JP5381146B2 - Fiber reinforced prepreg and cured product - Google Patents

Description

The present invention relates to a bismaleimide composition useful as a resin composition for fiber-reinforced composite materials, and more particularly to a bismaleimide composition useful as a matrix resin composition used in applications requiring heat resistance.
The present invention also relates to a fiber reinforced prepreg using such a bismaleimide composition and a cured product obtained by curing the bismaleimide composition and the fiber reinforced prepreg.

  The fiber reinforced composite material is composed of a matrix resin and reinforcing fibers such as carbon fiber, glass fiber, alumina fiber, boron fiber, and aramid fiber, and generally has light weight and high strength characteristics. Such fiber reinforced composite materials are used in aerospace materials such as airframes and wings of passenger aircraft, machine tool members represented by robot hand arms, construction and civil engineering repair materials, and golf shafts and tennis rackets. Widely used for leisure goods.

  In particular, in recent years, carbon fiber reinforced composite materials (hereinafter referred to as “CFRP”) have been used as machine tool members, and have been used in place of conventional aluminum hands as glass transfer robot hands during liquid crystal display manufacturing. . Due to the increase in processing temperature due to the increase in size and performance of the liquid crystal display, the robot hand for transporting liquid crystal glass maintains rigidity and has heat resistance in the temperature range from room temperature to about 200 ° C. It is required to be sufficiently high, that is, there is little thinning even when used under long-term high temperature conditions, and there is little deterioration in physical properties such as rigidity.

  CFRP is usually produced by impregnating a carbon fiber unidirectional or cross-knitted sheet with a matrix resin to form a prepreg, and then heat-curing while giving the shape and molding. Conventionally, epoxy resins have been widely used as matrix resins, but epoxy resins have low heat resistance and are unsuitable for robotic hand applications for transporting liquid crystal glass.

  A maleimide resin is widely known as a matrix resin that has high heat resistance and can withstand a use environment of 200 ° C. or higher. As the main component of the maleimide resin, a bismaleimide compound is used. However, since only this product has poor curability and the molded product becomes brittle, various modifiers have been developed to improve this.

  For example, Kelimide resin (Rhône-Poulenc, France) modified 4,4'-diphenylmethane bismaleimide, which is solid at room temperature, with an aromatic diamine such as methylenedianiline to reduce the crosslink density by polymerization of maleimide groups. It is stiff. However, since the kelimide resin is generally solid, it is necessary to use a solvent when impregnating the carbon fiber sheet, it is difficult to remove the solvent used, and the influence of the residual solvent when the CFRP is finally cured by heating. Therefore, voids are generated, which is not preferable in terms of the quality of CFRP.

  A method of modifying a maleimide resin with an allyl compound is also known. For example, Matrimide resin (Ciba Geigy) is a resin obtained by heating and melting and mixing 4,4′-diphenylmethane bismaleimide with o, o′-diallylbisphenol A, which is liquid at room temperature, and is a solvent-free carbon fiber sheet. It is possible to impregnate. However, the storage stability of the obtained prepreg is poor, and the maleimide component gradually precipitates at room temperature, and there is a problem that tackiness and draping properties necessary for the prepreg are lost.

In order to solve this problem, Compimido 353 resin (or H353 resin, German Techno Chemie) has been proposed (see Non-Patent Document 1). This is because the bismaleimide compound used is a 1,6-bismaleimide- (2,2,2) with respect to a eutectic mixture of 4,4′-diphenylmethane bismaleimide and 4-methyl-1,3-phenylenebismaleimide. The precipitation and solidification of the maleimide component is prevented by adding 10 to 15% of 4-trimethyl) hexane. By mixing o, o′-diallylbisphenol A with this resin, a matrix resin suitable for the production of CFRP can be obtained.
However, CFRP molded using this resin is brittle, and many cracks are observed in the molded product. Furthermore, since the weight loss when placed under a high temperature for a long period of time is large, the glass substrate is greatly contaminated with decomposition products, so there is a problem in product quality including reliability as a CFRP robot hand for transporting liquid crystal glass.

Technical Papers-Society of Plastics Engineers, Vol. 20, p. 88 (1974)

  The present invention has been made in view of the above-described conventional situation, and in a matrix resin having heat resistance suitable for a CFRP robot hand for transporting liquid crystal glass, etc., solvent-free impregnation, tackiness of prepreg, drape, An object of the present invention is to provide a matrix resin in which the cracks of CFRP are reduced and the weight loss is small when placed under a high temperature for a long time, that is, the heat resistance is further improved without impairing the storage stability.

As a result of intensive studies to solve the above problems, the inventor of the present invention uses a specific aromatic bismaleimide compound and an aliphatic bismaleimide compound as a bismaleimide compound, particularly, three or more aromatic rings in one molecule. By blending the aromatic bismaleimide compound, it has an appropriate viscosity even without a solvent, and therefore has excellent impregnation properties, and also has excellent tackiness, draping properties, and storage stability when used as a prepreg. Furthermore, it has been found that a highly heat-resistant maleimide resin with reduced cracks in the molded product can be obtained.
The present invention has been achieved based on such knowledge, and the gist thereof is as follows.

[1] A fiber-reinforced prepreg containing a bismaleimide-based composition containing the following components (A) to (D).
(A) Aromatic bismaleimide compound containing 3 or more aromatic rings in one molecule: 100 parts by weight (B) Aliphatic bismaleimide compound: 1 to 50 parts by weight (C) Two aromatic rings in one molecule Aromatic bismaleimide compound containing one: 30 to 300 parts by weight (D) Bisphenol compound represented by the following formula (1): 30 to 300 parts by weight

(In the formula (1), X represents a single bond, CH ₂ , O, S, SO ₂ , or C (CH ₃ ) ₂ ;
R represents an allyl group or a methallyl group. )

[2] The fiber-reinforced prepreg according to [1], wherein the bismaleimide composition further includes the following component (E).
(E) Polymerization accelerator: 0.005 to 5 parts by weight

[3] (A) component Ri aromatic bismaleimide compound der represented by the following formula (2), (B) the number of carbon atoms of residues obtained by removing two maleimide groups of the aliphatic bismaleimide compound of component Is a fiber-reinforced prepreg according to [1] or [2], wherein the component (C) is an aromatic bismaleimide compound represented by the following formula (3) or the following formula (4) .

（式（３）中、Ｒ _７ は、単結合、ＣＨ _２ 、Ｏ、Ｓ、ＳＯ _２ 、Ｃ（ＣＨ _３ ） _２ またはＮＨＣ（＝Ｏ）を表し、
Ｒ _８ およびＲ _９ は、それぞれ独立に、ヒドロキシ基、炭素数６以下のアルキル基、炭素数６以下のアルコキシ基、アシルオキシ基、アシル基、複素環基、またはハロゲン原子を表し、
ｐおよびｑはそれぞれ独立に０以上４以下の整数を表す。）

（式（４）中、Ｒ _１０ は、ヒドロキシ基、炭素数６以下のアルキル基、炭素数６以下のアルコキシ基、アシルオキシ基、アシル基、複素環基、またはハロゲン原子を表し、
ｒは０以上４以下の整数を表す。） (In Formula (2), R ₁ and R ₂ each independently represents a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O),
R ₃ , R ₄ and R ₅ each independently represent a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom;
n represents an integer of 1 to 5,
x, y, and z each independently represent an integer of 0 or more and 4 or less. )

(In Formula (3), R ₇ represents a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O),
R ₈ and R ₉ each independently represent a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom;
p and q each independently represent an integer of 0 or more and 4 or less. )

(In the formula (4), R ₁₀ represents a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom;
r represents an integer of 0 or more and 4 or less. )

[ 4 ] The fiber-reinforced prepreg according to any one of [1] to [ 3 ], wherein R in the formula (1) is an allyl group.

[ 5 ] The fiber-reinforced prepreg according to any one of [2] to [ 4 ], wherein the component (E) is an organic peroxide or an anionic polymerization accelerator .

[ 6 ] The fiber-reinforced prepreg according to [ 5 ], wherein the component (E) is selected from imidazoles and cyclic aliphatic amines represented by the following formula (5).

(In the formula (5), R ₁₁ , R ₁₂ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, chain alkyl group, cyclic alkyl group, aromatic group, heterocyclic group, alkoxy group, acyloxy group, acyl. And R ₁₁ and R ₁₂ , R ₁₄ and R ₁₅ , and R ₁₁ and R ₁₅ may be bonded to each other to form a ring condensed with an imidazole ring.)

[ 7 ] Component (E) is derived from imidazoles and DABCO (1,4-diazabicyclo [2.2.2] octane) in which R ₁₂ in formula (5) is an alkyl group having 2 or less carbon atoms or a hydrogen atom. The fiber-reinforced prepreg according to [ 6 ], which is selected.

