Reaction resin based on ethyl methacrylate

Abstract

The invention relates to reaction resin which contains at least ethyl methacrylate, a prepolymer with an acid number ranging from 1 to 12 mg (KOH) / g, and optionally either an initiator or an accelerator. The invention additionally relates to a 2K system which comprises the reaction resin according to the invention and a curing component and to the use of the 2K system as a lane marking, lane repair compound, intumescence coating, floor coating, casting resin, building protection, membrane, seal, coating agent, and / or laminating agent.

Description

[0001] Reactive resins based on ethyl methacrylate

[0002] Description

[0003] Field of the invention

[0004] The present invention relates to a reactive resin containing at least ethyl methacrylate, a prepolymer with an acid number in the range of 1 to 12 mg (KOH) / g, and optionally either an initiator or an accelerator. Furthermore, the invention relates to a 2K system comprising the reactive resin according to the invention and a hardener component, and to the use of the 2K system as a road marking, road repair compound, intumescent coating, floor coating, casting resin, building protection, membrane, sealant, coating agent, and / or laminating agent.

[0005] State of the art

[0006] Reactive resins and two-component systems containing them are well known. Reducing the volatile components of a reactive resin, and thus reducing processor exposure and odor nuisance during use, has been a long-standing goal of development. Such reactive resins are described in various prior art documents.

[0007] EP 2 739677 B1 relates to an odorless (meth)acrylic reactive resin containing high-boiling reactive (meth)acrylic monomers from the group of polar cyclic substituted esters. These are used as a replacement for methyl (meth)acrylate (MMA). Although these resins can be cured tack-free under laboratory conditions, the lack of reformation of the paraffin film when the film is subsequently disturbed within the pot life after the initial application of a coating proves to be problematic in practice. Due to the limited pot life, for example, fresh coating batches must usually be repeatedly applied to previously applied coatings. In this case, the previously applied coating must be re-rolled with the freshly applied coating a few minutes after application for the purpose of leveling.This destroys the initially formed paraffin film and requires it to fully reform to enable tack-free curing of the coating on the surface. This is not always guaranteed with reactive resins based on the described high-boiling reactive (meth)acrylic monomers. Large-area coatings, in particular, sometimes exhibit defects that tend to absorb dirt and facilitate the attack of media, potentially creating defects in the overcoating. These resins are therefore of very limited practical use. US 2019 / 0264042 A1 discloses cold-curing reactive resin formulations for floor coatings based on (meth)acrylates, in particular those based on methyl (meth)acrylate, which contain an odorant to improve the odor.However, the level of emission of volatile components, in particular the methyl (meth)acrylate emission, remains unchanged during application and the odor is merely masked.

[0008] WO 2016 / 026757 A1 discloses a dirt-repellent, cold-plastic-based reactive resin sealant for marking or coating floor surfaces or roadways, such as roads. This sealant reduces dirt adhesion, particularly in hot and / or dry, dusty environments. Thus, the marking remains more visible than conventional markings, even in dry, hot regions. A disadvantage of the described method is the additional effort required to apply two marking layers.

[0009] WO 2011 / 006767 A1 discloses formulations for marking road surfaces, such as roads, that can be used again after a shortened waiting time after application. The examples describe the use of polymers with an acid function. A disadvantage of the disclosed reactive resins is the high proportion of crosslinkers, which results in the road markings having little flexibility and a tendency toward embrittlement and flaking, particularly when applied in thicker layers.

[0010] WO 2013 / 185993 A1 discloses formulations (reactive resins) for marking or coating ground surfaces or roadways, such as roads. The formulations exhibit reduced health hazards and good mechanical properties. In particular, the aim is to provide rapidly curing reactive resins with a simultaneously low content of accelerating amines. The document particularly relates to reactive resins containing asymmetric aromatic tertiary amines as an accelerator component. A disadvantage of the disclosed reactive resins is that they exclusively address the health hazards posed by the accelerating amine component and its efficiency in the resins, while other performance properties remain unchanged, i.e., in particular, dirt absorption remains unchanged.Measures to reduce health risks for processors due to exposure to volatile components such as methyl (meth)acrylate or the use of phthalate-containing peroxides are not described.

[0011] CN 105 753 367 A describes a resin-containing composition for bridge repairs. The resin contains two different types of monomers, prepolymers, and an initiator. A prepolymer with an acid number of 1 to 12 mg (KOH) / g is not disclosed. CN 111 005287 A describes a method for repairing roads. It uses a surface repair material containing acrylate monomers, an acrylic resin polymer, silanes, fillers, an accelerator, and a polymerization inhibitor. A prepolymer with an acid number of 1 to 12 mg (KOH) / g is not disclosed.

[0012] EP 2 979 851 A1 relates to a process for producing composite semi-finished products and their further processing into molded parts. In this process, a fibrous carrier is impregnated with a resin composition containing, among other things, monomers and prepolymers. A prepolymer with an acid number of 1 to 12 mg (KOH) / g is not disclosed.

[0013] US 2017 / 0029563 A1 discloses a coating system containing a (meth)acrylic monomer and a reactive polymer, oligomer, or prepolymer containing acrylate or methacrylate groups. A prepolymer with an acid number of 1 to 12 mg (KOH) / g is not disclosed.

[0014] Some of the reactive resins described in the prior art already exhibit good odor properties. However, they often have disadvantages in processing and / or a tendency to cause contamination. Furthermore, they often do not offer a solution for reducing monomer emissions, but merely mask their odor by adding fragrances.

[0015] Task

[0016] There was therefore a need for alternative reactive resins and two-component systems that do not exhibit, or only to a reduced extent, the disadvantages of the reactive resins and two-component systems described in the prior art. In particular, the alternative reactive resins and two-component systems should exhibit reduced emissions of organic components during processing. Furthermore, the two-component system should be particularly suitable for use as road markings and floor coatings, especially those with reduced dirt absorption.

