DE2539448A1 - RESIN COMPOUNDS CURABLE BY UV RADIATION, PROCESS FOR THEIR PRODUCTION AND USE IN PLASTIC RESIN COMPOSITIONS - Google Patents

Description

Resin-like compounds curable by UV radiation , processes for their production and their use in synthetic resin compositions.

The invention relates to novel ethylenically unsaturated compounds of resinous character, a process for their manufacture and use. The invention Compounds can be cured by exposure to UV light and are particularly suitable for use in coating compounds and printing inks.

The ethylenically unsaturated compounds according to the invention are characterized in particular by the fact that they can be cured easily and quickly by irradiation with UV light and are no longer sticky after curing (stickiness after curing is one of the most troublesome disadvantages; it arises by delaying or even preventing the hardening by the influence of air, in English referred to as "air inhibition"

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net, which this type of synthetic resin is often subject to). The valuable properties of the synthetic resin compounds according to the invention are attributable to their structure and the choice of components in their manufacture.

The invention also relates to plastic compositions which, in addition to the compounds according to the invention, contain other ethylenically unsaturated ones Contain low viscosity compounds and plastic compounds with other types of additives, the photo-initiators, Contain fillers or colorants or pigments. Also the use of the new compounds in hardening processes Irradiation falls under the invention,

In recent years, methods have been developed in which Ethylenically unsaturated synthetic resins are hardened by irradiation, in particular with electron beams and UV light. Such irradiation methods are used in the field of surface coatings and applied to printing inks. They allow very rapid curing at ambient temperature, transferring flat substrates with a coating of uncured synthetic resin into place at high speed where they are briefly exposed to radiation that causes the plastics to harden; the so treated item can be processed further without delay.

The interest in electron beam curing has led to various proposals regarding certain types of synthetic resins guided. The particular advantage of this process is based on the high energy of the emitted electrons, which are usually between 100,000 and 500,000 electron volts; this energy is high enough to initiate the polymerization of practically all types to initiate ethylenically unsaturated compounds without other aids. However, the high ones are a disadvantage

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Costs for the electron generator and for the heavy and complicated shielding devices that are necessary around Protect the workforce against the X-rays that are emitted when the electrons are slowed down.

as
The UV irradiation polymerization initiator has the advantage of lower equipment and shielding costs; however, the energy quantum (3.3 electron volts for UV radiation of 360 nm) is considerably lower and photoinitiators (also known as sensitizers) must be used to initiate the polymerization. Since the UV rays have a lower energy than the electron beam, the synthetic resins must be specially selected if one wants to bring about complete and rapid curing. In practice, resins of the unsaturated polyester type have generally been chosen for curing with UV light.

A disadvantage that applies to most synthetic resins when curing by irradiation is that which has already been briefly mentioned and in The English technical language called "air inhibition", which consists in the fact that the body comes into contact with air standing surface of the hardened layer tends to remain sticky even if the one lying further down Parts of the layer are completely cured. This phenomenon was often prevented by additional measures, which the The surface of the not yet hardened plastics should protect against the effects of oxygen, e.g. B. by use a coating of paraffin wax over the surface or by using an inert gas over the conveyor line or by covering the surface with a thin, transparent thermoplastic film.

The invention relates to a synthetic resin material which is suitable for rapid curing by UV irradiation in contact with air and suitable without any special precautionary measures and

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hardened plastic layer with a non-sticky surface.

The ethylenically curable by UV light according to the invention unsaturated resin compounds are the reaction product of:

(I) one mole of a polyhydroxy compound having m hydroxyl groups per molecule, wherein m has a value of at least 2;

(II) η moles of a diisocyanate;

(III) 1 to η moles of an adduct of equivalent amounts of acrylic acid and a glycidyl ester of a saturated aliphatic monocarboxylic acid with 9-11 carbon atoms per molecule, in which the carboxyl group is on a tertiary or quarternary carbon atom sits; and

(IV) (n-1) to 0 mol of a hydroxyalkyl acrylate of the formula

¹¹ H.

HO - R - 0 - C - C = CH,

wherein R is a divalent alkyl group, the sum of the number of moles of components (III) and (IV) is equal to η and η has the value of at least 2, but is less than or at most equal to m.

