JPS58167612A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:The titled novel composition having quickly setting properties at high temperature, curable into a resin having improved heat resistance, containing a polyfunctional isocyanate compound, a polyfunctional epoxy compound and a cyanamide compound of a secondary amine-s-triazine. CONSTITUTION:A polyfunctional isocyanate compound (e.g., methane diisocyanate, etc.) and a polyfunctional epoxy compound (e.g., glycidyl ether of bisphenol A, etc.) are blended with 0.1-10pts.wt. cyanamide compound (e.g., 2-m- amino-anilino-4-N-cyano-p-toluidino-6-N-morpholino-s-triazine) of a secondary amine-s-triazine shown by the formula (T is s-triazinyl group) as a catalyst to form a hetero ring based on 100pts.wt. polyfunctional epoxy compound, and, if necessary, an inorganic filler, a flame-retardant, a solvent, etc., to give the desired thermosetting resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel resin composition that exhibits rapid curing properties at high temperatures of 1000° C. or higher and is capable of curing into a resin with excellent heat resistance.

In recent years, electrical equipment has become smaller and lighter, which has led to higher operating temperatures, and electronic components have become more reliable. There is a strong need for the development of organic insulating materials that have strength and excellent spinning properties.

At the same time, these materials are required to have rapid curing properties at high temperatures and good moldability.

Conventionally, epoxy resins, silicone resins, etc. have been mainly used for these purposes. The former has good workability and moldability, but the insulating material is heat resistant Z-minute H class (use temperature limit 180C)
It cannot be used for a long period of time under considerably higher conditions, and although the latter is a Hf1+ material, it has low strength and adhesiveness at product temperature and high moisture permeability.

In addition, there are heat-resistant materials of Class H or higher such as diphenyl ether resins and polyimide resins, but they contain bath agents and are polycondensation reaction type, which generate volatile byproducts during the curing process, and require a long time to cure, resulting in poor moldability. All the difficulties such as being
Application as a solvent-free festival or molding material is restricted.

In addition, highly thermoplastic resins having isiso-r-nurate compounds and oxazolidone rings are known by polyaddition reactions of polyfunctional incyanate compounds and polyfunctional epoxy compounds. As a catalyst for producing this -\terocycle, amine compounds, calibol salts, etc. have been mainly used. However, these methods were insufficient to provide faster curing properties than those of conventional methods, and in order to satisfy the desired properties, it was necessary to remove the cured product after molding.

In view of the above-mentioned circumstances, the present invention is a resin composition that has fast curing properties at high temperatures, has good moldability and can be converted into a cured product with excellent heat resistance by heating. The purpose is to provide all things.

The main point is that polyfunctional a-order iso7r nate compound (A),
A polyfunctional epoxy compound (B) and a 2-m-7 minol 4-N-cyano-
P-1 Luidino-6-N-morpholino-8-)srdi/
(C) H3CC6H4Ci' ]S-1 -r Dinyl group is a thermosetting resin composition characterized by having all essential components.

In the present invention, the compound (A), such as the blending ratio of the polyfunctional incyanate compound (A) and the polyfunctional epoxy compound (B)
The ratio of the number of moles per isocyanate group (number of moles per epoxy group of compound (B) (hereinafter abbreviated as E/E ratio)) is in the range of 05 to 30.

It is especially good to use one history in a circle.

