Coating and molding compositions containing alkyl vinyl ether polymers and use thereof as leveling agents or antifoam agents

Coating compositions and molding compositions containing an amount of alkyl vinyl ether polymer which is effective for improving leveling and/or preventing or eliminating foam, and the use of these copolymers for improving leveling and/or preventing or eliminating foam in coating compositions and molding compositions. The alkyl vinyl ether polymer is a copolymer containing identical or different repeating units of the formula ##STR1## in which R represents a C.sub.1-18 --alkyl group or C.sub.m F.sub.2m+1 --(CH.sub.2).sub.2 --group, where m is a number from 4 to 18, and identical or different repeating units of the formula ##STR2## in which R' represents various groups.

BACKGROUND OF THE INVENTION 
This invention relates to coating compositions and molding compositions 
containing an amount of alkyl vinyl ether polymer effective to improve 
leveling and/or prevent or eliminate foam, and to the use of these 
copolymers for improving leveling and/or preventing or eliminating foam in 
coating compositions and molding compositions. 
Coating compositions and molding compositions are resin systems which 
contain resins (natural resins and/or synthetic resins) as binders and are 
described below and in the referenced prior art. 
It is known to use polysiloxanes or polysiloxane copolymers as leveling 
agents in organic resin systems for coatings. The addition of low 
molecular weight dimethylpolysiloxanes and methylphenylpolysiloxanes is 
described in German Patent Nos. DE 1,111,320 and DE 1,092,585. It is also 
known to use polyoxyalkylene-modified dimethylpolysiloxanes in order to 
achieve similar effects. ("Goldschmidt informiert" 7/1982, No. 56, page 2; 
6th Fatipec Congress, 1962, page 332). It is also known to use 
polyacrylates of certain molecular weight ranges as leveling agents. 
The disadvantage with polysiloxanes is that, insofar as they are soluble in 
the resin systems, they have the property of greatly reducing the surface 
tension. The tendency of the resin system to foam is consequently 
increased. Furthermore, polysiloxanes tend to cause defects in the 
inter-layer adhesion. It is known that products of this type are also used 
as release agents. 
Polyacrylates, like the incompatible polysiloxanes, tend to cause 
cloudiness in unpigmented resin systems. The products generally used as 
leveling agents essentially function as a consequence of their ability to 
greatly reduce the surface tension, and have the disadvantages associated 
with reduced surface tension. 
Commonly used antifoam agents likewise include polysiloxanes, polysiloxane 
copolymers or polyacrylates. These polymers function by virtue of their 
limited solubility and reduction of the surface tension. These products 
have a tendency, due to their pronounced incompatibility, to cause craters 
and cloudiness in the coating systems. If these systems are not, as is 
usually the case, dissolved in organic solvents, but in water or in 
mixtures of water and water-miscible solvents, such as butyl glycol, the 
crater formation is still more pronounced due to the even greater 
incompatibility and the greater difference in surface tension. 
U.S. Pat. No. 3,127,352 describes high molecular weight polyalkyl vinyl 
ethers as antifoam agents for liquid hydrocarbons. These products are 
completely unsuitable in aqueous systems due to their incompatibility. 
When used in organic systems, high molecular weight polyvinyl alkyl ethers 
often cause coating defects, for example in the form of leveling defects 
and craters. A further disadvantage of these products, accounted for by 
their incompatibility, is the rapid separation of the resin systems during 
storage. In unpigmented resin systems this incompatibility also causes 
pronounced cloudiness in the coating. 
Polyalkyl vinyl ethers have been recommended as antifoam agents in aqueous 
media (U.S. Pat. No. 4,692,267). The fundamental disadvantage of these 
products is that they are generally incompatible in aqueous systems. 
According to the aforementioned patent, a slight improvement in the 
incorporation into aqueous media can be achieved by using emulsifiers. 
Such emulsifiers have, however, only a temporary effect during 
incorporation of the antifoam agents into the resin system. During storage 
of the resin systems, the incompatible substances tend to separate out 
from the resin system and, in the form of incompatible droplets or 
particles, cause defects in the coating systems. 
The copolymerization of these prior art polyalkyl vinyl ethers with other 
monomers, such as acrylic esters or methacrylic esters is limited, since 
according to the literature only alternating copolymerization produces 
yields which are of interest industrially. If however such large amounts 
of (meth)acryloyl monomers are used, the essential effect of the alkyl 
vinyl ethers is lost. 
SUMMARY OF THE INVENTION 
The object of the present invention is to use alkyl vinyl ether copolymers 
to promote leveling and antifoam effects. 
Another object of the invention is to provide coating and molding 
compositions containing alkyl vinyl ether copolymers which avoid the 
aforementioned disadvantages of the prior art. 
It is also an object of the invention to provide compositions containing 
alkyl vinyl ether copolymers which exhibit improved compatibility in 
various resin systems, even if these systems are dissolved in solvents of 
different polarity such as naphthas or water. 
