JP2011102345A - Polymaleimide-based composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymaleimide compound that achieves a cured product, having more excellent heat resistance and lesser thermal weight loss when put in a high-temperature state for a long period of time, compared with a conventional polymaleimide compound. <P>SOLUTION: A polymaleimide-based composition contains (A); a polymaleimide compound, (B); an aromatic liquid reactive diluent, (C); an anionic polymerization accelerator, and (D); a radical polymerization accelerator. The total content of the component (C) and the component (D) with respect to the total 100 pts.wt of the component (A) and the component (B) is ≥0.001 pts.wt. and ≤1 pts.wt. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a polymaleimide composition useful as a resin composition for fiber-reinforced composite materials, and in particular, by using together a polymerization accelerator having a different polymerization promoting action mechanism, the heat resistance of the cured product is increased, and The present invention also relates to a polymaleimide composition that suppresses thermal weight loss when kept under high temperature conditions for a long period of time.
The present invention also includes a method for producing and storing such a polymaleimide composition, a fiber reinforced prepreg using the polymaleimide composition, and curing the polymaleimide composition and the fiber reinforced prepreg. It relates to a cured product.

  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 (hereinafter referred to as “prior application”)).

  In the case of the bismaleimide composition of the prior application, by using a specific aromatic bismaleimide compound and an aliphatic bismaleimide compound in combination, an aromatic bismaleimide compound containing three or more aromatic rings in one molecule is obtained. By blending, it has an appropriate viscosity even without solvent, so it has excellent impregnation properties, and it has excellent tackiness, draping properties, and storage stability when used as a prepreg, and cracks in molded products. A highly heat-resistant maleimide resin with reduced content is also 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 them, as the polymerization accelerator, various imidazoles and organic peroxides are mentioned, but conventionally, the polymerization acceleration compounded in the bismaleimide compound As an agent, imidazoles and organic peroxides are not used in combination, and only one of imidazoles and organic peroxides is used (Patent Documents 1 and 2).

  In Patent Document 2, various organic peroxides and imidazoles are listed as imidazole polymerization accelerators. Among them, examples of imidazoles include those in which the substituent at the 2-position of the imidazole ring is a methyl group and those having no substituent at the 4-position, but they have been most commonly used as imidazole polymerization accelerators in the past. What is present is 2-ethyl-4-methylimidazole.

Japanese Patent Application No. 2009-032764 JP 11-246840 A

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

  According to the bismaleimide composition proposed in the prior application, a cured product having excellent heat resistance and low thermal weight loss when subjected to high temperature conditions for a long time is provided. Reduction in weight loss is desired.

  The present invention realizes a cured product that is more excellent in heat resistance than a polymaleimide-based composition such as a bismaleimide-based composition that has been provided in the past, and has a reduced thermal weight when kept under high-temperature conditions for a long period of time. An object is to provide a polymaleimide-based composition to be obtained.

  In order to solve the above-mentioned problems, the present inventor has intensively studied the polymerization promoting action of imidazoles, which are polymerization accelerators, and organic peroxides. As a result, the mechanism of promotion of polymerization differs between imidazoles and organic peroxides. When these are used in combination, a polymaleimide composition can be obtained that effectively exhibits the advantages of each, complements the disadvantages, and provides a cured product with excellent heat resistance and low thermal weight loss due to the synergistic effect of the combined use. I found.

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

[1] A polymaleimide composition containing the following components (A) to (D), wherein (C) component and (D) component with respect to a total of 100 parts by weight of component (A) and component (B) A polymaleimide composition having a total content of 0.001 to 1 part by weight.
(A); polymaleimide compound (B); aromatic liquid reactive diluent (C); anionic polymerization accelerator (D); radical polymerization accelerator

[2] The polymaleimide composition according to [1], wherein the content of the component (C) is from 1 part by weight to 99 parts by weight with respect to 100 parts by weight of the total of the component (C) and the component (D) object.

[3] In [1] or [2], the component (A) is one or more of bismaleimide compounds represented by any of the following formulas (1) to (4): Polymaleimide composition.

(In formula (1), R ₁ and R ₂ each independently represents a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), and 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, and n is 1 or more and 5 The following integers are represented, and x, y and z each independently represent an integer of 0 or more and 4 or less.)

(In Formula (2), R ₇ represents a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), and R ₈ and R ₉ 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 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, 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.)

