DE19902685B4 - Novel urethane (meth) acrylates, process for their preparation and their use - Google Patents

Abstract

Urethane (meth) acrylates having at least 3 reactive terminal ethylenically unsaturated functionalities obtainable by the reaction of
A)
a) hydroxyalkyl (meth) acrylic esters with
b) polyisocyanates and
c) polyoxyalkylenes, the
c1) have at least three hydroxyl functionalities,
c2) wherein the proportion of polyethylene oxide is less than 50 wt .-%, based on the total amount of polyoxyalkylene, or
B)
a) hydroxyalkyl (meth) acrylic esters with
b) mixtures of polyisocyanates, of which at least one polyisocyanate has 3 or more isocyanate groups, and
c) polyoxyalkylenes, the
c1) have at least two hydroxyl functionalities,
c2) wherein the proportion of polyethylene oxide is less than 50 wt .-%, based on the total amount of polyoxyalkylene, is.

Description

The The invention relates to novel urethane (meth) acrylates, processes for their preparation and their use, in particular in (meth) acrylate resins, the for the surface protection of traffic areas, especially bridges and parking decks, of flat roofs, for the backing of bathtubs or generally for Floor and wall coatings and sealants are used.

Bridges can pass through Coatings of plastic, acting as a membrane between concrete carriageway slabs and mastic asphalt be applied, from damage by penetrating water, de-icing salt solutions and dilute acids (acidic Rain) become. Therefor are (meth) acrylate resins in principle suitable, their flexibility but at low temperatures is insufficient.

When Measure of the flexibility of a Resin is in the context of the present invention, both the elongation at break as well as the tear strength Understood. These two mechanical properties of a resin are generally in opposite directions, so that one Resin with a high elongation at break very often only a low tear strength having.

When further measure of the flexibility of a Resin can be the ability serve for crack bridging. A measuring method for determining this property is for example in "Additional Technical Terms of Contract and Guidelines for Protection and Repair concrete components (ZTV-SIB 90) ", edited by the Federal Minister of Transport (1990).

additives the flexibility of (meth) acrylate resins are known per se and commercially available, such as difunctional Urethane (meth) acrylates. A disadvantage of these substances is that they are in relatively large Quantities must be used. this leads to especially at high cost, as they are quite expensive. Furthermore is the improvement that can be achieved by adding these substances can, for many purposes insufficient.

In the DE 4018183 Light-curing impression materials are preferably presented for dental applications. In this application, it depends primarily on the smallest possible dimensional change in the curing and high tear resistance. As chain terminators, ie as reactants of the isocyanate-containing prepolymer, hydroxyacrylates or methacrylates are always used which contain two or more unsaturated groups in the molecule. By using these reactants of the isocyanate-containing prepolymers arise in the polymerization of the mixture in any case in addition to the long-chain crosslinks derived from the macrodiol used, also kurzkezzige crosslinks on the low molecular weight crosslinkers, such as glycerol, Glycerindimethacrylat, Glycerinacrylatmethacrylat. These short-chain crosslinks lead to the high hardness of the material, which is also desirable for the applications. The high hardness of the material leads to a reduced elongation at break of the material and thus to a poorer flexibility.

In In view of the prior art, it was the task of the present Invention Additives for (meth) acrylate resins specify the flexibility increase of (meth) acrylate resins, especially at low temperatures.

A Another task was to specify substances that the tear strength of the (meth) acrylate resins.

Of Another object of the present invention was to provide substances put that the elongation at break of (meth) acrylate resins, especially at low temperatures.

Furthermore should (meth) acrylate resins having the additives, if possible be insensitive to temperature fluctuations.

The Additives should be as possible economical be produced.

The amount of additives needed to achieve the desired effect should be possible be low.

Be solved these tasks as well as others that are not literally called the but deduce themselves from the contexts discussed here as a matter of course urethane (meth) acrylates with all the features of the independent Claim 1.

advantageous Embodiments of the urethane (meth) acrylates according to the invention are Subject of the independent Product claim Claims.

Regarding the method according to the invention claim 7 provides the solution the underlying task, preferred embodiments in the referenced claims explained become. Uses according to the invention are shown in claim 10.

• A) a) Hydroxyalkyl(meth)acrylsäureestern mit b) Polyisocyanaten und c) Polyoxyalkylenen, die c1) mindestens drei Hydroxyfunktionalitäten aufweisen, c2) wobei der Anteil an Polyethylenoxid kleiner als 50 Gew.-%, bezogen auf die Gesamtmenge an Polyoxyalkylen, ist, oder
• B) a) Hydroxyalkyl(meth)acrylsäureestern mit b) Mischungen aus Polyisocyanaten, von denen mindestens ein Polyisocyanat 3 oder mehr Isocyanatgruppen aufweist, und c) Polyoxyalkylenen, die c1) mindestens zwei Hydroxyfunktionalitäten aufweisen, c2) wobei der Anteil an Polyethylenoxid kleiner als 50 Gew.-%, bezogen auf die Gesamtmenge an Polyoxyalkylen, ist,

als Zusatzstoff in (Meth)acrylatharzen einsetzt, wird die Flexibilität der Harze bei tiefen Temperaturen wesentlich erhöht.By reacting urethane (meth) acrylates having at least 3 reactive terminal ethylenically unsaturated functionalities obtainable by the reaction of

• A) a) hydroxyalkyl (meth) acrylic esters with b) polyisocyanates and c) polyoxyalkylenes which have c1) at least three hydroxyl functionalities, c2) where the proportion of polyethylene oxide is less than 50% by weight, based on the total amount of polyoxyalkylene, or
• B) a) hydroxyalkyl (meth) acrylic esters with b) mixtures of polyisocyanates, of which at least one polyisocyanate has 3 or more isocyanate groups, and c) polyoxyalkylenes, which c1) have at least two hydroxyl functionalities, c2) wherein the proportion of polyethylene oxide is less than 50 Wt .-%, based on the total amount of polyoxyalkylene, is,

As an additive in (meth) acrylate resins, the flexibility of the resins is significantly increased at low temperatures.