A further object of the invention is to provide coating and molding 
compositions with alkyl vinyl ether copolymer additives which promote 
leveling and antifoam effects, while exhibiting a lesser tendency to cause 
defects, such as crater formation. 
Yet another object of the invention is to provide coating and molding 
compositions with leveling agents and antifoam agents which do not impair 
the inter-layer adhesion between two successively applied layers. 
It has surprisingly been found that copolymers of alkyl vinyl ethers with 
polar alkyl vinyl ether derivatives have an improved compatibility in 
resin systems, and in aqueous resin systems have a self-emulsifying 
property and improved emulsion stability. Defects such as craters, 
cloudiness and separation phenomena are consequently substantially 
avoided. 
Not only is the tendency of these polyalkyl vinyl ethers to cause craters 
avoided, but also due to the leveling properties craters caused by other 
adverse factors (for example silicones, mineral oils, higher molecular 
weight resin particles, dust settling) are eliminated or reduced. 
The invention therefore relates to coating compositions and molding 
compositions containing an amount of alkyl vinyl ether polymer effective 
to improve leveling and/or prevent or eliminate foam, wherein the alkyl 
vinyl ether polymer is a copolymer which contains, per 100 identical or 
different repeating units of the formula 
##STR3## 
in which R represents a C.sub.1-18 -alkyl ground or DC.sub.m F.sub.1m+1 
--(CH.sub.2).sub.2 -group wherein m is a number from 4 to 18, 1 to 100 
identical or different repeating units of the formula 
##STR4## 
in which R' represents one of the following groups: --(CH.sub.2).sub.x --O 
--(CH.sub.2 --CHR.sub.1 --O).sub.y --R.sub.2 
--(CH.sub.2 --CHR.sub.1 --O).sub.z --R.sub.3 
--(CH.sub.2).sub.x --O--[CO--(CH.sub.2).sub.5 --O].sub.p ---R.sub.2 
--(CH.sub.2).sub.x --O--[CO--(CH.sub.2).sub.5 --O].sub.p --(CH.sub.2 
--CHR.sub.1 --O).sub.y --R.sub.2 
--(CH.sub.2).sub.x --O--(CH.sub.2 --CHR.sub.1 --O).sub.y 
--[CO--(CH.sub.2).sub.5 --O].sub.p --R.sub.2 
--(CH.sub.2).sub.x --Q--(CH.sub.2 --CHR.sub.1 --O).sub.y --R.sub.2 
--(CH.sub.2).sub.x --Q--[(CH.sub.2).sub.5 --CO--O].sub.p --R.sub.6 
--(CH.sub.2).sub.x --Q--[(CH.sub.2).sub.5 --CO--O].sub.9 --(CH.sub.2 
--CHR.sub.1 --O).sub.y --R.sub.3 
--(CH.sub.2).sub.x --Q--(CHR.sub.1 --CHR.sub.2 --O).sub.y 
--[(CH.sub.2).sub.5 --CO--O].sub.p --R.sub.6 
--(CH.sub.2).sub.2-4 --NR.sub.4 R.sub.5 
wherein 
R.sub.1 is CH.sub.3 or H, 
R.sub.2 is H, --C.sub.n H.sub.n+1 wherein n is a number from 1 to 4, 
--Co--CH.sub.3, or benzyl, 
R.sub.3 is C.sub.1-22 -alkyl or phenyl which may be substituted by 1 to 3 
C.sub.1-9 -alkyl groups, 
R.sub.4 and R.sub.5 represent alkyl groups having 1 to 4 carbon atoms or 
together with the nitrogen atom form a 5-membered or 6-membered ring free 
of Zerewittinoff hydrogen, 
R.sub.6 is C.sub.1-22 -alkyl, 
Q represents a --O--CO--NH--R.sub.7 --NH--CO--O-- group wherein R.sub.7 is 
alkylene having 6 or 9 carbon atoms, 
1,3,3-trimethylcyclohexylene-1-methylene or methylphenylene, 
x is a number from 2 to 6, 
y is a number from 0 to 50, 
z is a number from 1 to 50, and 
p is a number from 1 to 15. 
