Hydrophilic polyurethanes containing (meth)acryloyl groups, their use as reactive emulsifiers for radically curable synthetic resins, water-dispersible mixture of radically curable synthetic resins and an aqueous coating composition based on this mixture

A polyurethane is disclosed having improved properties as a reactive emulsifier for radically-curable synthetic resins. The polyurethane is obtained by the reaction of a) a polyisocyanate component; b) an alcohol component; and c) a polyethylene glycol component. The reactive emulsifiers are useful in aqueous coating compositions.

This invention relates to certain nonionic-hydrophilic polyurethanes 
containing (meth)acryloyl groups, to their use as reactive emulsifiers for 
radically curable synthetic resins in the production of aqueous synthetic 
resin dispersions, to a water-dispersible mixture of polyurethanes 
containing (meth)acryloyl groups containing these nonionic-hydrophilic 
polyurethanes as emulsifier component and to a coating composition of 
which the binder consists essentially of this mixture. 
Water-dispersible urethane acrylates are already known (cf. for example 
EP-A 00 98 752 or DE-OS 2 936 039). The hydrophilic character of these 
known systems is attributable to the presence of ionic centers, 
particularly carboxylate or sulfonate groups, containing as counterions 
alkali cations or ammonium cations which remain in the coatings ultimately 
obtained from the systems and seriously impair their resistance to water. 
In addition, the amines often present can cause yellowing of the paint 
coatings while the auxiliary solvents present, if any, can cause 
environmental pollution during the drying process. 
Another possibility of obtaining water-dilutable products is to use 
external emulsifiers. Thus, according to U.S. Pat. No. 4,070,323 for 
example, polyurethanes containing acryloyl groups are dispersed in water 
using anionic or cationic oil-in-water emulsifiers (for example sodium 
lauryl sulfate). These emulsifiers are not incorporated in the paint film 
during the radical crosslinking reaction. As a result, the degree of water 
resistance which the paint films are capable of achieving is considerably 
reduced. 
Accordingly, the object addressed by the present invention is to find 
reactive emulsifiers for radically curable synthetic resins which have 
few, if any, of the disadvantages attending known emulsifiers. 
This problem is solved by the provision of the reactive emulsifiers 
according to the invention which are described in detail hereinafter. 
The present invention relates to polyurethanes having a content of (i) 
olefinic double bonds (expressed as .dbd.C.dbd.C.dbd., molecular weight 
=24) of at least 1.0% by weight and (ii) ethylene oxide units incorporated 
through polyethylene glycol of from 20 to 80% by weight which have been 
obtained by reaction of 
a) 1.0 mol of a polyisocyanate component consisting of at least one organic 
polyisocyanate with 
b) 0.9 to 2.5 mol of an alcohol component containing (meth)acryloyl groups 
and consisting of at least one monohydric alcohol containing 
(meth)acryloyl groups and subsequent reaction of the reaction product 
formed from a) and b) with 
c) 0.25 to 0.55 mol of a polyethylene glycol component consisting of at 
least one polyethylene glycol at an NCO:OH equivalent ratio, based on all 
the starting components a) to c), maintained at 0.7:1 to 1.1:1. 
The present invention also relates to the use of polyurethanes having a 
content of (i) olefinic double bonds (expressed as .dbd.C.dbd.C.dbd., 
molecular weight =24) of at least 1.0% by weight and (ii) ethylene oxide 
units incorporated through polyethylene glycol of from 20 to 80% by weight 
which have been obtained by reaction of 
a) 1.0 mol of a polyisocyanate component consisting of at least one organic 
polyisocyanate with 
b) 0.9 to 2.5 mol of an alcohol component containing (meth)acryloyl groups 
and consisting of at least one monohydric alcohol containing 
(meth)acryloyl groups and subsequent reaction of the reaction product 
formed from a) and b) with 
c) 0.25 to 0.55 mol of a polyethylene glycol component consisting of at 
least one polyethylene glycol at an NCO:OH equivalent ratio, based on all 
the starting components a) to c), maintained at 0.7:1 to 1.1:1, as 
reactive emulsifiers for radically curable synthetic resins 
non-dispersible in water in the production of aqueous synthetic resin 
dispersions. 
