Reactive resins based on ethyl methacrylate

Abstract

The invention relates to a reactive resin containing at least ethyl methacrylate, a prepolymer having an acid number in the range of 1 to 12 mg (KOH) / g, and optionally either an initiator or an accelerator. The invention further relates to a two-component system comprising the reactive resin according to the invention and a curing agent component, and to the use of the two-component system as road marking, road repair compounds, intumescent coatings, floor coatings, casting resins, building protection materials, films, sealing materials, coating compositions and / or laminating compositions.

Description

Technical Field

[0001] The invention relates to a reactive resin which contains at least ethyl methacrylate, a prepolymer having an acid number in the range of 1 to 12 mg(KOH) / g, and optionally either an initiator or an accelerator. The invention also relates to a two-component (2K) system comprising a reactive resin according to the invention and a hardener component, and to the use of the two-component system as a road marking, road repair compound, intumescent coating, floor coating, casting resin, building protection material, membrane, sealant, coating composition and / or laminating composition. Background Art

[0002] Reactive resins and two-component systems containing them are known per se. Reducing the volatile components of reactive resins and thus reducing the exposure and odor load of operators during their use has long been a development goal. Such reactive resins are described in various prior art documents.

[0003] EP 2 739 677 B1 relates to an odorless (meth) acrylic reactive resin containing high-boiling reactive (meth) acrylic monomers selected from polar cyclic substituted esters. These are used as a substitute for methyl (meth) acrylate (MMA). Although these resins can be cured without tack under laboratory conditions, the insufficient reformation of the paraffin film in the case of subsequent disturbances of the film during the pot life after the first application of the coating has proven to be problematic in practice. Due to the limited pot life, for example, it is usually necessary to always apply a fresh coating batch repeatedly on the coating that has been previously applied. In this case, for equalization, the previously applied coating must be rolled again with a freshly prepared coating a few minutes after application. This causes the destruction of the paraffin film that has initially formed, which must be fully formed again to allow the coating to cure without tack at the surface. This cannot always be guaranteed with reactive resins based on the high-boiling reactive (meth) acrylic monomers. In particular, coatings covering large areas sometimes therefore have the disadvantage that they are susceptible to soiling and make the coating more susceptible to attack by media and can in turn cause defects in the topcoat, so that these resins can be used in practice only to a very limited extent.

[0004] US 2019 / 0264042 A1 discloses a cold-curing reactive resin formulation for floor coatings based on (meth)acrylates, in particular floor coatings based on methyl (meth)acrylate, which contains an odorant to improve the odor. However, the emission level of volatile components, in particular methyl (meth)acrylate, remains unchanged during the application process, and the odor is only masked.

[0005] WO 2016 / 026757 A1 discloses an antifouling reactive resin sealant based on cold plastic for marking or coating floor surfaces or roads, such as highways. This sealant leads to reduced dirt adhesion, especially in hot and / or dry dusty environments. This means that even in dry and hot areas, the marking remains more visible than conventional markings. A disadvantage of the method is the additional work involved in the application of the two marking layers.

[0006] WO 2011 / 006767 A1 discloses formulations for marking roads, such as highways, which after application can be driven on again after a shortened waiting time. The examples describe the use of acid-functional polymers. A disadvantage of the reactive resins disclosed is the high proportion of crosslinker, which results in road markings having only low flexibility and a tendency to become brittle and peel off, especially when applied in thicker layers.

[0007] WO 2013 / 185993 A1 discloses formulations (reactive resins) for marking or coating floor surfaces or roads, such as highways. The formulations are low in health hazards and have good mechanical properties. In particular, it is said to provide fast-curing reactive resins with a low content of accelerator amines. The document relates in particular to reactive resins containing asymmetric aromatic tertiary amines as accelerator components. The disadvantage of the reactive resins disclosed is that only the health hazards caused by the accelerator amine component and the efficiency of the component in the resin are addressed when other usage properties remain unchanged, i.e., in particular, when the staining properties remain unchanged. No measures are described to reduce the health hazards to operators due to exposure to volatile components such as methyl (meth)acrylate or due to the use of phthalate-containing peroxides.

[0008] CN 105 753 367 A describes a resin composition for bridge repair. The resin contains two different types of monomers, a prepolymer and an initiator. No prepolymer with an acid value of 1 to 12 mg (KOH) / g is disclosed.

[0009] CN 111 005 287 A describes a method for repairing roads. The method uses a surface repair material containing an acrylate monomer, an acrylic resin polymer, a silane, a filler, an accelerator and an inhibitor. No prepolymer with an acid value of 1 to 12 mg (KOH) / g is disclosed.

[0010] EP 2 979 851 A1 relates to a method for producing composite semi-finished products and further processing them into moldings. In this method, a fibrous support is impregnated with a resin composition containing, in particular, monomers and prepolymers. Prepolymers with an acid number of 1 to 12 mg (KOH) / g are not disclosed.

[0011] US 2017 / 0029563 A1 discloses a coating system containing a (meth) acrylic monomer and a reactive polymer, oligomer or prepolymer having acrylate or methacrylate groups. A prepolymer having an acid value of 1 to 12 mg(KOH) / g is not disclosed.

[0012] Some reactive resins described in the prior art already have partially good properties with regard to their odor. However, they often have disadvantages with regard to their processing and / or their tendency to stain. Furthermore, they often do not offer a solution for reducing monomer emissions, but instead simply mask their odor by adding fragrance substances. Summary of the invention

[0013] Purpose

[0014] Therefore, there is a need for alternative reactive resins and two-component systems which do not have the disadvantages of the reactive resins and two-component systems described in the prior art or have these disadvantages only to a reduced extent. In particular, the alternative reactive resins and two-component systems should have reduced emissions of organic components during processing. Furthermore, the two-component systems should be particularly suitable for use as road marking and floor coatings, especially those with reduced staining properties. Solution

[0015] This is achieved by reactive resins consisting of:

[0016] 5 to 94% by weight of ethyl methacrylate,

[0017] 5 to 50% by weight of at least one prepolymer having an acid number in the range of 1 to 12 mg (KOH) / g,

[0018] 0 to 50% by weight of at least one oligomer,

[0019] 0% to 30% by weight of at least one crosslinking agent,

[0020] 0 to 80% by weight of at least one comonomer,

[0021] and optionally, 0.1 to 10% by weight of at least one initiator or 0.1 to 5% by weight of at least one accelerator,

[0022] In each case this is based on the total weight of the reactive resin.