The invention further relates to the use of an amount of an alkyl vinyl 
ether copolymer which is effective for improving leveling and/or 
preventing or eliminating foam in coating compositions and molding 
compositions, said copolymer containing, per 100 identical or different 
repeating units of the formula 
##STR5## 
in which R represents a C.sub.1-18 -alkyl group or a C.sub.m F.sub.2m+1 
--(CH.sub.2).sub.2 --group wherein m is a number from 4 to 18, to 100 
identical or different repeating units of the formula 
##STR6## 
in which R' represents one of the following groups: --(CH.sub.2).sub.x 
--O--(CH.sub.2 --CHR.sub.1 --O).sub.y --R.sub.2 
--(CH.sub.2 --CHR.sub.1 O).sub.z --R.sub.3 
--(CH.sub.2).sub.x --O--[CO--(CH.sub.2).sub.5 --O].sub.p --R.sub.2 
--(CH.sub.2)--O--[CO--(CH.sub.2).sub.5 O].sub.9 --(CH.sub.2 --CHR.sub.1 
--O).sub.y --R.sub.2 
--(CH.sub.2).sub.x --O--(CH.sub.2 --CHR.sub.1 --O).sub.y 
--[CO--(CH.sub.2).sub.5 --O].sub.p --R.sub.2 
--(CH.sub.2).sub.x --Q--(CH.sub.2 --CHR.sub.1 --O).sub.y --R.sub.2 
--(CH.sub.2).sub.x --Q--[(CH.sub.2).sub.5 --CO--O].sub.p --R.sub.6 
--(CH.sub.2).sub.x --Q--[(CH.sub.2).sub.5 --CO--O].sub.p --(CH.sub.2 
--CHR.sub.1 O).sub.y --P.sub.3 
--(CH.sub.2).sub.x Q--(CHR.sub.1 --CH.sub.2 --O).sub.y [(CH.sub.2).sub.5 
--CO--O].sub.p --R.sub.6 
--(CH.sub.2).sub.2-4 --NR.sub.4 R.sub.5 
wherein 
R.sub.1 represents CH.sub.3 or H, 
R.sub.2 represents H, --C.sub.n H.sub.2n+1 wherein n is a number from 1 to 
4, --CO--CH.sub.3 or benzyl, 
R.sub.3 represents C.sub.1-22 -alkyl or phenyl which may be substituted by 
1 to 3 C.sub.1-9 -alkyl groups, 
R.sub.4 and R.sub.5 represent alkyl groups having 1 to 4 carbon atoms or 
together with the nitrogen atom form a 5-membered or 6-membered ring free 
of Zerewittinoff hydrogen, 
R.sub.6 represents C.sub.1-22 -alkyl 
Q represents a --O--CO--NH--R.sub.7 --NH--CO--O-- group wherein R.sub.7 
represents alkylene having 6 or 9 carbon atoms, 
1,3,3-trimethylcyclohexylene-1-methylene or methylphenylene, 
x is a number from 2 to 6, 
y is a number from 0 to 50, 
z is a number from 1 to 50, and 
p is a number from 1 to 15. 
The copolymers described above are therefore those containing monomers of 
the general formula 
EQU R--O--CH.dbd.CH.sub.2 (I) 
which, relative to 100 moles of identical or different monomers of the 
formula I, contain polymerized 1 to 100 moles of identical or different 
monomers of the formula 
EQU R'--O--CH.dbd.CH.sub.2 (II) 
wherein R and R' have the meanings given above. 
The copolymers used according to the invention can be prepared by 
copolymerizing the monomers with each other in a known manner as described 
in detail hereinafter. Monomers which do not yet contain the complete 
groups defined by the symbol R', but rather precursors of these groups 
with, for example, terminal hydroxyl groups may however also be 
copolymerized. After copolymerization these hydroxyl groups can be 
converted to add on the remaining molecular components the groups defined 
by the symbol R'. This is also explained below in detail. 
Examples of alkyl vinyl ether monomers corresponding to formula I, 
R--O--CH.dbd.CH.sub.2, include methyl vinyl ether, ethyl vinyl ether, 
propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, isobutyl 
vinyl ether, hexyl vinyl ether, 2-ethylhexyl vinyl ether, decyl vinyl 
ether and octadecyl vinyl ether. Ethyl vinyl ether and isobutyl vinyl 
ether are particularly preferred. 
Compounds of formula I in which R denotes a methyl group are as a rule not 
used as the only monomers of the formula I. Instead they are generally 
used in admixture with other monomers of formula I in which the symbol R 
represents alkyl groups containing 2 to 18 carbon atoms. 
Compounds of formula I in which hydrogen atoms are replaced by fluorine 
atoms include, for example, perfluorohexylethyl vinyl ether and 
perfluorooctylethyl vinyl ether. The use or concomitant use of these 
compounds, in particular, significantly increases the surface activity of 
the copolymers and improves the antifoam effect. 
Monomeric vinyl ethers corresponding to formula II, R'--O--CH.dbd.CH.sub.2, 
which may be used include vinyl ethers containing hydroxyl groups, such as 
hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl 
ether and alkoxylates of these vinyl ethers which contain hydroxyl groups. 
Vinyl ethers containing hydroxyl groups of both this and other types are 
described in U.S. Pat. No. 3,328,468. However, vinylated 
alkoxypolyoxyalkylene glycols, such .as methoxypolyethylene glycol 
monovinyl ether or butoxypolyethylenepolypropylene glycol monovinyl ether, 
are also suitable. Vinyl ethers of compounds containing tertiary nitrogen 
such as diethylaminoethyl vinyl ether or dimethylaminoethyl vinyl ether or 
morpholinoethyl vinyl ether are likewise suitable. Compounds of this type 
are obtainable by vinylating, for example, diethylaminoethanol by known 
processes. 
The vinyl ethers containing hydroxyl groups corresponding to formula II, 
R'--O--CH.dbd.CH.sub.2, can be reacted with lactones such as 
.epsilon.-caprolactone to form the corresponding monohydroxypolyester 
vinyl ethers. Examples of polymerizable lactones and methods of 
polymerization can be found in U.S. Pat. No. 4,360,643. 