[8] (E) component, fiber reinforced prepreg according to _{[7] R 12} is selected from imidazoles is a methyl group or a hydrogen atom in the formula (5).

（式（１）中、Ｘは、単結合、ＣＨ _２ 、Ｏ、Ｓ、ＳＯ _２ 、またはＣ（ＣＨ _３ ） _２ を表し、
Ｒはアリル基またはメタリル基を表す。）
［１１］ 前記ビスマレイミド系組成物が、さらに下記（Ｅ）成分を含む［１０］に記載の硬化物。
（Ｅ）重合促進剤：０．００５〜５重量部
［１２］ （Ａ）成分が下記式（２）で表される芳香族ビスマレイミド化合物であり、（Ｂ）成分の脂肪族ビスマレイミド化合物の２つのマレイミド基を除いた残基の炭素原子数が４以上２０以下であり、（Ｃ）成分が、下記式（３）または下記式（４）で表される芳香族ビスマレイミド化合物である［１０］または［１１］に記載の硬化物。

（式（２）中、Ｒ _１ およびＲ _２ は、それぞれ独立に、単結合、ＣＨ _２ 、Ｏ、Ｓ、ＳＯ _２ 、Ｃ（ＣＨ _３ ） _２ またはＮＨＣ（＝Ｏ）を表し、
Ｒ _３ 、Ｒ _４ およびＲ _５ は、それぞれ独立に、ヒドロキシ基、炭素数６以下のアルキル基、炭素数６以下のアルコキシ基、アシルオキシ基、アシル基、複素環基、またはハロゲン原子を表し、
ｎは１以上５以下の整数を表し、
ｘ、ｙおよびｚはそれぞれ独立に０以上４以下の整数を表す。）

（式（３）中、Ｒ _７ は、単結合、ＣＨ _２ 、Ｏ、Ｓ、ＳＯ _２ 、Ｃ（ＣＨ _３ ） _２ またはＮＨＣ（＝Ｏ）を表し、
Ｒ _８ およびＲ _９ は、それぞれ独立に、ヒドロキシ基、炭素数６以下のアルキル基、炭素数６以下のアルコキシ基、アシルオキシ基、アシル基、複素環基、またはハロゲン原子を表し、
ｐおよびｑはそれぞれ独立に０以上４以下の整数を表す。）

（式（４）中、Ｒ _１０ は、ヒドロキシ基、炭素数６以下のアルキル基、炭素数６以下のアルコキシ基、アシルオキシ基、アシル基、複素環基、またはハロゲン原子を表し、
ｒは０以上４以下の整数を表す。）
［１３］ 式（１）におけるＲがアリル基である［１０］ないし［１２］のいずれかに記載の硬化物。
［１４］ （Ｅ）成分が有機過酸化物又はアニオン重合促進剤である［１１］ないし［１３］のいずれかに記載の硬化物。
［１５］ （Ｅ）成分が下記式（５）で表されるイミダゾール類および環状脂肪族アミン類から選ばれる［１４］に記載の硬化物。

（式（５）中、Ｒ _１１ 、Ｒ _１２ 、Ｒ _１４ およびＲ _１５ は、それぞれ独立に水素原子、鎖状アルキル基、環状アルキル基、芳香族基、複素環基、アルコキシ基、アシルオキシ基、アシル基、またはヒドロキシ基を表す。また、Ｒ _１１ とＲ _１２ 、Ｒ _１４ とＲ _１５ 、Ｒ _１１ とＲ _１５ は、それぞれ互いに結合してイミダゾール環に縮合する環を形成していてもよい。）
［１６］ （Ｅ）成分が、前記式（５）におけるＲ _１２ が炭素数２以下のアルキル基または水素原子であるイミダゾール類およびＤＡＢＣＯ（１，４−ジアザビシクロ［２．２．２］オクタン）から選ばれる［１５］に記載の硬化物。
［１７］ （Ｅ）成分が、前記式（５）におけるＲ _１２ がメチル基または水素原子であるイミダゾール類から選ばれる［１６］に記載の硬化物。 [ 9 ] A cured product obtained by curing the fiber-reinforced prepreg according to any one of [1] to [8] .
[10] A cured product obtained by curing a bismaleimide composition containing the following components (A) to (D).
(A) Aromatic bismaleimide compound containing 3 or more aromatic rings in one molecule: 100 parts by weight
(B) Aliphatic bismaleimide compound: 1 to 50 parts by weight
(C) Aromatic bismaleimide compound containing two or one aromatic ring in one molecule: 30 to 300 parts by weight
(D) Bisphenol compound represented by the following formula (1): 30 to 300 parts by weight

(In the formula (1), X represents a single bond, CH ₂ , O, S, SO ₂ , or C (CH ₃ ) ₂ ;
R represents an allyl group or a methallyl group. )
[11] The cured product according to [10], wherein the bismaleimide composition further includes the following component (E).
(E) Polymerization accelerator: 0.005 to 5 parts by weight
[12] The component (A) is an aromatic bismaleimide compound represented by the following formula (2), and the number of carbon atoms of the residue excluding the two maleimide groups of the aliphatic bismaleimide compound (B) is 4 to 20 and the cured product according to [10] or [11], wherein the component (C) is an aromatic bismaleimide compound represented by the following formula (3) or the following formula (4).

(In Formula (2), R ₁ and R ₂ each independently represents a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O),
R ₃ , R ₄ and R ₅ each independently represent a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom;
n represents an integer of 1 to 5,
x, y, and z each independently represent an integer of 0 or more and 4 or less. )

(In Formula (3), R ₇ represents a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O),
R ₈ and R ₉ each independently represent a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom;
p and q each independently represent an integer of 0 or more and 4 or less. )

(In the formula (4), R ₁₀ represents a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom;
r represents an integer of 0 or more and 4 or less. )
[13] The cured product according to any one of [10] to [12], wherein R in Formula (1) is an allyl group.
[14] The cured product according to any one of [11] to [13], wherein the component (E) is an organic peroxide or an anionic polymerization accelerator.
[15] The cured product according to [14], wherein the component (E) is selected from imidazoles and cycloaliphatic amines represented by the following formula (5).

(In the formula (5), R ₁₁ , R ₁₂ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, chain alkyl group, cyclic alkyl group, aromatic group, heterocyclic group, alkoxy group, acyloxy group, acyl. And R ₁₁ and R ₁₂ , R ₁₄ and R ₁₅ , and R ₁₁ and R ₁₅ may be bonded to each other to form a ring condensed with an imidazole ring.)
[16] From the imidazoles and DABCO (1,4-diazabicyclo [2.2.2] octane) in which R ₁₂ in the formula (5) is an alkyl group having 2 or less carbon atoms or a hydrogen atom in the above formula (5), The cured product according to [15], which is selected.
[17] The cured product according to [16] , wherein the component (E) is selected from imidazoles in which R ₁₂ in the formula (5) is a methyl group or a hydrogen atom.

  According to the bismaleimide composition of the present invention, even if it is solventless, it has an appropriate viscosity and is fundamentally used as a matrix resin for CFRP, such as having tackiness, draping property and storage stability when used as a prepreg. Without damaging the properties required for CFRP, cracks in CFRP molded products are reduced, and there is little weight loss when placed under high temperature for a long period of time, and mechanical properties from room temperature to 200 ° C are superior to conventional products. A thing is obtained. Therefore, the bismaleimide composition of the present invention is particularly suitably used as a CFRP matrix resin for use in a robot hand for transporting liquid crystal glass substrates.

  Hereinafter, the best mode for carrying out the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

[Bismaleimide composition]
The bismaleimide composition of the present invention contains the following components (A) to (D), and more preferably contains the following component (E).
(A) Aromatic bismaleimide compound containing 3 or more aromatic rings in one molecule: 100 parts by weight (B) Aliphatic bismaleimide compound: 1 to 50 parts by weight (C) Two aromatic rings in one molecule 1-containing aromatic bismaleimide compound: 30 to 300 parts by weight (D) Bisphenol compound represented by the following formula (1): 30 to 300 parts by weight (E) Polymerization accelerator: 0.005 to 5 parts by weight

(In the formula (1), X represents a single bond, CH ₂ , O, S, SO ₂ , or C (CH ₃ ) ₂ ;
R represents an allyl group or a methallyl group. )

<(A) component>
(A) The aromatic bismaleimide compound containing 3 or more aromatic rings in one molecule is preferably represented by the following formula (2).

(In Formula (2), R ₁ and R ₂ each independently represents a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O),
R ₃ , R ₄ and R ₅ each independently represent a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom;
n represents an integer of 1 to 5,
x, y, and z each independently represent an integer of 0 or more and 4 or less. )

In formula (2), R ₁ and R ₂ are a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), which may be the same or different, From the economical viewpoint, a single bond, CH ₂ , O, or C (CH ₃ ) ₂ is particularly preferable.
n is 1 or more and 5 or less, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less.

