JPS5856565B2 - thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin composition that can be converted into a cured product with excellent heat resistance.

BACKGROUND ART In recent years, with the increase in capacity, high reliability, and miniaturization of electric machines and electronic devices, insulating materials with excellent heat resistance are required.

In order to meet this use, cured products of imides and aromatic diamines derived from diamines and unsaturated dicarboxylic acid anhydrides have been proposed.

However, in such a system, the components cannot be mixed substantially uniformly unless a solvent is used.

In other words, high temperature (over 100°C) is required for uniform melting without solvent.
At such temperatures, gelation occurs within a few minutes, and the viscosity of the molten liquid is high, making it difficult to use it as a casting or impregnating varnish.

The present invention solves these problems.

That is, the present invention provides an ester of acrylic acid and/or methacrylic acid of tris-(hydroxyalkyl)isocyanurate (8) aromatic polyamine, A divalent group represented by () or (where D and D are groups having an ethylenic carbon-carbon double bond, and D and D may be the same or different.

A is a divalent organic group. ) and/or a monoimide represented by the general formula () (where m is a group having an ethylenic carbon-carbon double bond and m is a divalent aromatic group). The present invention relates to a thermosetting resin composition.

Component (A) is obtained by a general esterification reaction of 2-(hydroxyethyl) isocyanurate or 2(hydroxypropyl) isocyanurate with acrylic acid or/and methacrylic acid, and contains an acrylic group and/or methacrylic acid. It is preferable that an average of 2 to 3 groups are bonded in one molecule.

In addition, as the aromatic polyamine of the component (8), for example, p-
Phenylene diamine, m-phenylene diamine, 4.4
'-diaminodiphenylmethane, ■.1bis(4-aminophenyl)ethane, 2.2-bis(4-aminophenyl)propane, 2-bis-(4-(4-aminophenoxy)-phenyl)propane, etc. .

In the above general formula (I), A is a divalent organic group, such as an alkylene group, a cyclic alkylene group, a divalent aromatic group (an optionally substituted phenylene group, an optionally substituted phenylene group, In addition, atoms such as oxygen, nitrogen, and sulfur, polycyclic aromatic groups that may be joined by alkylene groups, etc. It is a residue from which anhydride groups such as acids are removed.

As the bisimide represented by the general formula (I), N-N
'-ethylene-bis-maleimide, N-N'-hexamethylene-bis-maleimide, N-N'-metaphenylene-bis-maleimide, N-N'-paraphenylene-bis-maleimide, N-N'-4・4'-diphenylmethane-bis-maleimide, N-N'-4,4'-diphenylpropane-bis-maleimide, N-N'-4,4'-
Diphenyl ether-bismaleimide, N-N'-4.
41-diphenoxyphenylpropane-bis-maleimide, N-N'-4,4'-diphenylsulfone-bis-
Maleimide, N-N'-4, 4'-dicyclohexylmethane-bis-maleimide, N-N'-α, α'-4, 4
'-dimethylenecyclohexane-bis-maleimide, N
-N'-methaxylylene-bis-maleimide, N-N'
-diphenylcyclohexa-bis-maleimide, etc.

In addition, in the general formula (kawa), A' is a divalent aromatic group,
These include a phenylene group which may be substituted, a polycyclic aromatic group which may be substituted and connected by an atom such as oxygen, nitrogen, sulfur, or an alkylene group.

The middle of general formula (1) is the same as above and V.

As a monoimide represented by the general formula (river), N-(
2-aminoethyl)maleimide, N-(6-aminohexyl)maleimide, N-(3-aminophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(
4-(4-aminobenzyl)phenylcomaleimide, N
-44-(4-aminophenylpropyl)phenylcomaleimide, N-44-(4-aminophenoxy)phenylcomaleimide, N-(4-(4-aminophenylsulfonyl)phenylcomaleimide) and the like.

Among the compounds represented by general formula (1),
Bisimide represented by the general formula (III) (wherein the formula is a divalent aromatic group) is preferred.

Moreover, among the monoimides represented by the general formula (river), the monoimide represented by the general formula (IV) (wherein is a divalent aromatic group) is preferable.