• – Die erfindungsgemäßen Zusatzstoffe ermöglichen ein an die Anforderungen hervorragend anpaßbares Eigenschaftsspektrum.
• – Die Reißdehnung wird wesentlich erhöht, falls dieser Wert mit den von Harzen verglichen wird, die eine vergleichbare Reißfestigkeit aufweisen.
• – Die Reißfestigkeit wird verbessert, falls dieser Wert mit den von Harzen verglichen wird, die eine vergleichbare Reißdehnung aufweisen.
• – Durch Zusatz der erfindungsgemäßen Urethan(meth)acrylate wird die Stabilität gegenüber Temperaturschwankungen vergrößert.
• – Um eine gewünschte Verbesserung der Flexibilität bei tiefen Temperaturen zu erzielen, genügt der Einsatz der erfindungsgemäßen Urethan(meth)acrylate in relativ geringen Mengen, wodurch Kostenvorteile entstehen.
• – Für den Einsatz in Boden- und Wandbeschichtungen wird durch die erfindungsgemäßen Zusatzstoffe die Sprödigkeit gezielt je nach Einsatzmenge verringert bzw. die Schlagzähigkeit der Beschichtung erhöht. Dies gilt in gleicher Weise auch für die Versiegelung einer Beschichtung.
• – Weiterhin lassen sich durch die erfindungsgemäßen Zusatzstoffe glattere Oberflächen und bessere schmutzabweisende Eigenschaften der Beschichtungen und Versiegelungen erreichen.
• – Des weiteren wird beim Aufbringen eines Harzes für die Bodenbeschichtung der Verlauf durch die erfindungsgemäßen Zusatzstoffe verbessert.
• – Schließlich verbessern die erfindungsgemäßen Zusatzstoffe die Haftung zwischen einer Beschichtung und ihrer Versiegelung.

Furthermore, the following advantages are achieved by the present invention:

• The additives according to the invention make it possible to obtain a property spectrum which is excellently adaptable to the requirements.
• The elongation at break is substantially increased if this value is compared with that of resins which have comparable tear strength.
• The tear resistance is improved if this value is compared with that of resins having a comparable elongation at break.
• - By adding the urethane (meth) acrylates according to the invention the stability to temperature fluctuations is increased.
• In order to achieve a desired improvement in flexibility at low temperatures, it is sufficient to use the urethane (meth) acrylates according to the invention in relatively small amounts, which results in cost advantages.
• - For use in soil and wall coatings brittleness is selectively reduced depending on the amount used or increases the impact resistance of the coating by the additives of the invention. This applies equally to the sealing of a coating.
• - Furthermore, can be achieved by the additives of the invention smoother surfaces and better dirt-repellent properties of the coatings and sealants.
• - Furthermore, the course is improved by the additives of the invention when applying a resin for the bottom coating.
• Finally, the additives according to the invention improve the adhesion between a coating and its seal.

Urethane (meth) acrylates in the context of the present invention denote compounds which have (meth) acrylate functionalities, the above Urethane groups linked together are.

Urethane (meth) acrylates of the invention have at least three reactive terminal ethylenic unsaturated functionalities derived from (meth) acrylates.

she are by the reaction of hydroxyalkyl (meth) acrylic acid esters with polyisocyanates and polyoxyalkylenes having at least three hydroxy functionalities, wherein the proportion of polyethylene oxide is less than 50 wt .-%, based to the total amount of polyoxyalkylene available.

Of the Expression of (meth) acrylic acid herein denotes methacrylic acid, acrylic acid as well as mixtures of these acids.

Usable according to the invention Hydroxyalkyl (meth) acrylate are esters of (meth) acrylic acid with dihydric, aliphatic alcohols. These connections are Well known in the art. You can, for example, by the Reaction of (meth) acrylic acid be obtained with oxiranes.

The oxirane compounds include, but are not limited to, ethylene oxide, propylene oxide, 1,2-butylene oxide and / or 2,3-butylene oxide, cyclohexene oxide, styrene oxide, epichlorohydrin and glycidyl ester. These compounds can be used both individually and as a mixture. The conversion to the hydroxyalkyl (meth) acrylic esters is described, for example, in DE-A-24 39 352, DE-15 68 838 and US Pat GB 1 308 250 -described.

The so available Hydroxyalkyl (meth) acrylate are common commercially available and therefore for the purposes of the invention particularly suitable.

The Hydroxyalkyl (meth) acrylate can also substituents, such as, for example, phenyl radicals or amino groups, contain. Furthermore, the hydroxyalkyl group of the ester may also be Contain polyoxyalkylene groups which are both linear and branched could be, such as polyethylene oxide, polypropylene oxide and polytetramethylene oxide. These groups are common between 2 and 10 oxyalkylene units.

preferred Hydroxyalkyl (meth) acrylate include hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 6-hydroxyhexyl acrylate and 6-hydroxyhexyl methacrylate, 3-phenoxy-2-hydroxypropyl methacrylate, polyethoxymethacrylate, polypropoxymethacrylate, Polyethylene oxide / polytetramethylene oxide methacrylate, polyethylene oxide / polypropylene oxide methacrylate, Acrylic acid (4-hydroxybutyl) Acrylic acid (2-hydroxyethyl), Methacrylic acid (hydroxymethylamide) Caprolactone hydroxyethyl methacrylate and caprolactone hydroxyethyl acrylate, of these are hydroxyethyl methacrylate, hydroxyethyl acrylate, 2-hydroxypropyl methacrylate and 2-hydroxypropyl acrylate most preferred.

polyisocyanates in the context of the present invention denote low molecular weight Verb., In the molecule contain two or more isocyanate groups.

By Choice of the proportion of polyisocyanates with 3 or more isocyanate groups let yourself the property spectrum of elongation at break and tear strength to adjust. The higher the proportion of compounds with three or more functionalities is the bigger it gets the tear resistance. Here, however, the elongation at break decreases sharply. Accordingly it was found that the Proportion of these polyisocyanates with three or more functionalities not greater than 10 wt .-%, preferably not more than 5 wt .-%, based on the total mass Polyisocyanates, should be. These statements, however, relate only on the preparation of the urethane (meth) acrylates according to the invention according to the embodiment A). In the embodiment B) in which polyoxyalkylenes which have two hydroxy groups via polyisocyanates connected which have three or more isocyanate groups is the proportion the polyisocyanates with three or more functionalities accordingly greater.

To the polyisocyanates usable in the present invention are included Other 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-dicyclohexyl diisocyanate, meta- and para-tetramethylxylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (Isophorone diisocyanate), hexamethylene diisocyanate, 1,5-naphthylene diisocyanate, Dianisidine diisocyanate, di (2-isocyanatoethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate, 2,2,4- and 2,4,4-trimethylenehexamethylene diisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate, tris- (4-isocyanatophenyl) -thiophosphate, and Mixtures thereof.