R ₃ , R ₄ and R ₅ are each independently a hydroxy group; an optionally branched alkyl group having 6 or less carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group; a carbon such as a methoxy group Aliphatic alkoxy groups having 6 or less; acyloxy groups having 6 or less carbon atoms (aliphatic acyloxy groups) such as formyloxy group and acetoxy group; acyl groups such as acetyl group and benzoyl group, complex such as pyridyl group and furyl group A halogen atom such as a cyclic group, fluorine, chlorine, or bromine atom may be mentioned, and among these, an alkyl group having 3 or less carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.

x, y and z are each independently an integer of 0 or more and 4 or less, preferably 0 or more and 3 or less, more preferably 0 or 1.
When x, y, and z are 2 or more, a plurality of R ₃ , R _4, and R ₅ may be the same or different.

  Specific examples of the aromatic bismaleimide compound containing three or more aromatic rings in one molecule of the component (A) include 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis [4-maleimide (4-phenoxyphenyl)] sulfone, 1,1 ′-[1,4-phenylenebis (oxy-4,1-phenylene)] bismaleimide (CAS Registry No. [82577-60-4]), 1,1 '-[Sulfonylbis (4,1-phenyleneoxy-3,1-phenylene)] bismaleimide ([99391-93-2]), bis [4- (3-maleimidophenoxy) phenyl] ketone, 1,3- Bis (4-maleimidophenoxy) benzene, 1,1 ′-[oxybis (4,1-phenylenethio-4,1-phenylene)] bismaleimide ([294890 20-3]), 1,1 ′-[(2,2 ′, 3,3 ′, 5,5 ′, 6,6′-octafluoro [1,1′-biphenyl] -4,4′-diyl ) Bis (oxy-3,1-phenylene)] bismaleimide ([352217-51-7]) and the like. Preferably, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis [4-maleimido (4-phenoxyphenyl)] sulfone, 1,3-bis (4-maleimidophenoxy) benzene, Of these, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane is most preferred.

  These (A) components may be used individually by 1 type, and 2 or more types may be mixed and used for them.

<(B) component>
The (B) aliphatic bismaleimide compound is mainly composed of a hydrocarbon group in which a main chain connecting two maleimide groups may be substituted with one or more substituents. This main chain may contain an ether group, a sulfide group or a ketone group, an ester group, an amide group, etc., but refers to a compound that does not contain an aromatic ring in its molecular structure. The hydrocarbon group of the main chain may be linear or cyclic, and may further have a branched chain, but is preferably linear.

  There are no particular restrictions on the substituents substituted on the hydrocarbon group of the main chain, but an alkyl group having 6 or less carbon atoms that may be branched, such as a methyl group, an ethyl group, a propyl group, or a butyl group; Aliphatic alkoxy groups having 6 or less carbon atoms; acyloxy groups having 6 or less carbon atoms (aliphatic acyloxy groups) such as formyloxy group and acetoxy group; aliphatic acyl groups such as acetyl group and propionyl group, fluorine, chlorine, 1 type, or 2 or more types, such as a halogen atom like a bromine atom, are mentioned.

  In the aliphatic bismaleimide compound (B), the number of carbon atoms of the residue excluding two maleimide groups is usually 2 or more and 30 or less, particularly 4 or more and 20 or less, and particularly preferably 6 or more and 12 or less.

  Specific examples of the component (B) aliphatic bismaleimide compound include 1,6-bismaleimide- (2,2,4-trimethyl) hexane, N, N′-decamethylene bismaleimide, and N, N′-octamethylene. Bismaleimide, N, N′-heptamethylene bismaleimide, N, N′-hexamethylene bismaleimide, N, N′-pentamethylene bismaleimide, N, N′-tetramethylene bismaleimide, N, N′-trimethylene Bismaleimide, N, N′-ethylene bismaleimide, N, N ′-(oxydimethylene) bismaleimide, 1,13-bismaleimide-4,7,10-trioxatridecane, 1,11-bis (maleimide) ) -3,6,9-trioxaundecane and the like. Among these, 1,6-bismaleimide- (2,2,4-toe) Methyl) hexane and N, N'-hexamethylene-bis-maleimide is preferably used.

  These (B) components may be used individually by 1 type, and 2 or more types may be mixed and used for them.

<(C) component>
(C) The aromatic bismaleimide compound containing two or one aromatic ring in one molecule is preferably a compound represented by the following formula (3) or the following formula (4).

(In Formula (3), R ₇ represents a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O),
R ₈ and R ₉ each independently represent a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom;
p and q each independently represent an integer of 0 or more and 4 or less. )

(In the formula (4), R ₁₀ represents a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom;
r represents an integer of 0 or more and 4 or less. )

In the formula (3), R ₇ is a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), and particularly from the viewpoint of economy, a single bond, CH ₂ , O, or C (CH ₃ ) ₂ is preferred.

R ₈ and R ₉ are each independently a hydroxy group; an optionally branched alkyl group having 6 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group; and 6 or less carbon atoms such as a methoxy group. Aliphatic acyl groups such as formyloxy groups and acetoxy groups, such as acyloxy groups having 6 or less carbon atoms (aliphatic acyloxy groups); acyl groups such as acetyl groups and benzoyl groups; heterocyclic groups such as pyridyl groups and furyl groups; Halogen atoms such as fluorine, chlorine and bromine atoms may be mentioned. Among these, alkyl groups having 3 or less carbon atoms are preferred, and methyl groups or ethyl groups are more preferred.

p and q are each independently an integer of 0 or more and 4 or less, preferably 0 or more and 3 or less, more preferably 0 or 1.
When p and q are 2 or more, a plurality of R ₈ and R ₉ may be the same or different.

In the formula (4), R ₁₀ is a hydroxy group; an alkyl group having 6 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group; an alkyl group having 6 or less carbon atoms such as a methoxy group Alkoxy group; acyloxy group having 6 or less carbon atoms such as formyloxy group and acetoxy group (aliphatic acyloxy group); acyl group such as acetyl group and benzoyl group; heterocyclic group such as pyridyl group and furyl group; fluorine and chlorine And a halogen atom such as a bromine atom. Among these, an alkyl group having 3 or less carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.

r is an integer of 0 or more and 4 or less, preferably 0 or more and 3 or less, more preferably 0 or 1.
When r is 2 or more, the plurality of R ₁₀ may be the same or different.

  Specific examples of the aromatic bismaleimide compound containing two or one aromatic ring in one molecule of component (C) include compounds having two aromatic rings, such as 4,4′-diphenylmethane bismaleimide, N, N ′. -(4,4'-biphenylene) bismaleimide, N, N '-(sulfonyldi-p-phenylene) bismaleimide, N, N'-(oxydi-p-phenylene) bismaleimide, N, N '-(3 , 3′-dimethyl-4,4′-biphenylylene) bismaleimide, N, N ′-(benzylidenedi-p-phenylene) bismaleimide, 3,3′-dichloro-4,4′-diphenylmethane bismaleimide, 3, 3'-dimethyl-4,4'-diphenylmethane bismaleimide, 3,3'-dimethoxy-4,4'-diphenylmethane bismaleimide, 4,4'-dipheny Sulfide bismaleimide, 3,3′-benzophenone bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 1,1 ′-[1,4-butanediylbis (oxy- p-phenylene)] bismaleimide and the like, and as a compound having one aromatic ring, 4-methyl-1,3-phenylenebismaleimide, 1,3-phenylenebismaleimide, 1,4-phenylenebismaleimide, 1, Examples thereof include 2-phenylene bismaleimide, naphthalene-1,5-dimaleimide, 4-chloro-1,3-phenylene bismaleimide and the like. Among these, 4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, or 1,3-phenylene bismaleimide is preferably used.

  These (C) components may be used individually by 1 type, and 2 or more types may be mixed and used for them.

<(D) component>
(D) The bisphenol compound is represented by the following formula (1).

(In the formula (1), X represents a single bond, CH ₂ , O, S, SO ₂ , or C (CH ₃ ) ₂ ;
R represents an allyl group or a methallyl group. )

In formula (1), X is particularly preferably CH ₂ , O, or C (CH ₃ ) ₂ , and R is an allyl group (CH ₂ —CH═CH ₂ group) or a methallyl group (CH═CHCH ₃ group). ) Is preferably an allyl group.

  Specific examples of the component (D) bisphenol compound include o, o′-diallyl bisphenol A, o, o′-diallyl bisphenol F, o, o′-diallyl bisphenol S, 2,2′-diallyl-4,4. '-Biphenol, 3,3'-diallyl-4,4'-dihydroxy-diphenyl ether, 3,3'-diallyl-4,4'-dihydroxy-diphenyl sulfide, o, o'-dimethallylbisphenol A, o, o '-Dimethallylbisphenol F and the like can be mentioned, among which o, o'-diallylbisphenol A is preferably used.

