DE202022102002U1 - Curable compositions containing 2-octyl acrylate for floor and roadway coating - Google Patents

Abstract

Polymerizable and curable composition A containing
a1) 5 to 94.4% by weight of 2-octyl acrylate (2-OA),
a2) 0 to 89.4% by weight of one or more further monomers which can be copolymerized with 2-octyl acrylate,
a3) 5 to 80% by weight of one or more prepolymers, preferably poly(meth)acrylates and/or polyesters,
a4) 0.5 to 35% by weight of one or more crosslinkers,
a5) 0.1 to 8% by weight of one or more initiators,
a6) 0 to 5% by weight of one or more further additives, including accelerators such as amines, stabilizers, dispersing additives and rheological additives, and
a7) 0 to 50% by weight of one or more further components selected from pigments, fillers, core-shell particles, paraffins, waxes and/or plasticizers, the sum of components a1) to a7) being 100% by weight results.

Description

The present invention relates to curable compositions containing 2-octyl acrylate (2-OA), other monomers, prepolymers, crosslinkers and initiators.

These compositions find advantageous use as floor and pavement coatings, particularly pavement coatings, e.g., as a reactive resin seal for floor surfaces and as pavement markings.

The use of methyl (meth)acrylate in polymerizable and curable compositions (reactive resins) is known.

However, the processing of reaction resins based on methyl (meth)acrylate for markings and floor coatings is usually accompanied by a strong odor nuisance. However, odor-reduced (meth)acrylate systems are also known.

DE 198 26 412 A1 (Röhm GmbH) relates to an odor-reduced, polymerizable, cold-curing, reactive (meth)acrylate system for floor coatings containing mono- and polyfunctional (meth)acrylates. The use of relatively long-chain (meth)acrylates, in particular n-butyl acrylate, has the disadvantage of a lower glass transition temperature Tg (−43° C.) and associated higher levels of dirt adhesion.

EP 2 987 837 A1 (Evonik Rohm GmbH) teaches certain two-layer road markings or floor coatings, the bottom layer being a cured (meth)acrylate-based reaction resin. A disadvantage of the two-layer systems, however, is a higher complexity in the application.

DE20 2017 000 703 U1 discloses polymerizable and curable compositions containing tert-butyl (meth)acylate, other monomers, prepolymers, crosslinkers and initiators and their use as floor and roadway coatings.

The object on which the present invention is based is to provide further odor-reduced acrylate reactive resins for markings and floor coatings which produce particularly low odor nuisance when applied and at the same time have a reduced tendency for dirt to adhere and have improved mechanical properties.

• a1) 5 bis 94,4 Gew.-% 2-Octylacrylat (2-OA),
• a2) 0 bis 89,4 Gew.-% eines oder mehrerer mit 2-Octylacrylat copolymerisierbarer weiterer Monomere,
• a3) 5 bis 80 Gew.-% eines oder mehrerer Präpolymere, vorzugsweise Poly(meth)acrylate und/oder Polyester,
• a4) 0,5 bis 35 Gew.-% eines oder mehrerer Vernetzer,
• a5) 0,1 bis 8 Gew.-% eines oder mehrerer Initiatoren,
• a6) 0 bis 5 Gew.-% eines oder mehrerer weiterer Additive, umfassend Beschleuniger wie Amine, Stabilisatoren, Dispergieradditive und Rheologieadditive, und
• a7) 0 bis 50 Gew.-% einer oder mehrerer weiterer Komponenten, ausgewählt aus Pigmenten, Füllstoffen, Kern-Schale-Partikeln, Paraffinen, Wachsen und/oder Weichmachern,

wobei die Summe der Komponenten a1) bis a7) 100 Gew.-% ergibt.Accordingly, there is provided a polymerizable and curable composition A containing

• a1) 5 to 94.4% by weight of 2-octyl acrylate (2-OA),
• a2) 0 to 89.4% by weight of one or more further monomers which can be copolymerized with 2-octyl acrylate,
• a3) 5 to 80% by weight of one or more prepolymers, preferably poly(meth)acrylates and/or polyesters,
• a4) 0.5 to 35% by weight of one or more crosslinkers,
• a5) 0.1 to 8% by weight of one or more initiators,
• a6) 0 to 5% by weight of one or more further additives, including accelerators such as amines, stabilizers, dispersing additives and rheology additives, and
• a7) 0 to 50% by weight of one or more other components selected from pigments, fillers, core-shell particles, paraffins, waxes and/or plasticizers,

where the sum of components a1) to a7) is 100% by weight.