Suitable polyisocyanates can also be obtained, for example, by the reaction of polyhydric alcohols with diisocyanates or by the polymerization of diisocyanates. Furthermore, it is also possible to use polyisocyanates prepared by reacting hexamethylene diisocyanate with small amounts Water can be displayed. These products contain biuret groups.

These compounds are well known in the art and are for the most part commercially available. These include ^® Desmodur H, ^® Desmodur N 100 ^® Desmodur N 3300 (from Bayer), ^® Basonat PLR 8401, ^® Basonat PLR 8638 (BASF), ^® Tolonate HDB 75 MX, ^® Tolonate HDT 90 (from Rhone Poulenc ), ^® Vestanat IPD, ^® Vestanat T 1890/100 and ^® Vestanat T 2960 (from Hüls).

Prefers are compounds whose isocyanate groups have different reactivities. This property facilitates the reaction without this a restriction should be done. An example for such a preferred polyisocyanate is isophorone diisocyanate.

When Polyisocyanates are also suitable in the context of the present invention the analog isothiocyanates. Since these, however, less commercially available are, these compounds are less preferred.

polyoxyalkylenes, which have at least three hydroxyl functionalities can, for example, by Polyaddition of cyclic ethers, such as oxiranes and tetrahydrofuran.

To the oxiranes which can be used for polyaddition belong to Others the aforementioned. Of these, propylene oxide is preferred.

Around to obtain at least three hydroxy functionalities with isocyanate groups For example, you can respond Alcohols as starter molecules are used which have at least three hydroxyl groups.

For this belong including glycerol, trimethylolpropane, erythritol, pentaerythritol, Sorbitol and inositol, of these glycerol is preferred.

The Polyaddition of cyclic ethers to polyhydric alcohols is known in well-known to experts Valuable information finds the expert for example in Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., Keyword "polyoxyalkylene".

Of others can Polyoxyalkylenes having three or more hydroxy functionalities, also be prepared in situ. This is achieved by variant B) by polyoxyalkylenes with two hydroxy functionalities Polyisocyanates are linked with three or more isocyanate groups.

The Weight average molecular weight of the polyoxyalkylenes may be in vary widely. Preferably, it is in the range of 2,000 to 20,000, preferably in the range of 4,000 to 10,000 and most preferably in the range of 4,000 to 8,0000 g / mol. It is essential, however, that the Polyether chains induce a minimum flexibility. Accordingly, the chain length of the polyether chains in the Number average greater than 10 units, preferably greater than 20 units and more preferably be greater than 30 units.

The The cyclic ethers mentioned above can also be used as a mixture become, resulting in copolymers. They are also called block copolymers used of this type.

polyethylene glycols (PEG) are hygroscopic. The use of these polymers in acrylate resins, for example, for surface protection concrete bridges is therefore not recommended. Freezes in cold weather the water absorbed by the PEG and expands. These Expansion may be possible to cracking in the resin and thus to a destruction of the surface protection to lead. Therefore, the proportion of polyethylene oxide should be less than 50 wt .-%, based on the total amount of polyoxyalkylene, be. Preferably it is less than 25 wt .-%, more preferably less than 15 Wt .-%.

Some Polyoxyalkylenes having at least three hydroxy functionalities commercially available.

preferred Polyoxyalkylenes are polyoxypropylenes. Preference may also be given Polytetramethylene oxides which, together with the polyoxypropylenes can be used these polyoxyalkylenes each having at least three reactive, terminal hydroxy functionalities.

worin
R¹ Wasserstoff oder Methyl ist,
R² eine lineare oder verzweigte Alkylengruppe mit 2 bis 20 Kohlenstoffatomen oder Alkylenoxide mit 4 bis 50 Kohlenstoffatomen ist,
R³ eine bis 18 Kohlenstoffatome enthaltende aromatische, aliphatische oder cycloaliphatische Gruppe darstellt, die sich von Diisocyanaten oder Diisocyanatgemischen ableiten,
R⁴ einen Alkylenrest mit mindestens 2 Kohlenstoffatomen unter der Voraussetzung darstellt, daß mindestens die Hälfte aller Reste R⁴ des Urethan(meth)acrylats der Formel (I) 3 oder mehr Kohlenstoffatome aufweisen,
m eine ganze Zahl ≥ 1,
n eine ganze Zahl ≥ 10,
x eine ganze Zahl ≥ 3 und
Z eine von Alkoholen mit mindestens drei Hydroxygruppen oder von Polyisocyanaten mit mindestens drei Isocyanatgruppen abgeleitete Verbindungsgruppe ist.It is believed that at least a portion of the urethane (meth) acrylates of the present invention can be represented by the following formula (I):

wherein
R ^{1 is} hydrogen or methyl,
R ^{2 is} a linear or branched alkylene group having 2 to 20 carbon atoms or alkylene oxides having 4 to 50 carbon atoms,
R ^{3 represents} an aromatic, aliphatic or cycloaliphatic group containing up to 18 carbon atoms, which are derived from diisocyanates or diisocyanate mixtures,
R ^{4 represents} an alkylene radical having at least 2 carbon atoms, provided that at least half of all radicals R ^{4 of} the urethane (meth) acrylate of the formula (I) have 3 or more carbon atoms,
m is an integer ≥ 1,
n is an integer ≥ 10,
x is an integer ≥ 3 and
Z is a linking group derived from alcohols having at least three hydroxy groups or from polyisocyanates having at least three isocyanate groups.

Of the Term "alkylene" means a divalent one Rest, by removing two hydrogen atoms respectively from a non-adjacent carbon atom of an original one Hydrocarbon is obtained and includes alkylenes of 3 to 18 carbon atoms, including for example, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,8-octylene and 1,10-decylene. These radicals can branched as well as being linear. Furthermore, these groups can also be substituted be.

The groups R ² to R ⁴ and the numbers m and n are derived from the starting materials used in the reaction. These are described above. Accordingly, m is preferably equal to 1, but polyisocyanates having three or more functionalities can be used to increase the tear strength, so that consequently a part of the molecules can be represented by formulas in which m> 1.

gebildet werden, die durch Kopplung von zwei Polyoxyalkylenen mit Polyisocyanaten entstehen können, wobei R³, R⁴ und n die zuvor genannte Bedeutung haben. Es ist allerdings auch die Bildung von Makromolekülen denkbar, die durch die Kopplung von mehr als zwei Polyoxyalkylenen entstehen.The linking group Z and the number x are also dependent on the starting materials. In addition, the radical Z and the parameter x can also be influenced by the reaction procedure and the quantitative ratios of the starting materials. If, for example, glycerol is chosen as Z, it is possible, inter alia, to use therefrom also connecting groups of the formula (II)

can be formed, which can be formed by coupling of two polyoxyalkylenes with polyisocyanates, wherein R ³ , R ⁴ and n have the abovementioned meaning. However, it is also conceivable the formation of macromolecules, which arise through the coupling of more than two polyoxyalkylenes.

