Curing of reaction resins using unsaturated peroxides as initiators and organic phosphites as accelerators

Abstract

A novel reaction resin formulation having a significantly improved properties profile contains crosslinkers, monomers, urethane methacrylates, prepolymers, optional further auxiliaries, and a curing system containing permaleinates and a tertiary organic phosphite. The reaction resin formulation is useful for marking driving surfaces or coating surfaces. The reaction resins, above all based on a novel curing system, show an improved combination of higher long-term storage stability, improved toxicological profile, reduced curing time, a low yellowing tendency and a better colour fastness.

Claims

1: A (meth)acrylate-based 2K reaction resin, comprising: two components, wherein the two components of the 2K reaction resin together contain 0% by weight to 30% by weight of at least one crosslinker, 20% by weight to 85% by weight of at least one monomer, 0% by weight to 60% by weight of at least one urethane (meth)acrylate, 0% by weight to 40% by weight of at least one prepolymer, optionally, at least one further auxiliary, and 1.15% by weight to 10% by weight of a curing system based on the 2K reaction resin containing 0.15% by weight to 5% by weight of at least one permaleinate, and 1.0% by weight to 10% by weight of a tertiary organic phosphite, as ingredients, wherein the at least one permaleinate on the one hand and the tertiary organic phosphite on the other are contained in separate components of the 2K reaction resin before the two components are mixed together, and wherein the tertiary organic phosphite has the general formula P(OR1)(OR2)(OR3), wherein R1, R2 and R3 are identical or are groups differing from one another and at least one of these groups has more than 6 C atoms.

2: The 2K reaction resin according to claim 1, wherein the two components of the 2K reaction resin together contain 2% by weight to 20% by weight of at least one multifunctional (meth)acrylate, 25% by weight to 75% by weight of at least one (meth)acrylate and/or monomer copolymerisable with (meth)acrylates, wherein a content of acrylates is a maximum of 5% by weight of the 2K reaction resin, 0% by weight to 45% by weight of the at least one urethane (meth)acrylate, 10% by weight to 35% by weight of the at least one prepolymer, optionally, the at least one further auxiliary, and 2% by weight to 7.5% by weight of the curing system containing, based on the 2K reaction resin, 0.5% by weight to 4.0% by weight of the at least one permaleinate, and 1.5% by weight to 6.0% by weight of the tertiary organic phosphite as ingredients.

3: The 2K reaction resin according to claim 1, wherein the two components of the 2K reaction resin together contain 0% by weight to 20% by weight of at least one multifunctional (meth)acrylate, 25% by weight to 75% by weight of at least one (meth)acrylate and/or monomer copolymerisable with (meth)acrylates, wherein a content of acrylates is a maximum of 5% by weight of the 2K reaction resin, 10% by weight to 60% by weight of the at least one urethane (meth)acrylate, 10% by weight to 35% by weight of the at least one prepolymer, optionally, the at least one further auxiliary, and 2% by weight to 7.5% by weight of the curing system containing, based on the 2K reaction resin, 0.5% by weight to 4.0% by weight of the at least one permaleinate, and 1.5% by weight to 6.0% by weight of the tertiary organic phosphite, as ingredients.

4: The 2K reaction resin according to claim 1, wherein the two components of the 2K reaction resin together contain 3% by weight to 15% by weight of at least one multifunctional methacrylate, 30% by weight to 40% by weight of at least one (meth)acrylate and/or monomer copolymerisable with (meth)acrylates, wherein based on a total amount of the 2K reaction resin, a maximum of 5% by weight of the monomers are acrylates, 0% by weight to 30% by weight of the at least one urethane (meth)acrylate, 15% by weight to 25% by weight of the at least one prepolymer, optionally, the at least one further auxiliary, and 2% by weight to 7% by weight of the curing system containing 0.75% by weight to 3.5% by weight of the at least one permaleinate, and 2.0% by weight to 5.0% by weight of the tertiary organic phosphite, as ingredients.

5: The 2K reaction resin according to claim 1, wherein the at least one permaleinate is tert-butyl monoperoxomaleic acid ester.

