JP3250044B2 - Storage stable polyimide prepreg with improved processing properties - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a storage-stable polyimide prepreg with improved processing characteristics.

[0002]

BACKGROUND OF THE INVENTION It is known that polymaleimides can be used in the manufacture of various polyaddition and polypolymer products.
Of particular interest are bismaleimide materials that exhibit thermal stability and good mechanical properties and are therefore frequently used in high performance composites, for example, electronic circuit board applications.

[0003] Currently used bismaleimide systems include alkenyl phenols as coreactants. U.S. Patents 4,100,140, 4,127,615 and 4,131,63
No. 2 is an example of a patent that discloses a crosslinked polymer obtained by reacting a polymaleimide with an alkenylphenol or alkenylphenol ether, optionally in the presence of an epoxy resin.

[0004]

Standard polyimide prepregs for electronic circuit board applications are based on bismaleimide diphenylmethane and diallyl bisphenol A. The product usually must be stored at refrigerated temperatures due to the instability and advancement of the resin system at elevated temperatures.

It is a primary object of the present invention to provide a polyimide resin system which substantially eliminates the disadvantages of the prior art materials.

[0006] A further object is to provide such polyimide resin systems without any substantial adverse effect on their thermal and mechanical properties.

[0007] Various other objects and advantages of the invention will be apparent from the materials described below.

[0008]

SUMMARY OF THE INVENTION It has been found that the addition of phenothiazine to the polyimide resin system according to the present invention suppresses the oxidation reaction and improves the storage stability of the prepreg produced therefrom. Accordingly, the polyimide resin composition according to the present invention provides a manufactured prepreg that can be stored at room temperature without adversely affecting processing conditions.

Surprisingly, the addition of phenothiazine also improves the other processing properties of the resin.

For example, the pot life of the resin system according to the present invention is extended, improving the processability of the manufactured prepreg, reducing the residual volatiles in the prepreg, and shortening the curing time of the resin system. Thus, the polyimide resin composition according to the present invention provides improved coating and processing conditions for high quality materials.

The present invention provides: (A) (a)

Embedded image [In the formula, D represents a divalent group containing a C ＝ C bond. ]
A reaction product of a polyimide containing at least two groups represented by the formula (b) and about 0.05 to 2.0 moles of alkenylphenol, alkenylphenolether or a mixture thereof per mole of component (a); The present invention relates to a thermosetting composition comprising an ionic polymerization catalyst or a free radical polymerization catalyst, and (C) phenothiazine or a derivative thereof, and a prepreg produced therefrom.

The applicable polyimide is represented by the following formula:

Embedded image [In the formula, D represents a divalent group containing a C ＝ C bond. ]
At least two groups represented by These polyimides are known compounds, for example, U.S. Pat.
It is described in the specification of No. 0. They are preferably of the formula

Embedded image Wherein R ₁ represents a hydrogen atom or a methyl group, and X represents a divalent organic group having 2 to 30 carbon atoms, particularly —C
_{x H 2x - (x = 2~20} ), - CH 2 CH 2 SCH 2 C
H ₂ —, a phenylene group, a naphthylene group, a xylylene group,
Cyclopentylene group, 1,5,5-trimethyl-1,3
-Cyclohexylene group, 1,4-cyclohexylene group,
1,4-bis (methylene) -cyclohexylene group or the following formula

Embedded image 中 In the formula, R ₂ and R ₃ independently represent a chlorine atom, a bromine atom,
Represents a methyl group, an ethyl group or a hydrogen atom, and Z represents a direct bond or a methylene group, a 2,2-propylidene group, -CO
-, - O -, - S -, - SO- or -SO ₂ - represents a. Represents a group represented by｝. ] Is a polyimide represented by the formula: In a particularly preferred polyimide, R ₁ represents a hydrogen atom, and X represents a hexamethylene group, a trimethylhexamethylene group, a 1,5,5-trimethyl-1,3-cyclohexylene group, or a designated formula (where Z is Methylene group, 2,2
-Represents a propylidene group or -O-. ].

