U.S. patent application number 13/386855 was filed with the patent office on 2012-05-17 for coated container device, method of making the same.
This patent application is currently assigned to DOW GLOBAL TECHNOLOGIES INC.. Invention is credited to Charles F. Diehl, Ray E. Drumright, Bernhard Kainz, Richard A. Lundgard, David L. Malotky, Jodi M. Mecca.
Application Number | 20120118785 13/386855 |
Document ID | / |
Family ID | 43020396 |
Filed Date | 2012-05-17 |
United States Patent
Application |
20120118785 |
Kind Code |
A1 |
Kainz; Bernhard ; et
al. |
May 17, 2012 |
COATED CONTAINER DEVICE, METHOD OF MAKING THE SAME
Abstract
The instant invention provides a coated container device, and
method of making the same. The coated container device according to
the instant invention comprises: (1) a metal substrate; and (2) one
or more crosslinked coating layers associated with the metal
substrate, wherein the one or more crosslinked coating layers are
derived from the application of one or more aqueous dispersions to
at least one surface of the metal substrate, and wherein the one or
more aqueous dispersion comprise: (a) one or more a base polymer;
(b) one or more a stabilizing agent; (c) optionally one or more
neutralizing agents, (d) one or more crosslinking agents; and (e)
water.
Inventors: |
Kainz; Bernhard; (Lauf,
DE) ; Lundgard; Richard A.; (Midland, MI) ;
Malotky; David L.; (Midland, MI) ; Mecca; Jodi
M.; (Midland, MI) ; Diehl; Charles F.; (Lake
Jackson, TX) ; Drumright; Ray E.; (Midland,
MI) |
Assignee: |
DOW GLOBAL TECHNOLOGIES
INC.
Midland
MI
|
Family ID: |
43020396 |
Appl. No.: |
13/386855 |
Filed: |
July 23, 2010 |
PCT Filed: |
July 23, 2010 |
PCT NO: |
PCT/US2010/043086 |
371 Date: |
January 24, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61228366 |
Jul 24, 2009 |
|
|
|
Current U.S.
Class: |
206/524.3 ;
413/1 |
Current CPC
Class: |
B05D 2701/00 20130101;
B65D 25/14 20130101; B05D 2401/20 20130101; B05D 2202/00
20130101 |
Class at
Publication: |
206/524.3 ;
413/1 |
International
Class: |
B65D 79/00 20060101
B65D079/00; B21D 51/00 20060101 B21D051/00 |
Claims
1. A coated container device or a coated closure device comprising:
a metal substrate; and one or more crosslinked coating layers
associated with said metal substrate, and wherein said one or more
crosslinked coating layers are derived from the application of one
or more aqueous dispersions to at least one surface of said metal
substrate, and wherein said one or more aqueous dispersions
comprise; one or more base polymers; one or more stabilizing
agents; one or more crosslinking agents; and water.
2. A method for making a coated container device or a coated
closure device comprising the steps of: selecting a metal
substrate; selecting one or more aqueous dispersions comprising;
one or more base polymers; one or more stabilizing agents; one or
more crosslinking agents; and water; applying said one or more
aqueous dispersions to at least one surface of said metal
substrate; removing at least a portion of the water from said one
or more aqueous dispersions; thereby forming one or more
crosslinked coating layers associated with said metal substrate;
and forming said coated metal substrate into a coated container
device or a coated closure device.
3. A method for making a coated container device or a coated
closure device comprising the steps of: selecting a metal
substrate; forming said metal into a container device; selecting
one or more aqueous dispersions comprising; one or more base
polymers; one or more stabilizing agents; one or more crosslinking
agents; and water; applying said one or more aqueous dispersions to
at least one surface of said container device or said closure
device; removing at least a portion of the water from said one or
more aqueous dispersions; thereby forming one or more crosslinked
coating layers associated with at least one surface of said
container device or said closure device; and thereby forming said
coated container device or said coated closure device.
4. Any of the claims 1-3, wherein said base polymer comprises one
or more polyolefins.
5. Any of the claims 1-3, wherein said metal substrate is a
pre-coated metal substrate.
6. (canceled)
7. (canceled)
8. (canceled)
9. (canceled)
10. (canceled)
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a non-provisional application claiming
priority from the U.S. Provisional Patent Application No.
61/228,366, filed on Jul. 24, 2009, entitled "COATED CONTAINER
DEVICE, METHOD OF MAKING THE SAME," the teachings of which are
incorporated by reference herein, as if reproduced in full
hereinbelow.
FIELD OF INVENTION
[0002] The instant invention relates to a coated container device,
and method of making the same.
BACKGROUND OF THE INVENTION
[0003] The application of various treatment and pretreatment
solutions to metals to retard or inhibit corrosion is well
established. This is particularly true in the area of metal food
and beverage cans as well as non-food metal containers. Coatings
are applied to the interior of such containers to prevent the
contents from contacting the metal of the container. Contact
between the metal and the food or beverage as well as non-food
substances can lead to corrosion of the metal container, which can
then contaminate the food or beverage or the non-food contents of
such metal containers. Corrosion is particularly problematic when
food and beverage products are highly acidic nature and/or are
having a high salt content such as a rhubarb-based products or
isotonic drinks. Also strong alkaline contents of non-food
substances such as hair-dye may react with metal such as aluminum.
The coatings applied, for example, to the interior of food and
beverage cans also helps prevent corrosion in the head space of the
cans, which is the area between the fill line of the food product
and the can lid. The coatings may be applied to the outside of
metal containers to provide protection against the external
environment or to provide a decorative layer including fillers
and/or pigments. In addition to corrosion protection, coatings for
food and beverage cans should be non-toxic and inert, and, if
applied to the internal surface, should not adversely affect the
taste or appearance, e.g. color, of the food or beverage in the can
or contribute to a contamination of the contents of the can.
