DE102007026196A1 - Process for the preparation of water-emulsifiable polyurethane acrylates - Google Patents

Abstract

The present invention describes a process for the preparation of water-emulsifiable polyurethane acrylates and their use.

Description

The The present invention describes a process for preparing water-emulsifiable Polyurethane acrylates and their use.

at the urethane (meth) acrylates which can be prepared according to the invention these are those which contain at least one polyalkylene glycol and which are therefore dispersed or diluted in water can be. Process for the preparation of water-soluble, dilutable, or emulsifiable, radiation curable urethane (meth) acrylates are known. The hydrophilicity of such urethane (meth) acrylates is based on the water solubility of the polyethylene glycol or polypropylene glycol chain. In this way, the urethane (meth) acrylate becomes water-soluble. In addition, the water solubility can be increased are polymerized by copolymerization of monomers which are each acidic or base functions, forming an internal salt, which causes an increased water solubility.

Water-dispersible urethane acrylates are already known from z. B. EP-A 98 752 or DE-OS 2,936,039 , The hydrophilicity of these known systems is based on the presence of ionic centers, in particular of carboxylate or sulfonate groups, which have as their counterions alkali cations or ammonium ions. The added for neutralization compounds can cause yellowing of the paints.

It There is therefore a need for further urethane (meth) acrylates in which Neutralization is achieved without yellowing he follows.

Often are used for better solubilization auxiliary solvents used, which released during the drying process be able to lead to an environmental impact. So what is desired is a low so-called. VOC value (volatile organic compounds), for example, by replacing organic Solvent can be achieved by water.

Another possibility for obtaining water-dilutable products is the use of external emulsifiers. For example, according to U.S. Patent No. 4,070,323 Acryloyl-carrying polyurethanes are dispersed in water with the aid of anionic or cationic oil-in-water emulsifiers (for example sodium lauryl sulfate). These emulsifiers are not incorporated in the paint film in a radical crosslinking. As a result, the degree of attainable water resistance of the paint films is thus disadvantageously lowered.

The water-soluble urethane (meth) acrylates according to the invention are (meth) acryloyl groups and alkylene oxide units incorporated within polyether chains, and polyurethanes preferably having inner salt groups, which are prepared by a specific process. Such hydrophilic polyurethanes are for example made Polymer Science USSR, Vol. 15, No. 4, May 1974, pages 814-822 . EP-A-0 168 173 . EP-A-0 154 237 . EP-A-0 021 824 or EP-A-0 381 862 and from Journal of Applied Polymer Science, Vol. 84, 1818-1831 (2002) known.

According to DE-A-3 437 918 aqueous oligourethane dispersions of polyisocyanate, macrodiol and hydroxy acrylate are used as leather coating agent, however, the preparation of these compounds as well as the preparation of in EP-A-0 287 736 or in EP-A-0 381 862 described hydrophilic polyurethanes not in the manner according to the invention.

Not Also known is the particular invention Use of such urethane (meth) acrylates.

EP-A 287 736 discloses a preparation of urethane (meth) acrylates in which a polyol is presented in Example 1, to which first the isocyanate and finally a hydroxy-functional acrylate is added.

According to EP-A 381 862 For the preparation of urethane (meth) acrylates isocyanates are presented, to which polyol and hydroxy-functional acrylate are added.

This leads to a significant proportion of unreacted hydroxy-functional Acrylate.

WO 06/89935 describes the preparation of urethane (meth) acrylates by introducing a mixture of polyols and hydroxy-functional acrylate and adding to this isocyanate. However, polyethers as polyols are mentioned only within long lists.

task The object of the present invention was to provide a production method for radiation curable, water soluble or emulsifiable To develop urethane (meth) acrylates in which as the feedstock used hydroxy-functional (meth) acrylate as possible can be fully implemented, the one reduced Show yellowing and improved adhesion of the coating on the pretreated with the task substrate cause.

• (a) mindestens ein Isocyanat mit mindestens 2 Isocyanatfunktionen,
• (b) mindestens einen Polyalkylenoxidpolyether mit mindestens 2 Hydroxyfunktionen,
• (c) mindestens ein hydroxyfunktionelles (Meth)Acrylat mit genau einer Hydroxyfunktion und mindestens einer (Meth)acrylatfunktion,
• (d) mindestens einer Verbindung mit mindestens einer gegenüber Isocyanat reaktiven Gruppe und mindestens einer Säurefunktion,
• (e) optional mindestens eine Verbindung mit mindestens einer gegenüber Isocyanat reaktiven Gruppe und mindestens einer basischen Gruppe für eine Neutralisation der Säuregruppen der Komponente (d),
• (f) optional mindestens ein Monoalkohol, der genau eine Hydroxyfunktion aufweist,
• (g) optional mindestens ein Di- oder Polyamin,

wobei die Herstellung des Urethan(meth)acrylats (A) optional in Gegenwart mindestens eines Reaktivverdünners (B) und/oder optional in Gegenwart mindestens eines Lösungsmittels erfolgen kann,
in dem man von den Komponenten (a) bis (f) die Komponenten (b), (c), (d) sowie, soweit vorhanden, (e) zumindest teilweise vorlegt und zu diesem Gemisch der vorgelegt Komponenten das Isocyanat (a) hinzugibt.The object has been achieved by a process for the preparation of urethane (meth) acrylates (A) by reacting the components

• (a) at least one isocyanate having at least 2 isocyanate functions,
• (b) at least one polyalkylene oxide polyether having at least 2 hydroxyl functions,
• (c) at least one hydroxy-functional (meth) acrylate having exactly one hydroxyl function and at least one (meth) acrylate function,
• (d) at least one compound having at least one isocyanate-reactive group and at least one acid function,
• (e) optionally at least one compound having at least one isocyanate-reactive group and at least one basic group for neutralization of the acid groups of component (d),
• (f) optionally at least one monoalcohol having exactly one hydroxyl function,
• (g) optionally at least one di- or polyamine,

wherein the preparation of the urethane (meth) acrylate (A) can optionally be carried out in the presence of at least one reactive diluent (B) and / or optionally in the presence of at least one solvent,
in which the components (b), (c), (d) and, if present, (e) are at least partly introduced from the components (a) to (f) and the isocyanate (a) is added to this mixture of the components initially introduced ,

• – sie enthalten einen geringeren Gehalt an freier Komponente (c) als nach anderen Verfahren hergestellte Verbindungen (A),
• – sie zeigen in Lacken eine geringere Vergilbung als nach anderen Herstellugsverfahren erhaltene Produkte, und
• – verbessern die Haftung von weiteren Lackschichten auf dem Substrat.

The urethane (meth) acrylates (A) thus obtained have at least one of the following advantages:

• They contain a lower content of free component (c) than compounds (A) prepared by other processes,
• They show a lower yellowing in paints than products obtained by other manufacturing processes, and
• - improve the adhesion of further paint layers on the substrate.

With particular advantage can be obtained by the method described above available, especially those described above Processes obtained mixtures as a primer, especially as a primer of wood and wood containing substrates.

at the component (a) is at least one, preferably exactly one isocyanate with at least 2 isocyanate functions, preferred 2 to 3 and more preferably exactly 2 isocyanate functions.

at The isocyanates used may be polyisocyanates or preferably monomeric diisocyanates which are aromatic, aliphatic or cycloaliphatic may be what is in this document is briefly referred to as (cyclo) aliphatic, be.

aromatic Isocyanates are those containing at least one aromatic ring system contain both pure aromatic and araliphatic Links.

cycloaliphatic Isocyanates are those which contain at least one cycloaliphatic ring system contain.

aliphatic Isocyanates are those which are exclusively straight or contain branched chains, ie acyclic compounds.

at the monomeric isocyanates are preferably diisocyanates, which carry exactly two isocyanate groups.

It in principle also higher isocyanates come on average more than 2 isocyanate groups in consideration. Are suitable for this for example, triisocyanates such as triisocyanatononane, 2,4,6-triisocyanatotoluene, Triphenylmethane triisocyanate or 2,4,4'-triisocyanatodiphenyl ether or the mixtures of di-, tri- and higher polyisocyanates, obtained, for example, by phosgenation of corresponding aniline / formaldehyde condensates be and methylene bridges having polyphenyl polyisocyanates represent.

These monomeric isocyanates have essentially no reaction products the isocyanate groups with itself.

The monomeric isocyanates are preferably isocyanates having 4 to 20 C atoms. Examples of conventional diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1,4-, 1 , 3- or 1,2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate), 1 , 3- or 1,4-bis (isocyanatomethyl) cyclohexane or 2,4- or 2,6-diisocyanato-1-methylcyclohexane and also 3 (or 4), 8 (or 9) -bis (isocyanatomethyl) -tricyclo [5.2.1.0 ^2.6 ] decane isomer mixtures, and also aromatic diisocyanates such as 2,4- or 2,6-toluene diisocyanate and their mixtures of isomers, m- or p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane and their isomer mixtures , 1,3- or 1,4-phenyne lene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'- diisocyanate, tetramethylxylylene diisocyanate, 1,4-diisocyanatobenzene or diphenyl ether-4,4'-diisocyanate.

Especially preferred (cyclo) aliphatic isocyanates are 1,6-hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, most preferably are isophorone diisocyanate and 1,6-hexamethylene diisocyanate, in particular preferred is isophorone diisocyanate.

preferred aromatic isocyanates are 2,4- or 2,6-toluene diisocyanate and their isomer mixtures and 2,4'- or 4,4'-diisocyanatodiphenylmethane and their isomer mixtures, more preferably 2,4- or 2,6-toluene diisocyanate and their isomeric mixtures in the ratio of about 80:20. Also conceivable is the use of pure 2,4-toluene diisocyanate.

It may also be mixtures of said isocyanates.

isophorone is usually as a mixture, namely the cis and trans isomers before, usually in the ratio of about 60:40 to 80:20 (w / w), preferably in the ratio of about 70:30 to 75:25 and most preferably in the ratio of about 75:25.

Dicyclohexylmethane-4,4'-diisocyanate may also be a mixture of the different cis and trans isomers available.

For the present invention, it is possible to use both those diisocyanates which are obtained by phosgenation of the corresponding amines and those which are prepared without the use of phosgene, ie by phosgene-free processes. According to the EP-A-0 126 299 ( U.S. 4,596,678 ) EP-A-126,300 ( U.S. 4,596,679 ) and EP-A-355 443 ( US 5 087 739 For example, (cyclo) aliphatic diisocyanates, e.g. B. 1,6-hexamethylene diisocyanate (HDI), isomeric aliphatic diisocyanates having 6 carbon atoms in the alkylene radical, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane and 1-isocyanato-3-isocyanato-methyl-3, 5,5-trimethylcyclohexane (isophorone diisocyanate or IPDI) are prepared by reacting the (cyclo) aliphatic diamines with, for example, urea and alcohols to give (cyclo) aliphatic biscarbamic esters and their thermal cleavage into the corresponding diisocyanates and alcohols. The synthesis is usually carried out continuously in a cyclic process and optionally in the presence of N-unsubstituted carbamic acid esters, dialkyl carbonates and other by-products recycled from the reaction process. Thus obtained diisocyanates generally have a very low or even non-measurable proportion of chlorinated compounds, which is advantageous, for example, in applications in the electronics industry.