The following substances are particularly mentioned as examples of known polyimides suitable for use in the present invention: N, N'-ethylene-bismaleimide, N, N'-
Hexamethylene-bismaleimide, N, N'-m-phenylene-bismaleimide, N, N'-p-phenylene-
Bismaleimide, N, N'-4,4'-diphenylmethane-bismaleimide (which is preferably used),
N, N'-4,4'-3,3'-dichloro-diphenylmethane-bismaleimide, N, N'-4,4 '-(diphenylether) -bismaleimide, N, N'-4,
4'-di-phenylsulfone-bismaleimide, N,
N′-4,4′-dicyclohexylmethane-bismaleimide, N, N′-α, α′-4,4′-dimethylenecyclohexane-bismaleimide, N, N′-m-xylylene-bismaleimide, N'-p-xylylene-bismaleimide, N, N'-4,4'-diphenylcyclohexane-bismaleimide, N, N'-m-phenylene-
Bis-citraconimide, N, N'-4,4'-diphenylmethane-bis-citraconimide, N, N'-4,
4'-2,2-diphenylpropane-bismaleimide,
N, N'-α, α'-1,3-dipropylene-5,5-
Dimethyl-hydantoin-bismaleimide, N, N'-
4,4′-diphenylmethane-bis-itaconimide,
N, N′-p-phenylene-bis-itaconimide,
N, N'-4,4'-diphenylmethane-bis-dimethylmaleimide, N, N'-4,4'-2,2-diphenylpropane-bis-dimethylmaleimide, N, N'-hexamethylene-bis-dimethyl Maleimide, N, N'-
4,4 '-(diphenylether) -bis-dimethylmaleimide and N, N'-4,4'-di-phenylsulfone-bis-dimethylmaleimide.

According to the present invention, allylphenol and methallylphenol or their ethers are preferably used as alkenylphenol and alkenylphenol ether. Both mononuclear and polynuclear, preferably binuclear, alkenyl phenols and alkenyl phenol ethers can be used. Preferably, at least one of the nuclei contains an alkenyl group and a phenolic, optionally etherified OH group.

As is known, alkenyl phenols are prepared by the rearrangement of alkenyl ethers of phenols (eg allyl ethers of phenol) by the action of heat (Claisen rearrangement). These alkenylphenols can also be obtained by reacting phenol with, for example, allyl chloride in the presence of an alkali metal hydroxide and a solvent according to a known method. As is known, a condensation reaction takes place (elimination of alkali metal chloride).

Representative examples are as follows:

Embedded image [Wherein, R is a direct bond, methylene, isopropylidene, -O -, - S -, - SO- or -SO ₂ - represents a. A compound represented by the formula:

The following formula II

Embedded image Wherein R ₄ , R ₅ and R ₆ independently represent a hydrogen atom or an alkenyl group having 2 to 10 carbon atoms, preferably an allyl group or a propenyl group, provided that at least one of R ₄ to R ₆ One represents an alkenyl group, preferably a propenyl group. A propenyl-substituted phenol represented by the formula:

The following formula III

Embedded image [Wherein R ₄ , R ₅ , R ₆ and R ₇ independently represent a hydrogen atom or an alkenyl group having 2 to 10 carbon atoms, preferably an allyl group or a propenyl group, provided that R ₄
And at least one of R ₇ represents an alkenyl group, preferably a propenyl group, and R has the meaning as defined in formula I. A compound represented by the formula:

The following equation IV

Embedded image Wherein R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, preferably Represents an allyl group or a propenyl group, provided that at least one of R ₈ to R ₁₃ represents an alkenyl group, preferably a propenyl group, and a represents a value of 0 to 10. ] The compound represented by these.

In formula III, preference is given to compounds in which each R ₄ and R ₆ represents a propenyl group, each R ₅ and R ₇ represents a hydrogen atom and R represents a methylene group, an isopropylidene group or —O—.

It is also possible to use isomer mixtures of propenyl- and allyl-substituted mononuclear or polynuclear phenols. Among the isomeric mixtures, a mixture of propenyl- and allyl-substituted phenols of the formula III, preferably of the formula IIIa

Embedded image Wherein R is a methylene group, an isopropylidene group or -O
Represents-. It is preferable to use those obtained by partial isomerization of an allyl-substituted phenol represented by the formula:

According to the invention, the use of mixtures of polynuclear alkenyl phenols and / or alkenyl phenol ethers with mononuclear alkenyl phenols and / or alkenyl phenol ethers also gives good results. The alkenylphenol preferably used is represented by the following formula V

Embedded image -O-R ₃ (V) wherein, R ₃ is alkyl group having 1 to 10 carbon atoms,
Represents an aryl or alkenyl group, preferably an allyl or methallyl group, wherein the oxygen atom in Formula V represents a phenol ether bridge. ] The compound contains one or more molecular groups represented by the formula:

Further embodiments of the present invention include materials containing only one OH group and only one alkenyl group on the aromatic nucleus, and some OH and some alkenyl groups on the aromatic nucleus. Or a mixture of the corresponding phenolic ethers of these substances.
Corresponding methallyl compounds can also be used.

