely dissolved. The obtained resin composition was cooled to 50 ° C., BMI-2300, BMI-80, and GP-207-R were added, and the mixture was stirred at 120 ° C. for 30 minutes for complete dissolution. Thereafter, the obtained resin composition was cooled to 80 ° C., BMI-1100H, HYPRO ATBN 1300X16, and AURUM PD450M were added, and mixed and stirred for 30 minutes to prepare a thermosetting bismaleimide resin composition.

This thermosetting bismaleimide resin composition was applied onto a release film with a single-sided resin film basis weight shown in Table 2 using a film coater to obtain a resin sheet. Next, carbon fiber strands (IMS 65 E 23 24K 830 tex) are supplied between two resin sheets and uniformly arranged in one direction [weight per unit area (190 g / m ² )]. And pressurizing and heating at 120 ° C. using a roller to obtain a prepreg. The resin content relative to the entire prepreg was 35% by mass. Table 2 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg.

  The room temperature storage stability, tack retention, and drape of the prepreg were good, and the carbon fiber reinforced composite material produced using this prepreg had a very high value for the interlaminar fracture toughness mode I.

[Examples 6 to 8]
A prepreg was obtained in the same manner as in Example 5 except that the addition amount of HYPRO ATBN 1300X16 was changed. Table 2 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg.

  The room temperature storage stability, tack retention, and drape of the prepreg were good, and the carbon fiber reinforced composite material produced using this prepreg had a very high value for the interlaminar fracture toughness mode I.

[Example 9]
A prepreg was obtained in the same manner as in Example 5 except that AURUM PD450M was changed to P84. Table 2 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg.

  The room temperature storage stability, tack retention, and drape of the prepreg were good, and the carbon fiber reinforced composite material produced using this prepreg had a very high value for the interlaminar fracture toughness mode I.

[Example 10]
A prepreg was obtained in the same manner as in Example 9 except that Ultem 1000-1000 was changed to Sumika Excel 5003P. Table 2 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg.

  The room temperature storage stability, tack retention, and drape of the prepreg were good, and the carbon fiber reinforced composite material produced using this prepreg had a very high value for the interlaminar fracture toughness mode I.

[Comparative Example 4]
A prepreg was obtained in the same manner as in Example 5 except that HYPRO ATBN 1300X16 was not added. Table 2 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg.

  In Comparative Example 4 in which HYPRO ATBN 1300X16 was not added to the resin composition, the prepreg had good room temperature storage stability, tack retention, and draping properties. A carbon fiber reinforced composite material produced using this prepreg The interlaminar fracture toughness mode I was a low value as compared with Examples 5-10.

[Comparative Example 5]
A prepreg was obtained in the same manner as in Example 9 except that HYPRO ATBN 1300X16 was not added. Table 2 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg.

  In Comparative Example 5 in which HYPRO ATBN 1300X16 was not added to the resin composition, the room temperature storage stability, tack retention and drape of the prepreg were good, but the carbon fiber reinforced composite material produced using this prepreg The interlaminar fracture toughness mode I was a low value as compared with Examples 5-10.

[Comparative Example 6]
A prepreg was obtained in the same manner as in Example 5 except that HYPRO ATBN 1300X16 was changed to HYCAR CTBN 1300X13. Table 2 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg.

  Although the prepreg had good room temperature storage stability, tack retention, and draping properties, the interlaminar fracture toughness mode I of the carbon fiber reinforced composite material produced using this prepreg was low compared to Examples 5-10. Value.

[Comparative Example 7]
A prepreg was obtained in the same manner as in Example 5 except that HYPRO ATBN 1300X16 was changed to HYCAR CTBN 1300X13. Table 2 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg.

  Although the prepreg had good room temperature storage stability, tack retention, and draping properties, the interlaminar fracture toughness mode I of the carbon fiber reinforced composite material produced using this prepreg was low compared to Examples 5-10. Value.

[Comparative Example 8]
Matrimid 5292A and Matrimid 5292B were stirred at 120 ° C. for 30 minutes using a stirrer at the ratio shown in Table 3, and completely dissolved to obtain a resin composition. A prepreg was obtained in the same manner as in Example 1 using the obtained resin composition. Table 3 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg.

