JP2012201751A - Polymaleimide based composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymaleimide compound capable of attaining a cured product having more excellent heat resistance and greatly high glass transtion temperature.SOLUTION: The polymaleimide based composition includes, based on 100 pts.wt. of a polymaleimide compound (component (A)) having a specified structure and including two or more maleimide groups in one molecule, 15 to 200 pts.wt. of an aromatic liquid reactive diluent (component (B)) to be 3,3'-diallyl-4,4'-dihydroxydiphenyl ether and/or 4,4'-diallyloxydiphenyl ether, and preferably includes a polymerization promoter (component (C)).

Description

The present invention relates to a polymaleimide-based composition useful as a resin composition for fiber-reinforced composite materials, and particularly as an aromatic liquid reactive diluent for a specific polymaleimide compound having a para-bonded maleimide group. The present invention relates to a polymaleimide composition in which the heat resistance of a cured product is improved by using a specific diphenyl ether compound.
The present invention also relates to a fiber reinforced prepreg using the polymaleimide composition and a cured product obtained by curing the polymaleimide 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.

  In a matrix resin that solves such problems and has heat resistance suitable for a CFRP robot hand for transporting liquid crystal glass, etc., without impairing solvent-free impregnation, tackiness of prepreg, drape, and storage stability, In order to provide a matrix resin with reduced cracking and reduced weight loss when placed under high temperature for a long period of time, i.e., improved heat resistance, the present applicant has previously identified a specific aromatic as a bismaleimide compound. A bismaleimide composition in which a bismaleimide compound and an aliphatic bismaleimide compound are used in combination has been proposed (Patent Document 1).

  In the case of the bismaleimide composition of Patent Document 1, a specific aromatic bismaleimide compound and an aliphatic bismaleimide compound are used in combination, and in particular, an aromatic bismaleimide compound containing three or more aromatic rings in one molecule. In addition to having an appropriate viscosity even in the absence of a solvent, it has excellent impregnation properties, and is excellent in tackiness, draping properties, and storage stability when used as a prepreg, A highly heat-resistant maleimide resin with reduced cracks is provided.

The bismaleimide composition generally includes a bismaleimide compound, an aromatic liquid reactive diluent, a polymerization accelerator, and a coupling agent, a release agent, a flame retardant, and the like that are used as necessary. It is prepared by mixing other components at a predetermined ratio.
Among these, as for the aromatic liquid reactive diluent, in Patent Document 1, bisphenol compounds such as o, o′-diallylbisphenol A and polyphenylene compounds such as 4,4′-bis (o-propenylphenoxy) -benzophenone are used. Is used.

  It has also been proposed to use 3,3'-diallyl-4,4'-dihydroxydiphenyl ether used in the present invention as an aromatic liquid reactive diluent (Patent Document 2). In Patent Document 2, it is said that diallyl bisphenol compounds such as 3,3′-diallyl-4,4′-dihydroxydiphenyl ether are used in order to improve impact resistance and flexibility while maintaining heat resistance. ing. However, in Patent Document 2, as a bismaleimide compound, a compound in which a maleimide group is bonded to a meta position is used, and as a result, a heat resistance that is sufficiently satisfactory cannot be obtained.

JP 2009-263624 A Japanese Patent Laid-Open No. 2-145614

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

  The present invention provides a polymaleimide composition that is more excellent in heat resistance than a conventionally provided polymaleimide composition such as a bismaleimide composition and that can realize a cured product having a significantly high glass transition temperature. The purpose is to do.

  As a result of intensive studies to solve the above problems, the present inventor obtained a polymaleimide composition that gives a cured product excellent in heat resistance by a combination of a specific polymaleimide compound and an aromatic liquid reactive diluent. I found that I can do it.

  The present invention has been achieved based on such knowledge, and the gist thereof is as follows.

[1] A polymaleimide composition containing the following component (A) and component (B), wherein the content of component (B) relative to 100 parts by weight of component (A) is 15 parts by weight or more and 200 parts by weight or less. A polymaleimide composition characterized in that:
(A): One or more polymaleimide compounds containing two or more maleimide groups in one molecule represented by any of the following formulas (1) to (5) (B); , (7) Aromatic liquid reactive diluent containing one or more diphenyl ether compounds represented by any one of (7)

(In formula (1), R ₃₁ , R ₃₂ and R ₃₃ each independently represent a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), ₃₄ , R ₃₅ , R ₃₆ and R ₃₇ 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, and e, f, g, and h each independently represents an integer of 0 to 4.

(In Formula (2), R ₆ represents a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), and R ₇ and R ₈ are each independently 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, and p and q each independently represent an integer of 0 or more and 4 or less. .)

(In Formula (3), R ₉ 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, and r is 0 or more) Represents an integer of 4 or less.)

(In formula (4), Q represents a divalent linking group mainly composed of a hydrocarbon group which may be substituted with one or more substituents and not containing an aromatic ring.)

(In formula (5), t represents an integer of 0 or more and 20 or less, and is composed of a mixture of t different from each other.)

[2] The polymaleimide composition according to [1], wherein the component (B) further contains one or more benzene compounds represented by the following formula (8) or (9): .

(In formula (8), R ₁₁ represents a single bond, CH ₂ , O, S, SO ₂ , or C (CH ₃ ) ₂ , and R ₁₂ represents an allyl group or a methallyl group.)

(In formula (9), R ₂₄ and R ₂₅ each independently represent a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkenyl group, an alkynyl group, an alkoxy group, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom. R ₂₁ , R ₂₂ and R ₂₃ each independently represents a single bond, CH ₂ , O, C═O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), R ₂₆ , R ₂₇ , R ₂₈ and R ₂₉ each independently represent a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkenyl group, an alkynyl group, an alkoxy group, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom. M represents an integer of 0 to 5, and a, b, c and d each independently represent an integer of 0 to 4.

[3] A polymaleimide composition according to [1] or [2], further comprising 0.01 to 5 parts by weight of the following component (C) with respect to 100 parts by weight of component (A).
(C); polymerization accelerator

[4] A polymaleimide composition according to [3], wherein the component (C) is an anionic polymerization accelerator and / or a radical polymerization accelerator.

[5] A polymaleimide composition according to [4], wherein the anionic polymerization accelerator is an imidazole represented by the following formula (X).

(In the formula (X), R (1), R (2), R (4) and R (5) each independently represents a hydrogen atom or an arbitrary substituent, and R (1) and R (2 ), R (4) and R (5), R (1) and R (5) may be bonded to each other to form a ring condensed with an imidazole ring.)

