KR830000098B1 - Thermosetting resin composition - Google Patents

Abstract

None.

Description

Thermosetting resin composition

The present invention relates to a thermosetting resin composition excellent in heat resistance and fast curing.

There are various heat-resistant resins as insulating materials that meet the demands of large-capacity, small-sized, light weight, high reliability, high thermal stability, long life, and maytenans free of electronic devices. As such heat resistant resins, addition polymerization type imide resins such as bismaleimide resins or bismaleimide-aromatic diamine modified resins are known.

However, bismaleimide resins have excellent heat resistance but have a high melting point, a low curing rate, and low solubility in organic solvents. Thus, bismaleimide resins have a poor polarity such as N-methyl-2-pyrrolidone and dimethylformamide. There was a problem such as making Sanyo indispensable.

Moreover, although the method of using together organic peroxides, such as dichmil peroxide and benzoyl peroxide, is employ | adopted in order to accelerate hardening of a maleimide resin, when prepreg is processed using such a resin composition using the impregnation varnish for laminated boards, The cleavage of the organic peroxide remaining in the preflag causes deterioration of the quality and properties of the laminate, particularly in the case of the coated lamination, which causes copper to swell or peel and is not satisfactory.

Bismaleimide is already known to heat itself above its melting point or to produce three-dimensional network by the action of free radicals. However, for the effective crosslinking reaction, it is known that the presence of a catalytic amount of free radical generator is preferable (see, for example, J. Amer. Chem. Soc. 81, 1187 (1959)). The free radical generating agent has little activation energy for decomposition due to its properties, and is often unstable even at room temperature and easily decomposes, and requires special care for storage and handling.

An object of the present invention is to provide an improved thermosetting resin composition.

Still another object of the present invention is to provide a thermosetting resin composition having excellent storage stability, heat resistance and hygroscopicity, and giving a cured product having excellent electrical and mechanical properties.

It is further an object of the present invention to provide an improved thermosetting resin composition that can be used in impregnation resins, adhesives, powder roads and molding materials.

Moreover, the objective of this invention is providing the thermosetting resin composition which shows the outstanding effect as a crosslinking agent and a vulcanization accelerator in combination with vulcanization of rubber | gum.

The above various objects are attained by a thermosetting resin composition containing at least one compound selected from alkenylphenol derivatives, alkenylaniline derivatives, linear dimers thereof and their multimers in bis maleimide and / or polymaleimide compounds. .

Preferable resin composition in this invention is bis maleimide of (a) Formula (I)

기, 히드록시기 또는 시아노기에 의해서 치환된 페닐기이며, 또 서로 동일하거나 달라도 좋고, Z는 탄소수가 적어도 2이며, 2가의 유기기이다〕 및 식(Ⅱ)의 폴리말레이미드[Herein, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, halogen, alkyl group having 1 to 10 carbon atoms which may have a branch, phenyl group or alkyl group having 1 to 10 carbon atoms which may have a branch, halogen, R ₁₃ O − Group (hereinafter, R <_13> represents a C1-C5 aliphatic group and may be same or different),

A phenyl group substituted by a group, a hydroxy group or a cyano group, and may be the same or different from each other, Z has at least 2 carbon atoms and is a divalent organic group] and a polymaleimide of formula (II)

[In formula, R <_5> -R <_10> is hydrogen, a halogen, a C1-C10 alkyl group which may have a branch, a phenyl group, or a C1-C10 alkyl group which may have a branch, a halogen, a R <_13> O- group, R <_13> *** At least one maleimide compound selected from the group consisting of a phenyl group substituted by a -group, a hydroxy group or a cyano group, and which may be the same as or different from each other, and n is a number greater than 0; and (b) a formula (III) At least one alkenylphenyl compound selected from the group consisting of a compound thereof, a linear dimer thereof and a multimer thereof,

기, 히드록시기 또는 시아노기에 의해서 치환된 페닐기이며, 또 서로 동일하거나 달라도 좋고, X는 수소, 할로겐, 카르복실기,

기, R₁₃O－기 또는 시아노기이며,[In formula, R <_11> , R <_12> is hydrogen, a halogen, a C1-C10 alkyl group which may have a branch, a phenyl group, or a C1-C10 alkyl group which may have a branch, a halogen, a R <_13> -group,