[4] In any one of [1] to [3], the component (B) is one or more of benzene compounds represented by the following formula (5) or (6): Polymaleimide composition.

(In Formula (5), 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 the formula (6), R ₁₃ and R ₁₄ are each independently 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. Each of R ₁₅ and R ₁₆ independently represents a single bond, CH ₂ , O, C═O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), R ₁₇ , R ₁₈ and R ₁₉ 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, and m is 0 or more Represents an integer of 5 or less, and a, b and c each independently represent an integer of 0 or more and 4 or less.)

[5] The polymaleimide composition according to any one of [1] to [4], wherein the component (C) 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 [1] to [6], wherein the component (D) is an organic peroxide.

[8] The polymaleimide composition according to any one of [1] to [7], wherein the content of the component (B) is from 30 parts by weight to 90 parts by weight with respect to 100 parts by weight of the component (A) object.

[9] A solution in which the component (C) and the component (D) are dissolved in a part of the component (B) is added to a mixture of the component (A) and the remainder of the component (B) [1] ] The manufacturing method of the polymaleimide-type composition in any one of [8].

[10] The method for producing a polymaleimide composition according to [9], wherein the component (A) and the component (B) are mixed at a temperature of 50 ° C. or higher and 150 ° C. or lower.

[11] A mixture of the component (A) and the component (B) and a solution obtained by dissolving the component (C) and the component (D) in the component (B) are mixed at a temperature of 30 ° C. or higher and 120 ° C. or lower. [9] A method for producing a polymaleimide composition according to [10].

[12] A method for storing a polymaleimide composition, comprising storing the polymaleimide composition according to any one of [1] to [8] at 40 ° C. or lower.

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

[14] A cured product obtained by curing the polymaleimide composition according to any one of [1] to [8].

[15] A cured product obtained by curing the fiber-reinforced prepreg according to [13].

[16] A cured product according to [14], wherein TMA-Tg is 280 ° C. or higher.

[17] In [15], the DMA-Tg by tan δ and G ′ reading is 280 ° C. or more, and the thermal weight loss rate when held at 250 ° C. in an air atmosphere for 500 hours is 8% or less. Characterized cured product.

  According to the present invention, the combined use of an anionic polymerization accelerator and a radical polymerization accelerator as a polymerization accelerator increases the heat resistance of the resulting cured product, and reduces the thermal weight when left under high temperature conditions for a long time. A bismaleimide compound that can be suppressed can be provided.

The proportion of imidazoles (component (C)) in the polymerization accelerators (total of components (C) and (D)) in Examples 1 and 3 and Comparative Examples 1 and 2, DMA-Tg (tan δ) and heat It is a graph which shows the relationship with a weight decreasing rate.

  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) to (D), and (C) with respect to a total of 100 parts by weight of the components (A) and (B). The total content of the component and the component (D) is 0.001 part by weight or more and 1 part by weight or less.
(A); polymaleimide compound (B); aromatic liquid reactive diluent (C); anionic polymerization accelerator (D); radical polymerization accelerator

The component (C) anionic polymerization accelerator according to the present invention is excellent in the polymerization promotion effect, but since the polymerization promotion effect is low for some components, the radical polymerization of the component (D) As a result, the cured product obtained from the polymaleimide composition using only an anionic polymerization accelerator as a polymerization accelerator tends to have a lower Tg as an index of heat resistance.
On the other hand, the radical polymerization accelerator of component (D) exhibits a polymerization promoting effect on both components (A) and (B) used in the present invention, but is unstable with respect to the terminal of some components. Oxygen-carbon bonds are formed. 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. When it is placed underneath, the rate of thermal weight loss is significantly increased.

  In the present invention, the anionic polymerization accelerator (C) and the radical polymerization accelerator (D) are used in combination to make up for each of the advantages, thereby improving the heat resistance and heat. Reduce weight loss.

<(A) component>
There is no restriction | limiting in particular as a polymaleimide compound of (A) component, An aromatic polymaleimide compound may be sufficient and an aliphatic polymaleimide compound may be sufficient.

  The polymaleimide compound is preferably a bismaleimide compound represented by any one of the following formulas (1) to (4).

(In formula (1), R ₁ and R ₂ each independently represents a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), and 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, and n is 1 or more and 5 The following integers are represented, and x, y and z each independently represent an integer of 0 or more and 4 or less.)

(In Formula (2), R ₇ represents a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), and R ₈ and R ₉ 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 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, and r is 0 or more. Represents an integer of 4 or less.)