[6] A polymaleimide composition according to [5], wherein in formula (X), R (2) and R (4) are each independently a methyl group or a hydrogen atom.

[7] The polymaleimide composition according to any one of [4] to [6], wherein the radical polymerization accelerator is an organic peroxide.

[8] A fiber-reinforced prepreg containing the polymaleimide composition according to any one of [1] to [7].

[9] A cured product obtained by curing the polymaleimide composition according to any one of [1] to [7].

[10] A cured product obtained by curing the fiber-reinforced prepreg according to [8].

According to the present invention, by using a specific polymaleimide compound in combination with a specific diphenyl ether compound as an aromatic liquid reactive diluent, the glass transition temperature is remarkably high, and the heat resistance of the resulting cured product is greatly increased. A bismaleimide compound that can be improved can be provided.
That is, since the polymaleimide compound used in the present invention has high linearity and regularity in the structural formula, the polymaleimide compound itself has high crystallinity and therefore has a property of increasing the glass transition temperature of the composition. Thus, the glass transition temperature can be further improved by using such a polymaleimide compound in combination with an aromatic liquid reactive diluent containing a specific diphenyl ether compound.

  Hereinafter, embodiments of 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.

[Polymaleimide composition]
The polymaleimide composition of the present invention is a polymaleimide composition containing the following components (A) and (B), and the content of the component (B) is 15% by weight with respect to 100 parts by weight of the component (A). It is characterized by being not less than 200 parts and not more than 200 parts by weight, and preferably further contains 0.01 to 5 parts by weight of the following component (C) with respect to 100 parts by weight of component (A).

(A): One or more polymaleimide compounds containing two or more maleimide groups in one molecule represented by any of the following formulas (1) to (5) (B); , (7) Aromatic liquid reactive diluent containing one or more diphenyl ether compounds represented by any one of (7) (C); polymerization accelerator

<(A) component>
In the polymaleimide composition of the present invention, the polymaleimide compound as the component (A) contains two or more maleimide groups in one molecule represented by any of the following formulas (1) to (5).

(In formula (1), R ₃₁ , R ₃₂ and R ₃₃ each independently represent a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), ₃₄ , R ₃₅ , R ₃₆ and R ₃₇ 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, and e, f, g, and h each independently represents an integer of 0 to 4.

(In Formula (2), R ₆ represents a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), and R ₇ and R ₈ are each independently 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, and p and q each independently represent an integer of 0 or more and 4 or less. .)

(In Formula (3), R ₉ 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, and r is 0 or more) Represents an integer of 4 or less.)

(In formula (4), Q represents a divalent linking group mainly composed of a hydrocarbon group which may be substituted with one or more substituents and not containing an aromatic ring.)

(In formula (5), t represents an integer of 0 or more and 20 or less, and is composed of a mixture of t different from each other.)

In the formula (3), R ₃₁ , R ₃₂ and R ₃₃ are a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), and they are the same or different. However, from the viewpoint of economy, 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, and particularly preferably 1 or more and 2 or less.

R ₃₄ , R ₃₅ , R ₃₆ and R ₃₇ 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; An aliphatic alkoxy group having 6 or less carbon atoms; an acyloxy group having 6 or less carbon atoms (aliphatic acyloxy group) such as formyloxy group or acetoxy group; an acyl group such as acetyl group or benzoyl group, pyridyl group, furyl group And a halogen atom such as a fluorine, chlorine or bromine atom. Among them, an alkyl group having 3 or less carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.

e, f, g and h 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 e, f, g, and h are 2 or more, a plurality of R ₃₄ , R ₃₅ , R ₃₆ , and R ₃₇ may be the same or different.

  Specific examples of the aromatic bismaleimide compound (hereinafter sometimes referred to as “aromatic bismaleimide compound (1)”) containing three or more aromatic rings in one molecule represented by the formula (1) are as follows: 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis [4-maleimido (4-phenoxyphenyl)] sulfone, 1,1 ′-[1,4-phenylenebis (oxy-4,1) -Phenylene)] bismaleimide (CAS Registry No. [82577-60-4]), 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-fu Ylene) bismaleimide ([352217-5 (1) -7]) and the like. Preferred are 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane and bis [4-maleimido (4-phenoxyphenyl)] sulfone, among which 2,2 represented by the following formula (1A) -Bis [4- (4-maleimidophenoxy) phenyl] propane is most preferred.

In the formula (2), R ₆ is a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), and from the viewpoint of economy, a single bond, CH ₂ , O, SO ₂ or C (CH ₃ ) ₂ is preferred.

R ₇ and R ₈ 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; 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 ₇ and R ₈ may be the same or different.

  The aromatic bismaleimide compound containing two aromatic rings in one molecule represented by the formula (2) (hereinafter sometimes referred to as “aromatic bismaleimide compound (2)”) is 4,4 ′. -Diphenylmethane bismaleimide, N, N '-(4,4'-biphenylene) bismaleimide, N, N'-(sulfonyldi-p-phenylene) bismaleimide, N, N '-(oxydi-p-phenylene) bis Maleimide, 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′-diphenyl sulfide bismaleimide, 4,4′-diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 1,1 ′-[ 1,4-butanediylbis (oxy-p-phenylene)] bismaleimide, among others, 4,4′-diphenylsulfide bismaleimide, 4,4′-diphenyl ether bismaleimide, or the following formula (2A) 4,4′-diphenylmethane bismaleimide is preferably used.

In the formula (3), R ₉ is 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. An alkoxy 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, Halogen atoms such as chlorine and bromine atoms can 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.

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.

  As the aromatic bismaleimide compound containing one aromatic ring in one molecule represented by the formula (3) (hereinafter sometimes referred to as “aromatic bismaleimide compound (3)”), 4-methyl- 1,3-phenylene bismaleimide, 1,3-phenylene bismaleimide, 1,4-phenylene bismaleimide, 1,2-phenylene bismaleimide, naphthalene-1,5-dimaleimide, 4-chloro-1,3-phenylene bis Maleimide and the like can be mentioned, among which 4-methyl-1,3-phenylenebismaleimide and 1,3-phenylenebismaleimide are preferably used.

  In the formula (4), Q is a divalent linking group mainly composed of a hydrocarbon group which may be substituted with one or more substituents. This linking group may contain an ether group, sulfide group or ketone group, ester group, amide group, etc., but does not contain an aromatic ring in its molecular structure. The hydrocarbon group of the linking group 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.