• a1) 20 bis 74,8 Gew.-% 2-Octylacrylat (2-OA),
• a2) 10 bis 50 Gew.-% eines oder mehrerer mit 2-Octylacrylat copolymerisierbarer weiterer Monomere,
• a3) 10 bis 35 Gew.-% eines oder mehrerer Präpolymere, vorzugsweise Poly(meth)acrylate und/oder Polyester,
• a4) 5 bis 20 Gew.-% eines oder mehrerer Vernetzer,
• a5) 0,2 bis 4 Gew.-% eines oder mehrerer Initiatoren,
• a6) 0 bis 5 Gew.-% eines oder mehrerer weiterer Additive, umfassend Beschleuniger wie Amine, Stabilisatoren, Dispergieradditive und Rheologieadditive, und
• a7) 0 bis 50 Gew.-% eines oder mehrerer weiterer Komponenten, ausgewählt aus Pigmenten, Füllstoffen, Kern-Schale-Partikeln, Paraffinen, Wachsen und/oder Weichmachern,

wobei die Summe der Komponenten a1) bis a7) 100 Gew.-% ergibt.In a preferred embodiment, the polymerizable and curable composition contains A

• a1) 20 to 74.8% by weight of 2-octyl acrylate (2-OA),
• a2) 10 to 50% by weight of one or more further monomers which can be copolymerized with 2-octyl acrylate,
• a3) 10 to 35% by weight of one or more prepolymers, preferably poly(meth)acrylates and/or polyesters,
• a4) 5 to 20% by weight of one or more crosslinkers,
• a5) 0.2 to 4% by weight of one or more initiators,
• a6) 0 to 5% by weight of one or more further additives, including accelerators such as amines, stabilizers, dispersing additives and rheology additives, and
• a7) 0 to 50% by weight of one or more further components selected from pigments, fillers, core-shell particles, paraffins, waxes and/or plasticizers,

where the sum of components a1) to a7) is 100% by weight.

Compared to known compositions, the use of 2-octyl acrylate in the compositions (reactive resins) results in particular in the advantages of a lower vapor pressure of the acrylate, ie a reduction in odor, improved hydrolytic stability and an improved mechanical stability of the polymerized and cured composition, with otherwise unchanged or improved other properties.

2-Octyl acrylate can be prepared by esterification of acrylic acid with 2-octanol or transesterification of, for example, methyl acrylate or ethyl acrylate with 2-octanol. Bio-based 2-octyl acrylate is preferably produced by reacting 2-octanol with acrylic acid, methyl acrylate or ethyl acrylate, with 2-octanol and/or acrylic acid and/or methyl acrylate and/or ethyl acrylate being produced at least partially from renewable raw materials. Bio-based 2-octanol can be obtained from castor oil, for example. The production of acrylic acid from renewable raw materials, for example, is WO2006/092272 , DE 10 2006 039 203 A or EP 2 922 580 described.

It is also possible to produce at least part of the starting materials used for the synthesis of the monomers from renewable raw materials, in accordance with the mass balance approach. Accordingly, in addition to fossil feedstocks, renewable feedstocks such as bio-naphtha (such as in EP 2 290 045 or EP 2 290 034 described) used in chemical production, for example in a steam cracker. The renewable input materials are converted along the chemical value chain, for example to acrylic acid, alkyl acrylates, alkyl methacrylates or styrene. The content of these products in renewable (renewable) raw materials is defined by the mass balance approach and can be assigned to these products.

The compositions A according to the invention make it possible to reduce the odor nuisance and possible health hazards when these compositions are applied in a manner that is not readily foreseeable. At the same time, reaction resins according to the invention for floor coatings with an overall excellent range of properties (reduced tendency for dirt to adhere and improved mechanical properties) can be produced by suitable selection of the individual components in terms of type and quantity. Surprisingly, it was found that the use of 2-octyl acrylate compared to methyl (meth) acrylate significantly reduces the odor nuisance and a possible health hazard associated therewith. Compared to other methyl (meth)acrylate alternatives that are more neutral in odor and less harmful to health, the use of 2-octyl acrylate shows surprising performance advantages, such as a particularly low tendency to dirt adhesion and mechanical advantages.