Monohydroxypolyester vinyl ethers of this type may also be alkoxylated as 
disclosed in the prior art. Such measures enable the compatibility of the 
copolymers to be adapted to the respective resin systems. If it is not 
intended to have hydroxyl groups in the copolymers, for example due to 
possible reactions with the resin system, these hydroxyl groups can be 
protected, for example by acetylation. The measures mentioned for 
polyesterification with lactones and/or etherification with alkylene 
oxides can be applied in accordance with the prior art to hydroxyl 
group-containing copolymers. 
In the formulas, x preferably denotes an integer from 2 to 4, particularly 
preferably 4. 
y preferably is an integer from 0 to 30, particularly preferably 0 to 10. 
z preferably is an integer from 1 to 30, particularly preferably 1 to 10. 
p preferably is an integer from 1 to 10, particularly preferably 1 to 5. 
Compounds of formula II in which R.sub.1 represents hydrogen are compounds 
with polyoxyethylene groups. These compounds produce particularly good 
compatibility in aqueous resin systems. Compounds of formula II in which 
R.sub.1 denotes a methyl group have greater compatibility in resin systems 
based on organic solvents. As is also mentioned below, mixtures of these 
comonomers can be used, and a suitable choice of these comonomers and of 
their components enables the compatibility of the polymers used according 
to the invention to be regulated. As noted above R.sub.3 represents 
C.sub.1-22 -alkyl or phenyl which may be substituted by 1 to 3 C.sub.1-9 
-alkyl groups. Groups represented by the symbol R.sub.3 are groups which 
are conventionally present in nonionic surfactants. 
Monomers of formula I and/or formula II may also represent monomer mixtures 
and be copolymerized in the mixing ratio claimed. Surprisingly, even 
amounts of one mole of such monomers of the formula II, relative to 100 
moles of monomers of the formula I, are effective in the context of the 
invention. 
It is preferred to use up to 30 moles of monomers of the formula II per 100 
moles of monomers of the formula I. It is most particularly preferred to 
use 5 to 25 moles of monomers of the formula II so that the resulting 
copolymers contain 5 to 25 repeating units of formula IIa per 100 
repeating units of formula Ia. 
It is particularly preferred to use copolymers with repeating units of 
formula Ia in which the symbol R represents an alkyl radical containing 2 
to 8 carbon atoms, or still more preferably, 2 to 4 carbon atoms. 
According to another preferred embodiment, the copolymers contain at least 
in part repeating units of the formula Ia in which the symbol R represents 
a perfluoroalkylethyl radical having 4 to 10 carbon atoms in the 
perfluoroalkyl chain. In such a case it is preferable that, for every 100 
repeating units of formula Ia, there are at least 5 units in which the 
symbol R has the meaning given above. 
With regard to the repeating units of formula IIa, those in which the 
symbol R' represents a hydroxybutylene radical are preferred. According to 
another embodiment, copolymers which contain repeating units of formula 
IIa in which the symbol R' represents an alkoxypolyoxyalkylene radical 
with an average molecular weight M.sub.w of 300 to 1,000 are preferred. 
Preference is again given to those copolymers with repeating units of 
formula IIa in which the symbol R' represents a polyester corresponding to 
the formula 
EQU --(CH.sub.2).sub.4 --O--[CO--(CH.sub.2).sub.5 O].sub.p --CO--CH.sub.3 
wherein p represents a number from 2 to 8. 
The copolymers used according to the invention are prepared by conventional 
methods which have been well described in the literature. Cationic and 
free-radical methods are suitable. (Methoden der organischen Chemie, 
Houben Weyl E 20/II, pages 1071 et seq.) 
Vinyl ethers containing hydroxyl groups must be free-radical polymerized in 
order to avoid undesired side reactions. 
A preferred way to prepare the copolymers according to the invention is the 
stepwise reaction which has already been referred to, starting from 
polymeric precursors with hydroxyl groups and subsequently esterifying 
with lactones and/or alkoxylating. Furthermore, vinyl ether copolymers of 
this type containing polyether and/or polyester groups can also be 
obtained by an addition reaction of monoisocyanate-functional polyether 
adducts and/or polyester adducts. These adducts are prepared by reacting 
monohydroxy-functional polyesters or polyethers with diisocyanates in a 
ratio of the diisocyanate used to the OH groups such that preferably only 
one isocyanate group of the diisocyanate is reacted. This can be achieved, 
for example, by using diisocyanates with isocyanate groups of different 
reactivity. One example of such diisocyanates is isophorone diisocyanate. 
In this diisocyanate, the cycloaliphatically bonded -NCO group is about 
one-tenth as reactive as the aliphatically bonded -NCO group. 
Furthermore, control of the reaction to form the monoadduct can be made 
easier by using the diisocyanate in larger molar amounts in relation to 
the OH groups used than would be necessary for the formation of a 
monoadduct. The excess of diisocyanate used is subsequently removed by 
vacuum distillation, preferably using a thin-film evaporator. 