In an embodiment of the present invention the isocyanates used have a total content of hydrolyzable Chlorine of less than 200 ppm, preferably less than 120 ppm, more preferably less than 80 ppm, most preferably less than 50 ppm, especially less than 15 ppm and especially less than 10 ppm. This can be measured for example by ASTM D4663-98. It can of course also monomeric isocyanates with a higher chlorine content used, for example, up to 500 ppm.

Of course, mixtures of such monomeric isocyanates by Umset tion of (cyclo) aliphatic diamines with, for example, urea and alcohols and cleavage of the obtained (cyclo) aliphatic biscarbamic acid esters have been obtained with such diisocyanates, which have been obtained by phosgenation of the corresponding amines.

Conceivable, although less preferred, is the use of polyisocyanates in addition to or instead of the monomeric isocyanates.

The polyisocyanates to which the monomeric isocyanates can be oligomerized are typically characterized as follows:
The average NCO functionality of such compounds is generally at least 1.8 and may be up to 8, preferably 2 to 5 and particularly preferably 2.4 to 4.

Of the Content of isocyanate groups after the oligomerization, calculated as NCO = 42 g / mol, is usually from 5 to 25 wt .-%.

• 1) Isocyanuratgruppen aufweisende Polyisocyanate von aromatischen, aliphatischen und/oder cycloaliphatischen Diisocyanaten. Besonders bevorzugt sind hierbei die entsprechenden aliphatischen und/oder cycloaliphatischen Isocyanato-Isocyanurate und insbesondere die auf Basis von Hexamethylendiisocyanat und Isophorondiisocyanat. Bei den dabei vorliegenden Isocyanuraten handelt es sich insbesondere um Tris-isocyanatoalkyl- bzw. Tris-isocyanatocycloalkyl-Isocyanurate, welche cyclische Trimere der Diisocyanate darstellen, oder um Gemische mit ihren höheren, mehr als einen Isocyanuratring aufweisenden Homologen. Die Isocyanato-Isocyanurate haben im allgemeinen einen NCO-Gehalt von 10 bis 30 Gew.-%, insbesondere 15 bis 25 Gew.-% und eine mittlere NCO- Funktionalität von 2,6 bis 8.
• 2) Uretdiongruppen aufweisende Polyisocyanate mit aromatisch, aliphatisch und/oder cycloaliphatisch gebundenen Isocyanatgruppen, vorzugsweise aliphatisch und/oder cycloaliphatisch gebundenen und insbesondere die von Hexamethylendiisocyanat oder Isophorondiisocyanat abgeleiteten. Bei Uretdiondiisocyanaten handelt es sich um cyclische Dimerisierungsprodukte von Diisocyanaten. Die Uretdiongruppen aufweisenden Polyisocyanate werden im Rahmen dieser Erfindung im Gemisch mit anderen Polyisocyanaten, insbesondere den unter 1) genannten, erhalten. Dazu können die Diisocyanate unter Reaktionsbedingungen umgesetzt werden, unter denen sowohl Uretdiongruppen als auch die anderen Polyisocyanate gebildet werden, oder zunächst die Uretdiongruppen gebildet und diese anschließend zu den anderen Polyisocyanaten umgesetzt werden oder die Diisocyanate zunächst zu den andereren Polyisocyanaten und diese anschließend zu Uretdiongruppen-haltigen Produkten umgesetzt werden.
• 3) Biuretgruppen aufweisende Polyisocyanate mit aromatisch, cycloaliphatisch oder aliphatisch gebundenen, bevorzugt cycloaliphatisch oder aliphatisch gebundenen Isocyanatgruppen, insbesondere Tris-(6-isocyanatohexyl)-biuret oder dessen Gemische mit seinen höheren Homologen. Diese Biuretgruppen aufweisenden Polyisocyanate weisen im allgemeinen einen NCO-Gehalt von 18 bis 22 Gew.-% und eine mittlere NCO-Funktionalität von 2,8 bis 6 auf.
• 4) Urethan- und/oder Allophanatgruppen aufweisende Polyisocyanate mit aromatisch, aliphatisch oder cycloaliphatisch gebundenen, bevorzugt aliphatisch oder cycloaliphatisch gebundenen Isocyanatgruppen, wie sie beispielsweise durch Umsetzung von überschüssigen Mengen an Diisocyanat, beispielsweise Hexamethylendiisocyanat oder Isophorondiisocyanat, mit ein- oder mehrwertigen Alkoholen. Diese Urethan- und/oder Allophanatgruppen aufweisenden Polyisocyanate haben im allgemeinen einen NCO-Gehalt von 12 bis 24 Gew.-% und eine mittlere NCO-Funktionalität von 2,5 bis 4,5. Solche Urethan- und/oder Allophanatgruppen aufweisenden Polyisocyanate können unkatalysiert oder bevorzugt in Gegenwart von Katalysatoren, wie beispielsweise Ammoniumcarboxylaten oder -hydroxiden, oder Allophanatisierungskatalysatoren, z. B. Zn-(II)-Verbindungen, jeweils in Anwesenheit von ein-, zwei- oder mehrwertigen, bevorzugt einwertigen Alkoholen, hergestellt werden.
• 5) Oxadiazintriongruppen enthaltende Polyisocyanate, vorzugsweise von Hexamethylendiisocyanat oder Isophorondiisocyanat abgeleitet. Solche Oxadiazintriongruppen enthaltenden Polyisocyanate sind aus Diisocyanat und Kohlendioxid zugänglich.
• 6) Iminooxadiazindiongruppen enthaltende Polyisocyanate, vorzugsweise von Hexamethylendiisocyanat oder Isophorondiisocyanat abgeleitet. Solche Iminooxadiazin-diongruppen enthaltenden Polyisocyanate sind aus Diisocyanaten mittels spezieller Katalysatoren herstellbar.
• 7) Uretonimin-modifizierte Polyisocyanate.
• 8) Carbodiimid-modifizierte Polyisocyanate.
• 9) Hyperverzweigte Polyisocyanate, wie sie beispielsweise bekannt sind aus der DE-A1 10013186 oder DE-A1 10013187 .
• 10) Polyurethan-Polyisocyanat-Präpolymere, aus Di- und/oder Polyisocyanaten mit Alkoholen.
• 11) Polyharnstoff-Polyisocyanat-Präpolymere.
• 12) Die Polyisocyanate 1)–11), bevorzugt 1), 3), 4) und 6) können nach deren Herstellung in Biuretgruppen- oder Urethan-/Allophanat-Gruppen aufweisende Polyisocyanate mit aromatisch, cycloaliphatisch oder aliphatisch gebundenen, bevorzugt (cyclo)aliphatisch gebundenen Isocyanatgruppen, überführt werden. Die Bildung von Biuretgruppen erfolgt beispielsweise durch Zugabe von Wasser oder Umsetzung mit Aminen. Die Bildung von Urethan- und/oder Allophanatgruppen erfolgt durch Umsetzung mit ein-, zwei- oder mehrwertigen, bevorzugt einwertigen Alkoholen, gegebenenfalls in Gegenwart von geeigneten Katalysatoren. Diese Biuret- oder Urethan-/Allophanatgruppen aufweisenden Polyisocyanate weisen im allgemeinen einen NCO-Gehalt von 18 bis 22 Gew.-% und eine mittlere NCO-Funktionalität von 2,8 bis 6 auf.
• 13) Hydrophil modifizierte Polyisocyanate, d. h. Polyisocyanate, die neben den unter 1–12 beschriebenen Gruppen solche enthalten, die formal durch Addition von Molekülen mit NCO-reaktiven Gruppen und hydrophilierenden Gruppen an die Isocyanatgruppen obiger Moleküle entstehen. Bei letzteren handelt es sich um nichtionische Gruppen wie Alkyl-Polyethylenoxid und/oder ionische, welche von Phosphorsäure, Phosphonsäure, Schwefelsäure oder Sulfonsäure, bzw. ihren Salzen abgeleitet sind.
• 14) Modifizierte Polyisocyanate für Dual Cure Anwendungen, d. h. Polyisocyanate, die neben den unter 1–12 beschriebenen Gruppen solche enthalten, die formal durch Addition von Molekülen mit NCO-reaktiven Gruppen und durch UV- oder aktinische Strahlung vernetzbare Gruppen an die Isocyanatgruppen obiger Moleküle entstehen. Bei diesen Moleküle handelt es sich beispielsweise um Hydroxyallkyl(meth)acrylate und andere Hydroxy-Vinylverbindungen.

The polyisocyanates are preferably the following compounds:

• 1) isocyanurate-containing polyisocyanates of aromatic, aliphatic and / or cycloaliphatic diisocyanates. Particular preference is given here to the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanurates and in particular those based on hexamethylene diisocyanate and isophorone diisocyanate. The isocyanurates present are, in particular, trisisocyanatoalkyl or trisisocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologs having more than one isocyanurate ring. The isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt .-%, in particular 15 to 25 wt .-% and an average NCO functionality of 2.6 to 8.
• 2) polyisocyanates containing uretdione groups with aromatic, aliphatic and / or cycloaliphatic bonded isocyanate groups, preferably aliphatically and / or cycloaliphatically bonded and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate. Uretdione diisocyanates are cyclic dimerization products of diisocyanates. The polyisocyanates containing uretdione groups are obtained in the context of this invention in a mixture with other polyisocyanates, in particular those mentioned under 1). For this purpose, the diisocyanates can be reacted under reaction conditions under which both uretdione groups and the other polyisocyanates are formed, or first the uretdione groups formed and these are then reacted to the other polyisocyanates or the diisocyanates first to the other polyisocyanates and these then to uretdione groups-containing Products are implemented.
• 3) biuret polyisocyanates having aromatic, cycloaliphatic or aliphatic bound, preferably cycloaliphatic or aliphatic bound isocyanate groups, especially tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologues. These biuret polyisocyanates generally have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 2.8 to 6.
• 4) polyisocyanates containing urethane and / or allophanate groups with aromatic, aliphatic or cycloaliphatic bound, preferably aliphatically or cycloaliphatically bonded isocyanate groups, as for example by reacting excess amounts of diisocyanate, for example hexamethylene diisocyanate or isophorone diisocyanate, with monohydric or polyhydric alcohols. These urethane and / or allophanate-containing polyisocyanates generally have an NCO content of 12 to 24 wt .-% and an average NCO functionality of 2.5 to 4.5. Such urethane and / or allophanate groups containing polyisocyanates can uncatalyzed or preferably in the presence of catalysts such as ammonium carboxylates or hydroxides, or allophanatization catalysts, for. B. Zn (II) compounds, each in the presence of mono-, di- or polyhydric, preferably monohydric alcohols produced.
• 5) oxadiazinetrione-containing polyisocyanates, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such oxadiazinetrione-containing polyisocyanates are accessible from diisocyanate and carbon dioxide.
• 6) Iminooxadiazindiongruppen containing polyisocyanates, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such iminooxadiazine-dione-containing polyisocyanates can be prepared from diisocyanates by means of special catalysts.
• 7) Uretonimine-modified polyisocyanates.
• 8) carbodiimide-modified polyisocyanates.
• 9) hyperbranched polyisocyanates, as they are known for example from DE-A1 10013186 or DE-A1 10013187 ,
• 10) polyurethane-polyisocyanate prepolymers of di- and / or polyisocyanates with alcohols.
• 11) polyurea-polyisocyanate prepolymers.
• 12) The polyisocyanates 1) -11), preferably 1), 3), 4) and 6) may, after their preparation, comprise polyisocyanates having aryl, cycloaliphatic or aliphatic bound groups in biuret group or urethane / allophanate groups, preferably (cyclo) aliphatically bound isocyanate groups are transferred. The formation of biuret groups takes place, for example, by addition of water or reaction with amines. The formation of urethane and / or allophanate groups by reaction with mono-, di- or polyhydric, preferably monohydric alcohols, optionally in the presence of suitable catalysts. These biuret or urethane / allophanate groups containing polyisocyanates generally have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 2.8 to 6 on.
• 13) Hydrophilically modified polyisocyanates, ie polyisocyanates which, in addition to the groups described under 1-12, contain those which formally arise by adding molecules having NCO-reactive groups and hydrophilizing groups to the isocyanate groups of the above molecules. The latter are nonionic groups such as alkyl polyethylene oxide and / or ionic, which are derived from phosphoric acid, phosphonic acid, sulfuric acid or sulfonic acid, or their salts.
• 14) Modified polyisocyanates for dual-cure applications, ie polyisocyanates which contain, in addition to the groups described under 1-12, those which formally arise by addition of molecules with NCO-reactive groups and UV- or actinic radiation-crosslinkable groups to the isocyanate groups of the above molecules , These molecules are, for example, hydroxyalkyl (meth) acrylates and other hydroxy-vinyl compounds.

The listed above diisocyanates or polyisocyanates also be present at least partially in a blocked form.

Block classes used in blocking are described in DA Wicks, ZW Wicks, Progress in Organic Coatings, 36, 148-172 (1999), 41, 1-83 (2001) and 43, 131-140 (2001) ,

Examples are for connection classes used for blocking Phenols, imidazoles, triazoles, pyrazoles, oximes, N-hydroxyimides, hydroxybenzoic acid esters, secondary amines, lactams, CH-acidic cyclic ketones, malonic esters or alkyl acetoacetates.

In a preferred embodiment of the present invention the polyisocyanate is selected from the group consisting from isocyanurates, biurets, urethanes and allophanates from the group consisting of isocyanurates, urethanes and allophanates, particularly preferably from the group consisting of isocyanurates and Allophanates, in particular is an isocyanurate group-containing Polyisocyanate.

In an embodiment to be mentioned is the polyisocyanate is polyisocyanates containing isocyanurate groups of 1,6-hexamethylene diisocyanate.

In a further embodiment is in the Polyisocyanate to a mixture of isocyanurate groups Polyisocyanates of 1,6-hexamethylene diisocyanate and isophorone diisocyanate.

In a particularly preferred embodiment is the polyisocyanate is a mixture containing low viscosity Polyisocyanates, preferably polyisocyanates containing isocyanurate groups, with a viscosity of 600-1500 mPa · s, especially below 1200 mPa · s, low viscosity urethanes and / or allophanates with a viscosity of 200-1600 mPa · s, in particular 600-1500 mPa · s, and / or iminooxadiazinedione groups containing polyisocyanates.

at the component (b) is at least one, preferably exactly one polyalkylene oxide polyether having at least 2 hydroxyl functions, preferably 2 to 4 hydroxy functions, more preferably 2 to 3 and most preferably exactly 2 hydroxy functions.

handeln,
worin
R¹ und R² unabhängig voneinander Wasserstoff oder gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes C₁-C₁₈-Alkyl,
k, l, m, q unabhängig voneinander je für eine ganze Zahl von 1 bis 15, bevorzugt 1 bis 10 und besonders bevorzugt 1 bis 7 steht und
jedes X_i für i = 1 bis k, 1 bis l, 1 bis m und 1 bis q unabhängig voneinander ausgewählt sein kann aus der Gruppe -CH₂-CH₂-O-, -CH₂-CH(CH₃)-O-, -CH(CH₃)-CH₂-O-, -CH₂-C(CH₃)₂-O-, -C(CH₃)₂-CH₂-O-, -CH₂-CHVin-O-, -CHVin-CH₂-O-, -CH₂-CHPh-O- und -CHPh-CH₂-O-, bevorzugt aus der Gruppe -CH₂-CH₂-O-, -CH₂-CH(CH₃)-O- und -CH(CH₃)-CH₂-O-, und besonders bevorzugt -CH₂-CH₂-O-,
worin Ph für Phenyl und Vin für Vinyl steht.For example, component (b) may be alkoxylated diols or polyols of the formulas (Ia) to (Id),

act,
wherein
R ¹ and R ² independently of one another denote hydrogen or C ₁ -C ₁₈ -alkyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,
k, l, m, q independently of one another are each an integer from 1 to 15, preferably 1 to 10 and particularly preferably 1 to 7, and
each X _i for i = 1 to k, 1 to 1, 1 to m and 1 to q may independently be selected from the group -CH ₂ -CH ₂ -O-, -CH ₂ -CH (CH ₃ ) -O -, -CH (CH ₃ ) -CH ₂ -O-, -CH ₂ -C (CH ₃ ) ₂ -O-, -C (CH ₃ ) ₂ -CH ₂ -O-, -CH ₂ -CHVin-O -, -CHVin-CH ₂ -O-, -CH ₂ -CHPh-O- and -CHPh-CH ₂ -O-, preferably from the group -CH ₂ -CH ₂ -O-, -CH ₂ -CH (CH ₃ ) -O- and -CH (CH ₃ ) -CH ₂ -O-, and more preferably -CH ₂ -CH ₂ -O-,
where Ph is phenyl and Vin is vinyl.

Therein C ₁ -C ₁₈ -alkyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles are, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl , Heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl Methyl, ethyl or n-propyl, most preferably methyl or ethyl.

preferred However, components (b) are polyalkylene ethers having exactly 2 hydroxyl functions, essentially, preferably exclusively formally Ethylene oxide and / or propylene oxide are constructed. Such compounds are commonly used as polyethylene / -propylene glycols or in general referred to as polyalkylene glycols.

The structure of such polyalkylene glycols is usually as follows HO - [- X _i -] _n -H wherein
X _i for each i = 1 to n can be independently selected from the group consisting of -CH ₂ -CH ₂ -O-, -CH ₂ -CH (CH ₃ ) -O- and -CH (CH ₃ ) -CH ₂ -O- and more preferably -CH ₂ -CH ₂ -O- may be, and
n can be an integer from 5 to 60, preferably from 7 to 50 and particularly preferably from 10 to 45.

The number average molecular weight M _n is preferably between 500 and 2000 g / mol. The OH numbers (according to DIN 53240 , potentiometric) are preferably in a range of about 20 to 300 mg KOH / g polymer.

The reaction of the alcohols or water with an alkylene oxide is known per se to the person skilled in the art. Possible implementation forms can be found in Houben-Weyl, Methods of Organic Chemistry, 4th Edition, 1979, Thieme Verlag Stuttgart, Ed. Heinz Kropf, Volume 6 / 1a, Part 1, pages 373-385 ,

Preferably, the preparation is carried out as follows:
The polyhydric alcohol or water is, optionally in a suitable solvent, such as. B. benzene, toluene, xylene, tetrahydrofuran, hexane, pentane or petroleum ether, dissolved, at temperatures between 0 ° C and 120 ° C, preferably between 10 and 100 ° C and more preferably between 20 and 80 ° C, preferably under inert gas, such as As nitrogen, submitted. For this purpose, the alkylene oxide is added continuously or in portions, optionally at a temperature of -30 ° C to 50 ° C dissolved in one of the abovementioned solvents, with thorough mixing so that the temperature of the reaction mixture between 120 and 180 ° C, preferably between 120 and 150 ° C is maintained. The reaction can take place under a pressure of up to 60 bar, preferably up to 30 bar and particularly preferably up to 10 bar.

The Amount of alkylene oxide is adjusted so that per mol of polyhydric alcohol up to (1.1 × (k + l + m + q)) mol of alkylene oxide, preferably up to (1.05 x (k + l + m + q)) mol of alkylene oxide, and more preferably (k + 1 + m + q) mol Alkylene oxide are added, wherein k, l, m and q are the above Have meanings.

Possibly can be up to 50 mol% based on the polyhydric alcohol, especially preferably up to 25 mol% and most preferably up to 10 mol% of a catalyst can be added for acceleration, for example Water (as far as this is not already used as starting material in the reaction mixture is present), monoethanolamine, diethanolamine, triethanolamine, Dimethylaminoethanolamine, ethylene glycol or diethylene glycol, as well Alkali hydroxides, alcoholates or hydrotalcite, preferably alkali metal hydroxides in water.

To complete metered addition of the alkylene oxide is in the Rule 10 to 500 min, preferably 20 to 300 min, more preferably 30 to 180 minutes at temperatures between 30 and 220 ° C, preferably 80 to 200 ° C and more preferably 100 to 180 ° C left to react, the temperature remain the same or can be raised gradually or continuously.

Of the Conversion of alkylene oxide is preferably at least 90%, more preferably at least 95%, and most preferably at least 98%. Possible residues of alkylene oxide can by passing a gas, for example nitrogen, helium, Argon or water vapor stripped through the reaction mixture become.

The For example, reaction may be batchwise, semi-continuous or continuously in a stirred reactor or continuously carried out in a tubular reactor with static mixers become.

Prefers the reaction is completely in the liquid phase carried out.

The resulting reaction product may be crude or reclaimed Form be further processed.

If a reuse in pure form is desired, so For example, the product may be about crystallization and solid / liquid separation are purified.

The Yields are usually over 75%, mostly over 80% and often over 90%.

If the reaction with a basic catalyst, for example alkali metal hydroxides, preferably sodium or potassium hydroxide is carried out, so it may be useful after the remaining catalyst residues after the reaction then with, for example, acetic acid to neutralize. This results in that in the polyalkylene glycol alkali metal acetate is still present, in subsequent reactions catalytically active. But it is also possible Remove the contained alkali metal acetate, for example by Treat with an ion exchanger.

at the component (c) is at least one, preferably 1 to 2, particularly preferably exactly one hydroxy-functional (meth) acrylate with exactly one hydroxy function and at least one, preferred 1 to 3, particularly preferably exactly one (meth) acrylate function.

