JPH058212B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of Application of the Invention] The present invention relates to a resin composition having good storage stability and containing a polyfunctional epoxide and a polyfunctional isocyanate as curing components. [Background of the Invention] A composition containing a polyfunctional epoxide and a polyfunctional isocyanate as curable components has been disclosed in Japanese Patent Publication No. 1973-
As described in No. 31000, by adding a heterocycle-forming catalyst and heating, isocyanurate rings and oxazolidone rings are formed, resulting in a cured product with excellent properties. This composition is a resin with excellent mechanical strength and thermal stability of dielectric properties at high temperatures, and is therefore widely used as an impregnation casting or molding material. However, solvent-free varnishes (hereinafter simply referred to as varnishes) containing polyfunctional epoxides and polyfunctional isocyanates as curing components contain a heterocycle-forming catalyst as a curing catalyst, so the curing reaction occurs even at room temperature, and the pot life is long. is as short as about 1 day. In addition, the varnish polymerizes more rapidly in a heated state, and gels in several hours at 50°C. Such properties can be obtained by storing multiple layers of the varnish in a tank and repeatedly using it for impregnation, especially under heating, or by heating the varnish to lower its viscosity and uniformly dispersing silica, alumina, glass powder, etc. This has been a major obstacle in methods such as casting. The present inventors further studied the storage stability of a resin containing a polyfunctional epoxide and a polyfunctional isocyanate as curing components, and as a result, completed the present invention. [Object of the Invention] An object of the present invention is to provide a polyfunctional epoxide-polyfunctional isocyanate resin composition that has storage stability and heating stability, and can ensure a long pot life. [Summary of the Invention] The present invention comprises (A) a polyfunctional epoxide, (B) a polyfunctional isocyanate, (C) a heterocycle-forming catalyst, and (D) an organic acid, and at least one member selected from Va and Va groups of the periodic table. A resin composition characterized by containing a salt of a transition metal. In the present invention, examples of polyfunctional epoxides include diglycidyl ether of bisphenol A, butadiene diepoxide, 3,4-epoxycyclohexylmethyl-(3,4-epoxyethyl)cyclohexane carboxylate, vinylcyclohexene dioxide, 4,4 ′-di(1,
2-epoxyethyl)diphenyl ether, 4,
4'-(1,2-epoxyl)biphenyl, 2,2
- bis(3,4-epoxycyclohexyl)propane, diglycidyl ether of resorcinol, diglycidyl ether of phloroglucin, diglycidyl ether of methylphloroglucin, bis(2,3-epoxycyclopentyl) ether,
2-(3,4-epoxy)cyclohexane-5,
5-spiro(3,4-epoxy)-cisulohexane-m-dioxane, bis-(3,4-epoxyl-6-methylcyclohexyl)adipate,
N,N'-m-phenylenebis(4,5-epoxy-1,2-cyclohexanedicarboximide and other difunctional epoxides, para-aminophenol triglycidyl ether, polyallyl glycidyl ether, 1,3,5-tri( 1,2-epoxyethyl)benzene, 2,2',4,4'-tetraglycidoxybenzophenone, tetraglycidoxytetraphenylethane, polyglycidyl ether of phenol formaldehyde novolak,
3 such as triglycidyl ether of glycerin and triglycidyl ether of trimethylolpropane.
A more than functional epoxide is used. Among the polyfunctional epoxides mentioned above, polyglycidyl ethers of phenol formaldehyde novolak are particularly useful. Examples of polyfunctional isocyanates include methane diisocyanate, butane-1,1-isocyanate, ethane-1,2-diisocyanate, butane-1,2-diisocyanate, transvinylene diisocyanate, propane-1,3-diisocyanate, and butane-1,3-diisocyanate. -1,4-diisocyanate, 2
-Butene-1,4-diisocyanate, 2-methylbutane-1,4-diisocyanate, Pentane-1,5-diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, Hexane-1,6-diisocyanate, Heptane- 1,7
-diisocyanate, octane-1,8-diisocyanate, nonane-1,9-diisocyanate, decane-1,10-diisocyanate, dimethylsilane diisocyanate, diphenylsilane diisocyanate, ω, ω'-1,3-dimethylbenzenediisocyanate, ω , ω'-1,4-dimethylbenzene diisoanate, ω, ω'-1,
3-dimethylcyclohexane diisoanate,
ω, ω'-1,4-dimethylcyclohexane diisocyanate, ω, ω'-1,4-dimethylbenzene diisocyanate, ω, ω'-1,4-dimethylnaphthalene diisocyanate, ω-ω'-1,
5-dimethylnaphthalene diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate,
1,3-phenylene diisocyanate, 1,4-
Phenyl diisocyanate, 1-methylbenzene, 2,4-diisocyanate, 1-methylbenzene-2,5-diisocyanate, 1-methylbenzene-2,6-diisocyanate, 1-methylbenzene-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, 2,3'-
Dimethoxybiphenyl-4,4'-diisocyanate, diphenylmethane, 4,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-4,
Difunctional isocyanates such as 4'-diisocyanate, 4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate, diphenylsulfide-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate , polymethylene polyphenyl isocyanate, triphenylmethane triisocyanate, tris(4-phenyl isocyanate thiophosphate), 3,3',4,
A trifunctional or higher functional isocyanate such as 4'-diphenylmethanetetrisocyanate is used. Also usable are dimers and trimers of these isocyanates, or liquid isocyanates obtained by converting a portion of 4,4'-diphenylmethane diisocyanate into carbodiimide. The above-mentioned epoxides and isocyanates can be used alone or in combination of two or more. Preferably, 1.5% of the polyfunctional isocyanate is used per equivalent of the polyfunctional epoxide.