[0023] This is further achieved through a two-component system consisting of:

[0024] The reactive resin according to any one of claims 1 to 12 and

[0025] a hardener component which contains 0.1% to 10% by weight of at least one initiator or 0.1% to 5% by weight of at least one accelerator, in each case based on the total weight of the reactive resin, wherein

[0026] The reactive resin contains the at least one initiator and the curing agent component contains the at least one accelerator, or

[0027] The reactive resin contains the at least one accelerator, and the curing agent component contains the at least one initiator.

[0028] Surprisingly, it has been found that two-component systems containing the reactive resins of the invention cure tack-free even at low ambient temperatures and in contact with atmospheric oxygen. They also have particularly low staining properties on their surfaces, especially when used to produce road markings and / or floor coatings. The particularly low staining properties are due in particular to the use of ethyl methacrylate in combination with prepolymers having an acid number in the range of 1 to 12 mg (KOH) / g.

[0029] In addition, the reactive resin and the two-component system can be applied with reduced emissions, particularly reduced monomer emissions. In a particularly preferred embodiment of the present invention, this is especially true when the reactive resin is substantially free of (meth) methyl acrylate. The use of the curing agent for processing the novel two-component system, in particular, without phthalates, enables further reduction of health risks. This represents a further particularly preferred embodiment. The reactive resin and the two-component system of the present invention have a sufficiently long processing time for manual surface applications, in particular as road markings, road repair compounds, intumescent coatings, floor coatings, casting resins, building protection materials, sealing materials, films, coating compositions and / or laminating compositions. The reactive resin and / or the two-component system can therefore be covered with a processing tool for coating or roller coating multiple times to homogenize and / or shape the surface, and this will not cause curing interference at the surface. The reactive resin, in particular the reactive resin substantially free of (meth) methyl acrylate, also enables the preparation of coatings and marking compositions (two-component systems) with an increased flash point compared to the reactive resin containing (meth) methyl acrylate. They are therefore less flammable. The reactive resins also have increased flexibility and reduced shrinkage, which improves their impact resistance and reduces crack formation in coatings made therefrom. They also have lower water absorption. Together with the increased flexibility, this offers advantages when using two-component systems as intumescent coatings and as corrosion protection materials.

[0030] The reactive resin according to the present invention is described more specifically below.

[0031] Reactive resins are understood in the context of the present invention to mean mixtures of at least one monomer and at least one prepolymer which can be readily cured when used as a two-component system.

[0032] According to the present invention, the reactive resin contains the following components:

[0033] 5 to 94% by weight, preferably 10 to 70% by weight, of ethyl methacrylate,

[0034] 5 to 50% by weight, preferably 10 to 40% by weight, of at least one prepolymer having an acid number in the range of 1 to 12 mg (KOH) / g,

[0035] 0 to 50% by weight of at least one oligomer,

[0036] 0 to 30% by weight, preferably 0.1 to 15% by weight, of at least one crosslinking agent,

[0037] 0 to 80% by weight, preferably 0 to 40% by weight, of at least one comonomer,

[0038] and optionally 0.1 to 10% by weight, preferably 1 to 5% by weight, of at least one initiator, or 0.1 to 5% by weight, preferably 0.5 to 3% by weight, of at least one accelerator,

[0039] In each case this is based on the total weight of the reactive resin.

[0040] Preference is therefore also given to a reactive resin, wherein the reactive resin contains the following components:

[0041] 10 to 70% by weight of ethyl methacrylate,

[0042] 10 to 40% by weight of at least one prepolymer having an acid number in the range of 1 to 12 mg (KOH) / g,

[0043] 0 to 50% by weight of at least one oligomer,

[0044] 0.1% to 15% by weight of at least one crosslinking agent,

[0045] 0 to 40% by weight of at least one comonomer,

[0046] and optionally, 1 to 5% by weight of at least one initiator or 0.5 to 3% by weight of at least one accelerator,

[0047] In each case this is based on the total weight of the reactive resin.

[0048] It is obvious that all % by weight data are based on the % by weight before the components are reacted together with one another. During the reaction, the weight ratios of the components may change. This is known per se to the person skilled in the art.

[0049] Preferably, the weight % of ethyl methacrylate, the at least one prepolymer, the at least one oligomer, the at least one crosslinker, the at least one comonomer and optionally the at least one initiator and the at least one accelerator add up to 100 weight %. It is therefore preferred that the reactive resin consists of these components.

[0050] According to the invention, the reactive resin contains 5 to 94 wt %, preferably 10 to 70 wt %, of ethyl methacrylate, based on the total weight of the reactive resin. Ethyl methacrylate is known per se and is also referred to as ethyl methacrylate or EMA.

[0051] The reactive resin contains 5% to 50% by weight, preferably 10% to 40% by weight, based on the total weight of the reactive resin, of at least one prepolymer having an acid number in the range of 1 to 12 mg (KOH) / g.

[0052] The prepolymer preferably has an acid number in the range of 3 to 10 mg (KOH) / g. According to the invention, the acid number is determined in accordance with DIN EN ISO 2114:2002 "Plastics (polyesters) and coatings (binders) - Determination of partial and total acid numbers".

[0053] The term "at least one prepolymer" means in the present invention both exactly one prepolymer and mixtures of two or more prepolymers. A "prepolymer" for the purposes of the present invention has a weight-average molecular weight in the range of 25 000 g / mol to 80 000 g / mol, preferably in the range of 30 000 g / mol to 70 000 g / mol, determined by GPC (gel permeation chromatography) with PMMA as standard.

[0054] Preference is therefore also given to reactive resins in which the at least one prepolymer has a weight-average molecular weight in the range from 25 000 g / mol to 80 000 g / mol.