Components (c) may be partial esters of acrylic acid or methacrylic acid with di- or polyols, preferably having 2 to 20 carbon atoms and at least 2 hydroxy groups, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol , 1,1-dimethyl-l, 2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1,2-, 1,3- or 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1.6 Hexanediol, 2-methyl-1,5-pentanediol, 2-ethyl-l, 4-butanediol, 1,4-dimethylolcyclohexane, 2,2-bis (4-hydroxycyclohexyl) propane, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol , Ditrimethylolpropane, erythritol, sorbitol, poly-THF with a molecular weight between 162 and 2000, poly-1,3-propanediol having a molecular weight between 134 and 400 or polyethylene glycol having a molecular weight between 238 and 458. Furthermore, esters or amides of (meth) acrylic acid with amino alcohols z. For example, 2-aminoethanol, 2- (methylamino) ethanol, 3-amino-1-propanol, 1-amino-2-propanol or 2- (2-aminoethoxy) ethanol, 2-mercaptoethanol or polyaminoalkanes, such as ethylenediamine or diethylenetriamine ,

Examples for amides of ethylenically unsaturated carboxylic acids with amino alcohols are hydroxyalkyl (meth) acrylamides such as N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxymethylmethacrylamide and 5-hydroxy-3-oxapentyl (meth) acrylamide.

Prefers 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, Neopentyl glycol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, Glycerol di (meth) acrylate, trimethylol propane di (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-hydroxyethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide or 3-hydroxypropyl (meth) acrylamide. Particularly preferred are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 1,4-butanediol monoacrylate, 3- (acryloyloxy) -2-hydroxypropyl (meth) acrylate and the monoacrylates of polyethylene glycol of molecular weight from 106 to 238.

All particularly preferred is 2-hydroxyethyl acrylate.

Component (c) may also be technical mixtures of the acrylation of trimethylolpropane, pentaerythritol, ditrimethylolpropane or dipentaerythritol. These are mostly mixtures of complete and incomplete acrylated polyols. In this case, preference would be given to technical mixtures of the acrylation of pentaerythritol, which usually have an OH number according to DIN 53240 from 99 to 115 mg KOH / g and consist predominantly of pentaerythritol triacrylate and pentaerythritol tetraacrylate, and may contain minor amounts of pentaerythritol diacrylate. This has the advantage that pentaerythritol tetraacrylate is not incorporated into the polyurethane of the invention, but at the same time acts as a reactive diluent (B).

The Component (d) is at least one, preferably exactly one compound with at least one, for example 1 to 3, particularly preferred 2 to 3 and most preferably exactly 2 opposite Isocyanate-reactive group and at least one, preferably exactly an acidity function.

When Acid groups come carboxylic acid or sulfonic acid groups, preferably carboxylic acid groups into consideration.

Across from Isocyanate-reactive groups are selected from Hydroxy, mercapto, primary and / or secondary Amino groups, preferably are hydroxy groups.

When Compounds (d) are especially aliphatic monomercapto, Monohydroxy- and monoamino- and iminocarboxylic acids and corresponding Sulfonic acids in question such as mercaptoacetic acid (thioglycolic acid), Mercaptopropionic acid, mercaptosuccinic acid, Hydroxyacetic acid, hydroxypropionic acid (lactic acid), Hydroxysuccinic acid, hydroxypivalic acid, dimethylolpropionic acid, Dimethylol butyric acid, hydroxydecanoic acid, hydroxydodecanoic acid, 12-hydroxystearic acid, hydroxyethanesulfonic acid, Hydroxypropanesulfonic acid, mercaptoethanesulfonic acid, Mercaptopropanesulfonic acid, aminoethanesulfonic acid, Aminopropanesulfonic acid, glycine (aminoacetic acid), N-cyclohexylaminoethanesulfonic acid, N-cyclohexylaminopropanesulfonic acid, or iminodiacetic acid.

Prefers are dimethylolpropionic acid and dimethylolbutyric acid, dimethylolpropionic acid is particularly preferred.

at the optional component (e) is at least one, prefers exactly one compound with at least one, for example 1 to 3, more preferably 2 to 3, and most preferably exactly 2 isocyanate-reactive group and at least one, preferably just one basic group, for neutralization the acid groups of component (d) is capable.

Suitable basic groups are amines, for example primary, secondary or tertiary amines, particular preference is given to tertiary amines. Preferably, the neutralization or partial neutralization of the acid groups in (d) with amines such as ethanolamine or diethanolamine, or triethanolamine or 2-propanolamine or dipropanolamine, or tripropanolamine and especially with tert. Amines, such as triethylamine, Triethanolamine, dimethylethanolamine or diethylethanolamine. Particularly preferred are N-methyldiethanolamine and N-ethyldiethanolamine. The amounts of chemically bonded base groups introduced and the extent of neutralization of the acid groups (which is usually from 40 to 100% of the equivalence base) should preferably be sufficient to ensure dispersion of the polyurethanes in an aqueous medium, which is familiar to the person skilled in the art.

Instead of or in addition to component (e) may also be possible be acidic groups with inorganic or organic bases without isocyanate-reactive groups, such as alkali metal and alkaline earth metal hydroxides, -oxides, -carbonates, -hydrogencarbonates and ammonia or tert. Use amines for neutralization or partial neutralization. Prefers is the neutralization or partial neutralization with sodium hydroxide or potassium hydroxide or tert. Amines, such as triethylamine, tri-n-butylamine or ethyl diisopropylamine. The quantities imported chemically bound acid groups and the extent of Neutralization of the acid groups (usually at 40 to 100% the equivalence base is) preferably be sufficient to a dispersion of the polyurethanes in one aqueous medium, which is familiar to the expert is.

Be the optional component (f) is at least one Monoalcohol, which is exactly one hydroxy function and beyond has no further functional group.

Examples for this are methanol, ethanol, n-propanol, isopropanol and n-butanol, preferred is methanol.

The Function of the compounds (f) is in the production the urethane (meth) acrylates (A) optionally remaining, unreacted To saturate isocyanate groups.

The Viscosity of the urethane (meth) acrylate (A) may vary depending on the used Components up to 25, preferably less than 20 Pas amount.

Therefore the preparation of the urethane (meth) acrylate (A) can optionally, although less preferred, in the presence of at least one reactive diluent (B).

This is at least one radiation-curable compound which, in addition to radically polymerizable groups, preferably acrylate or methacrylate groups, contains no isocyanate- or hydroxyl-reactive groups and also has a low viscosity, preferably less than 150 mPas (in this document Viscosity at 25 ° C according to DIN EN ISO 3219 / A.3 in a cone-plate system with a rate slope of 1000 s ^-1 , unless otherwise noted).

preferred Compounds (B) have one to six (meth) acrylate groups, more preferably one to four, most preferably two until four.

Especially preferred compounds (B) have a boiling point of more than 200 ° C at atmospheric pressure.

Reactive thinners are common in PKT Oldring (Editor), Chemistry & Technology of UV & EB Formulations for Coatings, Inks & Paints, Vol. II, Chapter III: Reactive Diluents for UV & EB Curable Formulations, Wiley and SITA Technology, London 1997 described.

Reactive diluents are, for example, esters of (meth) acrylic acid with alcohols having 1 to 20 carbon atoms, eg. Methyl (meth) acrylate, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, dihydrodicyclopentadienyl acrylate, vinyl aromatic compounds, e.g. Styrene, divinylbenzene, α, β-unsaturated nitriles, e.g. For example, acrylonitrile, methacrylonitrile, α, β-unsaturated aldehydes, z. Acrolein, methacrolein, vinyl esters, e.g. For example, vinyl acetate, vinyl propionate, halogenated ethylenically unsaturated compounds, eg. Vinyl chloride, vinylidene chloride, conjugated unsaturated compounds, e.g. As butadiene, isoprene, chloroprene, monounsaturated compounds, eg. Ethylene, propylene, 1-butene, 2-butene, isobutene, cyclic monounsaturated compounds, e.g. B. cyclopentene, cyclohexene, cyclododecene, N-vinylformamide, allylacetic acid, vinylacetic acid, monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and their water-soluble alkali metal, alkaline earth metal or ammonium salts such as: acrylic acid, methacrylic acid, dimethylacrylic acid, ethacrylic acid, maleic acid, citraconic acid , Methylenemalonic acid, crotonic acid, fumaric acid, mesaconic acid and itaconic acid, maleic acid, N-vinylpyrrolidone, N-vinyllactams, such as. B. N-vinylcaprolactam, N-vinyl-N-alkylcarboxamides or N-vinylcarboxamides, such as. N-vinylacetamide, N-vinyl-N-methylformamide and N-vinyl-N-methylacetamide or vinyl ethers, e.g. For example, methyl vinyl ether, ethyl vinyl ethers, n-propyl vinyl ether, iso-propyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, and mixtures thereof.

Examples for compounds (B) having at least two free-radically polymerizable C = C double bonds are in particular the diesters and polyesters the aforementioned α, β-ethylenically unsaturated Mono- and / or dicarboxylic acids with diols or polyols. Particularly preferred are hexanediol diacrylate, hexanediol dimethacrylate, Octanediol diacrylate, octanediol dimethacrylate, nonanediol diacrylate, Nonandioldimethacrylate, decandioldiacrylate, decandioldimethacrylate, Pentaerythritol diacrylate, dipentaerythritol tetraacrylate, dipentaerythritol triacrylate, Pentaerythritol tetraacrylate, etc. The esters are also more preferably alkoxylated Polyols with α, β-ethylenically unsaturated Mono- and / or dicarboxylic acids such. As the polyacrylates or methacrylates of alkoxylated trimethylolpropane, glycerin or pentaerythritol and diethylene glycol, triethylene glycol, Dipropylene glycol or tripropylene glycol. Suitable are still the esters of alicyclic diols, such as cyclohexanediol di (meth) acrylate and bis (hydroxymethylethyl) cyclohexanedi (meth) acrylate. Other suitable Reactive diluents are trimethylolpropane monoformal acrylate, Glycerol formal acrylate, 4-tetrahydropyranyl acrylate, 2-tetrahydropyranyl methacrylate and tetrahydrofurfuryl acrylate.

optional For example, the preparation of the polyurethane in at least one may be preferred be carried out exactly one solvent. Preference is given here to water-miscible solvents, more preferably those having a lower boiling point than Water. Examples are acetone, tetrahydrofuran, butanone, Diethyl ketone, cyclic or open-chain carbonates, N-methylpyrrolidone or N-ethyl pyrrolidone.

the Urethane (meth) acrylate (A) and / or the reactive diluent (B) may optionally have a primary or secondary Amine (h) to be set to activate the (meth) acrylate groups.