  Q is preferably an alkylene group having 1 to 30 carbon atoms which may have a substituent (this carbon number includes the carbon number of the substituent when the alkylene group has a substituent), particularly An alkylene group having 1 to 20 carbon atoms, particularly 2 to 9 carbon atoms is preferable.

  Specific examples of the aliphatic bismaleimide compound represented by the formula (4) (hereinafter sometimes referred to as “aliphatic bismaleimide compound (4)”) include 1,6-bismaleimide- (2,2,4 -Trimethyl) hexane, 1,6-bismaleimide- (2,4,4-trimethyl) hexane, N, N'-decamethylene bismaleimide, N, N'-decamethylene bismaleimide, 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, , 10-trioxatridecane, 1,11-bis (maleimido) -3,6,9-trioxaundecane, etc., among these, 1,6-bis represented by the following formula (4A) Maleimide- (2,2,4-trimethyl) hexane and N, N′-hexamethylene bismaleimide are preferably used.

  Specific examples of the polyphenylmethane maleimide represented by the formula (5) include commercially available polyphenylmethane maleimide (“BMI-2000” and “BMI-2300” manufactured by Daiwa Kasei Kogyo Co., Ltd.).

  In the present invention, as the polymaleimide compound of the component (A), only one type of polymaleimide compound may be used, or two or more types of polymaleimide compounds may be mixed and used. It is preferable to use a combination of an aliphatic bismaleimide compound and an aliphatic bismaleimide compound (2) and / or an aromatic bis. The use of a combination of one or more maleimide compounds (3) and one or more aliphatic bismaleimide compounds (4) has an appropriate viscosity even without solvent, Therefore, it has excellent impregnation properties, has excellent tackiness, draping properties, and storage stability when used as a prepreg, and also reduces cracks in molded products. It is preferable that the high heat resistance of the maleimide resin is obtained.

In this case, the amount of the aromatic bismaleimide compound (2) and / or aromatic bismaleimide compound (3) used is usually 0.1 parts by weight or more and 100000 parts per 100 parts by weight of the aromatic bismaleimide compound (1). Parts by weight or less, preferably 1 part by weight or more and 10,000 parts by weight or less, more preferably 10 parts by weight or more and 1000 parts by weight or less.
The amount of the aliphatic bismaleimide compound (4) used is usually 1 part by weight or more and 10,000 parts by weight or less, preferably 5 parts by weight or more and 1000 parts by weight or less, with respect to 100 parts by weight of the aromatic bismaleimide compound (1). Preferably they are 10 weight part or more and 100 weight part or less.

  When there is less aromatic bismaleimide compound (2) and / or (3) than the said range, the heat resistance of hardened | cured material will deteriorate. If the amount of the aromatic bismaleimide compound (2) and / or (3) is larger than the above range, the maleimide component may crystallize and the tackiness may be lost.

  Moreover, when there are few aliphatic bismaleimide compounds (4) from the said range, although heat resistance improves, since hardened | cured material will become weak and the number of cracks will also increase, the quality of a molded article will fall. When the amount of the aliphatic bismaleimide compound (4) is larger than the above range, the heat resistance of the composition is deteriorated, and the curing rate at the time of heat molding becomes remarkably slow, so that molding becomes difficult.

<(B) component>
As the aromatic liquid reactive diluent of the component (B), 3,3′-diallyl-4,4′-dihydroxydiphenyl ether (hereinafter abbreviated as “DADPE”) represented by the following formula (6), and / Or 4,4′-diallyloxydiphenyl ether (hereinafter abbreviated as “DADPE-ether”) represented by the following formula (7) is used.

When DADPE and DADPE-ether are used in combination as the aromatic liquid reactive diluent, there is no particular limitation on the combined ratio.
That is, DADPE is more effective in terms of solubility in the bismaleimide component than DADPE-ether, and DADPE-ether is more effective in reducing the viscosity of the mixture in the molten state than DADPE. By using these together, the effect that the viscosity of the mixture can be reduced without lowering the heat resistance of the cured product is obtained, but in order to effectively obtain this effect, the use ratio of DADPE and DADPE-ether is The weight ratio of DADPE: DADPE-ether = 1: 0.01 to 100, particularly 1: 0.1 to 10 is preferable.

  In the present invention, an aromatic liquid reactive diluent other than the above DADPE and DADPE-ether may be used as the aromatic liquid reactive diluent of the component (B), and in this case, other aromatic liquids that can be used in combination. Examples of the liquid reactive diluent include a benzene compound represented by the following formula (8) or (9), preferably a benzene compound represented by the following formula (8).

(In formula (8), R ₁₁ represents a single bond, CH ₂ , O, S, SO ₂ , or C (CH ₃ ) ₂ , and R ₁₂ represents an allyl group or a methallyl group.)

(In formula (9), R ₂₄ and R ₂₅ each independently represent a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkenyl group, an alkynyl group, an alkoxy group, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom. R ₂₁ , R ₂₂ and R ₂₃ each independently represents a single bond, CH ₂ , O, C═O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), R ₂₆ , R ₂₇ , R ₂₈ and R ₂₉ each independently represent a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkenyl group, an alkynyl group, an alkoxy group, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom. M represents an integer of 0 to 5, and a, b, c and d each independently represent an integer of 0 to 4.

In Formula (8), R ₁₁ is particularly preferably CH ₂ , O, or C (CH ₃ ) ₂ , and R ₁₂ is an allyl group (—CH ₂ —CH═CH ₂ group) or a methallyl group (—CH ₂ ). _2- C (CH ₃ ) ═CH ₂ group) is preferably an allyl group.

  Specific examples of the benzene compound represented by the formula (8) (hereinafter sometimes referred to as “bisphenol compound (8)”) include o, o′-diallylbisphenol A, o, o′-diallylbisphenol F. O, o′-diallylbisphenol 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'-dimethallyl bisphenol A, o, o'-dimethallyl bisphenol F, and the like, among which o, o'-diallyl bisphenol A represented by the following formula (8A) is used. Preferably used.

In the formula (9), R ₂₄ and R ₂₅ are each independently preferably an alkyl group, an alkenyl group, an alkynyl group or a hydroxy group, more preferably an alkenyl group, still more preferably a propenyl group, an allyl group or methallyl. It is a group.
R ₂₁ , R ₂₂ and R ₂₃ are each independently a single bond, —CH ₂ —, —O—, —C (═O) —, —S—, —SO ₂ —, —C (CH ₃ ) ₂ — or —NHC (═O) — is preferred, more preferably O, —C (═O) —, and m is preferably 0, 1 or 2.