The present invention also relates to a water-dispersible mixture of 
radically curable synthetic resins containing (meth)acryloyl groups, 
characterized in that it consists essentially of 
A) 50 to 95 parts by weight of at least one non-water-dispersible 
polyurethane containing at least 2.5% by weight olefinic double bonds 
(expressed as .uparw.C.uparw.C.uparw., molecular weight 24) in the form of 
chemically incorporated (meth)acryloyl groups and having a molecular 
weight Mw in the range from 500 to 10,000 and 
B) 5 to 50 parts by weight of at least one polyurethane guaranteeing the 
dispersibility of the mixture in water and having a content of (i) 
olefinic double bonds (expressed as .dbd.C.dbd.C.dbd., molecular weight 
=24) of at least 1.0% by weight and (ii) ethylene oxide units incorporated 
through polyethylene glycol of from 20 to 80% by weight which have been 
obtained by reaction of 
a) 1.0 mol of a polyisocyanate component consisting of at least one organic 
polyisocyanate with 
b) 0.9 to 2.5 mol of an alcohol component containing (meth)acryloyl groups 
and consisting of at least one monohydric alcohol containing 
(meth)acryloyl groups and subsequent reaction of the reaction product 
formed from a) and b) with 
c) 0.25 to 0.55 mol of a polyethylene glycol component consisting of at 
least one polyethylene glycol 
at an NCO:OH equivalent ratio, based on all the starting components a) to 
c), maintained at 0.7:1 to 1.1:1, 
with the proviso that the total content in the mixture of ethylene oxide 
units emanating from component c) is at most 20% by weight and preferably 
at most 15% by weight. 
Finally, the present invention also relates to a coating composition which 
is characterized in that the binder consists essentially of a mixture of 
the type according to the invention. 
The compounds according to the invention, i.e. the nonionic-hydrophilic 
polyurethanes to be used in accordance with the invention as emulsifiers, 
are essentially reaction products of the above-mentioned starting 
components a) to c), from 1.0 to 2.2 mol component b) and from 0.4 to 0.5 
mol component c) preferably being used per mol component a) in the 
production of the polyurethanes. 
Component a) consists of at least one organic polyisocyanate. Suitable 
polyisocyanates are any organic polyisocyanates known per se from 
polyurethane chemistry containing aliphatically, cycloaliphatically and/or 
aromatically bound isocyanate groups which preferably have a molecular 
weight in the range from 168 to 1,000 and preferably in the range from 168 
to 300. Suitable organic polyisocyanates are, for example, 1, 
6-diisocyanatohexane (HDI), 1-isocyanato-3, 3, 
5-trimethyl-5-isocyanatomethyl cyclohexane (IPDI), 4, 
4'-diisocyanatodicyclohexylmethane,4, 4'-diisocyanatodiphenyl methane, 
technical mixtures thereof with 2, 4-diisocyanatodiphenyl methane and, 
optionally, the higher homologs of these diisocyanates, 2, 
4-diisocyanatotoluene and mixtures thereof with 2, 6-diisocyanatotoluene. 
Biuret-, isocyanurate- or urethane-modified polyisocyLe anates based on 
these simple polyisocyanates are also suitable. These derivatives 
generally have a molecular weight of up to 1,000. The production of such 
derivatives is described, for example, in U.S. Pat. Nos. 3,124,605, 
3,183,112, 3,919,218 or U.S. Pat. No. 4,324,879. 