In the compounds (h) is the number of aminic hydrogen atoms (N-H) of primary and / or secondary amino groups preferably 1 to 6, more preferably 2 to 4.

So is z. For example, the number of aminic hydrogen atoms in a compound having two primary amino groups 4 and when connected to a primary and a secondary Amino group 3.

primary or add secondary amino groups in compounds (h) according to a Michael addition to acrylic groups or methacrylic groups. This so-called amine modification causes an increase in the reactivity of the so modified (meth) acrylates and this increased reactivity then decreases the stickiness of the resulting coatings.

Out primary amino groups are added by Michael addition (Meth) acrylate groups secondary amino groups which are again to (meth) acrylic groups to form tertiary Can add amino groups.

suitable Compounds (h) having at least one primary and / or secondary amino group are generally low molecular weight and preferably have a molecular weight below 1000.

Mention may be made, for example, of primary monoamines such as C ₁ -C ₂₀ -alkylamines, in particular n-butylamine, n-hexylamine, 2-ethylhexylamine, octadecylamine, isopropanolamine or methoxypropylamine, cycloaliphatic amines such as cyclohexylamine and (hetero) aromatic-group-containing amines such as benzylamine, 1- ( 3-aminopropyl) imidazole and tetrahydrofurfurylamine.

Compounds with 2 primary amino groups are for. B. C ₁ -C ₂₀ alkylenediamines such as ethylenediamine, butylenediamine, neopentanediamine or hexamethylenediamine.

links with secondary amino groups are, for example, dimethylamine, Diethylamine, diisopropylamine or di-n-butylamine, as well as piperidine, Pyrrolidine and morpholine.

Farther 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine, 4,4'-diaminodicyclohexylmethane and isophoronediamine. As connections with primary or secondary amino groups with at least one hydroxy group may be mentioned alkanolamines, z. B. Mono- or diethanolamine, aminoethoxyethanol, aminoethylethanolamine, 2-aminopropan-1-ol, dipropanolamine, 2-aminobutan-1-ol, 3-aminopropan-1-ol, Hydroxyethylpiperazine, piperazine, imidazole, etc.

Compounds having primary and secondary amino groups are e.g. 3-amino-1-methylaminopropane, Diethylenetriamine, triethylenetetramine, dipropylenetriamine, N, N'-bis (3-aminopropyl) ethylenediamine.

Preferably are the compounds (h) with one or more primary and / or secondary amino groups used in such amounts, to 1 mol of the (meth) acrylate groups in the compounds (A) and / or (B) 0.005 to 0.4, preferably 0.01 to 0.2, moles, especially preferably 0.02 to 0.1 moles of primary amine hydrogen atoms or secondary amino groups in compounds (h).

there the optional addition of the compound (h) is usually followed by Completion of the preparation of the urethane (meth) acrylate, d. H. after the reaction of components (a) to (f) substantially is completed.

• (a) 100 mol% Isocyanatfunktionen,
• (b) 25 bis 75 mol% Hydroxyfunktionen (bezogen auf Isocyanatfunktionen in (a)), bevorzugt 40 bis 60 mol%,
• (c) 10 bis 80 mol% Hydroxyfunktionen (bezogen auf Isocyanatfunktionen in (a)), bevorzugt 20 bis 50 mol%,
• (d) 0 bis 20 mol% Hydroxyfunktionen (bezogen auf Isocyanatfunktionen in (a)), bevorzugt 0 bis 10 mol%,
• (e) 0 bis 5 mol% gegenüber Isocyanat reaktive Gruppen (bezogen auf Isocyanatfunktionen in (a)),
• (f) 0 bis 5 mol% Hydroxyfunktionen (bezogen auf Isocyanatfunktionen in (a)),

mit der Maßgabe, daß die Summe der Hydroxyfunktionen in den Komponenten (b), (c), (d), (e) und (f) 100 mol% Hydroxyfunktionen (bezogen auf Isocyanatfunktionen in (a)) ergibt.The composition of the urethane (meth) acrylates is usually as follows:

• (a) 100 mol% isocyanate functions,
• (b) 25 to 75 mol% of hydroxy functions (based on isocyanate functions in (a)), preferably 40 to 60 mol%,
• (c) 10 to 80 mol% of hydroxy functions (based on isocyanate functions in (a)), preferably 20 to 50 mol%,
• (d) 0 to 20 mol% of hydroxy functions (based on isocyanate functions in (a)), preferably 0 to 10 mol%,
• (e) 0 to 5 mol% isocyanate-reactive groups (based on isocyanate functions in (a)),
• (f) 0 to 5 mol% of hydroxy functions (based on isocyanate functions in (a)),

with the proviso that the sum of the hydroxy functions in components (b), (c), (d), (e) and (f) gives 100 mol% of hydroxy functions (based on isocyanate functions in (a)).

It may be useful, the component (a) containing isocyanate groups, to use in excess, for example up to 120 mol%, preferably up to 115 mol%, particularly preferably up to 110 mol% and most preferably up to 105 mol%. This is especially preferred when at least one of the used Components, in particular the hygroscopic compound (b), water Contains that with isocyanate functions in competition with hydroxy functions responding.

Of the Reactive diluent (B) can be in the 0 to 3 times the amount of Urethane (meth) acrylate (A) present during the reaction and / or after the preparation of the urethane (meth) acrylate (A) are added, preferably in the 0.1 to 2-fold amount.

The Production of the polyurethanes is expediently carried out such that the components are observed in accordance with the invention Order of addition in the melt or in the presence of an inert, water-miscible solvent (see above) at temperatures from 20 to 160, preferably 50 to 100 ° C, wherein the Reaction time is usually 2 to 10 hours. By the concomitant use of in a conventional manner catalytically active substances such as dibutyltin dilaurate, tin (II) octoate or 1,4-Diazobicyclo- (2,2,2) -octane, usually in amounts of from 10 to 500 ppm, based on the solvent-free reaction mixture, the implementation can be accelerated. Subsequently, will optionally with a water-miscible solvent diluted, ionogenic groups can, if not already done, optionally ionized by neutralization are added, water and optionally di- or polyamines to Chain extension stirred. After that, usually distilling off the optionally used organic solvent, why such solvents are preferred, their boiling point is below the boiling point of water. If necessary, you can the di- or polyamines for chain extension also before be added to the dispersion with water. The added amount of water is usually sized so that the inventive aqueous polyurethane preparations have a solids content from 10 to 80 wt .-% have.

According to the invention for preparing the urethane (meth) acrylate (A) from the components (a) to (f) at least the components (b) and (c) and optionally (d) at least partially, preferably fully submitted and to this mixture of the components presented, the isocyanate (a) added.

To it is preferable to put at least half of the planned quantity to component (b), preferably at least 65%, more preferably at least 75% and in particular the full amount.

Farther it is preferable to put at least half of the planned quantity to component (c) above, preferably at least 65%, more preferably at least 75% and in particular the full amount.

If component (d) is used, it is preferable to apply at least half of the planned one amount of component (d) before, preferably at least 65%, more preferably at least 75% and in particular the complete amount.

To this mixture of components (b) and (c) and optionally (d) then the isocyanate (a) is added. This can be continuous, in several portions or in one addition.

The Reaction mixture is then at temperatures of 50 to 80 ° C over a period of 4 to 10 hours, preferably 6 to 10 hours reacted with stirring or pumping together.

While In the reaction, the temperature can be constant or continuous or gradually increased.

The reaction is preferably accelerated by adding a suitable catalyst. Such catalysts are known from the literature, for example G. Oertel (ed.), Polyurethane, 3rd edition 1993, Carl Hanser Verlag, Munich - Vienna, pages 104 to 110, chapter 3.4.1. "Catalysts" Preferred are organic amines, in particular tertiary aliphatic, cycloaliphatic or aromatic amines, Brønsted acids and / or Lewis acidic organometallic compounds, particularly preferred are Lewis acidic organometallic compounds. These are preferably Lewis acidic organic metal compounds for which z. As tin compounds come into question, such as tin (II) salts of organic carboxylic acids, eg. Tin (II) diacetate, stannous (II) dioctoate, stannous (II) bis (ethylhexanoate) and stannous (II) dilaurate, and the dialkyzin (IV) salts of organic carboxylic acids, e.g. , Dimethyl tin diacetate, dibutyltin diacetate, dibutyltin dibutyrate, dibutyltin bis (2-ethylhexanoate), dibutyltin dilaurate, dibutyltin maleate, dioctyltin dilaurate and dioctyltin diacetate. In addition, zinc (II) salts can be used, such as zinc (II) dioctoate.

It it is also conceivable to carry out the reaction without a catalyst, in this case, however, the reaction mixture must be higher Temperatures are exposed and / or the reaction time extended become.

In order to avoid undesired polymerization of the (meth) acrylate groups during the reaction, polymerization inhibitors may be added. Such inhibitors are described, for example, in WO 03/035596 , Page 5, line 35 to page 10, line 4, to which reference is hereby made in the context of the present disclosure.

Around the prepolymers built up during the urethanization reaction they can be crosslinked for a further molecular weight buildup be reacted with a di- or polyamine (g). These are the prepolymers obtained from the above reaction, when the reaction of components (a) to (d) is essentially completed is, d. H. for example at least 95%, preferably at least 97% and more preferably at least 98%, to implement the nor contained free isocyanate groups with at least one, preferably exactly a di- or polyamine (g) implemented.

Diamines are, for example, 1,2-diaminoethane, 1,6-diaminohexane, piperazine, 2,5-dimethylpiperazine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 4,4'-di (aminocyclohexyl ) -methane, 1,4-diaminocyclohexane, 1,2- and 1,3-diaminopropane, hydrazine, hydrazine hydrate, triamines are, for example, diethylenetriamine or tetramines such as N, N'-bis (3-aminopropyl) -1,4-diaminobutane , But there are also ketimines, as in the DE-B 27 25 589 Ketazines, such as those of the DE-B 28 11 148 and the US-A 42 69 748 , Amine salts like those in the US-A 42 92 226 or oxazolidines as used in the DE-B 27 32 131 and the US-A 41 92 937 be considered. These are masked polyamines from which the corresponding polyamines are released in the presence of water as intermediates.

Prefers as compounds (g), however, di- or polyamines, which in turn a free or neutralized acid group, for example a carboxy or sulfonic acid group.

Especially preferred are the ammonium or alkali metal salts of 6-amino-4-aza-hexanecarboxylic acid (N- (2'-carboxyethyl) ethylenediamine) and 5-amino-3-aza-pentanesulfonic acid (N- (2'-sulfoethyl) ethylenediamine) their sodium, ammonium or potassium salts, particularly preferred their sodium salts.

Such products are described, for example, in EP 704469 A2 , Page 3, lines 47 to 49, for which the starting diamines mentioned there are 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,5-pentylenediamine or 1,6-hexylenediamine, in particular 1,2 -Ethylendiamin offer.