Such alkenyl-substituted phenols and polyols are described, for example, in US Pat. Nos. 4,100,140 and 4,371,
No. 719.

Representative materials include o, o'-diallyl-
Bisphenol A, 4,4'-dihydroxy-3,3 '
-Diallyldiphenyl, bis (4-hydroxy-3-allylphenyl) methane, 2,2-bis (4-hydroxy-3,5-diallylphenyl) propane, eugenol, o, o'-dimethallyl-bisphenol A, 4,
4'-dihydroxy-3,3'-dimethylalyldiphenyl, bis (4-hydroxy-3-methallylphenyl) methane, 2,2-bis (4-hydroxy-3,5-dimethallylphenyl) propane, 4- Methallyl-2-methoxyphenol, 2,2-bis (4-methoxy-3-allylphenyl) propane, 2,2-bis (4-methoxy-3
-Methallylphenyl) propane, 4,4'-dimethoxy-3,3'-diallyldiphenyl, 4,4'-dimethoxy-3,3'-dimethallyldiphenyl, bis (4-methoxy-3-allylphenyl) methane , Bis (4-methoxy-3-methallylphenyl) methane, 2,2-bis (4
-Methoxy-3,5-diallylphenyl) propane,
Includes 2,2-bis (4-methoxy-3,5-dimethallylphenyl) propane, 4-allylveratrol and 4-methallyl veratrol.

In terms of relative concentrations, the alkenylphenol component or mixture thereof is used in the range of 0.05 to 2.0 moles per mole of maleimide, preferably in the range of 0.1 to 1.0 mole. , Most preferably in a molar ratio of 1: 1.

[0027] The resin system further comprises an ionic or free radical polymerization catalyst. They are 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of reactants.
It must be present in a concentration of% by weight.

Among the ionic polymerization catalysts, those suitable for the present invention are especially tertiary, secondary and primary amines or amines containing several amino groups of different types (eg mixed tertiary / secondary amines). And quaternary ammonium compounds.
These amines may be either monoamines or polyamines. When primary and secondary amines are used,
Monoamines are preferred. Examples of such amine catalysts are as follows: diethylamine,
Tripropylamine, tributylamine, triethylamine, triamylamine, benzylamine, tetramethyldiaminodiphenylmethane, N, N-diisobutylaminoacetonitrile, N, N-dibutylaminoacetonitrile, heterocyclic bases such as quinoline, N-methylpyrrolidine, imidazole, Benzimidazole and homologs thereof, and also mercaptobenzothiazole. Examples of suitable quaternary ammonium compounds include benzyltrimethylammonium hydroxide and benzyltrimethylammonium methoxide. Tripropylamine is preferred.

[0029] Other suitable ionic polymerization catalysts are alkali metal compounds, such as alkali metal alcoholates and alkali metal hydroxides. Sodium methylate is particularly preferred.

Suitable free radical polymerization catalysts are the known organic peroxides and hydrogen peroxide and azoisobutyronitrile. Also in this case, the preferable concentration is 0.1 to 0.1.
5% by weight.

Another polymerization catalyst that can be used in the process of the present invention is acetyl-acetonate, especially the transition metal acetyl-acetonate. In particular, the corresponding vanadium compounds should be selected. These special polymerization catalysts are also used in the concentrations mentioned.

[0032] Phenothiazine itself has been found to be a particularly good inhibitor. The phenothiazine preferably used in the present invention has the following formula

Embedded image It is represented by

Further, phenothiazine having 1 to 3 substituents, and phenothiazine having 1 substituent selected from the following substituent groups: 1 to 6 carbon atoms
(E.g., 3-methyl-phenothiazine, 3
Aryl groups (e.g., 3-phenyl-phenothiazine, 3,7-diphenylphenothiazine); halogen atoms such as chlorine, bromine and iodine atoms (e.g., 3-phenyl-phenothiazine, 10-methyl-phenothiazine).
-Chlorophenothiazine, 2-chlorophenothiazine,
3-bromophenothiazine); a nitrogen function (eg, 3-
Nitrophenothiazine, 3-aminophenothiazine,
3,7-diaminophenothiazine); and sulfur functional groups (eg, 3-sulfonyl-phenothiazine, 3,7-disulfonyl-phenothiazine, 3,7-dithiocyanatophenothiazine) are also useful inhibitors of the present invention. In addition, N, N-dimers of phenothiazine and substituted N, N-dimers of phenothiazine are also useful inhibitors of the present invention. Preferred phenothiazines contain 0 to 1 substituent.

