DE2854011A1 - Compsn. hardening rapidly on heating - contg. polymerisable cpd., esp. epoxy or phenolic resin, aromatic onium salt, and reducing agent - Google Patents

Abstract

A heat-hardening compsn. contains (A) a cationic, polymerisable, organic material, (B) 0.1-15 wt.%, w.r.t. A, of an aromatic iodonium salt of formula (Y)+ (J)-, and (C) 0.5-25 wt.%, w.r.t. A, or a reducing agent. In B, Y is (i) an aromatic halonium cation of formula RaR'bD, (ii) an aromatic cation of formula Rfr2gR3hE (where E is N, P, As, Sb or Bi), or (iii) an aromatic cation of formula RjR4 kR5mG (where G is S, Se or Te); R and R' are aromatic gps.; R2 and R4 are (cyclo)aliphatic gps.; R3 and R5 are aliphatic or aromatic gps., forming a heterocyclic or condensed ring with E or G; D is halogen: a = O or 2: b = 0 or 1; a+b = 2 or the valency of D; f = 0-4; g and H = 0-2; f+g+h = 4 or the valency of E; j = 0-3; k = 0-2; m = 0 or 1; j+k+m = 3 or the valency of G. J is a non-nucleophilic anion. Hardening is more rapid in presence of the reducing agent. The prods. are high-mol. oils and gums. The compsns. can be applied to substrates, and are used as protective, decorative and insulating coatings, printing inks, sealants adhesives, moulding compsns.; textile coatings, laminates, impregnated tapes and lacquers. (A) The material may be an epoxy resin (claimed), a phenol-HCHO resin (claimed), a cyclic ether or acetal, a lactone or lactam, a cyclic amine or cyclic organo-Si cpd. a vinyl pre-polymer, or a HCHO resin. (B) J may be (i) MQd, where M is a metal(loid), Q is halogen, and d = 4-6, (ii) CF3SO-3, or (III) halide, nitrate or phosphate when A is a HCHO condensate. Claimed B are diaryliodonium salts. The amt. is esp. 1-15 wt.%. (C) reducing agents include thiophenols (claimed), ascorbic or citric acid, and salts of Fe, Co or Sn. The components may be mixed dry or in the melt.

Description

description

The invention relates to thermosetting, cationically polymerizable organic materials such as an epoxy resin, a cyclic ether, phenol / formaldehyde resin etc. using an aromatic onium salt as a polymerization initiator, such as a halonium salt, or one of the elements of group Va or VIa of the periodic table of the elements. The materials also contain a reducing agent such as a dicyclopentadienyl iron.

The thermosetting compositions of the invention comprise: (A) a cationically polymerizable organic material, (B) 0.1 to 15% by weight the thermosetting composition of an aromatic onium salt of aromatic Halonium salts and onium salts of the elements of groups Va and VIa of the periodic table of the elements and (C) 0.5 to 25% by weight based on (A) a reducing agent.

Aromatic onium salts can be used to cause curing of an epoxy resin can be used as a photoinitiator. If desired, epoxy resins can be used below Use of such aromatic onium salts also by heating and without the application hardened by radiant energy. The thermosetting of the epoxy resins with those described above aromatic onium salts, however, take place considerably more slowly than hardening with radiant energy, such as UV light. It has been found to be considerable faster thermosetting of epoxy resins as well as a wide variety of others cationic polymerizable organic materials is possible if one uses the aromatic Onium salts used in combination with a reducing agent.

Those employed in the compositions of the present invention aromatic onium salts have the general formula + (1) F3 rJ wherein J - is a non-nucleophilic counterion defined in more detail below and Y is a cation is selected from aromatic halonium cations - the formula <2) UR3a (R a (R1) D11 an aromatic cation with an element from group Va of Per iadensystems (3) £ R) f (R2) (R3) h and g E3 an aromatic cation with one element of Group VIa of the Periodic Table of Elements (4) F (R) j (R4) k (R5) M Qi, wherein R is a monovalent aromatic organic radical, R1 a divalent aromatic radical organic radical, R2 and R4 monovalent organic aliphatic radicals from alkyl, cycloalkyl and substituted alkyl radicals, R3 and R5 are polyvalent organic radicals with E or G form a heterocyclic or fused ring structure and are selected are made up of aliphatic and aromatic radicals, D is a halogen radical such as J, E- a Va group element selected from N, P, As, Sb and Bi, G is an element the group VIa selected from S, Se and Te, a is 0 or 2, b is 0 or 1, where the sum of a + b = 2 or the valence of D, f is an integer from 0 to 4 inclusive, g is an integer from 0 to 2 inclusive, h is an integer Number from 0 up to and including 2, where the sum of f + g + h has a value of 4 has or is equal to the valence of E, j is an integer from 0 up to and including 3, h is an integer from 0 to 2 inclusive and m is 0 or 1, where the Sum of j + k + m has a value of 3 or is equal to the valence of -G.