In usually 0-10 mol% di- or polyamine (g) (sum from primary and secondary amino groups, based used on isocyanate groups in (a)), preferably 0-8 mol%, more preferably 1-7, and most preferably 2-5 mol%.

Prefers are either at least one compound (g) or at least one Connection (s) available. Less preferred are both at least a compound (g) and at least one compound (e) present.

The Reaction can be considered terminated when the NCO value is theoretical Sales value of at least 95%, preferably at least 97% and especially preferably has reached at least 98%.

If still unreacted isocyanate groups should be present, so can the reaction by reaction with the monoalcohol (f) among the above Reaction conditions are completed.

It is possible, the reaction mixture after preparation to disperse or dilute in water.

The Reaction may preferably be in the presence of reactive diluents (B) carried out for both the individual components and for the urethane (meth) acrylate (A) as a solvent functions as well as later in the application component of Coating mass is.

To the entire amount of reactive diluent may already be too Beginning of the reaction to be submitted or during the course of the reaction be added. But it can also be useful to have a part of Reactive thinner (B) only after completion of the reaction to further dilute the urethane (meth) acrylate (A).

Prefers be 30 to 100% of the total reactive diluent used (B) already used in the reaction, more preferably 50 to 100%, most preferably 70 to 100% and especially 100%. The remainder may then be added after completion of the reaction.

The after the reaction of the invention urethane (meth) acrylate (A) obtained, optionally in reactive diluents (B) dissolved, may be beneficial as or in radiation-curable Coating materials are used.

These coating compositions may contain further constituents:
If the curing of the coating compositions does not take place with electron beams but by means of UV radiation, preferably at least one photoinitiator is present which can initiate the polymerization of ethylenically unsaturated double bonds.

Photoinitiators may be, for example, photoinitiators known to those skilled in the art, eg. B. such in "Advances in Polymer Science", volume 14, Springer Berlin 1974 or in KK Dietliker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3 ; Photoinitiators for Free Radical and Cationic Polymerization, PKT Oldring (Eds), SITA Technology Ltd, London , mentioned.

In consideration come z. B. mono- or Bisacylphosphinoxide as z. In EP-A 7 508 . EP-A 57 474 . DE-A 196 18 720 . EP-A 495 751 or EP-A 615 980 are described, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin ^® TPO from BASF AG), ethyl 2,4,6-trimethylbenzoylphenylphosphinate (Lucirin ^® TPO L from BASF AG), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Irgacure ^® 819 from Ciba specialty Chemicals), benzophenones, hydroxyacetophenones, phenylglyoxylic acid and its derivatives or mixtures of these photoinitiators. Examples which may be mentioned are benzophenone, acetophenone, acetonaphthoquinone, methyl ethyl ketone, valerophenone, hexanophenone, α-phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone, 4-morpholinodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-methoxyacetophenone, β-methylanthraquinone , tert-butyl anthraquinone, anthraquinone carboxylic acid ester, benzaldehyde, α-tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1-indanone, 1,3,4-triacetylbenzene, thioxanthene -9-one, xanthen-9-one, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyltrioxanthone, 2,4-dichlorothioxanthone, benzoin, benzoin isobutyl ether, chloroxanthenone, benzoin tetrahydropyranyl ether , Benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin isopropyl ether, 7-H-benzoin methyl ether, benz [de] anthracen-7-one, 1-naphthaldehyde, 4,4'-bis (dimethylamino) benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, Michler's K eton, 1-acetonaphthone, 2-acetonaphthone, 1-benzoylcy clohexan-1-ol, 2-hydroxy-2,2-dimethyl acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, acetophenone dimethyl ketal, o-methoxybenzophenone, triphenylphosphine, tri-o-tolylphosphine, benz [a] anthracene-7,12-dione, 2,2-diethoxyacetophenone, benzil ketals such as benzil dimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, anthraquinones such as 2-methylanthraquinone, 2- Ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone and 2,3-butanedione.

Also suitable are non- or slightly yellowing photoinitiators of the phenylglyoxalic acid ester type, as in DE-A 198 26 712 . DE-A 199 13 353 or WO 98/33761 described.

typical Mixtures include, for example, 2-hydroxy-2-methyl-1-phenyl-propan-2-one and 1-hydroxycyclohexyl phenyl ketone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone and 1-hydroxycyclohexyl phenyl ketone, Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,4,6-trimethylbenzophenone and 4-methylbenzophenone or 2,4,6-trimethylbenzophenone and 4-methylbenzophenone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Prefers among these photoinitiators are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphinate, Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, benzophenone, 1-benzoylcyclohexan-1-ol, 2-hydroxy-2,2-dimethylacetophenone and 2,2-dimethoxy-2-phenylacetophenone.

The Coating compositions preferably contain the photoinitiators in an amount of 0.05 to 10 wt .-%, particularly preferably 0.1 to 8 wt .-%, in particular 0.2 to 5 wt .-%, based on the total amount the components (a) to (f).

The Coating materials can be further customary Additives, such as leveling agents, defoamers, UV absorbers, Dyes, pigments and / or fillers.

Suitable fillers include silicates, e.g. For example, by hydrolysis of silicon tetrachloride available silicates such as Aerosil ^® R from. Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonates, etc. Suitable stabilizers include typical UV absorbers such as oxanilides, triazines and benzotriazole (the latter available as Tinuvin ^® R brands Ciba Specialty Chemicals) and benzophenones. These may be used alone or together with suitable radical scavengers, for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, eg. B. bis (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate used. Stabilizers are usually used in amounts of 0.1 to 5.0 wt .-% based on the "solid" components contained in the preparation.

The Coating materials are particularly suitable for coating Wood, wood-based materials and wood-containing substrates, such as fiberboard. Also conceivable is the coating of cellulose fibers, such as Paper, cardboard or cardboard.

It In particular, such woods are preferred, usually be used for parquet, such as oak, spruce, Pine, beech, maple, chestnut, sycamore, rubinia, ash, birch, Pine and elm, but also cork.

Especially are the coating compositions as precoating (primer, primer), preferably adhesion primer for wood, in particular for Parquet suitable. By application of such coating compositions leaves the adhesion will improve further coatings on this primer.

The substrates are coated by customary methods known to those skilled in the art, at least one coating composition being applied to the substrate to be coated in the desired thickness and the volatile constituents of the coating compositions being removed. If desired, this process can be repeated one or more times. The application to the substrate can in a known manner, for. B. by spraying, filling, doctoring, brushing, rolling, rolling or pouring done. The coating thickness is generally in a range of about 3 to 1000 g / m ² and preferably 10 to 200 g / m ² .

Possibly can if several layers of the coating agent on top of each other are applied, after each coating process radiation curing respectively.

The radiation curing is effected by the action of high-energy radiation, ie UV radiation or daylight, preferably light of wavelength 250 to 600 nm or by irradiation with high-energy electrons (electron radiation, 150 to 300 keV). The radiation sources used are, for example, high-pressure mercury vapor lamps, lasers, pulsed lamps (flash light), halogen lamps or excimer radiators. The radiation dose for UV curing, which is usually sufficient for crosslinking, is in the range from 80 to 3000 mJ / cm ² .

The irradiation may optionally also in the absence of oxygen, for. B. under inert gas atmosphere, are performed. Suitable inert gases are preferably nitrogen, noble gases, carbon dioxide or combustion gases. Furthermore, the irradiation can be carried out by covering the coating composition with transparent media. Transparent media are z. As plastic films, glass or liquids, eg. B. water. Particular preference is given to irradiation in the manner as described in US Pat DE-A1 199 57 900 is described.

In a preferred method, the curing takes place continuously, by bringing the treated with the coating composition substrate constant speed past a radiation source. Therefor It is necessary that the curing speed the coating composition is sufficiently high.

this different temporal course of curing can be especially to take advantage when applied to the coating the article still connects a processing step, where the film surface is in direct contact with a other object occurs or is mechanically processed.

Of the The advantage of the coating compositions is that they are coated Objects immediately after radiation curing can process further because the surface is no longer sticks. On the other hand, the dried film is still so flexible and stretchable, that the object can still be deformed, without the film thereby flakes off or rips.

The Invention will be apparent from the following non-limiting Examples explained in more detail.

Examples

Example 1.

In a three-necked flask with reflux condenser and stirrer 231 g Pluriol ^® E 600 were 165 g Pluriol ^® E 1000 (polyethylene glycols of average molecular weight 600 and 1000 g / mol, OH numbers 197 and 125, commercial products from BASF AG), 7, 6 g of dimethylolpropionic acid, 17.88 g of N-methyldiethanolamine, 46.44 g of 2-hydroxyethyl acrylate, 0.70 g of 2,6-di-tert-butyl-p-cresol and 0.35 g of methylhydroquinone are mixed at 60.degree. 0.30 g of dibutyltin dilaurate were added as catalyst to the well-mixed template. To this mixture 222 g of isophorone diisocyanate were added dropwise at 60 to 70 ° C within 50 minutes. It was then stirred for 2 hours at 60 to 65 ° C internal temperature until the NCO value of the reaction mixture was 0.3%. Then, 19.5 g of 6-amino-4-aza-hexanecarboxylic acid (sodium salt) was added, and the reaction mixture was diluted with 200 g of water.

Of the Solid body of the urethane acrylate was 75 wt .-%. The double bond density of the solvent-free urethane acrylate was 0.56 mol / kg, and the viscosity 11.5 Pa · s.

Example 2.

In a three-necked flask with reflux condenser and stirrer 330 g Pluriol E were ^® 600 (commercial product from BASF AG), 7.6 g of dimethylolpropionic acid, 17.88 g of N-methyldiethanolamine, 46.44 g 2-hydroxyethyl acrylate, 0.63 g of 2,6 -Di-tert-butyl-p-cresol and 0.32 methylhydroquinone at 60 ° C mixed. 0.30 g of dibutyltin dilaurate were added as catalyst to the well-mixed template. To this mixture 222 g of isophorone diisocyanate were added dropwise at 60 to 70 ° C within 40 minutes. It was then stirred for 4.5 hours at 60 to 65 ° C internal temperature until the NCO value of the reaction mixture was 0.89%. Then, 19.5 g of 6-amino-4-aza-hexanecarboxylic acid (sodium salt) was added, and the reaction mixture was diluted with 200 g of water.

Of the Solid body of the urethane acrylate was 75%. The double bond density of the solvent-free urethane acrylate was 0.63 mol / kg, and the viscosity 15.4 Pa · s.

Example 3.

In a three-necked flask with reflux condenser and stirrer 300 g Pluriol E were ^® 600 (commercial product from BASF AG), 7.6 g of dimethylolpropionic acid, N-methyldiethanolamine 8.94 g, 75.4 g 2-hydroxyethyl acrylate, 0.60 g of 2,6 -Di-tert-butyl-p-cresol and 0.30 methylhydroquinone at 60 ° C mixed. 0.30 g of dibutyltin dilaurate were added as catalyst to the well-mixed template. To this mixture 222 g of isophorone diisocyanate were added dropwise at 60 to 70 ° C within 45 minutes. It was then stirred for 5 hours at 60 to 65 ° C internal temperature until the NCO value of the reaction mixture was 0.77%. Then, 19.5 g of 6-amino-4-aza-hexanecarboxylic acid (sodium salt) was added, and the reaction mixture was diluted with 183.3 g of water.