Resistance to "popping", "blushing" and/or "blistering" is also
desired. Certain coatings are particularly applicable for
application onto coiled metal stock, such as the coiled metal stock
from which the ends of cans are made, "can end stock" and valve
cups, e.g. top ends of aerosol cans. Since coatings designed for
use on can end stock are applied prior to the ends being cut and
stamped out of the coiled metal stock, they are also typically
flexible and/or extensible. For example, can end stock is typically
coated on both sides. Thereafter, the coated metal stock is punched
and may be beaded or bended. It may also be scored for the
"pop-top" opening and the pop-top ring is then attached with a pin
that is separately fabricated. The end is then attached to the can
body by an edge rolling process. Accordingly, the coating applied
to the can end stock typically has a certain degree of toughness
and flexibility, such that it can withstand extensive fabrication
processes, in addition to some or all of the other desirable
features discussed above. Various coatings such as epoxy-based and
polyvinyl chloride-based, e.g. organosol type, coatings have been
used in the past to coat the interior of metal cans to prevent
corrosion. However, there is a need for food and beverage can
liners as well as non-food container liners that provide improved
properties such as having resistance to degradation in corrosive
media as well as appropriate level of flexibility.
SUMMARY OF THE INVENTION
[0004] The instant invention provides a coated container device,
and method of making the same.
[0005] In one embodiment, the instant invention provides a coated
container device comprising: (1) a metal substrate; and (2) one or
more crosslinked coating layers associated with the metal
substrate, wherein the one or more crosslinked coating layers are
derived from the application of one or more aqueous dispersions to
at least one surface of the metal substrate, and wherein the one or
more aqueous dispersions comprise: (a) one or more base polymers;
(b) one or more stabilizing agents; (c) optionally one or more
neutralizing agents, (d) one or more crosslinking agents; and (e)
water.
[0006] In an alternative embodiment, the instant invention further
provides a method for making a coated container device comprising
the steps of: (1) selecting a metal substrate; (2) selecting one or
more aqueous dispersions comprising: (a) one or more base polymers;
(b) one or more stabilizing agents; (c) optionally one or more
neutralizing agents, (d) one or more crosslinking agents; and (e)
water; (3) applying the one or more aqueous dispersions to at least
one surface of said metal substrate; (4) removing at least a
portion of the water from the one or more aqueous dispersions; (5)
thereby forming one or more crosslinked coating layers associated
with at least one surface of the metal substrate; and (6) forming
the coated metal substrate into a coated container device.
[0007] In another alternative embodiment, the instant invention
further provides a method for making a coated container device
comprising the steps of: (1) selecting a metal substrate; (2)
forming the metal into a container device; (3) selecting one or
more aqueous dispersions comprising; (a) one or more base polymers;
(b) one or more stabilizing agents; (c) optionally one or more
neutralizing agents, (d) one or more crosslinking agents; and (e)
water; and (4) applying the one or more aqueous dispersions to at
least one surface of the container device; (5) removing at least a
portion of the water from the one or more aqueous dispersions; (6)
thereby forming one or more crosslinked coating layers associated
with at least one surface of the container device; and (7) thereby
forming the coated container device.
[0008] In an alternative embodiment, the instant invention provides
a coated container device, a method for making a coated container
device, in accordance with any of the preceding embodiments, except
that the metal substrate is a pre-coated metal substrate.
[0009] In an alternative embodiment, the instant invention provides
a coated container device, a method for making a coated container
device, in accordance with any of the preceding embodiments, except
that the one or more base polymers comprises one or more
polyolefins.
[0010] In an alternative embodiment, the instant invention provides
a coated container device, a method for making a coated container
device, in accordance with any of the preceding embodiments, except
that the one or more base polymers comprises one or more
polyolefins selected from the group consisting of an ethylene base
polymer and a propylene based polymer.
[0011] In an alternative embodiment, the instant invention provides
a coated container device, a method for making a coated container
device, in accordance with any of the preceding embodiments, except
that the one or more base polymers comprises one or more
polyolefins having a crystalline melting point of greater than
60.degree. C.
[0012] In an alternative embodiment, the instant invention provides
a coated container device, a method for making a coated container
device, in accordance with any of the preceding embodiments, except
that the one or more base polymers comprises one or more
polyolefins having a crystalline melting point of greater than
90.degree. C.
[0013] In an alternative embodiment, the instant invention provides
a coated container device, a method for making a coated container
device, in accordance with any of the preceding embodiments, except
that the one or more base polymers comprises one or more
polyolefins having a crystalline melting point of greater than
100.degree. C.
[0014] In an alternative embodiment, the instant invention provides
a coated container device, a method for making a coated container
device, in accordance with any of the preceding embodiments, except
that the one or more base polymers comprises one or more
polyolefins having a crystalline melting point of greater than
120.degree. C.
[0015] In an alternative embodiment, the instant invention provides
a coated container device, a method for making a coated container
device, in accordance with any of the preceding embodiments, except
that the one or more base polymers comprises one or more
polyolefins having a crystalline melting point of greater than
130.degree. C.
DETAILED DESCRIPTION OF THE INVENTION
[0016] The instant invention provides a coated container device,
and method of making the same. The coated container device
according to the present invention comprises: (1) a metal
substrate; and (2) one or more crosslinked coating layers
associated with the metal substrate, wherein the one or more
crosslinked coating layers are derived from the application of one
or more aqueous dispersions to at least one surface of the metal
substrate, and wherein the one or more aqueous dispersions
comprise: (a) one or more base polymers; (b) one or more
stabilizing agents; (c) optionally one or more neutralizing agents,
(d) one or more crosslinking agents; and (e) water.
[0017] The metal substrate comprises one or more metals including,
but not limited to, aluminum and aluminum alloys, electrolytic
tinplate cold rolled low carbon mild steel ("ETP"), electrolytic
chromium/chromium oxide coated cold rolled low carbon mild steel
(ECCS), and any other pre-treated steel. Pretreatment may include,
but is not limited to, treatment with phosphoric acid, zirconium
phosphate, chromium phosphate, and the like as well as silanes for
reasons such as primary corrosion protection and improved adhesion.