Especially preferred urethane (meth) acrylates of the present invention three or four reactive terminal ones ethylenically unsaturated functionalities on.

• a) mindestens ein Hydroxyalkyl(meth)acrylsäureester mit
• b) mindestens einem Polyisocyanat und
• c) mindestens einem Polyoxyalkylen

umsetzt.The urethane (meth) acrylates according to the invention can be prepared by processes in which

• a) at least one hydroxyalkyl (meth) acrylic ester with
• b) at least one polyisocyanate and
• c) at least one polyoxyalkylene

implements.

Here, various reactions are conceivable. Thus, urethane (meth) acrylates of the present invention can be prepared in a two-step synthesis. In this case, for example, equimolar amounts of hydroxyalkyl (meth) acrylate and polyisocyanate are reacted, after which the reaction product thus obtained is allowed to react with a suitable amount of polyoxyalkylene. When choosing suitable polyisocyanates or by a clever reaction, in particular urethane (meth) acrylates with three re active terminal ethylenically unsaturated functionalities.

It is also conceivable to carry out the implementation in one step. in this connection arises a mixture of urethane (meth) acrylates with a different Number of ethylenically unsaturated Functionalities. It has been shown that at Use of trifunctional polyoxyalkylenes often tetrafunctional urethane (meth) acrylates with linking groups of the formula (II) arise, as this further are exemplified above. The mixtures thus obtained can be used as Additive in the (meth) acrylate resins without further purification be used.

The Reaction can be in bulk, i. without the use of another solvent be performed. if desired can also be an inert solvent be used. These include including benzene, toluene and methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK).

The Reaction of the isocyanate groups with the hydroxyl groups is in the Well known in the art. So the reaction temperature can over a wide range, but often the temperature is in the range of 30 ° C to 120 ° C, preferably in the range of 60 ° C to 90 ° C. something similar applies to the pressure at which the implementation is completed. That's the reaction take place both at negative pressure and at overpressure. Preferably but it is carried out at atmospheric pressure. The reaction can be under Air as well as under a protective gas atmosphere, preferably a low oxygen content is present, since this is a possible polymerization inhibited.

Around accelerate the implementation are often catalysts, such as tertiary Amines, belong to these including 1,4-diazabicyclo [2.2.2] octane, N-methylmorpholine, N, N-diethylcyclohexylamine and N.N.N ', N'-tetramethyldiaminomethane, or organic tin compounds, among these include dibutyltin dilaurate and tin dioctoate. These catalysts as well as the quantities, where these compounds are used are in the art well known and, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, keyword "Polyurethanes" described.

at the implementation can Inhibitors are added which undergo a radical polymerization the (meth) acrylates during prevent the reaction. These inhibitors are in the art well known.

worin
R¹ einen linearen oder verzweigten Alkylrest mit eins bis acht Kohlenstoffatomen, Halogen oder Aryl bedeutet, vorzugsweise einen Alkylrest mit eins bis vier Kohlenstoffatomen, besonders bevorzugt Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec-Butyl, tert.-Butyl, Cl, F oder Br;
n eine ganze Zahl im Bereich von eins bis vier, vorzugsweise eins oder zwei ist; und
R² Wasserstoff, einen linearen oder verzweigten Alkylrest mit eins bis acht Kohlenstoffatomen oder Aryl bedeutet, vorzugsweise einen Alkylrest mit eins bis vier Kohlenstoffatomen, besonders bevorzugt Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec-Butyl oder tert.-Butyl.Are used mainly 1,4-dihydroxybenzenes. However, it is also possible to use differently substituted dihydroxybenzenes. In general, such inhibitors can be represented by the general formula (III)

wherein
R ^{1 is} a linear or branched alkyl radical having one to eight carbon atoms, halogen or aryl, preferably an alkyl radical having one to four carbon atoms, more preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec Butyl, tert -butyl, Cl, F or Br;
n is an integer in the range of one to four, preferably one or two; and
R ^{2 is} hydrogen, a linear or branched alkyl radical having one to eight carbon atoms or aryl, preferably an alkyl radical having one to four carbon atoms, more preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec Butyl or tert-butyl.

worin
R¹ einen linearen oder verzweigten Alkylrest mit eins bis acht Kohlenstoffatomen, Halogen oder Aryl bedeutet, vorzugsweise einen Alkylrest mit eins bis vier Kohlenstoffatomen, besonders bevorzugt Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec-Butyl, tert.-Butyl, Cl, F oder Br; und
n eine ganze Zahl im Bereich von eins bis vier, vorzugsweise eins oder zwei ist.However, it is also possible to use compounds with 1,4-benzoquinone as the parent compound. These can be described by the formula (IV)

wherein
R ¹ denotes a linear or branched alkyl radical having one to eight carbon atoms, halogen or aryl, preferably an alkyl radical having one to four carbon atoms, particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, Cl, F or Br; and
n is an integer in the range of one to four, preferably one or two.

worin
R¹ einen linearen oder verzweigten Alkylrest mit eins bis acht Kohlenstoffatomen, Aryl oder Aralkyl, Proprionsäureester mit 1 bis 4 wertigen Alkoholen, welche auch Heteroatome wie S, O und N enthalten können, vorzugsweise einen Alkylrest mit eins bis vier Kohlenstoffatomen, besonders bevorzugt Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec-Butyl, tert.-Butyl, bedeutet.Likewise phenols of the general structure (V) are used

wherein
R ^{1 is} a linear or branched alkyl radical having one to eight carbon atoms, aryl or aralkyl, propionic acid esters having 1 to 4 valent alcohols, which may also contain heteroatoms such as S, O and N, preferably an alkyl radical having one to four carbon atoms, more preferably methyl, Ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl.

mit R = Verbindung der Formel (VII)

worin
R¹ = C_nH2_2n+1
mit n = 1 oder 2 ist.Another advantageous class of substances are hindered phenols based on triazine derivatives of the formula (VI)

with R = compound of the formula (VII)

wherein
R ¹ = C _n H _{2 2n + 1}
with n = 1 or 2.

