JPS59140218A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:The titled composition excellent in castability and capable of forming a cured product of good heat resistance, comprising a polyisocyanate, a specified aziridine compound and a polyepoxide. CONSTITUTION:0.05-10pts.wt. aziridine compound of formula I and/or formula II(wherein X is H or a lower alkyl, Y is H or hydroxyl, Z is H or an n-functional residue, and n is 1-6) is added to 100pts.wt. mixture containing 50- 95wt% polyisocyanate (e.g., tetramethylene 1,4-diisocyanate) and 50-5wt% polyepoxide (e.g., diglycidyl ether of bisphenol A). EFFECT:A resin composition having a pot life at room temperature of above 30hr can be obtained. This resin composition can provide a cured product which does not crack, foam, or soften when heated to about 250 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin composition which has excellent molding processability and the obtained cured product has good heat resistance.

Curing of a polyfunctional incyanate and a polyfunctional epoxide while forming an oxazolidone ring or an incyanurate ring by heating in the presence of a catalyst such as a tertiary amine or an alkali metal salt of a carboxylic acid. is well known. However, when conventional catalysts are used to complete the curing reaction, the real life of the blended resin composition is inevitably shortened, making injection molding extremely difficult. Furthermore, even at the cost of life, the curability is not sufficient, and when the cured product is exposed to high temperatures, defects such as softening, foaming, and cracking often occur. Such drawbacks tended to become more pronounced as the ratio of polyfunctional isocyanate to polyfunctional epoxide increased.

The present inventors have conducted intensive research and examination to find a thermosetting resin composition that does not have such conventional drawbacks, has excellent injection molding processability, and has good heat resistance in the resulting cured product. , which led to the present invention. That is, the thermosetting resin composition of the present invention is a resin composition containing a polyfunctional incyanate, an aziridine compound, and a polyfunctional epoxide as essential components, wherein the aziridine compound has the formula (wherein, X is H or a lower alkyl group, Y is H or a hydroxyl group, Z is H or an n-functional M group, n is a number from 1 to 6) and/or the formula (in the formula, X4H or a lower alkyl group) It is characterized by:

In the present invention, the polyfunctional incyanate includes aliphatic, alicyclic, aromatic-substituted aliphatic, aromatic, or heterocyclic polyfunctional incyanates, such as tetramethylene-1,4-diisocyanate. , hexamethylene-1
6-diisocyanate, octamethylene-1,8-diisocyanate, dodecamethylene-1,12-diisocyanate, 2.2.4 or 2.4.4-trimethylhexamethylene-1,6-diincyanate, 1-incyanato-3, 3,5-trimethyl-5-incyanatomethylcyclohexane, cis- or trans-cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-diincyanate, 1-methylcyclohexane-2,4- or -2, 6-diisocyanate, ω, ω'-diisocyanatomethyl-1.4-
or -1,3-cyclohexa7,3.10-diisocyanatotricyclo(5:2.1.0'',)decane,2
．． 2-bis[4-incyanatocyclohexyl)propane, 6,8-diisocyanatobicycloC3,3,0)octene, tolylene-2,4- or -2,6-diisocyanate, diphenylmethane-2,4'- or -4,
41-diisocyanate, naphthylene-1,5-diisocyanate, bitolylene diisocyanate, anisidine diisocyanate, diphenyl ether-4,4'-diisocyanate, m- or p-phenylene diisocyanate, lysine diisocyanate methyl ester,
N,N'-bis(ω-incyanatopropyl)oxadiazinetrione, xylylene-1,3- or -1,4
- diisocyanates, such as triphenylmethane-4,4',4"-triisocyanate,
Tri- or higher functional incyanates such as tris(4-incyanatophenyl)thiophosphate, undecane-1,6,10-) diisocyanate, diphenylmethane-3,3',4,4'-tetraisocyanate, aniline in formalin. A type of polyphenylpolymethylene polyisocyanate obtained by condensation with caraphosgenation,
Diphenylmethane diisocyanates that are liquid at room temperature and have a carbodiimide group or uretonimine group as described in German Patent No. 1092007, or urethane bonds, allophanate bonds, urea bonds, biuret bonds, oxazolidone bonds, incyanurate ring structures, uretidione ring structures Examples include the above-mentioned modified polyfunctional incyanates containing . These polyfunctional incyanates can be used alone or as a mixture of two or more. Furthermore, the incyanate masked with an active hydrogen compound such as phenol can also be used. Among the polyfunctional incyanates, diphenylmethane-based polyisocyanates are particularly useful.