Phenyl group substituted by a group, a hydroxy group or a cyano group, and may be the same or different from each other, X is hydrogen, a halogen, a carboxyl group,

Group, R ₁₃ O-group or cyano group,

기(이하 R은 탄소수 1∼20의 지방족기이며, 동일 또는 달라도 좋다), 아미노기, 글리시딜아미노기, 디글리시딜아미노기,

기(이하, R₁₅, R₁₆은 수소, 할로겐, 가지가 있어도 좋은 탄소수 1∼10의 알킬기이며, 동일 또는 달라도 좋다),

기,

기,

, 탄소수 1∼5의 알킬아미노기, 또는 각 알킬기의 탄소수가 1∼5의 디알킬아미노기이며, 또한 m₁, m₂및 m₃는 정의 정수이며, m₁＋m₂＋m₃＝5로 이루어진 것이다.Y is a hydroxy group, a R ₁₃ O- group, a glycidyloxy group, an aryloxy group, or an alkyl group having 1 to 5 carbon atoms which may have a branch or an aryloxy group substituted by a halogen, a propyloxy group, or a branch which may have a carbon number. A propargyloxy group substituted by an alkyl group or halogen of 1 to 5,

Group (hereinafter R is a C1-C20 aliphatic group, and may be same or different), an amino group, a glycidylamino group, a diglycidylamino group,

Group (hereinafter, R <_15> , R <_16> is hydrogen, a halogen, the C1-C10 alkyl group which may have a branch, and may be same or different),

group,

group,

, An alkylamino group having 1 to 5 carbon atoms, or a dialkylamino group having 1 to 5 carbon atoms for each alkyl group, and m ₁ , m ₂ and m ₃ are positive integers and consist of m ₁ + m ₂ + m ₃ = 5.

This thermosetting resin composition can contain (c) a polymerizable unsaturated compound further in addition to the component of said (a) and (b). The thermosetting resin composition containing the components of (a), (b) and (c) is substantially superior in performance to that made by the components of (a) and (b).

Especially preferable thermosetting resin composition in this invention is a C1-C5 alkyl group or phenyl group which R <_1> , R <_2> , R <_3> and R <_4> may have hydrogen, a halogen, or a branch, may be same or different,

An organic group of which Z is an aliphatic, alicyclic, aromatic, heterocyclic group or combination thereof having 2 or more carbon atoms, or groups thereof and -O-, -S-, -S-S-, -CO-, -SO-, _{-SO 2 -, -CO 2 -,} -N = N-, -NH-, bismaleimide and (or) of the organic group formula (ⅰ) is in combination with the -CONH-

R <_5> -R <_10> is hydrogen, a halogen, a C1-C5 alkyl group or phenyl group which may have, and may be same or different,

n is 0.1-10 polymaleimide of Formula (II), and R <_11> , R <_12> is hydrogen, a halogen, a C1-C10 alkyl group, or a phenyl group, and may be same or different,

X is hydrogen or halogen,

기, 말레이미드기, 글리시딜아미노기, 탄소수 1∼5의 알킬아미노기이며, 또한Y is a hydroxy group, an amino group, a R ₁₃ O- group, a glycidyloxy group,

Group, maleimide group, glycidylamino group, alkylamino group having 1 to 5 carbon atoms,

m <_1> , m <_2> and m <_3> are positive integers and consist of the alkenylphenyl compound of Formula (III) whose m <_1> + m <_2> + m <_3> = 5.

Specific examples of 2 in the equation (Ⅰ) is or by a simple valence bond, for example, -O-, -S-, alkylene of 1 to 3 carbon atoms, -CO-, -SO ₂ -, -NR _17- , -N = N-, -CONH-, -P (O) R _17- , -CONH-X ₁ -NHCO-,

(Herein, R ₁₇ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a cyclohexyl group, and X ₁ represents an alkylene group having 13 or less carbon atoms.)

Such as several phenylene or cyclohexylene groups bonded to each other by an atom or an inert group. Each phenylene or cyclohexylene group may be substituted by the methyl group, for example.