Component b) is selected from monohydric alcohols containing (meth)acryloyl 
groups or from mixtures of such alcohols which are understood to be esters 
of (meth)acrylic acid with polyhydric alcohols containing on average one 
free hydroxyl group per molecule. The esters have a number average 
molecular weight in the range from 116 to 1,000 and preferably in the 
range from 116 to 750. Examples of ethylenically unsaturated partial 
esters such as these are hydroxyethyl (meth)acrylate, 2- and 
3-hydroxypropyl (meth)acrylate, 2-, 3- and 4-hydroxybutyl (meth)acrylate 
and reaction products of (alkoxylated) trimethylol propane with 
(meth)acrylic acid such as, for example, the reaction product of 2 mol 
acrylic acid and 1 mol of an ethoxylated trimethylol propane (OH value 
550, degree of ethoxylation approx. 4). 
Component c) is selected from linear polyethylene glycols having a number 
average molecular weight in the range from 400 to 4,000 and preferably in 
the range from 600 to 2,000, in which at least 80% and preferably 100% of 
the alkylene oxide units are ethylene oxide units. Accordingly, the 
expression "polyethylene glycols" is understood to encompass not only 
genuine polyethylene glycols, of which the alkylene oxide units consist 
solely of ethylene oxide units, but also polyalkylene glycols in which the 
alkylene oxide units dominate, i.e. in which at least 80% of the alkylene 
oxide units are ethylene oxide units. "Mixed" polyalkylene glycols such as 
these are formed, for example, through the use of mixtures of different 
alkylene oxides, for example ethylene oxide and propylene oxide in a molar 
ratio of .gtoreq.8:1, in the production of the polyether glycols by 
alkoxylation of suitable difunctional starter molecules, such as for 
example water, ethylene glycol or propylene glycol. However, component c) 
preferably consists of pure polyethylene glycols. 
The production of the hydrophilic polyurethanes according to the invention 
to be used as emulsifiers may be carried out in bulk or in solvents inert 
to isocyanate groups, such as for example acetone, methyl ethyl ketone, 
ethyl acetate, butyl acetate, toluene, low molecular weight esters of 
(meth)acrylic acid or mixtures of such solvents, the reaction temperatures 
preferably being in the range from 20.degree. to 100.degree. C. and more 
preferably in the range from 20.degree. to 80.degree. C. In this reaction, 
from 0.9 to 2.5 mol and preferably from 1.0 to 2.2 mol component b) and 
from 0.25 to 0.55 mol and preferably from 0.4 to 0.5 mol component c) are 
used per mol component a), the reaction between component a) and component 
b) having to be carried out first in a first reaction step, after which 
the reaction product obtained is reacted with component c). 
In practice, therefore, the polyisocyanate may be initially introduced and 
reacted with the unsaturated monoalcohol b) under mild conditions, for 
example at a temperature in the range mentioned above, followed by 
reaction with the polyethylene glycol c), again at a temperature in the 
range mentioned above, until the NCO content has fallen to below 0.1% by 
weight. Basically, the nature of and quantitative ratios between the 
starting components are selected within the ranges mentioned so that, 
based on components a) to c), and NCO:OH equivalent ratio of 0.7:1 to 
1.1:1 is guaranteed. 
The urethanization reactions may be catalyzed iD known manner, for example 
with tin octoate, dibutyltin dilaurate or tertiary amines. The urethane 
acrylate may also be protected against premature and unwanted 
polymerization by addition of suitable inhibitors and antioxidants in a 
quantity of 0.001 to 0.3% by weight, based on the mixture as a whole. 
The hydrophilic polyurethanes containing (meth)acryloyl groups obtained in 
this way have a weight average molecular weight Mw, as determined by gel 
permeation chromatography, in the range from 1,000 to 10,000 and 
preferably in the range from 1,500 to 5,000, a content of olefinic double 
bonds (expressed as .dbd.C.dbd.C.dbd., molecular weight =24) of at least 
1.0% by weight and preferably from 1.5 to 6.0% by weight and a content of 
ethylene oxide units -CH.sub.2 -CH.sub.2 -O- incorporated through 
polyethylene glycol in the range from 20 to 80% by weight and preferably 
in the range from 30 to 75% by weight. 