R ₂₆ , R ₂₇ , R ₂₈ and R ₂₉ 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; Alkoxy group having 6 or less carbon atoms such as methoxy group; acyloxy group having 6 or less carbon atoms (aliphatic acyloxy group) such as formyloxy group or acetoxy group; acyl group such as acetyl group or benzoyl group, pyridyl group, furyl Examples thereof include a heterocyclic group such as a group, and halogen atoms such as fluorine, chlorine and bromine atoms. Among these, an alkyl group having 3 or less carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.
a, b, c and d are preferably each independently 0 to 2. When a, b, c and d are 2, two R ₂₆ , R ₂₇ , R ₂₈ and R ₂₉ may be the same or different.

  Specific examples of the benzene compound represented by the formula (9) (hereinafter sometimes referred to as “polyphenylene compound (9)”) include 4,4′-bis- (o-propenylphenoxy) -benzophenone, 2, 2′-dipropenyl bisphenol A, 1,3-di (4-allylphenoxy) benzene, 2,2-bis [4- (4-allylphenoxy) phenyl] propane and the like are mentioned, and among them, in the following formula (9A) The 4,4′-bis- (o-propenylphenoxy) -benzophenone represented is preferably used.

  The bisphenol compound (8) and the polyphenylene compound (9) may be used singly or in combination of two or more.

  By using DADPE and / or DADPE-ether in combination with bisphenol compound (8) and / or polyphenylene compound (9), preferably bisphenol compound (8), more preferably DADPE and bisphenol compound (8) are used in combination. By this, the effect that the mixture of the viscosity which is easy to handle can be obtained is produced.

  When DADPE and / or DADPE-ether is used in combination with one or more of bisphenol compound (8) and / or one or more of polyphenylene compound (9), the use ratio is not particularly limited. However, it is preferable that the ratio of DADPE and / or DADPE-ether is 10 parts by weight or more and 90 parts by weight or less with respect to a total of 100 parts by weight of the component (B) in order to effectively obtain the effect of the combination.

<(C) component>
A known polymerization accelerator can be further added to the polymaleimide composition of the present invention, although it is not essential, for the purpose of increasing the curing rate.

The polymerization accelerator used in the present invention is not particularly limited, and various anionic polymerization accelerators, radical polymerization accelerators, and the like can be used.
An anionic polymerization accelerator and a radical polymerization accelerator may be used in combination. That is, the anionic polymerization accelerator is excellent in the polymerization promotion effect, but since the polymerization promotion effect is low for some components, the degree of completion of the polymerization is lower than that of the radical polymerization accelerator, resulting in the polymerization accelerator. As a cured product obtained from a polymaleimide composition using only an anionic polymerization accelerator as, there is a tendency for Tg as a heat resistance index to be low.
On the other hand, the radical polymerization accelerator exerts a polymerization promoting effect on both components (A) and (B) used in the present invention, but has an unstable oxygen-carbon bond at the end of some components. Form. Since this oxygen-carbon bond burns at a high temperature and causes thermal weight loss, a cured product obtained from a polymaleimide composition using only a radical polymerization accelerator as a polymerization accelerator is used for a long time under high temperature conditions. The thermal weight reduction rate when placed underneath may increase.
By using an anionic polymerization accelerator and a radical polymerization accelerator in combination, the advantages of each can be utilized and the disadvantages can be compensated for, thereby improving heat resistance and suppressing thermal weight loss.

  Examples of the anionic 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-undecylimidazole, 2- Methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, TB (2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenyl-imidazolium trimellitate, 2- Imidazole compounds such as phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, N, N-diisopropyl Ethylamine, 1,4-dimethylpiperazine, triphenylamine, N, N′-dicyclohexylurea, tributylamine, 1-benzyl-4-piperidone, N, N-dimethylbenzylamine, N, N-phenyldibenzylamine, 1 -Benzylpiperidine, 1-methyl-2 2-dimethyl-6,6-dimethylpiperidine, quinoxaline, quinoline, tetramethylenehexamine, pyrazole, triazole, benzotriazole, hydroxybenzotriazole, 2-methylimidazoline, 2-phenylimidazoline, DABCO (1,4-diazabicyclo [2. 2.2] octane), tertiary amine compounds such as triphenylphosphine or trivalent phosphorus compounds such as triphenyl phosphite, and anionic polymerization accelerators. Among these, imidazole polymerization is accelerated. Agents are preferred.

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

(In the formula (X), R (1), R (2), R (4) and R (5) each independently represents a hydrogen atom or an arbitrary substituent, and R (1) and R (2 ), R (4) and R (5), R (1) and R (5) may be bonded to each other to form a ring condensed with an imidazole ring.)

  Here, the optional substituents of R (1) and R (2), R (4) and R (5) are imidazoles particularly preferable as the imidazoles in the present invention. In the formula (X), R (2) and R (4) are each independently exemplified below as an optional substituent of R (1) and R (5) when each is a methyl group or a hydrogen atom.

  R (1) may be combined with R (2) or R (5) to form a ring condensed with an imidazole ring (which may be an aliphatic ring, an aromatic ring or a heterocyclic ring). Good. R (1) is preferably a chain alkyl group having 4 or less carbon atoms or a hydrogen atom.

  R (2) may be bonded to R (1) to form a ring condensed with an imidazole ring (which may be an aliphatic ring, an aromatic ring or a heterocyclic ring). R (2) 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 further preferably a methyl group or hydrogen atom. .

  R (4) may be bonded to R (5) to form a ring condensed with an imidazole ring (which may be an aliphatic ring, an aromatic ring or a heterocyclic ring). R (4) is preferably a chain alkyl group having 3 or less carbon atoms or a hydrogen atom, more preferably a hydrogen atom.

  R (5) may combine with R (4) or R (1) to form a ring condensed with an imidazole ring (which may be an aliphatic ring, an aromatic ring or a heterocyclic ring). Good. R (5) 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 Zole, TBZ (2,3-dihydro-1H-pyrrolo [1.2-a] benzimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. Although it is mentioned, it is not limited to these.