[0055] The at least one prepolymer can be used, for example, to improve the polymerization properties, the mechanical properties, the adhesion to substrates and the optical properties of the reactive resins and of the two-component systems produced therefrom.

[0056] Suitable prepolymers are, for example, selected from polyesters, poly(meth)acrylates, polyvinyl acetate, polyvinyl chloride, polystyrene and copolymers thereof. Preferably, the at least one prepolymer is selected from polyesters and poly(meth)acrylates.

[0057] Preference is therefore also given to reactive resins in which the at least one prepolymer is selected from polyesters and poly(meth)acrylates.

[0058] "Polyalkyl (meth)acrylate" is understood in the present invention to mean polymers and copolymers of alkyl (meth)acrylate. "Alkyl (meth)acrylate" is understood to mean alkyl acrylate and alkyl methacrylate. Preferred are C1-C 18 -alkyl ester. "(Meth)acrylic acid C1-C 18 "-alkyl ester" is understood to mean an alkyl ester of (meth)acrylic acid having 1 to 18 carbon atoms in the alkyl group. The alkyl group may be linear, cyclic and / or branched. It may also comprise aromatic groups and / or heteroatoms. For example, the alkyl (meth)acrylates of the invention, the polymers or copolymers of which are the polyalkyl (meth)acrylates of the invention, are selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isopentyl (meth)acrylate, octadecyl (meth)acrylate, benzyl (meth)acrylate and dodecyl (meth)acrylate.

[0059] The term "(meth)acrylic acid" in the present invention includes acrylic acid and methacrylic acid.

[0060] The polyalkyl (meth)acrylates can be produced by methods known to those skilled in the art, for example by solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization and / or precipitation polymerization.

[0061] Suitable polyesters are known per se and are preferably obtainable by polycondensation or ring-opening polymerization.

[0062] Both the polyesters and the polyalkyl (meth)acrylates which can be used as the at least one prepolymer may have additional functional groups such as double bonds, for example for promoting adhesion or for copolymerization. Preferably, the prepolymer does not have any double bonds.

[0063] The reactive resin contains 0% to 50% by weight of at least one oligomer, based on the total weight of the reactive resin.

[0064] "At least one oligomer" is understood in the present invention to mean exactly one oligomer or a mixture of two or more oligomers. For the purposes of the present invention, an oligomer is understood to mean a macromolecule composed of a plurality of structurally identical or similar units.

[0065] The at least one oligomer is different from the at least one prepolymer.

[0066] The at least one oligomer according to the invention has, for example, a weight-average molecular weight in the range of >1000 g / mol to <25 000 g / mol, preferably in the range of 1500 g / mol to 20 000 g / mol, determined by GPC (gel permeation chromatography) with polyethylene glycol (PEG) as standard.

[0067] Preference is therefore also given to reactive resins in which the at least one oligomer has a weight-average molecular weight in the range from >1000 g / mol to <25 000 g / mol.

[0068] The at least one oligomer is, for example, selected from polyurethane (meth)acrylates, polyethers and polyesters. Polyethers are known per se and are, for example, selected from polyethylene glycol, polypropylene glycol and polytetrahydrofuran.

[0069] Preferably, the at least one oligomer is therefore selected from polyurethane (meth)acrylates, polyethylene glycol, polypropylene glycol and polytetrahydrofuran.

[0070] Also preferred according to the invention are therefore reactive resins in which the at least one oligomer is selected from the group consisting of polyurethane (meth)acrylates, polyethylene glycols, polypropylene glycols and polytetrahydrofurans.

[0071] In the present invention, “urethane (meth)acrylates” are understood to mean (meth)acrylates which are linked to one another via urethane groups. They can be obtained by reacting hydroxyalkyl (meth)acrylates with polyisocyanates and polyoxyalkylenes having at least two hydroxyl functions. Instead of hydroxyalkyl (meth)acrylates, it is also possible to use esters of (meth)acrylic acid with alkylene oxides, such as ethylene oxide or propylene oxide, and the corresponding oligomeric or polyalkylene oxides. Suitable urethane (meth)acrylates are known per se. An overview of urethane (meth)acrylates having a functionality of greater than 2 is given, for example, in DE 199 02 685. Commercially available examples of polyols, isocyanates and hydroxy-functional (meth)acrylates are obtainable, for example, under the trade name EBECRYL from Allnex, for example EBECRYL 210 and EBECRYL 230.

[0072] Polyurethane (meth)acrylates increase the flexibility, breaking strength and elongation at break of reactive resins without any relatively large temperature dependence. This increases the temperature stability of, for example, road markings made from reactive resins. Embrittlement caused by higher crosslinker contents can be compensated and adhesion to the road can be compensated.

[0073] The reactive resin contains 0% to 30% by weight, preferably 0.1% to 15% by weight, of at least one crosslinker, based on the total weight of the reactive resin.

[0074] “At least one crosslinking agent” in the context of the present invention means exactly one crosslinking agent or a mixture of two or more crosslinking agents.

[0075] A crosslinker is understood in the present invention to mean a compound which can link two or more prepolymers and / or polymers formed from ethyl methacrylate to one another. The crosslinker has at least two functional groups which are capable of reacting with the at least one prepolymer and / or ethyl methacrylate.

[0076] It is evident that the at least one crosslinking agent is different from the at least one oligomer.

[0077] For example, the at least one crosslinking agent is selected from difunctional, trifunctional, tetrafunctional, pentafunctional and hexafunctional (meth)acrylates. The at least one crosslinking agent is particularly preferably selected from difunctional and trifunctional (meth)acrylates.

[0078] Preference is therefore also given to reactive resins in which the at least one crosslinker is selected from difunctional, trifunctional, tetrafunctional, pentafunctional and hexafunctional (meth)acrylates.

[0079] Such crosslinkers are known per se, for example allyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, poly(urethane) (meth)acrylate, tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate and / or trimethylolpropane tri(meth)acrylate. Suitable crosslinkers are available, for example, under the trade names EBECRYL 140 and EBECRYL 895 from the company Allnex.