Another aspect of the present invention are (odour-reduced) floor and roadway coatings, e.g. markings, which are obtainable by applying composition A to a surface to be coated, polymerizing and curing the composition, e.g. at temperatures in the range from -10 to +45 ° C, especially at ambient temperature (+10 to +30 °C).

Reaction resins that harden at temperatures in the range of -10 to +45 °C are also called cold-hardening.

• - Alkylacrylate, wie tert-Butylacrylat, Isobutylacrylat, 2-Methyl(cis)acrylsäureester (iso-Crotonsäureester), 2-Methyl-(trans)acrylsäureester (Crotonsäureester);
• - Acrylate von halogenierten Alkoholen, wie Acrylsäure-1-trifluormethylester;
• - Arylacrylate, wie ggf. substituierte Benzylacrylate;
• - ungesättigte Alkylacrylate, wie Allylacrylat.

Examples of monomers a2) which can be used in the context of the invention and are copolymerizable with 2-octyl acrylate are acrylates a21), including, inter alia

• - Alkyl acrylates, such as tert-butyl acrylate, isobutyl acrylate, 2-methyl(cis)acrylic acid ester (iso-crotonic acid ester), 2-methyl(trans)acrylic acid ester (crotonic acid ester);
• - acrylates of halogenated alcohols, such as 1-trifluoromethyl acrylate;
• - aryl acrylates, such as optionally substituted benzyl acrylates;
• - unsaturated alkyl acrylates such as allyl acrylate.