The polyhydroxy compounds (I) preferably have 2 to 6, in particular 3 to 6, hydroxyl groups per molecule. Examples are polyhydric alcohols such as glycerine, pentaerythritol, trimethylethane, Trimethylolpropane, 1,2,6-hexanetriol, sorbitol and reaction products of these alcohols with ethylene oxide or propylene oxide in a molar ratio of 1: 1 to 1:20. These polyhydric alcohols, referred to in English as "tipped polyols" contribute to the flexibility of the cured product. Other polyhydroxy compounds are condensation products of polycarboxylic acids or their anhydrides and

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optionally monocarboxylic acids with an excess of polyhydric alcohol, such as compounds of the alkyd resin type. Other suitable polyhydroxy compounds are the solid reaction products of polyhydric phenols, e.g. B. of 2,2-bis (4-hydroxyphenyl) propane, with epichlorohydrin, whose softening points according to Durrans are between 60 and 100 ⁰ C and which have 2 to 4 hydroxyl groups per molecule; these reaction products also have 2 epoxy groups per molecule, which can be suitable for a secondary, slower curing process with polyamines. Also suitable as polyhydroxy compounds are diacrylates of diglycidyl ethers of polyhydric phenols, such as 2,2-bis (4-hydroxyphenyl) propane; the acrylates are obtained by reacting 2 moles of acrylic acid with 1 mole of the diglycidyl ether in question and contain 2 hydroxyl groups per molecule. Other polyhydroxy compounds are castor oil, optionally in hydrogenated form; Polymers of 2-hydroxyalkyl and optionally alkyl ethers of acrylic or methacrylic acid and triethanolamine. Mixtures of two or more of the above polyhydroxy compounds can also be used. Polyhydric alcohols are preferred, in particular those with 2-6 and preferably 3-6 hydroxyl groups per molecule; Trimethylpropane and its reaction products with ethylene oxide in a molar ratio of 1: 6 to 1:20, as well as sorbitol, are particularly preferred.

Examples of diisocyanates are meta- and paraphenylene diisocyanate, toluene-2,4- or -2,6-diisocyanate and mixtures of these isomers, m-xylene diisocyanate, naphthalene-1,5-diisocyanate, diphenylmethane diisocyanate, diphenyl-4,4'-diisocyanate, 3,3'-dichlorodiphenyl-4,4'-diisocyanate, 3.3 ^! -Dimethoxydiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-Bisphenyldiphenyl-4,4 ^t diisocyanate, 3,3'-dimethyldiphenylmethane-4,4 '- diisocyanate, diphenyl ether 4,4'-diisocyanate, N, N'-bis (4-methylphenyl) uretidinedione-3,3'-diisocyanate, butane-1,4-diisocyanate, hexane-1,5-diisocyanate, 2, 2,4-trimethylhexane diisocyanate, dodecane-1,12-diisocyanate, cyclohexane diisocyanate

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9 C ·? π / / ρ / .j - ο i + ν * ζ)

Di (cyclohexylmethane) -4,4'-diisocyanate, 2-butene-1,4-diisocyanate, Diethyl sulfide 2,2'-diisocyanate and isophorone diisocyanate. Mixtures of two or more of these diisocyanates can also be used. The diisocyanate can be used as Raw product or purified, e.g. B. can be used by distillation or recrystallization; solid diisocyanates can be liquefied to facilitate their handling. One mole of diisocyanate is defined as that amount that two Contains isocyanate equivalents.

Component III can be prepared by heating equimolar amounts of the components at 100 ° - 150 ⁰ C in the presence of a catalyst (an organic Phosphines, a phosphonium salt, a tertiary amine or a qua ternary ammonium salt), and preferably in the presence of an inhibitor, e.g. . B. of hydroquinone until a "determination of the epoxy content shows that the reaction is practically complete.

The acids from which the glycidyl esters are obtained are here, for the sake of simplicity, as "branched monocarboxylic acids" designated. In the definition of branched monocarboxylic acids, “aliphatic” is not only acyclic-aliphatic but also Meant cycloaliphatic. Branched monocarboxylic acids can be obtained by reacting formic acid or carbon monoxide and water with olefins such as cracked mineral oil fractions, propylene trimer, or diisobutylene in the presence of liquid, strongly acidic catalysts; These branched monocarboxylic acids are usually mixtures in which the carboxyl group predominantly bound to a square carbon atom is.

Component (IV) can be, for example, hydroxyethyl acrylate or hydroxypropyl acrylate.