[0080] For example, the at least one cross-linking agent has a molecular weight in the range of 150 g / mol to 1000 g / mol, preferably in the range of 170 g / mol to 800 g / mol.

[0081] Preference is therefore also given to reactive resins in which the at least one crosslinker has a molecular weight in the range from 150 g / mol to 1000 g / mol.

[0082] The reactive resin contains 0% to 80% by weight, preferably 0% to 40% by weight, of at least one comonomer, based on the total weight of the reactive resin.

[0083] "At least one comonomer" refers in the present invention both to exactly one comonomer, and to mixtures of two or more comonomers.

[0084] It is evident that the at least one comonomer is different from ethyl methacrylate. Likewise, the at least one comonomer is different from the at least one crosslinking agent and the at least one oligomer.

[0085] All compounds copolymerizable with ethyl methacrylate are suitable as the at least one comonomer. For example, the at least one comonomer is selected from (meth) acrylic acid C3-C 18 -alkyl esters, C1-C2-alkoxy (meth)acrylates, (meth)acrylic acid, itaconic acid, (meth)acrylamide, 1-olefins and styrene.

[0086] It is therefore also preferred according to the invention that the at least one comonomer is selected from (meth)acrylic acid C3-C 18 -alkyl esters, C1-C2-alkoxy (meth)acrylates, (meth)acrylic acid, itaconic acid, (meth)acrylamide, reactive resins of 1-olefins and styrene.

[0087] "(Meth)acrylic acid C3-C 18 "-alkyl ester" is understood in the present invention to mean an alkyl ester of (meth)acrylic acid having 3 to 18 carbon atoms in the alkyl group. The alkyl group may be linear, cyclic or branched. The alkyl group may also contain aromatic moieties. (Meth)acrylic acid C3-C 18 -alkyl esters include, for example, benzyl (meth)acrylate. In addition, the alkyl group may contain heteroatoms. 18 -alkyl esters include, for example, hydroxy-functional (meth) acrylic acid C3-C 18 - Alkyl esters, such as hydroxypropyl (meth)acrylate, and reaction products thereof with lactones, such as hydroxyethyl caprolactone (meth)acrylate, and ether (meth)acrylates, such as ethylene glycol (meth)acrylate.

[0088] Therefore, (meth) acrylic acid C3-C 18 The alkyl esters are preferably selected from the group consisting of benzyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxyethyl caprolactone (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-octyl (meth)acrylate, 2-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isopentyl (meth)acrylate, octadecyl (meth)acrylate and dodecyl (meth)acrylate.

[0089] "C1-C2-alkoxy (meth)acrylate" is understood in the present invention to mean an alkyl ester of (meth)acrylic acid having 1 to 2 carbon atoms and at least one oxygen atom in the alkyl group. For the purposes of the present invention, C1-C2-alkoxy (meth)acrylate includes, for example, ethylene glycol (meth)acrylate and hydroxyethyl (meth)acrylate.

[0090] As described above, the term "(meth)acrylic acid" in the present invention includes acrylic acid and methacrylic acid.

[0091] Itaconic acid itself is known and is also called methylenesuccinic acid.

[0092] The term "(meth)acrylamide" is understood to mean acrylamide and methacrylamide.

[0093] Suitable 1-olefin comonomers are known per se, for example 1-hexene, 1-heptene, vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl-1-diisobutylene and 4-methyl-1-pentene.

[0094] The term "styrene" is understood in the present invention as meaning not only styrene itself but also substituted styrenes, for example α-methylstyrene, α-ethylstyrene, vinyltoluene, p-methylstyrene, styrenesulfonic acid, monochlorostyrene, dichlorostyrene and tribromostyrene, of which α-methylstyrene, α-ethylstyrene, vinyltoluene, p-methylstyrene and styrenesulfonic acid are preferred.

[0095] Preferably, the at least one copolymer does not contain methyl (meth)acrylate. Particularly preferably, the reactive resin is essentially free of methyl (meth)acrylate.

[0096] Preference is therefore also given to reactive resins which are essentially free of methyl (meth)acrylate.

[0097] "Substantially free of methyl (meth)acrylate" is understood in the present invention to mean that the reactive resin contains not more than 2% by weight, preferably not more than 1% by weight, particularly preferably not more than 0.1% by weight of methyl (meth)acrylate, based on the total weight of the reactive resin. It is further preferred that the methyl (meth)acrylate that may be present in the reactive resin originates entirely from impurities in the components of the reactive resin, for example residual monomers present in the at least one prepolymer and / or the at least one oligomer. The methyl (meth)acrylate that may be present in the reactive resin may additionally originate from cross-contamination during the production of the reactive resin.

[0098] The reactive resin optionally contains either at least one initiator or at least one accelerator. In one embodiment of the present invention, the reactive resin is free of initiators and free of accelerators.

[0099] In the present invention, “either at least one initiator or at least one accelerator” means that the reactive resin preferably contains only the at least one initiator without an accelerator, or that the reactive resin contains only the at least one accelerator without an initiator.

[0100] The reactive resin preferably contains only accelerators. It is therefore preferred that the reactive resin contains no initiator.

[0101] The reactive resins may comprise 0.1% to 10% by weight, preferably 1% to 5% by weight, of at least one initiator, based in each case on the total weight of the reactive resin.

[0102] "At least one initiator" in the context of the present invention means exactly one initiator or a mixture of two or more initiators. Exactly one initiator is preferred.

[0103] Suitable as the at least one initiator are any compounds known to the person skilled in the art that are capable of initiating free radical polymerization of ethyl methacrylate. For example, the at least one initiator is selected from peroxides, azo compounds and persulfates.

[0104] Also preferred according to the invention are therefore reactive resins in which the at least one initiator is selected from the group consisting of peroxides, azo compounds and persulfates.

[0105] Suitable peroxides are, for example, selected from hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxydicarbonate, dilauroyl peroxide, methyl ethyl ketone peroxide, acetylacetone peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroctanoate, tert-butyl per-2-ethylhexanoate, tert-butyl perneodecanoate, tert-butyl peroxymaleate, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perbenzoate, di(tert-amyl) peroxide (DTAP), tert-butyl peroxy(2-ethylhexyl)carbonate (TBPEHC), diisopropyl peroxide, diisopropyl peroxydicarbonate and bis(4-tert-butylcyclohexyl) peroxydicarbonate.

