Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
2 ~ 0 ~
8 BACK~OUND OF THE I~VENTION
The present invention relates to aqueous polymer dispersions ;~
10 and more particularly to aqueous polymer dispersions prepared by
polymerizing ethylen~cally un~aturated monomers or mixtures of such
12 monomers in the presence of a polymeric dispersant. ~ :
U.S. Patent No. 4,151,143 discloses the preparation of
14 emul~iion coating compositions characterized as being surfactant-free
produced by a two stage process. The first stage involves production
16 of a conventional carboxyl group-containing polymer from a mixture of
monomers composed of about 3-15 percent of a polymerizable carboxylic
18 acid or anhydride and at least one other polymerizable monomer. The
resulting carboxyl group-containing polymer of the first ~tage i8 then
20 water-dispersed (or solubilized) by neutralization with an organic - -
amine or base. In the second stage, a blend of "partially
22 water-soluble and p-rtially water-insoluble" monomers, along with a
free radical initiator, is added to the neutralized polymer of the
24 first stage, ant the resulting mixture is heated to effect
polymerization and protuce the polymer emulsion product to which the
~; 26~patent~is directed.~ It i8~ further disclosed therein that the monomer
mixture for the socond stage contains no polymerizable acid, but is
- 28~composed of monomers such as methyl, ethyl, propyl, and butyl acrylates
or methacryiates, beta-hydroxyethyl and beta-hydroxypropyl acrylate or
30 methacrylate, acrylamite and isobutoxymethyl acrylamide, and optionally
acrylonitr~le and styrene. By eliminating the presence of external
32 surfactants from the resulting emulsion coating, the water and humidity
resistaDce of hardened films produced therefrom is improved.
`: :
h317
While such a two stage process as disclosed in U.S. Patent
2 No. 4,151,143 provides certain advantages, the resulting emulsion
coatings, unless formulated and cured with an external crosslinking
4 agent such as an amino resin-type crosslinking agent, exemplifled by
hexamethoxymethyl melamine, tend not to provide a desirable degree of
6 organic solvent reslstance.
One ob~ect o the present invention is to provide an anionic
8 emulsifier-free, aqueous dispersion which can provide hardened films
having both good water (and humidity) resistance and good organic
10 solvent resistance without the need for utilizing external crosslinking
agents. Other ob~ects of the invention will become apparent to the
12 reader infra.
14 ~UM~ OF T~ INVENTIQy
The present invention provides an anionic emulsifier-free,
16 aqueous dispersion which does not require an external crosfilinking
agent to provide films (coatings) having a desirable combination of
18 both good resistance to water and humidity as well as good resistance
to organic solvents. An aqueous dispersion of the invention comprises
20 an amine-containing polymer in combination with an acid-functional
polymeric dispersant (e.g., containing carboxyl, acid anhydride,
22 sulfonic acid or an acid group of a monophosphate) which has been
neutralized by a volatile (fugitive) amine. The "amine" of the
24 am~ne-containing polymer can be considered as being a "fixed" or
"bound" amine, that is fixed as a result of being chemically bound in
26 the polymer 80 as not to be volatile from a film from the final polymer
dispersion product and yet be capable of interaction with acid -~
28 functionality from the acid-functional polymeric dispersant. ~ -
Additionally,i typically the basicity of the "fugitive" amine for
30 neutralization is stronger than the basicity of the "fixed" amine for
the amine-containing polymer 80 as to enhance stability of an aqueous
32 dispersion of the invention.
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The present invention also provides a two stage method for
2 preparing a preferred anionic emulsifier-free polymer dispersion
product which does not require an external crosslinking agent to
4 provide films having the aforesaid combination of good water and
organic solvent resistance. The two stage method is characterized, in
6 part, in that the mixture of polymer~zable monomers for the first stage
polymerization comprises from 5.0 to 85 percent by weight of an
8 ethylenically unsaturated carboxylic acid or anhydride and from 15 to
95 percent by weight of at least one copolymerizable ethylenically
10 unsaturated monomer different from the carboxylic acid or anhydride.
