DE102007045944A1 - Production of urethane acrylates, useful as e.g. main component in radiation-hardenable coating materials, comprises reacting a carbonyl hydrogenated ketone-aldehyde resin with di- or polyisocyanate in presence of tin-free catalyst - Google Patents

Abstract

Procedure for the solvent-free, continuous production of tin-free, radiation-hardenable urethane acrylates with less molecular weight distribution, comprises intensively mixing (A) at least a carbonyl hydrogenated ketone-aldehyde resin, hydrogenated ketone resin and/or carbonyl hydrogenated and core hydrogenated ketone-aldehyde resin on the basis of aromatic ketones, with (B) at least an aromatic, aliphatic and/or cyclo-aliphatic di- or polyisocyanate that comprises at least an ethylenically unsaturated grouping, in the presence of tin-free catalysts and in the absence of an organic solvent. Procedure for the solvent-free, continuous production of tin-free, radiation-hardenable urethane acrylates with less molecular weight distribution, comprises intensively mixing (A) at least a carbonyl hydrogenated ketone-aldehyde resin and/or hydrogenated ketone resin and/or carbonyl hydrogenated and core hydrogenated ketone-aldehyde resin on the basis of aromatic ketones, with (B) at least an aromatic, aliphatic and/or cyclo-aliphatic di- or polyisocyanate that comprises at least an ethylenically unsaturated grouping, in the presence of tin-free catalysts and in the absence of an organic solvent, in an extruder, a flow pipe, an intensive kneader, an intensive mixer or a static mixer and temporarily reacting with heat supply; and isolating the end products. Independent claims are included for: (1) a solvent-free, tin-free, radiation-hardenable urethane acrylates with less molecular weight distribution and with a number average molar mass of 500-10000 g/mole and a weight average molar mass of 1000-20000 g/mole, obtained by the above method; and (2) articles produced under the use of the solvent-free, tin-free, radiation-hardenable urethane acrylates.

Description

The The invention relates to a method for solvent-free, continuous production of tin-free, radiation-curable Urethanacrylaten based on carbonyl-hydrogenated ketone-Aldehydharen and / or hydrogenated ketone resins and / or carbonyl-hydrogenated and nuclear-hydrogenated ketone-aldehyde resins based on aromatic ketones, in an extruder, flow tube, intensive kneader, intensive mixer or static mixers and their use, in particular as the main component, Basic component or additional component in radiation-curable Coating materials, adhesives, printing inks and inks, pigment pastes, Fillers, cosmetics and sealants and insulating materials.

Radiation-curable Coating materials have been increasing in recent years gained importance because u. a. the content of volatile organic compounds (VOC) of these systems is low.

The Film-forming components are relatively low molecular weight in the coating material and therefore low-viscosity, so that high levels of organic Solvent can be dispensed with. Durable coatings are obtained by applying the coating material a high molecular weight, polymeric network by z. B. UV light initiated Crosslinking reactions is formed.

Ketone-aldehyde be in coating materials z. B. used as additive resins, to certain properties such as drying speed, shine, To improve hardness or scratch resistance. Because of their relative low molecular weight have conventional ketone-aldehyde resins a low melt and solution viscosity and therefore serve in coating materials u. a. as film-forming functional fillers.

Usually ketone-aldehyde resins have hydroxy groups and can therefore only with z. As polyisocyanates or amine resins be networked. These crosslinking reactions usually become thermally initiated or accelerated.

For radiation-initiated crosslinking reactions after cationic and / or radical reaction mechanisms are not the ketone-aldehyde resins suitable because they do not carry groups that crosslink radiation-initiated can. Typical examples of such radiation initiated crosslinkable groups are unsaturated groups (radical Crosslinking) or epoxy groups or vinyl ether groups (cationic Networking).

Therefore The ketone-aldehyde resins are usually in radiation-curable Coating material systems z. B. as a film-forming, but not crosslinking additive component used. Have such coatings often because of the uncrosslinked parts a low resistance opposite z. As gasoline, chemicals or solvents.

DE 23 45 624 . EP 736 074 . DE 28 47 796 . DD 24 0318 . DE 24 38 724 . JP 09143396 describe the use of ketone-aldehyde and ketone resins, e.g. B. cyclohexanone-formaldehyde resins in radiation-curable systems. Radiation-induced crosslinking reactions of these resins are not described.

EP 0 902 065 describes the use of non-radiation-curable resins of urea (derivatives), ketone or aldehydes as an additional component in admixture with radiation-curable resins.

DE 24 38 712 describes radiation-curing inks from film-forming resins, ketone and ketone-formaldehyde resins and polymerizable components such as polyfunctional acrylate esters of polyhydric alcohols. It will be apparent to those skilled in the art that a radiation-induced crosslinking reaction of the modified ketone-aldehyde and ketone resins can only occur through the use of unsaturated fatty acids. However, it is known that resins with a high oil content tend to undesirable yellowing.

US 4,070,500 describes the use of nonradiation curable ketone-formaldehyde resins as a film-forming component in radiation-curable inks.

The conversion of the carbonyl groups into secondary alcohols by hydrogenation of ketone-aldehyde resins has been practiced for a long time ( DE-PS 8 70 022 . DE 32 41 735 ). A typical and well-known product is synthetic resin SK from Degussa AG. Also known are phenolic resin-based resins whose aromatic moieties have been converted to cycloaliphatic groups by hydrogenation to retain some of the hydroxy groups. The use of carbonyl- and ring-hydrogenated ketone-aldehyde resins based on ketones containing aromatic groups is also possible. Such a resin is in DE 33 34 631 described. The OH number of such products is very high at over 200 mg KOH / g.

• A) mindestens ein carbonylhydriertes Keton-Aldehydharz und/oder
• B) mindestens ein kernhydriertes Phenol-Aldehydharz und
• C) mindestens eine Verbindung, welche mindestens eine ethylenisch ungesättigte Gruppierung mit gleichzeitig mindestens einer gegenüber A) und/oder B) reaktive Gruppierung aufweist,

wobei
die Herstellung der Harze in der Schmelze oder in Lösung eines geeigneten, organischen Lösemittels des carbonylhydrierten Keton-Aldehydharzes und/oder kernhydrierten Phenol-Aldehydharzes erfolgen kann. DE 10338560 ( EP 1 508 582 / US 7,199,166 ) and DE 10 2004 005 208 ( EP 1 711 567 / US 2007/0123661 ) describe preparation and use of radiation-curable resins, essentially containing

• A) at least one carbonyl-hydrogenated ketone-aldehyde resin and / or
• B) at least one nuclear hydrogenated phenol-aldehyde resin and
• C) at least one compound which has at least one ethylenically unsaturated grouping with simultaneously at least one A and / or B reactive grouping,

in which
the preparation of the resins in the melt or in solution of a suitable organic solvent of the carbonyl-hydrogenated ketone-aldehyde resin and / or ring-hydrogenated phenol-aldehyde resin can be carried out.

As the examples show there, the synthesis is discontinuous in carried out organic solvents. The organic ones Solvents are separated after completion of the reaction. The If appropriate, preparation can also be carried out in a reactive diluent be performed. The resins thus obtained can only be used in formulations where this reactive diluent is used.