（式（４）中、Ｑは１以上の置換基で置換されていてもよい炭化水素基で主に構成され、芳香環を含まない２価の連結基を表す。）

(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 the formula (1), 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, and particularly preferably 1 or more and 2 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 (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 ′-[sulfonylbis (4,1-phenyleneoxy-3,1-phenylene)] bismaleimide ([99391-93 -2]), bis [4- (3-maleimidophenoxy) phenyl] ketone, 1,3-bis (4-maleimidophenoxy) benzene, 1,3-bis (3-maleimi Dophenoxy) 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 -5 (1) -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, 1, 3-bis (3-maleimidophenoxy) benzene, and 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane represented by the following formula (1A) is most preferable.

In the formula (2), 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, SO ₂ 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.

  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′-benzophenone bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane And bismaleimide, 1,1 ′-[1,4-butanediylbis (oxy-p-phenylene)] bismaleimide, among others, 4,4′-diphenyl sulfide bismaleimide, 4,4′-diphenyl ether bismaleimide, Alternatively, 4,4′-diphenylmethane bismaleimide represented by the following formula (2A) is preferably used.

In the formula (3), R ₁₀ represents 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 represented by the following formula (3A) or 1,3-phenylenebismaleimide represented by the following formula (3B) is 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.

  In the present invention, the component (A) is not limited to the bismaleimide compound as described above, but may be a polymaleimide compound having three or more maleimide groups, and examples thereof include polyphenylmethane maleimide. Specifically, the polymaleimide compound may be a commercially available polyphenylmethane maleimide represented by the following formula (“BMI-2000” or “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>
Although there is no restriction | limiting in particular as an aromatic liquid reactive diluent of (B) component, Preferably, the benzene type compound represented by following formula (5) or (6) is mentioned.

(In Formula (5), 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 the formula (6), R ₁₃ and R ₁₄ are each independently 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. Each of R ₁₅ and R ₁₆ independently represents a single bond, CH ₂ , O, C═O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), R ₁₇ , R ₁₈ and R ₁₉ 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, and m is 0 or more Represents an integer of 5 or less, and a, b and c each independently represent an integer of 0 or more and 4 or less.)

In Formula (5), 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═CHCH). Of the _three groups, an allyl group is preferred.

  Specific examples of the benzene compound represented by the formula (5) (hereinafter sometimes referred to as “bisphenol compound (5)”) 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 Examples include '-dihydroxy-diphenyl sulfide, o, o'-dimethallyl bisphenol A, o, o'-dimethallyl bisphenol F, and o, o'-diallyl bisphenol A represented by the following formula (5A). Preferably used.

In formula (6), R ₁₃ and R ₁₄ 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 or an allyl group. .
R ₁₅ and R ₁₆ 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 or -C (= O)-, and m is preferably 0, 1 or 2.

R ₁₇ , R ₁₈ and R ₁₉ 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; Such as alkoxy groups having 6 or less carbon atoms; acyloxy groups having 6 or less carbon atoms (aliphatic acyloxy groups) such as formyloxy groups and acetoxy groups; acyl groups such as acetyl groups and benzoyl groups, pyridyl groups, and furyl groups. A halogen atom such as a heterocyclic group, fluorine, chlorine, or bromine atom may be mentioned. 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, and c are each independently preferably 0 to 2.

  Specific examples of the benzene compound represented by the formula (6) (hereinafter sometimes referred to as “polyphenylene compound (6)”) 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, among others, are represented by the following formula (6A). The 4,4′-bis- (o-propenylphenoxy) -benzophenone represented is preferably used.

  The bisphenol compound (5) and the polyphenylene compound (6) may be used singly or in combination of two or more.

  Moreover, you may use together 1 type, or 2 or more types of a bisphenol compound (5), and 1 type or 2 or more types of a polyphenylene compound (6). The effects of improving tackiness and draping when formed into a prepreg, improving impregnation into a carbon fiber sheet, and improving heat resistance of CFRP are exhibited.

  When one or more of the bisphenol compound (5) and one or more of the polyphenylene compound (6) are used in combination, there are no particular restrictions on the use ratio, but the total of 100 weights of component (B) It is preferable that the amount of the bisphenol compound (5) is 20 parts by weight or more and 100 parts by weight or less with respect to parts, in order to effectively obtain the combined effect.

