JPH01287126A - Thermosetting reactive resin composition and production of heat-resistant molded article - Google Patents

Abstract

PURPOSE:To obtain the title thermosetting resin composition providing heat- resistant molded articles useful as electrical insulating material, by combining a polyisocyanate component having a specific composition with a polyepoxy component and a thermally activating catalyst such as a complex of an organotin halide and an onium salt. CONSTITUTION:(A) A component comprising two or more di-hexafunctional polyisocyanate compounds of 90-10% based on isocyanate group ratio of an aromatic polyisocyanate and 10-90% aliphatic and/or alicyclic polyisocyanate is combined with (B) a component comprising di-hexafunctional polyepoxy compound and the equivalent ratio of isocyanate group and epoxide group of 1:2-2:1 and (C) a thermally activating catalyst such as complex of an organotin halide and hexamethylphosphoramide, complex of the organotin halide and an onium salt or complex of a stibonium salt and a zinc halide to give the aimed composition. The composition is reacted in a mold at room temperature - 150 deg.C to give a heat-resistant molded article.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is a reactive resin composition consisting of a polyisocyanate, a polyepoxide, and a catalyst, which is used to produce a relatively small amount of trimerized polyin cyanurate. The present invention relates to a method for producing a heat-resistant molded article made of polyoxazolidone containing.

゛ Prior Art Thermosetting resins are used as materials for casting, impregnation, lamination, and molding, as well as various electrical insulation materials, structural materials, coatings, and adhesives. In recent years, the conditions for using materials in each of these applications have tended to become stricter, and in particular, the heat resistance of materials has become an important characteristic.

Plastics formed by the reaction of polyisocyanates and polyepoxides exhibit excellent thermal properties.
It is being developed as a new heat-resistant resin material. By the way, resins obtained by the reaction of polyisocyanate and polyepoxy I - generally have good heat resistance, but it has been pointed out that they are hard, brittle, and have particularly low impact strength. The good heat resistance is due to the ring structure based on the oxazolidone group and isocyanurate-I group produced by this reaction, while the low impact resistance is due to the extremely highly crosslinked structure due to the trimerized incyanurate group. It is thought that this is to form. For these reasons, it is necessary to react polyepoxide and polyisocyanate to form polyoxazolidone that does not contain a relatively small amount of trimerized isocyanurate-1-L, which is a tough resin with good heat resistance and excellent impact resistance. It is judged that it can be obtained.

The cyclization reaction of oxasilicon is generally carried out without a catalyst at high temperature or in the presence of a catalyst. Typical catalysts for this reaction include tertiary amines (imidazole, hexamethylenetetramine), quaternary ammonium salts (tetraethylammonium iodide), Lewis acids and bases of lead, aluminum chloride and pyrrolidone, aluminum chloride and phosphoric acid. ester), lithium halide, or a complex of lithium halide and phosphoric acid (lithium bromide and triphthylphosphine oxyto), ammonium salts of alkylated esters or acidic esters of organic phosphonic acids or phosphoric acids, and the like are known.

Recently, Detection et al., “J, Org.

Chem,” p2177-2184.51 (12)1
986 and 'Chemistry Letters'
, 'pp, 1963-1966.1986. reported that complexes of organotin halides and Lewis bases or stibonium are effective as oxazolidonation catalysts.

In the case of a reaction between a monoeboxide and a monofunctional compound such as a monoisocyanate, an oxazolidone compound can be formed using these catalysts at high temperature for a long time. However, in the case of the reaction of polyepoxides with higher functionality and polyisocyanates, the reaction process becomes even more complex and difficult, and large amounts of undesirable by-products are formed. The main by-products are isocyanure-1-, which is formed by trimerization of incyane-1 and polyethers produced by homopolymerization of epoxides.

Among these, polyoxazolidones form materials with very high functionality and provide very highly cross-linked brittle polymers to prevent polyoxazolidone reactions. Catalysts commonly used in the production are not only effective for the oxazolidone formation reaction, but also serve as catalysts for the incyanurate formation reaction, and polyoxazolidones produced by known methods contain 30 mol% or more of incyanurate. Furthermore, it has been pointed out that in the reaction between isocyanate and epoxide, when the amount of epoxide increases, a strong exothermic reaction occurs, resulting in scorch in the molded article and thermal deterioration of the molded article.