The first stage polymerization results in the formation of an
12 acid-functional polymeric dispersant having a weight average molecular
weight of from about 500 to about 100,000. The polymeric dispersant is
14 neutralized with a water-soluble, volatile amine (alternatively
referred to herein as a "fugitive amine") to an extent required to make
16 the polymeric di6persant water-dispersible or water-soluble.
The two stage method of the present invention is also
18 characterized, in part, in that the mixture of polymerizable monomers
for the second stage polymerization comprises from 8.0 to 50 percent by
20 weight of an ethylenically unsaturated monoamine, preferably having a
limited water solubility, the monoamine being present in tbe second
22 mixture in an amount sufficient to provide a ratio of equivalents of
amine groups from the monoamine to equivalents of acid (carboxyl)
24 groups from the polymeric dispersant in a range of from 0.15:1.0 to
1.0:1Ø The mixture of polymerizable monomers for the second stage
26 polymerization also comprises from 50 to 92 percent by weight of at
least one ethylenically unsaturated monomer different from and
28 copolymerizable with the ethylenically unsaturated monoamine.
' Afber or during film formation on a substrate from a polymer
30 dispersion product of the invention? fugitive amine evaporates from the
film; hence use of the word "fugitive". Also, after or during film
32 formation, as the fugitive amine evaporates, salt formation, believed
to result from interaction of the acid and fixed amine functionalitles
34 of the two polymers, occurs making the resultant film from the polymer
dispersion product surprisingly resistant to organic solvent such as
36 methylethyl ketone, acetone, etc.
~ 4
~ 0 1 7 ~ O ~
DET~IL~D D~SÇ~IPTIqN OF~GEi_L~ Iln~
2An anionic emulsifier-free, aqueous disper~ion of the
invention comprises an amine-containing polymer in combination with an
4 acid functional polymeric dispersant neutralized by a (fugitive)
volatile amine. The fixed amino groups from the amine-contalning
6 polymer and acid groups (e.g., carboxyl, acid anhydride, sulfonic acid
or acid group of a monophosphate) from the acid-functional polymeric
8 dispersant are present in the aqueous dispersion product in relative
amounts sufficient such that vaporization of the volatile amine from a
10 wet one mil thick film from the dispersion, devoid of any external
crosslinking agent, drawn down on a paper substrate and subjected to a
lZ predetermined temperature for a period of time, will result in salt
formation between the fixed amino groups from the amine-containing
14 polymer and acid groups from the carboxyl-functional polymeric
dispersant sufficient to provide a dry, organic solvent-resistant and
16 water-resistant, film.
Generally, the fixed amine functionality from the amine-
18 containing polymer and the acid functionality from the acid-functional -
polymeric dispersant are balanced such that a wet one mil thick film
20 from a polymer dispersion of the invention, devoid of any external -
crosslinking agent, when drawn down on a printed (simulated wood grain)
22 paper substrate (23 gramlmeter2 printing paper) laminated to a rigid
unterlying substrate such as particleboard and subjected to a ~-
24 predetermined temperature for a period of time to dry and harden the ~
film will result in a dry film which exhibits an acetone resistance of ~ ;
26 at least one minute, preferably at least 1 1/2 minutes, and a water
resistance of at least two minutes, preferably at least five minutes.
28 As used herein, acetone resistance of the dry film is
determined by placing 2 to 3 drops of acetone directly on the dry film,
30 allowing the acetone to remain on the film for a predetermined period
of time~ wiping the acetone away with a cloth, and observing the film
32 for breakthrough (failure) in the area tested. Failure occurs in this
test by dissolution of the film such that the film is broken through
34 allowing the acetone to attack the underlying substrate. For example,
~-:
~17~5
in thi6 te6t~utilizing the printed paper, when breakthrough occurs, the
2 acetone deteriorates the ink of the underlying printed area such that
the paper becomes discolored (e.g. lightens in the printed area).
4 As used herein, water resistance of the dry film ~s
determined by placing 2 to 3 drops of water directly on the dry film,
6 covering with a watch glass, allowing the water to remain on the film
for a predetermined period of time, wiping the water away with a cloth,
8 and observing the film for failure in the area tested. Failure occurs
in this test by softening of the film and the underlying paper such
10 that film and paper can be removed by scratching with a fingernail.