6: The 2K reaction resin according to claim 1, wherein the tertiary organic phosphite is triisodecyl phosphite.

7: The 2K reaction resin according to claim 1, wherein the 2K reaction resin contains no amine.

8. The 2K reaction resin according to claim 1, wherein the 2K reaction resin contains no acrylates.

9: The 2K reaction resin according to claim 1, wherein a second component of the 2K reaction resin consists exclusively of components of the curing system that are not contained in a first component.

10: The 2K reaction resin according to claim 1, wherein a first component and a second component of the 2K reaction resin have identical compositions, with the exception of components of the curing system.

11: The 2K reaction resin according to claim 1, wherein the 2K reaction resin contains 0.3% by weight to 3% by weight of one or more paraffins, a congealing point of which according to DIN-ISO 2207 is in the temperature range of 35° C. to 75° C.

12: The 2K reaction resin according to claim 1, wherein the 2K reaction resin, based on a total of acrylate and methacrylate groups, contains a maximum of 5% by weight of acrylate groups.

13. A method for application of a 2K reaction resin, the method comprising: mixing the two components of the 2K reaction resin according to claim 1 on a substrate, within 2 min to 40 min before or during application.

14: The method according to claim 13, wherein the substrate is a roadway, paving stones, concrete, screed, asphalt, ceramic, or steel.

15: Cold plastic for a road marking, seal, or floor coating, comprising: 5% by weight to 80% by weight of the 2K reaction resin according to claim 1, 0.15% by weight to 25% by weight of one or more pigment, 15% by weight to 90% by weight of one or more inorganic fillers, 0% by weight to 5% by weight of one or more further stabilisers and/or additives not contained in the 2K reaction resin, and 0% by weight to 90% by weight of one or more organic fillers, as components.

16: The cold plastic according to claim 15, wherein the cold plastic contains: 10% by weight to 60% by weight of the 2K reaction resin, 1.5% by weight to 15% by weight of one or more inorganic pigments, 0.3% by weight to 3% by weight of the one or more further stabilisers and/or additives not contained in the 2K reaction resin, and 50% by weight to 80% by weight of the one or more inorganic fillers and the one or more organic fillers in total, wherein the one or more organic fillers are polymers, as components.

17: The method according to claim 14, wherein the substrate is a steel girder.

18: The cold plastic according to claim 16, wherein the one or more inorganic pigments is titanium dioxide.

Description

DETAILED DESCRIPTION OF THE COMPONENTS OF THE COLD PLASTIC OR THE REACTION RESIN

[0075] Additionally, the cold plastic or cold spray plastic can contain further auxiliaries such as crosslinking or dispersing agents, a non-slip filler that improves slip resistance and anti-settling agents. Glass beads can also be added to improve reflection or may already be contained in a component of the cold plastic. Alternatively, the glass beads can be put into place after application to the surface. In this process, used for example in modern marking vehicles with a second nozzle, after application of the first two components, the beads are directly sprayed into these components. The advantage of this process is that only the portion of the glass beads embedded in the marking matrix is wetted with the ingredients of the other two components, and one thus obtains optimum reflection properties. Most particularly, however, in application of this process, particularly good embedding of the glass beads and correspondingly good adhesion of the marking matrix or the road marking formulation to the surface of the glass beads are important. Surprisingly, it was found that the reaction resin according to the invention or the cold spray plastic containing this reaction resin fulfil these required properties at least to the level of the prior art. The required properties for a street marking are precisely specified in DIN EN 1436.

[0076] In order to further improve the required properties, the glass beads can be applied together with adhesion promoters or be pre-treated with such adhesion promoters. In this manner, the retro-reflection properties and the day or night visibility of the cold plastic according to the invention are at least comparable to the prior art. The same applies to durability, particularly of embedding the glass beads.

[0077] In the novel curing system, unsaturated peroxides, particularly tert-butyl permaleinate, are used as initiators. In some cases, it can be advantageous to use a mixture of various initiators. As a rule, the peroxide in the second component is mixed with a diluent such as an oil or a plasticiser. However, the aforementioned concentrations in the reaction resins according to the invention refer only to the pure initiator.