For these reasons, it would be desirable to provide a process in which polyepoxides and polyisocyanates are reacted under mild conditions to form polio-6-xazol-1-hen containing only relatively small amounts of trimerized isocyanurates. There is.

SUMMARY OF THE INVENTION It is an object of the present invention to provide reactive resin compositions capable of reacting polyepoxides with polyisocyanates to produce high quality plastics having polyoxylidone groups, as well as to provide these compositions. It is an object of the present invention to provide a method for manufacturing a molded article to be used.

Means for Solving the Problems According to the present invention, the above object is achieved by (a) isocyanate group ratio of 90 to 10% aromatic polyisocyanate and 10 to 90% aliphatic polyisocyanate and/or
or (b) a polyepoxide component consisting of a mixture of at least two 2- to 6-functional polyisocyanate compounds with an alicyclic polyisocyanate; provided that the equivalent ratio of isocyanate groups to epoxide groups is 1.2 to 2:1.
and, furthermore, (C) at least one member selected from the group consisting of a complex of organic tin halide 1~ and hexamethylphosphoramide 1~, a complex of organic tin halide and oniuno salt, and a complex of stibonium salt and zinc halide. a thermally activated catalyst of (
A thermosetting reactive resin composition comprising components a) or (b); or, (a) an aromatic polyisocyanate with an isocyanate group ratio of 90 to 10% and 10 to 90%. aliphatic and/or
or at least 2 of 1 to 2 alicyclic polyisocyanates
(b) a polyepoxide component consisting of at least one type of 2- to 6-functional polyepoxide compound, provided that the equivalent ratio of isocyanate groups to epoxide groups is The ratio is 1.2 to 2:1 and is used as a thermally activated catalyst.

(C) One of the complex components of a complex of an organotin halide and hexamethylphosphoramide, a complex of an organotin halide and an onium salt, or a complex of a stibonium salt and a zinc halide is added to the polyisocyanate-1 component, and the other is The method of the present invention is achieved by using a thermosetting reactive resin composition present in a polyepoxide component, and in which the resin composition is reacted in a mold at a temperature of room temperature to 150°C to produce a molded article. This can be achieved by

This resin composition basically consists of polyepoxide, polyisocyanate, and a catalyst, and is characterized in that these resin compositions are heated and reacted under mild conditions for a relatively short period of time. In this method, the oxasoliton formation reaction is the main reaction and proceeds much faster than the trimerization reaction of polyisocyanates and the homopolymerization of polyepoxides. As a result, the product polymer or polymer precursor contains almost no isocyanurate groups, or even if it does contain them, it is present in surprisingly small amounts. Furthermore, the overall reaction rate is relatively fast, and desired molded products can be produced under mild conditions.

The reactive resin composition according to the present invention may be provided as a two-part or three-part composition, in which the first component, the polyincyane-1 component, is known to those skilled in the art of polyurethane chemistry. Any 2- to 6-functional organic polyisocyanate can be used. Examples of aromatic polyisocyanates that can be used include tolylene diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, I-lysine diisocyanate, and the like. Examples of aliphatic or alicyclic polyisocyanates include hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, and hydrogenated tolylene diisocyanate. By the way, these polyisocyanates can be reacted with active hydrogen compounds to modify them into isocyanate group-terminated prepolymers, and can also be modified by reacting with an active hydrogen compound to form a prepolymer with an isocyanate-terminated group.
It is also possible to use polyisocyanes 1- which have been modified to contain allophanate bonds, bi-, iuret-I bonds, and incyanurate ring structures.

The epoxide component can be a compound having at least two epoxy groups, ie any aliphatic, cycloaliphatic, aromatic or heterocyclic compound having 1,2-epoxy groups. The epoxide preferably used is 1
have 2 to 6, particularly preferably 2, epoxy groups per molecule and 90 to 500, preferably 170 to 220
It is desirable that the epoxy equivalent has an epoxy equivalent of . Epoxides that can be suitably used in the present invention include diglycidyl ether of hisphenol A derived from bisphenol A or the halogen-substituted derivative of bisphenol A and epihalo-phosphorus, bisphenol F diglycidyl ether, and polynuclear phenol. glycidyl ether derived resin,
Epoxide phenyl novolak resins, aromatic glycidyl amine resins based on aromatic amines and 4-phosphorus, crysyl ester resins of polybasic aromatic, aliphatic and cycloaliphatic carboxylic acids, aromatic or cycloaliphatic dicarboxylic acids Types include glycidyl ethers of reactants between acids and polyols, glycidyl ethers of polyols, epoxidation products of cycloolefins, epoxidation products of polyunsaturated compounds such as vegetable oils and their modified products, and epoxides of silicate compounds. These epoxy resins may be used alone or in combination of two or more.