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The quantitative ratio between component (III) and (IV) can be varied, but in the production of one mole of ethylenically unsaturated resinous compound such as defined above, at least one mole of component (III) must be used. The amount of component (III) per mole of ethylenic unsaturated resinous compound can be from 1 to: i Mo], where then the amount of component (IV) n-1 to 0 mol can be, so that the sum of the number of moles of component (III) and component (IV) is always η. The value for η is equal to or less than the value for m; the minimum value for both is 2. If η is less than m, the resinous one contains Compound m-n hydroxyl groups per molecule.

The preparation of the ethylenically unsaturated resinous compounds of the present invention from the above-mentioned components is preferably carried out in two ways, each of which is a two-step process.

The preferred route consists in first reacting component (III) and, if appropriate, also component (IV) with the diisocyanate, preferably in the presence of a catalyst for reactions between isocyanate and hydroxyl groups. Such catalysts are known; Examples are: dibutyltin dilaurate, cobalt naphthenate and tertiary amines such as triethylamine, N-methylmorpholine and triethylenediamine. Since the acrylate ester used may polymerize spontaneously, an inhibitor, e.g. B. hydroquinone, be present in sufficient quantities. As the reaction temperature range is from 20 to 10O ⁰ C into consideration, the preferred reaction temperature is (using dibutyltin dilaurate as a catalyst) at 40 to 8O ⁰ C. In order to increase the selectivity with regard to the conversion of only one isocyanate group of the diisocyanate, the monohydroxy compounds (III) and optionally (IV) are added to the diisocyanate as slowly as possible, ie over several hours. If both components (III) and (IV) are used, it is preferable, in view of the possibility of different reactivity, to use each of them in an equimolar amount

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React diisocyanate and mix the resulting products; on the other hand, if the reactivity is about the same, a mixture of (III) and (IV) can be added.

In the second stage of this first implementation, the Polyhydroxy compound added, optionally with additional amounts of catalyst and / or inhibitor; let the implementation, preferably at the same temperature as during the first stage, continue until an isocyanate analysis shows that they is practically complete. This form of implementation is permitted the production of resinous compounds with free hydroxyl groups (m-n per molecule).

The first implementation can therefore be defined as Process for the production of ethylenically unsaturated resin-like compounds curable by UV irradiation, which thereby is characterized in that one first η mol of a diisocyanate

(II) reacts with 1bjs η mol of component (III) and (n-1) up to 0 mol of component (IV), the sum of the number of moles of components (III) and (IV) being η, whereupon η moles of the obtained Product reacted in a second stage with 1 mol of a polyhydroxy compound (I) with m hydroxyl groups per molecule, wherein η is less than or equal to m.

The second implementation is the order of the stages the other way around as with the first: the polyhydroxy compound is first reacted with the diisocyanate and then the compounds are added

(III) and optionally (IV) to. As can be seen, this must second implementation form η be equal to m by too high a rise viscosity or even gelling as much as possible. The components (ill) and optionally (IV) can be used in excess, so that a hydroxyl-containing product is obtained in which the excess has the function of a reactive solvent. There are indications that the second implementation is not quite as selective as the first, d. H. it leads to a higher viscosity and occasionally to the

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Gel. The first embodiment is therefore usually preferred.

The second form of implementation can be defined as a procedure for the production of ethylenically unsaturated resin-like compounds curable by UV radiation, characterized in that that one first reacts one mole of a polyhydroxy compound with m hydroxyl groups per molecule with η mole of a diisocyanate and the product obtained in a second stage with 1 to η mol of a component (ill) and (n-1) to 0 mol of a Component (IV) reacts, the sum of the number of moles of components (III) and (IV) being at least equal to η and η being equal to m is.

As for the ethylenically unsaturated according to the invention defined above As regards resinous compounds, it should be noted that these compounds or their intermediates are not cleaned in the first stage and that therefore the resinous compounds mentioned contain all impurities that have been formed by side reaction levels. Incidentally, the amount of components added in the second stage is usually calculated on the basis of the Isocyanate equivalence of the product from the first stage to Side reactions to be considered in this first stage.

The ethylenically unsaturated compounds according to the invention according to above are usually solids or highly viscous liquids. The preferred among them have a mean more than two UV-polymerizable ethylenically unsaturated groups per molecule and can be referred to as "star-shaped".