As described above, imidazoles as polymerization accelerators are known, and the most commonly used conventional imidazole polymerization accelerator is 2-ethyl-4-methylimidazole. The imidazoles used are relatively expensive compared to other blending components of polymaleimide compositions, so they have high catalytic activity (polymerization promoting effect), and gelation of polymaleimide compositions with a small amount. By using an imidazole polymerization accelerator capable of lowering the temperature to an appropriate temperature, the required amount of the imidazole polymerization accelerator can be reduced to reduce the raw material cost of the polymaleimide composition, thereby reducing the product cost. Reduction is desired.
In addition, since a large amount of the polymerization accelerator is a cause of lowering the heat resistance of the resulting cured product, it is desirable to reduce the amount of the polymerization accelerator used in this respect as well.
Furthermore, the incorporation of a large amount of the polymerization accelerator increases the amount of the polymerization accelerator that volatilizes at the time of thermosetting, and it is desired to reduce the polymerization accelerator from the viewpoint of equipment protection.

  As a result of diligent investigations focusing on the structure of imidazoles that are polymerization accelerators, the present inventors have found that imidazoles having limited groups bonded to the 2- and 4-position carbon atoms of the imidazole ring, that is, the above formula (X ), R (2) and R (4), which are each independently a methyl group or a hydrogen atom, were found to be excellent in catalytic activity and show a high polymerization promoting effect in a small amount.

Although the details of this reason are not clear, it is estimated as follows.
The polymerization active point at which imidazoles exhibit catalytic activity is presumed to be the nitrogen atom at the 3-position of the imidazole ring, and in order for the nitrogen atom at the 3-position to exhibit high polymerization activity, It is necessary to secure a space as a polymerization starting point, and for this purpose, there are no bulky substituents on the 2-position carbon atom and 4-position carbon atom adjacent to the 3-position nitrogen atom. Is presumed to be advantageous. For these reasons, it is advantageous for the expression of the catalytic activity that the group bonded to the carbon atoms at the 2nd and 4th positions of the imidazole ring is a group having 1 or less carbon atoms, that is, a methyl group or a hydrogen atom.

  Accordingly, in the imidazole used as a polymerization accelerator, in the formula (X), R (2) and R (4) are preferably each independently a methyl group or a hydrogen atom, and particularly R (4) Is preferably a hydrogen atom.

Also in this case, R (1) and R (5) are each independently a hydrogen atom or an arbitrary substituent. Here, as an arbitrary substituent, for example, a hydroxy group or the following group which may further have a substituent, that is,
An alkyl group having 12 or less carbon atoms (which may be linear, branched or cyclic),
An alkenyl group having 12 or less carbon atoms (which may be linear, branched or cyclic),
An aromatic group having 12 or less carbon atoms,
A heterocyclic group having 12 or less carbon atoms,
An alkoxy group having 12 or less carbon atoms,
An acyloxy group having 12 or less carbon atoms,
And an acyl group having 12 or less carbon atoms (wherein, when the alkyl group, alkenyl group, aromatic group, heterocyclic group, alkoxy group, acyloxy group, acyl group has a substituent, the above carbon number is , Both refer to the total number of carbon atoms including the substituents.)

  However, imidazoles as polymerization accelerators are required to have not only catalytic activity but also solubility in the reaction system. From the viewpoint of solubility in the reaction system and other points, R (1) and R (5) Are suitable substituents as follows.

  That is, when the 1-position of the imidazole ring is unsubstituted, the solubility in a solvent is deteriorated due to the hydrogen bond via the 1-position hydrogen. On the other hand, if the substituent has an excessively low molecular weight, the molecular weight of the entire compound becomes small, resulting in a low boiling point compound, resulting in an increase in loss due to volatilization in a high-temperature reaction system. From such a viewpoint, the imidazole ring is bonded with a certain amount of substituents to increase the irregularity as a compound and to increase the molecular weight. However, the imidazoles according to the present invention are R ( 2) Since R (4) is a methyl group or a hydrogen atom, it may be desired that R (1) and R (5) are substituents having a molecular weight of a certain level or more.

As described above, the active site of imidazoles is the nitrogen atom at the 3-position, but it is considered that free electron pairs that do not contribute to the bond of the imidazole ring are involved in the polymerization activity. From this point of view, when the electron density inside the imidazole ring is low, the electron donating property of the lone pair of electrons does not increase, and it is difficult to obtain the polymerization activity at this portion.
On the other hand, when an electron-donating substituent such as an alkyl group is bonded to the nitrogen atom at the 1-position of the imidazole ring, the electron density inside the imidazole ring can be increased by pushing out electrons to the imidazole ring. R (1) of the substituent bonded to the nitrogen atom at the 1-position is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a benzyl group, or the like. An electron donating substituent such as a linear or branched alkyl group which may have a substituent and an alkenyl group such as a vinyl group is preferred.

  From the viewpoint of solubility, boiling point, polymerization activity, etc., the total number of carbon atoms of R (1), R (2) and R (4) in formula (X) is 0 or more and 8 or less, particularly 4 5 or 6 is preferable. More specifically, R (1) is a linear or branched alkyl group, alkenyl group, or substituent having 1 to 6 carbon atoms, preferably 3 to 6 which may have a substituent such as a phenyl group. And an acyl group which may have.

  R (5) includes a hydrogen atom, a linear or branched alkyl group having 1 to 6, preferably 3 to 6 carbon atoms, an alkenyl group, an alkoxy group, an acyl group which may have a substituent, amino Group, a mercapto group, etc. are mentioned, Preferably it is a hydrogen atom from the ease of acquisition of a commercial item.

  Specific examples of imidazoles in which R (2) and R (4) in the formula (X) are each independently a methyl group or a hydrogen atom include imidazole, 1-methylimidazole, and 1-ethylimidazole. 1-vinylimidazole, 1-methyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 1,1′-carbonylbis-1H-imidazole. -Isobutyl-2-methylimidazole is preferably used.

  These imidazoles may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  On the other hand, examples of the radical polymerization accelerator include organic peroxide polymerization accelerators and radical polymerization accelerators such as azobisisobutyronitrile, preferably organic peroxide polymerization accelerators. .

Examples of the organic peroxide as the polymerization accelerator include the following, but are not limited to the following.
Methyl ethyl ketone peroxide, cyclohexane peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis (t-butylperoxy) -3,3 , 5-trimethylhexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) Valate, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane 2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α'-bis (T-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) ) Hexin, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, benzoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, 2,4 -Dichlorobenzoyl peroxide, m-toluoy Ruperoxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, dimyristyl peroxydicarbonate, Di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, diallyl peroxydicarbonate, t-butyl peroxyacetate, t-butyl Peroxyisobutyrate, t-butylperoxypivalate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxy-2-ethylhexanate, t-butyl -Oxy-3,5,5-trimethylhexanate, t-butyl peroxylaurate, t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, 2,5-dimethyl-2,5-di (benzoyl) Peroxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, cumylperoxyoctate, t-hexylperoxyneodecanate, t-hexylperoxypivalate, t-butylperoxyneo Hexanate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyallyl carbonate.