[0078] An optional component of the reaction resin according to the invention are crosslinkers, in particular multifunctional methacrylates such as allyl (meth)acrylates. Particularly preferred are di- or tri-(meth)acrylates such as e.g. 1,4-butanediol di(meth)acrylate, poly(urethane) (meth)acrylates, tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate or trimethylolpropane tri(meth)acrylate.

[0079] The optionally contained urethane (meth)acrylates are understood in the context of this invention to refer to compounds that contain (meth)acrylate functionalities that are bonded to one another via urethane groups. They are obtainable by reacting hydroxyalkyl (meth)acrylates with polyisocyanates and polyoxyalkylenes that have at least two hydroxy functionalities. Instead of hydroxyalkyl (meth)acrylates, esters of (meth)acrylic acid with oxiranes, such as e.g. ethylene or propylene oxide, or corresponding oligo- or polyoxiranes can also be used. For example, an overview of urethane (meth)acrylates with a functionality of greater than two can be found in DE 19902685. A commercially available example produced from polyolene, isocyanates and hydroxyfunctional (meth)acrylates is EBECRYL 210-5129 from Allnex. In a reaction resin, urethane (meth)acrylates, without major temperature-dependency increase flexibility, tear resistance and elongation at break. Surprisingly, it was found that even urethane acrylates containing the novel curing system in higher contents show tack-free curing without problems. This opens up possibilities, while largely dispensing with acrylate monomers that typically have a low glass transition temperature, for producing flexible reaction resins such as those needed for e.g. roadway markings or sealing systems.

[0080] In particular, the monomers contained in the reaction resin are compounds selected from the group of (meth)acrylates such as e.g. alkyl (meth)acrylates of linear, branched or cycloaliphatic alcohols with 1 to 40 C atoms, such as e.g. methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate; aryl (meth)acrylates such as e.g. benzyl (meth)acrylate; mono(meth)acrylates of ethers, polyethylene glycolenes, polypropylene glycolenes or mixtures thereof with 5 to 80 C atoms, such as e.g. tetrahydrofurfuryl (meth)acrylate, methoxy(m)ethoxy ethyl (meth)acrylate, benzyloxymethyl (meth)acrylate, 1-ethoxybutyl (meth)acrylate, 1-ethoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate and poly(propylene glycol) methyl ether (meth)acrylate.

[0081] The group or the (meth)acrylates also comprises esters of (meth)acrylic acid with an acetal, ketal or carbonate of glycerol, substituted glycerol or trimethylolpropane or substituted trimethylolpropane.

[0082] Preferred examples of such monomers are glycerol formal (meth)acrylate, trimethylolpropane formal (meth)acrylate or isopropylidene glycerol (meth)acrylate (solketal methacrylate).

[0083] Surprisingly, it was found that the reaction resin composition according to the invention preferably contains a maximum of up to 5% by weight of acrylate monomers based on the 2K reaction resin. This allows short curing times relative to pot life to be achieved. In a most particularly preferred embodiment, the 2K reaction resin contains no acrylate monomers.

[0084] Also suitable as components or monomer mixtures are additional monomers with a further functional group, such as α,β-unsaturated mono- or dicarboxylic acids, for example acrylic acid, methacrylic acid or itaconic acid; esters of acrylic acid or methacrylic acid with divalent alcohols, for example hydroxyethyl (meth)acrylate or hydroxypropyl (meth)acrylate; acrylamide or methacrylamide; or dimethylaminoethyl (meth)acrylate. Further suitable components of monomer mixtures are for example glycidyl (meth)acrylate or silyl functional (meth)acrylate.

[0085] In addition to these (meth)acrylates, the monomer mixtures can also contain further unsaturated monomers that are copolymerisable with the aforementioned (meth)acrylates and by means of free-radical polymerisation. These include 1-alkenes or styrenes. In individual cases, the poly(meth)acrylate is selected as appropriate according to content and composition with respect to the desired technical function.