The radicals that stand for R can be identical or different and are selected from aromatic carbocyclic or heterocyclic radicals with 6 to 20 carbon atoms, which can be substituted with 1 to 4 monovalent radicals from alkoxy radicals with 1 to 8 carbon atoms, alkyl radicals with 3 to 8 Carbon atoms, the nitro group, chlorine, etc. R is especially phenyl, chlorophenyl, nitrophenyl, methoxyphenyl and pyridyl. The residues for R1 are divalent residues, such as The radicals for R2 and R4 include alkyl radicals with 1 to 8 carbon atoms, such as methyl, ethyl, etc., substituted alkyl radicals, such as -C2EI40CH3, -CH2COOC2H5 and -CH2COCH3, Q 'has the meaning given below, R3 and R are Leftovers like the following: where Q 'is selected from -0-, - (CH2) n-, and -S-, n is an integer from 1 to 4 inclusive, Z is selected from -O-, -S- and and 'is selected from hydrogen. Alkyl groups with 1 to 8 carbon atoms and aryl groups with 6 to 13 carbon atoms.

The non-nucleophilic counterions that stand for J in the above formula, are anions of the general formula MQdt where M is a metal or non-metal, Q is halogen and d is an integer from 4 to 6 inclusive. Additionally J in the above formula (1) can also mean those non-nucleophilic counterions, such as perchlorate, CF3S03 and C6H4S03 etc. In cases where the cationic polymerizable Material a phenol / formaldehyde resin or another condensed formaldehyde resin as with urea, halide can also be used as a counterion for J in the above formula (1) stand as Cl, Br, F etc. as well as Nu3 ', P043 3-The metals or non-metals that for M in the non-nucleophilic counterion MQd are transition metals, such as Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, Sc, V, Cr, Mn, Cs, rare earth metals, such as the lanthanides, e.g. Cd, Pr, Nd etc., actinides such as Th, Pa, U, Np, etc. and non-metals, like B, P, As. Examples of the complex anions MQd are BFq PF6, AsF6-, SbF6 , FeC14 SnCl6, SbCl6 and BiCl5.

Examples of halonium salts of the above formula (1) with cations of the above formula (2) are as follows: Examples of salts of the above formula (1) with cations of the above formula (3) with elements of group Va of the Periodic Table of the Elements are as follows: BF4-, examples of salts of formula (1) with cations of formula (4) with elements of group VIa of the periodic table are the following: BF4-, PF6-.

AsF6, SbF6 FeCl4-, SbC16-, BiCl5 = BF4-, PF6-, FeCl4, SnCl6, SbCl6, BiCl5, BF4-, PF6-, The term epoxy resin "as used in the present application includes monomeric, dimeric, oligomeric or polymeric Epoxy materials with one or more functional epoxy groups. For example, those resins belong to the epoxy resins according to the present application, which result from the reaction of bisphenol-A (the 4,4A-isopropylidenediphenol) with epichlorohydrin or from the reaction of low molecular weight phenol / formaldehyde Resins (novolak resins) with epichlorohydrin, which can be used either alone or in combination with a compound containing epoxy groups as a reactive diluent, such as phenylglycidyl ether, 4-vinylcyclohexene dioxide, limon dioxide, 1,2-cyclohexene oxide, glycidyl acrylate, glycidyl meth , Styrene oxide and allyl glycidyl ether can be added as viscosity modifying agents.

In addition to the aforementioned compounds, the epoxy resins, which can be used in the present invention, including such polymers Be materials that have terminal or pendant epoxy groups. Examples of these compounds are vinyl copolymers with glycidyl acrylate or methacrylate as one of the comonomers. Other classes of epoxy-containing polymers used under the compositions according to the invention are curable are epoxy-containing siloxane resins, epoxy-containing polyurethanes and epoxy-containing polyesters. Such polymers usually have functional epoxy groups at the ends of their chains. Epoxy-containing siloxane resins and processes for their preparation are more particularly described by E.P. Plueddemann and G. Fanger in J. Am. Chem. Soc.

