Curable epoxide compositions

The present invention relates to curable compositions comprising the following components:

a) an epoxy resin which is polymerizable to a higher molecular weight state and

b) an effective amount of at least one radiation-sensitive aromatic onium salt of a Group Va element of the Periodic Table which can effect the curing of a) by the release of a Lewis acid catalyst when exposed to ultraviolet light or an electron beam.

Epoxy resins have been widely used in a variety of applications requiring high performance materials. The curing of an epoxy resin can generally be achieved by means of two-component systems based on incorporation of active amine-containing compounds or carboxylic anhydrides into the resin. The systems require thorough mixing of the ingredients and, in addition, the cure time can be several hours.

Next, one can cure epoxy resins as so-called one-component systems, what to get a

Lewο Lewis acid catalyst used in the form of an amine complex, such as boron trifluoride / monoethylamine. The Lewis acid is released on heating and the curing takes place within 1 to 8 hours and can reach a temperature of 160⁰Require C or more.

As a result, these one component epoxy compositions can not be used to coat heat sensitive devices such as sensitive electronic components. Also, epoxy monomers with low boiling points can not be used since losses due to evaporation occur during curing.

Organoborates of the following formula have also been proposed for such a heat-curing of epoxy resins

R₄-MR₂

wherein M is phosphorus or arsenic and Ri-Rs are independently an alkyl, alkenyl or aryl radical (see US-PS 36 37 572).

In US-PS 37 08 296 the use of certain photosensitive aromatic diazonium salts for curing epoxy resins is described. By photolysis, these aromatic diazonium salts release in situ a Lewis acid catalyst which can initiate the rapid polymerization of the epoxy resin. Therefore, although these one-part epoxy resin blends can give rapidly curing compositions, since the diazonium salts are very unstable, a stabilizer must always be used (cf. US Pat. No. 3,816,280) in order to minimize the curing in the dark during the storage of these mixtures. However, it has been shown that despite this use of a stabilizer and storage in the dark, the gelation of the mixture often occurs.

In addition, gaseous nitrogen is released from the diazonium salts during UV curing, which can cause discoloration and blisters in the resulting film. In addition, diazonium salts are generally thermally unstable and therefore make the use of such materials dangerous because of the potential for uncontrolled decomposition.

In US-PS 35 67 453 photosensitive compositions for photoresist and lithography are described, which is a radiation-sensitive, organic

contain or consist of substituted borate salt. Insofar as these compositions additionally comprise binders, these binders are novolak or resole resins, ie lower, soluble, linear phenol formaldehyde prepared by acidic or alkaline condensation.

b5 dehyd condensates.

The use of these for the sole or with the above binders common use for photoresists and lithography known organically substituted borates

instead of the radiation-sensitive diazonium salts in the curable compositions according to US-PS 37 08 296 is not obvious to one skilled in the art and on the other shows a comparative experiment (see Examples) the ineffectiveness of these substituted borate salts for the radiation curing of epoxy resins.

The invention had the object of providing curable compositions of the type mentioned, which require no stabilizer and the ι ο disadvantages of the known curable compositions with diazonium salts do not have.

This object was inventively achieved by the use of 0.1 to 15 wt .-%, based on the weight of the composition, of an onium salt of the formula

wherein R is a monovalent aromatic radical selected from carbocyclic and heterocyclic radicals, R¹ is a monovalent aliphatic radical selected from alkyl, alkoxy, cycloalkyl and their substituted derivatives, R² is a polyvalent organic radical which forms an aromatic heterocyclic or fused ring structure with X, X is an element of group Va of the Periodic Table, selected from N, P, As, Sb and Bi, M is a metal or nonmetal, Q is a halogen radical , a is an integer from 0 to 4 inclusive, b is an integer from 0 to 2 inclusive, c is an integer from 0 to 2 inclusive, and the sum of a + b + c is 4 or equal to the valence of X. .

d = e - / ", where

/ = the valence of M and thus an integer

is from 2 to 7 inclusive, and e is greater than / and thus an integer of up to 8.