[0106] Suitable azo compounds are selected, for example, from 2,2-azobisiso-2,4-dimethylvaleronitrile, 2,2-azobisisobutyronitrile, 2,2′-azobis(2-amidinopropane) dihydrochloride, 2-(carbamoylazo)isobutyronitrile and 4,4′-azobis(cyanovaleric acid).

[0107] Suitable persulfates are, for example, selected from lithium peroxodisulphate, sodium peroxodisulphate, potassium peroxodisulphate and ammonium peroxodisulphate.

[0108] Preferably, the initiator is phthalate-free. Particularly preferably, the reactive resin is phthalate-free. It is therefore preferred that the reactive resin is phthalate-free.

[0109] As mentioned above, the reactive resin in a preferred embodiment of the invention contains no initiator.

[0110] The reactive resin may comprise 0.1% to 5% by weight, preferably 0.5% to 3% by weight, based in each case on the total weight of the reactive resin, of at least one accelerator.

[0111] "At least one accelerator" means in the context of the present invention exactly one accelerator or a mixture of two or more accelerators. Exactly one accelerator is preferred according to the present invention.

[0112] The one accelerator used may be a compound known to those skilled in the art that accelerates the curing of reactive resins. Suitable accelerators are, for example, aromatic substituted tertiary amines and / or phosphites. Preferably, the at least one accelerator is selected from aromatic substituted tertiary amines.

[0113] Preference is therefore also given according to the invention to reactive resins in which the at least one accelerator is selected from aromatically substituted tertiary amines.

[0114] The term "aromatic substituted tertiary amine" includes symmetrical aromatic substituted tertiary amines and asymmetrical aromatic substituted tertiary amines.

[0115] Suitable symmetrical aromatic substituted tertiary amines are, for example, selected from N,N-dimethyl-p-toluidine, N,N-dimethylaniline, N,N-diethylaniline, perethoxylated N,N-dihydroxyethyl-p-toluidine, perpropoxylated N,N-dihydroxypropyl-p-toluidine, N,N-bis-(2-hydroxyethyl)-p-toluidine and N,N-bis-(2-hydroxypropyl)-p-toluidine.

[0116] Suitable asymmetrically aromatic substituted tertiary amines are, for example, selected from N-methyl-N-(hydroxyethyl)-p-toluidine, N-methyl-N-(hydroxyethyl)-m-toluidine, N-methyl-N-(hydroxypropyl)-p-toluidine, N-methyl-N-(hydroxyethyl)-xylidine, N-methyl-N-(hydroxypropyl)-xylidine, N-methyl-N-(hydroxyethyl)aniline and N-methyl-N-(hydroxypropyl)aniline.

[0117] Suitable phosphites are selected, for example, from tri-2-ethylhexyl phosphite, tri-2-ethylhexyl trithiophosphite, tri-isooctyl phosphite, tri-isooctyl trithiophosphite, tridecyl phosphite, tridecyl trithiophosphite, trilauryl phosphite, trilauryl trithiophosphite, trioctadecyl phosphite, trioctadecyl trithiophosphite, phenyl didecyl phosphite, phenyl didec ... Laurel, distearyl phenyl phosphite, distearyl phenyl trithiophosphite, diphenyl decyl phosphite, diphenyl lauryl phosphite, diphenyl stearyl phosphite, diphenyl stearyl trithiophosphite, tri-p-cresyl phosphite, tri-m-cresyl phosphite, tri-o-cresyl phosphite, tri-p-cresyl dithiophosphite, tri-p-octylphenyl trithiophosphite, tri-o-octylphenyl phosphite, tri(dipropylene glycol) phosphite, phosphorous acid Phosphite triethoxyethyl ester, phosphite tributoxyethyl ester, phosphite tri(tetrahydrofurfuryl) ester, phosphite tri(tetrahydrofurfuryl) ester, phosphite triisodecyl, phosphite triphenyl, phosphite S-phenyl dilauryl monothiophosphite, phosphite S-phenyl didecyl monothiophosphite, dithiophosphite S,S-diphenyl lauryl, dithiophosphite S,S-diphenyldecyl, dithiophosphite tri-o-naphthyl ester, dithiophosphite S,S-diphenyldecyl , phenyl dilauryl trithiophosphite, tri(dodecyl)phenyl phosphite, trichlorophenyl phosphite, diphenyl lauryl trithiophosphite, S-lauryl diphenyl monothiophosphite, tri-p-methoxyphenyl phosphite, SO-diphenyl-S-lauryl dithiophosphite, tri-o-methoxyphenyl dithiophosphite, SS-dilaurylphenyl dithiophosphite and SO-dilauryl-S-phenyl dithiophosphite.

[0118] Based on the reactive resins according to the invention, cold plastics can be produced from two or three components. Preference is given to cold plastics consisting of two components, which are referred to as two-component systems. Cold plastics consisting of three components are also referred to as three-component (3K) systems.

[0119] According to the invention, a two-component system comprises the following components:

[0120] The reactive resin according to the invention and

[0121] a curing agent component comprising 0.1% to 10% by weight of at least one initiator or 0.1% to 5% by weight of at least one accelerator, in each case based on the total weight of the reactive resin, wherein

[0122] Either the reactive resin contains the at least one initiator and the curing agent component contains the at least one accelerator,

[0123] Either the reactive resin contains the at least one accelerator and the curing agent component contains the at least one initiator.

[0124] If the reactive resin is part of a two-component system, it generally contains either the at least one initiator or the at least one accelerator.

[0125] For the reactive resin present in the two-component system, the embodiments and preferences described above for the reactive resin according to the invention apply mutatis mutandis.

[0126] The hardener component, when mixed with the reactive resin, initiates and / or accelerates the polymerization of at least the ethyl methacrylate present in the reactive resin.