The aziridine compound of the present invention has the formula (wherein, X is H or a lower alkyl group, Y is H or a hydroxyl group, Z
is a H or n-functional residue, n is a number from 1 to 6), for example, 2-(1-aziridinyl)ethyl methacrylate, 2-(1-aziridinyl)ethyl acrylate, ω-aziridinyl Methyl rubupionate, ethylene glycol bis(ω-aziridinylpropionate), trimethylolpropane tris(ω-aziridinylpropionate), pentaerythritol tetra(ω-aziridinylpropionate),
Sorbitol hexa(ω-aziridinylpropionic acid ester), β-(2-methylaziridinyl)ethyl methacrylate, diethylene glycol bis[ω-(2-methylaziridinyl)furopionic acid ester), 1.3
．． '6-Hexanetriol tris [ω-(2-ethylaziridinyl) furopionate ester], diglycerin tetra[ω-(2-methylaziridinyl) propionate ester] and other compounds containing an ester bond; 1-(
2-hydroxyethyl)aziridine, 1-(2-hydroxyethyl)-2-methylaziridine, 1-(2-hydroxyethyl)-2-ethylaziridine, 1-(2-hydroxy-2-phenylethyl)aziridine, 1 −, (
Compounds containing hydroxyl groups, such as 2-hydroxy-2-phenylethyl)-2-methylaziridine, 1-(
Compounds containing nitrile groups such as 2-cyanoethyl)aziridine, 1-(2-cyanoethyl)-2-methylaziridine, 1-(2-cyanoethyl)-2-ethylaziridine, ω-aziridinylpropionic acid, ω- Compounds containing a carboxyl group such as (2-methylaziridinyl)propionic acid, ω-aziridinylpropionic acid amide,
Compounds containing an amide group such as ω-(2-ethylaziridinyl)propionic acid amide, ether bonds such as 1-(β-methoxyethyl)aziridine, i-(β-methoxyethyl)-2-ethylaziridine A compound containing 1
-ethylaziridine, 1-(β-phenylethyl)-2
-Methylaziridine, phenethyl-1-aziridine, β
-Compounds such as aziridinylpropionitrile.

Also, triethylene melamine derivatives represented by the formula % formula % (wherein X is H or a lower alkyl group) which are aziridine compounds, such as triethylene melamine, tris(2-methylethylene) melamine, tris(2-methylethylene) melamine, -ethylethylene) melamine, etc.

The above aziridine compounds can be used alone or as a mixture of two or more.

Examples of the polyfunctional epoxide in the present invention include diglycidyl ether of bisphenol A, butadiene gepoxide, 3,4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexane carboxylate, vinylcyclohexene dioxide, .4'
-di(1,2-epoxyethyl)diphenyl ether,
4.4'-di(1,2-epoxyethyl)biphenyl,
2.2-bis(3,4-epoxycyclohexyl) furonokun, resorcin diglycidyl ether, phloroglucin diglycidyl ether, methylphloroglucin diglycidyl ether, bis(2,3-epoxycyclopentyl) ether-2 -(3,4-epoxy)cyclohexane-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, bis-(3,4-epoxy-6-methylcyclohexyl)adipate, N, If
-m-phinidine bis(bifunctional epoxide such as 4,5-epoxy-1,2-cyclohexanedicarboximide, triglycidyl ether of paraaminophenol, polyallyl glycidyl ether, 1.3.5-h (1,2-epoxyethyl)benzene, 2.2',4
．． Trifunctional or higher functional epoxides such as 4'-tetraglycidoxybenzophenone, tetraglycidoxytetraphenylethane, polyglycidyl ether of phenol formaldehyde novolak, triclycidyl ether of glycerin, triglycidyl ether of trimethylolpropane are used. . The above-mentioned polyfunctional epoxide is used as one type or a mixture of two or more types. The blending ratio of the above-mentioned polyfunctional incyanate, aziridine compound, and polyfunctional epoxide is preferably within the following range. . First, the mixing ratio of polyfunctional incyanate and polyfunctional epoxide is 50
The latter is preferably 50-5% by weight compared to ~95% by weight.

If the proportion of polyfunctional incyanate is less than the above-mentioned lower limit, the mechanical properties of the cured product at high temperatures will tend to deteriorate, while if it is greater than the upper limit, the curing reaction will be difficult to complete.