One Solution, the hydrogenated ketone-aldehyde resins continuously in the melt to tin-free products, is not shown. As a comparative example in the present invention shows is the discontinuous, solvent-free production not possible. The reason is that due to the high melting point of the resins used there (component A) and B)) set a high temperature of over 140 ° C. It is necessary to have a sufficiently low viscosity that required for stirring in the batch reactor is to receive. Since the reaction of components A) and B) with C) take place discontinuously over a long period of time must, react the unsaturated groups of the component C) by thermally induced polymerization, so that insoluble Gel particles are formed.

In the examples given there is dibutyltin dilaurate used as a catalyst. However, the industry is stopped, these tin-containing catalysts from ecological and toxicological Reasons to substitute.

task It was the object of the present invention to provide a process for the solvent-free, continuous production of tin-free, radiation-curable Urethane acrylates based on carbonyl-hydrogenated ketone-aldehyde resins and / or hydrogenated ketone resins and / or carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resins based on aromatic ketones to find out what the hardness, the gloss, the solvent and chemical resistance and adhesion to metals, Plastics, wood, paper, glass and mineral substrates of coating material systems and adhesives. The products should have a good thermal resistance. The Products must be solvent-free, so that the coating material formulation the choice of which (reactive) solvent he has in uses its radiation-curable coating material. By The solvent-free products should make it possible be, instead of many products in different (reactive) solvents are solved, a product available to the market which can limit the product portfolio, what for cost and capacity reasons (warehousing, Reactor assignment times, registration and maintenance (EHSQ) of the products) important is.

The Products should have a low molecular weight distribution, so that their solution viscosity is low.

surprisingly Way, this task could be solved by a solvent-free and continuous process for producing tin-free, radiation-curable Urethane acrylates based on carbonyl-hydrogenated ketone resins, and / or Ketone-aldehyde resins, and / or hydrogenated ketone-aldehyde resins Base of aromatic ketones (aryl alkyl ketones), and isocyanates, which at least one ethylenically unsaturated group contained in special aggregates.

• A) mindestens einem carbonylhydrierten Keton-Aldehydharz und/oder hydrierten Ketonharz und/oder carbonylhydrierten und kernhydrierten Keton-Aldehydharz auf Basis von aromatischen Ketonen mit
• B) mindestens einem aromatischen, aliphatischen und/oder cycloaliphatischen Di- oder Polyisocyanat, dass zusätzlich zu der/den Isocyanatgruppe(n) über mindestens eine ethylenisch ungesättigte Gruppierung verfügt,

dadurch gekennzeichnet,
dass das Produkt aus A) und B) erhalten wird durch Reaktion der Ausgangskomponenten in Gegenwart zinnfreier Katalysatoren in Abwesenheit eines organischen Lösemittels in einem Extruder, Strömungsrohr, Intensiv-Kneter, Intensiv-Mischer oder statischen Mischer durch intensive Durchmischung und kurzzeitiger Reaktion bei Wärmezufuhr und nachfolgender Isolierung des Endproduktes, gegebenenfalls nachgeschalteter, kontinuierlicher Nachreaktion, bei der gegebenenfalls ein oder mehrere niedermolekulare Alkohole zur Vervollständigung der Reaktion als Quenchalkohole eingesetzt werden und gegebenenfalls nachfolgender Isolierung des Endproduktes durch Abkühlung und gegebenenfalls Lösung in einem geeigneten Lösemittel.The invention relates to a process for the solvent-free, continuous production of tin-free, radiation-curable urethane acrylates with a low molecular weight distribution,
essentially containing
the radiation-curable reaction product of

• A) at least one carbonyl-hydrogenated ketone-aldehyde resin and / or hydrogenated ketone resin and / or carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resin based on aromatic ketones
• B) at least one aromatic, aliphatic and / or cycloaliphatic di- or polyisocyanate, in addition to the isocyanate group (s) has at least one ethylenically unsaturated group,

characterized,
that the product of A) and B) is obtained by reacting the starting components in the presence of tin-free catalysts in the absence of an organic solvent in an extruder, flow tube, intensive kneader, intensive mixer or static mixer by intensive mixing and brief reaction with heat and subsequent Isolation of the end product, optionally downstream, continuous reaction, in which optionally one or more low molecular weight alcohols are used to complete the reaction as quench alcohols and optionally subsequent isolation of the final product by cooling and optionally solution in a suitable solvent.

The Principle of the preparation of the erfindungszugriefeliegenden resins from the components A) and B) and the tin-free catalysts in that the conversion of the starting products continuously in one Single or multi-screw extruder, in particular twin-screw extruder, Planetary roller extruder or ring extruder, flow tube, Intensive Kneader, Intensive Mixer or Static Mixer intensive mixing and short-term reaction with heat he follows.

It can reach temperatures of 50 to 325 ° C in the process be applied, the temperature being as the examples show varies depending on the product.

intensive Mixing and short-term reaction with heat means that the residence time of the starting materials in the above Aggregates usually 3 seconds to 15 minutes, preferably 3 seconds to 5 minutes, more preferably 5 to 180 seconds is. The reactants are thereby in the aggregates briefly with heat at temperatures of 50 ° C to 325 ° C, preferably from 120 to 300 ° C, very particularly preferably from 140 to 250 ° C reacted. Depending on Type of starting materials and end products can this Values for residence time and temperature, but others occupy preferred areas.

Possibly is followed by a continuous post-reaction. By subsequent rapid cooling then manages to obtain the final product.

When Aggregates are extruders such as single or multiple screw extruders, in particular Twin-screw extruder, planetary roller extruder or ring extruder, flow tube, Intensive kneader, intensive mixer such as thorax mixer, or static Mixer for the process according to the invention particularly suitable and are preferably used. Especially preferred are single or multiple screw extruder, especially a twin-screw extruder.

The Starting compounds are usually separated into the aggregates Added product streams. For more than two product streams These can also be bundled become. Various hydroxyl-containing starting materials (component A) can be combined into one product stream. It is also possible, this product stream in addition Catalysts and / or additives such as leveling agents and / or Add stabilizers. Likewise, component B) with catalysts and / or additives such as leveling agents and / or Stabilizers are summarized in a product stream. The Material flows can also be shared and so on supplied in different proportions at different locations the aggregates become. In this way, concentration gradients are targeted adjusted, which brings about the completeness of the reaction. The entry point of the product streams in the order can be handled variably and with a time lag. here we can also low molecular weight alcohols for secondary reaction (quench alcohols), be used as a separate stream. That way you can optionally still present isocyanate groups completely be implemented. As quench alcohols, all known Mono- and / or diols are added, preferably benzyl alcohol, Methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, Hexanol, isohexanol, ethylhexanol, trimethylcyclohexanol, methoxypropanol and / or ethylene glycol. It can also mixtures of different Alcohols are added.

by virtue of the disadvantage of a lower thermal stability less preferably, amines such as. B. all known mono- and / or diamines are added, such as. B. benzylamine and / or Isophoronediamine.

to Pre-reaction and / or completion of the reaction can several aggregates can also be combined. Also a melt filtration can be done if necessary.