[0017] Solution

[0018] This task was solved by a reactive resin containing the following components:

[0019] 5 to 94 wt% ethyl methacrylate,

[0020] 5 to 50 wt.% of at least one prepolymer having an acid number in the range of 1 to

[0021] 12 mg (KOH) / g,

[0022] 0 to 50 wt.% of at least one oligomer,

[0023] 0 to 30 wt.% of at least one crosslinking agent,

[0024] 0 to 80 wt. % of at least one comonomer, optionally either 0.1 to 10 wt. % of at least one initiator or 0.1 to 5 wt. % of at least one accelerator, in each case based on the total weight of the reactive resin. This object was further achieved by a 2K system comprising the following components: a reactive resin according to any one of claims 1 to 12 and a hardener component which contains either 0.1 to 10 wt. % of at least one initiator or 0.1 to 5 wt. % of at least one accelerator, in each case based on the total weight of the reactive resin, wherein either the reactive resin contains the at least one initiator and the hardener component contains the at least one accelerator or the reactive resin contains the at least one accelerator and the hardener component contains the at least one initiator.

[0025] It has surprisingly been found that two-component systems containing the reactive resins according to the invention cure tack-free even at low ambient temperatures and in contact with atmospheric oxygen. They also exhibit particularly low dirt absorption on their surfaces, particularly when used for the production of road markings and / or floor coatings. This particularly low dirt absorption is due in particular to the use of ethyl methacrylate in combination with a prepolymer with an acid number in the range of 1 to 12 mg (KOH) / g.

[0026] Furthermore, the reactive resin and the 2K system can be applied with reduced emissions, in particular reduced monomer emissions. This is particularly the case when, in a particularly preferred embodiment of the invention, the reactive resins are essentially free of methyl (meth)acrylate. In particular, the health risks can be further reduced when phthalate-free hardeners are used to process the novel 2K systems. This represents another particularly preferred embodiment. The reactive resin and 2K system according to the 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, waterproofing, membranes, coating agents, and / or laminating agents.The reactive resin and / or the 2K system can thus be painted or rolled over several times with processing tools to even out and / or shape the surface without causing curing problems on the surface. The reactive resin, especially the reactive resin that is essentially free of methyl (meth)acrylate, also allows the formulation of coating and marking compounds (2K systems) that have a higher flash point than those containing methyl (meth)acrylate. Therefore, they are less flammable. The reactive resins also exhibit increased flexibility and reduced shrinkage, which improves their impact resistance and reduces cracking in coatings produced from them. They also exhibit lower water absorption.Combined with the increased flexibility, this offers advantages when using the 2K system as an intumescent coating and as corrosion protection. The reactive resin according to the invention is described in more detail below.

[0027] In the context of the present invention, a reaction resin is understood to mean a mixture of at least one monomer and at least one prepolymer, which can be easily cured when used as a 2K system.

[0028] According to the invention, the reaction resin contains the following components:

[0029] 5 to 94% by weight, preferably 10 to 70% by weight, ethyl methacrylate,

[0030] 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,

[0031] 0 to 50 wt.% of at least one oligomer,

[0032] 0 to 30 wt.%, preferably 0.1 to 15 wt.% of at least one crosslinking agent,

[0033] 0 to 80% by weight, preferably 0 to 40% by weight of at least one comonomer, optionally either 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, in each case based on the total weight of the reaction resin.

[0034] A reaction resin is therefore also preferred, wherein the reaction resin contains the following components:

[0035] 10 to 70 wt% ethyl methacrylate,

[0036] 10 to 40 wt.% of at least one prepolymer having an acid number in the range of 1 to

[0037] 12 mg (KOH) / g,

[0038] 0 to 50 wt.% of at least one oligomer,

[0039] 0.1 to 15 wt.% of at least one crosslinking agent,

[0040] 0 to 40 wt.% of at least one comonomer, optionally either 1 to 5 wt.% of at least one initiator or 0.5 to 3 wt.% of at least one accelerator, in each case based on the total weight of the reaction resin.

[0041] It goes without saying that all weight percentages refer to the weight percentages before the components have reacted with each other. During the reaction, the weight ratios of the components may change. This is known to those skilled in the art.

[0042] Preferably, the wt. % of the 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 wt. %. It is therefore preferred that the reactive resin consists of these components. 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.

[0043] The reaction resin contains 5 to 50 wt.%, preferably 10 to 40 wt.%, based on the total weight of the reaction resin, of at least one prepolymer having an acid number in the range of 1 to 12 mg (KOH) / g.

[0044] The prepolymer preferably has an acid number in the range of 3 to 10 mg (KOH) / g. The acid number is determined according to DIN EN ISO 2114:2002 "Plastics (polyester) and coating materials (binders) - Determination of partial and total acid number."

[0045] In the context of the present invention, the term "at least one prepolymer" means both precisely one prepolymer and a mixture of two or more prepolymers. A "prepolymer" within the meaning of the present invention has a weight-average molecular weight in the range from 25,000 g / mol to 80,000 g / mol, preferably in the range from 30,000 g / mol to 70,000 g / mol, determined by GPC (gel permeation chromatography) with PMMA as the standard.

[0046] Therefore, a reaction resin is also preferred 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.

[0047] The at least one prepolymer can be used, for example, to improve the polymerization properties, the mechanical properties, the adhesion to the substrate and the optical properties of the reaction resin and 2K systems produced therefrom.