Examples of radicals for R are Q₆-I₃) aromatic hydrocarbon radicals such as phenyl, tolyl, naphthyl, anthryl and such radicals substituted with 1 to 4 monovalent radicals such as Qi _8> alkoxy, Qi -8) alkyl, nitro, chlorine, hydroxy, etc.; Arylacyl radicals such as phenylacyl, etc .; Arylalkyl radicals, such as phenylethyl; aromatic, heterocyclic radicals such as pyridyl, furfuryl, etc. radicals for R¹ are z. B. Qi _8> alkyl; Q₃-β) cycloalkyl; substituted alkyl such as haloalkyl, e.g. For example, chloroethyl; Alkoxy, such as -OCH₂C₆H₅ and -OCH₃; Alkoxyalkyl, such as -C₂H₄OCH₃ etc.; Alkylacyl, such as -CH₂COOC₂H₅; Ketoalkyl, such as -CH₂COCH₃ etc. Examples of radicals for R² are for example the following:

R'-N-

NN

R '

wherein Q 'is selected from O, CH₂, N, R and S; Z is selected off

25

- O- -S -

and -N- R '

and R 'is a monovalent radical selected from hydrogen and hydrocarbyl. Examples of complex anions of the formula [MQ_e] -f^e~ fl are z. B. BF₄-, PF₆-, asf₆-, SbF₆-, FeCl₄=, SnCl₆", SbCl₆-, BiCl₅etc., where M is especially a transition metal such as Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, Sc, V, Cr, Mn, Co, etc., rare earth metals such as lanthanides, e.g. Ce, Pr, Nd, etc., actinides such as Th, Pa, U, Np, etc., and nonmetals such as B, P, As, etc.

Onium salts preferably used in the compositions according to the invention are phosphonium salts, e.g. B. Phenylacylphosphoniumsalz, ammonium salts, z. B. phenylacylammonium salt; Arsonium. With regard to the complex anion, the tetrafluoroborate, z. B. Triphenylphenacylphosphonium tetrafluoroborate and the hexafluorophosphate.

Examples of further specific onium salts of elements of group Va, which fall under the formula 1 are z. B.

BF₄

BF₄

BF₄"

"°" T^f

(ζ O} \ - P-CH₂COOC₂H₅

BF₄-

Bi-CH, -C

The onium salts of elements of group Va of the formula I are known. Some of these compounds can be prepared by methods described by J. Goerdeler in Methods of Organic Chemistry, 11/12, 591-640 (1958) and K. S asse, also in the Methods of Organic Chemistry, 12/1, 79 112 (1963).

The term "epoxy resin" as used to describe the curable compositions of the present invention includes any monomeric, dimeric, oligomeric or polymeric epoxy materials containing one or more functional epoxy groups. So z. B. those resins obtained by reacting bisphenol-A, also called 4,4'-isopropylidenediphenol, with epichlorohydrin or by reacting phenol-formaldehyde resins of low molecular weight, also called novolak resins, with epichlorohydrin, used alone or in combination with an epoxy group-containing compound as the reactive diluent become. Such diluents as phenyl glycidyl ether, 4-vinylcyclohexene dioxide, limonene dioxide, 1,2-cyclohexene oxide, glycidyl acrylate, glycidyl methacrylate, styrene oxide, allyl glycidyl ether, etc. can be added as viscosity modifiers. In addition, the scope of these compounds can be extended to include polymeric materials

BF₄ include, the terminal, or in side groups

contain arranged epoxy groups. Examples of this

Compounds are vinyl copolymers, the glycidylacryne

o lat or methacrylate as one of the comonomers

contain. Other classes of epoxy-containing polymers

Asi-7, which are hardened with the above Kaialysa.'oren

can epoxy resins, epoxy polyurethanes and epoxy-polyester. Such polymers usually have