  These (D) components may be used individually by 1 type, and 2 or more types may be mixed and used for them.

<(E) component>
The bismaleimide composition of the present invention is not particularly essential, but a known polymerization accelerator can be further added for the purpose of increasing the curing rate.

  As the polymerization accelerator, imidazole, 1-methylimidazole, 1-ethylimidazole, 1-vinylimidazole, carbonyldiimidazole, 1-methyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, 1-benzyl-2 -Methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-undecylimidazole, 2-methyl Imidazole, 2-phenylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, TBZ (2, -Dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenyl-imidazolium trimellitate, 2-phenyl-4, Imidazole compounds such as 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, N, N-diisopropylethylamine, 1, 4-dimethylpiperazine, triphenylamine, N, N′-dicyclohexylurea, tributylamine, 1-benzyl-4-piperidone, N, N-dimethylbenzylamine, N, N-phenyldibenzylamine, 1-benzylpiperidine, 1-methyl-2,2-di Tyl-6,6-dimethylpiperidine, quinoxaline, quinoline, tetramethylenehexamine, pyrazole, triazole, benzotriazole, hydroxybenzotriazole, 2-methylimidazoline, 2-phenylimidazoline, DABCO (1,4-diazabicyclo [2.2. 2] a tertiary amine compound such as octane), an anionic polymerization accelerator such as triphenylphosphine or a trivalent phosphorus compound such as triphenyl phosphite, an organic peroxide polymerization accelerator, or azobis Examples include radical polymerization accelerators such as isobutyronitrile. Among these, anionic polymerization accelerators are preferable, and among them, imidazole polymerization accelerators and DABCO (1,4-diazabicyclo [2.2 .2] Cyclic aliphatic amines such as octane) System polymerization accelerators are preferred.

  As the imidazole polymerization accelerator, imidazoles represented by the following formula (5) are preferable.

(In the formula (5), R ₁₁ , R ₁₂ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, chain alkyl group, cyclic alkyl group, aromatic group, heterocyclic group, alkoxy group, acyloxy group, acyl. And R ₁₁ and R ₁₂ , R ₁₄ and R ₁₅ , and R ₁₁ and R ₁₅ may be bonded to each other to form a ring condensed with an imidazole ring.)

In formula (5), R ₁₁ represents a hydrogen atom, a chain (which may be linear or branched), a cyclic alkyl group, an aromatic group, a heterocyclic group, an alkoxy group, or an acyloxy group. Represents an acyl group or a hydroxy group. R ₁₁ may combine with R ₁₂ or R ₁₅ to form a ring condensed with an imidazole ring (which may be an aliphatic ring, an aromatic ring, or a heterocyclic ring). R ₁₁ is preferably a chain alkyl group having 4 or less carbon atoms or a hydrogen atom.

In the formula (5), R ₁₂ represents a hydrogen atom, a chain (which may be linear or branched), a cyclic alkyl group, an aromatic group, a heterocyclic group, an alkoxy group, an acyloxy group. Represents an acyl group or a hydroxy group. R ₁₂ may combine with R ₁₁ to form a ring condensed with an imidazole ring (which may be an aliphatic ring, an aromatic ring, or a heterocyclic ring). R ₁₂ is preferably a chain alkyl group having 4 or less carbon atoms or a hydrogen atom, more preferably a chain alkyl group having 2 or less carbon atoms or a hydrogen atom, and still more preferably a methyl group or hydrogen atom.

In the formula (5), R ₁₄ represents a hydrogen atom, a chain (which may be linear or branched), an alkyl group, a cyclic alkyl group, an aromatic group, a heterocyclic group, an alkoxy group, or an acyloxy group. Represents an acyl group or a hydroxy group. R ₁₄ may be bonded to R ₁₅ to form a ring condensed with an imidazole ring (which may be an aliphatic ring, an aromatic ring, or a heterocyclic ring). R ₁₄ is preferably a chain alkyl group having 3 or less carbon atoms or a hydrogen atom, more preferably a hydrogen atom.

In the formula (5), R ₁₅ represents a hydrogen atom, a chain (which may be linear or branched), an alkyl group, a cyclic alkyl group, an aromatic group, a heterocyclic group, an alkoxy group, or an acyloxy group. Represents an acyl group or a hydroxy group. R ₁₅ may combine with R ₁₄ or R ₁₁ to form a ring condensed with an imidazole ring (which may be an aliphatic ring, an aromatic ring, or a heterocyclic ring). R ₁₅ is preferably a chain alkyl group having 18 or less carbon atoms, a cyclic alkyl group, an aromatic group (for example, phenyl group, benzyl group, naphthyl group), a heterocyclic group (for example, pyridyl group, furyl group, oxazolyl group, An imidazolyl group, a thiazolyl group), or a hydrogen atom.

  Specific examples of the imidazole polymerization accelerator include imidazole, 1-methylimidazole, 1-ethylimidazole, 1-vinylimidazole, carbonyldiimidazole, 1-methyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-undecyl Imidazole, 2-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimi Sol, TBZ (2,3-dihydro-1H-pyrrolo [1.2-a] benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenyl-imidazolium trimellitate 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, especially 1-isobutyl-2-methyl Imidazole, 1-methyl-2-methylimidazole, 1-vinylimidazole, 1-benzyl-2-methylimidazole, imidazole, 1-methylimidazole, 1-ethylimidazole, carbonyldiimidazole, 2-ethyl-4-methylimidazole Preferably used That.

  Specific examples of the cycloaliphatic amine polymerization accelerator include DABCO (1,4-diazabicyclo [2.2.2] octane).

  Specific examples of the organic peroxide polymerization accelerator include dicumyl peroxide, cumene hydroperoxide, t-butylcumyl peroxide, methyl isobutyl ketone peroxide, t-butyl perbenzoate, t-butyl peroctanoate and the like. Among them, dicumyl peroxide or cumene hydroperoxide is preferably used.

These (E) components may be used individually by 1 type, and 2 or more types may be mixed and used for them.

<Blending amount>
The bismaleimide composition of the present invention contains the components (A) to (D) as essential components, and the blending amount thereof is usually 1 part by weight of component (B) with respect to 100 parts by weight of component (A). It is 50 parts by weight or less, preferably 2 parts by weight or more and 50 parts by weight or less, more preferably 5 parts by weight or more and 50 parts by weight or less.
Component (C) is usually 30 to 300 parts by weight, preferably 40 to 200 parts by weight, more preferably 50 to 150 parts by weight, relative to 100 parts by weight of component (A). is there.
Component (D) is usually 30 to 300 parts by weight, preferably 40 to 250 parts by weight, more preferably 50 to 200 parts by weight, relative to 100 parts by weight of component (A). is there.

  When the amount of the component (B) is less than the above range, the viscosity of the composition increases and it becomes difficult to form a prepreg, and the maleimide component may be crystallized to lose tackiness. When there are more (B) components than the said range, the heat resistance of hardened | cured material will deteriorate.

  Moreover, when there are few (C) components from the said range, the heat resistance of a composition will deteriorate, the hardening rate at the time of heat molding will become remarkably slow, and shaping | molding will become difficult. When the amount of the component (C) is larger than the above range, although the heat resistance is improved, the cured product becomes brittle and the number of cracks also increases, so that the quality of the molded product is deteriorated.

  Moreover, when there are few (D) components from the said range, the viscosity of a composition will rise and prepreg will become difficult. When there are more (D) components than the said range, the heat resistance of hardened | cured material will deteriorate.

The amount of the polymerization accelerator of component (E) used as necessary is usually 0.005 to 5 parts by weight, preferably 0.01 to 3 parts by weight per 100 parts by weight of component (A). Parts by weight or less, more preferably 0.15 parts by weight or more and 1 part by weight or less.
If the amount of the component (E) is less than the above range, the polymerization promoting effect due to the blending of the component cannot be sufficiently obtained, and if it is large, the heat resistance of the cured product is deteriorated.

<Method of blending each component>
In order to produce the bismaleimide composition of the present invention, the components (A), (B), (C) and (D) may be mixed to obtain a uniformly dissolved or uniformly dispersed composition. There is no particular limitation on the method. Although these components may be mixed at room temperature, heating is preferable for economical production. In this case, the heating temperature is usually 30 ° C. or higher and 180 ° C. or lower, preferably 50 ° C. or higher and 150 ° C. or lower, more preferably 60 ° C. or higher and 140 ° C. or lower. If the temperature exceeds 180 ° C., the polymerization reaction becomes fast, and there is a possibility that polymerization solidifies during mixing.
The mixing time is usually 5 minutes or longer and 6 hours or shorter, preferably 10 minutes or longer and 3 hours or shorter, more preferably 15 minutes or longer and 2 hours or shorter, excluding the time required for raising and lowering the temperature. When the mixing time is longer than necessary, the viscosity increases due to polymerization, and the handling property as a matrix resin is impaired.