Especially successful are the compounds 1,4-dihydroxybenzene, 4-methoxyphenol, 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,6-di-tert-butyl-4-methylphenol, 2,4 dimethyl-6-tert-butylphenol, 2,2-bis [3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl-1-oxoperopoxymethyl)) 1,3-propanediyl, 2,2'-Thiodiethylbis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl)) propionate; Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,5-Bis (1,1-dimethylethyl-2,2-methylene-bis- (4-methyl-6-tert-butyl) phenol, Tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -s-triazine-2,4,6 (1H, 3H, 5H) trione, Tris (3,5-di-tert-butyl-4-hydroxy) -s-triazine-2,46- (1H, 3H, 5H) trione or tert Butyl-3,5-dihydroxybenzene used.

Based on the weight of the entire Reationsmischung is the proportion the inhibitors individually or as a mixture generally 0.01-0.5% (wt / wt).

Lots These inhibitors are commercially available.

object The invention also relates to the use of inventive urethane (meth) acrylates described herein for the surface protection of flat roofs and traffic areas, especially bridges and parking decks, for the back-feeding from bathtubs or for Coatings and sealants.

The urethane (meth) acrylates according to the invention can for example, as an addition to (Meth) acrylate resins used for coating floors, concrete bridges, flat roofs and Parking decks, in particular for improving the flexibility at low Temperatures, such as increasing the ability to crack bridging, the Improvement of the elongation at break and tear strength, as well as for backfilling used by bathtubs. In these (meth) acrylate resins if the urethane (meth) acrylates are used in amounts greater than 5% by weight, otherwise the improvement in flexibility at low temperatures only insufficient is. The use of amounts above 30 wt .-% is possible, but because of economical reasons not preferred, because then no significant improvement in the properties more occurs.

• A) (Meth)acrylat 50–100 Gew.-% C₁-C₆ (Meth)acrylat 0–100 Gew.-% ≥ C₇ (Meth)acrylat 0–50 Gew.-% mehrwertige (Meth)acrylate 0–10 Gew.-% Comonomere 0–50 Gew.-% Vinylaromaten 0–30 Gew.-% Vinylester 0–30 Gew.-%, wobei die Bestandteile der Komponente A) 100 Gew.-% ergeben,
• B) 0–2 Gewichtsteilen auf 1 Gewichtsteil A) eines in A) löslichen oder quellbaren (Pre)polymers,
• C) 5 bis 30 Gewichtsteilen auf 100 Gewichtsteile (A + B) mindestens eines erfindungsgemäßen Urethan(meth)acrylats,
• D) 0,1 bis 5 Gewichtsteilen auf 100 Gewichtsteile (A + B +
• C) mindestens eines Paraffins und/oder Wachses,
• E) einem bis zur Polymerisation von den polymerisierbaren Bestandteilen des Systems wenigstens in Bezug auf eine Komponente des Redoxsystems getrennt zu haltendes Redoxsystem enthaltend einen Beschleuniger und einen peroxydischen Katalysator oder Initiator in einer Menge ausreichend zur Kalthärtung der Komponente A) und
• F) üblichen Additiven.

(Meth) acrylate resins for floor coatings may for example consist of the following constituents:

• A) (Meth) acrylate 50-100% by weight C ₁ -C ₆ (meth) acrylate 0-100% by weight ≥ C ₇ (meth) acrylate 0-50% by weight polyvalent (meth) acrylates 0-10% by weight comonomers 0-50% by weight vinylaromatics 0-30% by weight Vinylester 0-30% by weight, the constituents of component A) giving 100% by weight,
• B) 0-2 parts by weight per 1 part by weight of A) of a) soluble or swellable (A) polymer,
• C) 5 to 30 parts by weight per 100 parts by weight (A + B) of at least one urethane (meth) acrylate according to the invention,
• D) 0.1 to 5 parts by weight per 100 parts by weight (A + B +
• C) at least one paraffin and / or wax,
• E) a redox system to be kept separate from the polymerizable constituents of the system, at least with respect to one component of the redox system, comprising an accelerator and a peroxidic catalyst or initiator in an amount sufficient for cold curing of component A) and
• F) conventional additives.

Component A)

To for floor coatings (meth) acrylates which can be used with particular success include other methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, Propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate.

The Component A) may contain up to 10% by weight of one or more polyvalent ones Contain (meth) acrylates. about the amount of these crosslinkers can the property spectrum of the (meth) acrylate resins changed become. The higher the proportion gets bigger the tear resistance. However, this decreases the elongation at break.

To to count including di-, tri- and polyfunctional compounds. special Prefer to enjoy difunctional (meth) acrylates and trifunctional (meth) acrylates.

(a) Difunctional (meth) acrylates

worin R Wasserstoff oder Methyl ist und n eine positive ganze Zahl zwischen 3 und 20, wie z. B. Di(meth)acrylat des Propandiols, Butandiols, Hexandiols, Octandiols, Nonandiols, Decandiols und Eicosandiols; Compounds of the general formula:

wherein R is hydrogen or methyl and n is a positive integer between 3 and 20, such as. B. di (meth) acrylate of propanediol, butanediol, hexanediol, octanediols, nonanediols, decanediols and eicosanediols;

worin R Wasserstoff oder Methyl ist und n eine positive ganze Zahl zwischen 1 und 14 bedeutet, wie z. B. Di(meth)acrylat des Ethylenglycols, Diethylenglycols, Triethylenglycols, Tetraethylenglycols, Dodecaethylenglycols, Tetradecaethylenglycols, Propylenglycols, Dipropylglycols und Tetradecapropylenglycols;
und Glycerindi(meth)acrylat, 2,2'-Bis[p-(γ-methacryloxy-β-hydroxypropoxy)-phenylpropan] oder Bis-GMA, Biphenol-A-dimethacrylat, Neopentylglycoldi(meth)acrylat, 2,2'-Di(4-methacryloxypolyethoxyphenyl)propan mit 2 bis 10 Ethoxygruppen pro Molekül und 1,2-Bis(3-methacryloxy-2-hydroxypropoxy)butan.Compounds of the general formula

wherein R is hydrogen or methyl and n is a positive integer between 1 and 14, such as. Di (meth) acrylate of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dodecaethylene glycol, tetradecaethylene glycols, propylene glycols, dipropylglycols and tetradecapropylene glycols;
and glycerol di (meth) acrylate, 2,2'-bis [p- (γ-methacryloxy-β-hydroxypropoxy) phenylpropane] or bis-GMA, biphenol 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.