The catalyst component is a compound that promotes the oxasoliton cyclization reaction through the reaction of epoxide and isocyanate, and in the present invention, a) a complex of an organotin halide and hexamethyl phosphoramide, b) a complex of an organotin halide and an onium salt, C) Either a complex of a stibonium salt and a zinc halide is used.

The organotin halide compound used as the catalytic MnI component is preferably an organotin halide compound represented by the following formula (1).

Rm Sn m is an integer of 1 to 3, and R each independently represents an aliphatic, aromatic, or alicyclic group. The organic tin halide 1 to preferably used in the present invention includes trimethyltin iodide, trimethyltin bromide, dimethyltin diiodide, dimethyltin tribromide, tripropyltin iodide, tripropyltin bromide, and diiodide. Dipropylstin, dipropyltin tribromide, tributyltin iodide, tributyltin bromide, cyphtyltin diiodide, dibutyltin tribromide, trioctyltin iodide, trioctyltin bromide, dioctyltin diiodide,
Dioctyltin tribromide, triphenyltin iodide, triphenyltin bromide, diphenyltin diiodide, diphenyltin tribromide, tricyclohexyltin iodide, tricyclohexyltin bromide, dicyclohexyltin diiodide, Examples include dicyclohexyltin bromide.

Examples of onium salts include ammonium, phosphonium, and stibonium represented by the following formula (2).

In the above formula, Z is N, P, Il, or sb. R1-
R4 is the same or different i group. X is halo
□ Shows Gen.

Examples of ammonium compounds include tetramethylammonium iodide, tetramethylammonium bromide, tetraethylammonium iodide, Te1-laethylammonium bromide, Te1-lapropylammonium iodide, tetrapropylammonium bromide, and tetraethylammonium iodide. tetraphthylammonium,
Tetrabutylammonium bromide, Tetraisoamylammonium iodide, Tetraisoamylammonium bromide, Tetrabenzylammonium iodide, Tetrabenzylammonium bromide, Methyltriethylammonium iodide, Methyltriethylammonium bromide, Trimethylphenylammonium iodide, Bromide These are trimethylphenylammonium, trimethylhensylammonium iodide, and trimethylbenzylammonium bromide.

Examples of phosphonium compounds include tetrabutylphosphonium iodide, tetrabutylphosphonylam bromide, tetraphenylphosphonium iodide, tetraphenylphosphonium bromide, butyltriphenylphosphonium iodide, and methyl bromide. phenylphosphonium, methyltriphenylphosphonium iodide, methyltriphenylphosphonium bromide, butylphenylphosphonium iodide, and tributylphenylphosphonium bromide.

Examples of the stibonium compounds include tetraphenylantimony iodide, tetraphenylantimony bromide, tetrabenzylantimony iodide, tetrabenzylantimony bromide, tetrabutylantimony iodide, and tetrabutylantimony bromide.

As already mentioned, a combination of these components, i.e., a complex, is used as a thermally activated catalyst in the present invention, and the complexation is carried out by combining each component preferably in equimolar proportions in the presence or absence of a solvent. It can be easily produced by reacting at a temperature of room temperature to 150°C. The complex catalyst can be present together with a solvent in a three-component form independently of the polyisocyanate component and polyepoxide component, or can be present in the polyisocyanate component or polyepoxide component.

The amount of the catalyst used is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the mixture of polyepoxide and boisocyanate. Of course, a mixture of different catalysts can also be used.

Instead of using the above-mentioned complex catalyst, the present inventors have proposed that the catalyst components may be complexed in the process of heating and curing the resin composition using polyepoxide and polyisocyanate themselves as solvents for each catalyst component. 'We discovered that scales functioned as excellent thermally activated catalysts.