  There is no particular restriction on the order of adding each component during mixing, and all the components may be present at the same time, or each component may be separately added to the mixing tank, but is preferably liquid at low temperatures (D ) The components are put into a mixing tank in advance and heated to a predetermined temperature, and then the components (A), (B), and (C) are added to make the solution uniform or uniform. In mixing, it is preferable to properly stir the system.

  (E) As the timing of adding the polymerization accelerator of the component, the components (A), (B), (C) and (D) are heated and homogenized, and are usually 100 ° C. or less, preferably 90 ° C. In the following, it is more preferable to add it after cooling to 70 ° C. or lower. If it is added at a temperature higher than this, there is a risk that the polymerization proceeds rapidly and leads to solidification. The component (E) may be added directly to the mixture of the components (A), (B), (C) and (D) or may be added as a solution in which the component (E) is dissolved in the component (D). . In order to rapidly and uniformly mix the component (E), the component (E) is preferably added as a solution dissolved in the component (D). In this case, the amount of component (E) is 0.1 to 100 parts by weight, preferably 1 to 70 parts by weight, and more preferably 100 parts by weight of (D) component. 2 parts by weight or more and 50 parts by weight or less. After the addition of the polymerization accelerator, it is desirable that the composition is sufficiently stirred and mixed to uniformly mix the polymerization accelerator.

<Other ingredients>
The bismaleimide composition of the present invention may contain components other than the components (A) to (D) and the component (E) that is blended as necessary.
Such optional components are not particularly limited, but include coupling agents such as silane and titanate compounds, release agents such as higher fatty acids and waxes, flame retardants such as halogens and phosphorus compounds, antifoaming agents, and coloring. Agents, ultraviolet absorbers, low-temperature foaming agents, antioxidants, and the like, and the amount thereof is usually about 50 parts by weight or less per 100 parts by weight of component (A).

[Prepreg]
The bismaleimide composition of the present invention is compounded with one or more of reinforcing fibers such as carbon fiber, glass fiber, alumina fiber, boron fiber and aramid fiber by a known compounding method to form a fiber reinforced prepreg. (See, for example, “Introduction to Reinforced Plastic Materials for Product Development” written by Hiroo Miyairi and Toshimi Goto (Nikkan Kogyo Shimbun, 2007)).
Although there is no restriction | limiting in the reinforcing fiber to be used, Carbon fiber is especially preferable as a heat resistant robot hand use. There is no restriction | limiting in particular also in the form of a reinforced fiber, A unidirectional material, a woven fabric (cross), a braided woven fabric etc. are mentioned as an example.

  The method for impregnating these reinforcing fibers with the bismaleimide composition of the present invention is not particularly limited, but a method that does not use a solvent is preferable, so the bismaleimide composition of the present invention is heated to 60 to 110 ° C. However, a hot melt method of impregnation in a fluid state is preferable.

The proportion of the bismaleimide composition in the prepreg obtained (impregnated with the bismaleimide composition in the reinforcing fiber) is usually 20% by weight or more and 80% by weight or less, preferably 25% depending on the form of the reinforcing fiber. % By weight or more and 65% by weight or less, more preferably 30% by weight or more and 50% or less.
If the ratio of the bismaleimide composition is larger than this range, the ratio of the reinforcing fibers is relatively decreased, so that a sufficient reinforcing effect cannot be obtained. Conversely, if the bismaleimide composition is small, the moldability is impaired.

  This prepreg can be cured by a known method to obtain a final molded product. For example, a prepreg can be laminated, pressurized to 2 to 10 kgf / cm 2 in an autoclave, and heat-cured at 150 to 200 ° C. for 30 minutes to 3 hours to form a molded body, which further improves heat resistance. Therefore, a fiber reinforced composite material molded article can be obtained by performing post-cure treatment in the temperature range of 180 ° C. to 280 ° C. for 1 hour to 12 hours while stepwise heating.

  The bismaleimide composition or prepreg cured product of the present invention thus obtained, particularly a prepreg cured product, is particularly useful as a robot hand for transporting a liquid crystal glass substrate. However, the use of the cured product of the present invention is not limited to the use of a robotic hand for transporting a liquid crystal glass substrate, but is also lightweight, such as a use of a disk for transporting silicon wafers, a use for aerospace parts, a use for automobile engine parts, etc. It can be widely applied to members that require high strength and high heat resistance.

Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples and Reference Examples.
In the following, the method for measuring the physical properties of the composition and the method for evaluating the cured product are as follows.

<Viscosity>
The viscosity of the bismaleimide composition was measured with a viscoelasticity measuring apparatus PCR301 manufactured by Anton Paar.

<Catalytic activity>
The gelation temperature of the bismaleimide composition is measured when the temperature is raised from 40 ° C. to 200 ° C. at 3 ° C./minute, and the catalyst activity (polymerization acceleration of the polymerization accelerator is determined from the concentration of the polymerization accelerator that gels at 170 ° C. Effect).

<Stability at 80 ° C>
After raising the temperature from 40 ° C. to 80 ° C. at 3 ° C./min, the stability at 80 ° C. was evaluated from the change in viscosity of the bismaleimide composition when kept at 80 ° C. The value obtained by dividing the viscosity of the bismaleimide composition one hour after reaching 80 ° C. by the viscosity when reaching 80 ° C. is used as an index. The closer this value is to 1, the better the stability.

<Glass transition temperature (Tg)>
TMA: A bismaleimide composition heated to about 70 ° C. was poured between two glass plates through a 2 mm-thick spacer, treated at 170 ° C. for 3 hours, then taken out of the glass plate mold, and then at 190 ° C. A sample heat-treated for 1 hour, 220 ° C. for 1 hour, 250 ° C. for 4 hours, and 260 ° C. for 12 hours was cut into 5 mm × 5 mm. Using a TMA / SS120 manufactured by SII, this sample was heated from 40 ° C. to 380 ° C. at 10 ° C./min in a nitrogen atmosphere, and Tg was evaluated from the strain change of the compression probe.
DMS; Cast plate obtained by TMA section and CFRP plate obtained by <Manufacture of Carbon Fiber Reinforced Composite Material-1> were cut into 50 mm × 15 mm, and nitrogen was measured by a viscoelasticity measuring device PCR301 manufactured by Anton Paar. The temperature was raised from 50 ° C. to 420 ° C. at 5 ° C./min in the atmosphere, and Tg was evaluated from the peak of the value Tanδ obtained by dividing the obtained loss elastic modulus by the storage elastic modulus.

<Heat resistance>
The CFRP plate obtained by the production of carbon fiber reinforced composite material-1 was cut out to a size of 10 cm × 5 cm, and it was 1000 hours at 250 ° C. in an oven under air (however, in Example 14 and Comparative Example 1, 210 hours) ) After standing, the volatilization reduction rate of the weight was measured.

<Bending strength and flexural modulus>
The CFRP plate obtained by the production of carbon fiber reinforced composite material-1 was cut into a size of 10 cm × 1.5 cm, and in accordance with JIS K7074 (bending test method of carbon fiber reinforced plastic) at 23 ° C. and 200 ° C. Bending strength and flexural modulus were measured respectively.

<Crack interval>
The CFRP plate obtained by the production-2 of the carbon fiber reinforced composite material (each of those subjected to post-curing-1 and post-curing-2) was cut at right angles to the direction of the unidirectional prepreg, and the cut surface was polished. The cross section was observed with a polarizing microscope, and the average interval between cracks was calculated from the number of cracks between the width of 15 mm at the center of the cut surface.

[Example 1]
In a glass container (450 ml) equipped with a mechanical stirrer, 57.98 g of o, o′-diallylbisphenol A (Compimide TM124 manufactured by Degussa) was placed at room temperature. This container was immersed in an oil bath, and when the internal temperature reached 100 ° C., 15.00 g of 1,6-bismaleimide- (2,2,4-trimethyl) hexane (BMI-TMH manufactured by Daiwa Kasei Kogyo Co., Ltd.) was added for 10 minutes. Over time. Subsequently, 42.50 g of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80 manufactured by KEI Kasei Co., Ltd.) was added over 25 minutes. Subsequently, 42.50 g of 4,4′-diphenylmethane bismaleimide (BMI manufactured by KEI Kasei Co., Ltd. was pulverized with a Wonder Crush Mill WDL-1 manufactured by Osaka Chemical Co., Ltd.) was charged over 25 minutes. At this time, the input amount and the input interval were adjusted so that the internal temperature did not become 90 ° C. or less. Then, it stirred for 30 minutes, keeping internal temperature at 100 degreeC. After confirming that the powdered bismaleimide was uniformly dispersed, the internal temperature was set to 70 ° C. over 90 minutes with stirring. To this, a solution prepared by dissolving 0.225 g of 1-isobutyl-2-methylimidazole (IBMI12 manufactured by Japan Epoxy Resin) in 2.025 g of o, o′-diallylbisphenol A (Compigmide TM124 manufactured by Degussa) was added with stirring. Subsequently, after stirring for 60 minutes at an internal temperature of 70 ° C., the mixture was taken out and cooled to room temperature to obtain the desired bismaleimide composition. This bismaleimide composition could be stored in a refrigerator at 0 ° C. for one month or longer.