<(C) component>
(C) Component anionic polymerization accelerators 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-un Decylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimid TBZ (2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenyl-imidazolium trimellitate Imidazole compounds such as tate, 2-phenyl-4,5-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-phenyldi Benzylamine, 1-benzylpiperidine, 1- Tyl-2,2-dimethyl-6,6-dimethylpiperidine, quinoxaline, quinoline, tetramethylenehexamine, pyrazole, triazole, benzotriazole, hydroxybenzotriazole, 2-methylimidazoline, 2-phenylimidazoline, DABCO (1,4- Anionic polymerization accelerators such as tertiary amine compounds such as diazabicyclo [2.2.2] octane) and trivalent phosphorus compounds such as triphenylphosphine or triphenyl phosphite are mentioned. Among these, Imidazole polymerization accelerators 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 (3) 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.

  Therefore, in the imidazoles of the component (C) used in the present invention, in the formula (X), R (2) and R (4) are preferably each independently a methyl group or a hydrogen atom. 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.

<(D) component>
Examples of the radical polymerization accelerator of component (D) include organic peroxide polymerization accelerators or radical polymerization accelerators such as azobisisobutyronitrile, preferably organic peroxide polymerization accelerators. It is an agent.

Examples of the organic peroxide of component (D) 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 decomposes at the temperature in the step of preparing a polymaleimide composition by mixing the components (A), (B), (C), and (D), or in the step of impregnating the fiber into a fiber to produce a prepreg. However, it is preferable to have a property of efficiently decomposing at a temperature at which it is cured to produce a molded product (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.

<Blending amount>
The polymaleimide composition of the present invention contains the components (A) to (D) as essential components, and the blending amounts of the components (C) and (D) among them are the sum of the components (A) and (B ) 0.001 to 1 part by weight, preferably 0.005 to 0.5 part by weight, more preferably 0.01 to 0.5 part by weight, based on 100 parts by weight Parts by weight or less, particularly preferably 0.05 parts by weight or more and 0.5 parts by weight or less.
If the total blending amount of the component (C) and the component (D), which are polymerization accelerators, is less than the lower limit, sufficient polymerization promotion effect cannot be obtained, but if it exceeds the upper limit, the polymerization proceeds excessively. It is difficult to control the reaction or the polymerization proceeds more than necessary in the process before curing and molding, and the physical properties required for the polymaleimide composition and the prepreg obtained by impregnating the fiber with this are low. Since properties that facilitate handling such as viscosity, tackiness, and drapeability are lost, it is not preferable. In the present invention, particularly as component (C), an imidazole having excellent catalytic activity, wherein R (2) and R (4) are each independently a methyl group or a hydrogen atom in formula (X). By using it, the total amount of component (C) and component (D), which are polymerization accelerators, can be kept low by utilizing the advantage of the imidazoles that a small amount is sufficient.

  The content of the component (C) with respect to 100 parts by weight of the total of the component (C) and the component (D) is 1 part by weight or more and 99 parts by weight or less, particularly 10 parts by weight or more and 90 parts by weight or less, especially 20 parts by weight or more and 80 parts by weight. It is preferable that it is below the weight part. Even if the component (C) is more or less than this range, the effect of the present invention by using the component (C) and the component (D) together may not be sufficiently obtained.

The content of the component (B) with respect to 100 parts by weight of the component (A) is preferably 30 parts by weight or more and 90 parts by weight or less, more preferably 40 parts by weight or more and 80 parts by weight or less.
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. When there are more (B) components than the said range, the heat resistance of hardened | cured material will deteriorate.

<Other ingredients>
The polymaleimide composition of the present invention may contain other components other than the components (A) to (D).
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), (C) and (D), and other optional components used as necessary are mixed and dissolved uniformly. Alternatively, the composition may be a uniformly dispersed composition, and the method is not particularly limited. However, in the present invention, as the component (C) that is a polymerization accelerator, in the formula (X), the polymerization activity is remarkably excellent. R (2) and R (4) are each independently an imidazole in which a methyl group or a hydrogen atom is used, and the blending amount is an unprecedented small amount blending, and the sum of (C) component and (D) component Since it is preferable to use a small amount, the component (C) and the component (D) are preliminarily dissolved in a part of the component (B), and this solution is used as the component (A) and the component (B). Adding to and mixing with the rest of the ingredients is a minor ingredient C) Preferred component and (D) the surface of the uniformly dispersed mixture of the components of the composition.