(b) tri- or polyfunctional (Meth) acrylates

• Trimethylolpropane tri (meth) acrylates and pentaerythritol tetra (meth) acrylate.

(c) urethane (meth) acrylates

worin R Wasserstoff oder eine Methylgruppe bedeutet, R₂ eine Alkylengruppe und R₃ einen organischen Rest verkörpert.Reaction products of 2 moles of hydroxyl-containing (meth) acrylate monomer with one mole of diisocyanate and reaction products of a two NCO terminated Urethanprepolymers with a methacrylic monomer having a hydroxyl group, such as. B. be represented by the general formula:

wherein R is hydrogen or a methyl group, R _{2 represents} an alkylene group and R _{3 represents} an organic radical.

The mentioned crosslinking monomers a) to c) are either used alone or in the form of a mixture of several monomers.

To very particularly advantageous polyvalent used in the resin of the invention Monomers belong especially 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-diaza-hexadecane-1,16-dioxy-dimethacrylate (UDMA) and / or 1,4-butanediol dimethacrylate (1,4-BDMA).

The Component A) may also contain other comonomers, which are copolymerizable with the above-mentioned (meth) acrylates. To belong to these et al Vinyl esters, vinyl chloride, vinylidene chloride, vinyl acetate, styrene, substituted styrenes having an alkyl substituent in the side chain, such as. α-methylstyrene and α-ethylstyrene, substituted styrenes having an alkyl substituent on the ring, such as for example, vinyltoluene and p-methylstyrene, halogenated styrenes, such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and Tetrabromostyrenes, vinyl and isopropenyl ethers, maleic acid derivatives, such as maleic anhydride, methyl maleic anhydride, Maleimide, methylmaleimide, phenylmaleimide and cyclohexylmaleimide, and Dienes such as 1,3-butadiene and divinylbenzene.

Of the Proportion of comonomers is limited to 50 wt .-% of component A), since otherwise the mechanical properties of the polymerized Coatings can be adversely affected. The proportion of vinyl aromatics is limited to 30 wt .-% of component A), since higher proportions can lead to a segregation of the system. The proportion of vinyl esters is also limited to 30 wt .-% of component A), since these insufficient curing at low temperatures and unfavorable shrinkage behavior tend.

All above-mentioned monomers contained in the component A), are commercially available.

Component B)

to Adjustment of viscosity the reaction resin and the flow properties and for better curing or other properties of the resin or the polymerized coating it is possible to add a polymer or a prepolymer to components A) become. This (pre) polymer should be soluble in component A) or be swellable. On a part by weight of A) can be between 0 and 2 parts by weight of the (pre) polymer can be used.

Especially are e.g. Poly (meth) acrylates as component B) suitable as solid polymer dissolved in A) can be. You can also as so-called syrups, i. as partially polymerized Masses of corresponding monomers can be used.

Farther are u.a. Polyvinyl chlorides, polyvinyl acetates, polystyrenes, epoxy resins, Epoxy (meth) acrylates, unsaturated Polyester, polyurethanes or mixtures thereof or with the abovementioned poly (meth) acrylates suitable as component B). The (pre) polymers mentioned can also be used as copolymers.

Component C)

The Component C) has been described in detail above.

Component D)

methacrylate tend to harden for air inhibition. this leads to to that the upper resin layers, which may come into contact with air, in increased Dimensions sticky stay and not get stuck like the rest of the crowd. To prevent or improving this behavior are therefore the resin paraffins and / or Added waxes, the preferred concentration in their concentration, the solubility limit are located. When evaporating recipe components, the solubility limit is exceeded, It forms a fine paraffin film on the surface, which an air inhibition of the upper resin layers effectively prevented and so to a dry surface leads.

at Waxes and paraffins are generally nonpolar Substances that are in the liquid, uncured Release resin. With increasing networking during the polymerization decreases its compatibility with the resin, so that you form a second phase and to the surface of the polymerizing resin composition can migrate. They are then able to form a closed film on the surface, and can this mass opposite shut off the oxygen in the air. By this exclusion of oxygen the polymerization of the resin is supported on its surface. In particular, reduced the addition of waxes and / or paraffins thus the stickiness the surface, that the Inhibitory effect of oxygen can be counteracted.

in principle All substances are suitable that have the behavior described above a homogeneous surface layer formation below the solubility limits demonstrate.

To suitable waxes belong paraffin, microcrystalline wax, carnauba wax, beeswax, Lanolin, whale oil, polyolefin waxes, ceresin, candelilla wax and the same.

However, paraffins have proven to be particularly suitable. These consist predominantly of straight-chain hydrocarbons of the general formula C _n H _{2n + 1} with n = 10-70 and a proportion of iso- and cycloalkanes / paraffins of 0 to 60%. These waxes obtained from the vacuum distillation cuts of light and medium lubricating oils have the advantage that they are extremely unreactive under the conditions prevailing in (meth) acrylate resins. They are insoluble in water and hardly soluble in low molecular weight aliphatic alcohols and ethers. They are more soluble in ketones, chlorinated hydrocarbons, gasoline, benzene, toluene, xylene and higher aromatics. The solubility decreases with higher melting point, ie with increasing molecular weight of the wax. The softening points of the macrocrystalline paraffins are between 35 and 72. The commercially available products show viscosities at 100 ° C between 2 and 10 mm ² / s.

Preferred for use in the methacrylate resins for the floor coating have become their completely refined and de-oiled waxes. The oil content of these types is a maximum of 2.5%. Particular preference is given to products having a softening point between 40 and 60 ° C and a viscosity at 100 ° C of 2.0 to 5.5 mm ² / s.

The Waxes and / or paraffins are added in amounts of from 0.1 to 5% by weight, preferably up to 1% by weight and most preferably from about 0.5 % By weight, based on the total weight of components A) to C). exceeds the added amount of wax and / or paraffin is an amount of 5 % By weight, this can have an adverse effect on the Have strength of the floor coating. Falls below the added Amount of wax and / or paraffin an amount of 0.1 wt .-%, so cure the Resins not sticky.

Component E)

The Resin for Floor coatings A) to E) are suitable for cold curing, i. for polymerization contains it's a redox system of an accelerator and a peroxide Catalyst or initiator. The quantities in which these accelerators and initiators are added, are dependent on the particular system and to be determined by the specialist by routine examinations. You must, however for cold hardening of component A) suffice.