Examples of the maleimide compound are as follows.

Examples of the compound of formula (I) include N, N'-ethylene bismaleimide, N, N'-ethylene bis (2-methylmaleide), N, N'-trimethylene bismaleimide, N, and N'-tetraethylene Bismaleimide, N, N'-hexamethylenebismaleimide, N, N'-1, 4-cyclohexylenebismaleimide, N, N'-m-phenylene bismaleimide, N, N'-p -Phenylene bismaleimide, N, N'-2, 4-driren bismaleimide, N, N'-2, 6-driene bismaleimide, N, N '-(oxydi-p-phenylene ) Bismaleimide, N, N '-(oxydi- p-phenylene) bis-2-methylmaleimide, N, N'-(methylenedi-p-phenylene) bismaleimide, N, N'- (Methylenedi-p-phenylene) bis-2-methylmaleimide, N, N '-(methylenedi-p-phenylene) bis-2-phenylmaleimide, N, N'-(sulfonyldi-p- Phenylene) bismaleimide, N, N '-(thiodi-p-phenylene) bismaleimide, N, N'-(dithiodi-p Phenylene) bismaleimide, N, N '-(sulfonyldi-m-phenylene) bismaleimide, N, N'-(o, p-isopropylidenediphenylene) bismaleimide, N, N ' -Isopropylidenedi-p-phenylene) bismaleimide, N, N '-(o, p-cyclohexylidenediphenylene) bismaleimide, N, N'- (cyclohexylidenedi-p-phenyl Lene) bismaleimide, N, N '-(ethylenedi-p-phenylene) bismaleimide, N, N'-(m-xylene) bismaleimide, N, N '-(p-xylene) bismaleim Mid, N, N '-(4,4 "-p-triphenylene) bismaleimide, N, N'-(p-phenylenedioxy-p-phenylene) bismaleimide, N, N'- (Methylenebis-p-phenylene) bis-2,3-dichloromaleimide, N, N '-(oxydi-p-phenylene) bis-2-chloromaleimide, and general formula

In formula, R <_1> , R <_2> , R <_3> has the same meaning as the case of general formula (I), D represents aliphatic, alicyclic, and aromatic divalent organic group, and l is a number of 0-20.)

The terminal maleimated phenoxy compound represented by the above, for example, is a terminal maleimated phenoxy compound wherein D in Formula (IV) is methylene, dimethylene, trimethylene, hexamethylene, metaphenylene, paraphenylene.

As a compound of Formula (II), Formula (V) which is a condensate of aniline and formaldehyde.

Where n represents a number greater than 0 on average

The same thing as the polymethylene polyphenylene polymaleimide shown by Formula (VI) obtained by making maleic anhydride react with the polymethylene polyamine represented by the following by a well-known method,

(Where n is the same as electricity)

To polymers with a branched structure, including the moiety represented by the equation

It may also contain.

The maleimide compound of Formula (I) and (II) can be used 1 type (s) or 2 or more types.

Among the alkenylphenyl compounds represented by the general formula (III), examples of the alkenylphenol derivative include vinylphenol (ortho, meta and para), isopropenylphenol (ortho, meta and para), vinyl cresol isopropenyl cresol, Vinyl and isopropenylcatechol, ??-ethylvinylphenol, 3,5-dichloro-4-hydroxy-2-methylstyrene, vinylphenyl acetate, isopropenylphenyl acetate, vinylphenylbenzoate, isopropenylphenyl Benzoate, vinylphenylcinnamate, isopropenylphenylcinnamate, vinylphenylglycidyl ether, isopropenylphenylaryl ether, vinylphenyl propargyl ether, isopropenylphenyl propargyl ether and the like. Moreover, as alkenylaniline derivative, o-amino styrene, m-amino styrene, p-amino styrene, o-isopropenyl aniline, p-isopropenaniline, p-isopropenyl aniline, isopropenyl toluidine (1, 3, 2-; 1, 4, 2-; 1, 2, 3-, etc., isomers), vinyltoluidine (1, 3, 2-, 1, 4, 2-, 1, 2, 3-, etc.) , 4-amino-??-phenylstyrene, N- (p-vinyl) maleanilide acid, N- (p-isopropenylphenyl) maleamic acid, N- (2-chloro-p-isopropenylphenyl) Maleamic acid, N- (p-vinylphenyl) maleimide, N- (p-isopropenylphenyl) maleimide, N- (p-isopropenylphenyl) -2-methyl-maleimide, N- (m -Isopropenylphenyl) maleimide, N- (2-methyl-p-isopropenylphenyl) maleimide, N- (p-α-ethylvinylphenyl) maleimide, 1-vinyl-3-glycidylamino Benzene, 1-vinyl-4-glycidylaminobenzene, 1-vinyl 4-diglycidylaminobenzene, 1-isopropenyl 3-glycidylaminobenzene, 1-isopropenyl 4-glycidylaminobenzene, N- (p-isopropenylphenyl) isomaleimide And 1-isopropenyl-4-acetylaminobenzene, 1-isopropenyl-4-dimethylamino-benzene and the like. In addition, the linear dimer of the alkenylphenyl compound is a general formula.

