JPH04296319A - Liquid curable resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition useful for an electrical insulating material for impregnation, etc., not crystallizing during preservation, having excellent shelf stability and heat resistance, comprising a specific polymaleimide, a specific polymerizable unsaturated compound, a specific polyepoxy compound, a specific bismaleimide compound and a specific acid anhydride. CONSTITUTION:The objective composition comprising (A) a polyepoxy compound containing two more epoxy groups in one molecule, (B) a bismaleimide compound such as N,N'-ethylenebismaleimide, (C) a polymaleimide shown by the formula (X is H, halogen, 1-4C alkyl or 1-4C alkoxy), (D) a polymerizable unsaturated compound containing one or more polymerizable groups selected from allyl, allyl ester, (meth)acryl and vinyl bonded to aromatic ring and is liquid at 20 deg.C, and (E) an acid anhydride compound such as phthalic anhydride. The blending ratio of the composition is preferably component A/B+C of 0.5-10,0 and component B/C of 0.2-10.0. and components A+B+C/D of 1-20.

Description

[Detailed description of the invention]

0001

FIELD OF INDUSTRIAL APPLICATION The present invention relates to a liquid curable resin composition containing a maleimide compound which provides a cured product with excellent heat resistance, and is particularly suitable for use as an electrical insulating material for impregnation.

0002

[Background Art] With the demand for smaller size, higher performance, and higher reliability of electrical equipment, insulating materials for these electrical equipment are required to have chemical stability and physical reliability at high temperatures. became. In particular, as insulating materials for vehicles and motors, importance has been placed on solvent-free heat-resistant resins that can perform the desired insulation function even under severe temperature conditions.

Epoxy resin, which has conventionally been widely used as an impregnated insulating resin for electrical equipment, has low viscosity, good workability, and excellent compatibility with insulating materials such as glass cloth and mica, but has poor heat resistance. Class F (maximum operating temperature 1)
55°C).

Various types of polyimide-based impregnating resins have been proposed, but the ones proposed so far have had advantages and disadvantages. For example, the polyimide-based impregnated resin described in Japanese Patent Publication No. 52-5555 tends to increase in viscosity during storage, and because the compatibility of the main raw material bismaleimide resin is poor, crystals precipitate, resulting in poor workability. There's a problem. Furthermore, although the polyimide-based impregnated resin described in JP-A-54-100488 can prevent the crystallization of bismaleimide to some extent, it is inferior in long-term thermal stability because it uses monomaleimide. Also, epoxy resin,
A composition with bismaleimide and mono- or polymaleimide has also been proposed (Japanese Unexamined Patent Publication No. 1983-79216), but this resin composition has somewhat improved heat resistance compared to an epoxy resin alone, but the improvement is still poor. The degree of

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid curable resin composition that does not crystallize during storage and can provide a cured product with excellent heat resistance.

[0006]

[Means for Solving the Problems] The liquid curable resin composition of the present invention contains the following components (A), (B), (C), (D) and (E). This is a composition that provides a heat-resistant cured product. Component (A): a polyepoxy compound having at least two epoxy groups in one molecule. Component (B): bismaleimide compound. (C) Component: Chemical formula

[0007]

A polymaleimide represented by the formula (wherein, X represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms). (D) Component: allyl group, allyl ester group in one molecule,
20℃ containing one or more polymerizable unsaturated groups selected from acrylic groups, methacrylic groups, and vinyl groups bonded to aromatic rings.
A liquid polymerizable unsaturated compound. Component (E): acid anhydride compound.

[0008] The above components (A) to (E) in the present invention
The blending ratio of the components is (A) component/{(B) component + (C) component} ratio in weight ratio of 0.5 to 10.0, (B) component/
(C) component ratio is 0.2 to 10.0, {(A) component + (B
)component+(C)component}/(D)component ratio is preferably 1 to 20, and (A)component/(E)component ratio is 0.5 to 10.0.