The aziridine compound is preferably 0.05 to 10 parts by weight, more preferably 0.01 to 10 parts by weight, based on ioo parts by weight of the mixture of polyfunctional incyanate and polyfunctional epoxide as described above.
It is desirable to add 5 parts by weight. Note that this amount is 0.0
If it is less than 5% by weight, the curing reaction will be difficult to complete, and if it exceeds 10% by weight, the mechanical properties of the cured product at high temperatures will tend to deteriorate.

Even if the resin composition of the present invention has a pot life of 30 minutes or more at room temperature, the cured product obtained by heat curing shows no cracking, foaming, or softening even when heated to 250°C. do not have. As a conventional resin composition, for example, one consisting of a polyfunctional isocyanate, a polyfunctional epoxide, and a tertiary amine exhibits a pot life of 30 minutes or more at room temperature. When objects are heated to 250°C, defects such as cracks, foaming, or softening occur.

The thermosetting resin composition of the present invention may contain a filler, a mold release agent, a pigment, a flexibility imparting agent, a deterioration inhibitor, a flame retardant, or other additives as necessary. can.

The thermosetting resin composition of the present invention has excellent injection processability, and the cured product has excellent heat resistance, so it can be molded by casting, impregnating, coating, or 21M molding, and can be used for various applications. It can be useful in the field. Examples of applications include the main shell of televisions, VTRs, or audio equipment, electrical components such as switch covers, printed circuit boards, lamp covers, and household items such as frying pan handles, iron handles, and oven plates. , automobile parts such as engine compartment partition walls, lamp covers, structural members around heaters, structural materials for sliding parts, resin molds, etc., and are extremely important and useful.

Next, the present invention will be explained in more detail with reference to Examples.

In addition, each part in Examples and Comparative Examples is a part by weight.

Examples 1 to 4, Comparative Examples 1 to 8 20 parts of Epon 828 (diglycidyl ether of bisphenol A manufactured by Shell Chemical Co., Ltd.) and liquid MDI (diphenylmethane-4,4'-diisocyanate liquefied at room temperature by carbodiimidization) , NGO included, !28.
7% (hereinafter the same shall apply) were mixed well, 1 part of an aziridine compound was added thereto, and the gelation time at 50°C was measured. For comparison, the gelation time at room temperature of a conventionally used curing catalyst was also measured. at the same time,
The blended composition was poured into a mold preheated to 50°C, and 1
Heat at 40°C for 30 minutes to harden and remove from the mold, giving 180"0
After X4H, a test piece for measuring heat distortion temperature was prepared by applying a keyer. The heat distortion temperature of this test piece was measured based on JIS K7207, and at the same time, changes in the appearance of the test piece were examined. These results are shown in Table 1.

Margin table below 1 1) Trimethylolpropane tris (ω-azirinylp-bioheptadate ester) Nippon Shokubai Chemical Co., Ltd. product.

2) N,N,N”-)lis(dimethylamylablevir)hexahydro-8-)su7dine, a product of San Abbott.

3) A combination system of N,Nco,N”-)lith(dimethylaminobrobylnohexahydride a-6-)riazine and an alkali metal carboxylic acid salt, a product of Sun Abbott.

4) 2-ethyl-4-methylimidazole, a product of Shikoku Kasei Kogyo.

5) 1-(β-anoethyl)-2-ethyl-4-methylimidazole, a product of Shikoku Kasei Kogyo.

Examples 5-10. and Comparative Examples 9 to 13 Epon 828 and liquid IViDI and PAZ as an aziridine compound.
The gelation time, heat distortion temperature, and appearance of the test piece after measuring the heat distortion temperature were investigated in the same manner as in Example 1 for the formulations listed in Table 2 using Same as Example 1). For comparison, similar tests were conducted on formulations of Epon 828 and liquid MDI and N-methylmorboline as the conventional curing catalyst. These results are shown in Table 2.

Below margin

Claims (1)

[Scope of Claims] A thermosetting resin composition containing a polyfunctional incyanate, an aziridine compound, and a polyfunctional epoxide as essential acids, wherein the aziridine compound has the formula (wherein, X is H or lower alkyl group, Y is H or a hydroxyl group, Z is H or an n-functional residue, n is a number from 1 to 6) and/or the formula (wherein X is H or a lower alkyl group) A thermosetting resin composition.