When a complex catalyst is mixed and dissolved in a polyisocyanate component or a polyepoxide component, the storage stability decreases, which may pose a problem in industrial use. Therefore, it is an advantageous feature of the present invention that instead of the complex catalyst, the constituent catalyst components are separately present in the polyisocyanate component and the polyepoxide component, respectively. Specifically, in the case of an organotin-based complex, the catalyst component 1 to 1 is mixed with the polyisocyanate component, and one of the catalyst components, hexamethylphosphoramide or stibonium salt, is mixed with the polyepoxide component. I can do it. In the case of a complex of zinc halide and stibonium salt, the catalyst component zinc stibonium salt can be mixed with the polyisocyanate component, and one catalyst component, the zinc halide, can be mixed with the polyepoxide component. In other words, this catalyst system does not lose catalytic activity even if the catalyst components are separated and blended, and the polyisocyanate component,
The storage stability of the polyepoxide component is not affected, so
It is extremely important for industrial use.

In addition to the above essential ingredients, other auxiliaries and additives such as fillers, fiber reinforcing agents, antioxidants, flame retardants, internal mold release agents, pigments, surfactants, catalysts, and blowing agents may be added as desired. Such additives can be used in a conventional manner.

Oxazolidone groups in thermosetting resins according to the invention, like incyanurate groups, are known to impart enhanced heat distortion properties and thermal stability compared to urethane groups.

Furthermore, such polymers exhibit good chemical resistance and solvent stability.

By the way, the properties of the resulting polyoxazolidone resin vary depending on the relative quantitative ratio of the polyepoxide and polyisocyanate 1- used. In other words, if a stoichiometric excess of polyisocyanate is used, a polymer having an isocyanate group at the end and an oxazolidone bond in the main chain (isocyanate-terminated oxazolidone polymer precursor)
is obtained, and similarly when an excess of epoxide is used, a polymer having an epoxy group at the end and an oxazolidone bond in the main chain (epoxy-terminated oxazolidone polymer precursor) is formed. Also, using substantially equal amounts of polyepoxide and polyisocyanate results in higher molecular weight polymers (polyoxazolidones). Polymers or polymer precursors with different properties are expected depending on the ratio of polyepoxide and polyisocyanate used, and therefore the ratio can be considered to be used over a relatively wide range.

The isocyanate-terminated oxasolitone polymer precursor can be used to make waxes, elastomers, foams, adhesives, adhesives, etc. using conventional techniques to make polyurethanes or polyureas.

Epoxide-terminated oxazolidone polymer precursors can be reacted with epoxy curing agents in the usual manner to form coating agents.
It is also possible to form an adhesive or the like.

Oxasolitone polymers are particularly suitable for producing thermosetting resins as thermosetting resin moldings, coatings, and adhesives.

The method is further used as an impregnating composition for electrical insulation and glass fiber reinforced laminates 1 - and as a formulation for casting resins and wiring sheets 1 - in the production of printed circuit boards, computer-related electrical components. Can be used. It is also suitable for manufacturing materials that require high stress characteristics and heat resistance, such as automobiles and aircraft.

In this way, the reactive resin composition according to the present invention forms oxatritone when heated, and provides very little heat-resistant resin by-products such as trimerized incyanure-1 and epoxy resin, compared to conventional products. In addition, it is expected that the reaction will be interrupted midway through and the oxatritone polymer precursor will be used in various applications, but the most important application where the thermosetting properties of polyoxatritone are particularly demonstrated is in the production of heat-resistant molded products. This is the manufacturing of

Therefore, according to the second feature of the present invention, the above-mentioned resin composition is reacted in a mold at a temperature of room temperature to 150 DEG C., thereby providing a polyoxatritone molded article having excellent heat resistance.

The oxazolidone formation reaction is carried out by heating polyisocyanate I. and polyeboxide together in the presence of a catalyst. Although the reaction temperature may proceed at room temperature, it is usually advantageous to range from 40 to 150°C. The optimum temperature depends somewhat on the polyisocyanate, polyepoxide used, but the reaction temperature is between 60 and 120°C. To obtain further optimum properties, it is preferred to post-cure the polyoxazolidone resin obtained at a temperature of 100 to 300C, preferably 120 to 200C.