[0009] There are various types of polyepoxy compounds as component (A) in the present invention. for example,
Diglycidyl ether of bisphenol A (commercially available products include Epicote 825, 827, 828, and 834 from Yuka Ciel Epoxy Co., Ltd.), diglycidyl ether of bisphenol F, and brominated bisphenols. Diglycidyl ether of A, epoxidized phenol novolak, epoxidized cresol novolak, glycidyl ester compound obtained from phthalic acid or hexahydrophthalic acid, etc. and epichlorohydrin, and aromatic amine such as aminophenol or diaminodiphenylmethane and epichlorohydrin. The resulting epoxy resins include cycloaliphatic epoxy resins obtained from dicyclopentadiene and peracetic acid, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and the like.

Examples of the bismaleimide compound as component (B) in the present invention include N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-m-phenylene bismaleimide, N,
N'-p-phenylene bismaleimide, N,N'-(4
,4'-diphenylmethane) bismaleimide, N,N'
-(4,4'-diphenyl ether) bismaleimide,
N,N'-methylenebis(3-chloro-p-phenylene)bismaleimide, N,N'-(4,4'-diphenylsulfone)bismaleimide, N,N'-(4,4'-dicyclohexylmethane) Bismaleimide, N,N'-(
α,α′-4,4′-dimethylenecyclohexane) bismaleimide, N,N′-m-xylylenebismaleimide, N,N′-(4,4′-diphenylcyclohexane)
Bismaleimide, N,N'-(4,4'-diphenyl-
1,1-propane)bismaleimide, N,N'-(4,
4'-triphenyl-1,1,1-ethane)bismaleimide, N,N'-(4,4'-triphenylmethane)bismaleimide, N,N'-(3,5-triazole)-
1,2,4-bismaleimide, N,N'-(3,3'-
Examples include dimethyl-4,4'-diphenylmethane) bismaleimide and N,N'-(3,3'-diethyl-5,5'-dimethyl-4,4'-diphenylmethane) bismaleimide.

The polymaleimide represented by the general formula (1) as the component (C) in the present invention contains 2 aromatic amines represented by the following chemical formula (2) per mol of aromatic dialdehyde. It can be produced by reacting at a ratio of ~60 moles to obtain a polyamine, then adding maleic anhydride to this polyamine to obtain a polyamic acid, and cyclodehydrating the obtained polyamic acid (Japanese Patent Application Laid-Open No. 59-12931).

0012

[C3]

In the above chemical formula (2), X is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a C 1
-4 alkoxy group is shown.

The polymerizable unsaturated compound that is liquid at 20° C. as component (D) in the present invention includes the following (
Examples include compounds a) to (c).

(a) Allyl group-containing compound: Specific examples thereof include triallyl isocyanurate, diallyl phthalate, triallyl trimellitate, diallyl hexahydrophthalate, and the like.

(b) (meth)acrylate compounds: Specific examples include methyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, 1,4-
Butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, (meth)acryloxethyl succinate, trimethylolpropane tri(meth)acrylate, 2-hydroxy-3-tri Propyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisdiethylene glycol phthalate (meth)acrylate, bisphenol F di Oxydiethylene glycol di(meth)acrylate, bisphenol F dioxypropylene glycol di(meth)acrylate, bisphenol A dioxydiethylene glycol di(meth)acrylate, bisphenol F type epoxy di(meth)acrylate, bisphenol A type Epoxy di(meth)acrylate, 2-
Hydroxyethyl acryloyl phosphate, bis(2
-Hydroxyethyl acryloyl) phosphate, 2-
Polyester (meth)acrylate obtained by reacting hydroxyethyl acryloyl ethyl phosphate, dibasic acid or its anhydride, diol, and acrylic acid or methacrylic acid, reacting diisocyanates, diols, and acrylic acid or methacrylic acid. Examples include urethane (meth)acrylate obtained by In addition, "(meth)acrylate" described in this specification is a general term for acrylate and methacrylate.