The the reaction downstream cooling of the homogeneous stream, may be integrated in the reaction part, in the form of a multi-body Embodiment as with extruders or Conterna machines. used can also be tube bundles, pipe coils (stirred or unmoved), chill rolls, Air conveyors, conveyor belts of metal and water baths, with and without downstream granulator.

It it is also possible to dissolve the melt directly in an organic solvent. in the Generally, all in the literature for radiation-curable Paints as suitable solvents mentioned, preferably radiation-curable Reaktivverdünner be used, preferably mono-, di- or poly-acrylate functional compounds such. B. dipropylene glycol diacrylate (DPGDA) and / or tripropylene glycol diacrylate (TPGDA), hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA) and / or their alkoxylated derivatives as well as vinyl ethers.

to Packaging is the product, depending on the viscosity of the product leaving the aggregate or the post-reaction zone, first by further cooling by means of appropriate the aforementioned equipment to a suitable temperature brought. Then the pastillation or a comminution takes place in a desired particle size means Roll crusher, pin mill, classifier mill, hammer mill, Shingling rolls, strand granulator (eg in combination with a water bath), other granulators or similar.

It it is also possible to dissolve the melt directly as described above.

Surprised it was that implementation, in the discontinuous process difficult due to the thermal instability of component B) is possible to expire quickly and completely in said aggregates. In addition, the product falls in solid form on, and can after cooling a further work-up (For example, grinding or breaking) or directly to a storage (Silo) or packaging (bagging) are supplied. Of a fundamental nature is the fact that the short-term chemical reaction between the reactants in interaction with the mixing effect of Aggregates, and the temperature profile of the aggregates, sufficient to reacting the reactants completely or largely, without that there is a gagging or caking. The aggregates allow by suitable equipping of the mixing chambers or composition of the screw geometries intensive rapid mixing at the same time intensive heat exchange. on the other hand is also a uniform flow in the longitudinal direction with as uniform a residence time guaranteed. It also needs a different Temperature control in the individual device housings or sections are possible.

in the Start-up and shutdown process of the system used and in case of unwanted Fluctuations in the recipe, for example due to technical inadequacies, it may lead to the formation of higher molecular weight by-products, which can contaminate the melt stream.

Around It is possible to remove these products Reaction downstream of a melt filtration. Here are all suitable filter concepts. Preference is given to systems which allow a filter change during operation, such as Screen changers and rotary filter systems. The sieves used must be adapted to the nature of the substances to be separated (eg special sieves for gel particles).

Preferred embodiment

In a twin-screw extruder DSE 25, length 30 d, becomes the melt of component A) component B), in the presence a suitable catalyst. This is the component A) melted and either by means of a separate melt extruder, or dosed from a melt master into the reaction extruder.

Depending on the reactivity of component B) and the melt viscosity of component A), the temperature of the reaction is selected. Temperatures between 120 and 300 ° C, preferably between 140 and 250 ° C have proven. It has proved to be advantageous, 1 mol of component A) - based on M _n - with 0.25 to 15 mol, preferably 0.5 to 10 mol, especially 1 to 6 mol of the unsaturated compound (component B) for the reaction bring. To complete the reaction, an alcohol may optionally be added.

The tin-free urethane acrylates according to the invention are resistant to hydrolysis and are resistant to chemicals and have a high yellowing resistance. The reaction products produce in coatings or adhesives a high gloss, good hardness and adhesion to different substrates such. As metals, plastics such. Polyethylene, polypropylene or polycarbonate, wood, Pa Pier, glass and mineral substrates with high hardness.

• A) mindestens einem carbonylhydrierten Keton-Aldehydharz und/oder hydrierten Ketonharz und/oder carbonylhydrierten und kernhydrierten Keton-Aldehydharz auf Basis von aromatischen Ketonen mit
• B) mindestens einem aromatischen, aliphatischen und/oder cycloaliphatischen Di- oder Polyisocyanat, dass zusätzlich zu der/den Isocyanatgruppe(n) über mindestens eine ethylenisch ungesättigte Gruppierung verfügt,

dadurch gekennzeichnet,
dass das Produkt aus A) und B) erhalten wird durch Reaktion der Ausgangskomponenten in Gegenwart zinnfreier Katalysatoren in Abwesenheit eines organischen Lösemittels in einem Extruder, Strömungsrohr, Intensiv-Kneter, Intensiv-Mischer oder statischen Mischer durch intensive Durchmischung und kurzzeitiger Reaktion bei Wärmezufuhr und nachfolgender Isolierung des Endproduktes, gegebenenfalls nachgeschalteter, kontinuierlicher Nachreaktion, bei der gegebenenfalls ein oder mehrere niedermolekulare Alkohole zur Vervollständigung der Reaktion als Quenchalkohole eingesetzt werden,
und gegebenenfalls nachfolgender Isolierung des Endproduktes durch Abkühlung und gegebenenfalls Lösung in einem geeigneten Lösemittel.The invention relates to solvent-free, tin-free, radiation-curable urethane acrylates with a low molecular weight distribution and having an Mn of from 500 to 10,000 g / mol and a Mw of from 1,000 to 20,000 g / mol,
essentially containing
the radiation-curable reaction product of

• A) at least one carbonyl-hydrogenated ketone-aldehyde resin and / or hydrogenated ketone resin and / or carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resin based on aromatic ketones
• B) at least one aromatic, aliphatic and / or cycloaliphatic di- or polyisocyanate which has at least one ethylenically unsaturated grouping in addition to the isocyanate group (s),

characterized,
that the product of A) and B) is obtained by reacting the starting components in the presence of tin-free catalysts in the absence of an organic solvent in an extruder, flow tube, intensive kneader, intensive mixer or static mixer by intensive mixing and brief reaction with heat and subsequent Isolation of the end product, optionally downstream, continuous post-reaction, in which optionally one or more low molecular weight alcohols are used to complete the reaction as quench alcohols,
and optionally subsequent isolation of the final product by cooling and, if appropriate, solution in a suitable solvent.

• A) mindestens einem carbonylhydrierten Keton-Aldehydharz und/oder hydrierten Ketonharz und/oder carbonylhydrierten und kernhydrierten Keton-Aldehydharz auf Basis von aromatischen Ketonen mit
• B) mindestens einem aromatischen, aliphatischen und/oder cycloaliphatischen Di- oder Polyisocyanat, dass zusätzlich zu der/den Isocyanatgruppe(n) über mindestens eine ethylenisch ungesättigte Gruppierung verfügt,

als Hauptkomponente, Basiskomponente oder Zusatzkomponente in strahlungshärtbaren Beschichtungsstoffen, Klebstoffen, Druckfarben und Tinten, Polituren, Lasuren, Pigmentpasten, Spachtelmassen, Kosmetikartikeln und/oder Dicht- und Dämmstoffen, insbesondere zur Verbesserung von Haftungseigenschaften, Glanz, Lösemittel- und Chemikalienbeständigkeit sowie der Härte.The invention also provides the use of the solvent-free, tin-free, radiation-curable urethane acrylates according to the invention, with a low molecular weight distribution and an Mn of 500 to 10,000 g / mol and a Mw of 1000 to 20,000 g / mol,
essentially containing
the radiation-curable reaction product of

• A) at least one carbonyl-hydrogenated ketone-aldehyde resin and / or hydrogenated ketone resin and / or carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resin based on aromatic ketones
• B) at least one aromatic, aliphatic and / or cycloaliphatic di- or polyisocyanate which has at least one ethylenically unsaturated grouping in addition to the isocyanate group (s),

as the main component, base component or additional component in radiation-curable coating materials, adhesives, printing inks and inks, polishes, glazes, pigment pastes, fillers, cosmetic articles and / or sealing and insulating materials, in particular for improving adhesion properties, gloss, solvent and chemical resistance and hardness.