The average molecular weight M.sub.w of the polyalkyl vinyl ether 
copolymers used according to the invention should be between 400 and 
50,000. M.sub.w is preferably between 1,000 and 10,000, and most 
particularly preferably between 1,500 and 5,000. The average molecular 
weight M.sub.w can be determined, for example, by gel permeation 
chromatography. The weight average of the molecular weight is thereby 
defined as M.sub.w (Houben Weyl --Methoden der organischen Chemie--Georg 
Thieme Verlag, Stuttgart Volume XIV/I, page 19). 
The polyalkyl vinyl ether copolymers used according to the invention should 
preferably be added to the resin systems after they have been prepared or 
first during or after completion of the formulation. It is advantageous to 
add antioxidants to the polyalkyl vinyl ether copolymers in amounts of 
about 100 to 500 ppm in order to ensure stability against oxidation. 
Suitable antioxidants include, for example, p-tert-butylphenol and 
4-methoxyphenol. 
For use as leveling agents or anitfoam agents, the polyalkyl vinyl ether 
copolymers used in the invention may advantageously be dissolved in 
suitable solvents which for convenience may be similar to the solvents 
used in the resin formulations. Examples of suitable solvents include 
esters such as ethyl acetate, butyl acetate and diallyl phthalate, ketones 
such as diisobutyl ketone or methyl ethyl ketone, glycol ethers such as 
butyl glycol, ethyl glycol and propylene glycol monomethyl ether, glycol 
ether acetates such as ethyl glycol acetate, propylene glycol monomethyl 
ether acetate, aromatics such as toluene, xylene or styrene, white 
spirits, and also mixtures of these solvents with one another. The use of 
100% polymer material is also possible, particularly in resin systems 
which are to be processed in the absence of solvents. 
The antifoam effect can be increased in a known manner by preparing the 
copolymers used according to the invention, optionally in dissolved form 
as described above, in the presence of hydrophobic silica (German Pat. No. 
DE 3,442,727) or in the presence of urea derivatives formed in situ 
(European Pat. Appln. 115,585; U.S. Pat. No. 4,696,761) and using the 
resulting copolymers in the form of mixtures of this type, i.e. adding the 
latter to coating compositions and molding compositions. 
Coating compositions and molding compositions within the scope of the 
invention may comprise the most varied resin systems. Examples of coating 
compositions include paints, other coatings, and printing inks. 
These resins can be very different in their chemical composition and may 
cure physically or chemically as is known in the prior art. Examples of 
physically-drying binders include those based on nitrocellulose, 
acrylate-methacrylate, chlorinated rubber, PVC copolymers, polyvinyl 
esters, polystyrene, polystyrene copolymers and copolymers of butadiene. 
Examples of chemically curing or drying binders include air-drying alkyd 
resins, alkyd-melamine resins, acrylate-melamine resins, 
acrylate-isocyanate resins, polyester-isocyanate resins, epoxy resins, 
saturated and unsaturated polyester resins, phenol-formaldehyde resins and 
urea-alkyd resins. 
As a liquid phase, these binders may contain organic solvents and/or water 
or plasticizers as is known in the prior art. The liquid phase can also be 
present in the form of monomers or low molecular weight compounds which 
react with other binder components to form paint films. 
The resin systems can also be anodically or cathodically depositable 
synthetic resins (ATL/KTL). These systems comprise aqueous paints in which 
the resins contain, for example, carboxyl groups or amino groups and which 
achieve water solubility and the ability to be electrically deposited 
through salt formation. 
The resin systems according to the invention can also be powder coating 
resins which contain no liquid phase and are applied in the form of 
powders to the substrates which are to be coated and are caused to melt, 
and optionally to react, on the substrate. The resin systems according to 
the invention may also contain other customary additives, e.g. wetting and 
dispersing agents, fillers such as glass fibers, carbon fibers, polyamide 
fibers, silicates, inorganic carbonates and aluminum hydroxide, catalysts 
and/or accelerators for curing, rheologically active agents and so on. The 
manner of curing the coating compositions and molding compositions 
depends, as is known to those skilled in the art, on the binders which are 
contained therein, for example by free-radical polymerization or 
polyaddition. 
The resin systems can also be used in relatively thick layer systems such 
as floor coatings and roof coatings. If these resins are not applied to 
substrates but instead are processed in a self-supporting manner with the 
aid of molds or shaping tools, then they are termed laminates or moldings. 
The aforedescribed leveling defects and foaming problems also occur in 
such systems, and the polyvinyl ether copolymers according to the 
invention can be used just as successfully to solve such problems in these 
systems. 
The amount of polyalkyl vinyl ether copolymers added to the resin systems 
is, according to the prior art, large enough so that the desired effect is 
achieved with regard to adequately promoting leveling and/or antifoam 
effects. Very small amounts can be sufficient in order to achieve a 
significant effect. The amount of polyvinyl ether copolymers is preferably 
at least about 0.0001% by weight, particularly preferably at least about 
0.001 up to 0.01% by weight, relative to the total weight of the resin 
system. 
