JPH0670125B2 - Thermosetting resin composition - Google Patents

Description

The present invention relates to a thermosetting resin composition of heat-resistant category C (180 ° C. or higher) and its cured product, particularly impregnation, casting, lamination as a solventless varnish. The present invention relates to a thermosetting resin composition which gives a cured product having excellent heat resistance and thermal shock resistance suitable for applications such as molding and adhesion.

[Background of the Invention]

In recent years, the trend toward smaller and lighter electrical equipment and stricter usage conditions has become even stronger, and along with this, there is a growing demand for improved heat resistance of insulating materials.

The varnish for coil impregnation or casting has low viscosity and good workability (it must be 10 poise or less when impregnated),
It is desired that there be no voids (voids) after curing and that it has tough mechanical strength at high temperatures. Conventionally, heat-resistant insulating materials have been studied mainly in the field of solvent-type varnishes for enameled wires and laminated materials, and excellent materials such as polyamideimide, silicone, and polydiphenyl ether have been developed. Since these materials are generally solid, a solvent is required when these materials are used as a varnish. When a solvent-type varnish is cured, the solvent volatilizes and a large amount of voids tend to remain, so heat dissipation is poor, withstand voltage characteristics, adhesive strength is low, moisture resistance is poor, and heat deterioration is large compared to a solventless varnish. There is a drawback of. Therefore, it is very important that the insulating varnish for electric equipment is a solvent-free type that does not contain a solvent, and that it is an addition polymerization type (non-condensation type) that does not generate volatile components as the curing reaction proceeds. Come on.

Currently, epoxy resin is widely used as a solventless varnish with relatively excellent heat resistance because of its low viscosity and good workability, but the maximum operating temperature of epoxy resin is 180 ° C regardless of which combination is used. Is the limit. Solvent-free silicone varnishes have attracted attention because of their good thermal stability, but their use is limited because they have poor mechanical strength at high temperatures and poor solvent resistance.

On the other hand, the heat resistance of the bismaleimide polymer obtained by the reaction between an amine and maleic anhydride is not only excellent due to the donation of imide groups, but also because the polymerization reaction is an addition reaction, volatile components are generated. Since it does not, it is drawing attention (Japanese Patent Publication No. 44-206250). However, bismaleimide
It has a high melting point, and because it undergoes a three-dimensional cross-linking reaction by radical polymerization to form a high-density reticulated bond, thermal shrinkage during curing is also large, and the cured resin is brittle. There is a problem that it is easy to do, so it is not practical. Therefore, it has been proposed to combine bismaleimide with triallyl isocyanurate, diallyl isophthalate, isocyanuric acid, etc. (Japanese Patent Publication No. 53-2190).
No. 54-10595). However, even by these methods, the improvement of the thermal shock resistance of the cured product is still insufficient, and the melting point or the glass transition temperature of the resin composition is very high, so that it cannot be used as a solventless varnish.

In order to enable casting without a solvent, a method of adding a polyvalent carboxylic acid allyl ester or an epoxy resin to make the viscosity low is also proposed (Japanese Patent Publication No. 53-2191, 52-19598, 52-1951).
No. 9, 52-30167, 58-40974, 48-19238, 49-12600, 48
-8674, 53-53120, 49-20080). However, this method is generally difficult to use as a solventless varnish because it tends to precipitate at around room temperature, and the cured product has insufficient thermal shock resistance and heat resistance. Therefore, addition polymerization of bismaleimide with diamine has been proposed (Japanese Patent Publication No. 46-23250). Although this polymer is excellent in physical and chemical heat resistance and electrical properties, its resin composition has a very high melting point or glass transition point, and therefore must be heated to have a low viscosity. . If so, the pot life is shortened and it cannot be used as a solventless varnish.

On the other hand, recently, sialylbisphenol A has attracted attention as a reactive diluent for bismaleimide (Japanese Patent Publication No. 55-392).
42 publication). The polymer of diallyl bisphenol A and bismaleimide is excellent in physical and chemical heat resistance and electric characteristics. However, the resin composition is a solid and has a high melting point or glass transition point, or an extremely high-viscosity liquid (life cannot be impregnated with 10 poise or less), and it is difficult to use as a solventless varnish. It was Therefore,
Combination with epoxy resin (JP-B-57-28416,58-17532)
Was also proposed. However, compatibility of low viscosity, heat resistance and thermal shock resistance was insufficient.