As used herein, the term "anionic emulsifier-free" is to be
12 understood to apply to an aqueous dispersion of the invention
containing from 0 to 2.0 percent by weight, preferably less than 1.0
14 percent by weight, of anionic emulsifier based on the combined weight
of amine-containing polymer and acid-functional polymeric dispersant in
16 the aqueous dispersion.
Without intending to be bound thereby, it is believed that
18 the surprising organic solvent resistance of a dry film from a
composition of the invention results from the interaction between the
20 fixed amino groups from the amine-containing polymer and acid groups
from the Pcid-functional polymeric di~persant as in a ~alt or polysalt
22 formed from the respective polymers.
Generally, fixed amino groups from the amine-containing
24 polymer and acid groups from the acid-functional polymeric dispersant
are present in an aqueous dispersion of the invention in relative
26 amounts sufficient to provide a ratio of equivalents of the fixed amino
groups to equivalents of the acid groups in a range of from 0.15:1.0 to
28 1.0:1.0, preferably from 0.25:1.0 to 0.75:1Ø Generally, to enhance
stability of an aqueous composition of the invention, the
30 amine-containing polymer of an aqueous dispersion of the invention is
essentially acid-free, meaning that the composition of monomers
32 utilized to prepare the amine-containing polymer contains not more than
5 percent by weight, preferably not more than 2 percent by weight, and
34 most preferably 0 percent by weight, of acid-functional monomer.
~al7~0~
An aqueous dispersion product of the invention can be
2 prepared, for example, by emulsion polymerization or suspension
polymerization. For example, an aqueous dispersion product of the
4 invention can be prepared by the following two stage method, which
illustrate6 a preferred method for preparing a preferred aqueous
6 dispersion product of the in~entlon. Given the disclosure taken as a
whole herein, other methods will become apparent. In the first stage, ~ -
8 a first mixture of polymerizable monomers comprising by weight from 5.0 ~-
to 85 percent, preferably from 20 to 65 percent, of an
10 alpha,beta-ethylenically unsaturated carboxylic acid or anhydride and ~
fro~ 15 to 95 percent, preferably from 35 to 80 percent, of at least ~-
12 one copolymerizable alpha,beta-ethylenically unsaturated monomer
different from said carboxylic acid or anhydride, is polymerized at a
14 temperature generally in the range of from 65C to 125C, preferably - ~
from 90C to lI0C, in the presence of a polymerization initiator, a -;
16 suitable solvent, and optionally a molecular weight regulator to form a
polymeric dispersant (as yet unneutralized) having a weight average
18 molecular weight of from about 500 to about 100,000, preferably from
about 1,500 to about 40,000 as determined by gel permeation
20 chromatography (GPC) using a polystyrene standard. The resulting
polymeric dispersant is neutralized with a water-soluble, volatile
22 amine (i.e., the fugitive amine) to an extent required to make the
polymeric disperaant water-dispersible or water-soluble, and a ~
24 dispersion or solution of the polymeric dispersant is formed in the ~ ~-
aqueous medium. Examples of fugitive amines suitable for
26 neutralization of the polymeric dispersant include: ammonia (considered
herein to be an amine), ethanolamine, diethanolamine, -
28 N-methylethanolamine, N,N-dimethylethanolamine, methylamine,
ethylamine, diethylamine, tri~ethylamine, triethylamine and morpholine.