When Ketones for the preparation of hydrogenated ketone and carbonyl hydrogenated Ketone-aldehyde resins (component A) are all ketones, in particular Acetone, acetophenone, nuclear substituted acetophenone derivatives, such as Hydroxy, methyl, ethyl, tert-butyl, cyclohexyl-acetophenone, 4-tert-butyl methyl ketone, methyl ethyl ketone, heptanone-2, pentanone-3, Methyl isobutyl ketone, propiophenone, methyl naphthyl ketone, cyclopentanone, Cyclododecanone, mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanone, Cycloheptanone and cyclooctanone, cyclohexanone and all alkyl-substituted ones Cyclohexanones having one or more alkyl radicals, in total Have 1 to 8 hydrocarbon atoms, individually or in mixture. As examples of alkyl-substituted cyclohexanones can 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone to be named.

in the Generally, however, all in the literature for Ketone and ketone-aldehyde resin syntheses as suitable called ketones, usually all C-H-acidic ketones are used.

Prefers are hydrogenated ketone resins based on the ketones 4-tert-butyl methyl ketone, Cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone alone or mixed, but not based on Acetophenone.

Preference is given to carbonyl-hydrogenated ketone-aldehyde resins based on the ketones acetophenone, 4-tert-butyl methyl ketone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and hepta not alone or in mixture.

When Aldehyde component of the carbonyl-hydrogenated ketone-aldehyde resins (component A)) are in principle unsubstituted or branched aldehydes, such as As formaldehyde, acetaldehyde, n-butyraldehyde and / or iso-butyraldehyde, Valeric aldehyde and dodecanal. In general, you can all in the literature for ketone-aldehyde resin syntheses as suitable mentioned aldehydes are used. However, preferred is formaldehyde used alone or in mixtures.

The required formaldehyde is usually used as approx. From 20 to 40% by weight aqueous or alcoholic (eg methanol or butanol) solution. Other uses of the Formaldehyde such. B. also the use of para-formaldehyde or trioxane are also possible. Aromatic aldehydes, such as As benzaldehyde, may in mixture with formaldehyde Also included.

It also non-hydrogenated ketone-aldehyde resins can be used be, but then lower light fastness and thermal stabilities have.

The Resins of ketone or of ketone and aldehyde are in the presence of a Catalyst with hydrogen at pressures of up to 300 hydrogenated bar. The carbonyl group of the ketone resin or Ketone-aldehyde resin converted into a secondary hydroxy group. Depending on the reaction conditions, a part of the hydroxy groups can be split off so that methylene groups result. Other groupings like z. B. optionally present double bonds can be on also hydrogenate this way.

To illustrate, the following scheme is used:

When Ketones for the preparation of the carbonyl- and ring-hydrogenated ketone-aldehyde resins based on aromatic ketones (component A)) are all suitable Ketones, in addition to C-H-acidic protons via aromatic Have groups, in particular arylalkyl ketones such as z. As methyl naphthyl ketone, acetophenone and / or its derivatives such as B. nuclear substituted acetophenone derivatives such as hydroxy, methyl, Ethyl, tert-butyl, cyclohexyl-acetophenone. As aldehydes, are the ones described above are suitable.

By the choice of the hydrogenation conditions, in addition to the carbonyl groups and aromatic structures, the hydroxyl groups formed from the carbonyl groups by hydrogenation can be hydrogenated so that cycloaliphatic structural elements are formed without further functionality. The following figure is for illustration. The proportion of aromatic groups in the carbonyl- and ring-hydrogenated ketone-aldehyde resins (component A)) is less than 50% by weight, preferably less than 30% by weight, particularly preferably less than 10% by weight. One method is in DE 33 34 631 described.

• • der Gehalt an freiem Formaldehyd unter 3 ppm, bevorzugt unter 2,5 ppm, besonders bevorzugt unter 2,0 ppm liegt,
• • die Carbonylzahl zwischen 0 und 100 mg KOH/g, bevorzugt zwischen 0 und 50 mg KOH/g, besonders bevorzugt zwischen 0 und 25 mg KOH/g liegt,
• • die Hydroxylzahl zwischen 50 und 450 mg KOH/g, bevorzugt zwischen 100 und 400 mg KOH/g, besonders bevorzugt zwischen 150 und 375 mg KOH/g liegt,
• • die Farbzahl nach Gardner (50% in Ethylacetat) unter 1,5, bevorzugt unter 1,0, besonders bevorzugt unter 0,75 liegt,
• • die Farbzahl nach Gardner (50% in Ethylacetat) nach thermischer Belastung des Harzes (24 h, 150°C) unter 2,0, bevorzugt unter 1,5, besonders bevorzugt unter 1,0 liegt,
• • die Polydispersität (Mw/Mn) der Harze zwischen 1,35 und 1,6, besonders bevorzugt zwischen 1,4 und 1,58 liegt,
• • die Lösungsviskosität, 40%ig in Phenoxyethanol, zwischen 5000 und 12000 mPa·s, besonders bevorzugt zwischen 6000 und 10000 mPa·s liegt,
• • der Schmelzpunkt/-bereich zwischen 50 und 150°C, bevorzugt zwischen 75 und 140°C, besonders bevorzugt zwischen 100 und 130°C liegt und
• • der Gehalt an nicht flüchtigen Bestandteilen nach Temperung über 24 h bei 150°C über 97,0%, bevorzugt über 97,5% liegt.

The resins of component A are characterized in that

• The content of free formaldehyde is below 3 ppm, preferably below 2.5 ppm, particularly preferably below 2.0 ppm,
• The carbonyl number is between 0 and 100 mg KOH / g, preferably between 0 and 50 mg KOH / g, more preferably between 0 and 25 mg KOH / g,
• The hydroxyl number is between 50 and 450 mg KOH / g, preferably between 100 and 400 mg KOH / g, more preferably between 150 and 375 mg KOH / g,
• The Gardner color number (50% in ethyl acetate) is less than 1.5, preferably less than 1.0, more preferably less than 0.75,
• The Gardner color number (50% in ethyl acetate) after thermal loading of the resin (24 h, 150 ° C.) is below 2.0, preferably below 1.5, particularly preferably below 1.0,
• The polydispersity (Mw / Mn) of the resins is between 1.35 and 1.6, more preferably between 1.4 and 1.58,
• The solution viscosity, 40% in phenoxyethanol, is between 5000 and 12000 mPa.s, more preferably between 6000 and 10000 mPa.s,
• The melting point / range is between 50 and 150 ° C, preferably between 75 and 140 ° C, more preferably between 100 and 130 ° C, and
• • The content of non-volatile constituents after tempering for 24 h at 150 ° C over 97.0%, preferably above 97.5%.