80, 632-635 (1959). As also described in the literature, epoxy resins can also be modified in a number of standard ways, see above by reactions with amines, carboxylic acids, thiols, phenols and alcohols, such as U.S. Patents 2,935,488, 3,235,620, 3,369,055, 3,379,653, 3,398,211, 3,403,199, 3 563,850, 3,567,797 and 3,677,995. More examples of epoxy resins that Can be used in the compositions according to the invention are in the Encyclopedia of Polymer Science and Technologyy Volume 6, 1967, by Interscience Pub-isners, New York, pages 209-271.

Other cationically polymerizable organic materials, din in the inventive compositions can be used, are thermosetting formaldehyde resins, cyclic ethers, lactones, lactams, cyclic Acetals and vinyl organic prepolymers.

Examples of organic thermosetting condensation resins of formaldehyde which can be used in the compositions according to the invention are, for example, urea-containing resins such as [CH2 = N-CONH2] x.H2O [CH2 = NCONH2 JxCH3COOH [CH2 = NC0NHCH2NHCONCH2OH] x phenol / forxaldehyde resins such as where x and n are integers with a value of 1 or greater, as well as Furthermore, as polymeric organic material can be used melamine / thiourea resins, melamine or urea / aldehyde resins, cresol / formaldehyde resins and combinations with other carboxy, hydroxyl, amines and mercapto-containing resins, such as polyesters, alkyd resins and polysulfides.

Some of the vinyl organic prepolymers which can be used to prepare the polymerizable compositions of the present invention are e.g. B. CH2 = CH-O- (CH2-CH20) n-CH = CH2, where n is an integer with a value of up to 1,000 or more, further multifunctional vinyl ethers, such as 1,2,3-propane trivinyl ether, trimethylolpropane trivinyl ether , Prepolymers of the formula and low molecular weight butadiene having a viscosity in the range of 200 to 10,000 centipoise at 250 C. The products obtained upon curing these compositions are useful as printing inks and for other applications typical of thermosetting resins.

Another category of organic materials for manufacture of the polymerizable compositions according to the invention are cyclic ethers, which can be converted into thermoplastics. Examples of such cyclic ethers are oxetanes, such as 3,3-bis-chloromethyloxetane, Akoxyoxetaner as described in US-P $ 3,673,216, Oxolanes, such as tetrahydrofuran, oxepanes, oxygen-containing spiro compounds, trioxane and dioxolane.

In addition to the cyclic ethers, cyclic esters can also be used as organic material, such as (3-lactones, e.g. propiolactone, cyclic amines, e.g. 1,3,3-trimethylazetidine, and cyclic organosilicon compounds, e.g. materials of the formula where R is identical or different and is selected from monovalent organic radicals such as methyl or phenyl and m is an integer from 3 to 8 inclusive. An example of such a cyclic organosilicon compound is hexamethyltrisiloxane, another octamethyltetrasiloxane.

Those obtainable from the thermosetting compositions according to the invention Products are oils or rubbers with a high molecular weight.

Examples of the reducing agents in the composition according to the invention are thiophenols, reducing sugars, ascorbic acid, citric acid, iron (II) salts such as (C5H5) 2Fe, (C7H15C02) 2Fe, cobalt (II) salts such as (C7H15C02) 2Co, Co2 (CO) 6 [C6H5] 3P02. Tin (II) salts can also be used, such as CC7H15CO2) 2Sn, and copper (I) salts such as CuJ, CuBr and CuCl, The thermosetting compositions of the present invention can be prepared by blending the cationically polymerizable organic material with an effective amount of the aromatic onium salt and further with the reducing agent. In cases where the cationic polymerizable organic material is an epoxy resin, cyclic ether, cyclic ester, and the like, J in the above formula (1) may be MQd anion or CF3SO3 or C6H4SO3. However, if the cationically polymerizable material is a formaldehyde condensation resin, as defined above, then J can also be a halogen ion. The final curable composition can be in the form of a varnish having a viscosity of 1 to 100,000 centipoise at 25 ° C or as a free flowing powder.

The curable compositions can be in a conventional manner A variety of substrates can be applied and cured within 30 seconds up to 20 minutes depending on the temperature used in the range of 25 to 2500 C to the tack-free state.