• - Alkylmethacrylate, die sich von gesättigten Alkoholen ableiten, wie Methylmethacrylat, Ethylmethacrylat, Isopropylmethacrylat, Propylmethacrylat, n-Butylmethacrylat, Isobutylmethacrylat, tert-Butylmethacrylat, n-Hexylmethacrylat, n-Octylmethacrylat, n-Decylmethacrylat, Isooctylmethacrylat und Tetradecylmethacrylat;
• - Alkylmethacrylate, die sich von ungesättigten Alkoholen ableiten, wie z.B. Oleylmethacrylat, 2-Propinylmethacrylat, Allylmethacrylat und Vinylmethacrylat;
• - Amide und Nitrile der Methacrylsäure, wie N-(3-Dimethylaminopropyl)methacrylamid, N-(Diethylphosphono)methacrylamid, 1-Methacryloylamido-2-methyl-2-propanol, N-(3-Dibutyl-aminopropyl)methacrylamid, N-t-Butyl-N-(diethylphosphono)methacrylamid, N,N-bis(2-Diethylaminoethyl)methacrylamid, 4-Methacryloylamido-4-methyl-2-pentanol, Methacryloylamidoacetonitril, N-(Methoxymethyl)methacrylamid, N-(2-Hydroxyethyl)methacrylamid, N-Acetylmethacrylamid, N-(Dimethylaminoethyl)methacrylamid, N-Methyl-N-phenylmethacrylamid, N,N-Diethylmethacrylamid, N-Methylmethacrylamid, N,N-Dimethylmethacrylamid und N-Isopropylmethacrylamid;
• - Aminoalkylmethacrylate, wie tris(2-Methacryloxyethyl)amin, N-methylformamidoethyl methacrylat, 3-Diethylaminopropylmethacrylat und 2-Ureidoethylmethacrylat; andere stickstoffhaltige Methacrylate, wie N-(Methacryloyloxyethyl)diisobutylketimin, 2-Methacryloyloxyethylmethylcyanamid und Cyanomethylmethacrylat;
• - Arylmethacrylate, wie Nonylphenylmethacrylat, Benzylmethacrylat und Phenylmethacrylat, wobei die Arylreste jeweils unsubstituiert oder bis zu vierfach substituiert sein können;
• - carbonylhaltige Methacrylate, wie Carboxyethylmethacrylat, Carboxymethylmethacrylat, N-(2- Methacryloyloxyethyl-2-pyrrolidinon, N-(3- Methacryloyloxypropyl-2-pyrrolidinon, N-Methacryloylmorpholin, Oxazolidinylethylmethacrylat, N-(Methacryloyloxy)formamid, Acetonylmethacrylat und N-Methacryloy1-2-pyrrolidinon;
• - Cycloalkylmethacrylate, wie Cyclopentylmethacrylat, Cyclohexylmethacrylat, 3-Vinylcyclohexylmethacrylat, 3,3,5-Trimethylcyclohexyl- methacrylat, Bornylmethacrylat, Cyclopenta-2,4-dienylmethacrylat, Isobornyl-methacrylat und 1-Methylcyclohexylmethacrylat;
• - Glykoldimethacrylate, wie 1,4-Butandiolmethacrylat, Methylenmethacrylat, 1,3-Butandiolmethacrylat, Triethylenglykolmethacrylat, 2,5-Dimethyl-1,6-hexandiolmethacrylat, 1,10-Decandiolmethacrylat, 1,2-Propandiolmethacrylat und Diethylenglykolmethacrylat, Ethylenglykolmethacrylat;
• - Hydroxylalkylmethacrylate, wie 3-Hydroxypropylmethacrylat, 3,4-Dihydroxybutylmethacrylat, 2-Hydroxyethylmethacrylat und 2-Hydroxypropylmethacrylat;
• - Methacrylate von Etheralkoholen, wie Tetrahydrofurfurylmethacrylat, Vinyloxyethoxyethylmethacrylat, Methoxyethoxyethylmethacrylat, 1-Butoxypropylmethacrylat, 1-Methyl-(2-vinyloxy)-ethylmethacrylat, Cyclohexyloxymethylmethacrylat, Methoxymethoxyethylmethacrylat, Benzyloxymethylmethacrylat, Furfurylmethacrylat, 2-Butoxyethylmethacrylat, 2-Ethoxy-ethoxymethylmethacrylat, 2-Ethoxyethylmethacrylat, Allyloxymethylmethacrylat, 1-Ethoxybutylmethacrylat, Methoxymethylmethacrylat, 1-Ethoxyethylmethacrylat und Ethoxymethylmethacrylat;
• - Methacrylate von halogenierten Alkoholen, wie 2,3-Dibromopropylmethacrylat, 4-Bromo-phenylmethacrylat, 1,3-Dichloro-2-propylmethacrylat, 2-Bromoethylmethacrylat, 2-lodoethylmethacrylat und Chloromethylmethacrylat;
• - Oxiranylmethacrylate, wie 10,11 -Epoxyundecylmethacrylat, 2,3-Epoxycyclohexylmethacrylat, 2,3-Epoxybutylmethacrylat, 3,4-Epoxybutylmethacrylat und Glycidylmethacrylat;
• - Phosphor-, Bor- und/oder Silicium-haltige Methacrylate, wie 2-(Dibutylphosphono)ethyl- methacrylat, 2,3-Butylenmethacryloylethylborat, 2-(Dimethylphosphato)propylmethacrylat, Methyldiethoxymethacryloylethoxysilan, 2-(Ethylenphosphito)propylmethacrylat, Dimethylphosphinomethylmethacrylat, Dimethylphosphonoethylmethacrylat, Diethylmethacryloylphosphonat, Diethylphosphatoethylmethacrylat und Dipropylmethacryloylphosphat;
• - schwefelhaltige Methacrylate, wie Ethylsulfinylethylmethacrylat, 4-Thiocyanatobutylmethacrylat, Ethylsulfonylethylmethacrylat, Thiocyanatomethylmethacrylat, Methylsulfinylmethylmethacrylat und Bis(methacryloyloxyethyl)sulfid;
• - Trimethacrylate, wie Trimethyloylpropantrimethacrylat.