[Example 2]
In a glass container (450 ml) equipped with a mechanical stirrer, 50 g of o, o′-diallylbisphenol A (manufactured by Kodama Company) was placed at room temperature. When this container is immersed in an oil bath and the internal temperature reaches 100 ° C., 15.00 g of 1,6-bismaleimide- (2,2,4-trimethyl) hexane (BMI-TMH, manufactured by Daiwa Kasei Kogyo Co., Ltd.) is added for 1 minute. Over time. Subsequently, 42.50 g of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80 manufactured by KEI Kasei Co., Ltd.) was added over 10 minutes. Subsequently, 42.50 g of 4,4′-diphenylmethane bismaleimide (BMI manufactured by KEI Kasei Co., Ltd. was pulverized with a Wonder Crush Mill WDL-1 manufactured by Osaka Chemical Co., Ltd.) was charged over 10 minutes. At this time, the input amount and the input interval were adjusted so that the internal temperature did not become 90 ° C. or less. Then, it stirred for 60 minutes, keeping internal temperature at 100 degreeC. After confirming that the powdered bismaleimide was uniformly dispersed, the internal temperature was adjusted to 75 ° C. over 30 minutes with stirring. To this, a solution prepared by dissolving 0.225 g of 1-methyl-2-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) in 10.00 g of o, o′-diallylbisphenol A (manufactured by Kodama Co., Ltd.) was added with stirring. After stirring for 30 minutes at an internal temperature of 75 ° C., the mixture was taken out and cooled to room temperature to obtain the desired bismaleimide composition. This bismaleimide composition could be stored in a refrigerator at 0 ° C. for one month or longer.

[Example 3]
A glass container (450 ml) equipped with a mechanical stirrer was charged with 60 g of o, o′-diallylbisphenol A (Compimide TM124 manufactured by Degussa) at room temperature. When this container is immersed in an oil bath and the internal temperature reaches 100 ° C., 15.00 g of 1,6-bismaleimide- (2,2,4-trimethyl) hexane (BMI-TMH, manufactured by Daiwa Kasei Kogyo Co., Ltd.) is added for 1 minute. Over time. Subsequently, 42.50 g of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80 manufactured by KEI Kasei Co., Ltd.) was added over 10 minutes. Subsequently, 42.50 g of 4,4′-diphenylmethane bismaleimide (BMI manufactured by KEI Kasei Co., Ltd. was pulverized with a Wonder Crush Mill WDL-1 manufactured by Osaka Chemical Co., Ltd.) was charged over 10 minutes. At this time, the input amount and the input interval were adjusted so that the internal temperature did not become 90 ° C. or less. Then, it stirred for 60 minutes, keeping internal temperature at 100 degreeC. After confirming that the powdered bismaleimide was uniformly dispersed, the internal temperature was adjusted to 75 ° C. over 30 minutes with stirring. To this, 0.30 g of 1-vinylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was added with stirring. Subsequently, the mixture was stirred for 30 minutes at an internal temperature of 75 ° C., then the mixture was taken out and cooled to room temperature to obtain the desired bismaleimide. A system composition was obtained. This bismaleimide composition could be stored in a refrigerator at 0 ° C. for one month or longer.

[Example 4]
In a glass container (450 ml) equipped with a mechanical stirrer, 50 g of o, o′-diallylbisphenol A (Compigm TM124 manufactured by Degussa) at room temperature, 1,6-bismaleimide- (2,2,4-trimethyl) hexane (BMI-TMH manufactured by Daiwa Kasei Kogyo Co., Ltd.) 15.00 g, 42.50 g of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80 manufactured by KEI Kasei Co., Ltd.), and 4,4 42.50 g of '-diphenylmethane bismaleimide (BMI manufactured by KEI Kasei Co., Ltd. was pulverized with a Wonder Crush Mill WDL-1 manufactured by Osaka Chemical Co., Ltd.) was added. The vessel was immersed in an oil bath, and stirring was started when the internal temperature reached 90 ° C. After reaching 120 ° C, the vessel was cooled to an internal temperature of 85 ° C. To this, 0.45 g of 1-benzyl-2-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was added with stirring, and after stirring for 1 minute, the mixture was taken out and cooled to room temperature to achieve the desired bismaleimide composition. Got. This bismaleimide composition could be stored in a refrigerator at 0 ° C. for one month or longer.

[Example 5]
In a glass container (450 ml) equipped with a mechanical stirrer, 50 g of o, o′-diallylbisphenol A (Compigm TM124 manufactured by Degussa) at room temperature, 1,6-bismaleimide- (2,2,4-trimethyl) hexane (BMI-TMH manufactured by Daiwa Kasei Kogyo Co., Ltd.) 15.00 g, 42.50 g of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80 manufactured by KEI Kasei Co., Ltd.), and 4,4 42.50 g of '-diphenylmethane bismaleimide (BMI manufactured by KEI Kasei Co., Ltd. was pulverized with a Wonder Crush Mill WDL-1 manufactured by Osaka Chemical Co., Ltd.) was added. The vessel was immersed in an oil bath and stirring was started when the internal temperature reached 90 ° C., and the phenolic antioxidant 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) 1.5 g of -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (ADEKA STAB AO-20 manufactured by ADEKA) was added. After the internal temperature reached 120 ° C, the internal temperature was lowered to 85 ° C by cooling. A solution prepared by dissolving 3 g of 2-ethyl-4-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) in 3 g of o, o'-diallylbisphenol A (Compimid TM124 manufactured by Degussa Co., Ltd.) was added with stirring and stirred for 1 minute. Thereafter, the mixture was taken out and cooled to room temperature to obtain the desired bismaleimide composition. This bismaleimide composition could be stored in a refrigerator at 0 ° C. for one month or longer.

[Example 6]
In a glass container (450 ml) equipped with a mechanical stirrer, 50 g of o, o′-diallylbisphenol A (Compigm TM124 manufactured by Degussa) at room temperature, 1,6-bismaleimide- (2,2,4-trimethyl) hexane (BMI-TMH manufactured by Daiwa Kasei Kogyo Co., Ltd.) 15.00 g, 42.50 g of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80 manufactured by KEI Kasei Co., Ltd.), and 4,4 42.50 g of '-diphenylmethane bismaleimide (BMI manufactured by KEI Kasei Co., Ltd. was pulverized with a Wonder Crush Mill WDL-1 manufactured by Osaka Chemical Co., Ltd.) was added. The vessel was immersed in an oil bath and stirring was started when the internal temperature reached 90 ° C., and the phenolic antioxidant 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) 1.5 g of -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (ADEKA STAB AO-20 manufactured by ADEKA) was added. After the internal temperature reached 120 ° C, the internal temperature was lowered to 85 ° C by cooling. To this, 1.5 g of DABCO (1,4-diazabicyclo [2.2.2] octane) (manufactured by Tokyo Chemical Industry Co., Ltd.) finely pulverized in a mortar was added with stirring, the mixture was stirred for 1 minute, and the mixture was taken out. The desired bismaleimide composition was obtained by cooling to room temperature. This bismaleimide composition could be stored in a refrigerator at 0 ° C. for one month or longer.

[Example 7]
To a glass eggplant-shaped flask (100 ml), 6.67 g of o, o′-diallylbisphenol A (Compigimide TM124 manufactured by Degussa) was added at room temperature. This container is immersed in an oil bath, and when the internal temperature reaches 120 ° C., 2.00 g of 1,6-bismaleimide- (2,2,4-trimethyl) hexane (BMI-TMH manufactured by Daiwa Kasei Kogyo Co., Ltd.) 5.67 g of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80 manufactured by KEI Kasei Co., Ltd.) and then 4,4′-diphenylmethane bismaleimide (BMI manufactured by KAI Kasei Co., Ltd.) Was crushed with a wonder crush mill WDL-1 manufactured by Osaka Chemical Co., Ltd.) 5.67 g was charged over 10 minutes. At this time, the charging amount and the charging interval were adjusted so that the internal temperature did not become 110 ° C. or lower. Then, it stirred for 5 minutes, keeping internal temperature at 120 degreeC. After confirming that the powdered bismaleimide was uniformly dissolved, the internal temperature was set to 75 ° C. over 10 minutes with stirring. To this, a solution prepared by dissolving 0.03 g of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) in 1.33 g of o, o′-diallylbisphenol A (Compigimide TM124, manufactured by Degussa) was added with stirring, and subsequently at an internal temperature of 75 ° C. After stirring for 5 minutes, the mixture was taken out and cooled to room temperature to obtain the desired bismaleimide composition. This bismaleimide composition could be stored in a refrigerator at 0 ° C. for one month or longer.

