JPH0770243A - Production of cured material of heat-resistant resin - Google Patents

Abstract

PURPOSE:To obtain the subject cured material useful as an electrical insulating material, structural material, etc., having excellent heat resistance and machanical properties without forming water as a by-product by curing a specific resin composition by heating at a specific temperature. CONSTITUTION:This cured material is obtained by curing a resin composition comprising (A) a polymaleimide compound containing >=2 maleimide groups in a molecule of the formula (Z is a bifunctional or a polyfunctional residue; (n) is >=2). (B) a methallyl phenyl ether-based compound or a methallylphenol- based compound each containing >=two methallyl groups in the molecule and (C) an amino compound containing >=two amino groups in the molecule by heating continuously or by stages to 60-120 deg.C and to 120-180 deg.C for >=one hour, respectively, and further heating to 200-300 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a heat-resistant resin cured product (hereinafter referred to as a resin cured product). The production method of the present invention is effective when curing a resin composition, which is a raw material of a resin cured product, in a desired shape in various fields of use such as impregnation, casting, sealing or adhesion,
The resin cured product obtained by the method of the present invention has high heat resistance and excellent mechanical properties represented by bending strength, and is useful as a molding material such as an electric insulating material or a structural material or a laminated material.

[0002]

2. Description of the Related Art In recent years, miniaturization and weight reduction of electric equipment and further severer usage conditions have been required, and heat resistance of cured resin used as an insulating material or a substrate material of electric equipment is required. Is increasing. A typical cured resin is a cured polyimide, but ordinary polyimide is insoluble and infusible in various solvents, and it is difficult to use it as a material for molding or film formation as it is. Therefore, generally, acid dianhydride and diamine are solution-polymerized in a polar solvent to obtain a polyamic acid that is a precursor of a polyimide, and then the polyamic acid solution is cast or various fillers and fibers. After impregnating and removing the solvent, a molding material and a film are prepared by dehydration cyclization. However, this manufacturing method has a problem that water is by-produced during molding. In addition, as a polyimide obtained by an addition reaction, for example, there is an addition product of bis (4-maleimidophenyl) methane and bis (4-aminophenyl) methane, which is known as a cured resin product without water by-product. However, since the obtained polyimide is a straight chain having no cross-linking point, it has a relatively low glass transition point and cannot be used for applications requiring high heat resistance.

On the other hand, a polyimide obtained by a thermosetting reaction is known as a resin cured product, and as a typical example thereof, bis (4-maleimidophenyl) methane and 0,0 '.
There is a cured product with diallyl bisphenol A. However, this two-component thermosetting polyimide has insufficient mechanical properties such as bending strength and Shore hardness, and further improvement is desired as a practical material.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a method for producing a cured product of a polymaleimide resin, which is easy to mold, does not produce water as a by-product during curing, and has excellent heat resistance and mechanical properties. To do.

[0005]

The present invention provides (a) a polymaleimide compound, (b) a methallyl phenyl ether compound and / or a methallyl phenolic compound having at least two methallyl groups in one molecule, And (c) a resin composition containing an amino compound having at least two amino groups in one molecule, 60 to 120 ° C. and 120 to 1
In each temperature range of 80 ℃, heating for 1 hour or more while continuously or stepwise raising the temperature, and then heating in the first half, and then heating in the second half in the temperature range of 200 to 300 ℃ to cure. It is characterized by

The above-mentioned "polymaleimide compound" [hereinafter referred to as the component (a)] is a compound having two or more maleimide groups in the molecule represented by the following general formula (1).

[0007]

[Chemical 1]