In the second stage, a second mixture of polymerizable
monomers comprising by weight from 8.0 to 50 percent, preferably from
32 10 to 30 percent, of an alpha,beta-ethylenically unsaturated monoamine,
preferably having a limited water solubility, is combined with and
34 copolymerized with the dispersion or solution of the polymeric
dispersant in water from the first stage. The monoamine is present in
h (~ l 7
the second mixture in an amount gufficient to provide a ratio of
2 equivalent~ of amine groups from the monoamine to equivalents of
carboxyl groups from the polymeric dispersant in a range of from
4 0.15:1.0 to 1.0:1.0, preferably in a range of from 0.25:1.0 to 0.75 to
1Ø The Gecond mixture of polymerizable monomers al60 comprises by
6 weight from 50 to 92 percent of at least one copolymerizable
alpha,beta-ethylenically unsaturated monomer different from the
8 alpha,beta-ethylenically unsaturated monoamine. The relatlve amounts
of the first and second mixtures of polymerizable monomers for
10 preparation of a dispersion of the invention are such that the amount
of the second mixture of polymerizable monomers provides an amount by
12 weight of from about 40 to about 95 percent, of the total combined
weight of the first and second mixtures of polymerizable monomers. The
14 second mixture of polymerizable monomers and a polymerization initiator
is combined with the aqueous dispersion or solution produced in the
16 first stage discussed above. The combined mixture 80 formed is then
heated to effect polymerization and produce a polymer dispersion
18 product of the invention.
As discussed above, the first mixture of polymerizable
20 monomers contains an alpha,beta-ethylenically unsaturated carboxylic
acid or anhydride. The ethylenically unsaturated acid contains at
22 least one polymerizable double bond and at least one acid group,
preferably one CH2=0< group and one carboxylic acid group, and
24 preferably contains from 3 to 12 carbon atoms. While acrylic acid and
methacrylic acid are preferred, other suitable ethylenically
26 unsaturated carboxylic acid monomers may be used such as itaconic acid, ~-
crotonic acid, maleic acid, and Cl to C8 alkyl half-esters of maleic
28 and fumaric acids, such as butyl hydrogen maleate and ethyl hydrogen
fumarate, in~which one carboxyl group is esterified with an alcohol.
The first mixture of polymerizable monomers also contains at
least one copolymerizable alpha,beta-ethylenically unsaturated monomer
32 different from the unsaturated carboxylic acid or anhydride. Examples
of other ethylenically unsaturated monomers which can be used include
34 the alkyl acrylates, such as methyl acrylate, ethyl acrylate, butyl
acrylate, propyl acrylate, 2-ethylhexyl acrylate and isobornyl
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acrylate; the alkyl methacrylates, such as methyl methacrylate, butyl
2 methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl
methacrylate and isobornyl methacrylate; hydroxyalkyl acrylates and -~-
4 methacrylates such as hydroxyethyl acrylate, hydroxypropyl acrylate,
hydroxyethyl methacrylate and hydroxypropyl methacrylate;
6 N-alkoxymethyl acrylamides and methacrylamides such as N-butoxymethyl
acrylamide, N-butoxymethyl methacrylamide, N-ethoxymethyl acrylamide
8 and N-ethoxymethyl methacrylamide; and unsaturated nitriles, such as
acrylonitrile, methacrylonitrile and ethacrylonitrile. Other
10 ethylenically unsaturated monomers (vinyl monomers) which may be used
in addition to the aforesaid monomers include: vinyl aromatic
12 hydrocarbons (optionally substituted, for example, by halo atoms) such
as styrene, alpha-methyl styrene, alpha-chloromethyl styrene and vinyl
14 toluene; and vinyl aliphatic hydrocarbons (optionally substituted, for
example, by halo atoms) such as vinyl acetate and vinyl chloride. The :~
16 selection of such other ethylenically unsaturated monomers for the
first mixture of polymerizable monomers i8 not particularly limited
18 provided that such other monomers do not contain functionalities that
would, in the amounts employed, interfere with production of the
20 carboxyl-functional product, for example, utilization of interfering
amounts of unsaturated monomers, such as 1,2-epoxy functional
22 ethylenically unsaturated monomers, which would react with carboxyl
functionality of the ethylenically unsaturated carboxylic acid or
24 anhydride to a deleterious degree under the reaction conditions for
polymerization.