The metal substrate may comprise a sheet, strip or a coil. The
metal substrate may comprise one or more layers, and each layer may
have a thickness in the range of from 0.01 .mu.m to 2 mm; for
example, from 0.01 .mu.m to 1.5 mm; or in the alternative, from
0.01 .mu.m to 1 mm; or in the alternative, from 0.01 .mu.m to 0.5
mm; or in the alternative, from 0.01 .mu.m to 0.2 mm; or in the
alternative, from 0.01 .mu.m to 0.1 mm or in the alternative, from
0.01 .mu.m to 100 .mu.m; or in the alternative, from 0.01 .mu.m to
50 .mu.m; or in the alternative, from 1 .mu.m to 50 .mu.m; or in
the alternative, from 1 .mu.m to 15 .mu.m. The substrate may be
pre-coated with one or more pre-coating compositions. Such
pre-coating compositions may optionally further include, but are
not limited to, one or more resin binders, one or more resin
crosslinkers, one or more solvents, one or more additives, and one
or more pigments. Exemplary resin binders include, but are not
limited to, epoxy, polyester, polyvinyl chloride containing
organosols/vinyls, phenolic, alkyd, oleoresin, acrylic resin, and
the like. Exemplary crosslinkers include, but are not limited to,
phenol-formaldehyde resins; amino-formaldehyde resins including but
not limited to urea-formaldehyde, melamine formaldehyde,
benzoguanamine formaldehyde; anhydride resins, blocked isocyanate
resins and epoxy groups containing resins, including but not
limited to, epoxy resins, epoxy groups containing polyesters,
acrylic resins, vinyl resins or the like. Exemplary solvents and
thinners include, but are not limited to, glycol ethers, alcohols,
aromatics, e.g. aromatic hydrocarbons, white spirit, branched
ketones and esters. Exemplary additives include, but are not
limited to, catalysts, lubricants, wetting agents, defoamers, flow
agents, release agents, slip agents, anti-blocking agents,
additives to mask sulfur staining, pigment wetting/dispersion
agents, anti-settling agents, UV stabilizers, adhesion promoters.
Pigments include, but are not limited to titanium dioxide, zinc
oxide, aluminum oxide, zinc and aluminum. The substrate may also be
pre-coated with one or more pre-coated laminate compositions. Such
compositions may, for example, include polyethylene, polypropylene,
or polyester compositions, and may be applied either as a film via
film lamination process or melt-extrusion coating process onto the
metal surface.
[0018] The one or more coating layers are derived from the
application of one or more aqueous dispersions to at least one
surface of the metal substrate. The one or more aqueous dispersions
comprise the melt-blending product of one or more base polymers and
one or more stabilizing agents and one or more crosslinking agents
in the presence of water and optionally one or more neutralizing
agents under controlled pressure and temperature conditions. In the
alternative, the one or more aqueous dispersions comprise the
melt-blending product of one or more base polymers and one or more
stabilizing agents in the presence of water and optionally one or
more neutralizing agents under controlled pressure and temperature
conditions, and the post addition of one or more crosslinking
agents.
Base Polymer
[0019] The aqueous dispersion comprises from 1 to 99 percent by
weight of one or more base polymers based on the total weight of
the solid content of the aqueous dispersion. All individual values
and subranges from 1 to 99 weight percent are included herein and
disclosed herein; for example, the weight percent can be from a
lower limit of 1, 5, 8, 10, 15, 20, 25 weight percent to an upper
limit of 40, 50, 60, 70, 80, 90, 95, or 99 weight percent. For
example, the aqueous dispersion may comprise from 15 to 99, or from
15 to 90, or 15 to 80, or from 15 to 75, or from 30 to 70, or from
35 to 65 percent by weight of one or more base polymers, based on
the total weight of the solid content of the aqueous dispersion.
The aqueous dispersion comprises at least one or more base
polymers.
[0020] The base polymer may, for example, be selected from the
group consisting of a thermoplastic material, and a thermosetting
material. The one or more base polymers may comprise one or more
olefin based polymers, one or more acrylic based polymers, one or
more polyester based polymers, one or more epoxy based polymers,
one or more thermoplastic polyurethane polymers, one or more
styrenic based polymers, one or more vinyl based copolymers, one or
more polyamides, or combinations thereof.
[0021] In one embodiment, the one or more base polymers comprise
one or more polyolefins. The one or more base polymers comprising
one or more polyolefins may further include one or more
non-polyolefin thermoplastic materials and/or one or more
thermosetting materials. Such additional non-polyolefin base
polymers include, but are not limited to, one or more acrylic based
polymers, one or more polyester based polymers, one or more epoxy
based polymers, one or more thermoplastic polyurethane polymers,
one or more styrenic based polymers, one or more vinyl based
copolymers, one or more polyamides, or combinations thereof.
[0022] Examples of the polyolefins include, but are not limited to,
homopolymers and copolymers (including elastomers) of one or more
alpha-olefins such as ethylene, propylene, 1-butene,
3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene,
1-heptene, 1-hexene, 1-octene, 1-decene, and 1-dodecene, as
typically represented by polyethylene, polypropylene,
poly-1-butene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene,
poly-4-methyl-1-pentene, ethylene-propylene copolymer,
ethylene-1-butene copolymer, and propylene-1-butene copolymer;
copolymers (including elastomers) of an alpha-olefin with a
conjugated or non-conjugated diene, as typically represented by
ethylene-butadiene copolymer and ethylene-ethylidene norbornene
copolymer; and polyolefins (including elastomers) such as
copolymers of two or more alpha-olefins with a conjugated or
non-conjugated diene, as typically represented by
ethylene-propylene-butadiene copolymer,
ethylene-propylene-dicyclopentadiene copolymer,
ethylene-propylene-1,5-hexadiene copolymer, and
ethylene-propylene-ethylidene norbornene copolymer; ethylene-vinyl
compound copolymers such as ethylene-vinyl acetate copolymer,
ethylene-vinyl alcohol copolymer, ethylene-vinyl chloride
copolymer, ethylene acrylic acid or ethylene-(meth)acrylic acid
copolymers, and ethylene-(meth)acrylate copolymer,
[0023] In certain embodiments, one or more of the polyolefin base
polymers may be functionalized polyolefins such as polypropylene or
polyethylene homopolymer or copolymer in which the polymer has been
modified with hydroxyl, amine, aldehyde, epoxide, ethoxylate,
carboxylic acid, ester, or anhydride group. These functionalized
polyolefins such as polypropylene or polyethylene homopolymers or
copolymers are available, for example, from Baker Petrolite, a
subsidiary of Baker Hughes, Inc.