(In the formula, Z is a divalent or higher valent residue, and n is an integer of 2 or more.) Z in the general formula (1) is an aliphatic, aromatic, alicyclic or heterocyclic ring. It may be any of the formula residues. Specific polymaleimide compounds include bis (4-maleimidophenyl) methane, bis (3-maleimidophenyl) methane, bis (4-maleimidocyclohexyl) methane, bis (3-methyl-4-maleimidophenyl) methane, and bis (3-methyl-4-maleimidophenyl) methane. (3,5-Dimethyl-4-maleimidophenyl) methane, bis (3-butyl-4-maleimidophenyl) methane, bis (3,5-dibutyl-4-maleimidophenyl) methane, bis (3-ethyl-4-) Maleimide-5-
Methylphenyl) methane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-maleimidophenyloxy) phenyl] propane, 1,1,1,3
3,3-hexafluoro-2,2-bis (4-maleimidophenyl) propane, 2,2-bis (4-maleimidophenyl) propane, 2,2-bis [4- (4-maleimidophenyloxy) phenyl] Propane, bis (4-
Maleimidophenyl) ether, bis (3-maleimidophenyl) ether, bis (4-maleimidophenyl)
Ketone, bis (4-maleimidophenyl) sulfone, bis [4- (4-maleimidophenyloxy) phenyl]
Sulfone, bis (3-maleimidophenyl) sulfide, bis (4-maleimidophenyl) sulfoxide, bis (4-maleimidophenyl) diphenylsilane, 1,
4-bis (4-maleimidophenyl) cyclohexane,
1,4-dimaleimidonaphthalene, 1,8-dimaleimidonaphthalene, 4,4′-dimaleimidobiphenyl,
2,5-dimaleimide-1,3-xylene, 1,5-dimaleimide anthraquinone, 2,7-dimaleimide fluorene, 9,9-bis (4-maleimidophenyl) fluorene, 9,9-bis (4-maleimide) -3-methylphenyl) fluorene, 3,7-dimaleimido-2-methoxyfluorene, 9,10-dimaleimidophenanthrene, 3,6-dimaleimidoacridine, 1,2-dimaleimidoanthraquinone, 3,8-dimaleimido-6. -Phenylphenanthridine, 1,2-dimaleimidobenzene, 1,4-bis (4-maleimidophenyl) benzene, 2-methyl-1,4-dimaleimidobenzene, 2,
5-dimethyl-1,4-dimaleimidobenzene, 4-ethyl-1,3-dimaleimidobenzene, 4,6-dimethyl-1,3-dimaleimidobenzene, 2,4,6-trimethyl-1,3- Dimaleimidobenzene, 2, 3, 5,
Bismaleimide such as 6-tetramethyl-1,4-dimaleimidobenzene; tris (4-maleimidophenyl)
Trismaleimides such as methane; tetrakismaleimides such as bis (3,4-dimaleimidophenyl) methane; poly (4-maleimidostyrene) and poly (3-maleimidostyrene), and aniline resins obtained by the reaction of aniline and formaldehyde, etc. Examples thereof include polymaleimide obtained by maleimidizing an aromatic polyamine.

Among the above-exemplified components (a), aromatic bismaleimide compounds are particularly preferable because a resin cured product having excellent moldability and heat resistance can be easily obtained. The component (a) represented by the general formula (1) can be easily synthesized by reacting a polyamine compound represented by the following general formula (2) with maleic anhydride.

[0010]

[Chemical 2]

(Z in the formula is a divalent or higher valent residue, and n is an integer of 2 or more.)

The above-mentioned "methallyl phenyl ether compound having at least two methallyl groups in one molecule and /
Or methallylphenol-based compound "[hereinafter, component (b)
Of the above, "the methallyl phenyl ether-based compound having at least two methallyl groups in one molecule" includes the compounds described in (b-1) to (b-3) below. (B-1): dimethallyl phenyl ether compound of biphenyldiol 4,4′-bis (2-methyl-2-propenyloxy)
Biphenyl, 2,2'-bis (2-methyl-2-propenyloxy) biphenyl. (B-2): Dimethallyl phenyl ether compound of bisphenol 2,2′-bis [4- (2-methyl-2-propenyloxy) phenyl] propane, bis [4- (2-methyl-)
2-propenyloxy) phenyl] methane, bis [4-
(2-methyl-2-propenyloxy) phenyl] sulfoxide, bis [4- (2-methyl-2-propenyloxy) phenyl] sulfide, bis [4- (2-methyl-2-propenyloxy) phenyl] ether, Bis [4- (2-methyl-2-propenyloxy) phenyl] sulfone, 1,1-bis [4- (2-methyl-2-
Propenyloxy) phenyl] ethylbenzene, 1,1
-Bis [4- (2-methyl-2-propenyloxy) phenyl] cyclohexane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (2methyl-2-propenyloxy) ) Phenyl] propane, bis [4- (2
-Methyl-2-propenyloxy) phenyl] ketone,
9,9-bis [4- (2-methyl-2-propenyloxy) phenyl] fluorene, 3,3-bis [4- (2-
Methyl-2-propenyloxy) phenyl] phthalide,
2- (2-methyl-2-propenyloxy) phenyl
4- (2-methyl-2-propenyloxy) phenyl ketone.