26 Organic solvents which may be utilized in the polymerization
of the first mixture of polymerizable monomers include virtually any of
28 the organic solvents heretofore employed in preparing conventional --
!acrylic or vlnyl addition polymers such as, for example, alcohols,
30 ketones, aromatic hydrocarbons or mixtures thereof. Illustrative of
organic solvents of the above type which may be employed are alcohols ~--
32 such as lower alkanols containing 2 to 4 carbon atoms including
ethanol, propanol, isopropanol, and butanol, and simple glycols such as
34 ethylene glycol and propylene glycol; ether alcohols such as ethylene :~
glycol monoethyl ether, ethylene glycol monobutyl ether, propylene
,, , ~ , j; ' , !; ; . ` ' . ' ' ' ` ~ '
~730~ -
glycol monomethyl ether, and dipropylene glycol monoethyl ether;
2 ketones ~uch as methyl ethyl ketone, methyl N-butyl ketone, and methyl
isobutyl ketone; esters such as butyl acetate; and aromatic
4 hydrocarbons such as xylene, toluene, and naphtha.
A vinyl polymerization initiator i8 employed in the
6 preparation of a resin of the invention. Examples of initiators
include: perbenzoates such as tertiary-butyl perbenzoate; peroxides
8 such as benzoyl peroxide and cumene hydroperoxide; peracetates such as
tertiary butyl peracetate; azo compounds such as alpha
10 alpha'-azobis(isobutyronitrile); percarbonates such as isopropyl
percarbonate, peroxycarbonates 6uch as butyl isopropyl peroxy
12 carbonate, and similar compounds. The quantity of initiator employed
can be varied considerably however, in most instances, it is deslrable
14 to utilize from about 0.1 to about 10 percent by weight based on the
weight of ethylenically unsaturated monomers used. Where desired,
16 although not preferred, a molecular weight regulator such as a chain
modifying agent or chain transfer agent can be added to the -
18 polymerization mixture for control of the molecular weight of the
resulting polymeric disper~ant. Examples of such agents include the
20 mercaptans, such as tertiary dodecyl mercaptan, dodecyl mercaptan,
octyl mercaptan, and hexyl mercaptan.
22 Polymerization of the first mixture of polymerizable monomers
to farm the polymeric dispersant (as yet unneutralized) is typically
24 conducted by free radical, organic solution polymerization techniques
generally known in the art.
26 As discussed above, the second mixture of polymerizable
monomers compriseg an alpha,beta-ethylenically unsaturated monoamine,
28 preferably having a limited water solubility. The
alpha,beta-ethylenically unsaturated monoamine may be a primary,
30 secondary, or a tertiary amine. Examples of such unsaturated
monoamines include essentially water insoluble monoamines such as
32 tertiary-butylaminoethyl methacrylate and meta-isopropenyl-alpha,
alpha-dimethylbenzylamine, and partially water soluble monoamines such
34 as diethylaminoethyl methacrylate, the essentially insoluble monoamines
,
~7 ~ ... . . , .. . ~ . . , I
,, ~" 10
being preferred, t-butylaminoethyl methacrylate being particularly
2 preferred. The more water 801uble monoamines such as dimethylaminoethyl
methacrylate may also be employed where desired, for example, either
4 alone or in combination with an essentially water insoluble unsaturated
monoamine such a~ t-butylaminoethyl methacrylate or with a partially
6 soluble monoamine ~uch as diethylaminoethyl methacrylate, although - ~
monoamines having such higher degree of water solubility typically are ~-
8 not employed in preferred embodiments of the present invention. In the
preferred embodiment, the ethylenically unsaturated monoamine i8
10 selected to promote transfer of the monoamine into the particulate
phase during the second stage polymerization rather than remain in the
12 aqueous med~um. Unsaturated diamines or higher amino-functional
unsaturated amines typically are not employed, and if so, should not be
14 employed in amounts 80 as to cause flocculation or gelation in the
second stage polymerization.