Depending on the compatibility of the onium salts with the epoxy resin as well as the reducing agent, the onium salts can be in an organic solvent dissolved or dispersed in it together with the reducing agent, such as nitromethane, Acetonitrile, etc., before incorporating the onium salt and reducing agent into the epoxy resin. If the epoxy resin is a solid, then the onium salts can be incorporated dry milling or melt blending.

If desired, the salt can also be formed on the spot will. Experience has shown that the proportion of onium salt with respect to the Epoxy resin can vary widely because this salt is essentially inert is as long as it is not activated. Effective curing results are achieved when 1 to 15% by weight of the onium salt, based on the weight of the curable composition will.

The curable compositions can contain inactive ingredients hold, organic fillers, dyes, pigments, extenders, viscosity control agents, Processing aids and UV protection agents. Amounts of filler can be up to 100 parts per 100 parts of the epoxy resin are used. The curable compositions can be applied to such substrates as metal, rubber, plastic, molded Parts or films, paper, wood, glass fabric, concrete or ceramics.

Some of the uses for the curable compositions according to present invention are e.g. for protective, decorative or insulating coatings, for embedding, as printing inks, sealants, adhesives, molding compounds, for wire insulation, as textile covers, laminates, impregnated tapes and lacquers.

The invention is described in more detail below with the aid of examples. Unless otherwise specified, all parts are parts by weight.

Example 1 A mixture of 3% by weight tetramethylene phenacylsulfonium hexafluoroarsenate and 97% by weight Epon 828, a diglycidyl ether of bisphenol-A from Shell Chemical Company, was heated to 150 ° C in a reaction vessel. After heating for 20 minutes there was still no sign of gelation.

The above procedure was repeated except that the mixture now, in addition to the aforementioned ingredients, 3% by weight of pentachlorothiophenol contained. A hardened tack-free one Product became this time obtained after heating at 150 ° C. for 5 minutes. This curable composition would be useful for encapsulating electronic components.

Example 2 A uniform mixture of 3 parts of tetramethylene phenacylsulfonium hexafluoroantimonate and 97 parts of Epon 828 converted to one after 15 minutes of heating at 1500C Reaction vessel to the solid, tack-free state.

Another sample of the same mixture was added with 3 parts Pentachlorthophenol provided to 100 parts of the mixture.

This new mixture hardened in 2 1/2 minutes at 1500 ° C a tack-free state.

Example 3 A mixture of 97 parts of Epon 828 and 3 parts of tetramethylene phenacylsulfonium hexafluoroantimonate was mixed with 3 parts of thiophenol. A tack-free cure was achieved after Preserved at 1500 C for 5 minutes. Using the same procedure, a another mixture prepared, except that instead of the thiophenol thiosalicylic acid was used. The cure of the mixture to the tack-free state became achieved after 3 minutes at 1500 C.

Example 4 A mixture of 3 parts of tetramethylene phenacylsulfonium hexafluoroantimonate and 97 parts of CY-179, a bis-epoxy cycloaliphatic resin from Ciby-Geigy heated to 1500 C. After 3 minutes the mixture was hardened.

Example 5 A mixture of 97 parts of Epon 828 and 3 parts of diphenyliodonium hexafluoroarsenate was stirred in a reaction vessel and then heated to 1200 ° C. for 30 minutes. There was no noticeable change in the mixture.

The above procedure was repeated except this time 3 parts of pentachlorothiophenol had been mixed with the mixture. One received with the new mixture a tack-free product after 4 minutes of heating to 1200 C in a reaction vessel.

Example 6 A mixture of 97 parts of the CY-179 and 3 parts of Phenacyltriphenylphosphonium hexachloroantimonate was in a glass jar on 1300 C heated. After 20 minutes there was still no noticeable change in the mixture occurred.

The above procedure was repeated except that the mixture an additional 3 parts of pentachlorothiophenol were added. With this new mix a tack-free product was obtained after 5 minutes at 1300 C.

Examples 7-9 For every 10 ml of bisepoxide CY-179, 0.3 g of 4,4'-dimethyldiphenyliodonium hexafluoroarsenate and 0.3 g of each of the following Compounds ferrocene, tri-iron dodecacarbonyl, or

added n-octylferrocene. The three mixtures obtained were heated each in glass jars in a blad and received the following required curing times.

Reducing agent curing time none 4 hours 7. Ferrocene 6 - 7 Minutes 8. Triiron dodecacarbonyl 3 minutes 9. n-Octylferrocene 7 minutes.