  In Comparative Example 8 in which HYPRO ATBN 1300X16 was not added to the resin composition, the interlaminar fracture toughness mode I of the carbon fiber reinforced composite material was a low value as compared with Examples 5-10. Further, when a large amount of Matrimid 5292A was dissolved in Matrimid 5292B, the curing reaction of the resin composition progressed, and the prepreg could not follow the mold, resulting in deterioration in room temperature storage stability and drapeability. Moreover, Matrimid 5292A which melt | dissolved in large quantities at the time of storage at room temperature precipitated gradually with elapsed time, and tack maintenance property deteriorated.

[Comparative Example 9]
Matrimid 5292A and Matrimid 5292B were stirred with a stirrer at 80 ° C. for 30 minutes at the ratio shown in Table 3 to obtain a resin composition. A prepreg was obtained in the same manner as in Example 1 using the obtained resin composition. Table 3 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg.

  In Comparative Example 9 in which HYPRO ATBN 1300X16 was not added to the resin composition, the interlaminar fracture toughness mode I of the carbon fiber reinforced composite material was lower than in Examples 5 to 10. In addition, since Matrimid 5292A was not dissolved in Matrimid 5292B, many solid phase components of the resin composition were present on the prepreg surface during prepreg production. Therefore, room temperature storage stability and tackiness deteriorated.

[Example 11]
Matrimid 5292A, TMH-BMI, and Matrimid 5292B were stirred at 120 ° C. for 30 minutes using a stirrer at the ratio shown in Table 3, and completely dissolved. The obtained resin composition was cooled to 80 ° C., HYPRO ATBN 1300X16 was added, and the mixture was stirred for 30 minutes to prepare a thermosetting bismaleimide resin composition. Using this thermosetting bismaleimide resin composition, a prepreg was obtained in the same manner as in Example 1. Table 3 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg.

  In Example 11, when a large amount of Matrimid 5292A was dissolved in Matrimid 5292B, the curing reaction of the resin composition proceeded, making it somewhat difficult to fit the prepreg along the mold. Moreover, Matrimid 5292A which melt | dissolved in large quantities at the time of storage at room temperature gradually precipitated with elapsed time, and tack maintenance property deteriorated a little. However, the interlaminar fracture toughness mode I of the fiber reinforced composite material produced using this prepreg was a good value.

[Example 12]
BMI-1100H, GP-207-R, and Matrimid 5292B were stirred at 120 ° C. for 30 minutes using a stirrer at the ratio shown in Table 3, and completely dissolved. The resin composition was cooled to 80 ° C., Matrimid 5292A and HYPRO ATBN 1300X16 were added, and mixed and stirred for 30 minutes to prepare a thermosetting bismaleimide resin composition. Using this thermosetting bismaleimide resin composition, a prepreg was obtained in the same manner as in Example 1. Table 3 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg. In Example 12, when a large amount of BMI-1100H was dissolved in Matrimid 5292B, the curing reaction of the resin composition proceeded, making it somewhat difficult to fit the prepreg along the mold. Moreover, BMI-1100H which melt | dissolved in large quantities at the time of room temperature storage gradually precipitated with elapsed time, and tack maintenance property deteriorated a little. However, the interlaminar fracture toughness mode I of the fiber reinforced composite material produced using this prepreg was a good value.

[Example 13]
Matrimid 5292B, TMH-BMI, and BMI-80 were stirred at 120 ° C. for 30 minutes using a stirrer at the ratio shown in Table 3, and completely dissolved. The resin composition was cooled to 80 ° C., Matrimid 5292A and HYPRO ATBN 1300X16 were added, and mixed and stirred for 30 minutes to prepare a thermosetting bismaleimide resin composition. Using this thermosetting resin composition, a prepreg was obtained in the same manner as in Example 1. Table 3 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg.

  The prepreg obtained in Example 13 had good room temperature storage stability, tack retention, and drape. Moreover, the interlaminar fracture toughness mode I of the fiber reinforced composite material produced using this prepreg was a good value.

[Example 14]
TMH-BMI, BMI-1100H, and Matrimid 5292B were stirred at 120 ° C. for 30 minutes using a stirrer at the ratio shown in Table 3, and completely dissolved. The resin composition was cooled to 80 ° C., Matrimid 5292A and HYPRO ATBN 1300X16 were added, and mixed and stirred for 30 minutes to prepare a thermosetting bismaleimide resin composition. Using this thermosetting bismaleimide resin composition, a prepreg was obtained in the same manner as in Example 1. Table 3 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg.