[0024] Exemplary polyolefins include, but are not limited to, one
or more thermoplastic polyolefin homopolymers or copolymers of one
or more alpha-olefins such as ethylene, propylene, 1-butene,
3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene,
1-heptene, 1-hexene, 1-octene, 1-decene, and 1-dodecene, as
typically represented by polyethylene, polypropylene,
poly-1-butene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene,
poly-4-methyl-1-pentene, ethylene-propylene copolymer,
ethylene-1-butene copolymer, and propylene-1-butene copolymer. Such
exemplary polyolefins may have a molecular weight of greater than
800 grams/mole; for example, greater than 5,000 grams/mole; or in
the alternative, greater than 50,000 grams/mole.
[0025] In one embodiment, the one or more polyolefins have
crystalline melting point of greater than 60.degree. C.; for
example, greater than 95.degree. C.; or in the alternative, greater
than 100.degree. C.; or in the alternative, greater than
120.degree. C.; or in the alternative, greater than 130.degree.
C.
[0026] In one embodiment, at least one of the one or more base
polymers comprises a thermoplastic polar polyolefin polymer, having
a polar group as either a comonomer or grafted monomer. Exemplary
polar polyolefins include, but are not limited to, maleic anhydride
grafted polyethylene homopolymer or copolymer, maleic anhydride
grafted polypropylene homopolymer or copolymer, ethylene-acrylic
acid (EAA) and ethylene-methacrylic acid copolymers, such as those
available under the trademarks PRIMACOR.TM., commercially available
from The Dow Chemical Company, NUCREL.TM., commercially available
from E.I. DuPont de Nemours, and ESCOR.TM., commercially available
from ExxonMobil Chemical Company and described in U.S. Pat. Nos.
4,599,392, 4,988,781, and 5,938,437, each of which is incorporated
herein by reference to the extent describing such polar
polyolefins. Other exemplary polar polyolefins include, but are not
limited to, ethylene ethyl acrylate (EEA) copolymer, ethylene
methyl methacrylate (EMMA), and ethylene butyl acrylate (EBA).
[0027] In one embodiment, the polar polyolefin polymer is an
ethylene-acrylic acid (EAA) or ethylene-methacrylic acid copolymer,
which may be neutralized with one or more neutralizing agents, e.g.
a base such as an alkali metal hydroxide, ammonia, or an organic
amine, in the dispersion process.
[0028] Thermoplastic material may comprise non-polyolefin
thermoplastic materials. Such non-polyolefin thermoplastic
materials include polymers such as polystyrene, styrenic copolymers
(including elastomers), ABS, acrylonitrile-styrene copolymer,
.alpha.-methylstyrene-styrene copolymer, styrene vinyl alcohol,
styrene acrylates such as styrene methylacrylate, styrene butyl
acrylate, styrene butyl methacrylate, and styrene butadienes and
crosslinked styrene polymers; and styrene block copolymers
(including elastomers) such as styrene-butadiene copolymer and
hydrate thereof, and styrene-isoprene-styrene triblock copolymer;
polyvinyl compounds such as polyvinyl chloride, polyvinylidene
chloride, vinyl chloride-vinylidene chloride copolymer, copolymers
of vinyl chloride with vinyl acetate, vinyl alcohol, maleic acid
anhydride, hydroxyalkyl acrylate, glycidyl methacrylate and the
like, polymethyl acrylate, and polymethyl methacrylate; polyamides
such as nylon 6, nylon 6,6, and nylon 12; thermoplastic polyesters
such as polyethylene terephthalate and polybutylene terephthalate
and the like; epoxy resins such as polyhydroxy ethers,
polyhydroxyaminoethers and polyhydroxy esters and the like, for
example polyhydroxyether such as the reaction product of
diglycidylether of bisphenol-A with bisphenol-A or the like, for
example polyhydroxyaminoethers as the reaction product of
diglycidylether of bisphenol-A with ethanol amine and
polyhydroxyester such as the reaction product of diglycidylether of
bisphenol-A with isophthalic acid or terephthalic acid and the
like; polycarbonate, polyphenylene oxide, and the like; and glassy
hydrocarbon-based resins, including poly-dicyclopentadiene polymers
and related polymers (copolymers, terpolymers); esters of saturated
acids with mono-olefinic alcohols such as vinyl acetate, vinyl
propionate, vinyl versatate, and vinyl butyrate and the like; vinyl
esters such as esters of unsaturated monocarboxylic acids,
including methyl acrylate, ethyl acrylate, n-butyl acrylate,
isobutyl acrylate, 2-ethylhexyl acrylate, glycidyl methacrylate,
dodecyl acrylate, n-octyl acrylate, phenyl acrylate, methyl
methacrylate, ethyl methacrylate, and butyl methacrylate and the
like; acrylonitrile, methacrylonitrile, acrylamide, mixtures
thereof; resins produced by ring opening metathesis and cross
metathesis polymerization and the like. These resins may be used
either alone or in combinations of two or more.