In the present invention, polyfunctional incyanate compounds include methane diisocyanate, phthano 1.1 diisocyanate, ethane-1,2-diisocyanate, butane-1
, 2-diisocyanate, transvinylene diisodir
nate, propane-1,3 diisozonate, buta 71
1.4-diisocyanate, 2-butene-1,4-diisocyanate, 2-methylbutane-1,4-diisocyte, pentane-1,5-diiso/r-nate,
\xane-1,6-diitunrnate, \butane-1
,7-diisocyanate, octane-1,8-diisocyanate, nonane-1,9-diisocyanate, decane-1,10-diisocyanate, dimethylsilane diisocyanate, diphenylsilane diisocyanate,
ω, ω'-t, a-dimethylbenzenedison °r4-
) ω, ω'-1,4-dimethylbenzene diisocyanate, ω, ω'-1,3-dimethylcyclo\xane diisocyanate, ω, ω'-1,4-dimethylcyclo-\
Xane diisocyanate, ω, ω'-1.4-dimethylbenzene diisocyanate, ω, ω'-1.4-dimethylnaphthalene diisocyanate, ω, ω'-1.5-
Dimethylnaphthalene diisosonate, cyclo\xane-1,3-diisocyanate, cyclo\xane-1,4-diisocyanate, dicyclo\xylmethane-4,4'-diisocyanate), 1.3- phenylene diisocyanate 1゜4 phenylene diisocyanate
ate, 1-methylbenzene-2,4-diisocyanate, 1-methylbenzene-2,5-diisocyanate,
1-methylbenzene-2,6-diisocyanate, ]-
Methyl A/Hairbin-3,5 diisocyanate, diphenyl ether-4,4'-diisocyanate, diphenyl ether-2,4'-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5
-diisocyanate, biphenyl-4,4'-diisocyanate, 3,3'-dimethylbiphenyl 4,4'-
Diisocyanate, 2゜37-cymethoxybiphenyl-4.4'-diisocyanate, diphenylmethane-4,
4'-diisocyr4-1.3.3'-dimethoxydiphenylmethane-4,47-diisocyanate, 4.4'-
Dimethoxydiphenylmethane-3,3'-diiso7-r
Difunctional incyanate compounds such as ester, diphenylsulfide-4,47-diisocyanate, diphenylsulfone-4.4' diisocyanate, polymethylenepolyphenylisocyanate, triphenylmethanetrisinate, etc. Isodynate, tris(4-phenylisocyanate thiophonufate), 3.3', 4.
Trifunctional or higher functional isocyanate compounds such as 4'-diphenylmethane tetraisocyanate are used. In addition, 2-unit and 3-unit bodies of these incyanate compounds can also be used.

Next, in the present invention, polyfunctional epoxy compounds include glycidyl ether of bisphenol A, butadiene diepoxyside, 3,4-epoxycyclo-\xylmethyl-(3,4-epoxy)cyclo\xanecarboxylate, vinylcyclo -\xane dioxide, 4.4'-di(1°2-epoxyethyl)diphenyl ether, 4°4'=(1,2-epoxyethyl)biphenyl, 2.2-bis(3,4-epoxycyclo. \xyl)propane, glycidyl ether of resorcinol, diglycidyl ether of fluorocurnon, diglycidyl ether of methylphloroglucin, his-(2,3-epoxy 7 clobentyl) ether, 2-(3,4-epoxy)cyclohexane-5゜5-spiro(nee 1,4-epoxy)-7chloro\xane-m-dioxane, bis-
(3,4-epoxy-6-methylcyclo\xyl)r
dibate, N-N/m-phenylenebis(4,5-
Bifunctional epoxy compounds such as epoxy-1,2-cyclo-\xanedicarpoxyimide, triglycidyl ether of para-phenol, polyallyl glycidyl ether, 1.3.5-1 (1) ,2-epoxyethyl)benzene, 2.2',4.4'-tetraglycidoxybenzophenone, tetradalisidoxytetraphenylethane, polyglycidyl ether of phenol formaldehyde novolak, triglycidyl ether of glycerin, trimethylolpropane An epoxy compound having three or more functional groups such as triglycidyl ether is used.

In addition, the second 'l' mint vr represented by the general formula (C) shown as the -\teromonkey production catalyst mentioned above.
Examples of dir-toluidino compounds include 2-m-toluidino°γnilino-4-N-zir-p-toluidino-6-+
・N-morpholino-s-tri°rdine, 2-N-cyano°rnilino-4-N-imidazolyl-6
-mercapto-8-4-mercapto, 2-N-methylamino-4,6-hydroxy-8-)mercapto, 2-N-mercapto-8-mercapto Anilino-6-phenyl-8-)sr-zine, 2-N-', "r-methyl7minor-4-(2',4'-dihydroxyphenyl)-6-phenyl-8-tri"r-sine, etc. , In the present invention, in particular, 2-m-7 minnow °rnilino-4-
N-S'rNoP-)ru(Sino6-N-morpholino-)
8-) SuT gin is effective.