It is preferable to mix up to 5 equivalents. Examples of the heterocycle-forming catalyst in the present invention include tertiary amine compounds, N-substituted morpholine compounds, and imidazole compounds, and one or more of these can be used in combination. Tertiary amine compounds used as heterocycle-forming catalysts include trimethylamine, triethylamine, tetramethylbutanediamine, tetramethylpentanediamine, triethylenediamine, dimethylaminoethanol, dimethylaminopentanol, and triethanolamine. In addition, N-substituted morpholine includes N-methylmorpholine, N-ethylmorpholine, N-dodecylmorpholine, cyanoethylmorpholine, hexamethylenedimorpholine,
Examples include cyanoethylmorpholine and triazinoethylmorpholine. Furthermore, imidazole compounds include 2-methylimidazole, 2-ethylimidazole, 2-andecylimidazole, 2-
Heptadecylimidazole, 2-methyl-4-ethylimidazole, 1-butylimidazole, 1
-Propyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-andecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-azine- 2
-methylimidazole, 1-azine-2-methylimidazole, 1-azine-2-andecylimidazole, and the like. Among the above catalysts, it is particularly effective to use N-substituted morpholine compounds and imidazole derivatives as heterocycle-forming catalysts. At least one of the above catalysts can be used in an amount of 0.01 to 10% by weight based on the mixture of polyfunctional epoxide and polyfunctional isocyanate. Even more preferred amounts are in the range of 0.05 to 2% by weight. The salt of the present invention between an organic acid and at least one transition metal selected from group a and Va of the periodic table is a salt of titanium, zirconium, vanadium, etc. and an organic carboxylic acid, preferably fatty acid, resin acid, naphthenic acid, and especially It is a salt of octanoic acid and naphthenic acid. Among these, zirconium salts, vanadium salts, and titanium salts such as zirconium octoate, zirconium naphthenate, vanadium octoate, titanium octoate, and titanium naphthenate are particularly preferred. These transition metal salts are suitable for mixtures of polyfunctional epoxides and polyfunctional isocyanates.
It can be used in a range of 0.005 to 10% by weight.
Still more preferably the amount used is 0.01 to 2% by weight. Further, the heterocycle-forming catalyst and the transition metal salt can be added in advance in the form of an adduct instead of being added separately to the mixture of the polyfunctional epoxide and the polyfunctional isocyanate. Furthermore, known additives, fillers, pigments, storage stabilizers, or solvents may be added as necessary. [Examples of the Invention] Next, the present invention will be explained with reference to Examples. The polyfunctional epoxide, polyfunctional isocyanate, and heterocycle-forming catalyst used in the examples are as follows. DER332: Bisphenol A diglycidyl ether manufactured by Dow Chemical Company, USA. Equivalent weight: 174 DEN431: Novolak polyglycidyl ether manufactured by Dow. Equivalent weight 172 MDI: 4,4'-diphenylmethane diisocyanate. Equivalent weight: 125 Liquid MDI: MDI that is partially carbodiimidated and is liquid at room temperature. Equivalent weight approx. 1 40 TDI: Tolylene diisocyanate. A mixture consisting of 80% 2,4-isomer and 20% 2,6-isomer.
Equivalent weight 87 2PZ: 2-phenylimidazole Examples 1 to 14 Polyfunctional epoxide, polyfunctional isocyanate,
Heterocycle-forming catalysts and transition metal salts were blended in combinations and ratios as shown in Table 1. The gelation time G (min) of the obtained composition at 150°C is GE
The values shown in Table 1 were obtained by measuring with a formula gel timer. In addition, the obtained composition was stored at 30 °C, and 30 °C
Elapsed time until the viscosity reaches 10 times the initial value
(h) was determined, and the values shown in Table 1 were obtained as Shelf Life L. Then, as a criterion for indicating potential, the shelf life L(h) was divided by the gelation time G(h), and the results are shown in the last column of Table 1. A composition that does not contain a transition metal salt is also added to the table as a comparative example for comparison. In addition, in Example 4, 0.5 mol of zirconium octylate and 4.0 mol of 2PZ were added to 500 ml of methanol.
After refluxing on a water bath for 8 hours, methanol was distilled off and the adduct was dried under reduced pressure and used. It is observed that the composition of the present invention has 6 times more potential than the comparative example. Particularly effective is the use of transition metal salts such as zirconium and titanium. Further, from a comparison of Examples 4 and 5, it is recognized that the effect is the same whether the isocyanurate/oxadoridone forming catalyst is added separately or added as an adduct in advance. The compositions of Examples 4 and 5 and Comparative Example 1 shown in Table 1 were changed to 110°C/5 hours + 150°C/10 hours + 220°C/
A cured product was obtained by heating for 10 hours. When we examined the infrared absorption spectrum of this cured product, we found that the absorption at a wave number of 2250 cm ^-1 by the NCO group and the absorption at a wave number of 910 cm ^-1 by the epoxy group, both of which were present in the spectrum of the composition before curing, decreased. The absorption based on the carbonyl group of the isocionurate ring and the oxazolidone ring has a wavenumber of
It was observed at 1710 and 1750 cm ^-1 . This shows that the Examples and Comparative Examples are the same cured products. Further, the cured product exhibited mechanical properties, electrical properties, and thermal deterioration properties as shown in Table 2. The properties of the examples are equivalent to those of the comparative examples that do not contain transition metal salts.