[0127] The curing agent component thus contains either the at least one initiator or the at least one accelerator. Typically, when the reactive resin contains the at least one initiator, the curing agent component contains the at least one accelerator. When the reactive resin contains the at least one accelerator, the curing agent component contains the at least one initiator.

[0128] The hardener component contains, for example, 0.1% to 10% by weight, preferably 1% to 5% by weight, of at least one initiator, based in each case on the total weight of the reactive resins present in the two-component system.

[0129] For the at least one initiator optionally present in the curing agent component, the embodiments and preferences described previously for the at least one initiator optionally present in the reactive resin apply mutatis mutandis.

[0130] The hardener component contains, for example, 0.1% to 5% by weight, preferably 0.5% to 3% by weight, of at least one accelerator, based in each case on the total weight of the reactive resin present in the two-component system.

[0131] For the at least one accelerator optionally present in the hardener component, the embodiments and preferences described previously for the at least one accelerator optionally present in the reactive resin apply mutatis mutandis.

[0132] In one embodiment of the present invention, the curing agent component may consist of either the at least one initiator or the at least one accelerator. In this case, the reactive resin preferably contains no components constituting the curing agent component.

[0133] It is also possible that the curing agent component contains additional components besides the at least one initiator or the at least one accelerator, such as dyes and / or fillers and / or auxiliaries and additives mentioned further below. It is preferred according to the invention that the curing agent component is substantially free of ethyl methacrylate.

[0134] According to the invention it is preferred that the reactive resin in the two-component system contains the at least one accelerator. In this case, the curing agent component preferably contains the at least one initiator. In this embodiment, the reactive resin preferably does not contain an initiator. In this case, the curing agent component preferably does not contain an accelerator.

[0135] It is further preferred that the curing agent component in the two-component system is substantially free of phthalates. It is also preferred that the reactive resin in the two-component system is substantially free of phthalates.

[0136] Preference is therefore given according to the invention to two-component systems in which the hardener component and / or the reactive resin are essentially free of phthalates.

[0137] With particular preference, the two-component system is phthalate-free.

[0138] The two-component system can also contain dyes and / or fillers. For example, based on the total weight of the two-component system, the two-component system contains dyes and / or fillers in the range of 0 wt % to 90 wt %, preferably in the range of 5 wt % to 50 wt %.

[0139] Particularly suitable dyes are, for example, white, red, blue, green and / or yellow inorganic pigments. Particularly preferred are white inorganic pigments such as titanium dioxide.

[0140] The filler is in particular a mineral filler. The mineral filler is preferably selected from the group consisting of calcium carbonate, barium sulfate, quartz, quartz powder, precipitated silica, fumed silica, corundum, glass beads and cristobalite.

[0141] The two-component system may additionally contain auxiliaries and additives. For example, the two-component system contains auxiliaries and additives in the range of 0.1% by weight to 5% by weight, based on the total weight of the two-component system. The auxiliaries and additives for two-component systems are known per se and are selected, for example, from chain transfer agents, plasticizers, paraffins, stabilizers, inhibitors, waxes and / or oils.

[0142] For example, paraffin wax is added to prevent inhibition of polymerization by oxygen from the air. For this purpose, it is possible to use two or more paraffin waxes with different melting points in different concentrations.

[0143] The chain transfer agent used may be any compound known in free-radical polymerization. Preference is given to using mercaptans such as n-dodecyl mercaptan, and polyfunctional mercapto compounds such as pentaerythritol tetrathioglycolate.

[0144] Plasticizers used are preferably esters, polyols, oils or low molecular weight polyethers.

[0145] Useful stabilizers are in particular UV stabilizers. The UV stabilizers are preferably selected from benzophenone derivatives, benzotriazole derivatives, thioxanthonate derivatives, piperidinol carboxylate derivatives and cinnamate derivatives.

[0146] Among the inhibitors, preference is given to using substituted phenols, hydroquinone derivatives, phosphines and phosphites.

[0147] In order to use a two-component system, a reactive resin and a curing agent component are mixed with each other. After the reactive resin has been mixed with the curing agent component, the two-component system usually only has a limited open time, for example 2 to 40 minutes, which is left for the application of the two-component system, for example for application, pouring, coating or filling. Thereafter, the two-component system is usually cured. The term "open time" is therefore understood according to the present invention to refer to the time interval between the mixing of the reactive resin and the curing agent component and the curing of the two-component system. The open time therefore corresponds to such a time during which the two-component system is processable. The open time is also referred to as the pot life.

[0148] The two-component system of the invention can be used, for example, as road marking, as road repair compound, as membrane, as sealing material, as intumescent coating, as floor coating, as casting resin, as building protection material, as coating composition and / or as laminating composition.

[0149] The present invention therefore also provides for the use of the two-component system of the invention as road marking, road repair compound, membrane, sealant, intumescent coating, floor coating, casting resin, building protection material, coating composition and / or laminating composition.

[0150] Road markings are understood in the context of the present invention to mean all coatings which are applied to roads or sidewalks for marking purposes and which are not applied only temporarily, for example for short-term markings in the area of ​​building sites. This also includes, in particular, bicycle paths, sidewalks and / or airstrips. Floor coatings are further coatings of floor materials such as concrete, asphalt, screed or tar, which are located in particular outdoors. However, it is also possible to coat floor materials in indoor areas.

[0151] As sealants, two-component systems are particularly useful as sealants for roofs, bridges and kitchens and / or their joints.

[0152] For example, when it is used as a membrane, the two-component system can be used as a vapor barrier membrane, for example on a roof, and / or as a sealing membrane.

[0153] As coating compositions or as building protection materials, the two-component systems of the invention are particularly useful as corrosion protection materials.