16 As discussed above, the second mixture of polymerizable
monomers also comprises at least one copolymerizable ethylenically
18 unsaturated monomer different from the ethylenically unsaturated
monoamine. Examples of such copolymerizable monomers for the second ~-~
20 mixture which may be utilized include: alkyl acrylates, alkyl
methacrylates, hydroxyalkyl acrylates and methacrylates, N-alkoxymethyl
22 acrylamides and methacrylamides, unsaturated nitriles, vinyl aromatic ~- -
hydrocarbons (optionally substituted), and vinyl aliphatic hydrocarbons
24 (optionally substituted), examples of which copolymerizable monomers
are set forth above in the description of other ethylenically
26 unsaturated monomers which may be utilized in the first mixture of ;~
polymerizable monomers. The selection of such other copolymerizable
23 monomers for the ~econd mixture of polymerizable monomers is not
particularly limited. Of the examples of copolymerizable monomers set
30 forth above, the alkyl acrylates, alkyl methacrylates and vinyl ;~
aromatic hydrocarbons are preferred. In a particularly preferred
32 embodiment of the invention, the second mixture of polymerizable ;~
monomers additionally comprises by weight from 1 to 10 percent,
34 preferably from 1 to 2 percent, of a copolymerizable ethylenically
unsaturated monomer having one 1,2-epoxy group (a copolymerizable
~3~7~
ethylenically un~aturated monoepoxide). Examples of such unsaturated
2 monoepoxides include: glycidyl acrylate, glycidyl methacrylate, allyl
glycidyl ether, methallyl glycidyl ether and glycidyl esters of
4 polymerizable polycarboxylic acids such as maleic acid, fumaric acid,
and crotonic acid. Preferred are the epoxy-functional acrylates such
6 as glycidyl acrylate, epoxy-functional methacrylates such as glycidyl
methacrylate, or mixtures thereof, glycidyl methacrylate being
8 particularly preferred. It is believed that utilizat~on of a low level
of ethylenically unsaturated monoepoxide promotes chemical bonding of
10 the polymeric surfactant to the other copolymerized monomers (during
copolymerization~ and it helps to render more compatible the
12 acid-functional polymer and amine-containing polymer.
As discus~ed above, the second mixture of polymerizable
14 monomers and a polymerization initiator is combined with the aqueous
dispersion or solution produced in the first stage discussed above.
16 The combined mixture 80 formed is then heated to effect polymerization
and produce a polymer dispersion product of the invention.
18 Polymerization is usually conducted at a temperature below 100C,
typically at temperatures between 20C and 85C. Polymerization
20 initiators which may be used include one or more peroxides or
persulfates which are known to act as free radical initiators and which
22 are soluble in the aqueous medium. ~xamples include the persulfates
such as ammonium, sodium and potassium persulfates. Also, oil-soluble
24 initiator may be employed either alone or in addition to the
water-soluble initiator. Typical oil-soluble initiators include:
26 organic peroxides, such as benzoyl peroxide, tertiary-butyl peroxide
and cumene hydroperoxide; perbenzoates such as tertiary-butyl
28 perbenzoate; peracetates such as tertiary butyl peracetate; azo
initiators such as alpha alpha'-azobis(isobutyronitrile); percarbonates
30 sucb as isopropyl percarbonate; peroxycarbonates such as butyl
isopropyl peroxy carbonate; and similar compounds. The quantity of
32 initiator employed can be varied considerably; however, in most
instances, it is desirable to utilize from about 0.1 to about 10
34 percent, typically from about 0.50 to about 5.0 percent, by weight
based on the weight of ethylenically unsaturated monomers used.
- 12 - :
hal730
The following examples illustrate the invention and should
2 not be construed as a limitation on the scope thereof. Unlefis
specifically indicated otherwise, all percentage~ and amounts are
4 understood to be by weight. Wherever used herein "PBW" means part~ by
weight .
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Examp~,el
2 This example illustrates the preparation of a di~persion of
the lnvention.
Parts by weight Parts by weight
6 Ingredients (grams) (~olid~_
Initial C,,ha~g~
deionized water 217.5
12 ammonium persulfate 2.2 2.2
14 Pre-em~laiQn
16 deionized water 208.2
Acryllc disper~antl734.2 170.2
18 tertiary butylaminoethyl
methacrylate 87.4 87.4
20 methyl methacrylate324.0 324.0
ethyl acrylate 74.0 74.0
22 glycidyl methacrylate8.0 8.0
24
(1) This polymeric acrylic dispersant was prepared from 70 percent
26 styrene, 29 percent acrylic acid and 1 percent ethyl acrylate on a
weight basis.