[Examples 8 to 10]
A bismaleimide composition was obtained in the same manner as in Example 7, except that the polymerization accelerator shown in Table 1 was used instead of the imidazole in Example 7.

[Example 11]
To a glass eggplant-shaped flask (100 ml), 6.67 g of o, o′-diallylbisphenol A (Compigimide TM124 manufactured by Degussa) was added at room temperature. This container is immersed in an oil bath, and when the internal temperature reaches 120 ° C., 2.00 g of 1,6-bismaleimide- (2,2,4-trimethyl) hexane (BMI-TMH manufactured by Daiwa Kasei Kogyo Co., Ltd.) 5.67 g of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80 manufactured by KEI Kasei Co., Ltd.) and then 4,4′-diphenylmethane bismaleimide (BMI manufactured by KAI Kasei Co., Ltd.) Was crushed with a wonder crush mill WDL-1 manufactured by Osaka Chemical Co., Ltd.) 5.67 g was charged over 10 minutes. At this time, the charging amount and the charging interval were adjusted so that the internal temperature did not become 110 ° C. or lower. Then, it stirred for 5 minutes, keeping internal temperature at 120 degreeC. After confirming that the powdered bismaleimide was uniformly dissolved, the internal temperature was set to 75 ° C. over 10 minutes with stirring. To this, 0.2 g of 1-cyanoethyl-2-phenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) pulverized in a mortar was added with stirring, and after stirring for 5 minutes at an internal temperature of 75 ° C., the mixture was taken out and brought to room temperature. The desired bismaleimide composition was obtained by cooling. This bismaleimide composition could be stored in a refrigerator at 0 ° C. for one month or longer.

[Examples 12 to 13]
A bismaleimide composition was obtained in the same manner as in Example 11 except that the polymerization accelerator shown in Table 1 was used instead of 1-cyanoethyl-2-phenylimidazole in Example 11.

[Example 14]
A glass container (500 ml) equipped with a mechanical stirrer was charged with 78.62 g of o, o′-diallylbisphenol A (Compimido TM124 manufactured by Degussa) at room temperature, and the atmosphere was replaced with nitrogen. This container was immersed in an oil bath and heated with stirring so that the internal temperature reached a temperature increase rate of about 1 ° C./min. Immediately after the internal temperature exceeded 110 ° C., 25.10 g of 1,6-bismaleimide- (2,2,4-trimethyl) hexane (BMI-TMH manufactured by Daiwa Kasei Kogyo Co., Ltd.), 4,4′-diphenylmethane bismaleimide (BMI manufactured by KEI Kasei Co., Ltd., crushed with a Wonder Crush Mill WDL-1 manufactured by Osaka Chemical Co., Ltd.) 71.56 g, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (KI Kasei BMI-80) 71.29 g was gradually added in this order over 30 minutes with stirring. At this time, the amount and interval of one injection were adjusted so that the internal temperature would not be 90 ° C. or less. Thereafter, the internal temperature was raised to 125 ° C. while stirring, and the mixture was stirred at 125 ° C. for 30 minutes. After confirming that the mixture became a brown uniform liquid, the oil bath was removed, and the internal temperature was adjusted to 80 ° C. at a temperature lowering rate of about 1 ° C./min. While stirring, 490 mg of dicumyl peroxide (Nippon Park Mill D) was added, followed by stirring at an internal temperature of 80 ° C. for 30 minutes, and then cooling to room temperature to obtain the desired bismaleimide composition. This bismaleimide composition could be stored in a refrigerator at 0 ° C. for one month or longer.

[Comparative Example 1]
A glass separable flask (500 ml) equipped with a mechanical stirrer was charged with 152.65 g of o, o′-diallylbisphenol A (Degussa Compimide TM124) at room temperature, and the atmosphere was replaced with nitrogen. The flask was immersed in an oil bath and heated with stirring so that the internal temperature reached a temperature increase rate of about 1 ° C./min. Immediately after the internal temperature exceeded 110 ° C., 53.87 g of 1,6-bismaleimide- (2,2,4-trimethyl) hexane (BMI-TMH manufactured by Daiwa Kasei Kogyo Co., Ltd.), 4-methyl-1,3- Phenylene bismaleimide (BMI-7000 manufactured by Daiwa Kasei Kogyo Co., Ltd.) 85.72 g, 4,4′-diphenylmethane bismaleimide (BMI manufactured by KEI Kasei Co., Ltd. was crushed with a Wonder Crush Mill WDL-1 manufactured by Osaka Chemical Co., Ltd.) 221.55 g was added little by little in this order over 30 minutes with stirring. At this time, the injection amount and the injection interval are adjusted so that the internal temperature does not become 90 ° C. or less. Thereafter, the temperature was raised to 130 ° C. while stirring, and the mixture was stirred at 130 ° C. for 30 minutes. After confirming that the mixture became a brown uniform liquid, the oil bath was removed, and the internal temperature was adjusted to 80 ° C. at a temperature lowering rate of about 1 ° C./min. While stirring, 998 mg of dicumyl peroxide (Nippon Park Mill D) was added, and subsequently stirred at an internal temperature of 80 ° C. for 30 minutes, and then cooled to room temperature to obtain a resin composition.

[Reference Example 1]
To a glass eggplant-shaped flask (100 ml), 6.67 g of o, o′-diallylbisphenol A (Compigimide TM124 manufactured by Degussa) was added at room temperature. This container is immersed in an oil bath, and when the internal temperature reaches 120 ° C., 2.00 g of 1,6-bismaleimide- (2,2,4-trimethyl) hexane (BMI-TMH manufactured by Daiwa Kasei Kogyo Co., Ltd.) 5.67 g of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80 manufactured by KEI Kasei Co., Ltd.) and then 4,4′-diphenylmethane bismaleimide (BMI manufactured by KAI Kasei Co., Ltd.) Was crushed with a wonder crush mill WDL-1 manufactured by Osaka Chemical Co., Ltd.) 5.67 g was charged over 10 minutes. At this time, the charging amount and the charging interval were adjusted so that the internal temperature did not become 110 ° C. or lower. Then, it stirred for 5 minutes, keeping internal temperature at 120 degreeC. After confirming that the powdered bismaleimide was uniformly dissolved, the internal temperature was set to 75 ° C. over 10 minutes with stirring. 0.2 g of N, N-diisopropylethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added with stirring. Subsequently, the mixture was stirred at an internal temperature of 75 ° C. for 5 minutes, and then the mixture was taken out and cooled to room temperature. A composition was obtained.

[Reference Examples 2 to 14]
A bismaleimide composition was obtained in the same manner as in Reference Example 1 except that the polymerization accelerator shown in Table 1 was used instead of N, N-diisopropylamine in Reference Example 1.

<Production of carbon fiber reinforced composite material-1>
About 150 g / m ² of the resin film made of the bismaleimide composition obtained in Example 14 and Comparative Example 1 was hot in each carbon fiber sheet (PAN-based 3K plain weave cloth 235 GPa product, fiber basis weight about 200 g / m ² ). A carbon fiber prepreg was prepared by impregnation by a melt method. Even when the obtained prepreg was allowed to stand at room temperature for 2 weeks, changes in tackiness and drapeability were slight.
These prepregs were cut into 25 cm × 25 cm, laminated into 8 layers by a hand lay-up method, and autoclaved. Molding was performed by placing the laminated prepreg in a vacuum bag and heating at a pressure of 7 kgf (about 0.7 MPa) and a temperature of 170 ° C. for 3 hours while reducing the pressure with a vacuum pump. The cured prepreg was taken out as a molded plate. The resin ratio of the obtained CFRP plate was about 44 wt% when the bismaleimide composition of Example 14 was used, and about 46 wt% when the bismaleimide composition of Comparative Example 1 was used. This was further post-cured in the order of 190 ° C. for 2 hours, 220 ° C. for 2 hours, and 250 ° C. for 6 hours to obtain a CFRP plate.