As component B) are suitable aromatic, aliphatic and / or cycloaliphatic di- or polyisocyanate, which in addition to the / the isocyanate group (s) have at least one ethylenically unsaturated group, such as. B. (meth) acryloyl isocyanate, α, α-dimethyl-3-isopropenylbenzylisocyanat, (meth) acrylic alkyl isocyanate with alkyl spacers having one to 12, preferably 2 to 8, more preferably 2 to 6 carbon atoms, such as. B. or preferably methacrylethyl isocyanate, methacrylic acid isocyanate. In addition, reaction products of hydroxyalkyl (meth) acrylates whose alkyl spacers have one to 12, preferably 2 to 8, particularly preferably 2 to 6 carbon atoms, and diisocyanates and / or polyisocyanates such. For example, cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, phenylene diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, toluene diisocyanate, bis (isocyanatophenyl) methane, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate such as hexamethylene diisocyanate (HDI) or 1,5-diisocyanato-2-methylpentane (MPDI), heptane diisocyanate , Octane diisocyanate, nonane diisocyanate, such as 1,6-diisocyanato-2,4,4-trimethylhexane or 1,6-diisocyanato-2,2,4-trimethylhexane (TMDI), nonane triisocyanate, such as 4-isocyanatomethyl-1,8-octane diisocyanate ( TIN), decane diisocyanate and triisocyanate, undecanediisocyanate and triisocyanate, dodecandi- and triisocyanates, isophorone diisocyanate (IPDI), 2,2'- and 2,4'- and 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI) alone or in mixtures, preferably the H ₁₂ MDI consists of at least 80% by weight of the 4,4'-H ₁₂ MDI, preferably from 85 to 95% by weight, 2.5 (2.6) -bis (isocyanato) methyl) bicyclo [2.2.1] heptane (NBDI), 1,3-bis (isocyanatomethyl) cyclohexa n (1,3-H ₆ -XDI) or 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ -XDI), alone or in admixture. Preference is given to H ₁₂ MDI, IPDI, HDI, TMDI, very particularly preferably H ₁₂ MDI, IPDI and TMDI.

Another preferred class of diisocyanates and / or polyisocyanates for the preparation of component B) are the compounds prepared by dimerization, trimerization, allophanatization, biuretization and / or urethanization of simple diisocyanates having more than two isocyanate groups per molecule, for example the reaction products of these simple diisocyanates, such as As IPDI, TMDI, HDI and / or H ₁₂ MDI with polyhydric alcohols (eg, glycerol, trimethylolpropane, pentaerythritol) or polyhydric polyamines. Also preferred are the isocyanurates obtainable by trimerization of the simple diisocyanates such as IPDI, HDI and H ₁₂ MDI. Very particular preference is given to isocyanurates of IPDI and / or reaction products of IPDI, TMDI, HDI and / or H ₁₂ MDI with trimethylolpropane and / or pentaerythritol.

To accelerate the reaction for the preparation of the resins from A) and B), a tin-free catalyst is used. In principle, all tin-free compounds are suitable, which accelerate an OH-NCO reaction. A list can be found in EP 1801141 A1 [0042-0045].

catalysts based on the metals ibisut, zinc, zirconium, iron or aluminum are particularly suitable, such. For example, oxides, carboxylates, chelates and complexes. Preference is given to organometallic compounds of the metals Ice nut, zinc and / or aluminum.

The same applies to purely organic catalysts such. B. tert. Amines, for example, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), N, N-dimethylcyclohexylamine (DMCA) or 1,5-diazabicyclo [2.3.0] non-5-ene (THE). Preference is given to DABCO, DBU and / or DEN.

Surprisingly, it has been found that catalysts containing ibis and / or zinc, the reaction accelerate especially without further properties such. B. rheological behavior compared to products prepared tin-catalyzed be changed. The catalysts ver usually remain in the reaction product after completion of the reaction and can optionally be stabilized in a suitable manner. Stabilization by means of mono- or dicarboxylic acids has proved to be particularly effective. However, it is also possible to use all the compounds mentioned as suitable in the literature for the stabilization of metals. If desired, the catalysts can be separated, z. B. succeeds by the addition and subsequent separation of Tinex the company Goldschmidt TIB.

The Quantities of A) and B) are chosen so that 1 mol of the Component A) - based on Mn - and 0.25 to 15 mol, preferably 0.5 to 10 mol, especially 1 to 6 mol of the unsaturated Compound (component B) can be used.

Of the Melting range of the tin-free prepared reaction product A) and B) is between 70 and 150 ° C, preferably between 80 and 130 ° C, more preferably between 80 and 120 ° C.

Polymers usually do not have an exact molecular weight but a molecular weight distribution (dimer, trimer, tetramer, etc.). The breadth of the distribution is described by the polydispersity, which is the ratio of weight average (Mw) and number average molecular weight (Mn) [ Odian, George, Principles of Polymerization, Third Edition, John Wiley & Sons, New York, 1991, page 86 ,]. For a given Mn, the higher the polydispersity (broad distribution), the higher the viscosity of a polymer. This can be explained by the fact that high molecular weight fractions of a polymer have a significantly higher influence on the viscosity than low molecular weight fractions.

The number average molecular weight (Mn) of the products according to the invention is between 500 and 10,000, preferably between 600 and 5000 g / mol, more preferably between 1000 and 4000 g / mol and the weight average molecular weight (Mw) between 1000 and 20,000, preferably between 1000 and 10,000 g / mol, more preferably between 1500 and 8000 g / mol. The polydispersity of the molecular weight distribution of the products of the invention is between 1.5 and 15, preferably between 1.5 and 10, more preferably between 1.5 and 6.0, so that the products have a low solution viscosity measured at 23 ° C according to the DIN EN ISO 3219 , as a 40% solution in TPGDA between 30 and 15,000 mPa · s, preferably between 100 and 10,000, more preferably between 200 and 8,000 mPa · s have.

The Products according to the invention are in solvents soluble in the paint, paints, adhesives and printing inks industry be used, such as. As alcohols, acetates, ketones, ethers, glycol ethers, Aliphatic, aromatic, alone or in mixture. It can preferably the above-mentioned reactive diluents are used.

object The invention also provides articles made using the solvent-free, tin-free, radiation-curable Urethane acrylates with a low molecular weight distribution with a Mn of 500 to 10,000 g / mol and Mw of 1000 to 20000 g / mol, based on carbonyl-hydrogenated ketone and ketone-aldehyde resins and hydrogenated ketone-aldehyde resins based on aromatic Ketones (acrylic alkyl ketones) and isocyanates after at least one the previous claims.