[Object of the Invention]

An object of the present invention is to provide a solvent-free thermosetting resin composition and a cured product which are excellent in heat resistance and thermal shock resistance and are suitable for applications such as impregnation, casting, lamination, molding and adhesion as an electric insulating material. To provide.

[Outline of Invention]

Recently, in the field of thermosetting resins, IPN (Interpeneta
Composite materials with ting polymer networks (interpenetrating network) structure are attracting attention. This is a thermosetting resin Mole
Unlike conventional polymer blends and graft polymers, it is a polymer blend that uses cular topology, and is characterized in that the networks of two thermosetting resins are entangled with each other.

By adopting the IPN structure, the compatibility of polymers with each other increases due to the entanglement of two types of cross-linked chains, which leads to an increase in cross-link density, a finer phase structure, and an increase in interphase adhesiveness. It exhibits excellent mechanical properties, chemical resistance, and heat resistance that cannot be obtained. In particular, much research has been done to obtain a wide range of composite materials from high impact plastics to reinforced elastomers by combining glassy polymers and rubbery polymers.

In view of the above matters, the present inventors have earnestly studied to obtain an IPN structure by combining a high-crosslink density glassy polymer from bismaleimide and a rubbery polymer. As a result, (a) the general formula I (In the formula, D contains a polymerizable carbon-carbon double bond.
At least 2 groups in one molecule
Polyimide having at least one, (b) at least one alkenyl compound of alkenylphenol and alkenylphenyl ether,
And (c) general formula II (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are H, an alkyl group or a substituted alkyl group having 1 or 2 carbon atoms, m, n, p are each 0 or a positive integer. And m + n + p is 3 to 26, X is -CONH
-, - COO -, - OCOO -, - NH -, - NHCONH -, - OCH 2 O
-, -S-, -N = CHNH-, -N = CHO-) is a ring-opening polymerizable monomer represented by the formula) and may further contain (d) a polymerization catalyst. A characteristic thermosetting resin composition could be found.

This composition has extremely good compatibility between components, low viscosity, long-life life, excellent curability, and excellent heat resistance and thermal shock resistance due to heating. It gives a cured resin that exerts its properties.