  In Example 14, by dispersing a solid phase component in a large amount in the resin composition, the solid phase component on the surface of the prepreg increases, and the resin impregnation tendency tends to deteriorate, and room temperature storage stability and tack retention are observed. Sex was a little worse. However, the interlaminar fracture toughness mode I of the fiber reinforced composite material produced using this prepreg was a good value.

[Comparative Example 10]
BMI-1100H, GP-207-R, and Matrimid 5292B were stirred at 120 ° C. for 30 minutes using a stirrer at the ratio shown in Table 3, and completely dissolved. The resin composition was cooled to 80 ° C., Matrimid 5292A was added, and the mixture was stirred for 30 minutes to prepare a resin composition. Using this resin composition, a prepreg was obtained in the same manner as in Example 1. Table 3 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg.

  In Comparative Example 10 in which HYPRO ATBN 1300X16 was not added to the resin composition, the interlaminar fracture toughness mode I of the carbon fiber reinforced composite material was a low value as compared with Examples 11-14. Further, by dissolving BMI1100H in Matrimid 5292B, the curing reaction of the resin composition proceeds, making it difficult to fit the prepreg along the mold. In addition, BMI1100H dissolved during storage at room temperature gradually precipitated over time, and room temperature storage stability and tack retention deteriorated.

[Comparative Example 11]
Matrimid 5292B, TMH-BMI, and BMI-80 were stirred with a stirrer at 120 ° C. for 30 minutes and dissolved completely at the ratios shown in Table 3. The resin composition was cooled to 80 ° C., Matrimid 5292A was added, and the mixture was stirred for 30 minutes to prepare a resin composition. Using this resin composition, a prepreg was obtained in the same manner as in Example 1. Table 3 shows various performances of the obtained prepreg and various performances of the carbon fiber reinforced composite material produced using the prepreg.

  The prepreg obtained in Comparative Example 11 had good room temperature storage stability, tack retention, and drape. However, in Comparative Example 11 in which HYPRO ATBN 1300X16 was not added to the resin composition, the interlaminar fracture toughness mode I of the carbon fiber reinforced composite material was a low value as compared with Examples 11-14.

Claims (9)

The following (a) to (c) components (a) component: bismaleimide compound,
(B) component: alkenylphenol and / or alkenylphenol ether compound,
(C) component: an acrylonitrile-butadiene copolymer having amine end groups,
As an essential component,
(C) Content of component is 3-30 mass%, The thermosetting bismaleimide-type resin composition characterized by the above-mentioned.   The thermosetting bismaleimide resin composition according to claim 1, wherein a ratio of a solid phase component in the thermosetting bismaleimide resin composition is 5 to 50% by mass.   The thermosetting bismaleimide resin composition according to claim 1 or 2, wherein the component (a) comprises an aromatic bismaleimide compound and an aliphatic bismaleimide compound.   The thermosetting bismaleimide resin composition according to any one of claims 1 to 3, wherein the amine end group is a secondary amine end group.   The thermosetting bismaleimide-based resin composition according to any one of claims 1 to 4, comprising 0.1 to 15% by mass of a thermoplastic resin. The following (a) to (c) components (a) component: bismaleimide compound,
(B) component: alkenylphenol and / or alkenylphenol ether compound,
(C) component: an acrylonitrile-butadiene copolymer having amine end groups,
The method for producing a thermosetting bismaleimide resin composition according to claim 1, wherein the composition is mixed at a temperature of 60 to 140 ° C. A reinforcing fiber substrate;
The thermosetting bismaleimide resin composition according to claim 1 impregnated in the reinforcing fiber substrate;
A prepreg consisting of
The ratio of the said thermosetting bismaleimide-type resin composition in the said prepreg is 20-60 mass%, The prepreg characterized by the above-mentioned.   The prepreg according to claim 7, wherein the reinforcing fiber base is composed of carbon fibers.   The method for producing a prepreg according to claim 7 or 8, wherein the reinforcing fiber base material is impregnated with the thermosetting bismaleimide resin composition according to claim 1 at a temperature of 70 to 160 ° C.