Analytical methods

Determination of the melting range

The determination is carried out with a Kapillarschmelzpunkt-meter (Büchi B-545) based on the DIN 53181 ,

Determination of isocyanate content (NCO number)

The determination of the isocyanate content was based on the DIN EN ISO 11909 ,

Determination of color number according to Gardner and after thermal stress

The Gardner color number is determined in 50% strength solution of the resin in ethyl acetate in accordance with DIN EN ISO 4630 ,

Also in this way the color number is determined after thermal stress (thermal yellowing). For this purpose, the resin is first stored for 48 h at 80 ° C in an air atmosphere. The Gardner color number is then determined in 50% strength solution of the thermally loaded resin in ethyl acetate in accordance with DIN EN ISO 4630 ,

Determination of turbidity

The determination of the turbidity is carried out in 50% solution of the resin in ethyl acetate on the basis of DIN EN ISO 7027 at a wavelength of 860 nm.

Determination of the solution viscosity

The determination of the solution viscosity takes place after DIN EN ISO 3219 , The solid resin is dissolved in TPGDA, with a resin content of 40%. The viscosity is measured at 23 ° C using a plate / cone rotation viscometer (1/40 s).

Determination of molecular weight and polydispersity

The Measurement of the molecular weight distribution of the invention Resins are made by gel permeation chromatography in tetrahydrofuran against polystyrene as standard. The polydispersity D is calculated from the ratio of weight average (Mw) to number average (Mn).

Determination of liability

The Determination of the adhesion of the coatings was evaluated by a knife scratch adhesion test. For this purpose, a paint is applied to the respective substrate and cured. With a knife is scratched over the film and adhesion assessed. A value of 0 indicates a very good adhesion Value of 10 indicates insufficient liability.

Determination of gloss level

The determination was made according to DIN EN ISO 2813 at 60 °.

Determination of hardness

The hardness was determined by means of pendulum damping ( DIN EN ISO 1522 ).

MEK test

Around to judge if the crosslink density is sufficiently high the MEK test was used. This is a cotton ball with a Solvent soaked and with a 1 kg hammer on the film surface to and fro. The number of Double strokes are counted. Checked after every double stroke, whether the film surface swelled or dissolved is or whether the film peels off the ground. Is the Coating not damaged after 150 double strokes, is the resistance to the solvent good enough.

The The following examples are intended to further illustrate the invention made but do not limit their scope:

Non-inventive example (according to DE 10338560 in the absence of the solvent)

1 mol of a carbonyl-hydrogenated resin (based on Mn), that according to Example 1 of the invention DE 10 2006 009 079.9 was prepared were melted in a glass flask at a temperature of 150 ° C with stirring in a nitrogen atmosphere. Then, 0.1% of dibutyltin dilaurate as a catalyst and 0.2% (on resin) of 2,6-bis (tert-butyl) -4-methylphenol as a stabilizer were added to the total amount and homogenized. The addition of 1.5 mol of a reaction product of IPDI (Vestanat IPDI, Degussa) and hydroxyethyl acrylate (HEA, Degussa) was carried out in a ratio of 1: 1 over a period of 10 min. The temperature had to be increased to 180 ° C after about 10 minutes after the end of addition of the IPDI-HEA adduct because of the increasing viscosity. After a further 45 minutes, an NCO number of less than 0.1 was reached.
GPC: Mn = 1730 g / mol, Mw = 86100 g / mol, polydispersity = 49.8 (outside the calibrated range)

An attempt was made to dissolve the resin in TPGDA or ethyl acetate. In this case, a high proportion of insoluble gel particles was found, which with the broad molecular weight distribution due to an incipient Crosslinking (polymerization) can be explained by the required high temperature (in particular high Mw). This demonstrates that the synthesis discontinuously in the melt does not lead to the desired properties. Further investigations have therefore been omitted.

Inventive example 1

Of the used extruder consisted of 8 housings, which separately could be heated and cooled. Housing 1 and 2: 190 ° C, housing 3 to 8: 200 ° C, Head temperature 200 ° C.

It worked with three streams:
Stream 1 consisted of the reaction product of the reaction of 1 mol of isophorone diisocyanate (VESTANAT IPDI, Degussa) with 1 mol of 2-hydroxyethyl acrylate (Degussa). Stream 2 consisted of the carbonyl-hydrogenated resin prepared according to Inventive Example 1 of 102006009079.9. Stream 3 was the catalyst zinc octoate.

electricity 1 was in the second housing at a rate of 3600 g / h a twin-screw extruder (DSE 25, 30 D), at room temperature fed.

electricity 2 was in the first housing with a volume of 3890 g / h fed (temperature of the material flow 170 ° C).

electricity 3 was added to the second housing at a rate of 24 g / h, at room temperature, fed

All Temperatures represented nominal temperatures. The regulation took place over Electric heating or water cooling. The nozzle was also electrically heated. The screw speed was 250 rpm.

The Reaction product was cooled on a cooling belt and then broken.

Of the NCO content was below 0.1%.

Inventive example 2

It worked with three streams:
Stream 1 consisted of the reaction product of the reaction of 1 mol of isophorone diisocyanate (VESTANAT IPDI, Degussa) with 1 mol of 2-hydroxyethyl acrylate (Degussa). Stream 2 consisted of the carbonyl-hydrogenated resin prepared according to Inventive Example 1 of 102006009079.9. Stream 3 was the catalyst zinc octoate.

electricity 1 was in the first housing with a quantity of 2950 g / h a twin-screw extruder (DSE 25, 30 D), with a temperature of 50 ° C fed. Power 2 was in the first case fed with a quantity of 3100 g / h (temperature of the material flow 195 ° C). Stream 3 was in the first housing with an amount of 30.4 g / h, at room temperature, fed to the used Extruder consisted of 8 housings, which were heated separately and could be cooled. It was driven without a headboard. Housing 1: 210 ° C, Housing 2 to 8: 200 ° C.

All Temperatures represented nominal temperatures. The regulation took place over Electric heating or water cooling. The nozzle was also electrically heated. The screw speed was 280 rpm.

The Reaction product was cooled on a cooling belt and then broken. The NCO content was below 0.1%.

The following table shows the properties of the products according to the invention. example Appearance Mp. FZ Gardner cloudiness _Viscosity (40% in TPGDA) GPC Before / after thermal stress (FNU) Mn mw D [° C] (50% in ethyl acetate) [MPas] [G / mol] [G / mol] D ₁ Colorless, clear 96 0.3 / 0.5 2.6 5000 1500 4200 2.8 ₂ Colorless, clear 100 0.2 / 0.4 1.17 4200 1400 2800 2.0

To evaluate the paint properties, the compositions were prepared from the following table by stirring (in grams). For this purpose, the resins according to the invention from Examples 1 and 2 were first dissolved in the TPGDA and then the other components were added with stirring. A I II Craynor CN 104 (Cytec) 50 30 30 TPGDA 40 40 40 Darocur 1173 (Ciba) 5 5 5 Ebecryl P 115 (Cytec) 5 5 5 Resin from Example 1 20 Resin from Example 2 20 Viscosity in mPas 935 960 980

The Compositions A, I and II were coated with a squeegee (60 μm) on a glass plate, on pine wood as well as on different ones Applied plastic plates and metal. Then the films were by means of UV light (medium pressure mercury lamp, 70 W / optical Filter 350 nm) cured for about 12 sec. The before Sticky and soluble films are tack-free and no more soluble in methyl ethyl ketone.