(In formulas (VI) and (iii), R ₁₂ , X, m ₁ , m ₂ and m ₃ represent the same meaning as in the case of general formula (III).

In the specific example of the dimer of an alkenylphenyl derivative, 4-methyl-2, 4-bis (2-, 3- or 4-hydroxyphenyl) -1-pentene or 2-pentene, 4- Methyl-2, 4-bis (dihydroxyphenyl) -1-pentene or -2-pentene, 4-methyl-2, 4-bis- (3, 5-dichloro- 4-hydroxyphenyl) -1-pentene Or acetate esters, benzoic acid esters, cinnamic acid esters, glycidyl ethers, acryl ethers, or 2-pentene, 4-methyl-2, 4-bis (credyl) -1-pentene or 2-pentene and compounds thereof; Propargyl ether and the like.

Specific examples of the dimer of an alkenylaniline derivative include 4-methyl-2, 4-bis (o-aminophenyl) -1-pentene, 4-methyl-2, 4-bis (m-aminophenyl) -1-pentene. , 4-methyl-2, 4-bis (p-aminophenol) -1-pentene, 4-methyl-2, 4-bis (o-aminophenyl) -2-pentene, 4-methyl-2, 4-bis (m-aminophenyl) -2-pentene, 4-methyl-2, 4-bis (p-aminophenyl) -2-pentene, 4-methyl-2, 4-bis (p- (2'- carboxyvinylcarb) Carbonylamino) phenyl] -1-pentene, 4-methyl-2,4-bis [p- (2'-carboxyvinylcarbonylamino) phenyl] -2-pentene, 4-methyl-2,4-bis (p -N-maleimide phenyl) -1-pentene, 4-methyl-2, 4-bis (p-N-maleimide phenyl) -2-pentene, 4-methyl-2, 4-bis (p-N-iso) Maleimide phenyl) -1-pentene, 4-methyl-2, 4-bis (p-N-isomaleimide phenyl) -2-pentene, 4-methyl-2, 4-bis (3'-methyl-4 ') -N-Malay Dephenyl) -1-pentene, 4-methyl-2, 4-bis (3'-methyl-4'-N-maleimide phenyl) -2-pentene, 4-methyl-2, 4-bis (3 ', 5'-dichloro-4'-N-maleimidephenyl) -1-pentene, 4-methyl-2, 4-bis (3 ', 5'-dichloro-4'-N-maleimidephenyl) -2-pentene And so on.

The composition of the thermosetting resin composition of the present invention can be widely changed depending on the purpose of use, and the weight ratio of the electric maleimide compound and the alkenylphenyl compound is preferably 300: 1 to 1: 1, particularly 200: 1 to 1 The range of 5: 1 is good. If there is less maleimide compound than said range, the varnish of a resin composition will shorten a pot life, the thermal stability or heat resistance of hardened | cured material will fall, and in many cases, the hardening temperature of a resin composition is small, hardenability is bad, and the mechanical property of hardened | cured material is The strength is insufficient.

