Note: Descriptions are shown in the official language in which they were submitted.
lQ9;~Z35
_scriPtion of the Invention
In the use of aqueous dispersions of emulsion
polymers~ the particles of which are water-insoluble, the
effectiveness of the dispersion in forming a film after the
polymer dispersion has been coated upon a surface to be
painted depends upon the glass transition temperature of the
dispersed polymer and the temperature at which the coating is
allowed to dry. This is particularly well pointed out in the
B Conn et al U.S. Patent~ 2~795~564~ which discloses the
applicability of many acrylic polymers in the making of water-
based paints. As pointed out in that patent, the polymer
obtained in aqueous dispersion by emulsion polymerization of
one or more monoethylenically unsaturated monomers (having a
group H2C - C~) may have an apparent second order transition t
temperature~ or glass transition temperature which depends
upon the components and the proportion of such components in
the polymer. The patent points out that certain of this type
of monomer~ such as methyl methacrylate~ (styrene~ vinyl
acetate, vinyl chloride~ and acrylonitrile being similar in
this respect) tend to produce homopolymers which have
relatively high glass transition values~ the particular glass
transition temperature referred to in that patent being
designated by the symbol Ti as defined in the patent. The
monomers just referred to~ when homopolymerized, produce hard
1093Z35
polymers, that is, polymers having a glass transition tempera-
ture or Ti value above 200C. On the other hand~ the patent
,mentions numerous monomers of monoethylenically unsaturated
type which produce relatively soft homopolymers, this
characterization representing polymers having glass transi-
tion temperatures or Ti value of 200C. or less.
The patent referred to discloses that by
copolymerizing various hard and/or soft monomers in predeter-
mined proportions, a copolymer can be obtained having a pre-
determined glass transition temperature or Ti value in a wide
range from well below -400 C. up to 150 C. or higher. Coat-
ings made from aqueous dispersions of the various polymers
may be such that application of the coating compositions or
aqueous-based paints made from such polymers can be effected
at normal room temperature or even lower with expectation of
good film-forming qualities if the Ti value of the particular
polymer involved is not abDve the ambient temperatures at ',
which the coating is performed. For example~ coatings made
from aqueous-based paints containing a polymer having a Ti
value of about 15 C. generally can be applied at room
temperatures and result in good film formation simply by
drying of the coated film in the ambient atmosphere. On the
other hand, if the coating composition contains as its primary
film-forming component an emulsion polymcr having a Ti value
above room temperatures, such as from about 350 C. and up,
lQ93Z35
the coated film obtained from such a paint may require
elevated temperatures~ such as 35 C, and up~ during drying
in order to assure that the polymer particles are adequately
coalesced or fused into a continuous coherent film during
the drying. Some polymers may be characterized by a glass
transition temperature substantially above room temperature
such as up to 30-35 C. but still would be capable of forming
a continuous film at normal room temperatures because of an
affinity for water (hydrophilicity) of a particular polymerized
unit in the dispersed polymer particles. An example of such
a monomeric component is vinyl acetate. The hydrophilicity of
polymer as a result of its content in substantial amount of
vinyl acetate (or equivalent monomer) aids in coalescing the
polymer particles into a continuous film at temperatures lower
than the ~i value of such polymer as determined by a standard
test.
The making of water-based paints with polymers
having low Ti values to enable the aqueous-based paint to be
applied at normal room temperatures without the use of a
plasticizer results in films which in many cases are inade-
quately hard and tough after drying, On the other hand, the
use of polymers having high glass transition temperatures
substantially above room temperature such as above 35 C.
generally requires the presence of a permanent or fugitive
~5 plasticizer (the plasticized polymer having a lower Ti value)
lQ9;~Z35
or a high temperature of drying in order to provide good
continuous films on the surfaces coated.
U.S. Patent No. 4,131,580, granted
December 26, 1978, discloses the incorporation of
dicyclopentenyl acrylate or dicyclopentenyl methacrylate
as a coalescent in such aqueous film-forming polymer
dispersions, these compounds being individually designated
DCPA and DCPMA respectively~ and generically as DCP(M)A.
However~ these compounds~ in spite of their low volatility~
have an odor that is quite characteristic, pervasive,
persistent~ and objectionable under certain conditions when
put into use by certain operating personnel They are also
too volatile for use in certain aqueous finishes~ especially
those used or applied industrially~ which require baking at
elevated temperatures. DCP(M)A also tends to produce ex-
tremely hard and brittle products which may require plasti-
cizers.
In accordance with the present invention, these
disadvantages have been practically overcome by addition of
a monomeric material of formula I hereinafter to aqueous
coating compositions~ such as water-based paints, prepared
from aqueous dispersions of vinyl addition polymers including
water-soluble addition polymers dissolved therein and water-
insolu~ addition polymers dispersed therein as insoluble
particles of minute size~ e.g. from 0.1 to 5 or 10 microns
1{~9;~235
average diameter~ such as those obtainable by emulsion
polymerization. The use of these compounds provides a
versatility to such compositions not heretofore obtained
without great trouble and expense~ as explained hereinafter.
me compounds used in the present invention are
the ester-ether compounds of the general formula I following:
~2c=c(R)-c(o)-O-R~- o_
wherein R is H or CH3, and
R is an alkylene group having 2 to 12, preferably
2 to 6~ carbon atoms or an oxaalkylene group having at least
4 to 12 carbon atoms and having one or more oxygen atoms
joining distinct segments of the alkylene groups, each such
segment having at least two carbon atoms.