(B-3): Other methallyl phenyl ether compounds 1,4-bis (2-methyl-2-propenyloxy) benzene, 1,2,4-tris (2-methyl-2-propenyloxy) Benzene, 2,4-bis (2-methyl-2)
-Propenyloxy) acetophenone, 1,8-bis (2-methyl-2-propenyloxy) anthraquinone, 2,3-bis (2-methyl-2-propenyloxy) benzaldehyde, tris [4- (2-methyl-2)
-Propenyloxy) phenyl] methane, 1,1,1-
Tris [4- (2-methyl-2-propenyloxy) phenyl] ethane, 1- [1-methyl-1- (4- (2-
Methyl-2-propenyloxy) phenyl) ethyl]-
4- [1,1-bis (4- (2-methyl-2-propenyloxy) phenyl) ethyl] benzene, 1,2-bis (2-methyl-2-propenyloxy) naphthalene,
1,2-bis (2-methyl-2-propenyloxy) anthraquinone, 1,4-bis (2-methyl-2-propenyloxy) anthraquinone, 2,2′-bis (2-methyl-2-propenyloxy) Azobenzene and 5,8
-Bis (2-methyl-2-propenyloxy) -1,4
-Naphthoquinone. Among the components (b) exemplified above,
A methallyl phenyl ether compound having two methallyl groups is preferred.

As the "methallylphenol compound having at least two or more methallyl groups in one molecule" which is one of the components (b), the following (b'-1) to (b'-
The compounds described in 3) are mentioned. These compounds are
For example, it can be easily obtained by heating a methallyl phenyl ether compound to cause Claisen rearrangement of the methallyl group. (B'-1): dimethallylbiphenyldiol compound 3,3'-bis (2-methyl-2-propenyl) -4,
4'-biphenyldiol. (B′-2): dimethallyl bisphenol compound 2,2-bis [4-hydroxy-3- (2-methyl-2)
-Propenyl) phenyl] propane, bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl]
Methane, bis [4-hydroxy-3- (2-methyl-2)
-Propenyl) phenyl] sulfoxide, bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] sulfide, bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] ether, bis [4
-Hydroxy-3- (2-methyl-2-propenyl) phenyl] sulfone, 1,1-bis [4-hydroxy-3
-(2-methyl-2-propenyl) phenyl] ethylbenzene, 1,1-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] cyclohexane,
1,1,1,3,3,3-hexafluoro-2,2-bis- [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] propane, bis [4-hydroxy-3
-(2-methyl-2-propenyl) phenyl] ketone,
9,9-bis [4-hydroxy-3- (2-methyl-2)
-Propenyl) phenyl] fluorene, 3,3-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] phthalide, 2,2-bis [4-hydroxy-3-methyl-5- (2 -Methyl-2-propenyl)
Phenyl] propane and 2-hydroxy-3- (2-methyl-2-propenyl) phenyl 4-hydroxy-3
-(2-Methyl-2-propenyl) phenyl ketone.