PF "- functionally have epoxy groups at the ends of their

Chains. Epoxy silicone resins and methods for their preparation are described by EP Plueddemann and G. Fa ng er in Journal American Chemical Society 81,

_BF632-635 (1959). As in the literature

i5, epoxy resins can also be modified in a known manner, such as by reacting with amines, carboxylic acids, thiols, phenols, alcohols, etc., as in US Pat. Nos. 2,935,488, 3,235,620, 3,369,055, and 3,379,653, 33 98 211, 34 03 199, 35 63 850, 35 67 797, 36 77 995, etc. described. Further examples of epoxy fibrils that can be used in the present invention are described in the Encyclopedia of Polymer Science and Technology, Vol. 6, 1967, Interscience Publishers, New York, pages 209-271.

The curable compositions of the present invention may be prepared by blending the epoxy resin, which may subsequently be epoxy monomer, prepolymer, polymer or blends thereof, at 0.1 to 15 weight percent by weight the composition of at least one onium salt as defined above, hereinafter referred to as onium salt. The resulting curable composition, which may have the form j5 of a paint having a viscosity of 1 to 100,000 centipoise at 25 ° C, or may be a free-flowing powder, may be applied to a variety of substrates in the usual manner and within 1 second or less than 10 minutes or more

BF₄"40 are cured to a tack-free state.

Depending on the compatibility of the onium salt with the epoxy resin, the onium salt may be dissolved or dispersed in an organic solvent such as nitromethane, acetonitrile, etc., before being incorporated into the epoxy resin in cases where the epoxy resin is a solid the incorporation of the onium salt can be achieved by dry milling or melt blending the resin.

It has been found that the onium salt can also be generated in situ in the presence of the epoxy resin if so desired. B. an onium salt of the formula

BF₄"

BF₄-

wherein R₁R ', R², X, a, b and c are as defined above and Q "- is an anion such as Cl-, Br-, I-, F", HSO4-, NO3-, etc., separately or simultaneously with a Lewis acid salt of the formula

M'MQ

into the epoxy resin, where M 'is a metal cation, such as Na⁺, K⁺, Approx⁺+, Mg⁺+, Fe⁺+, Ni⁺⁴, Zn⁺+, Co⁺+ etc. or an organic cation such as ammonium, pyridinium, etc., and MQ has the value given in connection with formula I. Experience has shown that the proportion of

Oniumsalzes may vary in relation to the epoxy resin within wide limits, since the salt is substantially inert when it is not activated. Effective results can be obtained if a proportion of 0.1 to 15% by weight of the onium salt, based on the weight of the curable composition, is used. Larger or smaller amounts may be used, but this depends on factors such as the nature of the epoxy resin, the intensity of the irradiation, the desired cure time, etc.

The curable compositions may contain inactive ingredients such as inorganic fillers, dyes, pigments, extenders, viscosity control agents, processing aids, UV screening agents, etc., in amounts of up to 100 parts filler per 100 parts of the epoxy resin. The curable compositions can be applied to such substrates as metal, rubber, plastic, molded parts or films, paper, wood, glass cloth, concrete, ceramics, etc.

Some of the applications for which the curable compositions of the present invention can be used are e.g. As protective, decorative and insulating coatings, embedding masses, printing inks, sealants, adhesives, photoresists, wire insulation, textile coatings, laminates, impregnated tapes, printing plates, etc.