R, in preferred embodiments~ represents the
alkylene or oxaalkylene group of a (C2 to C6)-diol or of a
(C2 to C6)-glycol containing one or two oxygen atoms joining
2- or 3-carbon atom segments of the alkylene.groups. The
ester-ether chain may be connected to either the 5-position
or the 6-position of the ring nucleus as indicated in the
general formula I. In fact~ the product may comprise a mix-
ture of the two compounds in Gne of which the ester-ether
chain is substituted in the 5-position and in the other of
which the ester-ether chain is substituted .n the 6-position.
-6-
~93Z35
The monomers of formula I may be prepared by
first reacting dicyclopentadiene with excess diol, using
an acid catalyst to produce an intermediate ether
(hydroY~y-R-0-dicyclopentadiene) and then esterifying the
hydroxyl of the intermediate with acrylic or methacrylic
acid, using an acid catalyst, such as sulfuric acid, p-
toluenesulfonic acid, and boron trifluoride. Examples of
diols include ethylene glycol, propylene glycol, neopentyl
glycol, 1,3-butylene glycol, 1,6-hexanediol, diethylene
glycol, dipropylene glycol, and triethylene glycol. ~he
monohydroxyglycol ester obtained in the first step is
preferably isolated, as by distillation, and then is
esterified with acrylic or methacrylic acid, using an
acid catalyst. Instead, the second step may be an acylation
f the mono-ether with (meth)acrylic acid chloride or an-
hydride or a transesterification with a simple ester, such
as methyl (meth)acrylate, in the presence of a neutral or
basic catalyst.
In accordance with the present invention, it
has been found that the addition of a non-volatile reactive
monomer of formula I above to coating compositions based on
vinyl addition polymers of monoethylenically unsatu ated
B
lQ9;~;~3S
monomers~ particularly those having a terminal group
H2C = C <~ is extremely valuable and useful for the purpose
of favoring the ease of coating~ facility of film-forming
action during drying at normal room temperatures and also
by rendering the coated film of greater hardness and tough-
ness as a result of the reactive, air-curing characteristics
of the monomer of formula I above. In general~ a small
amount of a drier or siccative, by which is meant the type
of salt or complex of a polyvalent metal that is commonly
employed to hasten the oxidation of drying oils~ may be
added to accelerate the curing of the coating film during
drying. The proportion of formula I monomer in the coating
composition may fall within a wide range depending upon the
particular composition~ its components and particularly the
content of film-forming polymer therein and its apparent
second order transition temperature.
When added to an emulsion polymer dispersion~ the
formula I monomer plays a role that is quite advantageous.
Like DCP(M)A~ it can serve as a coalescent in that it acts
as a plasticizer for the dispersed polymer particles. If
the dispersed polymer has a Ti that is above room temperature~
e.g., 35 C.~ so that coating compositions~ such as water-
base paints~ made from the polymer dispersion would ordinarily
not form a continuous film on drying at ambient conditions~
enough formula I monomer can be mixed into the polymer
1093Z35
dispersion or coating composition containing such polymer
dispersion to lower the Ti and the effective film-forming
temperature sufficiently to enable the coatings obtained on
coating the compositions to form continuous films at ambient
temperature. At the same time, on air-drying of the films
the product becomes hard and block-resistant because of the
autoxidizable nature of the composition. However~ an
ester-ether of formula I has an advantage over DCP(M)A in
that it does not have an objectionable (or even a detectable)
odor that might bother operator personnel who prepare the
compositions and/or persons who use them under most conditions
of preparation and use. Even those compostions which are
subjected to elevated temperatures during preparation or use~
such as in applying the compositions in atmospheres of high
temperature or subjecting coated or impregnated articles to
baking temperatures as high as 150 C. or even higher~ emit
little or no objectionable odor because of the extremely low
volatility of the formula I monomer. By virtue of the extra
"0-R" present in the formula I compounds herein as compared
to DCP(~)A~ the extremely low volatility is apparently ob-
tained. In addition, the extensive variation in the specific
composition of the radical R provides a factor by which the
combination of hardness (brittleness) and softness (toughness)
in the cured product can be varied widely. The selection of
R and R can be made to correlate with the particular fi]m-
lC~9;~Z35
forming polymer in the aqueous polymer system to provide a
wide range of properties in the final product. Thus~ the
compounds of formula I provide versatility that allows a -
wider array of applications of polymer dispersions in which
one prefers not to replace a polymer of one constitution with
a polymer that has a different compositional structure.
Similarly~ when the formula I monomer is added to
coatings based on an aqueous dispersion of an emulsion
polymer having a low Ti such that film-formation at room
temperature would occur without the formula I monomer~ the
films obtained from the formula I monomer-containing polymer
composition are hardened and toughened upon the air-curing
of the formula I monomeric contents thereof.