Of the Solid body of the urethane acrylate was 75%. The double bond density of the solvent-free urethane acrylate was 1.06 mol / kg, and the viscosity is 9.0 Pa · s.

Example 4.

In a three-necked flask with reflux condenser and stirrer 330 g Pluriol E were ^® 600 (commercial product from BASF AG), 7.6 g of dimethylolpropionic acid, 8.94 g N-methyldiethanolamine, 75.4 g of 2-hydroxyethyl acrylate, 0.64 g of 2,6 -Di-tert-butyl-p-cresol and 0.32 methylhydroquinone at 60 ° C mixed. 0.30 g of dibutyltin dilaurate were added as catalyst to the well-mixed template. To this mixture 222 g of isophorone diisocyanate were added dropwise at 60 to 70 ° C within 50 minutes. It was then stirred for 5 hours at 60 to 65 ° C internal temperature until the NCO value of the reaction mixture was 0.5%. Then the reaction mixture was diluted with 214.3 g of water.

Of the Solid body of the urethane acrylate was 75%. The double bond density of the solvent-free urethane acrylate was 1.01 mol / kg, and the viscosity is 5.4 Pa · s.

Example 5.

In a three-necked flask with reflux condenser and stirrer 300 g Pluriol E were ^® 600 (commercial product from BASF AG), 7.6 g of dimethylolpropionic acid, 14.9 g of N-methyldiethanolamine, 75.4 g of 2-hydroxyethyl acrylate, 0.60 g of 2,6 -Di-tert-butyl-p-cresol and 0.30 methylhydroquinone at 60 ° C mixed. 0.30 g of dibutyltin dilaurate were added as catalyst to the well-mixed template. To this mixture 222 g of isophorone diisocyanate were added dropwise at 60 to 70 ° C within 45 minutes. It was then stirred for 5.5 hours at 70 to 75 ° C internal temperature until the NCO value of the reaction mixture was 0.30%. Then the reaction mixture was diluted with 206.3 g of water.

Of the Solid body of the urethane acrylate was 75%. The double bond density of the solvent-free urethane acrylate was 1.05 mol / kg, and the viscosity 7.5 Pa · s.

Example 6.

In a three-necked flask with reflux condenser and stirrer, 270 g Pluriol® ^® E, 600 (commercial product from BASF AG), 7.6 g of dimethylolpropionic acid, 14.9 g of N-methyl diethanolamine, 87 g 2-hydroxyethyl acrylate, 0.60 g of 2,6-di tert-butyl p-cresol and 0.30 methylhydroquinone at 60 ° C. 0.30 g of dibutyltin dilaurate were added as catalyst to the well-mixed template. To this mixture 222 g of isophorone diisocyanate were added dropwise at 60 to 70 ° C within 35 minutes. It was then stirred for 6 hours at 70 to 75 ° C internal temperature until the NCO value of the reaction mixture was 0.30%. Then, the reaction mixture was diluted with 200 g of water.

Of the Solid body of the urethane acrylate was 75%. The double bond density of the solvent-free urethane acrylate was 1.24 mol / kg, and the viscosity is 6.7 Pa · s.

Example 7.

In a three-necked flask with reflux condenser and stirrer were 315 g of Pluriol ^® E 600, (commercial product of BASF AG), 7.6 g of dimethylolpropionic acid, 87 g of 2-hydroxyethyl acrylate, 0.64 g of 2,6-di-tert-butyl-p cresol and 0.32 g methylhydroquinone at 60 ° C mixed. 0.30 g of dibutyltin dilaurate were added as catalyst to the well-mixed template. To this mixture 222 g of isophorone diisocyanate were added dropwise at 60 to 70 ° C within 45 minutes. It was then 5.5 hours at 70 to 75 ° C internal temperature stirred until the NCO value of the reaction mixture was 0.94%. Then, 19.5 g of 6-amino-4-azahexanecarboxylic acid (sodium salt) was added and the reaction mixture was diluted with 200 g of water.

Of the Solid body of the urethane acrylate was 75%. The double bond density of the solvent-free urethane acrylate was 1.17 mol / kg, and the viscosity is 5.1 Pa · s.

Example 8.

In a three-necked flask with reflux condenser and stirrer 270 g Pluriol E were ^® 600 (commercial product from BASF AG), 7.6 g of dimethylolpropionic acid, 8.94 g N-methyldiethanolamine, 87 g 2-hydroxyethyl acrylate, 0.64 g 2,6-di- tert.-butyl-p-cresol and 0.32 methylhydroquinone at 60 ° C mixed. 0.30 g of dibutyltin dilaurate were added as catalyst to the well-mixed template. To this mixture 222 g of isophorone diisocyanate were added dropwise at 60 to 70 ° C within 40 minutes. It was then stirred for 5.5 hours at 70 to 75 ° C internal temperature until the NCO value of the reaction mixture was 0.74%. Then, 19.5 g of 6-amino-4-aza-hexanecarboxylic acid (sodium salt) was added, and after 5 minutes, the reaction mixture was diluted with 189.1 g of water.

Of the Solid body of the urethane acrylate was 75%. The double bond density of the solvent-free urethane acrylate was 1.24 mol / kg, and the viscosity 7.5 Pa · s.

Example 9.

In a three-necked flask with reflux condenser and stirrer 300 g Pluriol E were ^® 600 (commercial product from BASF AG), 6.7 g of dimethylolpropionic acid, 14.9 g of N-methyldiethanolamine, 75.4 g of 2-hydroxyethyl acrylate, 0.63 g of 2,6 -Di-tert-butyl-p-cresol and 0.32 methylhydroquinone at 60 ° C mixed. 0.33 g of dibutyltin dilaurate were added as catalyst to the thoroughly mixed stock. To this mixture, 233.1 g of isophorone diisocyanate were added dropwise at 60 to 70 ° C within 50 minutes. It was then stirred for 7 hours at 75 ° C internal temperature until the NCO value of the reaction mixture was 0.29%. Then, the addition of 1.7 g of methanol. After 2 hours, the NCO content was 0.08% and the reaction mixture was diluted with 210 g of water.

Of the Solid body of the urethane acrylate was 75%. The double bond density of the solvent-free urethane acrylate was 1.03 mol / kg, and the viscosity is 9.6 Pa · s.

Example 10.

In a three-necked flask with reflux condenser and stirrer 300 g Pluriol E were ^® 600 (commercial product from BASF AG), 6.7 g of dimethylolpropionic acid, 14.9 g of N-methyldiethanolamine, 75.4 g of 2-hydroxyethyl acrylate, 0.63 g of 2,6 -Di-tert-butyl-p-cresol and 0.32 methylhydroquinone at 60 ° C mixed. 0.33 g of dibutyltin dilaurate were added as catalyst to the thoroughly mixed stock. To this mixture were added dropwise at 60 to 70 ° C 244.2 g of isophorone diisocyanate within 50 minutes. It was then stirred for 7 hours at 75 ° C internal temperature until the NCO value of the reaction mixture was 0.66%. Then, the addition of 4 g of methanol. After 4 hours, the NCO content was 0.1% and the reaction mixture was diluted with 213.7 g of water.

Of the Solid body of the urethane acrylate was 75%. The double bond density of the solvent-free urethane acrylate was 1.01 mol / kg, and the viscosity 10.2 Pa · s.

Example 11.

In a three-necked flask with reflux condenser and stirrer 315 g Pluriol ^® E 600, (commercial product from BASF AG), 6.7 g of dimethylolpropionic acid were 87 g 2-hydroxyethyl acrylate, 0.64 g 2,6-di-tert-butyl-p cresol and 0.32 g methylhydroquinone at 60 ° C mixed. 0.30 g of dibutyltin dilaurate were added as catalyst to the well-mixed template. To this mixture, 233.1 g of isophorone diisocyanate were added dropwise at 60 to 70 ° C within 45 minutes. It was then stirred for 8 hours at 75 to 77 ° C internal temperature until the NCO value of the reaction mixture was 0.68%. Then, 19.5 g of 6-amino-4-azahexanecarboxylic acid (sodium salt) was added 40% in water, and the reaction mixture was diluted with 205 g of water.

The solids of the urethane acrylate was 75%. The double bond density of the solvent-free Ure than acrylate was 1.15 mol / kg, and the viscosity 7.7 Pa · s.

Example 12.

In a three-necked flask with reflux condenser and stirrer were 315 g of Pluriol ^® E 600, (commercial product of BASF AG), 6.7 g of dimethylolpropionic acid, 87 g of 2-hydroxyethyl acrylate, 0.64 g of 2,6-di-tert-butyl-p cresol and 0.32 g methylhydroquinone at 60 ° C mixed. 0.30 g of dibutyltin dilaurate were added as catalyst to the well-mixed template. To this mixture 244.2 g of isophorone diisocyanate were added dropwise at 60 to 70 ° C within 45 minutes. It was then stirred for 8 hours at 75 to 77 ° C internal temperature until the NCO value of the reaction mixture was 1.25%. Then, the addition of 3 g of methanol and after 2 hours, the NCO value was 0.71%. Subsequently, 19.5 g of 6-amino-4-azahexancarbonsäure (sodium salt) were added and after 5 min, the reaction mixture was diluted with 208.5 g of water.

Of the Solid body of the urethane acrylate was 75%. The double bond density of the solvent-free urethane acrylate was 1.13 mol / kg, and the viscosity is 8.8 Pa · s.

Example 13.

In a three-necked flask with reflux condenser and stirrer were 315 g of Pluriol ^® E 600, (commercial product of BASF AG), 6.7 g of dimethylolpropionic acid, 87 g of 2-hydroxyethyl acrylate, 0.64 g of 2,6-di-tert-butyl-p cresol, 0.32 g of methylhydroquinone and 160 g of acetone mixed anhydrous at 60 ° C. 0.30 g of dibutyltin dilaurate were added as catalyst to the well-mixed template. 233.1 g of isophorone diisocyanate were added dropwise to this mixture at 60 to 70 ° C. within 40 minutes. It was then stirred for 15 hours at 75 to 77 ° C internal temperature until the NCO value of the reaction mixture was 0.68%. Then, 19.5 g of 6-amino-4-aza-hexanecarboxylic acid (sodium salt) was added 40% and the reaction mixture was diluted with 205 g of water. Finally, the acetone was distilled off at 45 ° C and 100 mbar.

Of the Solids of the urethane acrylate was 77%. The double bond density of the solvent-free urethane acrylate was 1.15 mol / kg, and the viscosity is 11.2 Pa · s.

Example 14.