In this case, the mixing temperature of the component (B), the component (C), and the component (D) is not particularly limited, and can be mixed at a wide temperature range from 40 ° C to 150 ° C. The (C) component and the (D) component are not particularly limited as long as the components are uniformly dissolved in the (B) component.
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 obtained by dissolving the component (C) and the component (D) in the component (B) are 30 ° C. or higher and 120 ° C. or lower, particularly 50 ° C. or higher and 100 ° C. or lower. In particular, it is preferable to mix by heating at 60 ° C. or higher and 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) and the component (D) are dissolved in advance is the component (C), the component (D) and the component (B), and further the component (A). However, it is usually 0.1% to 50% by weight, particularly 0.5% to 30% by weight of the total amount of component (B) (C). ) Component and (D) component used for dissolution, and the total concentration of (C) component and (D) component in the (B) component solution of (C) component and (D) component is 0.1 wt% or more and 50 wt% % Or less, particularly 0.5 wt% or more and 30 wt% or less is preferable. If the amount of the component (B) used for dissolving the component (C) and the component (D) is too small or too large, a composition in which the components (A) to (D) are uniformly mixed may not be obtained. There is.

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

<How to save>
Since the polymaleimide composition of the present invention preferably contains the component (C) as a polymerization accelerator excellent in polymerization activity, in order to prevent polymerization solidification during storage, 40 ° C. or less, particularly It is preferably stored at 20 ° C. or lower, particularly 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 in which the anionic polymerization accelerator of component (C) and the radical polymerization accelerator of component (D) are used in combination as a polymerization accelerator is measured by TMA. The high Tg is usually 280 ° C. or higher. TMA-Tg of the hardened | cured material of this invention becomes like this. Preferably it is 290 degreeC or more, for example, 300-400 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.

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 280 ° C. or more, and kept at 250 ° C. for 500 hours in an air atmosphere. Thus, the high heat resistance with a thermal weight reduction rate of 8% or less and a low thermal weight reduction rate can be satisfied. The DMA-Tg is more preferably 290 ° C. or more, for example, 300 to 400 ° C., and the thermal weight loss rate is more preferably 6% or less, for example, 0.5 to 5%.
The DMA-Ta and the thermal weight reduction rate of the cured product are performed by the methods described in the Examples section described later.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.
In the following, methods for measuring the activity and solubility of the catalyst and the physical properties of the composition are as follows.

<Catalytic activity>
The gelation temperature of the polymaleimide composition is measured from 40 ° C. to 200 ° C. at a rate of 3 ° C./minute, and the catalyst activity (polymerization of the polymerization accelerator is determined from the concentration of the polymerization accelerator that gels around 170 ° C. Promotion effect) was evaluated.

<TMA-Tg>
The polymaleimide composition heated to about 70 ° C. is poured between two glass plates through a 2 mm-thick spacer, treated at 170 ° C. for 3 hours, then removed from the glass plate mold, and then at 190 ° C. for 1 hour. A sample heat-treated at 220 ° C. for 1 hour, 250 ° C. for 4 hours, and further at 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.

<DMA-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 plate was cut to about 5 cm × about 1.5 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, an anton pearl viscoelasticity measuring device.

<Thermal weight reduction rate>
The CFRP plate obtained by the method described in <DMA-Tg> is cut into a size of about 1 cm × about 5 cm, and left in an oven at 250 ° C. or 280 ° C. for 500 hours in the air, and the volatilization reduction rate of the weight Was measured.
This thermal weight reduction rate indicates the rate of weight reduction, and the larger this negative value, the greater the thermal weight reduction rate, which is not preferable.

[Example 1]
In a glass container (450 ml) equipped with a mechanical stirrer, 57.12 g of o, o′-diallylbisphenol A (Compimido TM124 manufactured by Degussa) was placed. 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-1000H manufactured by Daiwa Kasei Kogyo Co., Ltd.) was added 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. Here, 0.160 g of 1-isobutyl-2-methylimidazole (IBMI12 manufactured by Japan Epoxy Resin) and 0.160 g of dicumyl peroxide (Park Mill D manufactured by Nippon Oil & Fats Co., Ltd.) were mixed with o, o′-diallylbisphenol A (Degussa). A solution dissolved in 2.88 g of Compimide TM124) was added with stirring. Subsequently, the mixture was stirred for 60 minutes at an internal temperature of 70 ° C., then the mixture was taken out and cooled to room temperature to obtain the desired bismaleimide composition. Obtained. This bismaleimide composition could be stored in a refrigerator at 0 ° C. for one month or longer.