The coating compositions preferably contain one
or more siccatives or driers. The drier used is any poly-
valent metal-containing complex or salt that catalyzes the
oxidative curing of drying oils or drying oil-modified alkyd
resins. Examples of the driers are various polyvalent metal
salts including calcium~ copper~ zinc~ manganese~ lead,
cobalt~ iron and zirconium as the cation. Simple inorganic
salts are useful such as the halide~ chloride, nitrate,
sulfate. Salts of organic acids such as the acetylacetonate,
acetate~ propionate~ butyrate and the like are also useful.
The driers may also be complex reaction products of metal
2~ oxides, acetates, or borates and vegetable oils.
-10-
lQ93Z35
Useful driers also include salts of naphthenic acids or of
(C8 to C30) aliphatic acids. Examples of the aliphatic or
fatty acid component or anion of the drier salt is that of
naphthenic acids, resinic acids, (that is~ rosin acids),
tall oil fatty acids~ linseed oil fatty acids, 2-ethylhexoic
acid~ lauric acid, palmitic acid, myristic acid, stearic
acid~ oleic acid, linoleic acid, linolenic acid, behenic
acid~ cerotic acid, montanic acid, and abietic acid. Preferred
drier salts are those of cobalt and manganese, such as
cobalt octoate, cobalt naphthenate and manganese octoate and
naphthenate. Mixtures of various driers may be used. The
driers mentioned in "Encyclopedia of Chemical Technology~"
Kirk-Othmer, Volume 5, pages 1~5-205, published by
Interscience Encyclopedia, Inc.~ N.Y. (1950) may be used.
The proportion of the drier may be quite low and
it is generally used in the amount of 0 0005 to 2% metal con-
tent by weight of the formula I monomeric material. The drier
may be added to the composition prior to storage provided
such addition is made in the absence of oxyge~ or a volatile
stabilizer is included in the composition to inhibit or pre-
vent the oxidizing action of the drier and the composition
is placed in closed storage containers to prevent volatiliza-
tion of the inhibitor.
Thus, a volatile stabilizer may be used in coating
compositions containing a reactive monomer of formula I to
-11-- .-
prevent adventitious polymerization thereof in the
formulated composition at any time prior to film formation.
The fugitive stabilizer must exhibit sufficient volatility
in thin films so as to not retard the development of film
properties to any appreciable extent. The stabilizer may be
used in a small proportion of 0 1% to 2% by weight based on
the weight of the formula I monomer component. The stabilizer
is generally a volatile ketone-oxime obtained from ketones
having 3 to lO carbon atoms or an aldehyde-oxime derived from
aldehydes having l to lO carbon atoms. Specific examples are
methyl ethyl ketone-oxi~e, methyl butyl ketone-oxime,
5-methyl-3-heptanone-oxime~ cyclohexanone-oxime~ and
butyraldehyde-oxime. Addition of such inhibitors is
essential if long stability and pot life of the aqueous com-
positions containing dispersed polymer formula I monomer and
drier are desired.
While the compositions of the present invention
comprising an aqueous dispersion of a vinyl-type addition
pol~ner~ a formula I monomer, a drier, and a volatile oxime
~0 have characteristic rapid development of tack-free cure of the
film by autoxidation~ the rate of cure can be accelerated by
replacing a part of the formula I monomer with a drying oi]
fatty acid or a salt thereof, such as the ammonium or alkali
metal (e.g. sodium~ potassium or lithium) salt. ~ince the
2~ aqueous coating compositions of the present invention~
1~J93Z35
especially the pigmented types, such as water base paints,
contain dispersing agents~ the drying oil fatty acid may be
in the form of alkaline earth salts, e.g. calcium or
magnesium~ but ordinarily the ammonium or alkali metal salts
are preferred. The extent of acceleration obtainable in this
way depends on the proportion of the formula I monomer that
is replaced by the drying oil fatty acid and while there may
be as much as one-third or more replacement by such fatty acid~
generally a replacement of from 1% to 25% by weight of the
ether-ester monomer of formula I provides quite a practical
operating range~ and preferably 5% to 10% replacement is the ;
most useful. Examples of drying oil fatty acids include;
linoleic~ linolenic~ linseed oil fatty acids~ tung oil fatty
- dehydrated
acids~ tall oil fatty acids~ soyabean oil fatty acids~castor
oil fatty acids~ etc. Since the coating compositions are
often alkaline~ the fatty acid may be in salt form~ especially
as the ammonium salt.
The coating compositions may contain~ of course~
other materials as pointed out in the patent referred to
earlier including pigments~ dispersing agents, sequestering
agents~ defoaming agents, humectants~ thickeners, bactericides,
fungicides~ odor-modifying agents~ and other resinous materi-
als in dispersed forms. The various pigments and other
materials that are mentioned in the earlier patent may be used.