[0048] Suitable prepolymers are selected, for example, from the group consisting of polyesters, poly(meth)acrylates, polyvinyl acetates, polyvinyl chlorides, polystyrenes, and copolymers thereof. Preferably, the at least one prepolymer is selected from the group consisting of polyesters and poly(meth)acrylates.

[0049] Therefore, a reaction resin is also preferred in which the at least one prepolymer is selected from the group consisting of polyesters and poly(meth)acrylates.

[0050] For the purposes of the present invention, "polyalkyl (meth)acrylates" are understood to mean polymers and copolymers of alkyl (meth)acrylates. "Alkyl (meth)acrylates" are understood to mean both alkyl acrylates and alkyl methacrylates. C1-C18 alkyl (meth)acrylates are preferred. C1-C18 alkyl (meth)acrylates are understood to mean alkyl esters of (meth)acrylic acid having 1 to 18 carbon atoms in the alkyl radical. The alkyl radical can be linear, cyclic, and / or branched. It can also contain aromatic radicals and / or heteroatoms. For example, alkyl (meth)acrylates according to the invention, the polymers or copolymers of which are polyalkyl (meth)acrylates according to the invention, are selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isopentyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate and lauryl (meth)acrylate.

[0051] In the context of the present invention, the term “(meth)acrylic acid” encompasses both acrylic acid and methacrylic acid.

[0052] Polyalkyl (meth)acrylates can be prepared by methods known to the person skilled in the art, for example by means of solution, emulsion, suspension, bulk and / or precipitation polymerization.

[0053] Suitable polyesters are known as such and are preferably available via polycondensation or ring-opening polymerization.

[0054] Both polyesters and polyalkyl (meth)acrylates, which can be used as the at least one prepolymer, can contain additional functional groups such as double bonds, for example, for adhesion promotion or copolymerization. The prepolymers preferably do not contain any double bonds.

[0055] The reaction resin contains 0 to 50 wt.% of at least one oligomer, based on the total weight of the reaction resin.

[0056] For the purposes of the present invention, "at least one oligomer" refers to both precisely one oligomer and a mixture of two or more oligomers. An oligomer, within the meaning of the present invention, is understood to be a macromolecule composed of several structurally identical or similar units.

[0057] The at least one oligomer is different from the at least one prepolymer.

[0058] The at least one oligomer according to the invention has, for example, a weight-average molecular weight in the range from > 1,000 g / mol to < 25,000 g / mol, preferably in the range from 1,500 g / mol to 20,000 g / mol, determined by GPC (gel permeation chromatography) with polyethylene glycol (PEG) as standard.

[0059] Therefore, a reactive resin in which the at least one oligomer has a weight-average molecular weight in the range from > 1,000 g / mol to < 25,000 g / mol is also preferred. The at least one oligomer is selected, for example, from the group consisting of polyurethane (meth)acrylates, polyethers, and polyesters. Polyethers are known per se and are selected, for example, from the group consisting of polyethylene glycol, polypropylene glycol, and polytetrahydrofuran.

[0060] Preferably, the at least one oligomer is therefore selected from the group consisting of polyurethane (meth)acrylates, polyethylene glycol, polypropylene glycol and polytetrahydrofuran.

[0061] According to the invention, therefore, a reaction resin is also preferred in which the at least one oligomer is selected from the group consisting of polyurethane (meth)acrylates, polyethylene glycol, polypropylene glycol and polytetrahydrofuran.

[0062] For the purposes of the present invention, "polyurethane (meth)acrylates" are (meth)acrylates linked to one another via urethane groups. They are obtainable by reacting hydroxyalkyl (meth)acrylates with polyisocyanates and polyoxyalkylenes having at least two hydroxy functionalities. Instead of hydroxyalkyl (meth)acrylates, esters of (meth)acrylic acid with oxiranes, such as ethylene oxide or propylene oxides and corresponding oligooxiranes or polyoxiranes, can also be used. Suitable polyurethane (meth)acrylates are known per se. An overview, for example, of urethane (meth)acrylates with a functionality greater than two, can be found in DE 199 02685.

[0063] Commercially available examples made from polyols, isocyanates and hydroxy-functional (meth)acrylates are available under the trade name EBECRYL from Allnex, such as EBECRYL 210 and EBECRYL 230.

[0064] Polyurethane (meth)acrylates increase flexibility, tensile strength, and elongation at break in a reactive resin without significant temperature dependence. This increases the temperature stability of, for example, road markings made from the reactive resin. Embrittlement caused by a higher crosslinker content can be compensated for, and adhesion to the road surface can be improved.

[0065] The reaction resin contains 0 to 30 wt.%, preferably 0.1 to 15 wt.%, of at least one crosslinker, based on the total weight of the reaction resin.

[0066] In the context of the present invention, “at least one crosslinker” means both exactly one crosslinker and a mixture of two or more crosslinkers.

[0067] In the context of the present invention, a crosslinker is understood to mean a compound that can bond two or more prepolymers and / or polymers formed from ethyl methacrylate. A crosslinker has at least two functional groups that can react with the at least one prepolymer and / or the ethyl methacrylate. It goes without saying that the at least one crosslinker is different from the at least one oligomer.

[0068] For example, the at least one crosslinker is selected from the group consisting of difunctional, trifunctional, tetrafunctional, pentafunctional, and hexafunctional (meth)acrylates. Particularly preferably, the at least one crosslinker is selected from the group consisting of difunctional and trifunctional (meth)acrylates.

[0069] Therefore, a reaction resin in which the at least one crosslinker is selected from the group consisting of difunctional, trifunctional, tetrafunctional, pentafunctional and hexafunctional (meth)acrylates is also preferred.

[0070] Such crosslinkers are known per se and include, for example, allyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, poly(urethane) (meth)acrylates, 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 allnex.

[0071] For example, the at least one crosslinker 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.