The upper limit for the polyvinyl alkyl ether copolymer content is 
determined by achievement of an adequate effect and by the desire to keep 
the amount as small as possible so that an excessive addition is avoided 
for cost reasons. The upper limit is generally about 3.0% by weight, 
preferably about 2.0% by weight and particularly preferably about 0.5% by 
weight relative to the total weight of the resin system. 
The preparation of the alkyl vinyl ether copolymers used according to the 
invention is described in the following Preparation Examples 1-11. 
The cationic polymerization of the polymers according to the invention is 
carried out in accordance with the following prescribed general method.

EXAMPLE 1 
100 g of toluene dried over a molecular sieve and 0.10 g of BF.sub.3 
-etherate were initially introduced under an atmosphere of nitrogen into a 
four-necked flask equipped with a stirrer, a reflux condenser, a 
thermometer and an inert gas feed. A mixture of 160 g of vinyl isobutyl 
ether and 40 g of CH.sub.2 .dbd.CH--O--(CH.sub.2).sub.4 --O--(CH.sub.2 
--CH.sub.2 O).sub.8 --CH.sub.3 were added dropwise over a period of 2.5 
hours at a reaction temperature of 30.degree. C. After the dropwise 
addition phase had ended, the time allowed for further reaction was 1 hour 
at 50.degree. C. After the reaction had ended, 0.5 g of 25% strength 
ammonia solution and 50 ml of twice-distilled water were added to the 
reaction mixture, and the mixture was stirred vigorously. Then, the lower, 
aqueous phase was separated. After two further washings, each with 100 ml 
of twice-distilled water, the toluene and the residual water were 
distilled off at 80.degree. C. and a pressure of 20 mbar. The clear, 
slightly yellowish product which was obtained had a viscosity of 810 mPas. 
Analysis by gel chromatography yielded a value for the weight average 
molecular weight of Mw =2230. 
Further copolymer examples are listed in Table 1. These copolymers were 
each prepared according to Example 1 by varying the monomers and the 
initiator concentration. 
TABLE 1 
__________________________________________________________________________ 
Weight 
Initiator Modification with 
Example 
Monomers Ratio [%] 
concentration 
M.sub.w 
hydrophobic solids 
__________________________________________________________________________ 
Example 2 
Ethyl vinyl ether 
85 100 ppm 
3950 
none 
CH.sub.2 .dbd.CH--O--(--CH.sub.2).sub.4 -- 
15 
O(CH.sub.2 --CH.sub.2 --O).sub.6 --CH.sub.3 
Example 3 
Isobutyl vinyl ether 
70 200 ppm 
3080 
For use as an antifoam 
2-Ethylhexyl vinyl 
20 agent, after the reaction, 
ether 5 g of hydrophobic silica 
CH.sub.2 .dbd.CH--O--(CH.sub.2).sub.4 --O(CH.sub.2 -- 
10 with a specific surface area 
CH.sub.2 --O).sub.4 --CH.sub.3 of 90 m.sup.2 /g are additionally 
incorporated by dispersion 
at room temperature. 
Example 4 
Isobutyl vinyl ether 
70 500 ppm 
1910 
Same modification as 
CH.sub.2 .dbd.CH--O--(CH.sub.2).sub.2 -- 
20 described in Example 3. 
(CF.sub.2).sub.6 --CF.sub. 3 
CH.sub.2 .dbd.CH--O--(CH.sub.2).sub.4 -- 
10 
O(CH.sub.2 --CH.sub.2 --O).sub.8 --CH.sub.3 
__________________________________________________________________________ 
The free-radical polymerization of the polymers according to the invention 
is carried out in accordance with the following prescribed general method. 
EXAMPLE 5 
160 g of isobutyl vinyl ether and 40 g of tetraethylene glycol monovinyl 
ether were initially introduced into a pressure reactor equipped with a 
stirrer and metering pump and heated under a nitrogen pressure of 10 bar 
to 120.degree. C. After the mixture had reached the prescribed 
temperature, 0.75 ml of tert-butyl peracetate were added. After the 
temperature had increased to 140.degree. C. as a result of the exothermic 
reaction, the mixture was allowed to react further for 30 minutes. Then 
0.75 ml of tert-butyl peracetate was added at a reaction temperature of 
140.degree. C. over a period of 45 minutes. The time allowed for further 
reaction was 45 minutes. The clear, slightly yellowish product which 
resulted had a viscosity of 960 mPas. Analysis by gel chromatography 
yielded a weight average molecular weight value of M.sub.w =1050. 
Other examples of copolymers prepared in accordance with Example 5 by 
varying the monomers and the initiator concentration are listed in the 
following Table 2. 