In order to lower the viscosity of the products to the extent that they can be used as coatings or for printing inks, they have to be diluted for which a large number of different ethylenically unsaturated compounds of low viscosity are available which can be used alone or in admixture. These low viscosity diluents polymerize and copolymerize during UV irradiation and thus contribute to reducing the viscosity and weight of the coating agent or

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Printing inks at. The low-viscosity compounds mentioned contain one or more ethylenically unsaturated groups the structure

-C = CHq
per molecule and can be represented by the formula

/ P

where ρ is a number from 1 to 4 and R represents a p-valent hydrocarbon, ether or ester radical with 18 carbon atoms, but which does not contain any urethane groups. Examples are: styrene, vinyl esters of monocarboxylic acids, such as vinyl acetate, or preferably vinyl esters of "branched monocarboxylic acids" as defined above; the adduct of acrylic acid and glycidyl esters of branched monocarboxylic acids ("Component III" as defined above); Esters of acrylic acid and monohydric or polyhydric alcohols, such as ethyl acrylate, butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, neopentyl glycol diacrylate, trimethylpropanedi- and triacrylate, pentaerythritol diacrylate, di- acrylate and acrylate and mixtures of these Diethylene glycol diacrylate or polyethylene glycol diacrylate. Diluents are preferably having a boiling point of at least 6O ⁰ C, preferably those boiling higher than 100 ⁰ C, in particular above 150 ° C at atmospheric pressure, since the diluent has the function to copolymerize and do not evaporate. The amount of the diluent is 5 to 60, preferably 20 to 40 parts by weight per 100 parts by weight of the resinous compound. Often the diluent can be added during the preparation of the resinous compound in the first and / or the second stage in order to facilitate the handling of the reaction mixture.

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Examples of photoinitiators in UV curing are: benzoin methyl ether, benzoin ethyl ether; 9,10-anthraquinone, 1,4-naphthoquinone and chlorine, methyl, phenyl and benzyl derivatives of these compounds. Benzoin methyl (or ethyl) ether and 2-tert-butyl anthraquinone are preferred , 5 to 5, preferably 0.5 to 2% by weight , based on the resinous compound plus diluent.

Compositions with a content of resinous compounds according to the invention, photoinitiators and optionally diluents, as defined above, as well as other ingredients have a wide range of uses, e.g. B. as undercoats on wood; for clear or colored lacquers on wood, pressed fiber board, cardboard, paper, steel or tinplate; or as printing inks for printing paper (resin about 5,000 poise, reduced to 1,000 ms 2,000 poise at 25 ⁰ C with diluent) and plastic films (resin about 500 poise, reduced to about poise at 5,000 ° C by diluent). The compositions can be applied to the substrate in a manner known to those skilled in the art and the coated or printed object is then passed at high speed under a source of UV radiation, usually a mercury lamp, which may also contain a source of IR radiation. The compositions are preferably free of volatile solvents which do not polymerize; however, non-volatile plasticizers can be present.

Masses also be hardened with a content of the inventive resinous compounds, optionally ärdünnungsmitteln ^v and other ingredients may (in this case jtvi ^ h without photoinitiator) by irradiation with electron beams.

The examples, in which parts and percentages mean parts by weight or percentages by weight, serve for a more detailed explanation the invention.

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Examples 1-20 are the preparation of resinous compounds with or without reactive diluents shown, the production always taking place under nitrogen; Examples 21 and 22 explain the evaluation the result.

The registered trade names used in the examples are explained as follows:

"CARDURA" E is a glycidyl ester of branched monocarboxylic acids with 9 to 11 carbon atoms;

"EPIKOTE" 1001 is a polyglycidyl polyether of 2,2-bis (4-hydroxyphenyl) propane. with 2 free hydroxyl groups per molecule.

"EPIKOTE" 828 is a polyglycidyl ether of 2,2-bis (4-hydroxyphenyl) propane · With an epoxy equivalent weight of 180 to 200. "VeoVa" 10 is a vinyl ester of branched monocarboxylic acids with 10 carbon atoms per molecule.