-13-
~093235
In general~ the proportion of formula I monomeric
material that is used in the coating composition may be from
about 1% to 200% by weight, preferably 5% to 150% based on
the weight of the vinyl addition polymer constituting the
main film-forming component of the coating composition. It
- is to be understood that the acrylic polymers described in
et al, U.S. Patent 2,795,564, m3~ioned here~ ve, are not the
only types of vinyl addition polymers that can be modified
and improved by the inclusion of the formula I monomer with
a drier. In the copolymer systems of the patent, the harden-
ing component is a lower me~hacrylate~ such as methyl
methacrylate~ but similar copolymer systems in which the
hard lower methacrylate is partly or completely replaced by
such hardening monomers as styrene, vinyltoluene,
acrylonitrile, methacrylonitrile, vinyl chloride~ vinylidene
chloride~ or vinyl acetate are also improved by the inclusion
of formula I monomer and a drier. It has been found that the
formula I monomer is also useful in conjunction with aqueous
coating systems based on natural latices or synthetic latices
produced from butadiene, chloroprene, styrene/butadiene
copolymers, acrylonitrile-butadiene-styrene copolym~rs and
related svnthetic rubber systems which have low Ti values.
~ilms obtained from these dispersions are also improved in
respect to hardness by the incorporation o~ a formula I
monomer wlth a drier.
-14-
l~)9;~Z3S
The use of a reactive monomer of formula I makes
it possible to obtain hard~ tough coating films from coating
compositions which comprise a polymer having a low Ti (which
would normally form a soft film). The benefits can be ob-
tained without the use of a plasticizer or with a greatly
reduced amount of permanent plasticizer in the compositions.
The incorporation of formula I monomer in coating
compositions is not restricted to those in which the film-
f~rming component comprises or consists essentially of
water- m soluble dispersed particles of a polymer or copolymer.
It is also useful in conjunction with aqueous solutions of
vinyl addition polymers wherein the solubility of the polymer
is essentially true solubility by virtue of low molecular
weight of the polymer containing hydrophilic groups as well
as those characterized ~y the formation of colloidal solutions.
The soluble polymers may derive their solubility
from a large content of hydrophilic groups such as acid mers
which can be in acid or in salt form. Examples of such acids
include acrylic acid~ methacrylic acid~ crotonic acid~ ita-onic
acid, maleic acid, citraconic acid, aconitic acid, and the
like. The salts may be those of ammonia, amines, such as
dimethylamlnoethanol, triethylamine~ 2-amino-2-methyl-1-pro-
panol, and the like~ or an alkali metal~ especially sodium,
potassium or lithium. Besides polymers containing large
proportions of acid units such as poly-acrylic acid,
., ~,
~Q~ 35
polymethacrylic acid~ or copolymers such as copolymers of
15% methacrylic acid and 85% butyl methacrylate, there may be
used copolymers containing a large proportion of acrylamide
or methacrylamide units or polymers containing a large
proportion of amine units such as homopolymers of
oxazolidinylethyl acrylate or copolymers of the latter amine-
containing polymer with up to 20% by weight of methyl
acrylate Water-solubility may also be derived from
polymerized mers containing hydroxyl groups, such as
hydroxyethyl acrylate or methacrylate~ 2-hydroxypropyl
acrylate~ 3-hydroxypropyl acrylate. Water-solubility can
also be the result of copolymerization of two or more types
of the hydrophilizing monomers mentioned herein. The use of
a formula I monomer with a drier in these instances serves to
modify the character of the final coating film
The use of the formula I monomer in the coating
compositions serves several functions or purposes In
aqueous solutions of water-soluble polymers it aids the
adjustment of viscosity to facilitate coating without the
necessity to dilute the solution excessively with water or
other water-miscible volati'e solvent. The formula I monomer
then becomes part of the binder component on air-drying and
contributes to the solvent-resistance, water-resistance,
alkali-resistance~ gloss~ hardness~ and toughness of the
cured coating films. In coating compositions based on
aqueous dispersions of water-insoluble po]ymer particles,
Z35
e.g., obtainable by emulsion polymerization~ the formula I
monomer serves as a coalescent~ hardener~ toughener~ viscosity-
controlling aid~ and so on. In all cases~ the formula I mono-
mer~ on air-dry curing of the coating compositions containing
the vinyl polymer~ formula I monomer~ and drier~ becomes part
of the binder in the final cured coating films. Avoidance of
volatile organic solvents also reduces pollution.