[0086] In so-called MO-PO systems, in addition to the listed monomers, polymers, which are referred to for better differentiation in this patent document as prepolymers, are also present, preferably polyesters or poly(meth)acrylates. These are added to the resins in order to improve polymerisation properties, mechanical properties, adhesion to the substrate and optical requirements. As only small amounts and acrylate monomers with a low glass transition temperature are used for flexibilisation of the reaction resins, in addition to methacrylate monomers with a corresponding glass transition temperature, prepolymers with a low glass transition temperature can also be used for this purpose, wherein the prepolymers themselves can in turn be composed of acrylate monomers.

[0087] Both the polyesters and the poly(meth)acrylates can have additional functional groups for adhesion promotion or copolymerisation in the crosslinking reaction, such as e.g. In the form of double bonds. Preferably, however, with respect to better colour-fastness of the road marking, the prepolymers do not have any double bonds. Said poly(meth)acrylates are generally composed of the same monomers as those already listed with respect to the monomers in the resin system. They can be obtained by solution, emulsion, suspension, substance or precipitation polymerisation and are added to the system as a pure substance. Said polyesters are obtained in substance via polycondensation or ring-opening polymerisation and are composed of the building blocks known for these applications.

[0088] Chain-transfer agents, plasticisers, paraffins, stabilisers, inhibitors, waxes and/or oils may be additionally used as auxiliaries and additives. Paraffins are added in order to prevent inhibition of polymerisation by oxygen in the air. Multiple paraffins with various melting points in various concentrations can be used for this purpose. It has been found to be highly advantageous if the 2K reaction resin according to the invention additionally contains 0.3% by weight to 3% by weight of one or more paraffins. These paraffins are characterised in that their congealing point according to DIN-ISO 2207 is in the temperature range of 35° C. to 75° C.

[0089] All compounds known from radical polymerisation can be used as chain-transfer agents. Preferably, mercaptans such as n-dodecyl mercaptan are used. Esters, polyols, oils, low-molecular-weight polyethers or phthalates are preferably used as plasticizers.

[0090] UV stabilisers can also be used. Preferably, the UV stabilisers are selected from the group of benzophenone derivatives, benzotriazole derivatives, thioxanthonate derivatives, piperidinecarboxylic acid ester derivatives or cinnamic acid ester derivatives. Among the group of stabilisers or inhibitors, substituted phenols and hydroquinone derivatives are preferably used.

[0091] The following components can optionally also be contained in the 2K reaction resin or cold plastic or in other final formulations based on the 2K reaction resins according to the invention:

[0092] wetting agents, dispersants and pyridonecarboxylic flow control agents are preferably selected from the group of the alcohols, hydrocarbons, glycol derivatives, derivatives of glycolic acid esters, acetic acid esters and polysiloxanes, polyethers, polysiloxanes, polycarboxylic acids and saturated and unsaturated polycarboxylic acid aminoamides.

[0093] Preferably used as rheology additives are polyhydroxycarboxylic acid amides, urea derivatives, salts of unsaturated carboxylic acid esters, alkylammonium salts of acidic phosphoric acid derivatives, ketoximes, amine salts of p-toluenesulfonic acid, amine salts of sulfonic acid derivatives and aqueous or organic solutions or mixtures of these compounds. It has been found that rheology additives based on pyrogenic or precipitated, optionally also silanised, silicic acids with a BET surface of 10 to 700 nm.sup.2/g are particularly suitable.

[0094] Defoaming agents selected from the group of the alcohols, hydrocarbons, paraffin-based mineral oils, glycol derivatives, derivatives of glycolic acid esters, acetic acid esters and polysiloxanes are preferably used.

[0095] Analogous components can be used for the auxiliaries and additives additionally used in the cold plastic.

[0096] As mentioned above, one can add to the cold plastics, usable e.g. for road marking, dyes, glass beads, fine and coarse filers, wetting agents, dispersants and flow control agents, UV stabilisers, defoaming agents and rheology additives. Auxiliaries and additives, preferably dyes, are added for areas of application of roadway markings such as e.g. lines, bars or symbols, or zone markings for the identification e.g. of bicycle paths or bus lanes or parking places. Particularly preferred are white, red, blue, green and yellow inorganic pigments, and particularly preferred are white pigments such as titanium dioxide.