【table】

【table】

〔Effect of the invention〕

As described above, according to the present invention, a resin composition containing a polyfunctional epoxide and a polyfunctional isocyanate as curable components, a heterocycle-forming catalyst and at least one organic acid of a transition metal selected from groups A and Va of the periodic table. By adding salt, the pot life is extended without affecting the mechanical properties, electrical properties, and thermal deterioration properties of the resin composition, and shelf life, that is, storage stability, as well as latency and heating stability are improved. can be improved.

Claims (1)

[Claims] 1 (A) polyfunctional epoxide, (B) polyfunctional isocyanate, (C) heterocycle-forming catalyst, (D) organic acid, and at least one transition metal selected from Va and Va groups of the periodic table. A resin composition characterized by containing a salt of. 2. In claim 1, the heterocycle-forming catalyst is 0.01 to 10% by weight based on the total amount of the polyfunctional epoxide and the polyfunctional isocyanate.
A resin composition characterized by: 3. In claim 1, the salt of the organic acid and at least one transition metal selected from the periodic laws a and Va is 0.005 to 10 based on the total amount of the polyfunctional epoxide and the polyfunctional isocyanate.
% by weight. 4. The resin composition according to claim 1, wherein the heterocycle-forming catalyst and the transition metal salt are adducts of the heterocycle-forming catalyst and the transition metal salt.