The phenothiazine is generally used in an amount ranging from about 0.5 to about 10 parts per 100 parts of resin, preferably in an amount ranging from about 1.5 to about 2 parts per 100 parts of resin.

The process for the production of the reaction product according to the invention is established for obtaining a preadvanced prepolymer. An important point is the amount of catalyst used in the precursor reaction. Also important is the step of adding a phenothiazine inhibitor to the prepolymer mixture to provide maximum effectiveness for future processing. Applicable catalyst concentrations are indicated above. In selecting the reaction conditions, the practitioner should consider that as long as the higher catalyst concentration maximizes the increase in solution stability, the lower concentration in the range improves other properties in preference to solution stability. , Catalyst concentration and other processing variables (process v
ariables) must be balanced. A balance of this variable will also allow the use of catalyst concentrations somewhat beyond the lower and upper limits. However, a catalyst concentration significantly below the minimum concentration does not result in a resin having improved solution or storage stability, while a catalyst concentration substantially above the above maximum results in a resin solution during production. It gels or yields a resin with high resin solution viscosity and poor mechanical and thermal properties.

Correspondingly, the degree of resin precursor is a function of reaction time and temperature after catalyst addition. This precursor parameter must be monitored by measuring the resin melt viscosity. Resin melt viscosity is 125 ° C. using an ICI Corn & Plate Viscometer using a 0-100 poise scale.
And is generally in the range of about 20 to 85 poise, preferably 50 to 70 poise for the precursor resin system. The gel time is used as an additional parameter and reflects the total gel formation time measured at a temperature of 170 ° C., and generally ranges from about 80 to 550 seconds for the precursor resin system of the present invention.

The addition of the phenothiazine inhibitor takes place after the prepolymer precursor reaction. This inhibitor has excellent solubility in the resin system and has a sufficiently high boiling point to remain in the prepolymer even during the vacuum concentration step. The addition of phenothiazine reduces the gel time of the prepolymer by 10 to 20.
% Expansion was found. Longer gel times are even more advantageous for future processing in the coating operation. In addition, phenothiazine can be used as a processing control parameter to obtain the desired reactivity of the prepolymer.

The advancement procedure therefore involves blending the polyimide with the alkenylphenol or alkenylphenol ether and heating the blend at a temperature of 25 to 125 ° C. until a clear melt is obtained. Including. Thereafter, the catalyst was added and the reaction
Continue for a suitable time at a temperature in the range of 0 to 130 ° C. Thereafter, the above amount of phenothiazine dissolved in the desired solvent system is added to the resin. A generally low viscosity solution of high solids (up to 75% by weight, preferably up to 60% by weight) is thus prepared, which may be impregnated glass or other fabrics.
cs) or can be used directly for fibers for laminate production. Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; glycol ethers and glycol ether acetates such as propylene glycol methyl ether, propylene glycol ethyl ether acetate; hydrocarbons such as toluene and anisole; methoxypropanol; dimethylformamide; and mixtures thereof. A variety of low boiling solvents (up to about 160 ° C., preferably up to 100 ° C.) may be used; of interest are ketones and ketone / ether blends (preferably 1: 1). Blends of ketones and certain high boiling solvents are also applicable.

The prepolymers as described above have application in a wide range of end uses, such as printed circuit boards, castings, composites, molding compounds, adhesives and coatings.
The resin solution or melt thus modified is used to impregnate various fibers or fabrics for end use in printed circuit boards or various laminating applications. Techniques for making laminates are well known. Such laminates are made by compression or autoclaving and may be of a wide variety of thicknesses. Prepreg manufacturing techniques are well known to those skilled in the art. Honeycomb skins and structural parts
By manufacturing, graphite, glass and Kevlar fiber reinforced skins and parts and others can be easily manufactured from the present system.