[0097] Glass beads are preferably used as reflecting agents in formulations for roadway markings and zone markings. The commercial beads ordinarily used have a diameter of 10 μm to 2000 μm, preferably 50 μm to 800 μm. The glass beads can be provided with an adhesion promoter for better processing and adhesion. Preferably, the glass beads can be silanised.

[0098] One or multiple mineral fine fillers and coarse fillers may also be added to the cold plastics. These materials also serve as anti-sip agents and are therefore used in particular for improving non-slip properties and additional colouring of the road marking. Fine fillers from the group of the calcium carbonates, barium sulphates, quartzes, quartz powders, precipitated and pyrogenic silicic acids, pigments and cristobalites and corundums are used. Quartzes, cristobalites, corundums and aluminium silicates are used as coarse fillers.

[0099] The 2K reaction resins according to the invention allow a freedom of formulation that is so great that said 2K reaction resin or the cold plastics/cold spray plastics according to the invention containing the reaction resin are just as capable of formulation and addition of additives as an established system of the prior art. Therefore, their abrasion resistance, durability, brightness, pigmentation and non-slip properties are at least as good as those of systems of the prior art.

[0100] This quality of being at least comparable to the prior art also applies correspondingly to the storage stability of the reaction resin. The system can also be optimised with respect to the substrate to be coated by selecting suitable monomers, prepolymers and/or adhesion promoters. Accordingly, the systems according to the invention can be variably optimised for the marking of asphalt, concrete or natural stone surfaces.

[0101] Use of the Reaction Resins or Cold Plastics/Cold Spray Plastics

[0102] In addition to the described 2K reaction resins according to the invention and the cold plastics containing them, a method for application of a 2K reaction resin is also a part of the present invention. This process is characterised in that the two components of a 2K reaction resin according to the invention, within 2 min to 40 min before or during application, are mixed with each other on a substrate. Here, the formulation “application to a substrate” is to be interpreted in the broad sense. It therefore includes not only e.g. the coating of surfaces, but also activities such as the filling of moulds.

[0103] In this case, the substrate can in particular be driving surfaces, paving stones, concrete, screed, asphalt, ceramic or steel, particularly in the form of a steel girder.

[0104] The 2K reaction resin according to the invention further allows the production of yellowing-free artificial stone mouldings at ambient temperature, e.g. the production of sanitary products in unheated moulds.

[0105] Preferably, the 2K reaction resins according to the invention or cold plastics containing these reaction resins are used for street marking, particularly for the production of durable roadway markings, or for the coating of floors or seats, particularly in the industrial or commercial field. However, this listing may not be used to limit the application of the reaction resins or cold plastics according to the invention in any way.

[0106] The systems according to the invention are also flexibly usable with respect to application technology. For example, the reaction resins or cold plastics according to the invention can be applied in the spraying, casting, or extrusion process or manually by means of a trowel, a roller or a spatula.

[0107] The individual components of the cold plastic such as e.g. the 2K reaction resin according to the invention can be mixed before, after or during the further processing, such as e.g. application to a driving surface. The method of mixing in before further processing is established, wherein it should be noted that after mixing in of the curing agent component, there is only a limited period of time available for application, e.g. of 2 or 40 min. Mixing prior to processing is possible for example in modern marking machines, which are equipped with a mixing chamber upstream of the application nozzle. Mixing in of the curing agent after application can e.g. be carried out by subsequent application with two or more nozzles or by applying glass beads that are coated with curing agents. Alternatively, a primer containing the curing components can be pre-sprayed before the cold plastic or cold spray plastic is applied.

[0108] Additionally, the mechanical properties of the road marking produced with the 2K reaction resins according to the invention are outstanding in a typical range of between 200 μm and 7000 μm, independently of the application thickness. The application thickness of the cold plastic or cold spray plastic according to the invention is preferably between 400 μm and 1000 μm and particularly preferably between 600 μm and 800 μm. Depending on the application, thicker and thinner layers are also possible.

[0109] Preferably, the 2K reaction resins according to the invention or the cold plastic produced therefrom are used for the production of durable roadway markings.