TABLE 2 
__________________________________________________________________________ 
Weight 
Initiator Modification with 
Example 
Monomers ratio [%] 
concentration 
M.sub.w 
hydrophobic solids 
__________________________________________________________________________ 
Example 6 
Isobutyl vinyl 
85 1% 1340 
None 
ether 
Hydroxybutyl 
15 
vinyl ether 
Example 7 
Isobutyl vinyl 
65 1% 1650 
None 
ether 
Ethyl vinyl ether 
20 
Hydroxybutyl 
15 
vinyl ether 
Example 8 
Ethyl vinyl ether 
80 2% 1950 
Same modification as 
Triethylene glycol 
20 described in Example 3 
vinyl ether 
Example 9 
2-Ethylhexyl vinyl 
75 2% 2400 
For use as as antifoam 
ether agent, after the reaction, 
Hydroxybutyl vinyl 
25 successive additions of 0.85 g 
ether of hexamethylene diisocyanate 
and 1.6 g of decylamine are 
made at room temperature 
and these additives are 
dispersed for 15 minutes. 
__________________________________________________________________________ 
EXAMPLE 10 
78 g of a copolymer according to Example 6 were initially introduced under 
an atmosphere of nitrogen into a four-necked flask equipped with a 
stirrer, reflux condenser, thermometer and inert gas feed and heated to 
70.degree. C. After the mixture reached the reaction temperature, 100 ppm 
of dibutyltin dilaurate and 56 g of a methoxypolyoxyethylene toluene 
diisocyanate adduct with the following structure 
EQU CH.sub.3 --(O--CH.sub.2 --CH.sub.2).sub.8 --O--CO--NH--(C.sub.6 H.sub.3 
CH.sub.3)--NCO 
were added over a period of 30 minutes. After allowing the stirring further 
for 60 minutes, a product was obtained which had a viscosity of 3850 mPas 
and a residual --NCO content of &lt;0.1%. Analysis by gel chromatography 
yielded a weight average molecular weight M.sub.w =3850. 
EXAMPLE 11 
58 g of .epsilon.-caprolactone were added to 78 g of copolymer according to 
Example 6 in a reaction vessel fitted with a stirrer and a reflux 
condenser, and after adding 100 ppm of dibutyltin dilaurate the mixture 
was heated under an atmosphere of nitrogen to 160.degree. C. After a 
reaction time of 6 hours, the product had a solids content of &gt;98%. 
Analysis by gel chromatography yielded a weight average molecular weight 
value of M.sub.w =2730. 
The copolymers listed in the examples were tested in the paint systems 1 
and 2 listed below. For comparison therewith, five homopolymers or 
copolymers of alkyl vinyl ethers, not according to the invention, were 
also tested. 
______________________________________ 
Comparison polymer 1: 
polyisobutyl vinyl ether 
M.sub.w 1150 
Comparison polymer 2: 
polyisobutyl vinyl ether 
M.sub.w 110000 
Comparison polymer 3: 
polyethyl vinyl ether 
M.sub.w 3650 
Comparison polymer 4: 
polyethyl vinyl ether 
M.sub.w 85000 
Comparison polymer 5: 
copolymer of 2-ethylhexyl 
M.sub.w 1250. 
vinyl ether and isobutyl 
vinyl ether 
______________________________________ 
Depending on the system being tested, the test criteria used were the 
leveling of the paint surface, the wetting of the substrate, the binder 
compatibility, and the foaming behavior during application. 
Leveling was assessed visually, with particular care being taken to observe 
the so-called "orange peel effect". A pronounced "orange peel effect" was 
considered a poor result, and a smooth homogeneous surface free from 
craters was regarded as a good result. 
Wetting was assessed visually and the result considered good if complete 
wetting of the substrate occurred. The result was considered poor if 
partial detachment of the wet paint film from the substrate occurred and 
consequently no homogeneous surface was produced. 
Binder compatibility was evaluated visually using transparent paint films 
100 .mu.m in thickness applied to glass plates. 
Foaming behavior was evaluted by visual assessment of emulsion paints 
applied using a foam-backed roller: 50 g of the emulsion paint were 
dispensed onto a penetration contrast card (500 cm.sup.2) and evenly 
distributed using a foam-backed roller in such a way that 12.5 g of wet 
paint (=250 g/m.sup.2) remained on the card. The use of a foam-backed 
roller (width 6 cm) composed of open-cell polyurethane foam enabled not 
only the foam bubbles entrapped in the paint to be assessed, but also the 
air which is incorporated in the paint film in a way similar to that with 
brush application. After drying, the paint film was visually assessed for 
air inclusions (bubble formation) in accordance with the following 
comparative scale: 
1=no air inclusions 
2=very little air inclusion 
3=little air inclusion 
4=moderate air inclusion 
5=pronounced air inclusion 
6=very pronounced air inclusion 
In addition, the air inclusion was assessed in % by volume by the following 
method: 80% by weight of the prepared emulsion paint was mixed with 20% by 
weight of water and stirred in each case for 1 minute at 2,000 rpm in a 
high speed mixer (rotor blade diameter 40 mm). The weight of 50 ml of this 
mixture was then determined. The higher the weight of the sample, the 
lower the air content and thus the greater the efficiency of the antifoam 
agent. 