This reaction can also be carried out in the presence of a suitable diluent or solvent, if desired. Suitable solvents are aromatic, ester, halocarbon, etc., which are inert to this reaction. In other words, it is preferable to use a solvent that has a negligible effect on catalyst (complex) formation and the catalyst (complex). This reaction can also be carried out in a batch or continuous manner, and by using the above-mentioned catalyst component splitting method, the thermosetting molded article can be manufactured using the conventional one-shot method or pre-forming method. Both polymer methods are used,
Molding methods such as vacuum defoaming molding, reaction injection molding, or other molding methods may also be used.

Hereinafter, the present invention will be explained in detail with reference to Examples. Parts and percentages are by weight unless otherwise specified.

21-Example-1 In a 100 ml flask containing 385 g of dichloromethane, 16.5 g of dimethylsiodide (Me2SnI2) and 22.0 g of tetraphenylantimony iodide (Ph4S) were added.
bl) was added and stirred at room temperature for about 1 hour to prepare a catalyst solvent.

Bisphenol A epichlorohydrin epoxy resin with epoxy equivalent weight 175 in a 50 ml flask 3.5
Add 0.19 g of the catalyst solution prepared earlier to g, stir,
Defoamed.

This solution contains 2.32 g of a low viscosity polyisocyanate compound based on diphenylmethane diisocyanate with an NCO content of 29% and Infuron diisocyanate J-0,4.
44 g was added at room temperature, mixed with stirring, and defoamed. This resin composition was heated at 80° C. for 1 hour to obtain a hard polymer.

When this polymer was analyzed by infrared absorption spectrum, it was found that epoxy groups <9], Ocm''), isocyanate groups (
2250 cm″+) disappears, and the oxazolidone group (1
750 cm'), but only slight formation of trimerized isocyanate groups (1705 cm') was observed.

Next, the above resin composition was injected into a mold (inner surface coated with Limurikei B-659-2 [wax-based mold release agent, registered trademark, Middle East Oils and Fats] as a mold release agent), and heated at 80°C for 1 hour. By not removing the product from the mold after the reaction, it was possible to obtain a molded product with excellent heat resistance.

Example-2 Bisphenol A epichloro 1 to phosphorus epoxy resin with epoxy equivalent weight 175 in a 50 ml flask 3.5
0.38 g of the catalyst solution prepared in Example 1 was added to the mixture, and the mixture was stirred and defoamed. 1.45 g of a low-viscosity polyunsocyanate compound based on diphenylmethane diisocyanate with an NGO content of 29% and 111 g of infron diisocyanate were added to this solution at room temperature, mixed with stirring, and defoamed. This resin composition was heated at 80° C. for 1 hour to obtain a hard polymer. When this polymer was analyzed by infrared absorption spectrophotometer, the epoxy group (910 cm') and isocyanate group (2250 cm'') disappeared, and the formation of oxasoliton group (1750 cm) was observed, or the formation of triple incyanuric acid groups was observed. -1~ group (1705 cm') formation was not observed.

Example-3 16.5g of modified dimethyltin ()le2sn12 was added to a 100ml flask containing 23.6g of dichloromethane.
) and 7.1 g of hexamethylphosphoramide ((Me2
N>3Po) was added and stirred at room temperature for about 1 hour to prepare a catalyst solution.

Hisphenol A Ebichloro 1 to 3.5 phosphorus epoxy resin with epoxy equivalent weight 175 in a 50 ml flask
0.238 g of the previously prepared catalyst solution was added to the solution, followed by stirring and defoaming. 2.32 g of a low-viscosity polyisocyanate compound based on diphenylmethane diisocyanate with an NCO content of 29% and 444 g of isophorone diisocyanate 1-0 were added to this solution at room temperature, mixed with stirring, and defoamed. This resin composition was heated at 80° C. for 1 hour to obtain a hard polymer. When this polymer was analyzed by infrared absorption spectrum 1~1, it was found that epoxy groups (910cm''),
Either the isocyanate group (2250 cm') disappears and the oxazolidone group (1750 cm) disappears, or the incyanurate group (1705cii') is substantially tripled.
It was observed that there was no evidence of formation of