In a three-necked flask with reflux condenser and stirrer were 315 g of Pluriol ^® E 600, (commercial product of BASF AG), 6.7 g of dimethylolpropionic acid, 87 g of 2-hydroxyethyl acrylate, 0.65 g of 2,6-di-tert-butyl-p cresol, 0.32 g of methylhydroquinone and 0.065 g of phenothiazine mixed at 60 ° C. 0.30 g of dibutyltin dilaurate were added as catalyst to the well-mixed template. To this mixture, 233.1 g of isophorone diisocyanate were added dropwise at 60 to 70 ° C within 50 minutes. It was then stirred for 8 hours at 75 to 77 ° C internal temperature until the NCO value of the reaction mixture was 0.95%. Then, 19.5 g of 6-amino-4-aza-hexanecarboxylic acid (sodium salt) was added 40% in water and then the reaction mixture was diluted with 205 g of water.

Of the Solid body of the urethane acrylate was 75%. The double bond density of the solvent-free urethane acrylate was 1.15 mol / kg, and the viscosity 7.7 Pa · s.

Comparative Example V1.

A commercial mixture of a water-soluble unsaturated polyester acrylate and Epoxidacrylats (Laromer ^® PE 22WN BASF AG, Ludwigshafen, Germany) was treated with a commercially available water-soluble epoxy acrylate (Laromer ^® LR 8765 from BASF AG, Ludwigshafen, Germany) 70 to 30 parts by weight of mixed The radiation-curable composition was by intensive mixing of 100 parts by weight of this mixture with 4 parts by weight of a commercial photoinitiator Irgacure ^® 500 (1: 1 mixture of 1-hydroxycyclohexyl pehnylketon and benzophenone) from Ciba Specialty Chemicals.

applications

The aqueous polyurethane preparations are applied as adhesive primer at 10 g / m ² on beech parquet and gelled in the UV system at a belt speed of 40 m / min. Subsequently, a primer is (Laromer ^® PE 56F (commercial mixture of polyester acrylate and epoxy acrylate BASF AG, Ludwigshafen): 1,6-hexanediol diacrylate; 70:30) applied with a view thickness of 25 g / m ^2, and the UV system at gelled at a belt speed of 35 m / min. The second layer of the primer is placed twice under the UV system cured at a belt speed of 10 m / min. The coating is sanded with 400 grit sandpaper. The topcoat (Laromer LR8986 / LR 8967; 70:30, mixture of polyether acrylate and epoxy acrylate, commercial products of BASF AG) is introduced at a layer thickness of 10 g / m ² and twice under the UV system at a belt speed of 10 m / min hardened.

(1: 1 mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone) and the photoinitiator Irgacure ^® 500 from Ciba Specialty Chemicals was used.

Coin test Exam: A coin goes down at a steep angle Pressing led over parquet surface. If there is a loss of adhesion of the UV coating, it shows this in the so-called "white break" (it forms a clear recognizable scratch mark). Can the wood be left without delamination deforming the UV coating is called a very good Coin test. 1 = very good, 2 = good, 3 = medium.

The Results are shown in Table 1.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - EP 98752 A [0003]
• - DE 2936039 A [0003]
• - US 4070323 [0006]
• - EP 0168173 A [0007]
• - EP 0154237 A [0007]
• - EP 0021824 A [0007]
• EP 0381862 A [0007, 0008]
• - DE 3437918 A [0008]
• EP 0287736 A [0008]
• EP 287736A [0010]
• - EP 381862 A [0011]
• WO 06/89935 [0013]
• EP 0126299A [0032]
• US 4596678 [0032]
• - EP 126300 A [0032]
• US 4596679 [0032]
• EP 355443A [0032]
• US 5087739 [0032]
• DE 10013186 A1 [0038]
• DE 10013187 A1 [0038]
• WO 03/035596 [0116]
• - DE 2725589 B [0118]
• - DB 2811148 B [0118]
• - US 4269748 A [0118]
• - US 4292226A [0118]
• DE 2732131 B [0118]
• - US 4192937 A [0118]
• - EP 704469 A2 [0121]
• - EP 7508 A [0133]
• EP 57474A [0133]
• - DE 19618720 A [0133]
• - EP 495751 A [0133]
• - EP 615980A [0133]
• - DE 19826712 A [0134]
• - DE 19913353 A [0134]
• WO 98/33761 [0134]
• - DE 19957900 A1 [0146]

Cited non-patent literature

• - Polymer Science USSR, Vol. 15, No. 4, May 1974, pages 814-822 [0007]
• - Journal of Applied Polymer Science, Vol. 84, 1818-1831 (2002) [0007]
• DA Wicks, ZW Wicks, Progress in Organic Coatings, 36, 148-172 (1999), 41, 1-83 (2001) and 43, 131-140 (2001) [0040]
• - DIN 53240 [0051]
• - Houben-Weyl, Methods of Organic Chemistry, 4th Edition, 1979, Thieme Verlag Stuttgart, Ed. Heinz Kropf, Volume 6 / 1a, Part 1, pages 373 to 385 [0052]
• - DIN 53240 [0069]
• - DIN EN ISO 3219 / A.3 [0083]
• - PKT Oldring (publisher), Chemistry & Technology of UV & EB Formulations for Coatings, Inks & Paints, Vol. II, Chapter III: Reactive Diluents for UV & EB Curable Formulations, Wiley and SITA Technology, London 1997 [0086]
• - G. Oertel (ed.), Polyurethane, 3rd edition 1993, Carl Hanser Verlag, Munich - Vienna, pages 104 to 110, chapter 3.4.1. "Catalysts" [0114]
• "Advances in Polymer Science", Volume 14, Springer Berlin 1974 [0132]
• KK Dietliker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3 [0132]
• Photoinitiators for Free Radical and Cationic Polymerization, PKT Oldring (Eds), SITA Technology Ltd, London [0132]

Claims (10)

Process for the preparation of urethane (meth) acrylates (A) by reacting the components (a) at least one isocyanate having at least 2 isocyanate functions, (b) at least one polyalkylene oxide polyether having at least 2 hydroxyl functions, (c) at least one hydroxyfunctional (meth) acrylate with exactly (d) at least one compound having at least one isocyanate-reactive group and at least one acid function, (e) optionally at least one compound having at least one isocyanate-reactive group and at least one basic group for a neutralization (f) optionally at least one monoalcohol having exactly one hydroxyl function, (g) optionally at least one di- or polyamine, wherein the preparation of the urethane (meth) acrylate (A) is optionally in the presence of at least one of the acid groups of component (d) Reactive diluent (B) and / or optionally in the presence of at least one Lösungsmitte ls can be carried out, characterized in that the components (a) to (f), the components (b), (c), (d) and, if present, (e) at least partially presents and to this mixture of the presented components the isocyanate (a) is added. Process according to claim 1, characterized characterized in that the isocyanate (a) is a (cyclo) aliphatic diisocyanate. Process according to one of the preceding claims, characterized in that component (b) is alkoxylated diols or polyols of the formula (Ia) to (Id),

wherein R ¹ and R ^{2 are} independently hydrogen or optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C ₁ -C ₁₈ alkyl, k, l, m, q independently of each other for an integer from 1 to 15, preferably 1 to 10 and more preferably 1 to 7 and each X for i = 1 to k, 1 to l, 1 to m and 1 to q may be independently selected from the group -CH ₂ -CH ₂ -O -, CH ₂ -CH (CH ₃ ) -O-, -CH (CH ₃ ) -CH ₂ -O-, -CH ₂ -C (CH ₃ ) ₂ -O-, -C (CH ₃ ) ₂ - CH ₂ -O-, -CH ₂ -CHVin-O-, -CHVin-CH ₂ -O-, -CH ₂ -CHPh-O- and -CHPh-CH ₂ -O-, preferably from the group -CH ₂ - CH ₂ -O-, -CH ₂ -CH (CH ₃ ) -O- and -CH (CH ₃ ) -CH ₂ -O-, and more preferably -CH ₂ -CH ₂ -O-, wherein Ph is phenyl and Vin stands for vinyl. Process according to one of Claims 1 or 2, characterized in that component (b) is a polyalkylene glycol of the formula HO - [- X _i -] _n -H in which X _i for each i = 1 to n can be independently selected from the group consisting of -CH ₂ -CH ₂ -O-, -CH ₂ -CH (CH ₃ ) -O- and -CH (CH ₃ ) -CH ₂ -O- and more preferably -CH ₂ -CH ₂ -O- may be, and n may be an integer from 5 to 60, preferably 7 to 50 and particularly preferably 10 to 45 may be. Method according to one of the preceding Claims, characterized in that component (c) is selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, Neopentyl glycol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, glycerol di (meth) acrylate, trimethylol propane di (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-hydroxyethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide and 3-hydroxypropyl (meth) acrylamide. Method according to one of the preceding Claims, characterized in that a component (d) is present, selected from the group consisting of mercaptoacetic acid (Thioglycolic acid), mercaptopropionic acid, mercaptosuccinic acid, Hydroxyacetic acid, hydroxypropionic acid (lactic acid), Hydroxysuccinic acid, hydroxypivalic acid, dimethylolpropionic acid, Dimethylol butyric acid, hydroxydecanoic acid, hydroxydodecanoic acid, 12-hydroxystearic acid, hydroxyethanesulfonic acid, Hydroxypropanesulfonic acid, mercaptoethanesulfonic acid, Mercaptopropanesulfonic acid, aminoethanesulfonic acid, Aminopropanesulfonic acid, glycine (aminoacetic acid), N-cyclohexylaminoethanesulfonic acid, N-cyclohexylaminopropanesulfonic acid and iminodiacetic acid. Method according to one of the preceding Claims, characterized in that the compound (e) is selected from the group consisting of diethanolamine, N-methyldiethanolamine and N-ethyldiethanolamine. Method according to one of the preceding Claims, characterized in that the composition of the urethane (meth) acrylate (A) is selected as follows: (A) 100 mol% isocyanate functions, (b) 25 to 75 mol% of hydroxy functions (based on isocyanate functions in (a)), preferably 40 to 60 mol%, (C) 25 to 75 mol% of hydroxy functions (based on isocyanate functions in (a)), preferably 30 to 50 mol%, (d) 0 to 15 mol% of hydroxy functions (based on isocyanate functions in (a)), preferably 0 to 8 mol%, (E) 0 to 5 mol% isocyanate-reactive groups (based on isocyanate functions in (a)), (f) 0 to 5 mol% of hydroxy functions (based on isocyanate functions in (a)), with the proviso that the sum of the hydroxy functions in the components (b), (c), (d), (e) and (f) 100 mol% of hydroxy functions (based on Isocyanate functions in (a)). Use of reaction mixtures available according to any one of the preceding claims in coating compositions for coating wood, wood-based materials, wood-containing substrates and cellulose fibers. Use of reaction mixtures available according to one of claims 1 to 8 in coating compositions for priming parquet.