(B'-3): Other methallylphenol compounds 2,3-bis (2-methyl-2-propenyl) -1,4
-Benzenediol, 3,5,6-tris (2-methyl-2-propenyl) -1,2,5-benzenetriol, 2,4-dihydroxy-3,5-bis (2-methyl-2-propenyl) Acetophenone, 3,5-dihydroxy-2,4-bis (2-methyl-2-propenyl) acetophenone, 1,8-dihydroxy-2,7-bis (2-methyl-2-propenyl) anthraquinone, 2,
4-dihydroxy-3,4-bis (2-methyl-2-propenyl) benzaldehyde, 3,4-dihydroxy-
2,5-bis (2-methyl-2-propenyl) benzaldehyde, tris [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] methane, 1,1,1-tris [4-hydroxy-3] -(2-Methyl-2-propenyl) phenyl] ethane, 2,2'-dihydroxy-
3,3 ′-(2-methyl-2-propenyl) azobenzene, 1- [1-methyl-1- (4-hydroxy-3-)
(2-Methyl-2-propenyl) phenyl) ethyl]-
4- [1,1-bis (4-hydroxy-3- (2-methyl-2-propenyl) phenyl) ethyl] benzene,
1,3-dihydroxy-2,4-bis (2-methyl-2)
-Propenyl) naphthalene, 2,6-dihydroxy-
1,5-bis (2-methyl-2-propenyl) naphthalene, 2,7-dihydroxy-3,6-bis (2-methyl-2-propenyl) naphthalene, 1,4-dihydroxy-2,3-bis ( 2-Methyl-2-propenyl) anthraquinone, 1,5-dihydroxy-2,6-bis (2-
Methyl-2-propenyl) anthraquinone, and 5,8
-Dihydroxy-6,7-bis (2-methyl-2-propenyl) -1,4-naphthoquinone. Among the components (b) exemplified above, a methallylphenol-based compound having two methallyl groups is preferable.

The above "amino compound having at least two amino groups in one molecule" [hereinafter referred to as component (c)]
Examples of the compound include the compounds described in (c-1) to (c-3) below. (C-1): Diamine-based amino compound This is an amino compound having two amino groups in one molecule. Isophorone diamine, m-phenylenediamine, bis (4-aminophenyl) methane, bis (4-aminophenyl) sulfone, bis (4-aminophenyl)
Ether, 2,4,6-trimethyl-1,3-phenylenediamine, ethylenediamine, tetramethylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, bis (4-amino-3-ethyl) -5-methylphenyl) methane, 1,4-naphthalenediamine, cyclohexylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-diaminobutane, 1,4
-Diamino-2-butanone, 2,5-diamino-1,3
-Xylene, bis (4-aminophenyl) sulfone,
1,10-diaminodecane, 2,7 diaminofluorene, 1,7-diaminoheptane, 2,5-diaminopyridine, 1,3-diamino 1,2-hydroxypropane,
9,10-diaminophenanthrene, diaminomaleonitrile, 3,6-diaminoacridine, 1,8-diamino-p-menthane, 1,2-diaminoanthraquinone,
2,8-diamino-6-phenylphenanthridine, bis (4-aminocyclohexyl) methane, 1,9-diaminononane, 1,8-diaminooctane, 1,4-bis (4-aminophenyl) benzene, 1, 5-diaminopentane, bis (4-aminophenyl) diphenylsilane, bis (4-aminophenyl) sulfide, 3,4-
Diaminobenzophenone, 2,4-diaminophenol, bis (4-aminophenyl) sulfoxide, 2,4
-Diaminotoluene, 2,2-bis [4- (4-aminophenyloxy) phenyl] propane, 1,3-adamantanediamine, 1,4-bis (3-aminopropyl)
Examples thereof include piperazine and 2,3-diaminopyridine.

(C-2): Triamine amine compound This is an amino compound having three amino groups in one molecule. Examples include tris (2-aminoethyl) amine, melamine, and 2,4,6-triaminopyrimidine. (C-3): Other amine compounds Triethylenetetramine, tetraethylenepentamine and the like. Among the components (c) exemplified above, aromatic diamines are preferable.

The "resin composition" comprising the above-mentioned component (a), component (b) and component (c) is first melt-kneaded at a temperature and for a time at which substantially no curing occurs. Although the kneading time depends on the temperature, about 5 to 30 minutes is usually sufficient. When the temperature is low, the kneading is performed for a relatively long time, and when the temperature is high, the kneading is performed for a relatively short time, but the low temperature and the long-time kneading is more preferable in order to obtain a homogeneous resin composition having a low viscosity. The heating in the present invention needs to be divided into heating in the first half of heating at 60 to 180 ° C. and heating in the second half of heating at 200 to 300 ° C. The heating in the first half is 60 to 120 ° C. and 120 to 180 ° C. In each temperature range of 1
It is performed by heating for more than an hour. The heating step in the first half of the present invention is an essential step for obtaining a heat-resistant resin cured product having excellent mechanical properties, and is characterized in that the temperature is gradually raised from a low temperature portion to a high temperature portion. Therefore, when the heating of the first period is omitted or when the heating of the first period is performed, 60 to 120
After heating in the temperature range of ℃ for less than 1 hour, 120 ℃ at a stretch
If heating is performed at a higher temperature, the resin cured product aimed at by the present invention cannot be obtained. In addition, heating of the first half is 6
Only heating in the temperature range of 0 to 120 ° C., 120 to
If the heating in the temperature range of 180 ° C. is omitted, the effect of the heating in the first half becomes insufficient.