[0029] Exemplary (meth)acrylates, as base polymers, include, but
are not limited to, methyl acrylate, ethyl acrylate, butyl
acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate and
isooctyl acrylate, n-decyl acrylate, isodecyl acrylate, tert-butyl
acrylate, methyl methacrylate, butyl methacrylate, hexyl
methacrylate, isobutyl methacrylate, isopropyl methacrylate as well
as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
2-hydroxypropyl acrylate, 2-hydroxypropyl, methacrylate, glycidyl
methacrylate and acrylamide. The preferred (meth)acrylates include,
but are not limited to, methyl acrylate, ethyl acrylate, butyl
acrylate, 2-ethylhexyl acrylate, octyl acrylate, isooctyl acrylate,
methyl methacrylate and butyl methacrylate 2-hydroxyethyl
methacrylate, 2-hydroxypropyl methacrylate, acrylamide. Other
suitable (meth)acrylates that can be polymerized from monomers
include lower alkyl acrylates and methacrylates including acrylic
and methacrylic ester monomers: methyl acrylate, ethyl acrylate,
n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl
acrylate, isobornyl acrylate, methyl methacrylate, ethyl
methacrylate, n-propyl methacrylate, isopropyl methacrylate,
n-butyl methacrylate, isobutyl methacrylate, sec-butyl
methacrylate, cyclohexyl methacrylate, isodecyl methacrylate,
isobornyl methacrylate, t-butylaminoethyl methacrylate, stearyl
methacrylate, glycidyl methacrylate, dicyclopentenyl methacrylate,
phenyl methacrylate.
[0030] In selected embodiments, the base polymer may, for example,
comprise one or more polyolefins selected from the group consisting
of ethylene-alpha olefin copolymers, propylene-alpha olefin
copolymers, and olefin block copolymers. In particular, in some
embodiments, the base polymer may comprise one or more non-polar
polyolefins.
[0031] In certain specific embodiments, polyolefins such as
polypropylene, polyethylene, copolymers thereof, and blends
thereof, as well as ethylene-propylene-diene terpolymers, may be
used. In some embodiments, exemplary olefinic polymers include
homogeneous polymers, as for example described in U.S. Pat. No.
3,645,992; high density polyethylene (HDPE), as for example
described in U.S. Pat. No. 4,076,698; heterogeneously branched
linear low density polyethylene (LLDPE); heterogeneously branched
ultra low linear density polyethylene (ULDPE); homogeneously
branched, linear ethylene/alpha-olefin copolymers; homogeneously
branched, substantially linear ethylene/alpha-olefin polymers,
which can be prepared, for example, by processes disclosed in U.S.
Pat. Nos. 5,272,236 and 5,278,272, the disclosures of which are
incorporated herein by reference; and high pressure, free radical
polymerized ethylene polymers and copolymers such as low density
polyethylene (LDPE) or ethylene vinyl acetate polymers (EVA).
[0032] In other particular embodiments, the base polymer may, for
example, be ethylene vinyl acetate (EVA) based polymers. In other
embodiments, the base polymer may, for example, be ethylene-methyl
acrylate (EMA) based polymers. In other particular embodiments, the
ethylene-alpha olefin copolymer may, for example, be
ethylene-butene, ethylene-hexene, or ethylene-octene copolymers or
interpolymers. In other particular embodiments, the propylene-alpha
olefin copolymer may, for example, be a propylene-ethylene or a
propylene-ethylene-butene copolymer or interpolymer.
[0033] In one particular embodiment, the base polymer may be a
propylene/alpha-olefin copolymer, which is characterized as having
substantially isotactic propylene sequences. "Substantially
isotactic propylene sequences" means that the sequences have an
isotactic triad (mm) measured by .sup.13C NMR of greater than about
0.85; in the alternative, greater than about 0.90; in another
alternative, greater than about 0.92; and in another alternative,
greater than about 0.93. Isotactic triads are well-known in the art
and are described in, for example, U.S. Pat. No. 5,504,172 and
International Publication No. WO 00/01745, which refer to the
isotactic sequence in terms of a triad unit in the copolymer
molecular chain determined by .sup.13C NMR spectra.
[0034] The propylene/alpha-olefin copolymer may have a
crystallinity in the range of from at least 1 percent by weight (a
heat of fusion of at least 2 Joules/gram) to 30 percent by weight
(a heat of fusion of less than 50 Joules/gram). All individual
values and subranges from 1 percent by weight (a heat of fusion of
at least 2 Joules/gram) to 30 percent by weight (a heat of fusion
of less than 50 Joules/gram) are included herein and disclosed
herein; for example, the crystallinity can be from a lower limit of
1 percent by weight (a heat of fusion of at least 2 Joules/gram),
2.5 percent (a heat of fusion of at least 4 Joules/gram), or 3
percent (a heat of fusion of at least 5 Joules/gram) to an upper
limit of 30 percent by weight (a heat of fusion of less than 50
Joules/gram), 24 percent by weight (a heat of fusion of less than
40 Joules/gram), 15 percent by weight (a heat of fusion of less
than 24.8 Joules/gram) or 7 percent by weight (a heat of fusion of
less than 11 Joules/gram). For example, the propylene/alpha-olefin
copolymer may have a crystallinity in the range of from at least 1
percent by weight (a heat of fusion of at least 2 Joules/gram) to
24 percent by weight (a heat of fusion of less than 40
Joules/gram); or in the alternative, the propylene/alpha-olefin
copolymer may have a crystallinity in the range of from at least 1
percent by weight (a heat of fusion of at least 2 Joules/gram) to
15 percent by weight (a heat of fusion of less than 24.8
Joules/gram); or in the alternative, the propylene/alpha-olefin
copolymer may have a crystallinity in the range of from at least 1
percent by weight (a heat of fusion of at least 2 Joules/gram) to 7
percent by weight (a heat of fusion of less than 11 Joules/gram);
or in the alternative, the propylene/alpha-olefin copolymer may
have a crystallinity in the range of from at least 1 percent by
weight (a heat of fusion of at least 2 Joules/gram) to 5 percent by
weight (a heat of fusion of less than 8.3 Joules/gram). The
crystallinity is measured via Differential scanning calorimetry
(DSC) method. The propylene/alpha-olefin copolymer comprises units
derived from propylene and polymeric units derived from one or more
alpha-olefin comonomers. Exemplary comonomers utilized to
manufacture the propylene/alpha-olefin copolymer are C.sub.2, and
C.sub.4 to C.sub.10 alpha-olefins; for example, C.sub.2, C.sub.4,
C.sub.6 and C.sub.8 alpha-olefins. The propylene/alpha-olefin
copolymer comprises from 1 to 40 percent by weight of units derived
from one or more alpha-olefin comonomers. All individual values and
subranges from 1 to 40 weight percent are included herein and
disclosed herein; for example, the weight percent of units derived
from one or more alpha-olefin comonomers can be from a lower limit
of 1, 3, 4, 5, 7, or 9 weight percent to an upper limit of 40, 35,
30, 27, 20, 15, 12, or 9 weight percent. For example, the
propylene/alpha-olefin copolymer comprises from 1 to 35 percent by
weight of units derived from one or more alpha-olefin comonomers;
or in the alternative, the propylene/alpha-olefin copolymer
comprises from 1 to 30 percent by weight of units derived from one
or more alpha-olefin comonomers; or in the alternative, the
propylene/alpha-olefin copolymer comprises from 3 to 27 percent by
weight of units derived from one or more alpha-olefin comonomers;
or in the alternative, the propylene/alpha-olefin copolymer
comprises from 3 to 20 percent by weight of units derived from one
or more alpha-olefin comonomers; or in the alternative, the
propylene/alpha-olefin copolymer comprises from 3 to 15 percent by
weight of units derived from one or more alpha-olefin
comonomers.