In a separate experiment, CY-179 was used in the presence of ferrocene heated alone but without the iodonium salt to 120 ° C, even after 16 hours Heating had not yet hardened.

Examples 10-13 The above experiment was repeated except that instead of the reducing iron compounds, the following cobalt-containing compounds were used.

Reducing agent curing time 10. none 4 hours 11. Co2 (CO) 6 [(C6H5) 3P] 2 2 minutes 12. C02 (Co) 6 [<c6H5) 2P-cH3C6H4] 2 4 minutes 13. (C7H15CO2) 2Co 7 minutes Example 14 A mixture of 3% by weight 4,4-dimethyldiphenyliodonium hexafluoroarsenate, 3% by weight tin (II) octoate and 94% CY-179 was heated to 1300 ° C., with within of 3 minutes of curing occurred. Without the tin compound it was a three hour cure Heating to 1300 C required.

Example 15 A mixture of 3% by weight 4,4'-dimethyldiphenyliodonium hexafluoroarsenate and 97% by weight of bisphenol-A type resin (Ciba Geigy Araldite 6060) was added Heated at 1700 C. It took an hour at this temperature to mix the mixture to harden.

The addition of 3% stannous octoate to this mixture resulted to a decrease in curing time to 4.3 minutes at this temperature, -BeSapi-el 16 A mixture of 76% Ciba Geigy Araldit-e6060, 2 t diphenyliodonium hexafluoroarsenate, 2% tin (II) octoate and 20% chopped glass fiber was added by mixing 1000 C. The mixture was placed in a heated mold for 4 minutes 1700 C. A white shaped rod was obtained which had good mechanical properties and had excellent solvent resistance.

Example 17 To a mixture of 3% 4,4'-dimethyldiphenyliodonium hexafluoroarsenate and 91% CY-179 was given 6% ascorbic acid. At 1300 C this mixture hardened in 2 1/2 minutes.

The addition of 6% ascorbic acid alone to the CY-179 resulted in this bisepoxide does not even if heated to 1300 C for over an hour hardened, Example 18 A mixture of 0.5 g of 4,4'-dimethyldXphenyliodonium hexafluoroarsenate and 40 grams of Epon 1002 solid bisphenol-A epoxy resin from Shell, 1 gram of AscorbXnsAure and 15 grams of chopped glass fibers were measured at 900 by blending in a Brabender torsional rheometer obtain. Part of this molding compound was placed between heated metal plates for 3 minutes pressed at 165 to 1700 C.

A flat film excellent in solvent resistance was obtained in hydrocarbon solvents.

Example 19 To a sample of a 3.24% solution of 4,4'-di-t-butyldiphenyliodonium hexafluorophosphate various amounts of ferrocene were added in CY-179. The samples were heated in glass vessels on 1300 C and provided the necessary to harden the mixtures Time fixed.

% Ferrocene curing time (seconds) 18 210 15 240 12 275 9 570 Example 20 A mixture of 3% di-t-butyldiphenyliodonium hexafluoroantimonate and 6% ferrocene in CY-179 cured at 1200 C-in 2.75 minutes.

3% by weight of BF3 monoethylamine in CY-179 required 30 minutes 1200 C to cure the mixture in the same way.

This example shows the advantage of using the cationic Systems of the present invention versus Lewis acid catalysts.

Example 21 A solution of 3% 4,4'-dimethyldiphenyliodonium hexafluoroarsenate and 6% ferrocene in CY-179 was stored for seven weeks. The solution gelled not and there was also no change in viscosity during this time.

In contrast, a solution of 3% BF3-monoethylamine in CY-179 gelled within of 3 days.

This example shows the high degree of storage stability of the cationic system of the present invention compared to blends of epoxy resins and Lewis acids.

Example 22 A mixture of 3% by weight 4,4'-dimethyldihenylodonium hexafluoroarsenate in bisphenol A diglycidyl ether (Shell Company Epon 828) was divided into 10 samples. A different amount of ferrocene was added to each of these samples. Samples were then heated in glass vessels and the temperature required for hardening at 1300 ° C Time determined.