After curing, the coated test plates were stored for 7 days under standard conditions (23 ° C., 50% relative humidity). Then the properties of the films were determined. Film properties: Paint no. Pendulum hardness (substrate glass) MEK test (substrate glass) Gloss 60 ° angle (substrate: pine wood) A 189 > 150 74 I 211 > 150 96 II 215 > 150 97

The gloss and the very high hardness of the comparative formulation A are improved by adding the resins (I and II) according to the invention. All films are resistant to MEK. Knife scratch adhesion on different substrates: Paint no. Glass SECTION PE PVC PC metal A 5 4 10 10 10 10 I 2 2 4 3 2 1 II 2 2 5 3 2 1

0 = very good adhesion; 10 = no liability

Abbreviations

• SECTION:

  Acrylonitrile-butadiene-styrene copolymer

  PC:

  polycarbonate

  PE:

  polyethylene

  PVC:

  polyvinylchloride

  TPGDA:

  tripropylene

  MEK:

  Methyl ethyl ketone (2-butanone)

  mp:

  melting point

  FZ:

  color number

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

• - DE 2345624 [0008]
• - EP 736074 [0008]
• - DE 2847796 [0008]
• - DD 240318 [0008]
• - DE 2438724 [0008]
• - JP 09143396 [0008]
• - EP 0902065 [0009]
• - DE 2438712 [0010]
• US 4070500 [0011]
• - DE 870022 [0012]
• - DE 3241735 [0012]
• - DE 3334631 [0012, 0051]
• - DE 10338560 [0013, 0076]
• EP 1508582 [0013]
• - US 7199166 [0013]
• - DE 102004005208 [0013]
• - EP 1711567 [0013]
• US 2007/0123661 [0013]
• EP 1801141 A1 [0055]
• - DE 102006009079 [0077]

Cited non-patent literature

• - Odian, George, Principles of Polymerization, Third Edition, John Wiley & Sons, New York, 1991, page 86 [0061]
• - DIN EN ISO 3219 [0062]
• - DIN 53181 [0065]
• - DIN EN ISO 11909 [0066]
• - DIN EN ISO 4630 [0067]
• - DIN EN ISO 4630 [0068]
• - DIN EN ISO 7027 [0069]
• - DIN EN ISO 3219 [0070]
• - DIN EN ISO 2813 [0073]
• - DIN EN ISO 1522 [0074]

Claims (40)