The non-volatile~ reactive component may~ and
preferably does~ consist essentially of formula I monomeric
material but~ if desired~it may comprise a mixture of at
least a major proportion (e.g. 51% to 99% by weight) thereof
and a minor proportion of other non-volatile reactive
ethylenically unsaturated monomeric material selected from
(1) a higher (C10-C20)aliphatic ester of acrylic or meth-
acryliC acid~ e-g- (C10-c20)alkyl and (C10 C20)
acrylates and methacrylates, and (2) a ~inyl ester of a
higher (C10-C20) aliphatic acid~ or a minor proportion of
non-volatile~ reactive di-(Cl-C8)alkyl maleates~ fumarates~
and itaconates. Optionally, to improve water~-, solvent-,
abrasion-~ and blocking-resistance, the non-volatile reactive
formula I monomer-containing material may also comprise a
small amount up to 30%~ preferably 2 to 20%, by weight, based
on binder weight, of a polyethylenically unsaturated material,
such as glycol or polyol (meth)acrylates~ e.g. ethylene glycol
di(meth)acrylate, l,~-butanediol di(meth)acrylate~ 1~6-hexane
diol di(m~th)acrylate5 1~3-butylene glycol dimethacrylate~
-17-
- 1~9323S
neopentyl glycol di(meth)acrylate, pentaerythritol tri- and
tetra-~meth)acrylate~ trimethylolpropane trimethacrylate;
also allyl-(meth)acrylates. Examples of the esters(l) are
decyl acrylate~ isodecyl acrylate~ undecyl acrylate, lauryl
acrylate~ cetyl acrylate~ pentadecyl acrylate, hexadecyl
acrylate, octadecyl acrylate, the corresponding methacrylates,
and the unsaturated analogs~ such as oleyl acrylate or
methacrylate~ linoleyl (meth)acrylate~ linolenyl (meth)acrylate,
and so on. Examples of (2) are vinyl decanoate~ vinyl
laurate, vinyl oleate, vinyl palmitate~ vinyl myristate~ and
vinyl stearate. Examples of the diesters inc]ude dimethyl,
diethy~ dibutyl, dihexyl, and di-(2-ethylhexyl) maleate~
fumarate~ and itaconate.
In the following examples~ which are illustrative
of the invention, the parts and percentages are by weight and
the temperatures are in C unless otherwise noted. Also~the
various latices of emulsion copolymers used are:
Latex A - copolymer of 42.5 EA/56.~MMA/l.OMAA~
neutralized with ammonia to a pH of about 9 5~ 47% solids,
Ti about 41C., particle size about 0.1 micron.
Latex B - copolymer of 35BA/64MMA/lMAA, pH of
9(NH3)~ 45% solids, Ti about 380 C.~ particle diameter about
0.15 micron,
-18_
1~9~235
Latex C - copolymer of 45.6BA/53.4MMA/lMAA~
pH of 9(NH3), 45% solids~ Ti about 240 C , particle diameter
about 0.15 micron.
Latex D - copolymer of 54.7BA/~3.8~MA/1. 5~IAA,
pH of 9(NH3)~ 45% solids~ Ti of 13 C.
Latex E - copolymer of 85% vinyl acetate and 15%
butyl acrylate~ 45% solids~ Ti about 15 C., pH of 4.
Latex F - copolymer of 40% vinyl acetate~ 37%
butyl acrylate and 23% vinyl chloride~ 45% solids, Ti about
15 C.~ pH of 4, and
Latex G - copolymer of 18BA/81. 5~A/0.5~AA,
neutralized to about 9.2 pH by trimethylamine, 37.3% solids,
Ti of 600 C.~ particle diameter about 0.1 micron.
NOTE: EA = ethyl acrylate~ BA = butyl acrylate~ MMA = methyl
methacrylate~ and MAA = methacrylic acid, the proportions in
the copolymer being weight proportions or weight ratios.
In some of the examples hereinafter~ comparisons
are made with conventional non- reactive materials heretofore
used as latex polymer coalescents~ such materials being
referred to herein as "fugitive" coalescents because of their
tendency to evaporate~ even though slowly~ in contrast with the
coalescent materials of the present invention. These non-
reactive, fugitive coalescents include:
2~2~4-trimethyl-1~3-pentanediol monoisobutyrate
hereinafter designated TPM
-19-
lU5~;~235
i
2-butoxyethanol hereinafter designated BE.
n-butoxypropanol hereinafter designated BP. ~-
acetate of the butyl ether of diethylene glycol
hereinafter designated BDA.
Example 1
Dicyclopentenyloxyethyl methacrylate (hereinafter
designated "Monomer la") is added gradually with stirring to
Latex A in a proportion of 40% on latex solids. Cobalt (II)
acetylacetonate (0.2% metal on latex solids plus monomer) and
methyl ethyl ketone oxime (0.26% on latex solids plus monomer)
stabilizer are added and the mixture is stirred overnight to
ensure complete solubilization of the metal drier.
TPM is added similarly to another sample of Latex
A in a proportion of 20% on ]atex solids.
Films are cast at room temperature and Table I
shows hardness development as a function of time.
TABLE I
- Room Temperature Knoop
Hardness Number (KHN) Development
64 hr. 72 hr. 88 hr. 9 days
Latex containing
40% Monomer la 4.5 4.1 5.1 6.0
Latex containing
20% TPM o.3 o.4 o.4 o 4
-20- ;
1(~93Z35
With the fugitive coalescent TPM and because of
its slow evaporation, this latex film requires several weeks
~p to months at ambient temperature to develop full hardness
(KHN = 4-5). In contrast, with the autoxidatively curable
coalescent (Monomer la), hardness development is much more
rapid and the ultimate hardness of the film is increased
(KHN = 6-7). Further~ Monomer la imparts no odor to the
formulation.
ExamPle 2
!
Monomer la is further tested as a convertible
latex coalescent versus the fugitive coalescents TPM, BE and
BP in Latices B andC~ neither of which without a coalescent
forms a coherent film at room temperature. In respect to
this latter characteristic, Latices B and C are like Latex A.