The hydrophilic polyurethanes are valuable emulsifiers for hydrophobic, 
non-water-dispersible, radically cross-linkable synthetic resins, more 
especially for hydrophobic polyester resins containing (meth)acryloyl 
groups and more preferably for polyurethane resins containing 
(meth)acryloyl groups. 
Hydrophobic polyurethane resins containing (meth)acryloyl groups, which may 
be combined with the hydrophilic polyurethanes mentioned to form the 
water-dispersible mixtures according to the invention, are in particular, 
water-dispersible polyurethanes which have a weight average molecular 
weight Mw, as determined by gel permeation chromatography, in the range 
from 500 to 10,000 and preferably in the range from 1,000 to 5,000, a 
content of olefinic double bonds (expressed as .dbd.C.dbd.C.dbd., 
molecular weight =24) in the form of chemically incorporated 
(meth)acryloyl groups of at least 2.5% by weight and preferably from 3 to 
15% by weight and a content of ethylene oxide units incorporated through 
polyethylene glycols of at most 5% by weight. In general, these 
hydrophobic polyurethanes are clear color-less liquids which, in the 
absence of solvents, have a viscosity at 23.degree. C. in the range from 
10 to a few thousand Pa.s or are even solid at room temperature. 
Polyurethanes such as these are produced by the reaction known per se of 
organic polyisocyanates of the type mentioned by way of example above 
under a) with hydroxyl-containing esters of acrylic or methacrylic acid of 
the type mentioned by way of example above under b) and, optionally, other 
synthesis components containing isocyanate-reactive groups. 
Synthesis components of the last-mentioned type include simple polyhydric 
alcohols having a molecular weight in the range from 62 to 400, such as 
for example ethylene glycol, propylene glycol, the isomeric butanediols of 
hexanediols, glycerol, trimethylol propane, diethylene glycol, triethylene 
glycol, dipropylene glycol; the polyether polyols known per se from 
polyurethane chemistry which may be obtained in known manner by 
alkoxylation of simple alcohols of the type mentioned by way of example 
and which have molecular weights of up to 2,000 and preferably of up to 
1,000; the polyester polyols known per se from polyurethane chemistry 
which may be obtained in known manner by reaction of the polyhydric 
alcohols mentioned by way of example with polybasic acids or anhydrides of 
polybasic acids, such as for example adipic acid, phthalic acid, phthalic 
anhydride, tetrahydrophthalic acid or tetrahydrophthalic anhydride; also 
sulfur-containing polyols of the type mentioned by way of example in DE-OS 
2 737 406, such as in particular thiodiglycol. 
To produce the hydrophobic polyurethanes, the starting materials mentioned 
by way of example are reacted in any order in an equivalent ratio of 
isocyanate groups to isocyanate-reactive groups of 0.7:1 to 1.1:1, again 
preferably at reaction temperatures in the range from 20 to 100.degree. C. 
and more preferably at reaction temperatures in the range from 20 to 
80.degree. C. The auxiliaries mentioned above may again be used. 
The water-dispersible mixtures according to the invention contain from 50 
to 95 parts by weight and preferably from 70 to 95 parts by weight of the 
hydrophobic polyurethanes mentioned in admixture with 5 to 50 parts by 
weight and preferably 5 to 30 parts by weight of the above-mentioned 
hydrophilic polyurethanes acting as emulsifiers. It is, however, important 
to select the ingredients of the mixtures and their amount so that the 
total content of the water-dispersible mixture of ethylene oxide units 
emanating from component c) is at most 20 % by weight and preferably at 
most 15 % by weight. 
The mixtures may be prepared simply by mixing the individual components, 
optionally in the presence of inert solvents of the type mentioned by way 
of example above. 
To prepare the aqueous coating compositions according to the invention, the 
mixtures according to the invention are dispersed in water which may be 
done, for example, simply by stirring water into a mixture of the 
polyurethanes using standard dissolvers. 