Example-4 3.5 g of bisphenol A epichlorohydrin epoxy resin having an epoxy equivalent weight of 175 in a 20 ml flask
An acetone solution containing 0.033 g of modified zinc (Znl2) and 0.05 g of tetraphenylantimony iodide (Ph4Sbl) was added to the mixture, followed by stirring and defoaming. 2 to this solution
Low viscosity polyisocyanate compound based on diphenylmethane diisocyanate with 9% NCO content 2.3
2 g and 0.444 g of isophorone diisocyanate were added at room temperature, mixed with stirring, and defoamed. This resin composition is
A hard polymer was obtained by heating at 0° C. for 1 hour. When this polymer was analyzed by infrared absorption spectrum, it was found that epoxy group (910cm), isocyanate group (2250cm)
disappearance of target, formation of oxazolidone group (1750 ci'), and virtually triplicated incyanurate group (17
It was observed that no formation of 05cni') was observed.

25-Example-5 In a 50ml flask, 3.5g of epoxide phenyl novolac resin having an epoxy equivalent weight of 175 was added to Example-5.
0.38 g of the catalyst solution prepared in step 1 was added, followed by stirring and defoaming. This solution contains 232 g of a low viscosity polyisocyanate compound based on diphenylmethane diisocyanate with an NCO content of 29% and 1-0.
444 g was added at room temperature, mixed with stirring, and defoamed. This resin composition was heated at 80°C for 1 hour to obtain a hard polymer. When this polymer was analyzed by infrared absorption spectrum, the epoxy group (910 car'), isocyanate group (2250 car') disappeared, and the oxazolidone group (
1750 cm'), but only a small amount of isocyanurate groups (1705 cml) were formed.

Example-6 Example-1 was added to 3.5 g of epoxide phenyl novolac resin having an epoxy equivalent weight of 175 in a 50 ml flask.
0.38 g of the catalyst solution prepared above was added, and the mixture was stirred and defoamed. To this solution were added 1.45 g of a low-viscosity polyisocyanate compound based on sipheny-26-lmethane diisocyanate with an NGO content of 28% and 1.11 g of isophorone diisocyanate at room temperature, mixed with stirring, and defoamed.

This resin composition was heated at 80° C. for 1 hour to obtain a hard polymer. Analysis of this polymer by infrared absorption spectra showed that the epoxy group (910 cm) and the isocyanate group (2250 cni') disappeared and formed an oxazolidone group (1750 cni'), but the trimerized isocyanurate group (1705ci') was not observed.

Example-7 1.58 g of iodized tetraphenyl antichine (Ph4Sbl) was added to 100 g of bisphenol A epichlorohydrin epoxy resin having an epoxy equivalent of 175, and the mixture was stirred.
A polyepoxy component solution was prepared by defoaming.

Low viscosity polyisocyanate compound 8 based on diphenylmethane diisocyanate with an NCO content of 29% on the other hand
To a mixed polyisocyanate of 3.4 g and 16.6 g of Inlon diisocyanate, modified dimethyltin (Me2
1.38 g of Sn12) was added, stirred, and defoamed to prepare a polyisocyanate component solution. 3.55g of this polyepoxide solution and 2.94g of mixed polyisocyanate solution
g was placed in a 50 ml flask, stirred at room temperature, and defoamed. This resin composition was heated at 80° C. for 1 hour to obtain a hard polymer. From infrared analysis, epoxy group (910cm')
, showing the disappearance of isocyanate groups (2250 cnr) and the formation of oxasoliton groups (1750 cni'), but substantially trimerized isocyanurate groups (1705 cni').
) does not show formation.

Both the polyepoxide solution and the polyisocyanate solution exhibited good storage stability.

Example-8 Hexamethylphosphoramide ((Me2N>3PO) 2; .

3.57 g of this polyepoxide solution and 3.06 g of the mixed polyisocyanate solution containing organic tin halide prepared in Example 8 were placed in a 50 ml flask, and the mixture was stirred and defoamed at room temperature. This resin composition was heated at 80° C. for 1 hour to obtain a hard polymer. From infrared analysis, epoxy group (91
0cffi'), indicating the disappearance of isocyanate groups (2250 ci) and the formation of oxazolidone groups (1750 cr), but substantially trimerized isocyanurate groups (170
5crn') formation.

This polyepoxide solution showed good storage stability.