Methacrylates a22) which can be used particularly advantageously in the context of the invention include, inter alia

• - alkyl methacrylates derived from saturated alcohols such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, n-decyl methacrylate, isooctyl methacrylate and tetradecyl methacrylate;
• - Alkyl methacrylates derived from unsaturated alcohols, such as oleyl methacrylate, 2-propynyl methacrylate, allyl methacrylate and vinyl methacrylate;
• - Amides and nitriles of methacrylic acid, such as N-(3-dimethylaminopropyl)methacrylamide, N-(diethylphosphono)methacrylamide, 1-methacryloylamido-2-methyl-2-propanol, N-(3-dibutylaminopropyl)methacrylamide, Nt-butyl -N-(diethylphosphono)methacrylamide, N,N-bis(2-diethylaminoethyl)methacrylamide, 4-methacryloylamido-4-methyl-2-pentanol, methacryloylamidoacetonitrile, N-(methoxymethyl)methacrylamide, N-(2-hydroxyethyl)methacrylamide, N-acetylmethacrylamide, N-(dimethylaminoethyl)methacrylamide, N-methyl-N-phenylmethacrylamide, N,N-diethylmethacrylamide, N- methyl methacrylamide, N,N-dimethyl methacrylamide and N-isopropyl methacrylamide;
• - aminoalkyl methacrylates such as tris(2-methacryloxyethyl)amine, N-methylformamidoethyl methacrylate, 3-diethylaminopropyl methacrylate and 2-ureidoethyl methacrylate; other nitrogen-containing methacrylates such as N-(methacryloyloxyethyl)diisobutyl ketimine, 2-methacryloyloxyethylmethylcyanamide and cyanomethyl methacrylate;
• - Aryl methacrylates, such as nonylphenyl methacrylate, benzyl methacrylate and phenyl methacrylate, where the aryl radicals can each be unsubstituted or substituted up to four times;
• - carbonyl-containing methacrylates such as carboxyethyl methacrylate, carboxymethyl methacrylate, N-(2-methacryloyloxyethyl-2-pyrrolidinone, N-(3-methacryloyloxypropyl-2-pyrrolidinone, N-methacryloylmorpholine, oxazolidinylethyl methacrylate, N-(methacryloyloxy)formamide, acetonyl methacrylate and N-methacryloy1- 2-pyrrolidinone;
• - cycloalkyl methacrylates such as cyclopentyl methacrylate, cyclohexyl methacrylate, 3-vinylcyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, bornyl methacrylate, cyclopenta-2,4-dienyl methacrylate, isobornyl methacrylate and 1-methylcyclohexyl methacrylate;
• - glycol dimethacrylates such as 1,4-butanediol methacrylate, methylene methacrylate, 1,3-butanediol methacrylate, triethylene glycol methacrylate, 2,5-dimethyl-1,6-hexanediol methacrylate, 1,10-decanediol methacrylate, 1,2-propanediol methacrylate and diethylene glycol methacrylate, ethylene glycol methacrylate;
• - hydroxyalkyl methacrylates such as 3-hydroxypropyl methacrylate, 3,4-dihydroxybutyl methacrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate;
• - methacrylates of ether alcohols such as tetrahydrofurfuryl methacrylate, vinyloxyethoxyethyl methacrylate, methoxyethoxyethyl methacrylate, 1-butoxypropyl methacrylate, 1-methyl-(2-vinyloxy)ethyl methacrylate, cyclohexyloxymethyl methacrylate, methoxymethoxyethyl methacrylate, benzyloxymethyl methacrylate, furfuryl methacrylate, 2-butoxyethyl methacrylate, 2-ethoxy-ethoxymethyl methacrylate, 2-ethoxyethyl methacrylate, allyloxymethyl methacrylate, 1-ethoxybutyl methacrylate, methoxymethyl methacrylate, 1-ethoxyethyl methacrylate and ethoxymethyl methacrylate;
• - methacrylates of halogenated alcohols such as 2,3-dibromopropyl methacrylate, 4-bromophenyl methacrylate, 1,3-dichloro-2-propyl methacrylate, 2-bromoethyl methacrylate, 2-iodoethyl methacrylate and chloromethyl methacrylate;
• - oxiranyl methacrylates such as 10,11-epoxyundecyl methacrylate, 2,3-epoxycyclohexyl methacrylate, 2,3-epoxybutyl methacrylate, 3,4-epoxybutyl methacrylate and glycidyl methacrylate;
• - Methacrylates containing phosphorus, boron and/or silicon, such as 2-(dibutylphosphono)ethyl methacrylate, 2,3-butylenemethacryloylethylborate, 2-(dimethylphosphato)propyl methacrylate, methyldiethoxymethacryloylethoxysilane, 2-(ethylenephosphito)propyl methacrylate, dimethylphosphinomethyl methacrylate, dimethylphosphonoethyl methacrylate, diethyl methacryloyl phosphonate, diethyl phosphatoethyl methacrylate and dipropyl methacryloyl phosphate;
• - sulphur-containing methacrylates such as ethylsulfinylethyl methacrylate, 4-thiocyanatobutyl methacrylate, ethylsulphonylethyl methacrylate, thiocyanatomethyl methacrylate, methylsulfinylmethyl methacrylate and bis(methacryloyloxyethyl) sulphide;
• - trimethacrylates such as trimethyloylpropane trimethacrylate.