The polyimide used in the present invention has the following formula I: (In the formula, D represents a divalent group containing a polymerizable carbon-carbon double bond) and at least 2 groups are present in one molecule.
It is a polyimide containing individual pieces. For example, N.N'-ethylene dimaleimide, N.N'-hexamethylene bismaleimide, N.N'-dodecamethylene bismaleimide, N.
N'-m-xylylene bismaleimide, N.N'-p-
Xylylene bismaleimide, N.N'-1,3-bismethylenecyclohexane bismaleimide, N.N'-1.4
-Bismethylene cyclohexane bismaleimide, N
N'-2,4-tolylene bismaleimide, N'N'-2
* 6-tolylene bismaleimide, N * N'-3 * 3'-
Diphenylmethane bismaleimide, N ・ N'-4,4 '
-Diphenylmethane bismaleimide, 3.3'-diphenylsulfone bismaleimide, 4.4'-diphenylsulfone bismaleimide, N.N'-4.4'-diphenylsulfide bismaleimide, N.N '-P-benzophenone bismaleimide, N.N'-diphenylethane bismaleimide, N.N'-diphenyl ether bismaleimide, N.N'-(methylene-ditetrahydrophenyl) bismaleimide, N. N '-(3-ethyl) 4.
4'-diphenylmethane bismaleimide, N.N'-
(3,3'-Dimethyl) 4,4'-diphenylmethane bismaleimide, N, N '-(3,3'-diethyl) diphenylmethane bismaleimide, N, N'-(3,3'-
Dichloro) -4,4'-diphenylmethane bismaleimide, N.N'-tolidine bismaleimide, N.N'-isophorone bismaleimide, N.N'-p.p-diphenyldimethylsilyl bismaleimide, N. N'-benzophenone bismaleimide, N.N'-diphenylpropane bismaleimide, N.N'-naphthalene bismaleimide, N.N'-p-phenylene bismaleimide, N.
N'-m-phenylene bismaleimide, N.N'-4.
4 '-(1.1-diphenyl-cyclohexane) -bismaleimide, N.N'-3.5- (1.2.4-triazole) bismaleimide, N.N'-pyridine-2.6
-Diyl bismaleimide, N * N'-5-methoxy-1
-3-phenylene bismaleimide, 1.2-bis (2-
Maleimidoethoxy) -ethane, 1.3-bis (3-maleimidopropoxylpropane, N · N′-4 · 4′-
Diphenylmethane-bis-dimethylmaleimide, N.
N'-hexamethylene-bis-dimethylmaleimide, N
Of N'-4,4 '-(diphenyl ether) -bis-dimethylmaleimide, N, N'-4,4'-diphenylsulfone-bisdimethylmaleimide, 4,4'-diamino-triphenylphosphate In addition to bifunctional maleimide compounds represented by N.N'-bismaleimide, N.N 'bismaleimide of 4,4'-diamino-triphenylthiophosphate, and the like, reaction products of aniline and formalin (polyamine Compound) A polyfunctional maleimide compound obtained by the reaction of 3,4,4'-triaminodiphenylmethane, trianophenol, etc. with maleic anhydride, tris- (4, aminophenyl) phosphate and tris (4, aminophenyl) Particularly, a trifunctional maleimide compound obtained by the reaction of thiophosphate and maleic anhydride is a group of the present invention. It is a typical example of a polyimide suitable object. Further, N.N'-m-phenylene-bis-citraconimide, N.N'-4.4'-diphenylmethane-bis-citraconimide, N.N'-4.4'-diphenylmethane-bis-itaconimide, N. A polyimide such as N'-p-phenylene-bis-itaconimide can also be used. Furthermore, the following formula III: (Wherein A ′ and A ″ represent an optionally substituted aromatic group or an oxygen atom, an aromatic group interrupted by an alkylene group or a sulfonyl group,
D has the meaning of D in formula (I) above, Z represents an oxygen atom or a sulfur atom, m represents 1 or 0,
And n'represents 2 or 3. It is also possible to use bisimide and trisimide represented by the formula (1).
Examples of such polyimide include the following. N · N′-bismaleimide of 4,4′-diamino-triphenyl phosphate, 4,4′-diamino-
N.N'-bismaleimide of triphenylthiophosphate, N.N'.N "of tris- (4-aminophenyl) phosphate, N.N'.N" of tris- (4-aminophenyl) thiophosphate -Such as trismaleimide.

It is also possible to use as the polyimide a mixture of two or more of the abovementioned polyimides. Also, a mixture of a monoimide containing a group represented by the above formula I and a polyimide can be used.

In the present invention, examples of the ring-opening polymerizable monomer represented by the general formula II include the following compounds.