The fugitive coalescents are added with stirring to
portions of each latex at levels of 10 and 20 weight percent
based on latex solids.
To other portions of each latex Monomer la is
added with stirring at levels of 10, 20, and 40 percent.
Cobalt (II) acetate (0.1% metal based on weight of monomer
and latex solids), 70% aqueous t-octylphenoxypoly(39)ethoxyeth-
anol (1% on latex solids), and methyl ethyl ketoxime (0.25%
on monomer and latex solids) are then added with thorough
stirring. A similar set of Monomer la-containing latex
preparations is made but with the cobalt and oxime omitted.
-21-
1093Z35
Films are cast at room temperature on aluminum test panels
to yield a dry film thickness of about 2.2 mils. Table II
shows the hardness development with time, impact resistance~
and cheesecloth prlnt resistance (wherein~ at 140 F.,
cheesecloth is placed against the film under a pressure of
2 lbs. per square inch for l hr.). The print resistance is
measured after two weeks at ambient conditions and rated
from 10 = no print to 0 = very heavy print.
With the commonly used coalescent TPM, development
of hardness and print resistance is exceedingly slow~ as is
also the case with uncatalyzed Monomer la. Use of the more
volatile BE and BP confers significantly more rapid property
development. However, use of Monomer la with cobalt
catalyst and oxime stabilizer not only confers excellent
property development to the coating but does so without
wastage of raw materials and without pollution and exposure
of personnel to solvent vapors.
-22-
1{~93~35
~,
. 1,
. '.
I ~o~o~o~ ~oo~
. I
~ I
~ l
, ~
o oo oo ooo
P; ~ ~ v V ~ v V V
oo~ ~ooo~ ooo~o~oooooc~ o
0 a
~ h
H
0
0~0~0 ~ ~ O O O ~ ~ 0 0~0~ ~0 0 0
r~o~o o ~oo o ~ ~ ~o ~ ooo
~O . . - . . . . . . . . . -
~ ~ O O~i 0 0~ C~oO a) O O ~i ~i ~ O O O O ~ ~ ~
~ .~
U~ U~
~q ~ a) a
~~ c~ ~O~D~OO~oO~ ~ 00~000~000~
al ~a . .. . . .. , ~ . . . . . .. . . .. ~1
c~h r' r-10~10000~ ~ 00000000000 0
E~ 0
P~ ~ a
O P~
a~o~ I~o ~o~ ~ o o ~ 0 ,~ ,~O
. . - - - - ta - ~ s 0 0 0
r~ oo~c~loo~oo~ ooooooo+~
v r~ ~/ v v v r~
0 ~
H H
H ~' H
`_
O V
~ 3 ~
oooooo ~ ooooo o
O ~ C~
o .~ 01 N
OO 0~ F I I a) O o ~ h
C)~ N O O a) ) C) r I (~ O O O ~ (o O
tl~ N N ~3 u) r 1 N ~1 N ~3 ~J
a~^ o-- -- -- -- -- u, a) o -- = = = _
_ _ - - - ~ V ~
0 P~ o ~ 0 ~ ~ ~ r~ ~ P~ O
~m~ ~ s~ O E~ m m
~ V ~ ~ V
+~ * * ~ 0 ~ * * *
~~~ 0 ~--~ ~ 0
~`J ~ ~) C~oo a,~o * ~ .--~ N ~1~D ~c~ c~ o ,~
23S
Example ~ i
Although the novel coatings of Example 2 contain-
ing monomer la and cobalt catalyst exhibit an excellent rate
of property development, this rate can be further accelerated
by formulating with low levels of drying oil fatty acids.
Thus~ the tack-free time of coating 9 of Table II is reduced J
from about 24 hours to about 16 hours and about 8 hours re-
spectively by replacement in part of monomer la with 5 a~d
10 percent of either tung oil fatty acid or linseed oil fatty
acid.
Example 4
Comparable results are obtained when Examples 1,
2~ and 3 are repeated~ substituting for monomer la~ a corres-
ponding proportion of each of the following monomers of
1~ formula I hereinabove, the chemical name of the monomer in
each instance being given a short designation for reference
hereinafter:
a) Dicyclopentenyloxyethyl acrylate (Monomer ]b)
b) Methacrylate ester of neopentyl glycol mono-
dicyclopentenyl ether (Monomer 2)
c) Acrylate ester of neopentyl glycol mono-
dicyclopentenyl ether (Monomer 3)
d) Methacrylate ester of 1,2-propylene glycol
monodicyclopentenyl ether (Monomer 4)
e) Acrylate ester of 1~2-propylene glycol
monodicyclopentenyl ether (Monomer ~)
-24-
1~ 235
f) Methacrylate ester of 1,3-butylene glycol
monodicyclopentenyl ether (Monomer 6)
g) The acrylate ester corresponding to the
methacrylate of f) above (Monomer 7)
h) Dicyclopentenyloxyhexyl- acrylate (Monomer 8)
i) Dicyclopentenyloxyhexyl methacrylate (Monomer 9)
j) Dicyclopentenyloxyethoxyethyl methacrylate
~onomer 10)
k) Dicyclopentenyloxyethoxyethyl acrylate
(Monomer 11)
All of these monomers of formula I exhibit the
same autoxidizable characteristic in the presence of a
siccative and air or oxygen while having at least as low a
vapor pressure as Monomer la.