[0072] Therefore, a reaction resin in which the at least one crosslinker has a molecular weight in the range from 150 g / mol to 1,000 g / mol is also preferred.

[0073] The reaction resin contains 0 to 80 wt.%, preferably 0 to 40 wt.% of at least one comonomer, based on the total weight of the reaction resin.

[0074] In the context of the present invention, “at least one comonomer” means both exactly one comonomer and a mixture of two or more comonomers.

[0075] It goes without saying that the at least one comonomer is different from ethyl methacrylate. Likewise, the at least one comonomer is different from the at least one crosslinker and the at least one oligomer.

[0076] All compounds that are copolymerizable with ethyl methacrylate are suitable as the at least one comonomer. For example, the at least one comonomer is selected from the group consisting of C3-C18 alkyl (meth)acrylates, C1-C2 alkoxy (meth)acrylate, (meth)acrylic acid, itaconic acid, (meth)acrylamides, 1-alkenes, and styrene. Therefore, a reaction resin in which the at least one comonomer is selected from the group consisting of C3-C18 alkyl (meth)acrylates, C1-C2 alkoxy (meth)acrylate, (meth)acrylic acid, itaconic acid, (meth)acrylamide, 1-alkenes, and styrene is also preferred according to the invention.

[0077] For the purposes of the present invention, a "C3-C18-alkyl (meth)acrylate" is understood to mean an alkyl ester of (meth)acrylic acid having 3 to 18 carbon atoms in the alkyl radical. The alkyl radical may be linear, cyclic, or branched. Likewise, the alkyl radical may contain aromatics. C3-C18-alkyl (meth)acrylates containing aromatics in the alkyl radical include, for example, benzyl (meth)acrylate. Furthermore, the alkyl radical may contain heteroatoms. C3-C18-alkyl (meth)acrylates in which the alkyl radical contains heteroatoms include, for example, hydroxy-functionalized C5-C18-alkyl (meth)acrylates, such as hydroxypropyl (meth)acrylate, and their reaction products with lactones, such as hydroxyethylcaprolactone (meth)acrylates, and ether (meth)acrylates, such as ethylene glycol (meth)acrylate.

[0078] A C3-Ci8-alkyl (meth)acrylate is therefore preferably selected from the group consisting of benzyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxyethylcaprolactone (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, stearyl (meth)acrylate and lauryl (meth)acrylate.

[0079] For the purposes of the present invention, a "Ci-C2-alkoxy(meth)acrylate" is understood to mean an alkyl ester of (meth)acrylic acid having 1 to 2 carbon atoms and at least one oxygen atom in the alkyl radical. Examples of Ci-C2-alkoxy(meth)acrylates within the meaning of the present invention include ethylene glycol (meth)acrylate and hydroxyethyl (meth)acrylate.

[0080] As already explained above, the term (meth)acrylic acid encompasses both acrylic acid and methacrylic acid in the context of the present invention.

[0081] Itaconic acid is known as such and is also called methylidene succinic acid

[0082] The term “(meth)acrylamide” refers to both acrylamide and methacrylamide.

[0083] Suitable 1-alkene comonomers are known as such and include, for example, hexene-1, heptene-1, vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl-1-diisobutylene and 4-methylpentene-1.

[0084] In the context of the present invention, the term "styrene" refers not only to styrene as such, but also to substituted styrenes such as, for example, α-methylstyrene, α-ethylstyrene, vinyltoluene, p-methylstyrene, styrenesulfonic acid, monochlorostyrenes, dichlorostyrenes, and tribromostyrenes, with α-methylstyrene, α-ethylstyrene, vinyltoluene, p-methylstyrene, and styrenesulfonic acid being preferred. Preferably, the at least one copolymer does not comprise methyl (meth)acrylate. Particularly preferably, the reactive resin is substantially free of methyl (meth)acrylate.

[0085] Therefore, a reaction resin that is essentially free of methyl (meth)acrylate is also preferred.

[0086] For the purposes of the present invention, “essentially free of methyl (meth)acrylate” means that the reaction resin contains at most 2% by weight, preferably at most 1% by weight, and particularly preferably at most 0.1% by weight of methyl (meth)acrylate, based on the total weight of the reaction resin. It is further preferred that any methyl (meth)acrylate present in the reaction resin originates exclusively from impurities in the components of the reaction resin, such as, for example, residual monomers present in the at least one prepolymer and / or in the at least one oligomer. Furthermore, any methyl (meth)acrylate present in the reaction resin may originate from cross-contamination during the production of the reaction resin.

[0087] The reaction resin optionally contains either at least one initiator or at least one accelerator. In one embodiment of the present invention, the reaction resin contains neither an initiator nor an accelerator.

[0088] In the context of the present invention, “either at least one initiator or at least one accelerator” means that preferably the reaction resin contains only the at least one initiator and no accelerator or the reaction resin contains only the at least one accelerator and no initiator.

[0089] Preferably, the reaction resin contains only the accelerator. It is therefore preferable that the reaction resin does not contain an initiator.

[0090] The reaction resin may contain 0.1 to 10 wt.%, preferably 1 to 5 wt.% of at least one initiator, in each case based on the total weight of the reaction resin.

[0091] In the context of the present invention, "at least one initiator" means both exactly one initiator and a mixture of two or more initiators. Exactly one initiator is preferred.

[0092] Suitable as the at least one initiator are all compounds known to the person skilled in the art that can initiate a radical polymerization of ethyl methacrylate. For example, the at least one initiator is selected from the group consisting of peroxides, azo compounds, and persulfates. Therefore, a reactive resin in which the at least one initiator is selected from the group consisting of peroxides, azo compounds, and persulfates is also preferred according to the invention.