To form a finely divided emulsion, it is of advantage to add water in 
portions at temperatures below 40.degree. C. Stable oil-in-water emulsions 
may be obtained in this way. 
The aqueous dispersions obtained in this way are valuable aqueous binders 
for coating compositions. They may be used as such or in combination with 
the auxiliaries and additives known from paint technology such as, for 
example, fillers, pigments, solvents, flow control agents and the like for 
the production of coatings on any substrates. 
Suitable substrates are paper, carton, leather, wood, plastics, nonwovens, 
textiles, ceramic materials, mineral materials, glass, metals, artificial 
leather and photographic materials, such as for example paper coated with 
a photographic layer. 
The coating compositions may be applied in known manner by spray coating, 
knife coating, roll coating, spread coating, dip coating or casting. After 
evaporation of the water and any inert solvents used, the coatings may be 
crosslinked either by high-energy radiation, such as UV light, electron 
beams or gamma rays, or by hardening with metal salts of siccative acids 
and (hydro)peroxides at temperatures in the range from 80.degree. C. to 
250.degree. C. 
Where the coatings are crosslinked by UV irradiation, photoinitiators have 
to be added to the coating compositions. 
Suitable photoinitiators are the compounds typically used, as described for 
example in the book by J. Korsar entitled Light-Sensitive Systems, J. 
Wiley & Sons, New York --London--Sydney, 1965. 
Other suitable photoinitiators are benzoin ethers, such as benzoin 
isopropyl ether, benzil ketals, such as for example benzil dimethyl ketal, 
and hydroxyalkyl phenones, such as for example 
2-hydroxy-2-methyl-1-phenyl-propan-1-one. 
The photoinitiators mentioned above which are used in quantities of from 
0.1 to 10% by weight and preferably in quantities of from 0.1 to 5% by 
weight, based on the weight of the dispersed hydrophilic and hydrophobic 
polyurethanes, depending on the application envisaged for the compounds 
according to the invention, may be used either individually or, by virtue 
of frequent advantageous synergistic effects, even in combination with one 
another. 
The metal salts of siccative acids used where cross-linking is carried out 
with peroxides are, for example, cobalt, lead and manganese salts of such 
acids as linseed oil fatty acids, tall oil fatty acids, soybean oil fatty 
acids, of resinic acids, such as abietic acid and naphthenic acid or of 
acetic acid and isooctanoic acid. They are used in the form of organic 
solutions in such quantities that the metal content, based on the weight 
of the dispersed hydrophilic and hydrophobic polyurethanes, corresponds to 
between 0.005 and 1% by weight. 
Examples of (hydro)peroxides are di-tert.-butyl peroxide, benzoyl peroxide, 
cyclohexanone peroxide, methyl ethyl ketone peroxide, acetyl acetone 
peroxide, dinonyl peroxide, 
bis-(4-tert.-butylcyclohexyl)-peroxydicarbonate, tert.-butyl 
hydroperoxide, cumene hydroperoxide, 2, 5-dimethyl hexane-2, 
5-hydroperoxide and diisopropyl benzene monohydroperoxide. These 
(hydro)peroxides are preferably used in quantities of 1 to 10% by weight, 
based on the weight of the dispersed hydrophilic and hydrophobic 
polyurethanes.

In the following Examples, all percentages are by weight. 
EXAMPLES 
Production of starting materials 
Hydrophobic polyurethane Al: 
A polyurethane containing acryloyl groups is prepared by reaction of 111 g 
(0.5 mol) isophorone diisocyanate with 46.4 g (0.4 mol) hydroxyethyl 
acrylate, 6.1 g (0.05 mol) thiodiglycol and 134 g (0.2 mol) of an 
ethoxylated trimethylol propane having an OH value of 250 (molecular 
weight 675). 