The curing of the curable composition of the invention is accomplished by activating the onium salt by UV light or electron beam to achieve the liberation of the Lewis acid catalyst. The electron beam curing can be effected at an accelerator voltage of about 100 to 1000 kV. The curing of the compositions is preferred using UV radiation having a wavelength of 1849 to 4000 A and an intensity of at least 5000 to 80,000 microwatts / cm² reached. The lamp systems for producing such beams may consist of UV lamps, such as 1 to 50 discharge lamps, for. B, xenon, metal halide metal arc lamps, such as low, medium or high pressure mercury vapor discharge lamps having an operating pressure of a few millimeters to 10 atmospheres, etc. The lamps may comprise pistons having light of a wavelength of about 1849 to 4000 λ and preferably 2400 to Let 4000 A through. The lamp bulb may be made of quartz, such as Spectrocil or Pyrex. Typical lamps for generating the UV radiation are z. B. medium pressure mercury arc lamps, such as the GE H3T7 and the Hanovia 450 lamp. The hardenings can be carried out with a combination of different lamps, some or all of which can operate in an inert atmosphere. When using UV lamps, the radiance on the substrate can be at least 0.01 watts / 6.45 cm² be to cause the curing of the organic resin within 1 to 20 seconds and a continuous curing of z. For example, an epoxy-coated steel strip may be added which is picked up at a speed of about 30 to 180 meters per minute. The strip may then be cut to a predetermined width for use as a transformer laminate, etc. A combination of heat and t> 5 light may be used to cure reactive compositions. Such a combination of heat and light can serve to reduce the total cure time.

The invention will be explained in more detail by way of examples. All parts are by weight.

example 1

A mixture of equal moles of triphenylphosphine and phenacyl bromide in aqueous acetone was stirred for 2 hours until crude triphenylphenacylphosphonium bromide separated. The crude product was isolated by filtration and dried. An aqueous mixture of approximately equal moles of the above crude aromatic phosphonium bromide and sodium tetrafluoroborate was stirred. Triphenylphenacyl phosphonium tetrafluoroborate separated rapidly as the fluoroborate salts are considerably less soluble than the corresponding bromides. There was obtained a quantitative yield of Triphenylphenacylphosphoniumtetrafluoroborat with a melting point of 24f to 248 ° C.

By incorporating 3% by weight of the above triphenylphenacylphosphonium tetrafluoroborate in a 60:40 mixture of diglycidyl ether of bisphenol A and 4-vinylcyclohexene dioxide, a curable composition was prepared. Part of the mixture was left in a transparent container for a longer time under normal daylight conditions. There was no change in the viscosity of the mixture.

A portion of the curable composition was applied to a steel strip as a 0.0025 mm thick film. The coated steel surface was exposed to UV radiation from a H3T7 lamp at a distance of 15 cm for 3 sec. A clear, tack-free film was formed which showed no signs of blistering or other defects.

The strip treated as above was then frozen in IOC hydrocarbon oil at 120 for 4 hours⁰C was dipped to determine its hydrolytic stability according to the IFT test ASTM D 971-50 "Interfacial Tension of Oi Against Water" as described on page 322 of the 1970's ASTM Standards, Part 17 (November) Oil of the oil was 39.0 dynes / cm. After the test, oil showed a surface tension of 37 dynes / cm, and to pass the above test, a value of at least 30 dynes / cm is required.

Example 2

A mixture similar to that of Example 1 was prepared using triphenylcarboxymethoxymethylphosphonium tetrafluoroborate instead of triphenylphenacylphosphonium tetrafluoroborate. It was found that the epoxy cured in 3 minutes to a tack-free state on a Glassiibstrai.

Example 3

Further curable compositions were prepared using the epoxy resin blend of Example 1 and a number of different phosphonium salts as listed in the following composition, wherein the cation is the organic moiety and the anion is the Lewis acid moiety, mp is the melting point of the crystalline onium salt and the cure time The time required is to convert the castable composition to a tack-free, rigid state.

cation

anion

mp (⁰C)

Hardening line (min)

HI

IV

VI

BF₄"BFf

SbF₍r Asf₆-

350 125—127

149—152 194-197 203—206 297—302

9 10

VII

P-CH - CH, 220-226

10

OH

BF₄

260

1,5

OH

IX

258—263

OH

Example 4

The following reaction was carried out in a nitrogen-filled drying vessel. To 5.0 g (0.021 mol) of diphenylmethylarsine was added 4.17 g (0.021 mol) of phenacyl bromide in 25 ml of acetone. The resulting pale yellow solution was stirred at room temperature for 6 hours during which time white crystalline diphenylmethylphenacylarsonium bromide precipitated out. Filtration of the product, washing with water and acetone gave 8.3 g (91.5%) of product.