28
A reaction vessel equipped with condenser, thermometer,
addition funnels and nitrogen inlet and outlet tubes was charged with
32 the initial charge and heated to about 78C. Ten (10) percent of the
pre emul~ion (about 150 ml) was added to the vessel and the mixture
34 held at 78C for about 20 minutes. The reaction exothermed and heating
was discontinued until the temperature fell to about 78C.
36 Subsequently, the remaining pre emulsion was added over a 2 hour
period. Thereafter? the reaction mixture was held at 78C for 'two
38 hours. The contents of the reactor vessel were cooled and filtered.
~7~
~xiample 2
2 This example illustrates the preparation of a further
dispersion of the invention.
4 Parts by weight Parts by weight
Ingredi~ts (grams) (solids)
8 Initial Charg~
10 deionized water 217.5 ~`
ammonium persulfate 2.2 2.2
12
14 Pre-emul6ion
delonized water 319.9
16 Acrylic dispersant2 586.2 170.2 ~-
tertiary butylaminoethyl ; -
18 methacrylate 46.8 46.8
methyl methacrylate 378.2 378.2
20 ethyl acrylate 88.7 88.7
glycidyl methacrylate 8.6 8.6
22
Addi~ion 1
24
28 percent ammonium solution 58.6
26
28 (2) This polymeric acrylic dispersant was prepared from 30 percent methyl
methacrylate, 30 percent ethyl acrylate and 40 percent acrylic acid on
30 a weight basis. ~-
32
A reactor vessel equipped as described in Example 1, above,
34 was charged with the initial charge and heated to about 78C. Ten - ~-
percent of the pre-emulsion was added to the vessel and the mixture
36 held at about 78C for 20 minutes. Sub6equently, the remaining
~ pre-emulsion was added over 2 hours. Thereafter, the reaction mixture
38 was held at about 78C for 2 hours followed by Addition 1 whic4 was
added over a 30 minute period. This reaction was scrapped because the
40 ammonium solution did not mix in.
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Example 3
2 Thi8 example illustrates the preparation of yet another
dispersion of the invention.
4 Parts by weight Parts by weight
In~redients (~rams) (sQlid~)
8 Initial Ch~g~
10 deionized water 217.5
ammonium persulfate 2.2 2.2
~re-emul~ion
14
deionized water 313.9
16 Acrylic dispersant of footnote 2 586.Z 170.2
ammonium hydroxide 58.6
18 tertiary butylaminoethyl
methacrylate 87.4 87.4
20 methyl methacrylate 324.0 324.0
methyl acrylate 74.0 74.0
22 glycidyl methacrylate 8.0 8.0
24 A reactor vessel equipped as described in Example 1, above,
was charged with the initial charge and heated to about 78C. In
26 preparing the pre-emulsion, the ammonium hydroxide solution was added
to the dispersant before adding to the other ingredients of the
28 pre-emul6ion. Ten percent of the pre-emulsion was added to the vessel
and the mixture held at about 78C for about 20 minutes. Subsequently,
30 the remaining pre-emulsion was added over a 2 hour period. Thereafter,
the reaction mixture was held at about 78C for 2 hours. The reaction
32 mixture was cooled and filtered.
34 Example 4
This example illustrates yet another dispersion accor!ding to
36 the present invention.
38 Parts by weight Parts by weight
IngFedi_nt~ ~gra~s) (solid9 ?
42 InitiaL Charge
44 deion~zed water 217.5
ammonium persulfate 2.2 2.2
- 16 -
~3~73~
Pre-emul6ion
deionized water 313.9
4 Acrylic dispersant of footnote 2 586.2 170.2
28% ammonium solution 58.6
6 tertiary butylaminoethyl
methacrylate 46.8 46.8
8 methyl methacrylate 378.2 378.2
ethyl acrylate 88.7 88.7
10 glycidyl methacrylate 8.6 8.6
12 A reactor vessel equipped as described in Example 1, above,
was charged with the initial charge and heated to 78C. Ten percent of
14 the pre-emulslon was added over a 5 minute period and held for 15
minutes at about 78C. The reaction exhibited a slight exotherm.
16 Subsequently, the remaining pre-emulsion was added over a 2 hour
period. Thereafter, the reaction mixture was held at about 78C for 2
18 hours. The mixture was allowed to cool and filtered.