As an example of molding compositions, glass fiber reinforced test plates 
(250 mm .times.250 mm .times.5 mm) were prepared by the injection molding 
process. After final curing and removal from the mold, the test plates 
were visually assessed for air entrapment, glass fiber wetting and 
transparency in accordance with the following comparative scales: 
air entrapment: 
1=no air entrapment 
2=very little air entrapment 
3=little air entrapment 
4=moderate air entrapment 
5=pronounced air entrapment 
6=very pronounced air entrapment. 
fiber wetting: 
1=very good fiber wetting 
2=good fiber wetting 
3=moderate fiber wetting. 
The results are compiled in Tables 3, 4 and 5 and clearly show the 
superiority of the agents of the invention. 
______________________________________ 
Paint 1: Photopolymerizable furniture varnish: 
Unsaturated polyester gloss resin 68% soln. 
92.59% by wt. 
in styrene 
Styrene 7.41% by wt. 
100.00% by wt. 
Curing: 
2 passes 
80 W/cm UV lamp 1.6 m/min. 
Paint 2: Gloss emulsion paint: 
Acrylate emulsion (Primal .RTM. AC 4800/Rohm and 
57.60% by wt. 
Haas) 40% conc. 
Preservative 0.10% by wt. 
TiO.sub.2 18.75% by wt. 
Dibutyl phthalate 2.34% by wt. 
Tri-n-butyl phosphate 3.50% by wt. 
Propylene glycol 7.50% by wt. 
Thickening agent 2.80% by wt. 
Wetting and dispersing agent 
0.85% by wt. 
Water 6.56% by wt. 
100.00% by wt. 
PVC: 18.5% 
Gloss 20.degree. (DIN 67,530): 80 
Injection Molding Resin: 
Unsaturated polyester resin based on 
98% by wt. 
isophthalic acid 
Cobalt octoate solution (1% solution) 
1% by wt. 
Peroxide hardener (MEKP) 1% by wt. 
100% by wt. 
______________________________________ 
TABLE 3 
______________________________________ 
Leveling test - Paint 1 
Con- Trans- 
Wetting of 
Example centration 
Leveling parency 
the substrate 
______________________________________ 
Comparison 
0.05% good cloudy 
good 
polymer 1 
Comparison 
0.05% craters cloudy 
craters 
polymer 2 
Comparison 
0.05% good cloudy 
good 
polymer 3 
Comparison 
0.05% craters cloudy 
craters 
polymer 4 
Comparison 
0.05% good cloudy 
good 
polymer 5 
Example 1 0.05% very good clear very good 
Example 2 0.05% very good clear very good 
Example 5 0.05% very good clear very good 
Example 6 0.05% very good clear very good 
Example 7 0.05% very good clear very good 
Example 10 
0.05% very good clear very good 
Example 11 
0.05% very good clear good 
______________________________________ 
TABLE 4 
______________________________________ 
Test of antifoam agent - Paint 2 
Con- Anti- Gloss degree 
Example centration 
foam Leveling 
at 20.degree. 
______________________________________ 
Comparison 
0.05% 4 good 74 
polymer 1 
Comparison 
0.15% 3 good 69 
polymer 1 
Comparison 
0.05% 6 craters not measurable 
polymer 2 
Comparison 
0.15% 6 craters not measurable 
polymer 2 
Comparison 
0.05% 5 good 73 
polymer 3 
Comparison 
0.15% 4 good 70 
polymer 3 
Comparison 
0.05% 6 craters not measurable 
polymer 4 
Comparison 
0.15% 5 craters not measurable 
polymer 4 
Comparison 
0.05% 4 poor 70 
polymer 5 
Comparison 
0.15% 3 poor 65 
polymer 5 
Example 3 
0.05% 3 good 79 
Example 3 
0.15% 1 very good 
81 
Example 4 
0.05% 3 good 80 
Example 4 
0.15% 1-2 good 80 
Example 8 
0.05% 2 good 80 
Example 8 
0.15% 1 very good 
79 
Example 9 
0.05% 3 good 80 
Example 9 
0.15% 2 good 79 
Blank Sample 
-- 6 good 80 
______________________________________ 
TABLE 5 
______________________________________ 
Evaluation of Injection Molded Test Plates 
Glass 
Air Fiber Trans- 
Example Dosing Entrapment 
Wetting 
parency 
______________________________________ 
Comparison Polymer 1 
0.05% 4 2 slightly 
turbid 
Comparison Polymer 2 
0.05% 1 2 turbid 
Comparison Polymer 3 
0.05% 5 3 slightly 
turbid 
Comparison Polymer 4 
0.05% 3 2 turbid 
Comparison Polymer 5 
0.05% 3 2 turbid 
Example 1 0.05% 3 2 clear 
Example 2 0.05% 3 2 clear 
Example 5 0.05% 2 1 clear 
Example 6 0.05% 1-2 1 clear 
Example 7 0.05% 2 2 clear 
Example 10 0.05% 2-3 2 clear 
Example 11 0.05% 2 1-2 clear 
______________________________________