[0110] By way of example, the 2K reaction resins or cold plastics are used in a process in which glass beads are added before, during or immediately after application of the cold plastic to a driving surface.

[0111] Alternatively, the reaction resins and/or cold plastics according to the invention can also be applied in other technical fields. Examples include floor coverings, preferably for industrial applications, for the production of castings, for the sealing or coating of rooves, bridges or joints thereof, particularly as sealing membranes, for bridge coating in general, as sealing membranes on rooves, for the production or plates, e.g. for re-use as worktops, for the production of protective coatings, particularly for metal surfaces, as channel resin, for the production of sanitary products, for the production of adhesives, for filling cracks, e.g. In buildings, or for use in the field of orthopaedics.

EXAMPLES

[0112] The examples listed below are given in order to better illustrate the present invention, but do not limit the invention to the features disclosed herein.

[0113] As a curing agent, a mixture of tert-butyl peroxomaleinate and plasticisers, desensitisers and further auxiliaries having a peroxide content of approx. 25% by weight was used. In particular, in the following—unless otherwise indicated—PEROXAN PM-25 S from the firm Pergan was used.

[0114] Pot life was determined as the time required by the material after stirring in of the curing agent to increase from room temperature, i.e. a temperature of between 20 and 22° C., to 32° C. after mixing of the components of the 2K resin. For this purpose, a sample amount of the 2K reaction resin of 20 g was mixed together in a plastic vessel.

[0115] In the so-called O test, the time was determined that was required to achieve a tack-free surface. For this purpose, timing was started on stirring of the curing agent into the material, and after complete mixing in of the curing agent, the mixture was poured in a layer thickness of 2 mm into a tin plate cover. The time was then measured until the surface was no longer found to be tacky on touching with a gloved finger. All of the tests were conducted by the same operator.

[0116] Curing of Methacrylate-Based Reaction Resins

Comparative Example 1

[0117] In this comparative example, curing of a 2K methacrylate-based reaction resin was carried out with a benzoyl peroxide/N,N′-dihydroxyethyl-p-toluidine curing system according to the prior art. 98.5 g of DEGADUR MDP Membrane SG (commercially available, accelerator-free methacrylate-based reaction resin, firm Röhm GmbH) was mixed with 1.50 g of N,N′-dihydroxyethyl-p-toluidine. After this, for curing, 2.0 g of Perkadox CH-50 (dibenzoyl peroxide powder 50% with dicyclohexyl phthalate, firm Nouryon) was added and stirred until the added peroxide had completely dissolved in the reaction resin.

[0118] The following results were obtained:

[0119] Pot life: 11 min

[0120] T.sub.max=119° C.

[0121] T.sub.max after 17 min

[0122] O test=23 min

[0123] After 24 h, the colour of the 2 mm-thick polymer film from the O test was visually evaluated against a white substrate. Clear yellowing was recognizable.

Example 1

[0124] In this example according to the invention, a corresponding 2K reaction resin was cured with a curing system based on TBPM (tert-butyl permaleinate) and a phosphite.

[0125] 98.0 g of DEGADUR MDP Membrane SG was mixed with 2.00 g of tris(2-ethylhexyl)phosphite. After this, for curing, 4.0 g of PEROXAN PM-25 S (25% by weight TBPM suspension of tert-butyl permaleinate with plasticisers from the firm Pergan) was added and stirred until the added peroxide had completely dissolved in the reaction resin.

[0126] The following results were obtained:

[0127] Pot life=10 min

[0128] T.sub.max=129° C.

[0129] T.sub.max after 15 min

[0130] O test=20 min

[0131] After 24 h, the colour of the 2 mm-thick polymer film from the O test was visually evaluated against a white substrate. No yellowing was visible.

[0132] A comparison of the respective results from comparative example 1 and example 1 shows that the reaction resin according to the invention shows comparable pot and curing times, but does not cause yellowing of the polymers.