The prepreg manufacturing process is called "B-stage" because the polymer is pioneered to an intermediate stage before final crosslinking. Usually, the prepreg is then stored at below freezing temperature to maintain the properties of the prepreg. This is an expensive process if a large amount of material is stored in this manner over a long period of time. Therefore, room temperature storage is highly desirable. However, it is well known that the polyimide polymer in the prepreg continues to pioneer at room temperature conditions, thus rendering the prepreg useless after a few weeks. The use of phenothiazines in this polymer resin system solves this problem. Phenothiazine slows oxidation and precursor reactions in the prepreg, thus enhancing the storage performance of the material at room temperature conditions at very low cost.

During the "B-stage" for making coatings and prepregs, the resin solution is heated to pioneer the polymer to the desired stage and also remove solvent from the material. The phenothiazine must remain in the prepreg during the heating and solvent evaporation stages since it needs to be an effective inhibitor in subsequent processing stages. The phenothiazine additive was therefore selected for this operation because of its high boiling point, and the levels were efficiently utilized to maintain a minimal amount in the final prepreg. During this experiment, phenothiazine improved other unexpected processing characteristics.
Phenothiazine has a gelation reactivity of prepreg of 10 to 2
0%, volatile solvent in prepreg 20-30%
Decrease the post cure times by 10
%. All these improvements are highly desirable processing characteristics, which increase productivity and reduce costs.

In a preferred embodiment, the polyimide solution (60% solids) is diluted with a suitable solvent to achieve the desired solution viscosity range. Glass fabric with a suitable adhesion promoter is dipped into a resin solution to impregnate the fabric.
The fabric is then heated at 150-170 ° C. in an oven to remove volatile solvents and forego the resin to the desired flow and gelation reactivity stage. The prepreg is then compression molded at 177 ° C. for 3 hours and post-cured at 240 ° C. for 4 hours to produce a final composite laminate (final com.
posite laminate).

The prepregs prepared according to the present invention may further comprise, at any stage prior to curing, extenders, fillers and fiber reinforcements, pigments, dyes, organic solvents, plasticizers, tackifiers, rubbers, accelerators, dilutions. It can be mixed with usual additives such as agents. Fillers, reinforcing agents, fillers and pigments that can be used in the curable mixture of the present invention include, for example, coal tar, bitumen, glass fiber, boron fiber, carbon fiber, cellulose, polyethylene powder, polypropylene powder, mica, asbestos, Quartz powder, gypsum, antimony trioxide, bentones, silica aerogel ("aerosil"), lithopone, barite, titanium dioxide, carbon black, graphite, iron powder. Other conventional additives such as flameproofing agents, thixotropic agents, flow control agents such as silicon, cellulose acetate butyrate, polyvinyl butyrate, wax, stearate, etc. (some of which are also used as mold release agents) Can be added to the curable mixture.

The thermosetting compositions of the present invention produce prepregs that can be stored at room temperature without adversely affecting processing conditions, resulting in improved coating and processing conditions.

[0045]

The following examples illustrate preferred embodiments of the present invention. In these examples, all parts are by weight unless otherwise specified.

Example 1 This example illustrates the preparation of a representative thermosetting composition of the present invention. Formulation parts by weight ──── ビ ス Bismaleimidodiphenylmethane [Ciba-Geigy Corp./XU292A] 31.88 Diallyl bisphenol A [Ciba-Geigy Corp./XU292B] 27.30 Tripropylamine 0.38 Phenothiazine 0.99 Methyl ethyl ketone 19.73 Methoxypropanol [manufactured by Dow Chemical Company / Dowanol PM] 19.73

Bismaleimide diphenylmethane and diallyl bisphenol A are put together in a reaction flask, mixed, and heated to 120 to 135 ° C. Tripropylamine is added to the flask and stirring is continued for 2 hours. The samples are then removed from the flask and tested for their melt viscosity at 125 ° C and their gel time at 171 ° C. When the melt viscosity of the resin reaches 40 poise, methyl ethyl ketone, methoxypropanol and phenothiazine are added to the reaction flask with continued stirring for 2-4 hours, and the resulting final resin product is removed from the reaction flask. The final resin product is 60.0% solids, 171
It has a gel time of 340 seconds at ℃ and a viscosity of 300 cps at 25 ° C.