The thermosetting resin composition of the present invention may contain a polymerizable unsaturated compound in addition to the maleimide compound and the alkenylphenyl compound, but the polymerizable unsaturated compound herein refers to a vinyl monomer, a radical polymerizable unsaturated polymer or a radical polymerizable unsaturated oligomer. And vinyl monomers, for example, styrene, nuclear substituted styrene, acrylonitrile, acrylic acid and ester derivatives thereof, methacrylic acid and ester derivatives thereof, acrylamide, glycidyl acrylate, glycidyl dimethacrylate, di Vinylbenzene, divinyl toluene, diacryl phthalate, triacryl cyanurate, tribromophenyl anyl ether, and the like. As a radical polymerizable unsaturated polymer compound or a radical polymerizable unsaturated oligomer, for example, unsaturated polyester, polybutadiene, Chloroprene rubber, polypentadiene, Diaryl phthalate prepolymers and polymers such as styrene, maleic acid, and epoxy resins of these compounds, or oligomers, cyclic oligomers such as dicyclopentadiene, cyclodecatoliene, terpenoids, and the like. 1 type, or 2 or more types of is used.

The amount of the polymerizable unsaturated compound used depends on whether it is a monomer, a high molecular compound or an oligomer, but the sum of the weights of the bismaleimides, polymaleimides or mixtures thereof and the olefinic aromatic compounds, linear dimers thereof or mixtures thereof and the polymerizability It is used in the range of 200: 1-1:50 by weight ratio with an unsaturated compound, Preferably it is the range of 100: 1-1:20. If the amount of the polymerizable unsaturated product is too large, the heat resistance and the storage stability of the cured product will be lowered. If the amount of the polymerizable unsaturated product is too small, the fluidity of the molding material will decrease, and good molding will not be obtained in molding processing.

The resin composition can be cured while heating, and the curing temperature is not particularly limited, but is preferably in the range of 30 to 300 ° C. Moreover, it is also possible to employ | adopt radiation irradiation which uses radiation, such as an ultraviolet-ray, Xtjs, (alpha) ray, (beta) ray, r ray, as a hardening method.

Although the resin composition of this invention can contain 1 type (s) or 2 or more types of each following cleaning agent according to various uses and objectives, Sometimes, it can also melt | dissolve in an organic solvent and can use it. That is, when used as a molding material, silica, quartz glass, clay, alumina hydroxide, asbestos, glass fiber, mica, gypsum, kaolin, cement tar, galvanized, graphite, magneside, molybdenum sulfide, titanium white, silica sand, Inorganic fillers such as carbon black, barium sulfate, and calcium carbonate may be used, and known flame retardants such as organic canceling compounds, antimony compounds, and phosphorus compounds may be used for imparting flame resistance. Moreover, when using in the form of a solution, a resin composition uses N-methyl- 2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, a cerebsolve, methyl acetate It can also be dissolved in organic solvents such as ethyl acetate, chloroform, benzene, toluene, xylene, and chlorobenzene.

The resin composition of the present invention provides an emulsion having excellent heat resistance, storage stability, hygroscopicity, electrical and mechanical properties, and furthermore, the efficiency of the work is brought about by the properties such as ease of molding and fast curing. It can be used for impregnating resins, adhesives, powder coatings, molding materials, etc., and when used in vulcanization of rubber, it has an effect as a crosslinking agent or a vulcanization accelerator, and the heat deterioration resistance of the obtained vulcanized rubber is significantly improved. It is an excellent cleaning agent that is rich in functionality such as imparting properties.

The present invention will be described in more detail with reference to the following examples.

Example 1

In maleic acid-N, N'-4, 4'- diphenylmethane bisimide, it contains 70 weight% of p-isopropenyl phenol linear dimers as a main component, and separately p-isopropenyl phenol monomer 2%, p Product containing 4.3% of isopropenyl phenol linear trimer, 4.5% of oligomers more than p-isopropenyl phenol linear tetramer, 1.1% phenol, 0.9% propyl phenol, 3.5% bisphenol A, and other 13.7 weight% of each other : Pamanol 200 Mitsui Toatsu Chemical Co., Ltd.) was mixed well at room temperature, and 21 g of the mixture was dissolved on a heat-preserved iron plate at a predetermined temperature shown in Table-1, and the time until gelation was performed while mixing well with a spatel. Saved. The results are shown in Table 1.