Acrylates corresponding to the methacrylates can also be used. The compounds mentioned can also be used as mixtures.

(Meth)acrylates whose alcohol residue contains three to five carbon atoms are preferred. Longer-chain esters, i.e. compounds whose alcohol residue has seven or more carbon atoms, make the coatings more flexible but also softer, so that their functional properties may be restricted. Their proportion is therefore limited to 50% by weight.

The particularly preferred (meth)acrylates a22) include methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, tert-butyl acrylate, isobutyl methacrylate, isobutyl acrylate, hexyl methacrylate, hexyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, cyclopentyl methacrylate, benzyl methacrylate and benzyl acrylate.

Other possible comonomers a23) include Vinyl esters, vinyl chloride, vinylidene chloride, vinyl acetate, styrene, substituted styrenes having an alkyl substituent in the side chain such as alpha-methyl styrene and alpha-ethyl styrene, substituted styrenes having an alkyl substituent on the ring such as vinyl toluene and p-methyl styrene, halogenated styrenes such as Monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes, vinyl and isopropenyl ethers, maleic acid derivatives such as maleic anhydride, methylmaleic anhydride, maleimide, methylmaleimide, phenylmaleimide and cyclohexylmaleimide, and dienes such as 1,3-butadiene and divinylbenzene.

A prepolymer a3) is added to adjust the viscosity of the reaction resin and the leveling properties and to improve curing or other properties of the resin or the fully polymerized coating. This prepolymer should be soluble or swellable in the monomers a1) and a2).

Poly(meth)acrylates, for example, which can be dissolved in the monomer as a solid polymer, are particularly suitable as the polymer or prepolymer. They can also be used as so-called syrups, i.e. as partially polymerized masses of corresponding monomers. Other suitable prepolymers include polyvinyl chloride, polyvinyl acetate, polystyrene, epoxy resins, epoxy (meth)acrylates, unsaturated polyesters, polyurethanes or mixtures thereof or with the abovementioned poly(meth)acrylates. The prepolymers mentioned can also be used as copolymers.

The above prepolymers are generally commercially available. However, they can also be produced in a manner known to those skilled in the art.

Polyfunctional (meth)acrylates are preferably used as crosslinkers a4). These include, inter alia, di-, tri- and polyfunctional compounds. Particular preference is given to difunctional (meth)acrylates a41), trifunctional (meth)acrylates a42) and urethane (meth)acrylates a43).

• - Verbindungen der allgemeinen Formel CH₂=C(R)-CO-O-(CH₂)_n-OCO-(R)C=CH₂ worin R Wasserstoff oder Methyl ist und n eine positive ganze Zahl zwischen 3 und 20 ist, wie z.B. Di(meth)acrylat des Propandiols, Butandiols, Hexandiols, Octandiols, Nonandiols, Decandiols und Eicosandiols;
• - Verbindungen der allgemeinen Formel CH₂=C(R)-CO-[O-CH₂-C(R)H]_n-OCO-(R)C=CH₂ worin R Wasserstoff oder Methyl ist und n eine positive ganze Zahl zwischen 1 und 14 bedeutet. Beispiele sind Di(meth)acrylate des Ethylenglykols, Diethylenglykols, Triethylenglykols, Tetraethylenglykols, Dodecaethylenglykols, Tetradecaethylenglykols, Propylenglykols, Dipropylglykols und Tetradecapropylenglykols;
• - Glycerindi(meth)acrylat, 2,2'-Bis[p-(gamma-methacryloxy-ß-hydroxypropoxy)-phenylpropan] oder Bisphenol-A-glycidylmethacrylat (Bis-GMA), Bisphenol-A-dimethacrylat, Neopentylglykoldi(meth)acrylat, 2,2'-Di(4-methacryloxypolyethoxyphenyl)propan mit 2 bis 10 Ethoxygruppen pro Molekül und 1,2-Bis(3-methacryloxy-2-hydroxypropoxy)butan.