% Ferrocene curing time (seconds) 21 66 18 65 15 75 10 75 9 85 6 95 4 135 3 210 2 220 435 0> 144,000 Example 23 A mixture of solid Ciba Geigy bisphenol-A epoxy resin with 1.5% by weight diphenyliodonium hexafluoroarsenate and 3% ascorbic acid was in a mixing cup of a Brabender mixer at 900 C manufactured. Both torque and torque as well as temperature were used as indicators the curing continuously monitored. After 45 minutes there was no change in the viscosity or the temperature took place. At this point the temperature became rapid heated to 1700 C. Cure started within 6 minutes after the temperature rise started as can be seen from the rapid increase in both the torque required and also the temperature showed. The resin obtained was a solid, highly crosslinked material, that couldn't be melted.

The same mixture of the above ingredients was added to the mixing cup a Brabender mixer at 1700 ° C., then hardening occurred within 45 seconds a.

The above two experiments demonstrate a unique feature of the cationic Redox system of the present invention that operates at temperatures of 900 C for extended periods Stored for times and then cured rapidly when exposed to elevated temperatures is heated.

Example 24 A mixture of 3 z 4,4'-dimethyldiphenyliodonium hexafluoroarsenate, 3% copper (I) bromide and 94% CY-179 were heated to 1200 ° C. in an aluminum beaker. The mixture cured to a non-meltable hard mass in 10 to 12 minutes.

Example 25 There were 2 parts of diphenyliodonium hexafluoroarsenate and 2 parts of ferrocene were added to 46 parts of diethylene glycol divinyl ether.

The mixture was poured into an aluminum beaker and heated 1000 C. It found a very rapid exothermic polymerization with the formation of a crosslinked one hard resin instead.

Example 26 2 parts of diphenyl iodonium perchlorate and 3 parts were added Ferrocene to 95 parts of a phenol / formaldehyde resin (Methylon 11 from General Electric Company) and heated the mixture in an aluminum beaker to 120 ° C. After 5 minutes cured the mixture to a hard crosslinked mass.

Claims (7)

Curable compositions and methods for curing them. Claims Curable compositions are indicated by (A) a cationically polymerizable organic material, (B) an aromatic iodonium salt represented by formula [Y] [j, and (C) a reducing agent, wherein in the curable composition, based on the Weight of (A), 0.1 to 15% by weight of (B) and 0.5 to 25% by weight of (C) are present, J is a non-nucleophilic counterion, Y is a cation from an aromatic halonium cation of the formula L (R) a (R1) b DJ an aromatic Cation with an element of group Va des Periodic table of formula [(R) f (R²) g (R³) h E], - and an aromatic cation with an element of the group VIa of the periodic table of the formula CLR) 3 ob) k (R5) mGJi where R is a monovalent aromatic organic radical, R1 a divalent aromatic organic radical, R2 and R4 monovalent organic aliphatic radicals from alkyl, cycloalkyl and substituted Alkyl, R3 and R5 are polyvalent organic radicals that are heterocyclic or form a condensed ring structure together with E or G, said radicals are selected from aliphatic or aromatic radicals, D is a halogen radical, such as J, E an element of group Va of the periodic table selected from N, P, As, Sb and Bi, G is a Group VIa element selected from S, Se and Te, a is the value Has 0 or 2, b has the value 0 or 1, where the sum of a + b = 2 or the valence of D, f is an integer from 0 to 4 inclusive, g is an integer of Is 0 to 2 inclusive, h is an integer from 0 to 2 inclusive, where the sum of f + g + h has a value of 4 or is equal to the valence of E, j is an integer from 0 to 3 inclusive; k is an integer from 0 to 3 inclusive Is 2 and m is 0 or 1, where the sum of j + k + m is 3 or the Valence of G is. 2. Thermosetting compositions according to claim 1, d a -d u r c h it is not noted that the cationically polymerizable organic material is an epoxy resin. 3. The thermosetting composition according to claim 1, d a -d u r c h g I do not know that this is cationic polymerizable organic material is a Piienol / Formaldehyde resin. 4. The thermosetting composition of claim 1, d a d u r c h g It is not noted that the aromatic onium salt is a diaryliodonium salt is. 5. The thermosetting composition of claim 1, d a d u r c h g It is not noted that the reducing agent is a thtphenol. 6. The thermosetting composition according to claim 1, g e k e n n drawn by (A) an epoxy resin, (B) 0.1 to 15% by weight based on the weight of (A), a diaryliodonium salt, and (C) 0.5 to 25% by weight based on weight of (A) a thiophenol. 7. Method of curing a thermosetting composition according to one or more of claims 1 to 6, d a d u r c h g e k e n n n z e i c h n e t that the composition is brought to a temperature in the range from 25 to 2500 C heated.