The adduct of "CARDURA" E and acrylic acid used in Examples 1 to 19 was prepared as follows:

A mixture of "Cardura" E (1235 g; 5 Eqoxyäquivalente), acrylic acid (360.5 g; 5 mol), triphenyl phosphine ^ (0.5 g) and hydroquinone (4.0 g) was stirred at 120 ⁰ C heated »- after the heating was interrupted, the temperature rose to 140 ° C by the heat of reaction, whereby it was maintained by alternating cooling and heating. After an epoxy equivalent weight of 50,000 had been reached (which showed that the reaction was more than 99 % was complete) the product was isolated and cooled. The cooled ACE adduct was a clear, slightly yellowish liquid of low viscosity. The determination of active hydrogen gave a value of 345 milliequivalents per 100 g, corresponding to a hydroxyl equivalent weight of 289.5. In Example 20, a corresponding ACE adduct was used which had a hydroxy equivalent weight of 314 (ACE adduct II).

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EXAMPLE 1

A mixture of hexamethylene diisocyanate (433 g; 2.56 mol), dibutyltin dilaurate (1.5 g) and hydroquinone (0.6 g) was heated with stirring to 70 ⁰ C. Then the mixture while maintaining the agitation and the reaction temperature of 70 ⁰ C a solution of ACE-adduct (743 g; 2.56 hydroxy equivalents) in 394 g styrene added gradually over 6 hours. A few minutes after the total amount had been added, the isocyanate equivalent weight was 650. A mixture of trimethylolpropane (110 g), styrene (37 g), dibutyltin dilaurate (1.64 g) and hydroquinone (0.6 g) was then added. The reaction ^{temperature was kept at 70 °} C. until the isocyanate equivalent weight was 40,000 (conversion 98 %). The resinous product was a clear, slightly colored viscous liquid on cooling.

EXAMPLE 2

Isophorone diisocyanate (167 g; 0.75 mol), ACE adduct (217 g; 0.75 hydroxy equivalent), dibutylzimylilaurate (0.2 g), "VeoVa" 10 (96 g) and hydroquinone (0.8 g) were added with stirring mixed, the temperature being allowed to rise to 40 ^° C. as a result of the heat of reaction and held there until the isocyanate equivalent weight was 631. Then the mixture of trimethylolpropane (33.6 g), dibutyltin dilaurate (0.1 g) and "VeoVa" 10 were added (8.4 g) and the mixture heated to 70 ⁰ C and held there until the isocyanate equivalent weight was about 5,000. After cooling, the resinous product was a clear, colorless, highly viscous liquid.

EXAMPLE 3

Trimethylolpropane (115 g; 2.56 hydroxy equivalents) was added to a mixture of hexamethylene diisocyanate (433 g; 2.56 mol), styrene (350 g) and butyltin dilaurate (1.5 g) with stirring; the temperature was maintained at 50 ° C until the mixture homogeneously then added slowly over 4 hours 740 g ACE-adduct and 1.5 g dibutyltin dilaurate were added and the temperature was allowed to rise to 70 ⁰ C and held there until the isocyanate equivalent weight 51,000 fraud. After cooling, a clear, colorless, highly viscous liquid was obtained. - 14 -

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EXAMPLE 4

Example 1 was repeated, but using the trimethylolpropane was replaced by an equivalent amount of triethanolamine. The resin was a clear, yellow, viscous liquid after cooling.

EXAMPLE 5

Example 1 was repeated, but using the trimethylolpropane by an equivalent amount of an adduct of trimethylolpropane and ethylene oxide with 14 moles of ethylene oxide per mole Trimethylolpropane was replaced.

EXAMPLE 6

Example 1 was repeated, but using the trimethylolpropane was replaced by an equivalent amount (calculated on hydroxyl) of "EPIKOTE" 1001.

EXAMPLE 7

Example 1 was repeated, but using the trimethylolpropane was replaced by an equivalent amount (calculated on hydroxyl) of diacrylate from "EPIKOTE" 828.

EXAMPLE 8

Example 1 was repeated, but the hexamethylene diisocyanate was replaced by an equivalent amount (calculated on isocyanate) of isophorone diisocyanate.

EXAMPLE 9

Example 1 was repeated, but the hexamethylene lisocyanate was replaced by an equivalent amount (calculated on isocyanate) of trimethylhexamethylene diisocyanate.

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EXAMPLE 10

Example 1 was repeated, but the styrene replaced by the same amount by weight of 2-ethylhexyl acrylate became.

EXAMPLE 11

Example 1 was repeated, but the styrene was omitted entirely.

EXAMPLE 12

Example 11 was repeated, but using the trimethylolpropane was replaced by an equivalent amount (calculated on hydroxyl) of the diacrylate from "EPIKOTE" 828.