[0154] When used as an intumescent coating, the two-component system is applied, for example, as a flame retardant coating to steel structures. DETAILED DESCRIPTION Example Embodiment 1 to 6:

[0155] Preparation of reactive resins

[0156] Into a 2000 ml (milliliter) capacity jacketed glass reactor with a reflux condenser and a mechanical stirrer (anchor stirrer), 607 g of the alkyl (meth)acrylate specified in Tables 1 and 2, 50 g of triethylene glycol dimethacrylate, 323.5 g of DEGALAN AD 932 (Röhm, copolymer of methyl methacrylate and n-butyl methacrylate, Mw (weight average molecular weight) of 65 000 g / mol and acid value of 3.5 mg (KOH) / g), 5.0 g of triisodecyl phosphite, 0.5 g of 2,6-di-tert-butyl-4-methylphenol, 5.0 g of a paraffin mixture (melting point 46 to 55° C.) and 9.0 g of N,N-bis(2-hydroxypropyl)-p-toluidine were added and the mixture was stirred. The jacket was heated with 60° C. warm water until the components reached a temperature of 55° C. The mixture was stirred until all the components were dissolved, and then the resulting reactive resin was cooled to 23° C. while stirring.

[0157] At 23 ℃ Lower curing

[0158] For curing, 100 g of the resulting reactive resin were mixed with 3.0 g of a curing agent component in powder form (50% dibenzoyl peroxide, Perkadox GB-50X, from Nouryon) at 23° C. and stirred for 2 minutes. The mixture was then poured onto a polymethyl methacrylate plate and applied evenly to a layer thickness of 300 µm in 3 minutes at 23° C. in an open atmosphere with a short-fiber paint roller (mohair, 4 mm nap height). 60 minutes after application, the curing was checked by touching the surface with gloves. If curing is incomplete, the surface remains tacky.

[0159] Parafilm reformation / at 23 ℃ Post-processability

[0160] For curing, 100 g of the resulting reactive resin was mixed with 3.0 g of a curing agent component in powder form (50% dibenzoyl peroxide, Perkadox GB-50X, from Nouryon) at 23 ° C and stirred for 2 minutes. The mixture was then poured onto a polymethyl methacrylate plate and applied evenly to a layer thickness of 300 µm in 3 minutes at 23 ° C in an open atmosphere with a short-fiber paint roller (mohair, 4 mm nap height). 120 minutes after the application was completed, the coating surface was rolled over once again with a short-fiber paint roller, during which the paraffin film that had formed was destroyed. The curing was then checked again 60 minutes after the coating was applied by touching the re-rolled surface with gloves. Only when the re-rolled coating has cured without tack after 60 minutes is it considered to be reprocessable. Due to the limited pot life of two-component systems (coating compositions), two or more mixtures of coating compositions are usually required in practice to coat the coating surface. This means that in practice a coating that has been applied once needs to be rolled or knifed from above again during the application of the next fresh coating composition in order to achieve a uniform coating. This means that the coating composition must be capable of post-processing a few minutes after spreading on the coating surface.

[0161] In 5 ℃ Lower curing

[0162] For curing, 100 g of the resulting reactive resin were mixed with 6.0 g of a curing agent component in powder form (50% dibenzoyl peroxide, Perkadox GB-50X from Nouryon) at 5° C. and stirred for 3 minutes. The mixture was then poured onto a polymethyl methacrylate plate stored at 5° C. and applied evenly to a layer thickness of 300 µm using a short-fiber paint roller (mohair, 4 mm nap height) at 5° C. in an open atmosphere within 3 minutes. After 60 minutes, the curing was checked by touching the surface with gloves.

[0163] The results of the above experiments are shown in Table 1.

[0164] Table 1

[0165] The examples in Table 1 show that tack-free curing at low temperatures is only possible in the presence of short-chain methacrylates (methyl methacrylate, ethyl methacrylate). Due to insufficient post-processability, longer-chain alkyl methacrylates (n-propyl methacrylate, n-butyl methacrylate) cannot be laid on practically relevant surfaces without curing problems, i.e. defects, even at 23°C. At the same time, the use of methyl methacrylate leads to a higher degree of exposure of the operator and a greater degree of odor contamination.

[0166] Viscosity measurement

[0167] The viscosity of the obtained reactive resin was measured using a Brookfield DV2T viscometer.

[0168] In order to determine the pot life, the curing time and the proportion of volatile compounds during the curing process, for each test, 100 g of the resulting reactive resin were mixed in a 200 ml plastic beaker with 3.0 g of a curing agent component in powder form (50% dibenzoyl peroxide, Perkadox GB-50X from Nouryon) at 23° C. and stirred for 3 minutes at 20° C. The two-component system thus obtained was then tested.

[0169] Determination of shelf life

[0170] Measure the time it takes for a two-component system to heat up to 32°C on its own after the curing agent component is added.

[0171] Determination of curing time

[0172] The two-component system was stirred for 3 minutes and then poured into a shallow aluminum pan (2 mm layer thickness). The time taken until tack-free cure was determined.

[0173] Determination of the proportion of volatile compounds during curing

[0174] The two-component system was stirred for 3 minutes and then poured into a shallow aluminum pan with a diameter of 5 cm (layer thickness 1.5 mm) and the initial weight was accurately determined on an analytical balance. After 60 minutes, the weight loss was determined gravimetrically.

[0175] Determination of shrinkage during curing

[0176] Prior to the test, the inside of a 1000 mm long stainless steel tank (equilateral triangle cross section with a side length of 35 mm) was rubbed with paraffin wax. 500 g of the resulting reactive resin was mixed with 15.0 g of a curing agent component in powder form (50% dibenzoyl peroxide, Perkadox GB-50X from Nouryon) at 23°C and stirred for 2 minutes. The stainless steel tank was then filled to the top with the resulting two-component system (approximately 230 g). After 7 days of storage, the formed prisms were removed from the tank and the reduction in linear dimensions was measured.

[0177] Determination of staining properties of labels

[0178] Flame black and iron (II, III) oxide were rubbed onto the surface of the sample of the cured coating composition. The surface was then cleaned evenly with water and a sponge to remove dirt until there was no visually perceptible improvement in dirtiness. The dirtiness was assessed by visual inspection and comparison with the sample.

[0179] The results of the above tests are shown in Table 2.