  Among these organic peroxides, those that decompose and generate radicals are preferably higher than a certain level. That is, it is not decomposed and cured at a temperature in the step of preparing a polymaleimide composition by mixing the components (A), (B), and (C), and in the step of impregnating the fiber into a fiber to produce a prepreg. It is preferable to have a property of efficiently decomposing at a temperature at which a molded product is produced (usually higher than the mixing and impregnation steps). Examples of such organic peroxides include t-butyl peroxide, benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, and the like. preferable.

  These organic peroxides may be used alone or in combination of two or more.

  When the anionic polymerization accelerator and the radical polymerization accelerator are used in combination, an anionic polymerization accelerator for a total of 100 parts by weight of the anionic polymerization accelerator and the radical polymerization accelerator is obtained in order to effectively obtain the effect of using these together. The content of is preferably 1 to 99 parts by weight, particularly 10 to 90 parts by weight, particularly 20 to 80 parts by weight. Even if there are more or less anionic polymerization accelerators than this range, the effect of the present invention by using an anionic polymerization accelerator and a radical polymerization accelerator in combination may not be sufficiently obtained.

<Blending amount>
The polymaleimide composition of the present invention contains components (A) and (B) as essential components, and the content of component (B) relative to 100 parts by weight of component (A) is at least 15 parts by weight, preferably 30 parts. It is not less than 200 parts by weight, preferably not more than 100 parts by weight.
When the amount of the component (B) is less than the above range, the viscosity of the composition increases, and it becomes difficult to dissolve and disperse, making it difficult to form a prepreg. When there are more (B) components than the said range, the heat resistance of hardened | cured material will deteriorate.

The amount of the polymerization accelerator for component (C) used as necessary is usually 0.01 parts by weight or more and 5 parts by weight or less, preferably 0.01 parts by weight or more and 3 parts by weight per 100 parts by weight of component (A). Parts by weight or less, more preferably 0.01 parts by weight or more and 1 part by weight or less.
If the amount of the component (C) is less than the above range, the effect of promoting polymerization 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.

<Other ingredients>
The polymaleimide composition of the present invention may contain other components other than the components (A) to (C).
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).

<Manufacturing method>
In order to produce the polymaleimide composition of the present invention, the components (A), (B) and (C), and other optional components used as necessary are mixed and uniformly dissolved or uniformly dispersed. The method is not particularly limited, but in the present invention, in order to uniformly disperse and mix the polymerization accelerator of component (C), which is a small amount of component, in the composition, (C) It is preferable to prepare a solution in which the component is previously dissolved in a part of the component (B), and add and mix this solution to the mixture of the component (A) and the remainder of the component (B).

In this case, there is no restriction | limiting in particular in the mixing temperature of (B) component and (C) component, it can mix in the wide temperature of 40 to 150 degreeC, Moreover, the mixing time is also (C) component. Is not particularly limited as long as it is a time for uniformly dissolving in the component (B).
Mixing of the component (A) and the component (B) is preferably performed by heating at 50 ° C. or higher and 150 ° C. or lower, particularly 80 ° C. or higher and 130 ° C. or lower, particularly 90 ° C. or higher and 120 ° C. or lower. If the temperature is too low, uniform mixing of the component (A) and the component (B) becomes difficult. If the temperature is too high, the polymerization reaction is promoted during the mixing, and there is a possibility that the polymerization solidifies during the mixing.
In addition, the mixing time of the component (A) and the component (B) is usually 10 minutes or longer and 6 hours or shorter, preferably 20 minutes or longer and 5 hours or shorter, more preferably 30 minutes or longer and 4 hours or shorter, excluding the time required for raising and lowering the temperature. It is. When the mixing time is longer than necessary, the viscosity increases due to polymerization, and the handling property as a matrix resin is impaired.

  The mixture of the component (A) and the component (B) and the solution in which the component (C) is dissolved in the component (B) are 30 ° C. or higher and 120 ° C. or lower, particularly 50 ° C. or higher and 100 ° C. or lower, especially 60 ° C. or higher. It is preferable to mix by heating at 90 ° C. or lower. If this temperature is too low, uniform mixing of the catalyst becomes difficult. If it is too high, the polymerization reaction is promoted during mixing, and polymerization solidification may occur during mixing. The mixing time is usually 1 minute or more and 3 hours or less, preferably 2 minutes or more and 2 hours or less, more preferably 5 minutes or more and 1 hour or less, 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.

  The amount of the component (B) in which the component (C) is dissolved in advance differs depending on the type and amount of the component (C) and the component (B) and further the component (A) to be blended in the composition. Although it cannot be determined, usually 0.1 wt% or more and 50 wt% or less, particularly 0.5 wt% or more and 30 wt% or less of the total amount of component (B) is used for dissolving component (C), and (C) It is preferable that the total concentration of the component (C) in the component (B) component solution is 0.001% by weight to 20% by weight, particularly 0.01% by weight to 10% by weight. When the amount of the component (B) used for dissolving the component (C) is too small, it may not be possible to obtain a composition in which the components (A) to (C) are uniformly mixed. It becomes difficult to dissolve or disperse in the liquid reactive diluent.

  Regarding other optional components, the mixing timing is not particularly limited, but usually, when mixing (A) component and (B) component, or a mixture of (A) component and the remaining component (B). It is preferable to mix when mixing the solution which melt | dissolved (C) component in a part of (B) component.

<How to save>
The polymaleimide composition of the present invention, when blended with the component (C) as a polymerization accelerator having excellent polymerization activity, is 40 ° C. or less, particularly 20 ° C. or less, in particular, to prevent polymerization solidification during storage. It is preferable to store at 0 ° C. or lower, for example, −60 ° C. to 0 ° C. If the storage temperature of the polymaleimide composition of the present invention is too high, polymerization may accelerate during storage and solidify, which may render it unusable.

[Prepreg]
The polymaleimide 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.

  There is no particular limitation on the method for impregnating the reinforcing fiber with the polymaleimide composition of the present invention, but a method that does not use a solvent is preferable. Therefore, the polymaleimide 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 polymaleimide composition in the prepreg obtained (impregnated with the polymaleimide 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 proportion of the polymaleimide composition is larger than this range, a sufficient reinforcing effect cannot be obtained because the proportion of the reinforcing fibers is relatively reduced. Conversely, if the amount of the polymaleimide 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 cured by heating at 150 ° C. to 200 ° C. for 30 minutes to 3 hours. Therefore, a fiber reinforced composite material molded article can be obtained by treating for 1 hour to 12 hours while heating stepwise in the temperature range of 180 ° C. to 280 ° C. as a post cure.