[Example 2]
To a glass eggplant-shaped flask (100 ml), 6.67 g of o, o′-diallylbisphenol A (Compimide TM124 manufactured by Degussa) was placed. When this container was immersed in an oil bath and the internal temperature reached 100 ° C., 1,6-bismaleimide- (2,2,4-trimethyl) hexane (BMI-manufactured by Daiwa Kasei Kogyo Co., Ltd.) was stirred with a magnetic stirrer. TMH) 2.00 g, then 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (KMI Kasei BMI-80) 5.67 g, and then 4,4′-diphenylmethane bismaleimide 5.67 g (BMI-1000H manufactured by Daiwa Kasei Kogyo Co., Ltd.) 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. After confirming that the powdered bismaleimide was uniformly dispersed, the internal temperature was set to 80 ° C. over 10 minutes while stirring. 0.021 g of 1-isobutyl-2-methylimidazole (IBMI12 manufactured by Japan Epoxy Resin) and 0.021 g of dicumyl peroxide (Park Mill D manufactured by Nippon Oil & Fats Co., Ltd.) were combined with o, o′-diallylbisphenol A (Compigimide manufactured by Degussa). TM124) A solution dissolved in 1.33 g was added with stirring, and the mixture was stirred at an internal temperature of 80 ° C. for 5 minutes. Then, 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 bismaleimide composition was produced in the same manner as in Example 1 except that the amount of the polymerization accelerator was as shown in Table 1. This bismaleimide composition could be stored in a refrigerator at 0 ° C. for one month or longer.

[Examples 4 and 5]
A bismaleimide composition was produced in the same manner as in Example 2 except that the amount of the polymerization accelerator was as shown in Table 1. Any bismaleimide composition could be stored in a refrigerator at 0 ° C. for one month or longer.

[Example 6]
Except that the blending amount of the polymerization accelerator is as shown in Table 1, and 4,4′-bis- (o-propenylphenoxy) -benzophenone (Compimide TM123 manufactured by Degussa) was added as component (B). In the same manner as in Example 2, a bismaleimide compound was produced. This bismaleimide composition could be stored in a refrigerator at 0 ° C. for one month or longer.

[Comparative Example 1]
In a glass container (450 ml) equipped with a mechanical stirrer, 57.70 g of o, o′-diallylbisphenol A (Compimido TM124 manufactured by Degussa) was placed. 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-I Kasei Co., Ltd.) was added over 25 minutes. Subsequently, 42.50 g of 4,4′-diphenylmethane bismaleimide (BMI-1000H manufactured by Daiwa Kasei Kogyo Co., Ltd.) was added 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. A solution prepared by dissolving 0.256 g of 1-isobutyl-2-methylimidazole (IBMI 12 manufactured by Japan Epoxy Resin) in 2.30 g of o, o′-diallylbisphenol A (Compimide TM124 manufactured by Degussa) was added with stirring. After stirring at an internal temperature of 70 ° C. for 60 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.

[Comparative Example 2]
As a polymerization accelerator, a bismaleimide compound was produced in the same manner as in Comparative Example 1 except that dicumyl peroxide was used in the amount shown in Table 1 instead of 1-isobutyl-2-methylimidazole. This bismaleimide composition could be stored in a refrigerator at 0 ° C. for one month or longer.

[Comparative Example 3]
To a glass eggplant-shaped flask (100 ml), 2.67 g of o, o′-diallylbisphenol A (Degussa Compimide TM124) and 4,4′-bis- (o-propenylphenoxy) -benzophenone (Degussa Compimido TM123) ) 4.00 was added. When this container was immersed in an oil bath and the internal temperature reached 100 ° C., 1,6-bismaleimide- (2,2,4-trimethyl) hexane (BMI-manufactured by Daiwa Kasei Kogyo Co., Ltd.) was stirred with a magnetic stirrer. TMH), 3.00 g, then 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (KMI Kasei BMI-80), 5.17 g, and then 4,4′-diphenylmethanebis 5.17 g of maleimide (BMI-1000H manufactured by Daiwa Kasei Kogyo Co., Ltd.) 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. After confirming that the powdered bismaleimide was uniformly dispersed, the internal temperature was set to 80 ° C. over 10 minutes while stirring. A solution prepared by dissolving 0.032 g of 1-isobutyl-2-methylimidazole (IBMI 12 manufactured by Japan Epoxy Resin) in 1.33 g of o, o′-diallylbisphenol A (Compimide TM124 manufactured by Degussa) was added with stirring. After stirring at 80 ° C. 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.