The catalyst may be added in an amount of 0.1 to 10 parts per 100 parts of the polyfunctional epoxy compound. If the amount is less than 0.1 part by weight, the curing will be insufficient or it will take an extremely long time to cure, and if the amount is more than 10 parts by weight, the storage stability of the material will simply be lost. However, there is a risk of deterioration of the cured product.

In addition, the composition of the present invention may include, depending on various uses and purposes,
1ai or more of the following various materials may be used in combination (9).

In other words, considering its use as a molding material,
Zircon, silica, fused silica glass, clay, alumina hydroxide, calcium carbonate, quartz glass, glass, irrbestos, whisker, gypsum, magne, site, mica,
Kaolin, talc, graphite, cement, carbonyl
Inorganic fillers such as iron, barium, ferrite, lead compounds, molyfden disulfide, zinc white, titanium white, carbon black, silica sand, and wollastonite; mold release agents such as fatty acids and waxes; epoxy silane, vinyl silane, and borane. Coupling agents such as R-based compounds and r-rukoxy titanate-based compounds can be used. Also, if necessary, a known flame retardant material or flexible material made from nitrogen, phosphorus, etc. can be used.

Furthermore, so-called solvents can be used for applications such as varnishes. For example, organic polar solvents include N-methyl-2-pyrrolidone, N-N-dimethyl-sedromide, N-N-dimethylformmide, N-N-diethylformide, N-
-Methylform'rmi(10), dimethyl sulfoxide, N,N-diethyl 7-esteramide, N,N-dimethylmethoxyr-7-esteramide, \
Examples include hexamethylphosphoramide, hyridine, dimethylsulfone, tetramethylsulfone, dimethyltetramethylene sulfone, and phenolic solvents include phenol, cresol, xylenol, and the like.

The above buildings may be used alone or in combination of two or more buildings.

°If the amount is still small, toluene, xylene,
A non-solvent such as petroleum naphtha can be used in combination.

Examples 1 to 4 As a polyfunctional isodynate compound, 4,4'-diphenylmethane diisocyanate (hereinafter referred to as MDI)
79 parts by weight, as a polyfunctional hiepoxy compound, novolak type epoxy resin ECN1273 (epoxy equivalent weight 225 manufactured by Chipa), 100 parts by weight, 2nd rmin-8-tri°r
As a dir-namide compound of gin, 2-m-'7 minnowy
Nilino 4-N-C (11) γNo P-1 Luigi No 6-N Molpoline S-Tri°
0.1 parts by weight of r resin, 05 parts by weight, 1.01 parts by weight,
Four types of blended compositions were prepared by separately blending 3.0 parts by weight.

To these, as a mold release agent, \Kistwax E (manufactured by \Kist Japan Co., Ltd.) double layer, as a coupling agent, epoxy silane KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) 21 Sababe, as a filler, 1 part by weight of carbon flake was added.

Next, the above blended composition was roll kneaded for 7 to 10 minutes using two rolls of 60 to 70 C, and then cooled to obtain the desired resin composition.

Table 1 shows the heat resistance of the above four types of compositions (measured with a hardness A935 hardness meter immediately after molding at 170C, 3 minutes and 70 to 9/- conditions).

(12) Table 1 *)1 Heat resistance RI225C, bending strength retention rate after 30 days of storage (%) (13)

Claims (1)

[Scope of Claims] 1. Essential for the polyfunctional isocyanate compound (A), the polyfunctional epoxy compound (B), and the resin cylinamide compound (C) A thermosetting resin composition as a component. 2. In claim 1, a polyfunctional isolator
nate compound LP/I (A), polyfunctional epoxy compound (B), and 2-m-7 minnow'r=Lino 4-N-
1. A thermosetting resin composition containing as an essential component silino-6-N-morpholino-s-to-v'rgin (C).