For example, β-propiolactone, β-butyrolactone,
α, α-bis (chloromethyl) propiolactone, δ-
Valerolactone, 3,4,5-trimethoxy-δ-valerolactone, 1,4-dioxan-2-one, glycolide,
Lactide, 1,4-dithian-2,5-dione, trimethylene carbonate, neopentylene, carbonate, ethylene oxalate, propylene oxalate, ε-caprolactone, 4-methyl-7-isopropyl-ε-caprolactone, 4-hydroxycyclohexane Lactones from carboxylic acids, cis disalicylide, di-o-cresotide, trisalicylide, α, γ-trimethylene-γ
-Butyrolactone, α, γ-dimethyl-α, γ-trimethylene-γ-butyrolactone, α-anilino-γ-phenyl-γ-butyrolactone, β, δ-dimethyl-δ-valerolactone, α, δ-ethylene-δ- Valerolactone, cyclic ester such as α, δ-ethylene-α, δ-dimethyl-δ-valerolactone, 2-azetidinone, 2-pyrrolidinone, 2,5-piperazinedione, 2-oxohexamethyleneimine, 3-methyl- 2-oxohexamethyleneimine, 4-methyl-2-oxohexamethyleneimine, 5-methyl-2-oxohexamethyleneimine,
6-methyl-2-oxohexamethyleneimine, 7-methyl-2-oxohexamethyleneimine, 5-ethyl-
2-oxohexamethyleneimine, endo-methylene-
2-oxohexamethyleneimine, endo-ethylene-
2-oxohexamethyleneimine, 2-hexamethyleneimithione, 2-oxoheptamethyleneimine, 2-heptamethyleneimithione, 1,5-diazacyclooctane-2,6-dione, 2-oxooctamethyleneimine, Two
-Cyclic amides such as oxomethyleneiminothione, cyclic ureas such as 2-imidazolidinone and N, N'-tetramethylurea, cyclic urethanes such as tetrahydro-2H-1,3-oxazin-2-one, 5,6 -Dihydro-4H-1,3-oxazine, 2-oxazoline and derivatives thereof, cyclic imino ethers, norbornene, norbornadiene, dicyclopentadiene, bicyclo [2.2.2] oct-1-ene,
Cyclobutene, cyclopentene, cis-cyclooctene, etc. and their derivatives such as cycloolefin, trioxane, tetraoxane, 1,3-dioxolane, 1,3-dioxepane, etc. and their cyclic derivatives, ethyleneimine / azabicyclo [3.1.0] ] Cyclic imines such as hexane and conidine, and their derivatives, cyclic sulfides such as ethylene sulphide, propylene sulphide, butylene nalphide, oxetane, cyclic ethers such as 3,3-bis (chloromethyl) oxetane, 1,4,6 -Trioxaspiro [4,4] nonane, 1,4,6,10,12,15,16,19-
Examples thereof include spiro orthoesters such as octaoxatrispyro [4,2,2,4,2,2] nonadecane and spiro orthocarbonates.

These ring-opening polymerizable monomers can also be used as a multiple mixture.

The alkenylphenol in the present invention is obtained by subjecting its isomer alkenylphenyl ether to heat treatment at a high temperature of usually 180 to 250 ° C. to cause Claisen transition. Alkeniphenyl ether is synthesized according to a known method in which a phenol compound and an alkenyl halide are reacted in the presence of an alkali metal hydroxide and a solvent. Examples of the phenol-based compound used in the synthesis of the above alkenylphenol or alkenylphenol ether include monohydric phenols represented by phenol, cresol, xylenol, p-tert-butylphenol, and 4,4'dihydroxydiphenyl. Propane (bisphenol A), 4,4'-dihydroxydiphenylethane (bisphenol F), 4,4-dihydroxydiphenylsulfone (bisphenol S),
3,3'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenyl ether, 4,4'dihydroxy-2,
Examples include polyvalent phenols such as 2'-dimethyldiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, hydroquinone, resorcinol, catechol, phenol resin and cresol resin.

Another method for producing an alkenylphenol is a method in which an o-allylphenol is reacted with an aldehyde or ketone to produce it. In addition, eugenol,
Natural products such as isoeugenol and eugenol methyl ether, or derivatives thereof can also be used.

These alkenylphenols and alkenylphenyl ethers may be used alone or in a mixture of two or more.

The blending amounts of the polyimide and the ring-opening polymerizable monomer differ depending on the types, the intended varnish properties, the properties of the cured product, etc., and cannot be uniquely determined. That is, the blending ratio can be changed according to the purpose of use, and there is no limitation. However, increasing the proportion of polyimide increases the viscosity of the varnish, and tends to increase the heat resistance of the cured product. Conversely, increasing the ring-opening polymerizable monomer decreases the viscosity of the varnish, resulting in a cured product. Becomes more flexible. In particular, a composition prepared by mixing 10 to 200 parts by weight of a ring-opening polymerizable monomer with 100 parts by weight of a polyimide has a relatively high bonding density based on a polyimide bond portion and a ring-opening polymerizable monomer unit. Since the flexible portion and the flexible portion coexist on a proper balance, a cured product excellent in mechanical and heat resistance is produced, which is preferable.