  The polymaleimide 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.

  The cured product of the present invention obtained by curing the polymaleimide composition of the present invention has high heat resistance such that Tg measured by TMA is usually 330 ° C. or higher. TMA-Tg of the hardened | cured material of this invention becomes like this. Preferably it is 340 degreeC or more, for example, 340-500 degreeC.

  In addition, the measurement of TMA-Tg of hardened | cured material is performed by the method described in the term of the below-mentioned Example.

Among the cured products of the present invention obtained by curing the prepreg of the present invention, Tg measured by TMA is usually high heat resistance of 330 ° C. or higher. TMA-Tg of the hardened | cured material of this invention becomes like this. Preferably it is 340 degreeC or more, for example, 340-500 degreeC.
Further, among the cured products of the present invention obtained by curing the prepreg of the present invention, DMA-Tg by tan δ and G ′ reading is 330 ° C. or higher, and this DMA-Tg is more preferably 340 ° C. or higher. For example, it is 340-500 degreeC.
In addition, TMA-Tg and DMA-Tg of hardened | cured material are performed by the method described in the term of the below-mentioned Example.

Hereinafter, the present invention will be described more specifically with reference to production examples, examples and comparative examples.
In addition, in the following, the measuring method of the physical property of hardened | cured material is as follows.

<TMA-Tg of cured product>
The bismaleimide composition degassed by heating to about 70 ° C. is poured between two glass plates through a spacer having a thickness of 2 mm, treated at 170 ° C. for 3 hours, removed from 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 TMA / SS120 manufactured by SII, this sample was heated from 40 ° C. to 400 ° C. at 10 ° C./min in a nitrogen atmosphere, and Tg (glass transition temperature) was evaluated from the strain change of the compression probe.

<CFRP TMA-Tg>
A resin film made of bismaleimide-based composition: the (basis weight of about 150 g / ^{m 2),} respectively the carbon fiber sheet (PAN-based 3K plain weave cloth 235GPa products, fiber basis weight: about 200 g / ^{m 2)} was impregnated with the hot melt method A carbon fiber prepreg was prepared. 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. This was further post-cured in the order of 200 ° C. for 2 hours, 230 ° C. for 2 hours, and 260 ° C. for 12 hours to obtain a CFRP plate.
This CFRP sample was cut into 5 mm × 5 mm, and the sample was heated from 50 ° C. to 450 ° C. at 10 ° C./min in a nitrogen atmosphere using TMA / SS120 manufactured by SII. Glass transition temperature) was evaluated. Two points were measured for each sample. Table 1 shows the measurement results at two points for n1 and n2.

<DMA-Tg of CFRP>
A resin film made of bismaleimide-based composition: the (basis weight of about 150 g / ^{m 2),} respectively the carbon fiber sheet (PAN-based 3K plain weave cloth 235GPa products, fiber basis weight: about 200 g / ^{m 2)} was impregnated with the hot melt method A carbon fiber prepreg was prepared. 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. This was further post-cured in the order of 200 ° C. for 2 hours, 230 ° C. for 2 hours, and 260 ° C. for 12 hours to obtain a CFRP plate.
This CFRP plate was cut into about 5 cm × about 1 cm, and Tg was evaluated by raising the temperature from 50 ° C. to 420 ° C. at 5 ° C./min in a nitrogen atmosphere by PCR 301, a viscoelasticity measuring device manufactured by Anton Paar.

  The raw material compounds of the components (A) to (C) used for the production of the bismaleimide composition are as follows.

<(A) component>
2,2-bis [4- (4-maleimidophenoxy) phenyl] propane: “BMI-80” (hereinafter abbreviated as “BMI-80”) manufactured by Kay Kasei Co., Ltd.

1,6-bismaleimide- (2,2,4-trimethyl) hexane: “BMI-TMH” (hereinafter abbreviated as “BMI-TMH”) manufactured by Daiwa Kasei Kogyo Co., Ltd.

・ 4,4′-diphenylmethane bismaleimide: “BMI-1000H” (hereinafter abbreviated as “BMI-1000H” manufactured by Kay Kasei Co., Ltd. BMI-1000H was pulverized with a Wonder Crush Mill WDL-1 manufactured by Osaka Chemical Co., Ltd. Used.)

Polyphenylmethane maleimide: “BMI-2300” (t = 0.35) manufactured by Daiwa Kasei Kogyo Co., Ltd. (hereinafter abbreviated as “BMI-2300”)

M-phenylene bismaleimide: “BMI-3000” manufactured by Daiwa Kasei Kogyo Co., Ltd. (hereinafter abbreviated as “BMI-3000”)

4-methyl-1,3-phenylenebismaleimide: “BMI-7000” (hereinafter abbreviated as “BMI-7000”) manufactured by Daiwa Kasei Kogyo Co., Ltd.

<(B) component>
・ 4,4'-diallyloxydiphenyl ether (DADPE-ether)

It was manufactured by the following method.
In a 1 L four-necked flask through a nitrogen line, 30.2 g (149 mmol) of 4,4′-dihydroxydiphenyl ether (hereinafter abbreviated as “DHDPE”), 123.6 g of potassium carbonate (890 mmol, 6.0 against DHDPE) Equivalent)), acetone (600 mL), and 45.1 g of allyl bromide (373 mmol, 2.5 equivalents to DHDPE) were added, and the flask was immersed in an oil bath while stirring and heated to an internal temperature of 55 ° C. I let you. During this time, acetone was observed to gently reflux in the flask. The reaction was continued for 6 hours while monitoring the reaction by liquid chromatography (LC). After completion of the reaction, the reaction solution was cooled to room temperature and filtered through a filter paper, and the obtained filtrate was concentrated by a rotary evaporator. The concentrated liquid was dried under reduced pressure at room temperature with a vacuum pump to obtain 40.4 g of a liquid crude product. This was dissolved by adding 34 g of ethyl acetate, and further 32 g of n-hexane was added, heated, cooled and recrystallized to obtain 30.1 g of a first crystal (colorless plate crystal, LC purity of 99. 1%), and recrystallized from an ethyl acetate-n-hexane mixed solvent system to obtain 6.3 g (LC purity 98.3%) of the second crystal. This was identified by NMR and confirmed to be 4,4′-diallyloxydiphenyl ether (DADPE-ether).
The combined yield of the first crystal and the second crystal was 87%. This reaction was repeated twice to obtain 71.9 g of DADPE-ether together.