(c) Aromatic vinyl compound: Specific examples thereof include styrene, α-methylstyrene, divinylbenzene, and vinyltoluene.

Examples of acid anhydride compounds as component (E) in the present invention include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bis(anhydrotrimellitic anhydride), tate), glycerol tris (anhydrotrimellitate), maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexanhydride hydrophthalic acid,
4-(4-methyl-3-pentenyl)tetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride,
Examples include dodecenyl succinic anhydride, maleated fatty acid anhydride, methylcyclohexenetetracarboxylic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, chlorendic anhydride, and tetrabromophthalic anhydride.

The curable resin composition of the present invention can have various resin physical properties by changing the blending ratio of component (A), component (B), component (C), component (D), and component (E). Can be adjusted. For example, when trying to obtain a cured product that particularly requires heat resistance, component (B) and (C)
Increase the proportion of the component and decrease the proportion of the component (D). Moreover, when it is desired to lower the resin viscosity, the amount of component (D) is increased and the amount of component (B) and component (C) is decreased. Moreover, when trying to obtain a cured product that requires adhesive properties, the proportion of component (A) is increased. Moreover, when it is desired to prevent crystallization of the resin composition, the proportion of component (C) is increased and the proportion of component (B) is decreased. Furthermore, component (E) acts as a curing agent for component (A), but in general, if the ratio of component (E) is too high, the heat resistance of the cured product will deteriorate, and conversely if it is too low, the heat resistance of the cured product will deteriorate. and the cured product becomes brittle.

[0020] In general, as described above, (A) to (
The blending ratio of each component in E) is (A) component/{
(B) component + (C) component} ratio is 0.5 to 10.0, (B
) component/(C) component ratio is 0.2 to 10.0, {(A) component + (B) component + (C) component}/(D) component ratio is 1 to 2
0, and the (A) component/(E) component ratio is 0.5 to 10.
It is preferable to satisfy each condition that the value becomes 0.

[0021] The resin composition of the present invention may contain (
A radical initiator can be added for the purpose of promoting polymerization of component B), component (C), and component (D). Examples of the radical initiator include peroxides such as benzoyl peroxide, diisopropyl peroxycarbonate, lauroyl peroxide, dicumyl peroxide, and t-butyl peroxypivalate, azoisobutyronitrile, 2,2'- Examples include azo compounds such as azobis(2-methylbutyronitrile).

Furthermore, a catalyst may be added to the resin composition of the present invention, if necessary, to promote the reaction between component (A) and component (E) as a curing agent. Examples of the catalyst include tri-n-butylamine,
Tertiary amines such as tris(dimethylaminomethyl)phenol, salts of these tertiary amines, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, triphenylphosphine, tri-n-butylphosphine Examples include phosphine derivatives such as phosphorine.

The resin composition of the present invention is prepared by heating and melting components (A), (B), (C), (D), and (E) to form a uniform composition. This is done by a mixing method.

The composition of the present invention can be easily cured by heating at an appropriate temperature, for example, 100 to 250° C. for 1 to 20 hours, resulting in a cured product with excellent heat resistance.

[0025]

[Examples] Hereinafter, the present invention will be explained in more detail by giving examples and comparative examples. As the polymaleimide compound as component (C) in the Examples, the following Polymaleimide A or Polymaleimide B manufactured by the method described in JP-A-59-12931 was used.

Polymaleimide A: Polymaleimide represented by the above chemical formula (1) obtained from 1,3-benzenedialdehyde, aniline and maleic anhydride.

002
7] Polymaleimide B: Polymaleimide represented by the above chemical formula (1) obtained from 1,4-benzenedialdehyde, aniline, o-toluidine and maleic anhydride.