[0180] Table 2

[0181] The examples show that, in a comparison between alkyl methacrylates, ethyl methacrylate and methyl methacrylate give almost the same properties in terms of resin viscosity, pot life and curing time. However, when ethyl methacrylate is used, a smaller weight loss during curing or a proportion of volatile compounds can be measured, and there is a much lower shrinkage after curing. Embodiment 7 to 12:

[0182] Production of reactive resins

[0183] Into a 2000 ml (milliliter) capacity jacketed glass reactor having a reflux condenser and a mechanical stirrer (anchor stirrer), 329.70 g of the (meth) alkyl acrylate specified in Table 3, 335 g of n-butyl acrylate, 20.0 g of triethylene glycol dimethacrylate, 20 g of trimethylolpropane trimethacrylate, 270 g of prepolymer, 0.300 g of 2,6-di-tert-butyl-4-methylphenol, 5.0 g of paraffin (melting point 52 to 54° C.) and 20.0 g of N,N-bis(2-hydroxypropyl)-p-toluidine were added and the mixture was stirred. The jacket was then heated with 60° C. warm water until the components reached a temperature of 55° C. The mixture was stirred until all the components were dissolved, and the resulting reactive resin was then cooled to 23° C. under stirring.

[0184] Preparation of cold spray plastics from reactive resins according to Examples 7 to 12 (two-component system)

[0185] For example, for road markings, two-component cold spray plastic compounds are formulated based on the resulting reactive resins as follows:

[0186] Cold spray plastic formulations:

[0187] Reactive resin: 32% by weight

[0188] Dispersing additive: 0.2 wt% Disperbyk 167

[0189] Rheological additive: 0.15 wt% Bentone 27

[0190] Pigment: 10% by weight titanium dioxide

[0191] Fine filler: 57.65 wt% Omyacarb 15GU

[0192] The cold plastic compound was intensively mixed with 2% by weight of a curing agent component in powder form (50% dibenzoyl peroxide, Perkadox GB-50X from Nouryon) and applied using a scribing machine with a gap width of 1 mm to a surface at 23° C. After 1 hour, the cured cold sprayed plastic was tested for its tendency to stain.

[0193] Table 3

[0194] Comparative Examples 11 and 12 show that when methyl methacrylate is used as a monomer, the acid value of the polymer component has no negative effect on the staining of the marking. Comparative Example 8 shows that when ethyl methacrylate is used as a monomer, the staining results in high staining due to the absence of acid in the polymer component. Comparative Example 10 shows that when ethyl methacrylate is used as a monomer and a polymer component with a high acid value is used, high staining occurs. In order to achieve low staining in ethyl methacrylate resins, the acid value of the polymer component must be within the range according to the present invention.

Claims

1. A reactive resin comprising the following components: 5 to 94% by weight of ethyl methacrylate, 5 to 50% by weight of at least one prepolymer having an acid number in the range of 1 to 12 mg (KOH) / g, 0 to 50% by weight of at least one oligomer, 0% to 30% by weight of at least one crosslinking agent, 0 to 80% by weight of at least one comonomer, and optionally, 0.1 to 10% by weight of at least one initiator or 0.1 to 5% by weight of at least one accelerator, In each case this is based on the total weight of the reactive resin.

2. The reactive resin according to claim 1, characterized in that The reactive resin contains the following components: 10 to 70% by weight of ethyl methacrylate, 10 to 40% by weight of at least one prepolymer having an acid number in the range of 1 to 12 mg (KOH) / g, 0 to 50% by weight of at least one oligomer, 0.1% to 15% by weight of at least one crosslinking agent, 0 to 40% by weight of at least one comonomer, and optionally, 1 to 5% by weight of at least one initiator or 0.5 to 3% by weight of at least one accelerator, In each case this is based on the total weight of the reactive resin.

3. The reactive resin according to claim 1 or 2, characterized in that The at least one prepolymer has a weight average molecular weight in the range of 25 000 g / mol to 80 000 g / mol.

4. The reactive resin according to any one of claims 1 to 3, characterized in that The at least one prepolymer is selected from polyesters and poly(meth)acrylates.

5. The reactive resin according to any one of claims 1 to 4, characterized in that The at least one oligomer has a weight average molecular weight in the range of >1000 g / mol to <25 000 g / mol.

6. The reactive resin according to any one of claims 1 to 5, characterized in that The at least one oligomer is selected from the group consisting of polyurethane (meth)acrylate, polyethylene glycol, polypropylene glycol and polytetramethylene glycol.

7. The reactive resin according to any one of claims 1 to 6, characterized in that The at least one cross-linking agent has a molecular weight in the range of 150 g / mol to 1000 g / mol.

8. The reactive resin according to any one of claims 1 to 7, characterized in that The at least one crosslinking agent is selected from difunctional, trifunctional, tetrafunctional, pentafunctional and hexafunctional (meth)acrylates.

9. The reactive resin according to any one of claims 1 to 8, characterized in that The at least one comonomer is selected from (meth)acrylic acid C3-C 18 -alkyl esters, C1-C2-alkoxy (meth)acrylates, (meth)acrylic acid, itaconic acid, (meth)acrylamide, 1-olefins and styrene.

10. The reactive resin according to any one of claims 1 to 9, characterized in that The reactive resin is substantially free of methyl (meth)acrylate.

11. The reactive resin according to any one of claims 1 to 10, characterized in that The at least one initiator is selected from peroxides, azo compounds and persulfates.

12. The reactive resin according to any one of claims 1 to 11, characterized in that The at least one accelerator is selected from aromatic substituted tertiary amines.

13. A two-component system comprising the following components: The reactive resin according to any one of claims 1 to 12, and a curing agent component comprising 0.1% to 10% by weight of at least one initiator or 0.1% to 5% by weight of at least one accelerator, in each case based on the total weight of the reactive resin, wherein The reactive resin contains the at least one initiator and the curing agent component contains the at least one accelerator, or The reactive resin comprises the at least one accelerator, and the curing agent component comprises the at least one initiator.

14. The two-component system according to claim 13, characterized in that The curing agent component and / or the reactive resin are substantially free of phthalates.

15. Use of the two-component system according to claim 13 or 14 as road marking, road repair compound, membrane, sealant, intumescent coating, floor coating, casting resin, building protection material, coating composition and / or laminating composition.

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