[0035] The propylene/alpha-olefin copolymer has a molecular weight
distribution (MWD), defined as weight average molecular weight
divided by number average molecular weight (M.sub.w/M.sub.n) of 3.5
or less; in the alternative 3.0 or less; or in another alternative
from 1.8 to 3.0.
Such propylene/alpha-olefin copolymers are further described in
details in the U.S. Pat. Nos. 6,960,635 and 6,525,157, incorporated
herein by reference. Such propylene/alpha-olefin copolymers are
commercially available from The Dow Chemical Company, under the
tradename VERSIFY.TM., or from ExxonMobil Chemical Company, under
the tradename VISTAMAXX.TM..
[0036] In one embodiment, the propylene/alpha-olefin copolymers are
further characterized as comprising (A) between 60 and less than
100, preferably between 80 and 99 and more preferably between 85
and 99, weight percent units derived from propylene, and (B)
between greater than zero and 40, preferably between 1 and 20, more
preferably between 4 and 16 and even more preferably between 4 and
15, weight percent units derived from at least one of ethylene
and/or a C.sub.4-10 .alpha.-olefin; and containing an average of at
least 0.001, preferably an average of at least 0.005 and more
preferably an average of at least 0.01, long chain branches/1000
total carbons, wherein the term long chain branch, as used herein,
refers to a chain length of at least one (1) carbon more than a
short chain branch, and short chain branch, as used herein, refers
to a chain length of two (2) carbons less than the number of
carbons in the comonomer. For example, a propylene/1-octene
interpolymer has backbones with long chain branches of at least
seven (7) carbons in length, but these backbones also have short
chain branches of only six (6) carbons in length. The maximum
number of long chain branches typically it does not exceed 3 long
chain branches/1000 total carbons. Such propylene/alpha-olefin
copolymers are further described in details in the U.S. Provisional
Patent Application No. 60/988,999 and International Patent
Application No. PCT/US08/082599, each of which is incorporated
herein by reference.
[0037] In other selected embodiments, olefin block copolymers,
e.g., ethylene multi-block copolymer, such as those described in
the International Publication No. WO2005/090427 and U.S. Patent
Application Publication No. US 2006/0199930, incorporated herein by
reference to the extent describing such olefin block copolymers,
may be used as the base polymer. Such olefin block copolymer may be
an ethylene/.alpha.-olefin interpolymer: [0038] (a) having a
M.sub.w/M.sub.n from about 1.7 to about 3.5, at least one melting
point, T.sub.m, in degrees Celsius, and a density, d, in
grams/cubic centimeter, wherein the numerical values of T.sub.m and
d corresponding to the relationship:
[0038] T.sub.m>-2002.9+4538.5(d)-2422.2(d).sup.2; or [0039] (b)
having a M.sub.w/M.sub.n from about 1.7 to about 3.5, and being
characterized by a heat of fusion, .DELTA.H in J/g, and a delta
quantity, .DELTA.T, in degrees Celsius defined as the temperature
difference between the tallest DSC peak and the tallest CRYSTAF
peak, wherein the numerical values of .DELTA.T and .DELTA.H having
the following relationships:
[0039] .DELTA.T>-0.1299(.DELTA.H)+62.81 for .DELTA.H greater
than zero and up to 130 J/g,
.DELTA.T.gtoreq.48.degree. C. for .DELTA.Hgreater than 130 J/g,
wherein the CRYSTAF peak being determined using at least 5 percent
of the cumulative polymer, and if less than 5 percent of the
polymer having an identifiable CRYSTAF peak, then the CRYSTAF
temperature being 30.degree. C.; or [0040] (c) being characterized
by an elastic recovery, Re, in percent at 300 percent strain and 1
cycle measured with a compression-molded film of the
ethylene/.alpha.-olefin interpolymer, and having a density, d, in
grams/cubic centimeter, wherein the numerical values of Re and d
satisfying the following relationship when ethylene/.alpha.-olefin
interpolymer being substantially free of a cross-linked phase:
[0040] Re>1481-1629(d); or [0041] (d) having a molecular
fraction which elutes between 40.degree. C. and 130.degree. C. when
fractionated using TREF, characterized in that the fraction having
a molar comonomer content of at least 5 percent higher than that of
a comparable random ethylene interpolymer fraction eluting between
the same temperatures, wherein said comparable random ethylene
interpolymer having the same comonomer(s) and having a melt index,
density, and molar comonomer content (based on the whole polymer)
within 10 percent of that of the ethylene/.alpha.-olefin
interpolymer; or [0042] (e) having a storage modulus at 25.degree.