':
~xampl~_5
This example illustrates yet another dispersion according to ~
22 the present invention. -
24 Parts by weight Parts by weight
Ingrediell~ (gr~m~ (solids)
26
28 Initial Charge
30 deionized water 217.5 -~
ammonium persulfate 2.2 2.2
32 - -
Pre-emulsion
34
delonized water 313.9
36 Acrylic dispersant of footnote 2 506.2 170.2
28% ammonium solution 58.6
38 tertiary butylaminoethyl -
methacrylate 23.4 23.4
40 methyl methacrylate 428.4 428.4
ethyl acrylate 96.0 96.0
42 glycidyl methacrylate 8.3 8.3
44 This example was prepared in the manner described above for
the previous examples. -
- 17 -
~017a~
Example 6
2 This example illustrateg yet another di~persion according to
the present invention.
Parts by weight Parts by weight
6 Ingre~lents (~ram~) (solids)
Initial ~ha~g~
deionized water 217.5
12 ammonium persulfate 2.2 2.2
14 Pre-~mul~iQn
16 deionized water 313.9
Acrylic dispersant of footnote 2 586.2 170.2
18 28% ammonium solution58.6
tertiary butyla~inoethyl
20 methacrylate 22.0 22.0
methyl methacrylate 428.4 428.4
22 methyl acrylate 96.0 96.0
glycidyl methacrylate 8.3 8.3
24
Th~s example was prepared in the manner described above for
26 the previous examples.
28 ExampLe_7
This example illustrates the preparation of and properties of
30 a coating from a coating composition utilizing a dispersion of the
invention.
32 . -~
Parts by weight
34 Ingredien~$ (grams)
36 Dispersion of Example 5 298.00
, , ethylene glycol monobutyl ether 6.25
38 M-PYROL 1.88
Q 2-71193 3.76
40 SURFYNOL 104A4 3.76
28% ammonia water 3.50
- 42
44 (3) This is a polymethyl siloxane silicone fluid from Dow Corning.
46 (4) This is a non-ionic surfactant from Air Products.
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- - 18 -
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The resulting coating composition of the invention had a
2 solids content of 42.0 percent.
A first, thin layer of clear, wet film of coating composition
4 was applied by direct roll coat to the surface of a 23 gram/meter2
decorative paper imprinted with a wood pattern which paper was
6 laminated to 8 particleboard sub~tri~te. The resulting wet film wa6
dried by passing the coated laminate through a high velocity air oven.
8 The dwell time for the film in the oven was 11 seconds and the oven
temperature was 400 degreea Fahrenheit (204C). A second, thin layer
10 of clear, wet film of coating composition was applied in the same -
manner directly over the resulting dry film from the first layer of
12 coating composition. The second layer was dried in the same manner as
the first layer.
14 The re~ulting clear, dried film had a total maximum dry film
thickness of about 0.8 mils. The film cratered severely.
16
Example 8 -~
18
Parts by weight
20 Ingre~ie~ts (grams)
22 Dispersion of Ex5ample 1 100.00 --
TEGO FOAMEX 7447 1 90
24 28 percent ammonia water 4 50 -~
SURFYNOL 4406 0.80
26 AEROSOL OT 757 1.00
TEGO GLIDE 1008 0.30
28 ethylene glycol monophenol ether 8.10
deionized water 20.00
32 (5) This defoamer is commercially available from TEGO Chemie. It is an
oil in water emulsion of a hydrophobic polysiloxane polyether
34 copolymer.
36 (6) This is an ethoxylated tetramethyl decyndiol from Air Products.
38 (7) Sodium dioctyl sulfosuccinate from American Cyanamid.
40 (8) This mar resistance and flow additive from TEGO Chemie is a
polysiloxane polyether copolymer.
-- 19 --
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This composition was applied as has been deta~led above in
2 Example 7.
The resultant clear, dry fllm was te~ted for solvent
4 resistance and water resi~tance accordlng to the tests described
herein. The film had an acetone resistance of 1 minute and a water
6 resistance in excess of 10 minutes.
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