[0093] Suitable peroxides are, for example, selected from the group consisting of

[0094] Hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxodicarbonate, 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), dicumyl peroxide, diisopropyl peroxydicarbonate and bis(4-t-butylcyclohexyl) peroxydicarbonate.

[0095] Suitable azo compounds are, for example, selected from the group consisting of 2,2-azobisiso-2,4-dimethylvaleronitrile, 2,2-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2-(carbamoylazo)isobutyronitrile and 4,4'-azobis(cyanovaleric acid).

[0096] Suitable persulfates are, for example, selected from the group consisting of lithium peroxodisulfate, sodium peroxodisulfate, potassium peroxodisulfate and ammonium peroxodisulfate.

[0097] The initiator preferably contains no phthalates. The reaction resin particularly preferably contains no phthalates. It is therefore preferred that the reaction resin be free of phthalates.

[0098] As stated above, in a preferred embodiment of the present invention the reaction resin does not contain an initiator.

[0099] The reaction resin may contain 0.1 to 5 wt.%, preferably 0.5 to 3 wt.%, of at least one accelerator, in each case based on the total weight of the reaction resin.

[0100] In the context of the present invention, "at least one accelerator" means both exactly one accelerator and a mixture of two or more accelerators. Exactly one accelerator is preferred according to the invention.

[0101] Compounds known to those skilled in the art that accelerate the curing of the reactive resin can be used as the at least one accelerator. Suitable accelerators include, for example, tertiary aromatic-substituted amines and / or phosphites. Preferably, the at least one accelerator is selected from the group consisting of tertiary aromatic-substituted amines. Therefore, a reactive resin in which the at least one accelerator is selected from the group consisting of tertiary aromatic-substituted amines is also preferred according to the invention.

[0102] The term “tertiary aromatic-substituted amines” includes both symmetric tertiary aromatic-substituted amines and asymmetric tertiary aromatic-substituted amines.

[0103] Suitable symmetrical tertiary aromatic substituted amines are, for example, selected from the group consisting of N,N-dimethyl-p-toluidine, N,N-dimethylaniline, N,N-diethylaniline, overethoxylated N,N-dihydroxyethyl-p-toluidine, overpropoxylated N,N-dihydroxypropyl-p-toluidine, N,N-bis-(2-hydroxyethyl)-p-toluidine and N,N-bis-(2-hydroxypropyl)-p-toluidine.

[0104] Suitable asymmetric tertiary aromatic substituted amines are, for example, selected from the group consisting of N-methyl-N-(hydroxyethyl)-p-toluidine, N-methyl-N-(hydroxyethyl)-m-toluidine, N-methyl-N-(hydroxypropyl)-p-toluidine, an N-methyl-N-(hydroxyethyl)-xylidine, an N-methyl-N-(hydroxypropyl)-xylidine, N-methyl-N-(hydroxyethyl)-aniline and N-methyl-N-(hydroxypropyl)-aniline.

[0105] Geeignete Phosphite sind beispielsweise ausgewählt aus der Gruppe bestehend aus Tri-2- ethylhexylphosphit, Tri-2-ethylhexyltrithiophosphit, Triisooctylphosphit, Triisooctyltrithiophosphit, Tridecylphosphit, Tridecyltrithiophosphit, Trilaurylphosphit, Trilauryltrithiophosphit, Trioctadecylphosphit, Trioctadecyltrithiophosphit, Phenyldidecylphosphit, Phenyldidecyltrithiophosphit, Phenyldilaurylphosphit, Phenyldistearylphosphit, Phenyldistearyltrithiophosphite, Diphenyldecylphosphit, Diphenyllaurylphosphit, Diphenylstearylphosphit, Diphenylstearyltrithiophosphit, Tri-para-kresylphosphit, Tri-meta- kresylphosphit, Tri-ortho-kresylphosphite, Tri-para-Kresyldithiophosphit, Tri-para- octylphenyltrithiophosphit, Tri-ortho-octylphenylphosphit, Tris(dipropyleneglycol)phosphit, Triethoxyethylphosphit, Tributoxyethylphosphit, Tritetrahydrofurfurylphosphit, Tritetrahydrofurfuryltrithiophosphit, Triisodecylphosphit, Triphenylethylphosphit, S- Phenyldilaurylmonothiophosphit,S-Phenyldidecylmonothiophosphite, SS-Diphenyllauryldithiophosphite, SS-Diphenyldecyldithiophosphite, Tri-ortho-naphthylphosphite, SS-diphenyldecyldithiophosphite, Phenyldilauryltrithiophosphite, Tridodecylphenylphosphite, Triochlorophenylphosphite, Diphenyllauryltrithiophosphite, S-Iauryldiphenylmonothiophosphite, tri-p-methoxyphenylphosphite, SO-diphenyl-S-lauryldithiophosphite, tri-o-methoxyphenyldithiophosphite, SS-dilaurylphenyldithiophosphite and SO-dilauryl-S-phenyldithiophosphite.,

[0106] Based on the reaction resins according to the invention, cold plastics can be produced from two or three components. Cold plastics from two components, so-called 2K systems, are preferred. Cold plastics from three components are also referred to as 3K systems. According to the invention, a 2K system comprises the following components: a reaction resin according to the invention and a hardener component which contains either 0.1 to 10 wt.% of at least one initiator or 0.1 to

[0107] 5 wt.% of at least one accelerator, in each case based on the total weight of the reaction resin, wherein either the reaction resin contains the at least one initiator and the hardener component contains the at least one accelerator or the reaction resin contains the at least one accelerator and the hardener component contains the at least one initiator.

[0108] If the reaction resin is part of a 2K system, the reaction resin usually contains either at least one initiator or at least one accelerator.

[0109] The statements and preferences previously described for the reaction resin according to the invention apply accordingly to the reaction resin contained in the 2K system.