Example 1 70 parts by weight of diglycidyl ether of bisphenol A (trade name Epicote 828, manufactured by Yuka Ciel Epoxy Co., Ltd.), 15 parts by weight of N,N'-(4,4'-diphenylmethane) bismaleimide, 15 parts by weight of Polymaleimide A, 30 parts by weight of trimethylolpropane trimethacrylate, and 56 parts by weight of methyltetrahydrophthalic anhydride (trade name HN-2200, manufactured by Hitachi Chemical Co., Ltd.) were added at a temperature of 10%.
The mixture was stirred and mixed at 0° C. for 20 minutes to form a homogeneous solution.

Next, the temperature was lowered to 80°C, and 0.15 parts by weight of dicumyl peroxide and 1 part by weight of 2-undecylimidazole (trade name C11Z, manufactured by Shikoku Kasei Co., Ltd.) were added, stirred, and mixed. Pour inside, 10
It was cured by heating at 0° C. for 3 hours and then at 200° C. for 5 hours to obtain a cured product measuring 127 mm long, 12.7 mm wide, and 6.4 mm thick. This resin composition and resin physical properties are shown in Table 1 below.
It was shown to.

Examples 2 to 6 Comparative Example 1 As shown in Tables 1 and 2 below, various polyepoxy compounds, bismaleimide compounds, polymaleimide compounds, polymerizable unsaturated compounds, and acid anhydride compounds were used, respectively. Other than that, various curable resin compositions were prepared in accordance with the method described in Example 1, and cured in the same manner. The resin composition and resin physical properties were as shown in Tables 1 and 2.

[0031]

[Table 1]

[0032]

[Table 2]

Notes to Tables 1 and 2: *1...Yuka Ciel Epoxy Co., Ltd. trade name, diglycidyl ether of bisphenol A*2...Yuka Ciel Epoxy Co., Ltd. trade name, bisphenol F Diglycidyl ether*3... N,N'-(4,4'-diphenylmethane) bismaleimide*4... N,N'-(3,3'-diethyl-5,5
'-dimethyl-4,4'-diphenylmethane)bismaleimide*5... 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane*6... Shin-Nakamura Chemical Industry Co., Ltd. product name , trimethylolpropane trimethacrylate*7... Nippon Kasei Co., Ltd. trade name, triallylisocyanurate*8... Neopentyl glycol dimethacrylate*9... Hitachi Chemical Co., Ltd. trade name, methyltetrahydrophthalic anhydride*10 ...Hexahydrophthalic anhydride*11...
Shikoku Kasei Co., Ltd. product name, 2-undecylimidazole *12... Shikoku Kasei Co., Ltd. product name, 2-ethyl-4-methyl-imidazole *13... Dicumyl peroxide *14...
According to ASTM-D-648 *15... In air, 1
Decomposition start temperature when temperature is increased at 0℃/min

[0034]

Effects of the Invention The resin composition of the present invention is liquid at room temperature, does not crystallize during storage, has excellent storage stability, and can provide a cured product with excellent heat resistance. It is excellent for insulating materials, etc.

Claims (2)

[Claims] [Claim 1] The following (A) component, (B) component, (C
), a liquid curable resin composition comprising a component (D) and a component (E). Component (A): a polyepoxy compound having at least two epoxy groups in one molecule. Component (B): bismaleimide compound. Component (C): A polymaleimide represented by the chemical formula [Formula 1] (wherein, X represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms). (D) Component: allyl group, allyl ester group in one molecule,
20℃ containing one or more polymerizable unsaturated groups selected from acrylic groups, methacrylic groups, and vinyl groups bonded to aromatic rings.
A liquid polymerizable unsaturated compound. Component (E): acid anhydride compound. Claim 2: The blending proportions of component (A), component (B), component (C), component (D) and component (E) are as follows:
(A) component/{(B) component + (C) component} ratio is 0.5~
10.0, the (B) component/(C) component ratio is 0.2 to 10.
0, {(A) component + (B) component + (C) component}/(D)
The component ratio is 1 to 20, and the (A) component/(E) component ratio is 0.
．． The liquid curable resin composition according to claim 1, which satisfies each condition of 5 to 10.0.