Example 5 - Semi~loss Paints of hard latex ~polYmers
A pigment paste is prepared by mixing and
grinding (e.g. in a Cowles dissolver at 3500 fpm for 20
minutes) the following materials in the specified weight
proportions: Parts
Dispersant (an ammonium salt
methacrylic acid copolymer) 7.48
,. .. *
Defoamer (Nopco NDW) 2.00
Propylene glycol 59.8
Rutile TiO2 269.6
The resulting pigment dispersion is then let-down with the
following materials (Table III) dcpending on the paint prepared:
* ~ra~r~ -25-
lQ9;~ S
TABLE III
MATERIAL PARTS in PAINT No.
? ~ -4
Propylene glycol 57. 8 57 . 8 57 . 8 57 . 8
Latex B (45~ solids) 578 578 __ __
Latex C (4~ solids) -- ~~ 578 578
Preser~ative ( Super-
Ad-It")~ 1.0 1.0 l.0 l.0
Water 15.2 15.2 15.2 15.2
Coalescent
TPM 25.9 __ 25.9 --
Monomer la -- 98 . 4 -- 98 . 4
Linseed oil fatty acid -- 5. 2 -- 5. 2
Methyl et~Yl ketoxime -- 0.9 -- 0.9
l~ Surfactan* (64~) 2 2 2 2
Defoamer ("Nopco NDW"**) 2 9 2 . 9 2 . 9 2 . 9
- Thickener ~-Natrosol
250 MR2*)2 63.0 63.0 63.0 63.0
Co II acetate
(2.37% Co II) __ 15.0 __ 15.0
dioctyl sodium sulfosuccinate
2 2. 5% aqueous hydroxyethyl cellulose
.
After mixing the paints, they are adjusted to
pH of 9.6 by addition of ammonium hydroxide.
The paints are applied to aluminum panels to
yield a dry film thickness of 1.5-2.0 mils~ The development
of film hardness (Knoop Hardness Number), and specular gloss
are followed with time and are shown in Table IV.
The coatings containing Monomer la, cobalt,
and oxime exhibit good gloss and wet state stabillty. Hardness
development is excellent, and, moreover, the coatings do not
waste raw materials and are non-polluting.
Super -Ad-It" is a trademark for a mercurial preservative
made by Tenneco Chemicals.
. Trademark
** Trademark
P~
l~9;~Z35
U ~ o
C
~ ~ ~ o ,, oo o
U ~1 ~D ~ ~ ~ ~ ~
C
P ~o
~ ~ C~
c 1~ ~ O O ~ N 00 ~
~t
C~J t U h
~ ~
c
t~
C . C)
~ ~t
P C'
O ~i ,~
t~ ~ . t~ ~ O
C ~1 ~D ~ , 'D
~ ~ '
~;
tP
O
r~t
:~
V) ~
h u~ ~ tn
a~ v~ ~, rt ~~a.) h
,~. ~ ~ ~ U) ,~
Eta ~ ~) ~C~
:~
~;~ ~n ~~ u~
u~ u~ o~ ~, O ~
V) u~ ~ h I_t ~ ~
o a~ ~ ~ _ ~a rt
~ . ~ E3 _ ~1 ;3 ~:
C~ h ~ ~ Q. O ~ lr~
:~ ~ ~S ~ Ei r~
:~ ~ ,t ,-t a~ --~ t
h ~1 ;~- u) ~ ~ a) h
q~ ~ O O "~ 1:~ N a~ '~
Q ~ O .,~ - c) ~ ~ o a~ ~ "
o o O o O ~~ O O a~ ~ ~;
h ~ O O ~:; E3~t ~ O ~ h t~
P~ U~ ~O ~ ~c~ ~ ~,i h ,~ ~ r-t
." , i
,~
1~93Z35
Example 6
Latex E and Latex F above are formulated using
the conventional fugitive coalescent TPM and Monomer la for
comparison. The coalescents (10, 20, or 30% by weight on
latex solids) are slowly added to the latex copolymers with
stirring. Where herein indicated, Co(II) acetate (0.10%
metal on latex solids and monomer) is added with thorough
stirring. Films are cast on aluminum test panels and allowed
to dry at room temperature to give a dry film thickness of
about 1.7 mils. The latex copolymers even without coalescent
~. ' .
form apparently continuous films at room temperature. The
.~ ,
development of film hardness and cheesecloth print resistance
is shown in Table V.