Examples of difunctional (meth)acrylates a41) are:

• - Compounds of general formula CH ₂ =C(R)-CO-O-(CH ₂ ) _n -OCO-(R)C=CH ₂ wherein R is hydrogen or methyl and n is a positive integer between 3 and 20, such as di(meth)acrylate of propanediol, butanediol, hexanediol, octanediol, nonanediol, decanediol and eicosanediol;
• - Compounds of general formula CH ₂ =C(R)-CO-[O-CH ₂ -C(R)H] _n -OCO-(R)C=CH ₂ wherein R is hydrogen or methyl and n is a positive integer between 1 and 14. Examples are di(meth)acrylates of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dodecaethylene glycol, tetradecaethylene glycol, propylene glycol, dipropyl glycol and tetradecapropylene glycol;
• - Glycerol di(meth)acrylate, 2,2'-bis[p-(gamma-methacryloxy-ß-hydroxypropoxy)-phenylpropane] or bisphenol A glycidyl methacrylate (Bis-GMA), bisphenol A dimethacrylate, neopentyl glycol di(meth) acrylate, 2,2'-di(4-methacryloxypolyethoxyphenyl)propane having 2 to 10 ethoxy groups per molecule and 1,2-bis(3-methacryloxy-2-hydroxypropoxy)butane.

Examples of tri- or polyfunctional (meth)acrylates a42) are trimethylolpropane tri(meth)acrylate and pentaerythritol tetra(meth)acrylate.

Urethane (meth)acrylates a43) are, for example, reaction products of 2 moles of hydroxyl-containing (meth)acrylate monomer with one mole of diisocyanate and reaction products of a urethane prepolymer containing two NCO end groups with a methacrylic monomer containing a hydroxyl group, as represented, for example, by the general formula : CH ₂ =C(R ¹ )-CO-OR ² -O(CO)-N(H)-R ³ -N(H)-(CO)O-OR ² -CO-(R ¹ )C=CH ₂
wherein R ¹ is hydrogen or a methyl group, R ² is an alkylene group such as -CH ₂ -, -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ - or -(CH ₂ ) ₄ -, and R ³ is an organic group Rest, such as -(CH2) ₆ -, embodies.

Said crosslinking monomers a41) to a43) are used either alone or in the form of mixtures of two or more monomers.

Polyfunctional monomers a4) used very particularly advantageously in the compositions according to the invention include above all trimethylolpropane trimethacrylate (TRIM), 2,2-bis-4(3-methacryloxy-2-hydroxypropoxy)phenylpropane (bis-GMA), 3,6-dioxaoctamethylene dimethacrylate (TEDMA), 7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-dioxydimethacrylate (UDMA) and/or 1,4-butanediol dimethacrylate (1st ,4-BDMA). Of these, 1,4-butanediol dimethacrylate is very particularly preferred.

Peroxides or azo compounds are preferably used as initiators a5). Under certain circumstances, it can be advantageous to use a mixture of different initiators. Since the compositions according to the invention are also suitable for cold curing, they contain a redox system composed of an accelerator and a peroxide catalyst or initiator for the polymerization. The amounts in which these accelerators and initiators are added depend on the particular system and can be determined by a person skilled in the art through routine tests. However, they must be sufficient for the cold curing of the monomers.

Additives a6) are optional.

Compounds which are particularly useful as accelerators include amines and mercaptans such as dimethyl-p-toluidine, diisopropoxy-p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, dimethylaniline and glycol dimercaptoacetate, where N, N-bis(2-hydroxyethyl)-p-toluidine and dimethyl-p-toluidine are most preferred.

Furthermore, organic metal salts can serve as accelerators. These include copper naphthenate and copper oleate.

Particularly suitable peroxide catalysts or initiators are groups of compounds such as ketone peroxides, diacyl peroxides, peresters, perketals and mixtures of compounds from these groups with one another and with other effective hardeners and initiators.