After the entire quantity of isocyanate had been introduced, the higher 
diglycol was added dropwise while cooling and stirring over a period of 2 
hours at 40 to 50.degree. C. The reaction temperature should not exceed 
60.degree. C. during the addition. After the addition of 0.1 g tin octoate 
and 0.15 g benzoquinone and while air is passed over, the hydroxyethyl 
acrylate is introduced dropwise with cooling at 50.degree. to 60.degree. 
C. at such a rate that the temperature does not exceed 65.degree. C. After 
an NCO value of approximately 14% has been reached (approx. 4 h), the 
ethoxylated trimethylol propane is added dropwise. 
The mixture is stirred at 60.degree. C. while dry air is passed over until 
the NCO value is 0.1% by weight. A colorless and odorless resin of medium 
viscosity (viscosity of a 90% solution in butyl acetate: approx. 15 
Pa.s/23.degree. C.) containing 3.2% by weight olefinic double bonds 
(molecular weight 24) is obtained. 
Hydrophobic polyurethane A2; 
A partial ester containing OH groups and acryloyl groups is initially 
prepared by azeotropically esterifying a propoxylated trimethylol propane 
(OH value =550 (mg KOH/g)) with acrylic acid. 
925 g (3.0 mol) propoxylated trimethylol propane are heated with 430 g (6.0 
mol) acrylic acid, 12 g p-toluene sulfonic acid, 1 g p-methoxyphenol, 1.2 
g di-tert.-butyl hydroquinone and 280 g toluene to the reflux temperature 
while air is passed through and the water of reaction formed is 
azeotropically removed. After an acid value below 3 (mg KOH/g substance) 
has been reached, the solvent is removed in vacuo and the product is 
clarified by filtration An OH-group-containing ethylenically unsaturated 
partial ester having the following characteristic data is obtained: 
Acid value: 2 
OH value : 115 
The intermediate product mentioned above is then reacted with 2, 
4-diisocyanatotoluene: 
174 g (1.0 mol) 2, 4-diisocyanatotoluene and 0.7 g-methoxyphenol are 
introduced into a stirred reactor while dry air is passed over and heated 
to 40.degree.-65.degree. C. 980 g of the intermediate product mentioned 
above are then added over a period of about 2 hours, followed by stirring 
at the stated temperature until the NCO value is below 0.1% by weight. The 
hydrophobic acrylate prepolymer A2 has a viscosity of 46 Pa.s (23.degree. 
C.). The content of olefinic double bonds is 9.7% by weight. 
Hydrophobic polyurethane A3 
An isocyanurate polyisocyanate based on hexamethylene diisocyanate (HDI) is 
initially prepared. 
1 ml 2-dimethylaminomethyl nonylphenol is added to 1344 g (8.0 mo)) HDI at 
23.degree. C. After stirring for 5 minutes, 40 ml of a 2% solution of 
2-hydroxyethyl trimethyl ammonium hydroxide in dimethyl formamide/methanol 
(8:1) are added dropwise over a period of 15 minutes, again at 23.degree. 
C. 
Over this period, the temperature rises to 35.degree. C. and, after another 
45 minutes, to 40.degree. C. The trimerization reaction is maintained at 
that temperature. After 6 hours, an NCO content of 40.5% is reached. The 
reaction product is stabilized with 0.3 ml monofluorobutane sulfonic acid 
in 1 ml dimethyl formamide and then subjected to thin-layer distillation 
in a high vacuum. 
Iodine color value: 3 
NCO content : 22.0% 
Viscosity (25.degree. C.) : 3,100 mPa.s 
The polyisocyanate obtained as described above is then reacted with 
hydroxyethyl acrylate to form the acrylate prepolymer A3: 
283 g (0.5 mol) NCO of the polyisocyanate are dissolved in 365 parts 
anhydrous toluene and 174 g (1.5 mol) hydroxyethyl acrylate are added to 
the resulting solution at room temperature. After the addition of 0.5 g 
tin dioctoate, the temperature is slowly increased to 60.degree. C. and 
the mixture is stirred until the NCO content has fallen to 0. After 
cooling to room temperature, 1.8 g 2, 6-di-t-butylphenol are added and 
solvent is removed by vacuum distillation until the concentration is 70%. 