The heating in the first half of the present invention may be continuous heating in which the temperature is changed while heating, or stepwise heating in which the temperature is maintained for a predetermined time. In the case of continuous heating, the heating rate need not necessarily be constant. Further, in the case of stepwise heating, the temperature to be maintained for a predetermined time may be set at one point or more in each temperature range of 60 to 120 ° C and 120 to 180 ° C. In the heating step of the first half of the present invention, as a preferred stepwise heating method for setting the temperature to be maintained for a predetermined time at N (integer of 2 or more)
For example, there is a method of heating for k / N (where k is 2 when N is an even number and 3 when it is an odd number) times in each temperature range obtained by equally dividing the temperature range of 60 to 180 into N. The latter heating in the present invention is a step for completely curing the resin, and the heating method may be continuous heating or stepwise heating as in the first heating.

The properties of the resin cured product obtained by the method of the present invention are appropriately controlled by changing the blending ratio of the components (a), (b) and (c) depending on the method of use, the required performance and the intended use. be able to. For example, to increase the heat resistance, the amount of (c) may be reduced, and to increase the toughness, the amount of the component (c) may be increased. Further, the molar ratio of the maleimide group of the component (a) of the resin composition is preferably in the range of 1.5 to 3.0 with respect to 1 mol of the methallyl group of the component (b).
If this ratio is less than 1.5, the heat resistance of the cured resin may decrease, and if it exceeds 3.0, the mechanical strength of the cured resin may decrease. Moreover, the molar ratio of the amino group of the component (c) is preferably in the range of 0.5 to 2.0 with respect to 1 mol of the methallyl group of the component (b). If this ratio is less than 0.5, the mechanical strength of the cured resin may decrease,
If it exceeds 2.0, the heat resistance of the cured resin may decrease.

The resin composition used in the method of the present invention may contain, as the component (d), a radical initiator for curing the composition. As the radical initiator, those conventionally used can be used without particular limitation. Preferred radical initiators include cumyl peroxide, acetyl peroxide, benzoyl peroxide, potassium persulfate, diisopropyl peroxycarbonate,
Tetralin hydroperoxide, tert-butyl peracetate,
Peroxides such as tert-butyl perN- (3-toluyl) carbamate; 2,2'-azobispropane, 1,1'-azo (methylethyl) diacetate, 2,2'-azobis (2- Amidinopropane) hydrochloride, 2,2′-azobis (2-amidinopropane) nitrate, 2,2′-azobisisobutane, 2,2′-azobisisobutyramide,
2,2′-azobisisobutyronitrile, 2,2′-methyl azobis-2-methylpropionate, 1,1′-azobis (1-methylbutyronitrile-3-sulfonic acid sodium salt), 2- ( 4-methylphenylazo) -2-methylmalonodinitrile, 4,4'-azobis-4-cyanovaleric acid, 1,1'-azobis-1-chlorophenylethane, 1,1'-azobiscumene, 4-nitrophenyl Azo compounds such as ethyl azobenzyl cyanoacetate and phenylazotriphenylmethane; 1,4-bis (pentaethylene 1-2-tetrazene, benzenesulfonyl azide and 1,4-dimethoxycarbonyl-1,4-diphenyl-2-tetrazene The preferred addition amount of these radical initiators varies depending on the use, but the total amount of components (a) and (b) is From 0 for 00 parts by weight of 5
It is 0 part by weight, preferably 0 to 10 parts by weight.