C., G' (25.degree. C.), and a storage modulus at 100.degree. C., G'
(100.degree. C.), wherein the ratio of G' (25.degree. C.) to G'
(100.degree. C.) being in the range of about 1:1 to about 9:1. Such
olefin block copolymer, e.g. ethylene/.alpha.-olefin interpolymer
may also: [0043] (a) have a molecular fraction which elutes between
40.degree. C. and 130.degree. C. when fractionated using TREF,
characterized in that the fraction having a block index of at least
0.5 and up to about 1 and a molecular weight distribution,
M.sub.w/M.sub.n, greater than about 1.3; or [0044] (b) have an
average block index greater than zero and up to about 1.0 and a
molecular weight distribution, M.sub.w/M.sub.n, greater than about
1.3.
[0045] In certain embodiments, the base polymer may, for example,
comprise a polar polymer, having a polar group as either a
comonomer or grafted monomer. In exemplary embodiments, the base
polymer may, for example, comprise one or more polar polyolefins,
having a polar group as either a comonomer or grafted monomer.
Exemplary polar polyolefins include, but are not limited to,
ethylene-acrylic acid (EAA) and ethylene-methacrylic acid
copolymers, such as those available under the trademarks
PRIMACOR.TM., commercially available from The Dow Chemical Company,
NUCREL.TM., commercially available from E.I. DuPont de Nemours, and
ESCOR.TM., commercially available from ExxonMobil Chemical Company
and described in U.S. Pat. Nos. 4,599,392, 4,988,781, and
5,938,437, each of which is incorporated herein by reference in its
entirety. Other exemplary base polymers include, but are not
limited to, ethylene ethyl acrylate (EEA) copolymer, ethylene
methyl methacrylate (EMMA), and ethylene butyl acrylate (EBA).
[0046] Other ethylene-carboxylic acid copolymer may also be used.
The one or more base polymers could also derived by chemical
modification of the functional acid group in the one or more polar
polymers to form hydroxyl ester groups or to an amide and the like.
Those having ordinary skill in the art will recognize that a number
of other useful polymers may also be used. Another base polymer
might include copolymers as ethylene vinyl alcohol and ethylene
vinyl acetate and the like.
[0047] In one embodiment, the base polymer may, for example,
comprise a polar polyolefin selected from the group consisting of
ethylene-acrylic acid (EAA) copolymer, ethylene-methacrylic acid
copolymer, and combinations thereof, and the stabilizing agent may,
for example, comprise a polar polyolefin selected from the group
consisting of ethylene-acrylic acid (EAA) copolymer,
ethylene-methacrylic acid copolymer, and combinations thereof;
provided, however, that base polymer may, for example, have a lower
acid number, measured according to ASTM D-974, than the stabilizing
agent.
[0048] In certain embodiments, the base polymer may, for example,
comprise a polyester resin. Polyester resin refers to thermoplastic
or thermosetting resins that may include polymers containing at
least one ester bond. They can be hydroxyl functional or carboxyl
functional. For example, polyester may be prepared via a
conventional esterification process using a molar excess of an
aliphatic diol or glycol with relation to a polycarboxylic acid or
anhydride thereof. Triols or polyols can be used to provide
branched polyesters. Illustrative of the glycols, triols and
polyols that can be employed to prepare the polyesters include, but
are not limited to ethylene glycol, diethylene glycol, triethylene
glycol and higher polyethylene glycols, propylene glycol,
dipropylene glycol, tripropylene glycol and higher polypropylene
glycols, 1,3-propanediol, 1,4-butanediol and other butanediols,
1,5-pentanediol and other pentane diols, hexanediols, decanediols,
and dodecanediols, glycerol, trimethylolpropane, trimethylolethane,
neopentyl glycol, pentaerythritol, cyclohexanedimethanol, a
polyethylene or polypropylene glycol having an mw of about 500 or
less, isopropylidene bis (p-phenylene-oxypropanol-2), and mixtures
thereof. In some embodiments, the aliphatic glycol may contain from
2 to about 8 carbon atoms.
[0049] Illustrative of the polycarboxylic acids or anhydrides, that
may be used to prepare the polyesters include, but are not limited
to maleic acid, maleic anhydride, malonic acid, fumaric acid,
succinic acid, succinic anhydride, glutaric acid, adipic acid,
2-methyl-1,6-hexanoic acid, pimelic acid, suberic acid,
dodecanedioic acids. phthalic acid, phthalic anhydride, 5-tert
butyl isophthalic acid, tetrahydrophthalic anhydride,
hexahydrophthalic acid, hexahydrophthalic anhydride,
endomethylenetetrahydrophthalic anhydride, azelaic acid, sebacic
acid, tetrachloro-phthalic anhydride, chlorendic acid, isophthalic
acid, trimellitic anhydride, terephthalic acid, naphthalene
dicarboxylic acid, cyclohexane-dicarboxylic acid, and mixtures
thereof. In some embodiments, the alkanedioic acids may contain
from 4 to 12 carbon atoms. It is also understood that an
esterifiable derivative of a polycarboxylic acid, such as a
dimethyl ester or anhydride of a polycarboxylic acid, can be used
to prepare the polyester.
[0050] Other embodiments of the present invention use polyester
resins containing aliphatic diols such as UNOXOL.TM. (a mixture of
cis and trans 1,3- and 1,4-cyclohexanedimethanol) available from
The Dow Chemical Company (Midland, Mich.).
[0051] In certain embodiments, base polymer may, for example,
comprise a thermosetting material comprising an epoxy resin. Epoxy
resin refers to a composition which possesses one or more vicinal
epoxy groups per molecule, i.e. at least one 1,2-epoxy group per
molecule. In general, such compound is a saturated or unsaturated
aliphatic, cycloaliphatic, aromatic or heterocyclic compound which
possesses at least one 1,2-epoxy group. Such compound can be
substituted, if desired, with one or more non-interfering
substituents, such as halogen atoms, hydroxy groups, ether
radicals, lower alkyls and the like. Also one or more epoxy
containing substance can be combined in making the desired epoxy
resin.
[0052] Illustrative epoxies are described in the Handbook of Epoxy
Resins by H. E. Lee and K. Neville published in 1967 by
McGraw-Hill, New York and U.S. Pat. No. 4,066,628, incorporated
herein by reference.