Example-9 25% of processed zinc was added to 100 g of bisphenol A epichlorohydrin epoxy resin having an epoxy equivalent weight of 175.
3.6 g of acetone solution was added, stirred and defoamed to prepare a polyepoxide component solution. On the other hand, mixed polyisocyanates 1 to 83.4 g of a low-viscosity polyisocyanate compound based on diphenylmethane diisocyanate with an NGO content of 29% and 16.6 g of infron diisocyanate
, tetraphenylantimony iodide (Ph4SbI)
1.9 g was added, stirred, and defoamed to prepare a polyisocyanate component solution. In a 50ml flask, add 3.53g of this polyepoxide solution and 2.95g of polyisocyanate solution.
g was added thereto, and the mixture was stirred and defoamed at room temperature. 80% of this resin composition
A hard polymer was obtained by heating at ℃ for 1 hour. Infrared analysis revealed that the epoxy group (910cffi') and isocyanate group (2250cn+') disappeared, and the oxazolidone group (1
750 ci'), but substantially no formation of trimerized incyanurate groups (1705 cm).

Both the polyepoxide solution and the polyisocyanate solution exhibited good storage stability.

Comparative Example-1 3.5 g of bisphenol A epichlorohydrin epoxy resin having an epoxy equivalent weight of 175 in a 50 ml flask
38 g of the catalyst solution prepared in Example-1 was added to the mixture, followed by stirring and defoaming. 2.9 g of a low viscosity polyisocyanate compound based on diphenylmethane diisocyanate with an NCO content of 29% is added to this solution at room temperature and mixed with stirring,
Defoamed. This resin composition was heated at 80°C for 1 hour to obtain a polymer. This polymer was analyzed by infrared absorption spectroscopy. The epoxy group (910cni'), the isocyanate group (2250ci') disappear, indicating the formation of an oxazolidone group (1750ci'), and there is no indication of the formation of a substantially triplicated isocyanurate group (1705cnT'). However, the appearance of the obtained polymer was not good, as it turned brown in the foamed state and scorch was observed.

Comparative Examples 2 to 5 A thermosetting reaction was attempted in the same manner as in Comparative Example 1 using the same formulation and reaction conditions as in Comparative Example 1, using the compounds shown in Table 1 as catalysts. In both systems, solid polymers were obtained under these conditions. Infrared analysis of the resulting polymer showed the presence of a large amount of triplicated incyanurate along with the formation of oxasoliton groups.

, (margin below)

Claims (4)

[Claims] (1) (a) Isocyanate group ratio of 90 to 10% aromatic polyisocyanate and 10 to 90% aliphatic polyisocyanate and/or
or a polyisocyanate component consisting of a mixture of at least two types of 2- to 6-functional polyisocyanate compounds with an alicyclic polyisocyanate, and (b) a polyepoxide component consisting of at least one type of 2- to 6-functional polyepoxide compounds, However, the equivalent ratio of isocyanate groups to epoxide groups is 1:2 to 2:1, and (c) a complex of an organotin halide and hexamethylphosphoramide, a complex of an organotin halide and an onium salt, a stibonium salt and a halogenated A thermosetting reactivity comprising at least one thermally activated catalyst selected from the group consisting of zinc complexes, present as an independent component or contained in either component (a) or (b). Resin composition. (2) (a) Isocyanate group ratio of 90 to 10% aromatic polyisocyanate and 10 to 90% aliphatic polyisocyanate and/or
or a polyisocyanate component consisting of a mixture of at least two types of 2- to 6-functional polyisocyanate compounds with an alicyclic polyisocyanate, and (b) a polyepoxide component consisting of at least one type of 2- to 6-functional polyepoxide compounds, However, the equivalent ratio of isocyanate groups to epoxide groups is 1.2 to 2:1, and it is used as a thermally activated catalyst. A thermosetting reactive resin composition comprising one of the complex constituent components of a complex or a complex of a stibonium salt and a zinc halide present in the polyisocyanate component and the other in the polyepoxide component. (3) The composition according to claim 1 is placed in a mold at room temperature to 15°C.
A method for producing a heat-resistant molded product, characterized by carrying out the reaction at a temperature of 0°C. (4) The composition according to claim 2 is placed in a mold at room temperature to 15°C.
A method for producing a heat-resistant molded product, characterized by carrying out the reaction at a temperature of 0°C.