If necessary, the resin composition used in the method of the present invention may contain the following components (e-1) to (e-4). (1) Inorganic filler (e-1) This component is a component for further increasing the mechanical strength of the cured resin product, and any of those conventionally used can be used. Preferred specific examples include metal oxides such as aluminum oxide and magnesium oxide; metal hydroxides such as aluminum hydroxide; metal carbonates such as calcium carbonate and magnesium carbonate; diatomaceous earth powder; basic magnesium silicate; calcined clay. Finely divided silica, quartz powder,
Fused silica, crystalline silica; kaolin, talc; carbon black; antimony trioxide; finely powdered mica; graphite; molybdenum disulfide; carbon fiber; glass fiber; rock wool; ceramic fiber; inorganic fibers such as asbestos; paper, pulp, wood materials And synthetic fibers such as polyamide fiber, aramid fiber and boron fiber.

(2) Colorant (e-2) This component is a component for coloring the resin cured product,
Any of those conventionally used can be used.
Preferred specific examples include titanium dioxide, yellow lead, carbon black, iron black, molybdenum red, navy blue, ultramarine blue, cadmium yellow, cadmium red and boron nitride. (3) Flame Retardant (e-3) This component is a component for imparting flame retardancy to the cured resin product, and any of those conventionally used can be used. Preferred specific examples include tetrabromobisphenol A, hexabromobenzene, tris (2,3-
Brominated flame retardants such as dibromopropyl) isocyanurate, inorganic flame retardants such as antimony trichloride, zirconium hydroxide and tin oxide, aromatic phosphoric ester-based flame retardants such as triphenyl phosphate and phenylene bis (phenyl cresyl phosphate) Combustion agent and its polycondensate, Tris (2
(Halo) alkyl phosphate ester-based flame retardants such as -chloroethyl) phosphate and polycondensates thereof, and inorganic phosphorus-based flame retardants such as red phosphorus.

(4) Components (e) for imparting various characteristics
-4) This component is a component for imparting various properties other than the above to the resin cured product, and any component conventionally used as a component for modifying certain properties can be used. Preferable specific examples include synthetic resins such as phenol resin, alkyd resin, melamine resin, fluororesin, vinyl chloride resin, acrylic resin, silicone resin and polyester resin. The preferable addition amount of each of these powdery or fibrous reinforcing materials or fillers, colorants, pigments, flame retardants, flame retardant aids and synthetic resins varies depending on the use, but a resin cured product is used as a molding material or a laminate. When used, the total amount of components (a), (b) and (c) is 10
It is up to 500 parts by weight with respect to 0 parts by weight.

[0025]

The present invention will be described in more detail below with reference to Examples and Comparative Examples. The various physical properties evaluated in the following Examples and Comparative Examples are measured as follows. (1) Bending strength Measured according to JIS K7203. (2) Shore D hardness Measured according to JIS Z2246. (3) 5%, 10%, and 20% weight loss temperature Thermogravimetric differential thermal method (TG.
The temperature at which the weight loss of 5%, 10% and 20% was measured by DTA). (4) Decomposition temperature The temperature at which the temperature rise rate was 20 ° C./min, and the temperature at which abrupt heat generation and weight loss occurred due to TG / DTA was taken as the decomposition temperature.

Example 1 2 mol of bis [4-maleimidophenyl] methane [compound of formula (3)] as component (a) and 2,2 as component (b).
2-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] propane [compound of formula (4)] 1
1 mol of bis (4-aminophenyl) methane [compound of formula (5)] as component (c) was melt-kneaded at 100 ° C. for 10 minutes, and then poured into a polytetrafluoroethylene mold and heated at 120 ° C. for 2 minutes. For 1 hour at 160 ° C. for 1 hour, then at 200 ° C. for 1 hour and at 240 ° C. for 2 hours for the latter period to cure,
A plate-shaped resin cured product was obtained.

[0027]

[Chemical 3]

[0028]

[Chemical 4]

[0029]

[Chemical 5]

The details of the heating conditions in the previous heating of this example are as follows. Start heating from 100 ° C., raise the temperature to 120 ° C. after 30 minutes at a constant heating rate, hold at the same temperature for 2 hours, then 160 ° C. after 5 minutes at a constant heating rate.
The temperature was raised to 180 ° C. and held at the same temperature for 1 hour, then heating was restarted again at a constant heating rate, and the temperature was raised to 180 ° C., which is the upper limit temperature of the previous heating, in 2 minutes. Table 1 shows the composition of the resin composition of Example 1 and the physical properties of the obtained resin cured product.