The solution obtained is almost colorless with a slight yellow tinge and 
has a viscosity of approximately 5,000 mPa.s (23.degree. C.). The content 
of olefinic double bonds is 7.9% by weight. 
Hydrophobic polyurethane A4 
116 g (1.0 mol) hydroxyethyl acrylate are added dropwise over a period of 2 
hours with cooling and stirring to 222 g (1.0 mol) isophorone diisocyanate 
and 0.5 g hydroquinone monomethyl ether at such a rate that the 
temperature does not exceed 65.degree. C. After the addition of 0.5 g tin 
dioctoate and 42 g butyl acetate, 38 g (0.5 mol) 1, 2-propanediol are 
added dropwise and the mixture is stirred at 60 to 70.degree. C. until the 
NCO content has fallen to below 0.1% by weight. A colorless, almost solid 
substance having an olefinic double bond content of 6.4% by weight is 
obtained. 
Hydrophilic polyurethanes B 
The polyisocyanates shown in Table 1 are each heated to 50-60.degree. C. 
with 0.1% hydroquinone monomethyl ether. The particular monoalcohol 
containing acryloyl groups is then added dropwise with stirring at such a 
rate that the temperature does not exceed 65.C. After the addition of 
butyl acetate and 0.2% by weight tin dioctoate, the particular 
polyethylene glycol is added in portions with stirring. The mixture is 
then stirred at 60 to 70.degree. C. until the NCO content is below 0.1% by 
weight. Colorless to light yellow, clear, highly viscous liquids are 
formed, partly crystallizing out after a short time. 
TABLE 1 
______________________________________ 
Starting materials (mol) 
B1 B2 B3 B4 
______________________________________ 
Isophorone diisocyanate 
1.0 1.0 
Tolylene diisocyanate 1.0 
Trimerized hexamethylene dissocyanate 1.0 
(see A3) 
Hydroxyethyl acrylate 
1.0 2.1 
Propoxylated trimethylol propane 
1.0 1.0 
diacrylate (see A2) 
Polyethylene glycol (MW 1,000) 
0.5 0.45 
Polyethylene glycol (MW 1,550) 
0.5 0.5 
Solids content (%) 90 90 90 80 
Ethylene oxide units, % by weight, 
69.6 43.9 56.7 35.7 
based on solids: 
Olefinic double bonds (MW = 24), 
2.2 4.2 3.5 4.0 
based on solids: 
______________________________________ 
EXAMPLES 
To prepare the emulsions, the quantities of hydrophobic polyurethanes A and 
hydrophilic polyurethanes B shown in Table 2 are mixed, the resulting 
mixtures are each sheared for 2 minutes with 110 g water in a dissolver at 
8,000 r.p.m. and then adjusted with water while stirring (1,000 r.p.m.) to 
a solids content of 50%. Finely divided oil-in-water emulsions are formed. 
TABLE 2 
______________________________________ 
Example 
Components (g) 1 2 3 4 5 
______________________________________ 
A1 200 
A2 200 
A3 200 175 
A4 200 
B1 50 50 
B2 50 
B3 50 
B4 75 
Ethylene oxide units 
13.9 10.4 14.1 11.7 13.9 
% by weight, based 
on solids: 
Olefinic double bonds 
3.0 8.6 7.0 6.6 5.5 
(MW = 24), % by weight, 
based on solids: 
______________________________________ 
COMISON EXAMPLES 
COMISON EXAMPLE 1 
Instead of separate preparation of the polyurethanes A4 and B1 (Example 5) 
and subsequent mixing, an "one-pot synthesis" was carried out: 
116 g (1.0 mol) hydroxyethyl acrylate were added drop-wise over a period of 
2 hours with stirring and cooling to 222 g (1.0 mol) isophorone 
diisocyanate and 0.5 g hydroquinone monomethyl ether at such a rate that 
the temperature does not exceed 65.degree. C. After the addition of 0.5 g 
tin dioctoate and 98 g butyl acetate, 35 g (0.46 mol) 1, 2-propanediol and 
60 g (0.04 mol) polyethylene glycol (MW 1,550) are added dropwise and the 
mixture stirred at 60 to 70.degree. C. until the NCO content has fallen to 
below 0.1% by weight. A clear liquid (viscosity at 23.degree. C.: 22,000 
mPa.s) is formed. The content of olefinic double bonds is 5.5% by weight 
and the content of ethylene oxide units 13.9% by weight, corresponding to 
Example 5. 