Particularly preferred for this purpose are compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane, tert-butylperoxy-2 -ethyl hexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)3,3,5-trimethylcyclohexane, cumyl hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide , Bis(4-tert-butylcyclohexyl) peroxydicarbonate, mixtures of ketone peroxide types, perester types, and mixtures of two or more of the aforementioned compounds. Of the above compounds, dibenzoyl peroxide is particularly preferred.

The accelerators, e.g. dimethylparatoluidine, can be contained in the reaction resin without polymerization taking place at ambient temperature. The reaction is started by adding the initiators, with initiators and accelerators usually being proportioned in such a way that the (meth)acrylate system has a pot life of 10 to 20 minutes.

Components a7) are optional. These include a large number of additives that are customary in (meth)acrylate reactive resins for floor coatings. Examples include: setting agents, antistatic agents, antioxidants, biostabilizers, chemical blowing agents, mold release agents, flame retardants, lubricants, colorants, flow improvers, fillers, glidants, adhesion promoters, inhibitors, catalysts, light stabilizers, optical brighteners, organic phosphites, oils, pigments, impact modifiers, Reinforcing agents, reinforcing fibers, anti-weathering agents and plasticizers.

QUOTES INCLUDED IN DESCRIPTION

This list of the documents cited by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent Literature Cited

• DE 19826412 A1 [0005]
• EP 2987837 A1 [0006]
• DE 202017000703 U1 [0007]
• WO 2006/092272 [0012]
• DE 102006039203 A [0012]
• EP 2922580 [0012]
• EP 2290045 [0013]
• EP 2290034 [0013]

Claims (11)

Polymerizable and curable composition A containing a1) 5 to 94.4% by weight of 2-octyl acrylate (2-OA), a2) 0 to 89.4% by weight of one or more further monomers which can be copolymerized with 2-octyl acrylate, a3) 5 to 80% by weight of one or more prepolymers, preferably poly(meth)acrylates and/or polyesters, a4) 0.5 to 35% by weight of one or more crosslinkers, a5) 0.1 to 8% by weight of one or more initiators, a6) 0 to 5% by weight of one or more further additives, including accelerators such as amines, stabilizers, dispersing additives and rheological additives, and a7) 0 to 50% by weight of one or more further components selected from pigments, fillers, core-shell particles, paraffins, waxes and/or plasticizers, the sum of components a1) to a7) being 100% by weight results. Composition A according to claim 1 , containing a1) 20 to 74.8% by weight of 2-octyl acrylate (2-OA), a2) 10 to 50% by weight of one or more further monomers which can be copolymerized with 2-octyl acrylate, a3) 10 to 35% by weight % of one or more prepolymers, preferably poly(meth)acrylates and/or polyesters, a4) 5 to 20% by weight of one or more crosslinkers, a5) 0.2 to 4% by weight of one or more initiators, a6) 0 up to 5% by weight of one or more other additives, including accelerators such as amines, stabilizers, dispersing additives and rheology additives, and a7) 0 to 50% by weight of one or more other components selected from pigments, fillers, core-shell particles , paraffins, waxes and/or plasticizers, the sum of components a1) to a7) being 100% by weight. Composition A according to claim 1 or 2 , wherein the monomers a2) are alkyl (meth)acrylates. Composition A according to any of Claims 1 until 3 , wherein the prepolymers a3) are poly(meth)acrylates and/or polyesters. Composition A according to any of Claims 1 until 4 , wherein the crosslinkers a4) are polyfunctional (meth)acrylates. Composition A according to any of Claims 1 until 5 , the initiators a5) being peroxides and/or azo compounds. Composition A according to any of Claims 1 until 6 , where the additives a6) are amines as accelerators, stabilizers, dispersing additives and/or rheology additives. Floor coating obtainable by applying composition A according to any of Claims 1 until 7 onto a floor surface to be coated, polymerizing and curing composition A. Road coating obtainable by applying the composition A according to one of Claims 1 until 7 onto a road surface to be coated, polymerizing and curing composition A. floor or roadway coating claim 8 or 9 , whereby curing takes place at temperatures in the range from -10 to +45 °C. floor or roadway coating claim 10 , whereby curing takes place at temperatures in the range from +10 to +30 °C.