Of the Accelerator is usually in an amount of 0.01 to 5 wt .-%, preferably 0.5 to 1.5 wt .-%, based on the sum of components A) to D) used. The compounds which are particularly suitable as accelerators belong to other amines and mercaptans, such as dimethyl-p-toluidine, Diisopropoxy-p-toluidine, n, n-bis (2-hydroxyethyl) -p-toluidine, dimethylaniline and glycol dimercaptoacetate, wherein n, n-bis (2-hydroxyethyl) -p-toluidine and dimethyl-p-toluidine are most preferred.

Of others can serve as an accelerator organic metal salts, usually in the range of 0.001 to 2 wt .-%, based on the sum of the Components A) to E) are used. These include, i.a. Copper naphthenate and copper oleate.

When peroxide catalyst or initiator are particularly suitable Linking groups such as ketone peroxides, diacyl peroxides, peresters, Perketals and mixtures of compounds of these groups with each other as well as with unspecified effective hardeners and initiators.

Especially are preferred for compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, Ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butylperoxy isopopyl carbonate, 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane, tert-butylperoxy-2-ethylhexanoate, tert-butyl peroxy-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, as well as mixtures of two or more of the aforementioned Connections with each other. Of the above compounds is Dibenzoyl peroxide is preferred.

The Initiators usually become in an amount ranging from 0.1 to 10% by weight, preferably from 0.5 to 5 wt .-%, based on the sum of the components A) to D) used. In the Harz can from the component E) already the accelerator, z. B. dimethylparatoluidine, be included without any polymerization takes place at ambient temperature. By adding the remaining Components of component E), the reaction is started, wherein the component E) usually is dimensioned so that the (meth) acrylate system has a pot life of 10 minutes to 20 minutes. The (meth) acrylate system of the invention thus contains just before application the full component E), until Use component E) is not or only partially contained, or in other words, the full-featured redox system is up to the polymerization of the polymerizable components of to keep it off while individuals Components of the redox system already with polymerizable substances may be premixed.

Component F)

Component F) is optional. These include a variety of common in (meth) acrylate reaction resin for floor coatings additives. By way of example, only:
Setting agents, antistatics, antioxidants, biostabilizers, chemical blowing agents, mold release agents, flame retardants, lubricants, colorants, flow improvers, fillers, lubricants, primers, inhibitors, catalysts, light stabilizers, optical brighteners, organic phosphites, oils, pigments, impact tougheners, reinforcing agents, reinforcing fibers, weathering inhibitors and plasticizers.

ever according to application purpose the proportions of these additives vary widely. In general However, the amounts are in the range of 0 to 3 parts by weight per Part by weight of components A) to E).

object The invention also relates to the use of the urethane (meth) acrylates described herein (Meth) acrylate resins for the surface protection of bridges, flat roofs and parking decks, for the back-feeding from bathtubs or for Coatings and sealants.

in the The present invention will be explained in more detail by way of examples, by but no limitation should be done.

1.) Synthesis of urethane (meth) acrylates

Example 1)

Preparation of trifunctional Urethane methacrylate in a two-stage reaction

In a round bottom flask with reflux condenser, thermometer, stirrer and dropping funnel, 0.3 mol of IPDI and 3 × 10 ^-4 mol of dibutyltin dilaurate (DBTDL) are introduced. This mixture is heated to 80 ° C. For this purpose, over a period of 30 minutes, a total of 0.3 mol of hydroxyethyl methacrylate (HEMA), which was mixed with 500 ppm of 2,6-di-tert-butyl-4-methylphenol (Fluka), based on the anticipated amount of the final product , added with stirring. After the addition, the temperature is maintained at 80 ° C until the content of isocyanate groups has fallen to half, with above the mixture, a nitrogen-oxygen mixture is about 7 vol .-% oxygen. The content of isocyanate groups was determined according to DIN 53 185, from 12.1974. In general, this step took about 5 hours.

Subsequently, a further 3 × 10 ^-4 mol of DBTDL are added. 0.1 moles of Polyethertriol ^® Voranol CP 6055 (Dow) are metered in, with the exact metering by the determined NCO content and the OH number of the Voranols directed, with stoichiometric amounts are used. The addition takes place within one hour, the temperature is kept at 80 ° C. The mixture is then stirred under the nitrogen-oxygen atmosphere described above at 80 ° C until the content of the isocyanate groups is less than 0.1%. If this value is not reached, one adds to the residual isocyanate content stoichiometric amount of HEMA, and allowed to continue to react until the NCO content is less than 0.1%. Subsequently, 500 ppm of 2-tert-butyl-4,6-dimethylphenol (Aldrich), based on the total mass of the final product, are added to the product.

The the product thus obtained can be further processed without further processing Reactions are used.

Example 2)

Production of polyvalent Urethane methacrylate in a one-step synthesis

In a round bottomed flask with reflux condenser, thermometer, stirrer and dropping funnel, 0.2 moles of Polyethertriol ^® Voranol CP 6055 (DOW), 0.4 moles of hydroxyethyl methacrylate (HEMA), 500 ppm of 2,6-di-tert-butyl-4-methylphenol , Based on the anticipated amount of the final product, 0.46 mol of IPDI and 2 x 10 ^-3 mol of dibutyltin dilaurate (DBTDL) and stirred for one hour at room temperature. Subsequently, the temperature of the mixture is continuously raised to 80 ° C within one hour. Thereafter, the temperature is maintained at 80 ° C for about 5 hours until the content of isocyanate groups has fallen to below 0.1%, with above the mixture, a nitrogen-oxygen mixture with about 7 vol .-% oxygen located. Residual amounts of isocyanate groups are reacted with a stoichiometric amount of HEMA, provided that the isocyanate content does not decrease to below 0.1% despite a prolonged after-reaction time. Subsequently, 500 ppm of 2-tert-butyl-4,6-dimethylphenol, based on the total mass of the final product, are added to the mixture.

It In this reaction, a mixture of urethane methacrylates is obtained, used without further workup in further reactions can be.

A SEC (size exclusion chromatography) curve of the product is in 1 shown.

2.) Tests - Methods

2.1.) Production of the plates

The The plates were produced by curing a methacrylate resin with the help of dimethyl-p-toluidine (DMPT) or another accelerator amine and dibenzoyl peroxide in a mold at room temperature. The mold consisted of two with polyester film (Hostaphan film, type RN / 36, 0.036mm thick, colorless, from company Pütz GmbH + Co., 65232 Taunusstein-Wehen) covered glass plates (25 cm × 22 cm × 0.4 cm) and about 2 mm thick piping (Vitroband, type 63020, from company Xaver Bayer, 79215 Elzach). The mixture was at least 24 hours hardened.