The product formed is sheared with water in a dissolver as in Examples 1 to 
5, but could not be converted into an oil-in-water emulsion. 
COMISON EXAMPLE 2 
In order nevertheless to obtain water-dilutable products by "one-pot 
synthesis" (Comparison Example 1), the quantity of polyethylene glycol was 
increased. The procedure is exactly the same as in Comparison Example 1 
except that 124 g (0.08 mol) rather than 60 g polyethylene glycol are 
used. To keep the molar percentage of OH groups constant, 32 g (0.42 mol) 
rather than 35 g 1, 2-propanediol are used. A clear liquid (viscosity at 
23.degree. C., 1,150 mPa.s) is formed. The content of olefinic double 
bonds is 4.9% by weight and the content of ethylene oxide units 25.1% by 
weight. 
The product formed is sheared with water in a dissolver as in Examples 1 to 
5 and adjusted to a solids content of 50%. An emulsion is formed, but 
cannot be diluted any further. 
COMISON EXAMPLE 3 
To show that the method of preparation of the hydrophilic polyurethanes B 
is crucial to the desired emulsifying effect, polyurethane B1 was not 
prepared in accordance with the invention: 
The procedure is exactly the same as for the preparation of polyurethane 
Bl, except that the polyethylene glycol is first reacted with the 
diisocyanate and the hydroxyethyl acrylate is added thereafter. 
A viscous product is formed and crystallizes out after a short time. If 
this product is mixed with polyurethane A4 as in Example 5 and sheared 
with water in a dissolver, a coarse oil-in-water emulsion is formed, 
separating after a few days. 
APPLICATION EXAMPLES 
a) Peroxidic hardening 
1% by weight of an aqueous cobalt acetate solution (5% by weight metal 
content) and 3% by weight tert.-butyl perbenzoate are added to the aqueous 
emulsions of Examples 1 to 5 and of Comparison Example 2 and the emulsions 
subsequently coated onto glass plates (wet film thickness: 90 .mu.m). 
These paint films are heated for 30 minutes at 125.degree. C. The 
resistance of the hardened films to water was tested by wetting the films 
with water and evaluating them after a contact time of 16 hours at room 
temperature. Water-resistant means no visible changes in the film through 
staining, softening and separation of the film from the substrate. 
The paint film surfaces of Examples 1 to 5 are water-resistant and 
scratch-resistant and have pendulum hardness values (according to Konig 
DIN 53 157) of more than 150 s. The paint film surface of Comparison 
Example 2 is neither water-resistant nor scratch-resistant and has a 
pendulum hardness of 100 s. 
b) Photochemical hardening 
Examples 1 to 5 and Comparison Example 2 are mixed before emulsification 
with quantities of 5 g photoinitiator (1, 
4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one). After emulsification, 
the products are applied to a veneered chipboard in such a way that, after 
evaporation of the solvent, a dry film thickness of 30 .mu.m is obtained. 
The board is moved past an overhead Hanovia lamp (80 W/cm, 10 cm distance) 
at a speed of 5 m/minute. 
Only the paints of Examples 1 to 5 give coatings that are hard and 
resistant to scratching, water and chemicals. The paint of Comparison 
Example 2 shows inadequate water resistance and inadequate hardness.