A process for the solvent-free, continuous production of tin-free, radiation-curable urethane acrylates with low molecular weight distribution, comprising essentially the radiation-curable reaction product of A) at least one carbonyl-hydrogenated ketone-aldehyde resin and / or hydrogenated ketone resin and / or carbonyl-hydrogenated and ring-hydrogenated ketone-based aromatic ketone-aldehyde resin B) at least one aromatic, aliphatic and / or cycloaliphatic di- or polyisocyanate, which in addition to the isocyanate group (s) has at least one ethylenically unsaturated group, characterized in that the product of A) and B) is obtained by reaction the starting components in the presence of tin-free catalysts in the absence of an organic solvent in an extruder, flow tube, intensive kneader, intensive mixer or static mixer by intensive mixing and short-term reaction with heat and na subsequent isolation of the final product. Method according to claim 1, characterized in that that the residence time of the starting materials in the aggregates 3 seconds to 15 minutes, preferably 3 seconds to 5 minutes, more preferably 5 to 180 seconds. Method according to at least one of the preceding claims, characterized in that the reaction in the single, twin or multi-screw extruder, Ring extruder or planetary roller extruder takes place. Method according to claim 3, characterized that the reaction takes place in a twin-screw extruder. Method according to one of claims 1 or 2, characterized in that the reaction in a flow tube, Intensive mixer or intensive kneader takes place. Method according to at least one of the preceding claims, characterized in that the reaction in a static mixer he follows. Method according to at least one of the preceding claims, characterized in that the reaction in an extruder, intensive kneader, Intensive mixer or static mixer with several equal or different Enclosures that are thermally independent can be controlled takes place. Method according to at least one of the preceding claims, characterized in that the temperature in the aggregates 50 to 325 ° C, preferably 120 to 300 ° C, especially preferably 140 to 250 ° C. Method according to at least one of the preceding claims, characterized in that the extruder or intensive kneader suitable equipping of the mixing chambers and compilation the screw geometry on the one hand to an intensive rapid mixing and fast reaction with simultaneous intensive heat exchange lead, and on the other hand a uniform Flow in the longitudinal direction with as possible effect uniform residence time. Method according to at least one of the preceding claims, characterized in that the starting materials and / or catalysts and / or aggregates together or in separate product streams, in liquid or solid form, the extruder, flow tube, Intensive kneader, intensive mixer or static mixer supplied become. Method according to claim 10, characterized in that that the aggregates together with the input materials to a Product stream are summarized. Method according to at least one of the preceding claims, characterized in that an after-reaction is added becomes. Method according to claim 12, characterized in that that the postreaction in continuously operated systems, such as Tubular reactors, stirred or unstirred dwell containers, Tube bundles, done. Method according to at least one of the preceding claims, characterized in that a con continuous reaction takes place, in which one or more low molecular weight alcohols (quench alcohols) are used to complete the reaction. Method according to at least one of the preceding claims characterized in that the isolation of the end product by Cooling and optionally solution in a suitable Solvent, takes place. Solvent-free, tin-free, radiation-curable Urethane acrylates with a low molecular weight distribution and with Mn of 500 to 10,000 g / mol and Mw of 1,000 to 20,000 g / mol, essentially containing the radiation-curable Reaction product of A) at least one carbonyl-hydrogenated Ketone-aldehyde resin and / or hydrogenated ketone resin and / or carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resin based on aromatic ketones With B) at least one aromatic, aliphatic and / or cycloaliphatic di- or polyisocyanate, in addition to the isocyanate group (s) via at least one ethylenic has unsaturated grouping, available by the reaction of the starting components from A) and B) in the presence tin-free catalysts and in the absence of an organic solvent in an extruder, flow tube, intensive kneader, intensive mixer or static mixer due to intensive mixing and short-term Reaction with heat input and subsequent isolation of the Final product. Urethane acrylates according to at least one of the previous Claims, characterized in that C-H-acidic ketones used in component A). Urethane acrylates according to at least one of the previous Claims, characterized in that in the hydrogenated Ketone- and carbonyl-hydrogenated ketone-aldehyde resins of the component A), ketones selected from acetone, acetophenone, nucleus-substituted Acetophenone derivatives, such as hydroxy, methyl, ethyl, tert-butyl, Cyclohexyl acetophenone, 4-tert-butyl methyl ketone, methyl ethyl ketone, Heptanone-2, pentanone-3, methyl isobutyl ketone, propiophenone, methyl naphthyl ketone, Cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanone, Cycloheptanone and cyclooctanone, cyclohexanone and all alkyl-substituted ones Cyclohexanone be used alone or in mixture. Urethane acrylates according to at least one of the previous Claims, characterized in that in the hydrogenated Ketone- and carbonyl-hydrogenated ketone-aldehyde resins of the component A) alkyl-substituted cyclohexanones having one or more alkyl radicals, which have a total of 1 to 8 hydrocarbon atoms, individually or in mixture, be used as starting compounds. Urethane acrylates according to Claim 19, characterized 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and / or 3,3,5-trimethylcyclohexanone be used. Urethane acrylates according to at least one of the previous Claims, characterized in that as the aldehyde component the carbonyl-hydrogenated ketone-aldehyde resins in component A) formaldehyde, Acetaldehyde, n-butyraldehyde and / or isobutyraldehyde, valeric aldehyde, Dodecanal, used alone or in mixtures. Urethane acrylates according to the previous claim, characterized characterized in that formaldehyde and / or para-formaldehyde and / or Trioxane can be used. Urethane acrylates according to at least one of the previous Claims, characterized in that carbonyl hydrogenated Ketone-aldehyde resins of acetophenone, 4-tert-butyl methyl ketone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone, heptanone, alone or in admixture, and formaldehyde are used as component A). Urethane acrylates according to at least one of the previous Claims, characterized in that the hydrogenated Ketone resins of component A) containing ketones selected from 4-tert-butyl methyl ketone, cycohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone, singly or in admixture. Urethane acrylates according to at least one of the preceding claims, characterized in that in the carbonyl- and ring-hydrogenated ketone-aldehyde resins based on aromatic ketones of the component A), aryl-alkyl ketones are used. Urethane acrylates according to at least one of the previous Claims, characterized in that in the carbonyl and nuclear-hydrogenated ketone-aldehyde resins based on aromatic Ketones of component A), ketones selected from acetophenone, nuclear substituted acetophenone derivatives such as hydroxy, methyl, ethyl, tert.-butyl, cyclohexyl-acetophenone, methylnaphthyl ketone are. Urethane acrylates according to at least one of the previous Claims, characterized in that in the aldehyde component the carbonyl- and ring-hydrogenated ketone-aldehyde resins based on aromatic ketones of component A), formaldehyde, acetaldehyde, n-butyraldehyde and / or isobutyraldehyde, valeric aldehyde, dodecanal, used alone or in mixtures, preferably formaldehyde. Urethane acrylates according to at least one of the previous Claims, characterized in that as a component B) (meth) acryloyl isocyanate, α, α-dimethyl-3-isopropenyl benzyl isocyanate, (Meth) acrylic alkyl isocyanate with Alkylspacern, the on a to 12, preferably 2 to 8, more preferably 2 to 6 carbon atoms such as methacrylethyl isocyanate, methacrylic butyl isocyanate, used alone or in mixtures. Urethane acrylates according to at least one of the previous Claims, characterized in that as a component B) reaction products of hydroxyalkyl (meth) acrylates, their alkyl spacer over one to 12, preferably 2 to 8, more preferably 2 to 6 carbon atoms and di- and / or polyisocyanates, alone or in mixtures. Urethane acrylates according to the preceding claim, characterized in that as di- and / or polyisocyanates cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, phenylene diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, tolylene diisocyanate, bis (isocyanatophenyl) methane, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, such as hexamethylene diisocyanate (HDI) or 1,5-diisocyanato-2-methylpentane (MPDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate such as 1,6-diisocyanato-2,4,4-trimethylhexane or 1,6-diisocyanato-2,2,4-trimethylhexane (TMDI ), Nonanetriisocyanate such as 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), decane diisocyanate and triisocyanate, undecanediisocyanate and triisocyanate, dodecane diisocyanate and triisocyanate, isophorone diisocyanate (IPDI), 2,2'- and 2,4-diisocyanate '- And 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI) alone or in mixtures, preferably the H ₁₂ MDI consists of at least 80 wt .-% of 4,4'-H ₁₂ MDI, preferably 85-9 5% by weight, 2.5 (2.6) bis (isocyanato-methyl) bicyclo [2.2.1] heptane (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane (1,3-H ₆ -XDI ) or 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ -XDI), alone or in mixtures, for the preparation of component B). Urethane acrylates according to at least one of the previous Claims, characterized in that polyisocyanates, prepared by dimerization, trimerization, allophanatization, Biuretization and / or urethanization of simple diisocyanates, alone or in mixtures, for the preparation of component B) become. Urethane acrylates according to at least one of the preceding claims, characterized in that isocyanates based on IPDI, TMDI, H ₁₂ MDI and / or HDI, alone or in mixtures, for the preparation of component B) are used. Urethane acrylates according to at least one of the preceding claims, characterized in that isocyanurates of the diisocyanates IPDI, HDI and / or H ₁₂ MDI, alone or in mixtures, for the preparation of component B) are used. Urethane acrylates according to at least one of the preceding claims, characterized in that reaction products of IPDI, TMDI, HDI and / or H ₁₂ MDI with trimethylolpropane and / or pentaerythritol, alone or mixtures, are used for the preparation of component B). Urethane acrylates according to at least one of the previous Claims, characterized in that 1 mol of the component A) based on Mn, and 0.25 to 15 mol, preferably 0.5 to 10 mol, especially 1 to 6 mol of component B) are used. Urethane acrylates according to at least one of the previous Claims, characterized in that the melting range the reaction product of A) and B) between 70 and 150 ° C, preferably between 80 and 130 ° C, more preferably between 80 and 120 ° C is located. Urethane acrylates according to at least one of the previous Claims, characterized in that polydispersity the molecular weight distribution between 1.5 and 15, preferably between 1.5 and 10, more preferably between 1.5 and 6.0 for the preparation component B) can be used. Urethane acrylates according to at least one of the previous Claims, characterized in that solution viscosity measured at 23 ° C according to DIN EN ISO 3219, as a 40% solution in TPGDA between 30 and 15,000 mPa · s, preferably between 100 and 10,000, more preferably between 200 and 8000 mPa.s for the preparation of the component B) is used. Use of solvent-free, tin-free, Radiation-curable urethane acrylates with a low molecular weight distribution with a Mn of 500 to 10,000 g / mol and a Mw of 1000 to 20,000 g / mol, according to at least one of the preceding claims, in the Containing substantially the radiation-curable reaction product from A) at least one carbonyl-hydrogenated ketone-aldehyde resin and / or hydrogenated ketone resin and / or carbonyl-hydrogenated and ring-hydrogenated Ketone-aldehyde resin based on aromatic ketones With B) at least one aromatic, aliphatic and / or cycloaliphatic Di- or polyisocyanate, in addition to the / the isocyanate group (s) over has at least one ethylenically unsaturated group, as Main component, basic component or additional component in radiation-curable Coating materials, adhesives, printing inks and inks, pigment pastes, Fillers, cosmetics and sealants and insulating materials, especially for improving adhesion properties, gloss, Solvent and chemical resistance as well the hardness. Objects made using the solvent-free, tin-free, radiation-curable Urethane acrylates with a low molecular weight distribution with a Mn of 500 to 10,000 g / mol and Mw of 1,000 to 20,000 g / mol based on carbonyl-hydrogenated ketone and ketone-aldehyde resins and hydrogenated ketone-aldehyde resins based on aromatic Ketones (arylalkyl ketones) and isocyanates after at least one the previous claims.