<Manufacture of carbon fiber reinforced composite material-2>
About 150 g / m ² of the resin film made of the bismaleimide composition obtained in Example 14 and Comparative Example 1 was hot on each carbon fiber sheet (PA-based 3K plain weave cloth 235 GPa product, fiber basis weight about 200 g / m ² ). A carbon fiber prepreg (hereinafter referred to as “PP1”) was prepared by impregnation by a melt method. Similarly, a prepreg (hereinafter referred to as “PP2”) is impregnated into a unidirectional carbon fiber sheet (“Repelark” HM type (MRK-M6-30) manufactured by Mitsubishi Plastics, fiber basis weight of about 300 g / m ² ) using the same resin film. Created). Even when the obtained prepreg was allowed to stand at room temperature for 2 weeks, changes in tackiness and drapeability were slight.
These prepregs are cut into 10 cm × 10 cm, and PP1 (0 ° · 90 ° 1PLY) / PP2 (0 ° 3PLY) / PP1 (0 ° · 90 ° 1PLY) / PP2 (0 ° 3PLY) by hand lay-up method. / PP1 (0 ° / 90 ° 1PLY) was laminated in 9 layers and autoclave molded. Molding was performed by placing the laminated prepreg in a vacuum bag and heating at a pressure of 7 kgf (about 0.7 MPa) and a temperature of 170 ° C. for 3 hours while reducing the pressure with a vacuum pump. The cured prepreg was taken out as a molded plate. The resin ratio of the obtained CFRP plate was about 43% by weight when the bismaleimide composition of Example 14 was used, and about 44% by weight when the bismaleimide composition of Comparative Example 1 was used. This was further post-cured in the order of 190 ° C. for 1 hour, 220 ° C. for 1 hour, and 250 ° C. for 4 hours (this post-curing treatment is referred to as “post-curing-1”). The obtained CFRP plate was cut, and one side was further subjected to heat treatment at 260 ° C. for 12 hours (this post-curing treatment is referred to as “post-curing-2”).

  The evaluation results are summarized in Tables 1 and 2.

From Table 1, it can be seen that, according to the present invention, a high strength CFRP plate excellent in catalytic activity, 80 ° C. stability, and heat resistance can be obtained by a bismaleimide composition excellent in solvent-free impregnation.
In TMA of Example 1, Tg was observed only at a high temperature of 328 ° C. On the other hand, in Examples 2, 3, and 4, inflection points were observed at low temperatures of 139, 151, and 161 ° C., respectively, in addition to Tg at high temperatures of 331, 324, and 333 ° C. It is desirable in terms of heat resistance that no inflection point is observed at low temperatures.
In addition, from Table 2, the material of Example 14 is superior to the material of Comparative Example 1 in that (1) the resin weight loss ratio by heat resistance evaluation is small, and thus the stability at high temperature is excellent. It can be seen that the mechanical property value is high, and further, (3) the crack interval generated in the resin by post-curing is wide, so that the crack is hardly generated. Therefore, it can be seen that by using the composition of the present invention, a high strength CFRP plate excellent in heat resistance and crack resistance can be obtained by a bismaleimide composition excellent in useless impregnation.

Claims (17)

A fiber-reinforced prepreg comprising a bismaleimide-based composition containing the following components (A) to (D).
(A) Aromatic bismaleimide compound containing 3 or more aromatic rings in one molecule: 100 parts by weight (B) Aliphatic bismaleimide compound: 1 to 50 parts by weight (C) Two aromatic rings in one molecule Aromatic bismaleimide compound containing one: 30 to 300 parts by weight (D) Bisphenol compound represented by the following formula (1): 30 to 300 parts by weight

(In the formula (1), X represents a single bond, CH ₂ , O, S, SO ₂ , or C (CH ₃ ) ₂ ;
R represents an allyl group or a methallyl group. ) The fiber-reinforced prepreg according to claim 1, wherein the bismaleimide composition further contains the following component (E).
(E) Polymerization accelerator: 0.005 to 5 parts by weight Component (A) Ri aromatic bismaleimide compound der represented by the following formula (2), (B) the number of carbon atoms of residues obtained by removing two maleimide groups of the aliphatic bismaleimide compound of the component is 4 or more The fiber-reinforced prepreg according to claim 1 or 2, wherein the fiber reinforced prepreg is 20 or less and the component (C) is an aromatic bismaleimide compound represented by the following formula (3) or the following formula (4) .

(In Formula (2), R ₁ and R ₂ each independently represents a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O),
R ₃ , R ₄ and R ₅ each independently represent a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom;
n represents an integer of 1 to 5,
x, y, and z each independently represent an integer of 0 or more and 4 or less. )

(In Formula (3), R ₇ represents a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O),
R ₈ and R ₉ each independently represent a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom;
p and q each independently represent an integer of 0 or more and 4 or less. )

(In the formula (4), R ₁₀ represents a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom;
r represents an integer of 0 or more and 4 or less. ) The fiber-reinforced prepreg according to any one of claims 1 to 3 , wherein R in the formula (1) is an allyl group. The fiber-reinforced prepreg according to any one of claims 2 to 4 , wherein the component (E) is an organic peroxide or an anionic polymerization accelerator . The fiber-reinforced prepreg according to claim 5 , wherein the component (E) is selected from imidazoles represented by the following formula (5) and cycloaliphatic amines.

(In the formula (5), R ₁₁ , R ₁₂ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, chain alkyl group, cyclic alkyl group, aromatic group, heterocyclic group, alkoxy group, acyloxy group, acyl. And R ₁₁ and R ₁₂ , R ₁₄ and R ₁₅ , and R ₁₁ and R ₁₅ may be bonded to each other to form a ring condensed with an imidazole ring.) The component (E) is selected from imidazoles in which R ₁₂ in the formula (5) is an alkyl group having 2 or less carbon atoms or a hydrogen atom, and DABCO (1,4-diazabicyclo [2.2.2] octane). Item 7. A fiber-reinforced prepreg according to Item 6 . The fiber-reinforced prepreg according to claim 7 , wherein the component (E) is selected from imidazoles in which R ₁₂ in the formula (5) is a methyl group or a hydrogen atom. A cured product obtained by curing the fiber-reinforced prepreg according to any one of claims 1 to 8 . A cured product obtained by curing a bismaleimide composition containing the following components (A) to (D).
(A) Aromatic bismaleimide compound containing 3 or more aromatic rings in one molecule: 100 parts by weight (B) Aliphatic bismaleimide compound: 1 to 50 parts by weight (C) Two aromatic rings in one molecule Aromatic bismaleimide compound containing one: 30 to 300 parts by weight (D) Bisphenol compound represented by the following formula (1): 30 to 300 parts by weight

(In the formula (1), X represents a single bond, CH ₂ , O, S, SO ₂ , or C (CH ₃ ) ₂ ;
R represents an allyl group or a methallyl group. ) The cured product according to claim 10 , wherein the bismaleimide composition further comprises the following component (E).
(E) Polymerization accelerator: 0.005 to 5 parts by weight Component (A) Ri aromatic bismaleimide compound der represented by the following formula (2), (B) the number of carbon atoms of residues obtained by removing two maleimide groups of the aliphatic bismaleimide compound of the component is 4 or more The cured product according to claim 10 or 11 , which is 20 or less and the component (C) is an aromatic bismaleimide compound represented by the following formula (3) or the following formula (4) .

(In Formula (2), R ₁ and R ₂ each independently represents a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O),
R ₃ , R ₄ and R ₅ each independently represent a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom;
n represents an integer of 1 to 5,
x, y, and z each independently represent an integer of 0 or more and 4 or less. )

(In Formula (3), R ₇ represents a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O),
R ₈ and R ₉ each independently represent a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom;
p and q each independently represent an integer of 0 or more and 4 or less. )

(In the formula (4), R ₁₀ represents a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom;
r represents an integer of 0 or more and 4 or less. ) R in Formula (1) is an allyl group, The hardened | cured material of any one of Claim 10 thru | or 12 . The cured product according to any one of claims 11 to 13 , wherein the component (E) is an organic peroxide or an anionic polymerization accelerator . The cured product according to claim 14 , wherein the component (E) is selected from imidazoles represented by the following formula (5) and cycloaliphatic amines.

(In the formula (5), R ₁₁ , R ₁₂ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, chain alkyl group, cyclic alkyl group, aromatic group, heterocyclic group, alkoxy group, acyloxy group, acyl. And R ₁₁ and R ₁₂ , R ₁₄ and R ₁₅ , and R ₁₁ and R ₁₅ may be bonded to each other to form a ring condensed with an imidazole ring.) The component (E) is selected from imidazoles in which R ₁₂ in the formula (5) is an alkyl group having 2 or less carbon atoms or a hydrogen atom, and DABCO (1,4-diazabicyclo [2.2.2] octane). Item 16. A cured product according to item 15 . The cured product according to claim 16 , wherein the component (E) is selected from imidazoles in which R ₁₂ in the formula (5) is a methyl group or a hydrogen atom .