・ 3,3′-diallyl-4,4′-dihydroxydiphenyl ether (DADPE)

It was manufactured by the following method.
71.7 g (254 mmol) of DADPE-ether synthesized as described above was placed in a 100 mL eggplant flask, immersed in a 180 ° C. oil bath while passing through nitrogen, and heated for 8.75 hours with stirring. The obtained light pink oily substance 71.0 g (99.0% yield, solidified to light pink crystals upon cooling) was analyzed by LC. As a result, an area ratio of 3,3′-diallyl-4, It was found to be a mixture of 4′-dihydroxydiphenyl ether (DADPE) / 3-allyl-4-hydroxy-4′-allyloxydiphenyl ether = 85.7 / 3.1. The total purity was 88.8%. This 88.8% pure mixture was used as DADPE.

3-allyl-4-hydroxy-4'-allyloxydiphenyl ether

O, o′-diallylbisphenol A: “Compimide TM124” manufactured by Evonik Degussa Japan (hereinafter abbreviated as “DABA”)

<(C) component>
1-isobutyl-2-methylimidazole: jER cure “IBMI12” manufactured by Mitsubishi Chemical (hereinafter abbreviated as “IBMI”)
Dicumyl peroxide: “PARK MILL D” manufactured by NOF Corporation (hereinafter abbreviated as “DCPO”)

[Example 1]
In a 100 ml eggplant-shaped flask containing a magnetic stirrer, 0.67 g of DABA and 1.00 g of DADPE were placed at room temperature. This container was immersed in an oil bath, and when the internal temperature reached 100 ° C., BMI-TMH: 0.50 g and BMI-80: 1.42 g were added while stirring. After 5 minutes, BMI-1000H: 1.42 g was added. 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 15 minutes, keeping internal temperature at 100 degreeC. After confirming that the powdered bismaleimide was uniformly dispersed, the internal temperature was set to 80 ° C. over 5 minutes. Here, a solution prepared by dissolving 8 mg of IBMI in 0.33 g of DABA was added to the above mixture with stirring, and the mixture was held at an internal temperature of 80 ° C. for 5 minutes. Then, the mixture was taken out, cooled to room temperature, and the desired bismaleimide system A composition was obtained. This bismaleimide composition could be stored in a refrigerator at 0 ° C. for one month or longer.

  The proportions of the components (A) to (C) used for the production of this bismaleimide composition are as shown in Table 1. The evaluation results of the obtained bismaleimide composition are shown in Table 1.

[Examples 2-6, Comparative Examples 1-6]
A bismaleimide composition was produced in the same manner as in Example 1 except that the use ratio of the components (A) to (C) was changed to the values shown in Table 1, and the evaluation results are shown in Table 1.

  Table 1 shows that according to the polymaleimide composition of the present invention, a cured product having a high Tg and excellent heat resistance can be obtained.

Claims (10)

A polymaleimide composition containing the following component (A) and component (B), wherein the content of component (B) relative to 100 parts by weight of component (A) is 15 parts by weight or more and 200 parts by weight or less. A polymaleimide composition characterized by the above.
(A): One or more polymaleimide compounds containing two or more maleimide groups in one molecule represented by any of the following formulas (1) to (5) (B); , (7) Aromatic liquid reactive diluent containing one or more diphenyl ether compounds represented by any one of (7)

(In formula (1), R ₃₁ , R ₃₂ and R ₃₃ each independently represent a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), ₃₄ , R ₃₅ , R ₃₆ and R ₃₇ 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, and e, f, g, and h each independently represents an integer of 0 to 4.

(In Formula (2), R ₆ represents a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), and R ₇ and R ₈ are each independently 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, and p and q each independently represent an integer of 0 or more and 4 or less. .)

(In Formula (3), R ₉ 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, and r is 0 or more) Represents an integer of 4 or less.)

(In formula (4), Q represents a divalent linking group mainly composed of a hydrocarbon group which may be substituted with one or more substituents and not containing an aromatic ring.)

(In formula (5), t represents an integer of 0 or more and 20 or less, and is composed of a mixture of t different.)

2. The polymaleimide composition according to claim 1, wherein the component (B) further contains one or more benzene compounds represented by the following formula (8) or (9).

(In formula (8), R ₁₁ represents a single bond, CH ₂ , O, S, SO ₂ , or C (CH ₃ ) ₂ , and R ₁₂ represents an allyl group or a methallyl group.)

(In formula (9), R ₂₄ and R ₂₅ each independently represent a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkenyl group, an alkynyl group, an alkoxy group, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom. R ₂₁ , R ₂₂ and R ₂₃ each independently represents a single bond, CH ₂ , O, C═O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), R ₂₆ , R ₂₇ , R ₂₈ and R ₂₉ each independently represent a hydroxy group, an alkyl group having 6 or less carbon atoms, an alkenyl group, an alkynyl group, an alkoxy group, an acyloxy group, an acyl group, a heterocyclic group, or a halogen atom. M represents an integer of 0 to 5, and a, b, c and d each independently represent an integer of 0 to 4. The polymaleimide composition according to claim 1 or 2, further comprising 0.01 to 5 parts by weight of the following component (C) with respect to 100 parts by weight of component (A).
(C); polymerization accelerator   The polymaleimide composition according to claim 3, wherein the component (C) is an anionic polymerization accelerator and / or a radical polymerization accelerator. 5. The polymaleimide composition according to claim 4, wherein the anionic polymerization accelerator is an imidazole represented by the following formula (X).

(In the formula (X), R (1), R (2), R (4) and R (5) each independently represents a hydrogen atom or an arbitrary substituent, and R (1) and R (2 ), R (4) and R (5), R (1) and R (5) may be bonded to each other to form a ring condensed with an imidazole ring.)   6. The polymaleimide composition according to claim 5, wherein in formula (X), R (2) and R (4) are each independently a methyl group or a hydrogen atom.   The polymaleimide composition according to any one of claims 4 to 6, wherein the radical polymerization accelerator is an organic peroxide.   A fiber-reinforced prepreg comprising the polymaleimide composition according to any one of claims 1 to 7.   Hardened | cured material formed by hardening | curing the polymaleimide-type composition of any one of Claim 1 thru | or 7.   A cured product obtained by curing the fiber-reinforced prepreg according to claim 8.