Example 2 This example illustrates the preparation of a representative prepreg according to the present invention and a laminate therefrom. The reaction product of Example 1 was purified by Clark-Schwebel (South Carolina, An., South Carolina).
derson)] glass fiber woven fabric. The weave style is 7628 with CS309 finish. The material is B-staged at 190 ° C. for 3 hours. The resulting prepreg has a resin content of 40%, a volatile content of 0.9%, a gelling reactivity of 190 seconds at 171 ° C. and a prepreg stability of more than 6 months at 25 ° C.

The prepreg was then hydraulically pressed with copper foil at 177 ° C. for 3 hours and
Post-cured at 40 ° C. The finished laminate has the following properties: Laminate properties Glass transition temperature 265 ° C Decomposition temperature 410 ° C CTE * (Z Axis) 39 ppm /
℃ Solder dip resistance> 10 min Peel strength 1.58 N /
mm (9.0 lbs / in) Dielectric Constant 4.4 Dissipation factor 0.01 * Thermal expansion coefficient

Comparative Example 1 : Using the operation described in Example 1,
The following formulation is manufactured: Formulation parts by weight ──── ───── Bismaleimidodiphenylmethane [Ciba-Geigy Corp./XU292A] 31.88 Diallyl bisphenol A [Ciba-Geigy Corp. ) / XU292B] 27.30 Tripropylamine 0.38 Methyl ethyl ketone 20.00 Methoxypropanol [Dow Chemical Company / Dowanol PM] 20.00 The final resin product has a gelling reactivity of 230 seconds. , It makes processing difficult.

Comparative Example 2: Using the procedure described in Example 2,
A prepreg and a laminate therefrom are produced from the final resin product of Comparative Example 1. The prepreg has the following properties: Prepreg properties Resin content 40% Volatile content 2.9% Gelling reactivity 80 seconds Prepreg stability 2 weeks Prepreg stability at room temperature is very limited and volatiles are high. The laminate made therefrom exhibits a glass transition temperature of 245 ° C.

Example 3 Using the procedure described in Example 1,
The following formulation is manufactured: Formulation parts by weight ──── ビ ス Bismaleimidodiphenylmethane [manufactured by Ciba-Geigy (CIBB-GEIGY Corpration) / XU292A] 32.00 Diallyl bisphenol A [Ciba-Geigy Corporation (CIBB-GEIGY Corpration) ) / XU292B] 27.53 Tripropylamine 0.38 Phenothiazine 0.40 Methyl ethyl ketone 19.84 Methoxypropanol [Dow Chemical Company / Dowanol PM] 19.84 The final resin product has a gelling reactivity of 250 seconds.

Example 4: Using the procedure described in Example 2,
A prepreg and a laminate therefrom are produced from the final resin product of Example 3. Prepreg has the following properties: Prepreg properties Resin content 40% Volatile content 2.0% Gelation reactivity 98 seconds Prepreg stability 1 month

────────────────────────────────────────────────── (5) References JP-A-55-92714 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 65/00-65/48 C08G 67 / 00

Claims (21)