EXAMPLE 15

Example 3 was repeated, but the hexamethylene diisocyanate was replaced by an equivalent amount (calculated on isocyanate) of isophorone diisocyanate.

EXAMPLE 14

Example 3 was repeated, but the styrene was replaced by the same amount by weight of "VeoVa" 10.

EXAMPLE 15

Example 3 was repeated, but the unsaturated solvent (styrene) was completely omitted.

EXAMPLE 16

Example 3 was repeated, except that the trimethylolpropane was replaced by an equivalent amount (calculated on hydroxyl) of triethanolamine was replaced.

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EXAMPLE 17

Example 2 was repeated, but using "VeoVa" 10 entirely was omitted. The resulting resin was a clear, highly viscous mass.

EXAMPLE 18

Example 1 was repeated, but the hexamethylene diisocyanate by an equivalent amount of 2,4-tolylene diisocyanate replaced and the styrene was omitted entirely. The product was a yellow, brittle solid.

EXAMPLE 19

Example 2 was repeated, but with the trimethylolpropane was replaced by an equivalent amount of a triol derived from glycerin and propylene oxide and having an average molecular weight of 300 had.

EXAMPLE 20

Isophorone diisocyanate (167 g; 0.75 moles), ACE adduct II (235.5 g; 0.75 hydroxy equivalent), dibutyltin dilaurate (0.2 g) and hydroquinone (0.8 g) were mixed with stirring. The heat of reaction allowed the temperature to rise to 40 ° C. and maintained them until the isocyanate equivalent weight was 525. Then sorbitol (45.5 g; 0.25 mol) and dibutyltin dilaurate (0.1 g) added and the mixture was heated to 100 C and held at this temperature until the isocyanate equivalent weight approximately 5,000. The resinous product obtained after cooling was a clear, brittle material.

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EXAMPLE 21

Evaluation of the products from Examples 1 to 8 and 10 to 16

The utility of the above products as coatings (about 15 - thick) on paper was evaluated by determination the curing speed when irradiated with a UV lamp. Benzoin ethyl ether (1% by weight) was used as the photoinitiator and the products from Examples 11, 12 and 15 were reactive Solvent added as given in table.

In all cases, two mercury vapor lamps were used as radiation sources (Philips HOK-5.5000 watts, medium pressure, air-cooled) with a flow rate of 80 watts / cm. Both fittings included elliptical reflectors. The lamps were aimed at one of the focal points. Served to control the exposure time a variable speed treadmill. The lamps were arranged so that the object to be irradiated had the second focal point happened at a distance of 12 cm from the lamp.

The evaluation results are given in Table 1 as the number of passes under the UV lamp at a given running speed of the tape, with the number of passes recorded when the coating was dry to the touch (determined by dabbing with cotton wool).

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Tabel

product the end Added Fast Number of passes example reactive lo running solvent "bandes - (Wt. Ji) (m / min) example 1 30th 8th example 2 - 120 1 example 3 - 30th 9 example 4th - 30th 2 example 5, - 30th 3 example 6th - 30th 10 example 7th - 30th 3 example 8th - 30th 2 example 10 - 30th 2 example 11 ACE (30 wt. 96) 30th 5 example 12th ACE (20 wt. 96) 50 1 example 13th - 30th 5 example 14th - 50 1 example 15th 2-ethyl 30th 2 hexyl acrylate (20 wt. 96) example 16 30th 2

% By weight = percent by weight of product from the relevant example,

EXAMPLE 22 Evaluation of the products according to Examples 17 to 20

All systems examined here contained a photo initiator
2.5% by weight benzoin ethyl ether. The drying speed (up to

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dry to touch condition) was determined as in Example 21. In addition, the resinous products were evaluated as coating agents. They were 40 to 50 μm thick clear films on phosphatized steel panels (Bonder 97, protected trade name).

The coated panels were cured by running them twice at a belt speed of 30 m / min below the in Example 21 described UV source passed through. There were the following properties are determined: König pendulum hardness, impact strength from backwards, adhesion (cross-section and tape test) and resistance to solvents. The latter property was determined by rubbing with a cloth dampened with methyl ethyl ketone (MEK), u.z. until the The coating could be removed by scraping with a fingernail,

The results are shown in Table 2.