[0110] When mixed with the reaction resin, the hardener component initiates and / or accelerates the polymerization of at least the ethyl methacrylate contained in the reaction resin.

[0111] The hardener component therefore contains either the at least one initiator or the at least one accelerator. Typically, the hardener component contains the at least one accelerator if the reactive resin contains the at least one initiator. The hardener component contains the at least one initiator if the reactive resin contains the at least one accelerator.

[0112] The hardener component contains, for example, 0.1 to 10 wt.%, preferably 1 to 5 wt.% of at least one initiator, in each case based on the total weight of the reaction resin contained in the 2K system.

[0113] For the at least one initiator optionally contained in the hardener component, the explanations and preferences previously described for the at least one initiator optionally contained in the reaction resin apply accordingly.

[0114] The hardener component contains, for example, 0.1 to 5 wt.%, preferably 0.5 to 3 wt.%, of at least one accelerator, in each case based on the total weight of the reaction resin contained in the 2K system.

[0115] The above-described embodiments and preferences for the at least one accelerator optionally contained in the hardener component apply accordingly to the at least one accelerator optionally contained in the reactive resin. In one embodiment of the present invention, the hardener component can consist either of the at least one initiator or of the at least one accelerator. Preferably, the reactive resin then does not contain the component from which the hardener component consists.

[0116] It is also possible for the hardener component to contain, in addition to either the at least one initiator or the at least one accelerator, further components, such as the dyes and / or fillers and / or auxiliaries and additives mentioned below. According to the invention, it is preferred that the hardener component be substantially free of ethyl methacrylate.

[0117] According to the invention, in the 2-component system, the reactive resin preferably contains at least one accelerator. The hardener component then preferably contains at least one initiator. In this embodiment, the reactive resin preferably does not contain an initiator. The hardener component then preferably does not contain an accelerator.

[0118] It is further preferred that the hardener component in the 2K system be substantially free of phthalates. It is also preferred that the reaction resin in the 2K system be substantially free of phthalates.

[0119] According to the invention, therefore, a 2K system is preferred in which the hardener component and / or the reaction resin is substantially free of phthalates.

[0120] The 2K system is particularly preferably free of phthalates.

[0121] The two-component system may also contain dyes and / or fillers. For example, the two-component system contains dyes and / or fillers in the range of 0 to 90 wt.%, preferably in the range of 5 to 50 wt.%, based on the total weight of the two-component system.

[0122] Particularly suitable dyes include white, red, blue, green, and / or yellow inorganic pigments. White inorganic pigments such as titanium dioxide are particularly preferred.

[0123] Fillers are, in particular, mineral fillers. Mineral fillers are preferably selected from the group consisting of calcium carbonate, barium sulfate, quartz, quartz powder, precipitated silicas, pyrogenic silicas, corundum, glass beads, and cristobalites.

[0124] The 2K system may also contain auxiliary materials and additives. For example, the 2K system contains auxiliary materials and additives in the range of 0.1 to 5% by weight, based on the

[0125] Total weight of the 2K system. Auxiliaries and additives for 2K systems are known as such and are selected, for example, from the group consisting of regulators, plasticizers, paraffins, stabilizers, inhibitors, waxes, and / or oils.

[0126] For example, paraffins are added to prevent inhibition of polymerization by oxygen in the air. For this purpose, several paraffins with different melting points can be used in different concentrations.

[0127] All compounds known from radical polymerization can be used as regulators. Mercaptans such as n-dodecyl mercaptan are preferred, but polyvalent mercapto compounds such as pentaerythritol tetrathioglycolate are also used.

[0128] Esters, polyols, oils or low molecular weight polyethers are preferably used as plasticizers.

[0129] UV stabilizers are particularly suitable as stabilizers. The UV stabilizers are preferably selected from the group consisting of benzophenone derivatives, benzotriazole derivatives, thioxanthonate derivatives, piperidinolcarboxylic acid ester derivatives, and cinnamic acid ester derivatives.

[0130] From the group of inhibitors, substituted phenols, hydroquinone derivatives, phosphines and phosphites are preferably used.

[0131] To use the 2K system, the reactive resin and the hardener component are mixed together. After mixing the reactive resin with the hardener component, the 2K system typically only has a limited open time of, for example, 2 to 40 minutes, which remains for the 2K system to be used, for example, for applying, pouring, coating, or filling. The 2K system then typically cures. For the purposes of the invention, the term "open time" refers to the period between mixing the reactive resin with the hardener component and the curing of the 2K system. The open time therefore corresponds to the time during which the 2K system is processable. The open time is also referred to as the pot life.

[0132] The 2K systems according to the invention can be used, for example, as road markings, as road repair compounds, as membranes, as waterproofing, as intumescent coatings, as floor coatings, as casting resins, as building protection, as coating agents and / or as laminating agents.

[0133] A further subject of the present invention is therefore also the use of a 2K system according to the invention as a road marking, road repair compound, membrane, sealant, intumescent coating, floor coating, casting resin, building protection, coating agent and / or laminating agent.

[0134] For the purposes of the present invention, road markings are understood to mean all coatings applied to roadways or sidewalks for marking purposes, which are not merely temporary, e.g., for short-term marking in a construction site area. This particularly includes bicycle paths, sidewalks, and / or runways for air traffic. Floor coatings refer to other coatings on floor materials such as concrete, asphalt, screed, or tar, which are particularly found outdoors. However, the coating of floor materials indoors is also possible.

[0135] The 2K systems can be used in particular for waterproofing roofs, bridges, kitchens and / or their joints.

[0136] For example, when used as a membrane, the 2K systems can be used as a vapor barrier membrane, for example on roofs, and / or waterproofing membrane.