When alkenylphenol or alkenylphenyl ether is added to the composition, the alkenyl compound can be selected in the range of 0.1 to 10 equivalents, preferably 0.2 to 1.0 equivalents per equivalent of polyimide. By the latter formulation, it is possible to obtain curing that improves the brittleness of the cured product, but when the formulation amount exceeds 1.0 equivalent, the phenolic hydroxyl group remains, which inhibits the polymerization of the alkenyl group and heat resistance of the cured product. There is a tendency to decrease the sex.

The resin composition of the present invention can be sufficiently cured without a catalyst depending on the kind of the polyimide and the ring-opening polymerizable monomer and the curing conditions, but a polymerization catalyst may be added to further accelerate the reaction. The amount of the catalyst used is not particularly limited, but is 0.001 to 10% by weight, particularly 0.1 to 5% by weight based on the total weight of the composition.
A weight% range is preferred. The polymerization catalysts may be used in an appropriate combination.

Polymerization catalysts include polyimide polymerization catalysts and ring-opening polymerizable monomer catalysts. Benzoyl peroxide, t-butyl hydroperoxide, di-
t-butyl peroxide, dicumyl peroxide,
Known free radical catalysts such as azobisisobutyronitrile and azobiscyclohexanecarbonitrile are effective. Further, as the catalyst for the ring-opening polymerizable monomer, (a)
Bronsted acid such as hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, perchloric acid, acetic acid, chlorosulfonic acid, benzenesulfonic acid, and toluenesulfonic acid, (b) boron trifluoride, anhydrous aluminum chloride, anhydrous stannic chloride, Anhydrous stannic fluoride,
Lewis acids such as anhydrous ferric chloride, cupric chloride, titanium tetrachloride, antimony pentafluoride, and phosphorus pentafluoride, trialkyloxonium salts formed from a metal halide and an alkylene oxide in (c) ether, Dialkoxycarbonic acid made from ortho acid ester and metal halide,
(D) Carbonyl salts or diazonium salts such as (Ph) ₃ C ⁺ , trophlium ⁺ , p-ClC ₆ H ₄ N ₂ ⁺ , (e) benzyl halides, allyl halides or tertiary butyl halides, and amine nitrogen Quaternary ammonium salts obtained by reaction, (f) phenylnaphthylamine, pyridine, dimethylaniline, triethylamine, trimethylamine oxide, imidazole, tertiary amines such as morpholine,
(G) Boron trifluoride monoethylamine complex salt, boron trifluoride piperidine complex salt and other boron trifluoride amine complexes,
(H) organophosphorus compounds such as triphenylphosphine, triphenylphosphine sulfide, dihexylphosphine oxide, trioctylphosphine oxide,
(I) Alkali metals such as sodium metal, potassium metal, and lithium, alkali metal hydroxides such as (nu) sodium hydroxide and potassium hydroxide, (le) sodium methylate, sodium naphthalate, potassium methylate, etc. Examples include organic substances of alkali metals and organometallic compounds such as (wo) Ziegler catalyst.

It is effective to modify the resin composition according to the present invention depending on the intended use of the insulating material. For example, modification with epoxy resins and various curing agents, modification with vinyl monomers such as styrene and methyl methacrylate, modification with synthetic rubber such as polybutadiene and polychloroprene, unsaturated polyester modification, diallyl phthalate and triallyl phthalate prepolymer modification, Modification with amines such as aliphatic amines, aromatic amines and allylamines, modification with furan compounds and phenolic resins, or inorganic fillers, glass fibers, organic fibers, flame retardants, pigments, coupling agents, mold release agents, etc. can do.

Since the thermosetting resin composition is a solventless type as described above, it has various uses, and is easily cured by heating at 100 to 300 ° C. for 1 to 50 hours, and has heat resistance, impact resistance, and electrical resistance. It has excellent properties, chemical resistance, and self-extinguishing property, so it has a wide range of applications such as heat-resistant insulating varnish, casting resin, impregnating resin, laminated board resin, printed wiring resin, and interior material resin. There is. or,
Depending on the application, a solvent may be added to the resin composition, or it may be used as a prepolymer. Furthermore, in order to obtain the cured product of the present invention for applications such as molding materials and powder coatings, instead of the ring-opening polymerizable monomer, a polymer of polyimide and ring-opening polymerizable monomer glue (for example, polycaprolactone) is used from the beginning. ,
Polycaprolactam, etc.) can be mixed and heat-cured.