Table 1 shows the evaluation results of the bismaleimide compositions of the above Examples and Comparative Examples.
Further, the ratio of imidazoles (component (C)) in the polymerization accelerators (total of components (C) and (D)) in Examples 1 and 3 and Comparative Examples 1 and 2, DMA-Tg, and thermogravimetric weight. The relationship with the decrease rate is shown in FIG.

  From Tables 1 and 2 and FIG. 1, according to the present invention, it is possible to improve the heat resistance of the bismaleimide compound and its cured product, and to suppress the thermogravimetric reduction rate when kept under high temperature conditions for a long time. I understand.

Claims (17)

A polymaleimide composition containing the following components (A) to (D), the total content of (C) component and (D) component with respect to 100 parts by weight of the total of (A) component and (B) component A polymaleimide composition characterized in that the amount is 0.001 part by weight or more and 1 part by weight or less.
(A); polymaleimide compound (B); aromatic liquid reactive diluent (C); anionic polymerization accelerator (D); radical polymerization accelerator   2. The polymaleimide composition according to claim 1, wherein the content of the component (C) is from 1 part by weight to 99 parts by weight with respect to 100 parts by weight in total of the component (C) and the component (D). 3. The polymaleimide composition according to claim 1 or 2, wherein the component (A) is one or more of bismaleimide compounds represented by any one of the following formulas (1) to (4). .

(In formula (1), R ₁ and R ₂ each independently represents a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), and 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, and n is 1 or more and 5 The following integers are represented, and x, y and z each independently represent an integer of 0 or more and 4 or less.)

(In Formula (2), R ₇ represents a single bond, CH ₂ , O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), and R ₈ and R ₉ 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 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, 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.) 4. The polymaleimide type according to claim 1, wherein the component (B) is one or more benzene compounds represented by the following formula (5) or (6): 5. Composition.

(In Formula (5), 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 the formula (6), R ₁₃ and R ₁₄ are each independently 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. Each of R ₁₅ and R ₁₆ independently represents a single bond, CH ₂ , O, C═O, S, SO ₂ , C (CH ₃ ) ₂ or NHC (═O), R ₁₇ , R ₁₈ and R ₁₉ 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, and m is 0 or more Represents an integer of 5 or less, and a, b and c each independently represent an integer of 0 or more and 4 or less.) The polymaleimide composition according to any one of claims 1 to 4, wherein the component (C) 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 1 to 6, wherein the component (D) is an organic peroxide.   The polymaleimide composition according to any one of claims 1 to 7, wherein the content of the component (B) is from 30 parts by weight to 90 parts by weight with respect to 100 parts by weight of the component (A).   9. A solution in which the component (C) and the component (D) are dissolved in a part of the component (B) is added to a mixture of the component (A) and the remainder of the component (B). The manufacturing method of the polymaleimide-type composition of any one of these.   The method for producing a polymaleimide composition according to claim 9, wherein the component (A) and the component (B) are mixed at a temperature of 50 ° C to 150 ° C.   A mixture of the component (A) and the component (B) and a solution in which the component (C) and the component (D) are dissolved in the component (B) are mixed at a temperature of 30 ° C to 120 ° C. Item 11. A method for producing a polymaleimide composition according to Item 9 or 10.   A method for storing a polymaleimide composition, comprising storing the polymaleimide composition according to any one of claims 1 to 8 at 40 ° C or lower.   A fiber-reinforced prepreg comprising the polymaleimide composition according to any one of claims 1 to 8.   Hardened | cured material formed by hardening | curing the polymaleimide-type composition of any one of Claim 1 thru | or 8.   A cured product obtained by curing the fiber-reinforced prepreg according to claim 13.   The cured product according to claim 14, wherein TMA-Tg is 280 ° C. or higher.   In Claim 15, DMA-Tg by tan-delta and G 'reading is 280 degreeC or more, The thermal weight reduction | decrease rate when hold | maintaining at 250 degreeC in an air atmosphere for 500 hours is 8% or less, It is characterized by the above-mentioned. Cured product.

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