The bromide was distilled in 50 ml of hot

Dissolved water and added 2.1 g of NaBF4. An abundant white precipitate of the tetrafluoroborate salt formed and this was isolated by filtration and washed with water to remove the sodium chloride. The elemental analysis showed 56.1% C and 4.5% H. The calculation was for the formula C.₂bra₂OAsOBF₄, 56.0% C and 4.4% H.

Three parts of the arsonium tetrafluoroborate were combined with 97 parts of a 70:30 mixture of commercial novolak epoxy resin and 4-vinylcyclohexene dioxide. The sensitized mixture was applied to a glass plate by means of a doctor blade to form a film about 0.05 mm thick

Exposing the film for 1.5 minutes produced a hard clear film that could not be scratched with a fingernail.

Example 5

N-Phenacylpyridinium bromide was prepared by slowly adding phenacyl bromide to a stirred equimolar amount of pyridine in a bottle. The slightly exothermic reaction was accompanied by the precipitation of the solid N-phenacylpyridinium bromide. The salt was then filtered and washed thoroughly with anhydrous ether.

Active photocatalysts were prepared by dissolving 0.025 mole of this pyridinium salt in 100 ml of water. Then, to various proportions of the pyridinium salt, 0.03 mole of NaBF₄, KASF₆, NaSbF₆ and KPF₆ added. In all cases, white salts precipitated out of the solution. The salts were washed with distilled water and dried in vacuo at 60 ° C overnight. The following table lists the melting points of the salts and the results of a comparative cure study of blends containing 3% of the salt in 4-vinylcyclohexene dioxide. The mixtures were cured with a GE H3T7 lamp at a distance of 15 cm to a tack-free state.

salt

Melting point (⁰C)

Hardening time (min) until tack-free state

C-CH₁-NO \

Il +/-

C-CH₂-NO ">

BF₄- 173—175 1,5

197—203 0,3

AsF_f; 202—205 0,3

SbF₆" 166—174 1,0

Example 6

A curable composition was prepared from 97 parts of a mixture of 60% Epoxynovolak having an epoxy equivalent weight of 206 and 40% 4-vinylcyclohexene dioxide with 3 parts of N-phenacylacridinium tetrafluoroborate. The mixture was used to impregnate two 15χ 15 cm glass cloth pieces which were cut and folded. The resulting laminate was cured with a GE H3T7 lamp. The cure time was 1 minute exposure from each side. It was obtained a completely dry rigid laminate, which was connected in one piece. The laminate could be used to make circuit boards.

Example 7

To 95 g of limonene dioxide was added 2.7 g of phenacylpyridinium bromide and 2.1 g of sodium hexafluoroarsenate. This composition was thoroughly mixed by rolling on a ball mill for 8 hours. The insoluble salts were then removed by filtration and the remaining epoxy solution was examined for photosensitivity. A cured 0.05 ml thick solvent resistant film was obtained using the method of Example I in 30 seconds.

Example 8

There were added 18.35 g (0.01 mol) of 48% aqueous fluoroboric acid to 24.6 g (0.2 mol) of 2,6-lutidine-N-oxide dissolved in 100 ml of absolute ethanol. A very pale yellow crystalline precipitate was formed and filtered off after standing for 30 minutes and washed thoroughly with diethyl ether. Recrystallization from ethanol gave the pure salt.

To a 500 ml bottle was added 26.5 g (0.0793 mol) of the amine oxide salt in 64.3 ml (1.19 mol) nitromethane. The solution was at 30 to 40⁰C

Stirred while 15.6 g (0.159 mol) of 1,2-Epoxyeyclohexan were added dropwise. After stirring for one hour, the reaction mixture was cooled to room temperature and poured into 500 ml of diethyl ether. The white crystalline product was

filtered and washed thoroughly with ether. After recrystallization from absolute ethanol, the product was obtained in 81% yield with a melting point of 122-126 ° C. According to the manufacturing process

and C13H20NO2BF.1 calculated 50.5% C, 6.47% H, and 4.53% N, found 50.7% C, 6.51% H, and 4.50% N, was the product a compound of the following formula

BF₄"

0.2 part of the above salt was added to 10 parts of an epoxidized butadiene resin dissolved in 2 g of 4-vinylcyclohexene dioxide. After thoroughly mixing the reagents, the mixture was applied as a 0.025 mm thick coating to a glass plate about 1.5 mm thick. Another glass plate was placed on the first and the whole of the

Exposure of a GE H3T7 lamp with an intensity of 200 watts / 6.45 cm² exposed from a distance of 7.5 cm. The total exposure time was 1 minute. A glass laminate was obtained.

Because of the properties of the resulting laminate, those skilled in the art will appreciate that a rupture resistant automotive windshield can be made by a similar process.

Example 9

The following table shows various onium salts and their respective melting points. These salts were derived from aromatic nitrogen-containing bases by alkylation with phenacyl halides or ct-bromotoluene, followed by anion exchange with the appropriate inorganic salt in water. Also listed in the Table are the cure times of 0.05 mm thick films of mixtures of 4-vinylcyclohexene dioxide containing 3% by weight of the respective onium salt using the procedure described in Example 1 for curing.

cation

anion

Melting point ("C)

Hardening time (see)

(ool Il ^^

X / VN-CH₂-C-ς ^>

III IOIOIO

iv

^Vl

BF₄"

165—169

120

BF₄"

160—167

!209—219

120

20

BF₄

128—132

30

BF₄"

212--2Γ

60

BF₄"

I 22-126

20

IK)

Example! 0

Three parts of O- (2-hydroxycyclohexyl) -2,6-lutidinium N-oxide tetrafluorobo. at the formula

CH.,

BF₄"

HO

Example 13

15

30

were ground to a fine powder and then intimately mixed with 97 parts of a commercial powder coating resin by mixing for 30 minutes. The powder was then electrostatically applied to 7.5 χ 15 cm steel plates in the form of an approximately 0.05 mm thick coating using a GEMA Model 171 spray gun. Thereafter, the plates were briefly heated to 150 ° C to melt the powder and then hot-exposed to radiation from a GE H3T7 lamp at a distance of 7.5 cm. After 15 seconds of irradiation, cured samples were obtained.

Example 11

80 parts of bisphenol A diglycidyl ether and a solution of 2 parts of N-phenacylpyridinium hexafluoroarsenate in 18 parts of 4-vinylcyclohexene dioxide were mixed together. Using a draw bar, a 0.025 mm thick coating was applied to a 7.5 × 15 cm steel plate. A mask was placed over the plate and clamped in place. The whole was exposed to ultraviolet light for 20 seconds as described in Example 9 and then immersed in an isopropanol bath, removing the unexposed portions of the coating leaving a sharp negative image of the mask.

Example 12

10 parts of solid multifunctional aromatic glycidyl ether having an epoxy equivalent weight of 210 to 240 were added to 40 parts of limonene dioxide. The mixture was combined with 1 part of N-phenylacylpyridinium hexafluorophosphate and allowed to stand at 50 for half an hour⁰C heated to obtain a homogeneous solution of the ingredients. The mixture was then applied to glass using a 0.012 mm tensile bar and 10 seconds from a distance of 7.5 cm with a GE H3T7 lamp at 200 watts / 6.45 cm intensity² exposed while maintaining a hard coating.

applied in the form of a 0.0025 mm thick film on 7.5 χ 15 large steel plates and cured for 20 seconds with a GE H3T7 lamp from a distance of 1 cm. The plates were then partially immersed in methylene chloride for 5 hours at room temperature and partly in acetone for 4 hours. In all cases, no visible signs of attack by the coating were observed through this center. The plates were heated to 160 for 1 hour⁰C., and then separate experiments were carried out in boiling 5% KOH solution for 30 minutes and boiling distilled water for 4 hours. After these tests, the coatings were intact and showed no signs of degradation.

Comparative test

In this comparative experiment, dissolvers of various triphenylphenacylphosphonium salts ir 4-vinylcyclohexene dioxide to a thickness of about 0.075 mm were placed on glass slides. These salts once contained a Tetraphenylboratanion according to US-PS 35 67 453 and on the other hand, the anions SbF₆According to the present invention, these films were exposed to UV radiation from a General Electric H3T7 mercury vapor lamp at a distance of about 15 cm. Cure times were measured as the required exposure time to produce a tack-free film. Tack-free film is a film that is tack-free at average thumb pressure and the surface of the film does not receive a detectable print. In the following table, the respective anions of the photoinitiators used, their amount in weight percent in the 4-vinylcyclohexene dioxide solution, whether or not curing occurred, and the exposure time thereof are given in seconds.

table

b0

Sufficient N-phenacylpyridinium hexafluoroarsenate was added to a mixture of 67% by weight of a novolak epoxy resin having an epoxy equivalent weight of 172-178, 33% 4-vinylcyclohexene dioxide, and> 0.5% surfactant to provide a curable mixture which contained 1% of the ammonium salt. It became a coating

<p><tgroup cols="4"><tbody><row><entry>anion</entry><entry>weight</entry><entry>hardening</entry><entry>exposure</entry></row><row><entry></entry><entry>percent</entry><entry></entry><entry>Time</entry></row><row><entry></entry><entry></entry><entry></entry><entry>(Seconds)</entry></row><row><entry>B (C₆H₅)4</entry><entry>3</entry><entry>No</entry><entry>&gt;300</entry></row><row><entry></entry><entry>10</entry><entry>No</entry><entry>&gt;300</entry></row><row><entry>SbF₆-</entry><entry>0,5</entry><entry>Yes</entry><entry>7</entry></row><row><entry></entry><entry>1</entry><entry>Yes</entry><entry>5</entry></row><row><entry></entry><entry>2</entry><entry>Yes</entry><entry>3</entry></row><row><entry></entry><entry>3</entry><entry>Yes</entry><entry>3</entry></row><row><entry>AsF₆-</entry><entry>0,5</entry><entry>Yes</entry><entry>8</entry></row><row><entry></entry><entry>1</entry><entry>Yes</entry><entry>6</entry></row><row><entry></entry><entry>2</entry><entry>Yes</entry><entry>5</entry></row><row><entry></entry><entry>3</entry><entry>Yes</entry><entry>5</entry></row><row><entry>BF₄'</entry><entry>0,5</entry><entry>Yes</entry><entry>20</entry></row><row><entry></entry><entry>1</entry><entry>Yes</entry><entry>14</entry></row><row><entry></entry><entry>2</entry><entry>Yes</entry><entry>12</entry></row><row><entry></entry><entry>3</entry><entry>Yes</entry><entry>10</entry></row></tbody></tgroup></p>

It is readily apparent from this table that the organically substituted borates known from US-PS 35 67 453 are completely unsuitable for the radiation curing of epoxy resins.

The above examples give only a few of very many curable compositions and their

809 541/300

17 18

Uses in the context of the present invention th. The onium salts of the formula 1 are compounds again. Thus, the curable compositions comprise the moiety

also those in which Oniumpolymere used ₊

which are an onium functionality of an element -N = N

Group Va of the Periodic Table as part of the 5

Do not include the polymer backbone or in a side position.