Example of Invention

 Hereinafter, the present invention will be specifically described with reference to examples.

Reference Example 1 Production of o, o′-diallyl bisphenol F Bisphenol F (200 g), NaOH (82.5 g) and n-propanol (1) are heated under reflux. After all the ingredients are dissolved, add 200 ml of allyl chloride gently.
After 3 hours, the mixture is essentially neutral. 3 more
Stir under reflux for a period of time with boiling. After cooling to room temperature, the precipitated NaCl is removed and then n-propanol is distilled off. The crude diallyl ether of bisphenol F (280 g) thus obtained is dissolved in methylene chloride and washed with water. After separating the aqueous phase, the methylene chloride is distilled off again. Next, diethylene glycol monoethyl ether was added to bisphenol F diallyl ether to adjust the concentration to 50%, Claisen transition was performed at 200 to 250 ° C., and diethylene glycol monoethyl ether was distilled off under reduced pressure. ′ -Diallyl bisphenol F is obtained. This product has a viscosity of 12 poise and a refractive index of 1.
At 59, the chlorine content is below 50 ppm. This was abbreviated as DABF and used in the following examples.

Reference Example 2 Production of o, o'-diallyl bisphenol A O, o'-diallyl bisphenol A was obtained in the same manner as in Example 1 except that bisphenol A (228 g) was used instead of bisphenol F. . This was further distilled under reduced pressure, and bp19
A fraction of 0 ° C / 0.5 mmHg was obtained. This is hereafter abbreviated as DABA,
Used in the examples below.

Example 1-10, Comparative Example 1 N, N ′-(methylenedi-p-phenylene) dimaleimide (BMI) as polyimide, o, o′-diallylbisphenol F described in Reference Example 1 as allylphenol
(DABA), a cyclic ester as a ring-opening polymerizable monomer: ε-
Caprolactone (ε-CLN) and / or cyclic amide: ε
-The 3 to 4 components of caprolactam (ε-CLM) were mixed in the proportions shown in Table 1 and then heated and mixed at 120 ° C for 50 minutes to obtain a liquid composition comprising a prepolymer. The viscosity of this composition was measured using a B-type viscometer, and the gelation time at 150 ° C. was measured using a GE gel timer. The results are shown in Table 1.

Next, this liquid composition was poured into a molding die, degassed under vacuum, and then heated at 150 ° C for 15 hours, 200 ° C for 5 hours, and 250 ° C for 15 hours to be cured. At that time, the loss on curing, the glass transition temperature (Tg) of the obtained cured product, and the bending property were measured. The characteristic values were as shown in Table 1.

Also, in order to evaluate the thermal shock resistance (crack resistance),
30 pieces of polyimide-coated electric wires IMW (1 type, 2φ, length 100 mm) were bundled and stored in an 18φ test tube, and then the composition was injected and cured to obtain a mold sample. Next, a cooling / heating cycle test was carried out by repeating the operation of leaving the mold sample at the upper temperature for 1 hour and then immediately leaving it at the lower temperature for 1 hour. However, the upper temperature of this test is 180 ℃, and the lower temperature is 0 ℃.
℃, -10 ℃, -20 ℃, -30 ℃, -40 ℃, -50 ℃, -60 ℃
Then, the temperature was lowered by −10 ° C. for each cycle. At this time, the crack resistance was evaluated based on the temperature at which cracks occurred in the test piece. The results of these measurements are also shown in Table 1.

Next, FIG. 1 shows the relationship between the blending amount of ε-caprolactone (ε-CLN) and the bending strength and strain, and the relation between the blending amount of ε-caprolactam (ε-CLM) and the bending strength and strain. It is shown in FIG.

Further, the viscoelasticity of the cured products of Comparative Example 1 and Examples 2, 3 and 4 (E ′ is a storage elastic modulus, E ″ is a loss elastic modulus) obtained by using a Ropex Analyzer RPX-706 type manufactured by Iwamoto Seisakusho. The temperature dispersion curve is shown in FIG.