[0137] As a coating agent or as building protection, the 2K system according to the invention can be used in particular as corrosion protection.

[0138] When used as an intumescent coating, the 2K system is applied, for example, as a flame-retardant coating to steel structures.

[0139] Examples

[0140] Examples 1 to 6

[0141] Production of reaction resin

[0142] 607 g of the alkyl (meth)acrylate listed 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 with Mw (weight-average molecular weight) of 65,000 g / mol and an acid number 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 paraffin mixture (melting point 46 to 55 °C), and 9.0 g of N,N-bis-(2-hydroxypropyl)-p-toluidine were added to a 2000 mL (milliliter) double-jacketed glass reactor equipped with a reflux condenser and a mechanical stirrer (anchor stirrer). and stirred. The double jacket was heated with 60 °C warm water until the components reached a temperature of 55 °C. Stirring was continued until all components were dissolved, then the resulting reaction resin was cooled to 23 °C while stirring.

[0143] Curing at 23°C For curing, 100 g of the resulting reaction resin was mixed with 3.0 g of hardener powder (50% dibenzoyl peroxide, Perkadox GB-50X, Nouryon) at 23°C and stirred for 2 minutes. The mixture was then poured onto a polymethyl methacrylate plate and applied homogeneously to a layer thickness of 300 μm in the open atmosphere at 23°C using a short-fiber paint roller (mohair, 4 mm pile height) within 3 minutes. 60 minutes after application, the curing was checked by feeling the surface with a glove. In the event of incomplete curing, the surface remains tacky.

[0144] Paraffin film reversion / reworkability at 23 °C

[0145] For curing, 100 g of the resulting reactive resin was mixed with 3.0 g of hardener component in powder form (50% dibenzoyl peroxide, Perkadox GB-50X, Nouryon) at 23 °C and stirred for 2 minutes. The mixture was then poured onto a polymethyl methacrylate plate and applied homogeneously to a layer thickness of 300 μm in an open atmosphere at 23 °C using a short-fiber paint roller (mohair, 4 mm pile height) within 3 minutes. 120 seconds after application, the coating surface was rolled over again once with the short-fiber paint roller, breaking up the paraffin film that had formed in the meantime. Curing was then checked again 60 minutes after application of the coating by feeling the rolled-over surface with a glove. The rolled-over coating is only considered ready for rework if it has cured tack-free after 60 minutes.Due to the limited pot life of the 2K system (the coating compound), several mixes of the coating compound are usually required to coat a single surface. This means that, in practice, a coating that has already been applied must be rolled over or troweled over again when applying the next fresh coating compound to achieve an even coating. This means that the coating compound must be able to be worked on for several minutes after it has been applied to the surface.

[0146] For curing, 100 g of the resulting reaction resin was mixed with 6.0 g of hardener powder (50% dibenzoyl peroxide, Perkadox GB-50X, 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 homogeneously to a layer thickness of 300 μm in the open atmosphere at 5°C using a short-fiber mohair roller (4 mm pile height). After 60 minutes, the curing was checked by touching the surface with a glove.

[0147] The results of the experiments described above are shown in Table 1.

[0148] Table 1

[0149]

[0150] The examples in Table 1 show that tack-free curing at low temperatures is only possible with the presence of short-chain methacrylates (methyl methacrylate, ethyl methacrylate). Longer-chain alkyl methacrylates (n-propyl methacrylate, n-butyl methacrylate) cannot be applied without curing problems, i.e., defects, even at 23°C on practical surfaces due to the lack of reworkability. At the same time, the use of methyl methacrylate leads to high exposure of the installer and unpleasant odors.

[0151] Viscosity measurement

[0152] The viscosity of the resulting reaction resin was determined using a Brookfield DV2T viscometer.

[0153] To determine the pot life, curing time, and proportions of volatile compounds during curing, 100 g of the resulting reaction resin was mixed with 3.0 g of a hardener powder (50% dibenzoyl peroxide, Perkadox GB-50X, Nouryon) in a 200 ml plastic beaker at 20 °C for each test and stirred for 3 minutes. The resulting 2K system was then subjected to the tests.

[0154] Determination of pot life

[0155] The time required for the 2K system to heat up to 32 °C after adding the hardener component was measured.

[0156] Determination of curing time

[0157] After stirring for 3 minutes, the two-component system was poured into a shallow aluminum tray (2 mm layer thickness). The time required for tack-free curing was determined. Determination of the proportion of volatile compounds during curing.

[0158] After stirring for 3 minutes, the two-component system was poured into a shallow aluminum dish (5 cm diameter) (1.5 mm layer thickness), and the sample weight was precisely determined on an analytical balance. After 60 minutes, the weight loss was determined gravimetrically.

[0159] Determination of shrinkage during curing

[0160] Before conducting the tests, the insides of a 1000 mm long stainless steel trough (cross-section of an equilateral triangle with an edge length of 35 mm) were coated with paraffin wax. 500 g of the resulting reaction resin were mixed with 15.0 g of a hardener component in powder form (50% dibenzoyl peroxide, Perkadox GB-50X, Nouryon) at 23 °C and stirred for 2 minutes. The stainless steel trough was then filled to the top with the resulting 2K system (approximately 230 g). After 7 days of storage, the resulting prism was removed from the trough, and the reduction in linear expansion was measured.

[0161] Determination of dirt absorption of markings

[0162] Lamp black and iron oxide are rubbed onto the surface of test specimens of the cured coating compounds. The surface is then evenly cleaned of the contamination with water and a sponge until no visually perceptible improvement in the contamination occurs. The contamination is assessed visually and by comparing samples with each other.

[0163] The results of the experiments described above are shown in Table 2.