In the compounds represented by general formulas (III) and (■), (provided that R and R' are hydrogen or a methyl group)
A group represented by the following formula or a group represented by the formula (where π and R/// are hydrogen or a methyl group) is preferable.

In addition, from the viewpoint of improving heat resistance, etc., the general formula (
It is preferable that the bisimide represented by 1) is used in an amount of 90% by weight or more.

In the present invention, the composition of the ingredients, ■, and ◎ is the double bond (a) of the ingredient and the component 0, and the amino group (b) of the ingredient (6) and the amino group of the ingredient (b), Ya) Ab) [equivalence ratio]. 0.5/1~2
．． It is preferable to blend them in a ratio of 0/1 since unreacted substances will not remain and the properties will not deteriorate.

In particular, (a)/(b) is preferably 0.871 to 1.2/1.

Furthermore, by adding 20 to 200 parts by weight of the active ingredient to 100 parts by weight of the total amount of ingredients (8) and 0, a composition with low viscosity and a long gel time, which is the object of the present invention, can be obtained.

In the present invention, addition of 100 to 11,000 pp of a radical polymerization inhibitor in addition to the three components 1, 2, and 0 prevents the homopolymerization of the 3 components, and is a preferred polymerization inhibitor in terms of gel time and physical properties of the cured product. General hydroquinone p-tert-butylcatechol, hydroquinone monomethyl ether α-naphthol, phenothiazine, etc. can be used.

** Although the curing conditions for the composition of the present invention are not particularly limited, the composition is cured by heating at 100° C. or higher, preferably 150° C. to 200° C. for several hours.

Alternatively, a photosensitizer such as a benzoyl compound or the like may be added to the composition of the present invention, and after precure by irradiation with ultraviolet rays, the composition may be cured by heating.

Applications of the composition of the present invention are not particularly limited, but the composition has a low melt viscosity, a long gel time, and a good heat resistance of the cured product, so it can be used for casting of electric machines, impregnation varnish, glass cloth, cotton cloth, etc. , it can be impregnated into a substrate such as paper and used in the production of laminates or laminate products.

Examples 1 to 3 and Comparative Examples 1 to 2 Acrylic ester of tris-(2-hydroxyethyl) isocyanurate [93% by weight of triester, 7% by weight of diester (hereinafter abbreviated as THE I CTA)
] and 4,41-diaminodiphenylmethane (hereinafter referred to as DA
(abbreviated as M), 2-bis[4-(4-aminophenoxy)phenyl]propane (hereinafter abbreviated as BAPP)
Table 1 shows the gel time at 100° C. and the viscosity immediately after melting of the mixture of bismaleimide of DAM and bismaleimide of BAPP.

Examples 4 to 6 Table 2 shows the compositions of bis**maleimides of THE-IC-TA, DAM, and BAPP and the properties of the cured products.

The present invention discloses tris(hydroxyalkyl)in cyanurate as a method for improving the high viscosity and short gel time during melting, which are disadvantages of compositions consisting of aromatic polyamines and bisimide compounds or monoimide compounds, that is, poor workability. esters of acrylic acid and/or methacrylic acid are blended into the above system, and as a result, it has become possible to apply it as a casting and impregnating varnish for electrical equipment.

Claims (1)

[Scope of Claims] IQ)'J Soot-hydroxyalkyl)-isocyanurates of acrylic acid and/or methacrylic acid esters] aromatic polyamines and 0 general formula (I) (provided that D and ethylenic carbon - A group having a carbon double bond, and the D jumps may be the same or different. A is a divalent organic group. A thermosetting resin composition containing a monoimide represented by the following formula (A' is a divalent aromatic group). 2. The thermosetting resin composition according to claim 1, wherein the carrier component is an ester of acrylic acid and/or methacrylic acid of tris-(2-hydroxyethyl)isocyanurate. 3rK: Bisimide whose J component is represented by general formula (III) (provided that is a divalent aromatic group) and/or general formula (IV) (provided that is a divalent aromatic group) The thermosetting resin composition according to claim 1 or 2, which is a monoimide represented by: 4 N' is (however, "movement" and "R" are hydrogen or methyl group)
The thermosetting resin composition according to claim 3, which is a divalent group represented by: