WO2002046263A1

WO2002046263A1 - Resin formulation, method for curing the same, and its use

Info

Publication number: WO2002046263A1
Application number: PCT/DE2001/004649
Authority: WO
Inventors: Andreas Hartwig; Monika Sebald
Original assignee: Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
Priority date: 2000-12-08
Filing date: 2001-12-07
Publication date: 2002-06-13

Abstract

The invention relates to a thermally or thermally and photochemically curing resin formulation, which comprises cationically curable epoxy resins or vinyl ethers, an onium salt that serves as an initiator, and an activator that accelerates the thermal curing. The invention also relates to a method for curing said resin formulation. The aim of the invention is to provide formulations which quickly cure at moderate temperatures and which are highly stabile in storage. This is achieved by appropriately selecting a novel actuator and the molar ratio of actuator, initiator and monomer. This enables curing to ensue at room temperature, the reaction time to be reduced in terms of minutes, and also the stability in storage at room temperatures to be increased to periods longer than a week.

Description

Patent Application:

Resin formulation, process for its hardening and its use

description

Technical field

The invention relates to a resin formulation according to the preamble of the main claim, a process for its catalytic curing and its use. Due to the high speed of curing and the moderate temperatures used, as well as the high storage stability of the uncured resin formulation at room temperature, the formulations curing by this process are particularly suitable for use in electronics, electrical engineering, precision engineering and optics.

State of the art

The cationic curing of epoxy resins and vinyl ethers takes place catalytically and can be carried out thermally or photochemically. Due to the increased economic importance of this production method, there is a general interest in economical reaction management with variable choice of process parameters.

According to the general state of the art, onium salts are usually used as catalysts for curing epoxy resins and vinyl ethers. These are mostly iodonium or sulfonium salts with the non-nucleophilic anions SbF ₆ \ AsF ₅ ^" , PF ₆ ^" or BF ₄ ^" . The reactivity of these initiators decreases in the order given Anions assuming the same organic substituents on the anion. The influence of the anion on the reactivity is attributed to the following three factors: starch of Lewis or Bronsted acid; Degree of ion pair separation between the growing cationic polymer chain and the anion; Ability of the anion to cleave fluoride to form a nucleophilic anion that terminates the reaction. In order to be able to photochemically excite the initiator with the technically customary light sources in the case of photochemical curing, the addition of a photosensitizer is necessary.

These initiators have the disadvantage that they often have poor solubility in the formulations to be cured. In addition, they are for applications in electronics,

Electrical engineering or precision engineering is not optimally suited because the anions mentioned

Can split off fluoride, which is particularly corrosive in the presence of moisture.

In applications where the resin is in contact with a base metal, these fluoride ions can cause corrosion of the metal and subsequent delamination of the adhesive bond.

For use as phase transfer catalysts in heterogeneous aqueous / organic reaction media, hydrophobic anions have been developed that are chemically stable and do not release fluoride. Examples include tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the corresponding fluoro- or trifluoromethyl-substituted tetraphenylborates. These anions are also part of initiators which are used for the photochemical cationic curing of epoxides and have good solubility in resins, in particular in silicone epoxides. US 5,468,902 and EP 0 562 897 disclose syntheses of these photoinitiators. The optimal effect of these photoinitiators can be achieved by adding photosensitizers such as anthracene or its derivatives.

These methods of photochemical curing have the disadvantage that they are disadvantageous or even impossible in many applications. In the event that the resin is in in a closed environment (eg casting molds or adhesive joints), and in the event that the resin contains pigments or other fillers that are opaque to the stimulating light, these resins must be thermally hardened. For this purpose, BF ₃ complexes, organometallic compounds, salts of amines, imidazoles and similar compounds are usually used as initiators.

These formulations for thermal curing have the disadvantage that curing at elevated temperatures is often too slow and / or the storage stability at room temperature is too low for numerous applications. In order to achieve special processing or usage properties, additives often have to be added to the

Formulations are introduced, from which the media resistance suffers, and which promote the corrosion of the substrates to be bonded.

The above-described curing of epoxy resins and vinyl ethers thermally induced with onium salts also has the disadvantages of high curing temperatures, which are often above 150 ° C., and extremely long process times.

Various additives are known for lowering the onset temperature of the curing reaction. DE 28 54 01 1 describes the use of thiophenol in the hardening by means of onium salts with the anions SbF ₆ ^" , AsF ₆ ^" , PF ₆ ^" or BF ₄ ^" . However, the initiators used for this have the disadvantages mentioned above of the corrosion-promoting effect of the fluoride and the poor solubility in the monomer. US Pat. No. 5,703,137 and US Pat. No. 5,693,688 disclose methods for curing silicone coatings in which an accelerating effect in the photochemical curing of epoxides and vinyl ethers by means of onium salts with boron organic counterions is achieved by the addition of α-hydroxycarboxylic acid esters or benzyl alcohol derivatives. However, those skilled in the art are unable to derive any practical teaching from these documents for carrying out thermal curing of the epoxides and vinyl ethers, since this is not disclosed here. Presentation of the invention

The object of the present invention is to overcome the disadvantages of the prior art and to provide a resin formulation based on vinyl ethers and / or epoxides which can be cured in particular thermally at a high reaction rate at low temperatures and which has a high storage stability

Has room temperature and can be processed economically advantageous. In addition, the resin formulation should not contain any compounds or anions that promote corrosion and contain no toxic antimony or arsenic compounds.

This object is achieved by the resin formulation described in claim 1 and in

Process described for their hardening and solved by the use according to claims 15-17. The subclaims indicate advantageous further developments.

It has been found that epoxides and / or vinyl ethers can be cured not only photochemically, but also thermally by adding a whole range of substances, using onium salts with boron organic counterions at moderate temperatures. These substances act as activators and increase reactivity, i.e. the reaction rate is increased and / or the onset temperature is lowered. The onset temperature is the temperature at which a chemical reaction takes place at a technically reasonable rate. The exact determination of the onset temperature is described in DIN53765, thermal analysis. The curable resin formulations of the invention include: one or more monomers containing one or more epoxy groups and / or vinyl ether groups.

an initiator in an amount of 0.005 to 10% by weight, comprising one or more onium borates of the general formula [X (R ¹ ) _n (R ² ) ⁺ [BY _a (R ³ ) _b ] ^" (n, m , a and b are integers; n + m = v + 1 where v is the valency of the element X; a = 0 to 3, b = 1 to 4 where a + b = 4) where

- - X is selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, bromine and iodine - - R ¹ and R ^{2 are the} same or different and are carbocyclic or heterocyclic

Aryl radicals having 5 to 20 carbon atoms and / or linear or branched alkyl or alkylene radicals having 1 to 30 carbon atoms,

- - Y are fluorine, chlorine and / or hydroxyl groups, and

- - R ^{3 is the} same or different and is an aryl radical which is substituted by one or more electron-withdrawing substituents. an activator in an amount of 0.005 to 10%; comprising one or more components selected from the group consisting of sulfimides, hydroperoxides, peroxides, carboxylic acids, esters with the exception of α-hydroxycarboxylic esters, carboxylic acid anhydrides, aromatic aldehydes, nitriles, lactones, lactides, N-bromosuccinimide, hydroquinone, glucose, glucose derivatives, amylose or amylose derivatives.

The curable resin formulation according to the invention preferably comprises, as monomers, cycloaliphatic epoxides (for example cyclohexene epoxide, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate, vinylcyclohexene diepoxide), glycidyl ethers (for example phenylglycidyl ether, bisphenol A diglyomeric diglycidylphenol oligomeric diglycidylphenol ether) , polymeric epoxides (eg poly (methyl methacrylate-co-3,4-epoxycyclohexylmethyl methacrylate), isobutyl vinyl ether and / or polytetrahydrofuran divinyl ether.

The use of vinyl ethers alone or in combination with epoxy resins is particularly advantageous if a very high reactivity and / or a very low viscosity of the formulation to be produced is required.

In the onium borates of the formula [X (R (R ² ) _m ] ⁺ [BY _a (R ³ ) J-, R ¹ , R ² , B, Y and R ^{3 are} preferably defined as follows:

- - R ¹ and R ² are the same or different and are phenyl, tolyl or xylyl radicals, and / or linear or branched alkyl or alkylene radicals with 1 to 30 carbon atoms; the radicals R ¹ and R ² are with one or more groups, in particular with alkyl, alkenyl, alkoxy, nitro, fluoro, chloro, bromo, cyano, carboxyl, hydroxyl and / or carbonyl groups, substituted alone or in combination, and / or contain heteroatoms, such as in particular nitrogen, oxygen and / or sulfur.

- - R ³ is the same or different and is a phenyl, biphenyl, naphthyl or anthracenyl radical with the electron-withdrawing substituents F, OCF ₃ , CF ₃ , N0 ₂ , CN and / or Cl. Particularly preferred onium borates are sulfonium or iodonium salts with borate anions of the formula [B (C ₆ F ₅ ) ₄ ] \ [B (C ₅ H ₃ F ₂ ) ₄ ] -, [B (C ₆ F ₄ OCF ₃ ) ₄ ] -, [BF ₂ (C ₆ F ₅₎ _2] ^", [B (C ₆ F ₄ CF ₃₎ _4] -and / or [B (C ₆ H ₃ (CF ₃₎ ₂₎ _4] -.

The onium borates [X (R ¹ ) _n (R ² ) J ⁺ [BY _a (R ³ ) _b ] ^" have the same radicals R \ R ² , B, Y and R ³ in the following order for X increasing activity: 0 "S" Se <P <N <S <1. The initiator is contained in a curable resin formulation with particularly high activity, preferably in an amount of 0.1 to 5% by weight.

The stated activators bring about a reduction in the curing temperature (at which curing can be carried out) or the onset temperature and / or an increase in the reaction rate. The use of the specified activators and the possibility to choose from a large number of activators which can be used offers several advantages. The desired reactivity of the resin formulation can be influenced in a targeted manner by suitable selection of the activators on the one hand and the ratio of activator, initiator and monomer on the other hand. It is possible to set the onset temperature or to lower the onset temperature while the reaction rate remains the same. With a suitable formulation, curing of the resin formulations containing vinyl ether and / or epoxy groups is also possible at room temperature or lower. Likewise, the duration of the hardening can be reduced to the second range while the reaction temperature remains the same.

The activity of the activators increases in the following order: sulfimides «hydroperoxides * peroxides« N-bromosuccinimide »hydroquinones» aromatic aldehydes »nitriles * lactides < Lactones <glucose * glucose derivatives «amylose» amylose derivatives <esters <carboxylic acids <carboxylic anhydrides.

If a mixture of different activators is used, this often leads to a further acceleration of the curing reaction and / or lowering of the onset temperature. The many different activators also offer the possibility, in the case of one

Side reaction of an activator with the monomer, the initiator or another substance contained in the resin formulation to avoid another activator with completely different functional groups. Furthermore, the curable resin formulations according to the invention have high storage stability at room temperature. For example, storage stabilities of more than one week are achieved if the storage temperature is at least 60 ° C below the curing temperature. The resin formulation according to the invention also offers the advantage that it contains no compounds with components such as BF ₃ , PF ₅ ^" , SbF ₆ ^" , AsF ₆ ^" or BF ₄ ^" , and therefore no corrosive fluoride ions can form under the action of moisture. In addition, the resin formulation according to the invention contains no toxic components such as antimony or arsenic compounds.

For a particularly advantageous resin formulation according to the invention, the activator is selected from the group consisting of o-benzoic acid sulfimide, terephthalic acid, maleic acid, ethyl acetate, methyl salicylate, maleic anhydride,

Ascorbic acid, ascorbic acid derivatives, γ-butyrolactone, glucose, glucose acetates and

Amylose.

These bring about a particularly strong reduction in the curing temperature and / or a particularly strong increase in the reaction rate. The activity of these particularly advantageous activators increases in the following order: o-benzoic acid sulfimide <γ-butyrolactone <glucose «amylose« glucose acetate <

Ethyl acetate "Salicylic acid methyl ester <maleic acid" Terephthalic acid <

Maleic anhydride <ascorbic acid <ascorbic acid derivatives. The activator is contained in a particularly advantageous curable resin formulation in an amount of 0.1 to 5% by weight.

In the range of activator added, there is also a sharp reduction in the curing temperature or the onset temperature and / or a particularly sharp increase in the reaction rate. If more activator is added, the above parameters change only slightly; From an economic point of view, the addition of more than 5% by weight of activator is rarely useful.

For a particularly advantageous resin formulation according to the invention, the activator can furthermore be a component of the monomer as a functional group. This means that the activator cannot be extracted when exposed to media. For example, in the hardened state there can be no undesirable change in properties (e.g. optical, mechanical or electrical properties) of the resin formulation due to the extraction of the activator.

In an advantageous development of the resin formulation according to the invention, it additionally contains mono- and / or polyhydric alcohols or mixtures thereof. Surprisingly, it has been found that alcohols which are added to the resin formulation according to the invention are incorporated into the resulting polymer or polymer network during curing. It is therefore possible to adjust the degree of polymerization or the network density when curing epoxides and vinyl ethers using onium salts and thus to influence the dynamic mechanical properties of the cured polymer and also to control the viscosity of the resin formulation by adding alcohols. Depending on the desired effect, monohydric or polyhydric alcohols, such as poly (ethylene glycol), poly (tetrahydrofuran) and / or polyester polyols, can be used for this purpose. In a further advantageous development of the resin formulation according to the invention, it additionally contains one or more photosensitizers in an amount of 0.05 to 5% based on the overall formulation.

This opens up the possibility for the resin formulations according to the invention to carry out not only thermal curing but also photochemical curing. This is particularly advantageous if, in the case of adhesive processes, parts to be joined are first fixed photochemically and only then can or should a complete hardening take place thermally. Suitable photosensitizers are, in particular, anthracene, phenanthrene and isopropylthioxanthone or mixtures thereof, which are particularly preferably added in an amount of 0.1 to 2% based on the overall formulation.

In a further advantageous development of the resin formulation according to the invention, it additionally contains a stabilizer in an amount of 0.001 to 5% by weight. Despite the fact that the resin formulations according to the invention have a very good storage stability, a further increase in the storage stability and an influence on the curing temperature are nevertheless possible. Amines or amine derivatives are preferably used as stabilizers, which are particularly preferably incorporated into the resin formulation in an amount of 0.05 to 0.5%. Particularly suitable stabilizers are diethylaniline, aniline, dicyandiamide and methylimidazole.

In an advantageous development, the resin formulation according to the invention additionally contains fillers, pigments, plasticizers, adhesion promoters, solvents, non-reactive polymers or oligomers and / or further cationically and / or free-radically curable monomers.

This allows the material properties, in particular the optical, mechanical and electrical properties of the resin formulation, to be influenced in a targeted manner. In a particularly advantageous resin formulation, the fillers are silver flakes, graphite, metal-coated polymer balls, metal-coated polymer particles, metal-coated glass balls and / or metal-coated glass particles.

It can thereby be achieved that the resin formulation according to the invention becomes electrically conductive.

The curable resin formulations according to the invention are advantageously cured in a process in which the curing is carried out either thermally or thermally and photochemically. In the process according to the invention, curing takes place in a catalytic reaction. A lowering of the curing temperature or the onset temperature is possible due to the contained activators; Due to the moderate temperatures during curing, thermal curing of resin formulations that contain temperature-sensitive additives is also possible. Due to the many different activators, it is possible to set the curing temperature while maintaining the same reaction rate. Likewise, the duration of the hardening can be reduced to the second range while the reaction temperature remains the same. The method according to the invention is particularly suitable for resin formulations for use in electronics, electrical engineering, precision engineering and optics. By lowering the curing temperature, the process according to the invention is furthermore considerably less cost-intensive and more economical. Another advantage of the method according to the invention is that many different activators are available. Therefore, the curing temperature and / or the curing rate can be controlled by the choice and the amount of activator or activator mixture added.

The process according to the invention is advantageously carried out in such a way that the curing temperature is below 130 ° C. and the curing takes less than one hour at this temperature. This makes it possible, in particular, to thermally harden resin formulations which contain temperature-sensitive additives. The danger of unwanted Side reactions such as decomposition due to excessive temperatures can be reduced in this way.

The process according to the invention is particularly advantageously carried out in such a way that the curing temperature is below 100 ° C. and the curing takes less than two hours at this temperature. This makes it possible, in particular, to thermally harden resin formulations which contain particularly temperature-sensitive additives, and to connect or coat temperature-sensitive components or materials by means of thermal hardening. This is particularly advantageous when the resin formulation is used in electronics, electrical engineering, precision engineering and optics. The risk of undesirable side reactions such as Decomposition due to excessively high temperatures can be greatly reduced when hardening with the process parameters just mentioned.

The resin formulation according to the invention is advantageously used as an adhesive, lacquer,

Protective layer, casting compound or printing ink used.

The resin formulation according to the invention is also advantageously used as an underfiller,

Glob top mass or coil potting compound used.

A particularly preferred form of application is use in electronics, precision engineering or optics, since the resin formulation according to the invention does not

Contains fluoride ions; these render electronic components unusable, particularly in the presence of moisture, and can have a corrosive effect on optical components or, for example, in contact with silicon or aluminum.

A resin formulation in which silver flakes, graphite, and metal-coated fillers

Polymer balls, metal-coated polymer particles, metal-coated glass balls and / or metal-coated glass particles are particularly suitable for the production of electrically conductive adhesives or printing pastes. These can be used, for example, for electronic circuits in automotive engineering. applications

Without restricting generality, the curable resin formulation according to the invention and the process for curing it are explained in more detail below with the aid of application examples.

Example 1 - Comparative Example

Hardening an epoxy resin without adding an activator:

10 g of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate are mixed with 0.1 g of tolylcumyliodonium tetrakis (pentaf luorphenyI) borate and stirred until the initiator dissolves. The hardening behavior of the mixture is examined by means of DSC (differential thermal analysis) with a heating rate of 10 K / min. The onset temperature of the thermally induced curing reaction is 146 ° C. When hardening samples with a mass of 0.2 g in an oven, the resin mixture is unchanged after 6 h at 100 ° C. The IR spectroscopic characterization shows that no curing reaction has taken place.

Example 2

Hardening an epoxy resin with the addition of an activator:

0.05 g of ascorbic acid 6-hexadecanate is added to 5 g of the mixture from Example 1.

In the DSC examination, the addition of the activator leads to a lowering of the onset

Temperature to 84 ° C. When hardening samples with a mass of 0.2 g in one

The resin mixture is hard after 5 min at 100 ° C or 60 min at 80 ° C and the surface is tack-free. Epoxy groups can no longer be detected by IR spectroscopy. Example 3 - Comparative Example

Curing an epoxy resin with a conventional thermal initiator

5 g of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate are mixed with 0.05 g of the boron fluoride complex BF3 500 (Bakelite). After the initiator has dissolved, a sample with a mass of 0.2 g is cured in an oven at 100 ° C. The sample begins to gel after 5 minutes and is solid after 10 minutes, but the sample is deformable and has a sticky surface. The sample is therefore insufficiently hardened. The IR spectroscopic analysis of the sample shows that about 50% of the epoxy groups present did not react.

Example 4

Hardening a glycidyl ether

10 g Epikote 828 LV (Shell) are mixed with 0.1 g tolylcumyliodonium tetrakis entafluorophenyl) borate and 0.1 g ascorbic acid 6-hexadecanate. And stirred until the initiator and activator are dissolved. The 0.2 g samples are completely hardened after 4 h at 90 ° C or after 30 min at 1 10 ° C in the oven and have a non-stick surface. IR spectroscopy shows complete hardening.

Example 5

Hardening a vinyl ether

1 g of isobutyl vinyl ether is mixed with 0.02 g of a mixture of equal parts of tolylcumyl iodonium tetrakis (pentafluorophenyl) borate and ascorbic acid 6-hexadecanate and stirred until the additives have dissolved. The curing sets in after a few minutes at room temperature and a tack-free polymer results. No more vinyl groups can be detected by IR spectroscopy. Example 6

Use of different activators

20 g of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate are mixed with 0.1 g of tolylcumyliodonium tetrakis (pentafluorophenyl) borate. After the initiator has been dissolved, 0.01 g of the following activators are added to samples of this 2 g mixture: terephthalic acid, methyl salicylate, ethyl acetate, maleic acid or maleic anhydride. All prepared mixtures harden in the oven at 85 ° C within 4 hours. In the case of the cured samples, no unreacted epoxy can be detected by IR spectroscopy. At room temperature, no change in the samples was observed after one week, i.e. the pot life at room temperature is greater than one week.

Example 7 Addition of an alcohol

8 g of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate, 2 g of poly (tetrahydrofuran) with an M _n = 250, 0.1 g of tolylcumyliodonium tetrakis (pentafluorophenyl) borate and 0.04 g of ascorbic acid 6-hexadecanate are stirred until the components have come apart. Part of the sample cures at 80 ° C within 5 minutes to form a tack-free polymer. In the cured polymer, no unreacted epoxy can be detected by IR spectroscopy. At room temperature, the sample begins to gel after 4 days.

Example 8 Adjusting the reactivity by varying the activator concentration and combining different activators

10 g of 3,4-epoxycyclohexylmethyl-3 ^' , 4'-epoxycyclohexane carboxylate are mixed with the corresponding amount of (tolylcumyl) iodonium tetrakis (pentafluorophenyl) borate and stirred until the initiator dissolves. The activators are then added and the mixture is stirred again until a homogeneous mixture has formed. The hardening behavior of the mixtures was examined by means of DSC at a heating rate of 10 K / min. The onset temperature of the thermally induced curing reaction is characteristic of the curing reaction and is summarized in the table together with the composition of the mixtures. The following abbreviations were used for the activators: ascorbic acid 6-hexadecanate ASHD, maleic anhydride MSA, phthalic anhydride PA.

The results show that the reactivity increases both with increasing catalyst content and with increasing activator content. The curing temperature can be adjusted by combining activators. Ascorbic acid 6-hexadecanate is more reactive in combination with phthalic anhydride than with maleic anhydride.

Example 9:

Combination of photocuring and thermal curing 10 g of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate, 0.05 g of tolylcumyliodonium tetrakis (pentafluorophenyl) borate, 0.05 g of maleic anhydride and 0.05 g of anthracene are mixed together. With this mixture, 5 x 5 mm silicon joining parts are glued together. The adhesive joint thickness is about 50 μm, a small amount of the resin formulation forms a meniscus along the adhesive joint. This meniscus is irradiated for 100 s with a mercury lamp with a radiation intensity of 80 mW / cm ² . In normal handling, the parts to be joined are no longer moved against each other, since the edge of the adhesive joint has been hardened photochemically. The actual hardening then takes place in 30 minutes in an oven at 100 ° C, after which the parts to be joined are firmly connected.

Claims

claims

1. A curable resin formulation comprising

- one or more monomers containing one or more epoxy groups and / or vinyl ether groups; an initiator in an amount of 0.005 to 10% by weight, comprising one or more onium borates of the general formula [X (R ¹ ) _n (R ² ) _m ] ⁺ [BY _a (R ³ ) _b ] ^" ( n, m, a and b are integers; n + m = v + 1 where v is the valency of the element X; a = 0 to 3, b = 1 to 4 where a + b = 4) where X is selected from the group consisting of nitrogen, oxygen, phosphorus,

Sulfur, selenium, bromine and iodine,

R ¹ and R ^{2 are the} same or different and are carbocyclic or heterocyclic

Aryl radicals having 5 to 20 carbon atoms and / or linear or branched alkyl or alkylene radicals having 1 to 30 carbon atoms, Y are fluorine, chlorine and / or hydroxyl groups, and

R ^{3 is the} same or different and is an aryl group substituted with one or more electron-withdrawing substituents;

an activator in an amount of 0.005 to 10% by weight, comprising one or more components selected from the group consisting of sulfimides, hydroperoxides, peroxides, carboxylic acids, esters -

Hydroxycarboxylic acid esters, carboxylic acid anhydrides, aromatic aldehydes, nitriles, lactones, lactides, N-bromosuccinimide, hydroquinone, glucose, glucose derivatives, amylose or amylose derivatives.

2. Resin formulation according to claim 1, characterized in that 0.1 to 5 wt .-% initiator are included.

3. Resin formulation according to claim 1 or 2, characterized in that the initiator is a sulfonium or iodonium salt with borate anions of the formula [B (C ₆ F ₅ ) ₄ ] ^" , [B (C ₆ H ₃ F ₂ ) ₄ ] -, [B (C ₆ F ₄ OCF ₃ ) ₄ ] ^" , [BF ₂ (C ₆ F ₅ ) ₂ ] ^" , [B (C ₆ F ₄ CF ₃ ) ₄ ] - and / or [B (C ₅ H ₃ (CF ₃ ) ₂ ) ₄ ] - is.

4. Resin formulation according to one or more of claims 1 to 3, characterized in that the activator is selected from the group consisting of o-benzoic acid sulfimide, terephthalic acid, maleic acid, ethyl acetate, salicylic acid methyl ester, maleic anhydride, ascorbic acid, ascorbic acid derivatives, γ-butyrolactone,

Glucose acetates and amylose.

5. Resin formulation according to one or more of claims 1 to 4, characterized in that 0.1 to 5 wt .-% activator are included.

6. Resin formulation according to one or more of claims 1 to 5, characterized in that the activator as a functional group is part of the monomer.

7. Resin formulation according to one or more of claims 1 to 6, characterized in that it additionally contains mono- and / or polyhydric alcohols or mixtures thereof.

8. Resin formulation according to one or more of claims 1 to 7, characterized in that a photosensitizer is additionally present in an amount of 0.05 to 5% by weight, based on the overall formulation.

9. Resin formulation according to one or more of claims 1 to 8, characterized in that a stabilizer is additionally contained in an amount of 0.001 to 5 wt .-%.

10. Resin formulation according to one or more of claims 1 to 9, characterized in that it additionally contains fillers, pigments, plasticizers, adhesion promoters, solvents, non-reactive polymers or oligomers and / or further cationically and / or radically curable monomers.

1 1. Resin formulation according to claim 10, characterized in that the fillers are silver flakes, graphite, metal-coated polymer balls, metal-coated polymer particles, metal-coated glass balls and / or metal-coated glass particles.

12. A process for the catalytic curing of the resin formulations as described in one or more of claims 1 to 11, characterized in that the curing is carried out thermally or thermally and photochemically.

13. A method for catalytic thermal curing according to claim 12, characterized in that the resin formulations are cured below 130 ° C and at this temperature the curing takes less than an hour.

14. A method for catalytic thermal curing according to claim 12, characterized in that the resin formulations are cured at 100 ° C and at this temperature Hardening takes less than two hours.

15. Use of the resin formulation as described in one or more of claims 1 to 1 1, as an adhesive, lacquer, protective layer, casting compound or printing ink.

16. Use of the resin formulation as described in one or more of claims 1 to 1 1, as an underfiller, glob top mass or coil sealing compound.

17. Use of the resin formulation as described in claim 1 1, for the production of electrically conductive adhesives or printing pastes.