[0164] Table 2

[0165] The examples show that, when comparing the alkyl methacrylates, ethyl methacrylate and methyl methacrylate result in almost identical properties in terms of resin viscosity, pot life, and curing time. However, when using ethyl methacrylate, a lower weight loss and the proportion of volatile compounds during curing are measurable, and there is significantly less shrinkage after curing.

[0166] Examples 7 to 12 Preparation of reaction resin

[0167] 329.70 g of the alkyl (meth)acrylate listed 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 wax (melting point 52 to 54°C), and 20.0 g of N,N-bis-(2-hydroxypropyl)-p-toluidine were added to a 2000 mL (milliliter) jacketed glass reactor equipped with a reflux condenser and mechanical stirrer (anchor stirrer) and stirred. The jacket was then heated with 60°C warm water until the temperature of the components reached 55°C. Stirring continued until all components were dissolved. The resulting reaction resin was then cooled to 23 °C while stirring.

[0168] Formulation of cold spray plastic (2K system) from reaction resin according to Examples 7 to 12 2-component cold spray plastic compounds were formulated as an example for a road marking as follows based on the reaction resins obtained:

[0169] Cold spray plastic formulation:

[0170] Reaction resin: 32 wt.%

[0171] Dispersing additive: 0.2% by weight Disperbyk 167

[0172] Rheology additive: 0.15 wt.% Bentone 27

[0173] Pigment: 10 wt% titanium dioxide

[0174] Fine filler: 57.65 wt% Omyacarb 15GU

[0175] The cold-sprayed plastic compound is intensively mixed with a 2 wt.% hardener powder (50% dibenzoyl peroxide, Perkadox GB-50X, Nouryon) and applied to a surface at 23°C using a squeegee with a 1 mm gap. After one hour, the cured cold-sprayed plastics are tested for soiling resistance.

[0176] Table 3

[0177] Comparative Examples 11 and 12 show that when methyl methacrylate is used as

[0178] The acid number of the polymer component has no negative impact on the dirt absorption of the marking. Comparative Example 8 shows that when ethyl methacrylate is used as the monomer, the dirt absorption is improved due to the absence of acid in the polymer component. Comparative Example 10 shows that when ethyl methacrylate is used as the monomer and a polymer component with a high acid number, strong dirt absorption results. To achieve low dirt absorption with ethyl methacrylate resins, the acid number of the polymer component must be within the range of the invention.

Claims

Claims for a reactive resin containing the following components: 5 to 94 wt% ethyl methacrylate, 5 to 50 wt% of at least one prepolymer with an acid number in the range of 1 to 12 mg (KOH) / g, 0 to 50 wt% of at least one oligomer, 0 to 30 wt.% of at least one crosslinking agent, 0 to 80 wt.% of at least one comonomer, optionally either 0.1 to 10 wt.% of at least one initiator or 0.1 to 5 wt.% of at least one accelerator, each based on the total weight of the reaction resin. Reaction resin according to claim 1, characterized in that the reaction resin contains the following components: 10 to 70 wt.% ethyl methacrylate, 10 to 40 wt% of at least one prepolymer with an acid number in the range of 1 to 12 mg (KOH) / g, 0 to 50 wt% of at least one oligomer, 0.1 to 15 wt.% of at least one crosslinking agent, 0 to 40 wt.% at least one comonomer, optionally either 1 to 5 wt.% at least one initiator or 0.5 to 3 wt.% at least one accelerator, each based on the total weight of the reaction resin. Reaction 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. Reaction resin according to any one of claims 1 to 3, characterized in that the at least one prepolymer is selected from the group consisting of polyesters and poly(meth)acrylates. Reaction 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 > 1,000 g / mol to < 25,000 g / mol. Reaction resin according to one of claims 1 to 5, characterized in that the at least one oligomer is selected from the group consisting of polyurethane (meth)acrylates, polyethylene glycol, polypropylene glycol and polytetrahydrofuran.

7. Reaction resin according to one of claims 1 to 6, characterized in that the at least one crosslinking agent has a molecular weight in the range of 150 g / mol to 1,000 g / mol.

8. Reaction resin according to one of claims 1 to 7, characterized in that the at least one crosslinker is selected from the group consisting of difunctional, trifunctional, tetrafunctional, pentafunctional and hexafunctional (meth)acrylates.

9. Reaction resin according to one of claims 1 to 8, characterized in that the at least one comonomer is selected from the group consisting of C3-C18 alkyl(meth)acrylates, Ci-C2 alkoxy(meth)acrylates, (meth)acrylic acid, itaconic acid, (meth)acrylamide, 1-alkenes and styrene.

10. Reaction resin according to one of claims 1 to 9, characterized in that the reaction resin is essentially free of methyl(meth)acrylate.

11. Reaction resin according to one of claims 1 to 10, characterized in that the at least one initiator is selected from the group consisting of peroxides, azo compounds and persulfates.

12. Reaction resin according to one of claims 1 to 11, characterized in that the at least one accelerator is selected from the group consisting of tertiary aromatically substituted amines.

13. 2K system comprising the following components: a reaction resin according to any one of claims 1 to 12 and a hardener component, which contains either 0.1 to 10 wt.% of at least one initiator or 0.1 to 5 wt.% of at least one accelerator, each based on the total weight of the reaction resin, wherein either the reaction resin contains the at least one initiator and the hardener component contains the at least one accelerator or the reaction resin contains the at least one accelerator and the hardener component contains the at least one initiator.

14. 2K system according to claim 13, characterized in that the hardener component and / or the reaction resin is substantially free of phthalates.

15. Use of the 2K system according to claim 13 or 14 as a road marking, road repair compound, membrane, sealant, intumescent coating, Floor coatings, casting resins, building protection, coating agents and / or laminating agents.

Images