Examples 2 to 4

[0133] Curing of the 2K reaction resins of these examples according to the invention with TBPM/phosphite curing systems was carried out as follows:

[0134] DEGADUR MDP Membrane SG was mixed in each case with triisodecyl phosphite as an accelerator. The reaction resin was then placed in a climate chamber for heat treatment. After adjustment of the temperature, PEROXAN PM-25 S was then added for curing and stirred until the added peroxide had completely dissolved in the reaction resin. The curing of the reaction resin was also carried out in a climate chamber. The external temperature, respective mixing ratios and measurement results are shown in Table 1:

TABLE-US-00001 TABLE 1 Curing Reaction resin Accelerator agent/peroxide Example Temperature (component 1) (component 1) (component 2) Pot life O test 2 23° C. 96.0 g of 4.0 g of triisodecyl 4.0 g of  7 min 16 min DEGADUR phosphite PEROXAN MDP PM-25 S Membrane SG 3 10° C. 96.0 g of 4.0 g of triisodecyl 6.0 g of  8 min 27 min DEGADUR phosphite PEROXAN MDP PM-25 S Membrane SG 4  5° C. 96.0 g of 4.0 g of triisodecyl 6.0 g of 15 min 38 min DEGADUR phosphite PEROXAN MDP PM-25 S Membrane SG

[0135] It was shown in examples 2 to 4 that in use of the 2K reaction resin according to the invention, by adjusting the amount of the curing agent over a broad temperature range, even down to low temperatures, it was possible to achieve complete, tack-free curing in a short period, with a pot life long enough for processing practice.

[0136] Curing of Reaction Resins Containing Methacrylates and Acrylates

[0137] In the following, the effect of acrylates in reaction resins on curing behaviour is to be investigated. In examples 5 to 12, DEGADUR MDP Primer SG B (commercially available, amine-free methacrylate-based reaction resin, firm Röhm GmbH, contains 0.5% by weight of triisodecyl phosphite) was mixed in each case with varying amounts of 2-ethylhexylacrlate and additional triisodecyl phosphite as an accelerator. After this, for curing, PEROXAN PM-25 S (tert-butyl permaleinate, 25%, suspension with plasticisers, firm Pergan) was added and stirred until the added peroxide had completely dissolved in the reaction resin. The respective mixing ratios and the measurement results for examples 5 to 8 are shown in Table 2.

TABLE-US-00002 TABLE 2 Addition of Reaction Addition further Curing Example Temperature resin of acrylate accelerators agent/peroxide Pot life O test 5 23° C. 100.0 g of — 3.5 g of 4.0 g of 10 min 40 min DEGADUR triisodecyl PEROXAN MDP Primer phosphite PM-25 S SG B 6 23° C. 95.0 g of 5.0 g of 2- 3.5 g of 4.0 g of 10 min 60 min DEGADUR ethylhexylacrlate triisodecyl PEROXAN MDP Primer phosphite PM-25 S SG B 7 23° C. 90.0 g of 10.0 g of 2- 3.5 g of 4.0 g of 13 min >150 DEGADUR ethylhexylacrlate triisodecyl PEROXAN min MDP Primer phosphite PM-25 S Surface SG B remains liquid 8 23° C. 80.0 g of 20.0 g of 2- 3.5 g of 4.0 g of 13 min >150 DEGADUR ethylhexylacrlate triisodecyl PEROXAN min MDP Primer phosphite PM-25 S Surface SG B remains liquid

[0138] It was shown in examples 5 to 8 that the curing properties deteriorated with an increasing content by weight of acrylate monomers. A higher acrylate content is therefore disadvantageous in such novel systems.

[0139] The results and compositions of the initiator systems for examples 9 to 12 are shown in Table 3. Large amounts of phosphites were used in these examples 9 to 12.