[0031]

[Table 1]

Example 2 Components (a), (b) and (c) were melted and kneaded, and then 0.06 mol of dicumyl peroxide was added, and the final curing temperature was 220 ° C. A plate-shaped resin cured product was obtained in the same manner as in Example 1. The heating conditions for the previous heating in this example are the same as in Example 1. Table 1 shows the composition of the resin composition of Example 2 and the physical properties of the obtained resin cured product.

Comparative Examples 1 to 3 The resin composition was melt-kneaded in the same manner as in Example 1 and cast into a mold, and then a resin cured product was produced under the following conditions.
In Comparative Example 1, heating was started at 100 ° C., heated to 140 ° C. after 30 minutes at a constant heating rate, held at the same temperature for 2 hours, and then restarted at a constant heating rate again in 5 minutes. The temperature was raised to 180 ° C., which is the upper limit temperature of the previous heating. The temperature was further increased at the same rate, and when the temperature reached 240 ° C., the temperature was kept at the same temperature for 2 hours, and the latter heating was performed to cure.

In Comparative Example 2, heating was started at 100 ° C., and after 30 minutes at a constant heating rate, the temperature was raised to 120 ° C.
After holding at the same temperature for 2 hours, heating was restarted again at a constant heating rate, the temperature was raised to 180 ° C., which is the upper limit temperature of the previous heating in 8 minutes, and this temperature was held for 2 hours to complete the heating operation.

In Comparative Example 3, heating was started at 100 ° C., and after 30 minutes at a constant heating rate, the temperature was raised to 120 ° C.
After holding at the same temperature for 2 hours, at a constant heating rate 4 minutes later, 1
After raising the temperature to 50 ° C and maintaining it at the same temperature for 1 hour, heating is restarted at a constant heating rate again, and in 4 minutes the temperature is raised to 180 ° C, which is the upper limit temperature of the previous period, and kept at this temperature for 2 hours. Then, the heating operation was completed.

From the results shown in Table 1, the resin composition comprising the components (a), (b) and (c) was added in the previous heating step.
By heating stepwise in each temperature range of 60 to 120 ° C. and 120 to 180 ° C. and then heating stepwise and curing in the latter heating step, a cured resin product having excellent heat resistance and mechanical properties is obtained. You can see that you can get it. On the other hand, in Comparative Example 1 in which heating at 60 to 120 ° C. was omitted in the first heating step and Comparative Examples 2 and 3 in which the heating and curing step was not included, a large number of voids were generated and resin curing that can be used for physical property measurement. I couldn't get anything. Incidentally, the present invention is not limited to those shown in the above-mentioned specific examples, but may be variously modified examples within the scope of the present invention depending on the purpose and application, for example, in the latter stage stepwise heating. The holding time at a constant temperature is not limited to 1 to 2 hours, and may be shorter or longer than this.

[0037]

EFFECTS OF THE INVENTION According to the method for producing a heat-resistant resin cured product of the present invention, a resin cured product having excellent heat resistance and mechanical properties, which is easy to mold and does not produce water as a by-product during curing, can be obtained. can get. INDUSTRIAL APPLICABILITY The production method of the present invention is extremely effective when curing a resin composition, which is a raw material for a resin cured product, into a desired shape in various fields of use such as impregnation, casting, sealing and adhesion. The resin cured product obtained by the method can be used as a molding material such as an electric insulating material or a structural material, or a laminated material.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kaoru Kimura 1-1, Funami-cho, Minato-ku, Nagoya-shi, Aichi Toagosei Chemical Industry Co., Ltd. Nagoya Research Institute

Claims (1)

[Claims] 1. A polymaleimide compound, (b) a methallylphenyl ether compound and / or a methallylphenol compound having at least two methallyl groups in one molecule, and (c) one molecule. A resin composition containing an amino compound having at least two amino groups,
In each temperature range of 60 to 120 ° C. and 120 to 180 ° C., 200 to 300 ° C. after heating for 1 hour or more while continuously or stepwise raising the temperature, respectively.
A method for producing a cured product of a heat-resistant resin, characterized in that it is heated in the latter half of the temperature range to be cured.