TABLE V
Latex E _Knoop Hardness Number Print
~lescent L dav ~ dav 7 daY 1.4 dav
TPM~ 10% II<0.10 <0.10 0.13 0.13
Mon. la~ 10%, Co ~0.10 0.23 0.27 0.28 3
" -- 20% '~ ~0.10 o.35 0.44 0.41 3
" 3% " ~0.10 0.38 0.35 0.47 4
None 0.26 0.33 0.32 0.32 3
Latex F
TPM, 10% II<0.10 0.16 0.18 0.17 2
Mon. la, 10%, Co C0,10 0.16 0.27 0.25 3
~ 20% " ~0.10 0.21 0.34 0.28 3
" 30% " <0.10 0.20 0.47 o.38 3
None 0.17 0.52 0.40 0.31 4
-
*Measured after 2 weeks drying;
at 250 G. under 2 psi for 24 hours.
-28-
lV9;~Z35
The coatings containing the conventional fugitive
coalescent required for film formation at temperatures below
normal room temperature remain tacky through two weeks. In
contrast, the coating compositions containing Monomer la
yield tack-free films within 2-3 days. In addition, the
hardness development and print resistance developed by the
films containing Monomer la is comparable to or even better
than that of films obtained without added coalescents.
Example 7 - Low TemPerature Bakin~ Latex Polymer Coatin~s
Monomer la is used as a coalescent and compared
with the fugitive coalescent TPM in Latex B using short time
baking at moderately elevated temperatures to accelerate cure.
The coatings are prepared by mixing,in the order given:
Com~osition No.
1 2
Latex B (45~) 27.8 27.8 27.8
"Triton x-405"* (70%) 0.27 0.27 0.27
Monomer la 5.0 5.0
TPM . 5
Cobalt acetate (10~ aqueous)0.7~
The freshly prepared coatings are cast on test
panels and evaluated for hardness at severai times after
various cure conditions as given below:
* Trademark for an a ~ l~yl polyether nonionic dispersant
sold by the Rohm and Haas ~any.
1~235
Comp.
No. Cure Tukon Hardness after:
2 hours 2~ hours _8 hours
1 180F/60 min. 3.3 2.6 5.1
120F/60 min. 0.3 1.4 4.0
Room Temp. <0.2 0.2 2.8
2 180F/60 min. 0.4 1.1 o.8
120F/60 min. 0.2 0.2 0.2
Room Temp. <0.2 <0.2 0.2
; 10 3 180F/60 min. 1.9 1.6 2.4
120F/60 min. 0.4 0.~ 0.5
Room Temp. <0.2 0.2 0.3
me system containing monomer la with cobalt catalyst has
excellent response to accelerated cure at elevated temperature
and without wastage of raw materials and pollution of the
environment.
Example 8 ---Coating Compositions Comprising a Soft Acrylic
-~ Latex Copolymer
Monomer la is tested as a latex coalescent in
Latex D which is capable of forming a f'ilm at room temperature
without the use of a coalescent. The latex is formulated
variously with TPM (fugitive coalescent) and Monomer la
with cobalt acetate catalyst (0.1~ metal on latex solids plus
monomer). The freshly prepared compositions are cast on
steel test panels to yield 1.7 mil films when dry and after
one and two weeks at room temperature they are tested
for hardness and cheesecloth print resistance with the
results shown in Table VI. ~onomer la confers significantly
improved hardness and print resistance to the films of
soft latex.
-3
109;~;~35
TABLE VI
Coalescent Knoop Hardness Print Resistance*
lweek 2 weeks 1 week 2 weeks
None 0.18 O. 24 4 4
TPM~ 10% O. 24 0. 23 4 4
Mon. la~ 10% O. 42 0 . 34 7 7
" 20% o. 84 o. 58 7 6
: 30% 1.15 1.06 8 7
250 c., 2 psi for 24 hrs.
.
10E~ample_~
Monomer la is used in Latex G as a convertible
latex coalescent to yield a hard~ rapidly air-drying, non-
polluting latex coating vehicle and is compared to a similar ,
coating employing BDA as fugitive coalescent. Ti of the latex
polymer is 600 C. and it is incapable of forming~a film at
room temperature without coalescent. Coating compositions
are prepared by mixing~ in the order given:
Latex G ( 37 . 3%)
Water 6.5 6.5 6.5
Surfactant* (70%) o. 86 o. 86 o. 86
Monomer la 4. 0 4. 0 --
BDA
Cobalt acetate tlO% aqueous) O. 59 -- --
* t-octylphenoxypoly(39)ethoxyethanol
lQ9;~235
The freshly prepared compositions are cast on
aluminum test panels to yield 1.8-mi~ thick films when dry andare
evaluated for hardness development with the following results:
1 2
Knoop Hardness No.
2 days 16.0 0.6 3.0
7 days 19.2 0.9 12.7
Print Resistance at
9 days (1~0F/l hr.,
2 psi) 7 4 6
- ExamPle 10
Examples 5 through 9 are repeated, replacing
Monomer la with a corresponding proportion of each of the
following reactive monomers of formula I:
1) Monomer lb.
2) Monomer 4.
3) Monomer 5.
~) Monomer 6
5) Monomer 8.
6) Monomer 9.
7) Monomer 10.
The results obtained are quite comparable with those obtained
when Monomer la is used. As in all the examples above employing
the latter monomer, the incorporation of these other monome~s
of formula~I is free of any odor so that formulators do not
encounter this objection to their use.