2.2) Examination of the plates

After 24 hours, specimens in the form of shoulder bars were punched from the plates produced according to 2.1. The shoulder bars are in 2 shown. They were 140 mm long and 25 mm wide at the ends, this width remaining constant over a length of 25 mm in each case in order to clamp the test specimen into the test apparatus. In the middle zone, the width was 6.5 mm. The length of the central zone was 65 mm.

The exams was carried out on the basis of DIN 53455 (1981), these being carried out on 5 test specimens each was in the normal climate for at least 16 h before the measurement DIN 50014-23 / 50-2 (1968) were stored. According to the "Technical Test Instructions for surface protection systems (TP OS) (The Federal Minister for Transport, 1990) were the exams at room temperature at a test speed of 100 mm / min performed. The exam at -20 ° C, deviating from the TP OS, with a speed of 50 instead 10 mm / min.

When tensile testing machine served a universal testing machine the company Zwick, type 1478.

Example 3)

According to the method described above, a plate was prepared containing a urethane methacrylate, the preparation of which is described in Example 2. To this was added a mixture of 63 parts by weight of ^® Degaroute VP 480 (a monomer-based polymer based on MMA as an essential component, available from Degussa AG), 1.2 parts by weight of methyl methacrylate (MMA), 15.6% by weight. Butyl acrylate (BA) and 20 parts by weight of urethane methacrylate produced. This mixture was admixed with 0.2 parts by weight DMPT and cured with 3 parts by weight dibenzoyl peroxide as previously described.

The obtained plate was prepared according to the in 2.2 methods described. The results for the tensile strength and the elongation at break are listed in Table 1.

Example 4)

According to the method described above, a plate was prepared containing a urethane methacrylate, the preparation of which is described in Example 2. To this was prepared a mixture of 63 parts by weight of ^® Degaroute VP 480, 6.2 parts by weight of methyl methacrylate (MMA), 10.6 parts by weight of butyl acrylate (BA) and 20 parts by weight of urethane methacrylate. This mixture was admixed with 0.2 parts by weight DMPT and cured with 3 parts by weight dibenzoyl peroxide as previously described.

The obtained plate was prepared according to the in 2.2 methods described. The results for the tensile strength and the elongation at break are listed in Table 1.

Comparative Example 1)

According to the method described above, a plate was prepared, but does not contain urethane (meth) acrylate according to the invention. Here, the resin composition of Example 3 was used, except that 20 parts by weight of ^® Ebecryl 230 (a divalent urethane (meth) acrylate from UBC) was used in place of the urethane (meth) acrylate of the present invention.

The resulting plate was examined according to the methods described in 2.2. The results for the tensile strength and elongation at break are shown in Table 1.

Comparative Example 2)

According to the method described above, a plate was prepared, but does not contain urethane (meth) acrylate according to the invention. Here, the resin composition of Example 4 was used, except that 20 parts by weight of ^® Ebecryl 230 was used instead of the urethane (meth) acrylate of the present invention.

The obtained plate was prepared according to the in 2.2 methods described. The results for the tensile strength and the elongation at break are listed in Table 1.

Table 1

Claims (10)

Urethane (meth) acrylates having at least 3 reactive terminal ethylenically unsaturated functionalities available through the implementation of A) a) hydroxyalkyl (meth) acrylic esters With b) polyisocyanates and c) polyoxyalkylenes, the c1) have at least three hydroxyl functionalities, c2) where the proportion of polyethylene oxide less than 50 wt .-%, based on the Total amount of polyoxyalkylene, is, or B) a) hydroxyalkyl (meth) acrylic esters With b) mixtures of polyisocyanates, of which at least a polyisocyanate has 3 or more isocyanate groups, and c) Polyoxyalkylenes, the c1) have at least two hydroxyl functionalities, c2) wherein the proportion of polyethylene oxide less than 50 wt .-%, based on the Total amount of polyoxyalkylene, is. Urethane (meth) acrylates according to Claim 1, characterized that these by the reaction of hydroxyethyl methacrylate, hydroxyethyl acrylate, Hydroxypropyl methacrylate and hydroxypropyl acrylate and mixtures of these compounds are obtainable as hydroxyalkyl (meth) acrylic esters. Urethane (meth) acrylates according to claim 1 or claim 2, characterized in that this by reaction of 2,4-toluenediisocyanate, 2,6-toluenediisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-dicyclohexyl diisocyanate, meta- and para-tetramethyl-xylene-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethyl (Isophorone diisocyanate), hexamethylene diisocyanate, 1,5-naphthylene diisocyanate, Dianisidine diisocyanate, di (2-isocyanatoethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate, 2,2,4- and 2,4,4-trimethylenehexamethylene diisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate, tris- (4-isocyanatophenyl) -thiophosphate and Mixtures thereof are available as polyisocyanate. Urethane (meth) acrylates according to one of the preceding Claims, characterized in that this by the reaction of polyoxypropylene and / or polytetramethylene oxides, each having at least three reactive, terminal hydroxy functionalities, available as polyoxyalkylene are. Urethane (meth) acrylates according to one of the preceding Claims, characterized in that this three or four reactive terminal ones ethylenically unsaturated functionalities exhibit. Urethane (meth) acrylates according to one of the preceding Claims, characterized in that the polyoxyalkylenes a weight average molecular weight in the range of 2,000 to 20,000. Process for the preparation of urethane (meth) acrylates according to at least one of the claims 1 to 6, characterized in that one a) at least one Hydroxyalkyl (meth) acrylate With b) at least one polyisocyanate and c) at least a polyoxyalkylene at 30 ° C-120 ° C during 5 Hours. Method according to claim 7, characterized in that the Reaction in the presence of an inhibitor takes place. Method according to claim 7 or 8, characterized in that the reaction in the presence from tertiary Amines and / or organic tin compounds, in particular dibutyltin dilaurate, takes place. Use of urethane (meth) acrylates obtainable according to at least one of the claims 1 to 6 or preparable according to at least one method according to claims 7 to 9 in (meth) acrylate resins for the surface protection of flat roofs and traffic areas, especially bridges and parking decks, for the back-feeding from bathtubs or for Coatings and sealants.