Table 1

Example 2

0.2 mol of acetic acid ester of 0-isopropenyl phenol was added to 0.1 mol of maleic acid-N, N'-4, and 4'- diphenylmethane bisimide, the 1g was taken, and it heated and heat-preserved at 160 degreeC beforehand. It melt | dissolved in the phase and it was 60 second when the gelation time was measured. Only bismaleimide did not gelate even if it reacted for 60 minutes.

Example 3

It was 70 second when the gelation time was calculated | required using the benzoic acid ester of p-isopropenyl phenol similarly to Example 2.

Example 4

In the same manner as in Example 2, the gelation time was determined using cinnamic acid ester of p-isopropenylphenol and was 100 seconds.

Example 5

Citylene 10g, maleic acid-N, N'-4, 4'- diphenylmethane-bisimide 7g, and p-isopropenylphenol 1.5g were mixed well, and it hardened | cured at 35 minutes when heated to 120 degreeC. Moreover, as styrene only, even if it reacted at this temperature for 3 hours, the polymer was hardly recognized. The same was true for the mixture of styrene and the bismaleimide.

Example 6

It cured using the resin composition (brand name: ESTAR-XE 7472 made by Mitsui Toatsu Chemical Co., Ltd.) containing about 55% of unsaturated polyester, about 45% of styrene, and 0.02% of hydroquinone. As the curing accelerator, a mixture of maleic acid-N, N′-4,4 ″ -diphenylmethane-bisimide and palmol 200 or p-isopropenylphenol was used. The results are shown in Table 2.

TABLE 2

Example 7

In the same manner as in Example 2, the gelation time was determined using the aryl ether of p-isopropenylphenol, which was 80 seconds.

Example 8

It was 70 second when gelation time was calculated | required using the glycidyl ether of p-isopropenyl phenol similarly to Example 2.

Example 9

Liquid polybutadiene (brand name: NISSO-PB-1000 Nippon Soda Co., Ltd.) 10g, styrene 10g, maleic acid-N, N'-4, 4'- diphenylmethane bisimide 7g, acetic acid of p-isopropenyl phenol 2.0 g of ester was mixed well and cured after 28 minutes when heated to 120 ° C.

Example 10

10 g of liquid polybutadiene (brand name: New Polyyl X-5 Nippon Zeon Co., Ltd.), 10 g of styrene, maleic acid-N, N'-4, 4'- diphenylmethane bisimide, 7 g of p-isopropenylphenol 2.1 g of acetic acid ester was mixed well and cured after 34 minutes when heated to 120 ° C.

Examples 11-15

To 53.7 g of N, N '-(methylenedi-p-phenylene) bis maleimide, 10.5 g, 3.5 g, 2.5 g, 1.5 g, and 0.8 g of N- (p-isopropenylphenyl) maleimide were respectively added, It mixed enough and obtained 5 types of resin compositions in total. The composition was melted on an iron plate heated at 180 ° C., and mixed with a spatel to determine time for gelation. In addition, the weight loss due to thermal decomposition of the gelled product was measured by thermal balance and used as a standard for viewing heat resistance.

Table 3 shows the results.

TABLE 3

Examples 16-21

N, N '-(methylenedi-p-phenylene) bismaleimide 53.7g 4-methyl- 2, 4-bis (p-aminophenyl)-1-pentene and 4-methyl-2, 4-bis ( 10.0 g, 0.7 g, 3.3 g, 2.4 g, 1.3 g, and 0.5 g of a sugar molar mixture with p-aminophenyl) -2-pentene were respectively added and mixed thoroughly, and a total of 6 types of resin compositions were obtained. The gelation time and thermal decomposition weight loss of this composition were determined by the method of Example 11. The results are shown in Table 4.

Table 4

1) Equivalent mixture of 4-methyl-2, 4-bis (p-aminophenyl) -1-pentene and 4-methyl-2, 4-bis (p-aminophenyl) -2-pentene.