TABLE-US-00003 TABLE 3 Reaction Addition of Addition of Curing Example Temperature resin acrylate further accelerators agent/peroxide Pot life O test 9 23° C. 100.0 g of — 7.5 g of 4.0 g of 5 min 23 min DEGADUR triisodecyl PEROXAN MDP Primer phosphite PM-25 S SG B 10 23° C. 95.0 g of 5.0 g of 2- 7.5 g of 4.0 g of 7 min 24 min DEGADUR ethylhexylacrlate triisodecyl PEROXAN MDP Primer phosphite PM-25 S SG B 11 23° C. 90.0 g of 10.0 g of 2- 7.5 g of 4.0 g of 7 min 30 min DEGADUR ethylhexylacrlate triisodecyl PEROXAN MDP Primer phosphite PM-25 S SG B 12 23° C. 80.0 g of 20.0 g of 2- 7.5 g of 4.0 g of 6 min 60 min DEGADUR ethylhexylacrlate triisodecyl PEROXAN Surface MDP Primer phosphite PM-25 S remains SG B slightly tacky

[0140] Surprisingly, it was found in examples 9 to 12 that in use of larger amounts of the organic phosphite, complete and tack-free curing is also possible with high contents by weight of acrylate monomers.

[0141] Calculation of Content of Acrylate Groups in the Compositions According to Examples 5 to 12

[0142] For illustrative purposes, the contents by weight of acrylate groups in the resin components of examples 5 to 12 are calculated below.

##STR00001##

[0143] An acrylate group has an equivalent weight of 55.06 g/mol, giving for example a content by weight of 29.9% in 2-ethylhexyacrlate (55.06 g/mol/184.28 g/mol=29.9%).

TABLE-US-00004 TABLE 4 Content of acrylate Percent groups in content of reaction 2-ethylhexylacrlate resin Addition in the (without Reaction Addition of further Amount of reaction resin curing Example resin of acrylate accelerators reaction resin (without curing agent) agent) 5 100.0 g of — 3.5 g of triisodecyl 103.5 g   10%   0% DEGADUR phosphite MDP Primer SG B 6 95.0 g of 5.0 g of 2- 3.5 g of triisodecyl 103.5 g 4.83% 1.44% DEGADUR ethylhexylacrlate phosphite MDP Primer SG B 7 90.0 g of 10.0 g of 2- 3.5 g of triisodecyl 103.5 g 9.66% 2.88% DEGADUR ethylhexylacrlate phosphite MDP Primer SG B 8 80.0 g of 20.0 g of 2- 3.5 g of triisodecyl 103.5 g 19.32%  5.78% DEGADUR ethylhexylacrlate phosphite MDP Primer SG B 9 100.0 g of — 7.5 g of triisodecyl 107.5 g   0%   0% DEGADUR phosphite MDP Primer SG B 10 95.0 g of 5.0 g of 2- 7.5 g of triisodecyl 107.5 g 4.65% 1.39% DEGADUR ethylhexylacrlate phosphite MDP Primer SG B 11 90.0 g of 10.0 g of 2- 7.5 g of triisodecyl 107.5 g 9.30% 2.78% DEGADUR ethylhexylacrlate phosphite MDP Primer SG B 12 80.0 g of 20.0 g of 2- 7.5 g of triisodecyl 107.5 g 18.60%  5.56% DEGADUR ethylhexylacrlate phosphite MDP Primer SG B

Example 13

[0144] 49.0 g of Ebecryl 230 (commercially available urethane acrylate, firm Allnex) was mixed with 46.2 g of methyl methacrylate, 0.80 g of paraffin (Sasolwax 5105) and 4.0 g of trilsodecyl phosphite as an accelerator at 55° C. until the paraffin has completely dissolved. The resin was then cooled to 23° C.

[0145] After this, for curing, 4.0 g of PEROXAN PM-25 S (tert-butyl permaleinate, 25%, suspension with plasticisers, firm Pergan) was added and stirred until the added peroxide had completely dissolved in the reaction resin. The composition and results are shown in Table 5.

TABLE-US-00005 TABLE 5 Reaction Content of urethane Curing Example Temperature resin acrylate in reaction resin agent/peroxide Pot life O test 13 23° C. 100.0 g of 49.0% 4.0 g of 12 min 35 min resin from PEROXAN PM- example 25 S 13

[0146] Example 13 shows that it is not the content by weight of acrylate compounds that is relevant for tack-free curing, but the content by volume of functional acrylate groups. Therefore, although there is a high content of acrylate compounds in the form of urethane acrylate, because of the low content by weight of functional acrylate groups, this does not cause any substantial impairment of curing.