(57) [Claims] (A) (a) The following formula: [In the formula, D represents a divalent group containing a C ＝ C bond. A reaction product of a polyimide containing at least two groups represented by the formula (b) and 0.05 to 2.0 moles of alkenyl phenol, alkenyl phenol ether or a mixture thereof per mole of component (a); A) a thermosetting composition comprising an ion polymerization catalyst and (C) phenothiazine or a derivative thereof; 2. Component (a) is represented by the following formula: [In the formula, R ₁ represents a hydrogen atom or a methyl group, and X represents a divalent organic group having 2 to 30 carbon atoms. ] The composition of Claim 1 represented by these. 3. X is -C _x H _2x- (x = 2-20),-
CH ₂ CH ₂ SCH ₂ CH ₂ —, phenylene group, naphthylene group, xylylene group, cyclopentylene group, 1,5,
5-trimethyl-1,3-cyclohexylene group, 1,4
-Cyclohexylene group, 1,4-bis (methylene) -cyclohexylene group, or the following formula: Wherein R ₂ and R ₃ are independently a chlorine atom, a bromine atom,
Represents a methyl group, an ethyl group or a hydrogen atom, and Z represents a direct bond or a methylene group, a 2,2-propylidene group, -CO
-, - O -, - S -, - SO- or -SO ₂ - represents a. The composition according to claim 2, which is a group represented by the formula: 4. The method according to claim 3, wherein R ₁ is a hydrogen atom and Z is a methylene group, a 2,2-propylidene group or —O—.
A composition as described. 5. The composition according to claim 4, wherein component (a) is 4,4′-bismaleimidodiphenylmethane. 6. The component (b) has the following formula: [Wherein, R is a direct bond, methylene, isopropylidene, -O -, - S -, - SO- or -SO ₂ - represents,
R ₄ , R ₅ , R ₆ and R ₇ independently represent a hydrogen atom or an alkenyl group having 2 to 10 carbon atoms, provided that R ₄
And at least one of R ₇ represents an alkenyl group. ], Embedded image Wherein R ₄ , R ₅ and R ₆ independently represent a hydrogen atom or an alkenyl group having 2 to 10 carbon atoms, provided that R
_At least one of ₄ to R ₆ represents an alkenyl group. Or [Wherein R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Provided that at least one of R ₈ to R ₁₃ represents an alkenyl group. Or an ether thereof containing at least one --OR ₃ group (R ₃ represents an alkyl group, an aryl group or an alkenyl group having 1 to 10 carbon atoms). A composition as described. 7. The composition according to claim 6, wherein the alkenyl group is an allyl group or a propenyl group. 8. The method according to claim 8, wherein the alkenylphenol is o, o'-
The composition according to claim 6, which is diallyl-bisphenol A. 9. The composition according to claim 1, wherein the ionic polymerization catalyst is present in a concentration ranging from 0.1 to 10% by weight, based on the total weight of the reactants. 10. The catalyst according to claim 9, wherein said catalyst is present in a concentration ranging from 0.1 to 5% by weight, based on the total weight of the reactants.
A composition as described. 11. The composition according to claim 1, wherein the composition is dissolved in a non-aqueous solvent. 12. The solvent according to claim 1, wherein the solvent is ketone, glycol ether, glycol ether acetate, hydrocarbon, dimethylformamide or a mixture thereof.
A composition according to claim 11 having a maximum boiling point of 60 ° C. 13. A phenothiazine derivative comprising an alkyl group having 1 to 6 carbon atoms, an aryl group, an olefin group,
C-substituted phenothiazine having 1 to 3 substituents selected from the group consisting of halogen atom, oxygen function group, nitrogen function group and sulfur function group; alkyl group having 1 to 6 carbon atoms, aryl group, olefin group , Halogen atom,
N-substituted phenothiazines having one to three substituents selected from the group consisting of oxygen, nitrogen and sulfur functionalities; N, N'-dimers of phenothiazine; and N, N substituted phenothiazines The composition of claim 1, wherein the composition is selected from '-dimers. 14. The composition according to claim 1, wherein said component (C) is phenothiazine. 15. A product obtained by removing the solvent of the composition of claim 11 and curing the substantially solvent-free reaction product obtained. 16. A laminate comprising a cured product of a woven or wound yarn impregnated with the composition of claim 11. 17. A prepreg structure comprising a cured product of a woven fabric or a wound yarn impregnated with the composition according to claim 11. 18. At an elevated temperature, (A) the following formula: [In the formula, D represents a divalent group containing a C ＝ C bond. And (B) 0.05 to 2.0 moles of alkenyl phenol, alkenyl phenol ether or a mixture thereof per mole of component (A). In the presence, ICI cone and plate viscometer (ICI Cor
n & Plate Viscometer) 2
The reaction is allowed to proceed for a time sufficient to produce the above reaction product having a resin melt viscosity of 0 to 85 poise, phenothiazine or a derivative thereof in a sufficient solvent to give a solid content of 40 to 60% is added, and then the resin solution A glass fiber with a suitable adhesion promoter, and then heating the woven fabric to 150-170 ° C. to remove the solvent to form a prepreg. 19. The polyimide (A) is 4,4′-bismaleimidodiphenylmethane, and (B) is o, o′-
19. The method of claim 18 wherein the catalyst is diallyl bisphenol A and the catalyst is tripropylamine. 20. The solvent is a ketone, a glycol ether,
Glycol ether acetate, hydrocarbon, dimethylformamide or a mixture thereof, wherein the solvent is
19. The method of claim 18 having a maximum boiling point of ° C. 21. The method according to claim 20, wherein the solvent is a mixture of methyl ethyl ketone and methoxypropanol.