From FIGS. 1 and 2, it can be seen that the flexural strength of the cured product of both the polyimide and the ring-opening polymerizable monomer alone is large and the strain is large as compared with the polyimide alone or the ring-opening polymerizable monomer alone cured product. This is probably because the cured product has an IPN structure. This can be inferred from the fact that the E'decreases in FIG. 3 although the position and spread of the α dispersion hardly change even if the amount of the ring-opening polymerizable monomer added increases.

Examples 11 to 17 and Comparative Example 2 Bismaleimides BMI and PMI were used as polyimides, the above DABA was used as allylphenol, and the mixture was mixed with various ring-opening polymerizable monomers in the proportions shown in Table 2 and then 120 ° C.
The mixture was heated and mixed for 30 minutes to obtain a liquid composition composed of a prepolymer. These compositions were cured in the same manner as in Example 1 and the properties of the cured products were measured and tested. The results were all good, as shown in Table 2.

Examples 18 to 24 BMI as polyimide, DABF as allylphenol,
The three components of ε-caprolactone as a ring-opening polymerizable monomer
A liquid composition consisting of a prepolymer with a weight ratio of 100: 30: 50 was obtained in the same manner as in the above example. Various polymerization catalysts shown in Table 3 were added to this composition and cured in exactly the same manner as in the above examples, and the cured product characteristics were measured and tested. Good results were obtained as shown in Table 3.

[Effect of the Invention] According to the present invention, a thermosetting resin composition having excellent moldability capable of being solvent-free even though it is a polyimide-based resin can be obtained, and the curing thereof makes it resistant to heat. A resin having excellent properties, mechanical properties and thermal shock resistance can be obtained.

[Brief description of drawings]

Figures 1 and 2 show the relationship between the compounding amount of ring-opening polymerizable monomer and the bending strength and bending strain of the cured product, and Figure 3 shows the storage elasticity of cured products with different compounding ratios of ring-opening polymerizable monomer. Shows the temperature dispersion of modulus and loss elastic modulus. E '... storage modulus, E "... loss modulus, 1 ... ε-
Caprolactone blending ratio (same below) 0.00, 2 …… 0.33,
3 …… 0.41, 4 …… 0.50.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08G 73/00 NTB 9285-4J 75/06 NTW 7308-4J C08L 101/00 LTA 7242-4J

Claims (5)

[Claims] 1. (a) General formula I (In the formula, D contains a polymerizable carbon-carbon double bond.
At least 2 groups in one molecule
Polyimide having at least one, (b) at least one alkenyl compound of alkenylphenol and alkenylphenyl ether,
And (c) general formula II (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are H, an alkyl group or a substituted alkyl group having 1 or 2 carbon atoms, m, n, and p are 0 or positive, respectively. An integer, m + n + p is 3 to 26, and X is -CONH
-, - COO -, - OCOO -, - NH -, - NHCONH -, - OCH 2 O
-, -S-, -N = CHNH-, -N = CHO-) is a thermosetting resin composition containing a ring-opening polymerizable monomer. 2. The thermosetting resin composition according to claim 1, which contains the (a) polyimide and the (b) alkenyl compound in the form of a prepolymer. 3. The thermosetting resin composition according to claim 1, which contains the polyimide (a), the alkenyl compound (b) and the ring-opening polymerizable monomer (c) in the form of a prepolymer. 4. The thermosetting resin composition according to claim 1, 2 or 3, wherein the polyimide (a) is bismaleimide. 5. (a) General formula I (In the formula, D contains a polymerizable carbon-carbon double bond.
At least 2 groups in one molecule
Having at least one polyimide, (b) at least one alkenyl compound selected from alkenylphenol and alkenylphenyl ether, (c) general formula II (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are H, an alkyl group or a substituted alkyl group having 1 or 2 carbon atoms, m, n, and p are 0 or positive, respectively. An integer, m + n + p is 3 to 26, and X is -CONH
-, - COO -, - OCOO -, - NH -, - NHCONH -, - OCH 2 O
-, -S-, -N = CHNH-, -N = CHO- atomic group selected from), a ring-opening polymerizable monomer represented by (d) a polymerization catalyst, and Curable resin composition.