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Table 2

product
from At
game added
tes reak
tive lo
solvent *! touching
dry
after number
Continuous Film properties
Passes at 3C Blow
tough
v.
backward
in cmkg (after 2
m / min) 45 in wt -.% Run
Schwin
age
m / min 1 hardness
(King) 4.5 Adhä- MEK Wi-
sion ** jtierst.
(No.
Friction
before
corridors) 35 17th (VeoVa (20)
+ (VA (5) 120 1 78 3.3 2 25th 17th HEA (25) 120 1 158 2.2 4th 50 18th (VeoVa (20)
+ (VA (5) 90 1 60 4.5 2 **> 10 ***) 18th HEA (25) 120 2 155 13.5 ***) 4th 45 19th VA (5) 30th 1 50 ***) 4.5 5 * 45 20th HEA (25) 120 1 144 6.7 3 20th (VeoVa (20)
+ VA (5) 120 78 2

VA: vinyl acetate, HEA: 2-hydroxyethyl acrylate TMPTA: trimethylolpropane triacrylate HDDA: 1,6-hexanediol diacrylate

5: excellent adhesion 0: no adhesion after 5 D ¹ 'or 30 m / min.

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Claims (10)

2539U8 - 21 - 1A-46 866 Claims Iy Ethylenically unsaturated compounds curable by UV radiation resinous compounds in the form of the reaction product (I) one mole of a polyhydroxy compound having m hydroxyl groups per molecule, where m has a value of at least 2 has (II) η mol of a diisocyanate, (III) 1 to η mol of an adduct of equivalent amounts of acrylic acid and a glycidyl ester of saturated aliphatic monocarboxylic acids with 9 to 11 carbon atoms per molecule, in which the carboxyl group is bonded to a tertiary or quaternary carbon atom, and
(IV) (n-1) to 0 mol of a hydroxyalkyl acrylate of the formula " H
HO - R --0 - C - C = CH, wherein R represents a divalent alkyl group, the sum of the number of moles of components (III) and (IV) is η, η is less than or equal to m and the value of η is at least 2. 2. Compounds according to claim 1, in which the polyhydroxy compound (i) has 2 to 6 hydroxyl groups per molecule. 3. Compounds according to claim 1 or 2, in which the polyhydroxy compound (I) has 3 Ms 6 hydroxyl groups per molecule. - 22 - 609 812/0986 - 22 - 1A-46 866 4. Compounds according to any one of claims 1 to 3, in which the polyhydroxy compound (I) is a polyhydric alcohol, in particular Is trimethylolpropane or sorbitol. 5. Compounds according to any one of claims 1 to 3, in which the polyhydroxy compound (i) is the reaction product of a polyvalent Alcohol with ethylene or propylene oxide in "a molar ratio is from 1: 1 to 1:20. 6. Compounds according to any one of claims 1 to 5, in which the diisocyanate (II) is isophorone diisocyanate. 7. Process for the preparation of the compounds according to Claim 1 to 6, characterized in that in a first stage η mol of a diisocyanate (II) with 1 to η mol of component (III) and (n-1) to 0 mol of component (IV) converts, the sum of the number of moles of components (III) and (IV) being η, and that in one second stage η mol of the product obtained in the first stage is reacted with one mole of the hydroxyl groups having m per molecule Polyhydroxy compound (I), where η is less than or equal to m. 8. Modification of the process for the preparation of the compounds according to one of claims 1 to ^: 6 characterized in that one mole of a polyhydroxy compound m hydroxyl groups per molecule is reacted in a first stage with η moles of a diisocyanate and then in a second stage that from the The product obtained in the first stage reacts with 1 to η mol of component (III) and (n-1) to 0 mol of component (IV), the sum of the number of moles of components (III) and (IV) being at least equal to η and η is equal to m. - 23 - 6098 12/0986 2539U8 - 23 - 1A-46 866 9. Use of the compounds according to claim Ibis 6 in by UV-radiation curable plastic masses, which are suitable for overages or printing inks and which are composed sino. the end (A) 100 parts by weight of the resinous compound concerned according to claims 1 to 6 and (B) 5 to 60 parts by weight of one or more different ethylenically unsaturated compounds curable by UV radiation Compounds with one or more ethylenically unsaturated groups of the structure C = CH, per molecule. 10. Use of the compounds according to claim 1 to 6 in synthetic resin compositions according to claim 9, which also contain a photoinitiator. 60981 2/0986