Example 22

N, N '-(methylenedi-p-phenylene) bismaleimide 53.7g p-isopropenyl aniline 7.5%, 4-methyl-2, 4-bis (p-aminophenyl) -1-pentene 63% And 2.4 g of a mixture consisting of 20.7% of 4-methyl-2- and 4-bis (p-aminophenyl) -2-pentene and 8.8% of a trimer of p-isopropenyl aniline were sufficiently mixed to obtain a resin composition.

The gelation time of this composition obtained in accordance with Example 11 was 124 seconds, and the temperature at 1% weight loss was 472 ° C.

Comparative Example 1

Only N and N '-(methylene-p-phenylene) bismaleimide melt | dissolved on the iron plate heated at 180 degreeC, and the gelation time was 1307 second, mixing well with a spatel.

Example 23

10 g of styrene, 7 g of N '-(methylenedi-p-phenylene) bismaleimide, and 1.5 g of N- (p-isopropenylphenyl) maleimide were mixed well and cured at 28 minutes after heating to 120 ° C. did.

Moreover, as for styrene only, even if it stirred at this temperature for 3 hours, the polymer was hardly recognized. The same was true of the mixture of styrene and the bismaleimide.

Example 24

Resin composition containing about 55% of unsaturated polyester, about 45% of styrene, and 0.02% of hydroquinone (brand name: Esta-xe 7472 manufactured by Mitsui Atsu Chemical Co., Ltd.) 7.0 g, N, N '-(methylenedi-p-phenylene ) 1.0 g of bismaleimide and 0.2 g of N- (p-isopropenylphenyl) maleimide were mixed well, and when it heated at 120 degreeC, it hardened | cured at 13 minutes.

And even if it stirred only at this temperature for 200 minutes only in Esta-XE 7472, the synthesis | combination was hardly recognized.

Example 25

Liquid polybutadiene (brand name: NISSO-PB G-1000, Nippon Soda Co., Ltd.) 10g, styrene 10g, N, N '-(methylenedi-p-phenylene) bismaleimide 7g, 4-methyl-2, 4- 2.0 g of bis (p-aminophenyl) -1-pentene was mixed well and it heated at 120 degreeC, and it hardened after 21 minutes.

Example 26

Polymethylene of the following formula which is 10 g of liquid polybutadiene (brand name: New Polyyl X-5 Nippon Xeon Co., Ltd.), 10 g of styrene, and 0.8% of flatness of n.

7 g of polyphenylene polymaleimide was mixed well, and when it heated at 120 degreeC, it hardened within 27 minutes.

Example 27

Resin composition containing about 55% of unsaturated polyester, about 45% of styrene, and 0.02% of hydroquinone (brand name: ESTAR-XE-7472, Mitsui Toatsu Chemical Co., Ltd.) 7.0 g, N, N'- (methylenedi-p 1.0 g of -phenylene) bismaleimide and 7.5% of p-isopropenyl anilines, 4-methyl-2, 4-bis (p-aminophenyl) -1-pentene 42.0%, 4-methyl-2, 4- 0.2 g of a mixture of 30.2% of bis (p-aminophenyl) -2-pentene and 20.3% of a trimer of p-isopromethylaniline was sufficiently mixed and cured in 11.5 minutes when heated to 120 ° C.

Example 28

0.90 g of p-isopropenylphenol and 10.74 g of polymethylene polyphenylene polymaleimide of the formula

Mix well and heat to 150 ° C. and cure in 86 seconds.

In addition, only polymethylene polyphenylene polymaleimide required 32 minutes to cure at this temperature.

Example 29

0.61 g of p-isopropenyl, 1.77 g of N, N '-(methylene-p-phenylene) bis (2,3-dichloromaleimide) and 0.19 g of N- (p-isopropenylphenyl) maleimide The mixture was heated to 200 ° C. and cured in 3 minutes 37 seconds.

Moreover, only N and N '-(methylenedi-p-phenylene) bis (2, 3- dichloro maleimide) did not harden even if it heated at this temperature for 2 hours.

Claims (1)

At least one maleimide compound selected from the group consisting of bismaleimide and polymaleimide: and at least one alkenylphenol compound selected from the group consisting of alkenylphenol derivatives, alkenylaniline derivatives, linear dimers thereof and multimers thereof A thermosetting resin composition containing the.