[0053] Particularly useful compounds which can be used in the
practice of the present invention are epoxy resins having the
following formula:
##STR00001##
wherein n has an average value of 0 or more.
[0054] The epoxy resins useful in the present invention may
include, for example, the glycidyl polyethers of polyhydric phenols
and polyhydric alcohols. As an illustration of the present
invention, examples of known epoxy resins that may be used in the
present invention, include for example, the diglycidyl ethers of
resorcinol, catechol, hydroquinone, biphenol, bisphenol A,
bisphenol AP (1,1-bis(4-hydroxylphenyl)-1-phenyl ethane), bisphenol
F, bisphenol K, bisphenol S, tetrabromobisphenol A,
phenol-formaldehyde novolac resins, alkyl substituted
phenol-formaldehyde resins, phenol-hydroxybenzaldehyde resins,
cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenol resins,
dicyclopentadiene-substituted phenol resins tetramethylbiphenol,
tetramethyl-tetrabromobiphenol, tetramethyltribromobiphenol,
tetrachlorobisphenol A and any combination thereof.
[0055] Examples of diepoxides particularly useful in the present
invention include diglycidyl ether of 2,2-bis(4-hydroxyphenyl)
propane (generally referred to as bisphenol A) and diglycidyl ether
of 2,2-bis(3,5-dibromo-4-hydroxyphenyl) propane (generally referred
to as tetrabromobisphenol A). Mixtures of any two or more
polyepoxides can also be used in the practice of the present
invention.
[0056] Other exemplary diepoxides include the diglycidyl ethers of
dihydric phenols, such as those described in U.S. Pat. Nos.
5,246,751; 5,115,075; 5,089,588; 4,480,082 and 4,438,254, all of
which are incorporated herein by reference, or the diglycidyl
esters of dicarboxylic acids such as those described in U.S. Pat.
No. 5,171,820. Other exemplary diepoxides include for example,
.alpha..omega.-diglycidyloxyisopropylidene-bisphenol-based epoxy
resins (commercially known as D.E.R..RTM. 300 and 600 series epoxy
resins, products of The Dow Chemical Company, Midland, Mich.).
[0057] The epoxy resins which can be employed in the practice of
the present invention also include epoxy resins prepared either by
reaction of diglycidyl ethers of dihydric phenols with dihydric
phenols or by reaction of dihydric phenols with epichlorohydrin
(also known as "taffy resins").
[0058] Exemplary epoxy resins include, for example, the diglycidyl
ethers of bisphenol A; 4,4'-sulfonyldiphenol; 4,4- oxydiphenol;
4,4'-dihydroxybenzophenone; resorcinol; hydroquinone; catechol;
9,9'- bis(4-hydroxyphenyl)fluorene; 4,4'-dihydroxybiphenyl or
4,4'-dihydroxy-.alpha.-methylstilbene and the diglycidyl esters of
the dicarboxylic acids.
[0059] Other useful epoxide compounds include aliphatic epoxides
such as polypropylene glycol diglycidyl ether, dipropylene glycol
diglycidyl ether, 1,4 butanediol digylcidyl ether, neopentylglycol
digylcidyl ether, 1,6 hexanediol diglycidyl ether,
cyclohexanedimethanol diglycidylether, trimethylolpropane
triglycidyl ether, glycerol triglycidylether or the like.
[0060] Other useful epoxide compounds include cycloaliphatic
epoxides. A cycloaliphatic epoxide consists of a saturated carbon
ring having an epoxy oxygen bonded to two vicinal atoms in the
carbon ring for example as illustrated by the following general
formula:
##STR00002##
wherein R is a hydrocarbon group optionally comprising one or more
heteroatoms (such as, without limitation thereto Cl, Br, and S), or
an atom or group of atoms forming a stable bond with carbon (such
as, without limitation thereto, Si, P and B) and wherein n is
greater than or equal to 1.
[0061] The cycloaliphatic epoxide may be a monoepoxide, a
diepoxide, a polyepoxide, or a mixture of those. For example, any
of the cycloaliphatic epoxide described in U.S. Pat. No. 3,686,359,
incorporated herein by reference, may be used in the present
invention. As an illustration, the cycloaliphatic epoxides that may
be used in the present invention include, for example,
(3,4-epoxycyclohexyl-methyl)-3,4-epoxy-cyclohexane carboxylate,
bis-(3,4-epoxycyclohexyl) adipate, vinylcyclohexene monoxide and
mixtures thereof.
[0062] In certain embodiments, the base polymer may, for example,
comprise a thermosetting material comprising a modified epoxy resin
which has been generated by co-reacting one of the aforementioned
epoxy resins with a dioic acid such as, but not limited to adipic
acid, 2-methyl-1,6-hexanoic acid, pimelic acid, suberic acid,
dodecanedioic acids. phthalic acid, 5-tert butyl isophthalic acid,
hexahydrophthalic acid, azelaic acid, sebacic acid, isophthalic
acid, terephthalic acid, naphthalene dicarboxylic acid,
cyclohexane-dicarboxylic acid, and mixtures thereof.
[0063] In certain embodiments, the base polymer may, for example,
comprise a thermosetting material comprising a modified epoxy
resin. Modifications could be originated by reaction of the
terminal epoxy groups of the epoxy resin with a nucleophilic group
containing substance such as a carboxylic group, phenolic hydroxyl,
alkyl or glycolic hydroxyl, thiol, amine group or the like. It may
be also the reaction product of the aforementioned epoxy group with
an acid such as phosphoric acid, hydrogen chloride, hydrogen
bromide, or the like. It may also be the reaction product of the
aforementioned epoxy group with water or a phenolic compound such
as bisphenol-A. It may also be the reaction product of the
aforementioned epoxy group with an acid functional polyester
resin.
[0064] In certain embodiments, the base polymer may, for example,
comprise a thermoplastic or thermosetting polyurethane polymer.
Such polyurethane polymers are generally known, and further
described, for example, in the International Publication No.
2008/057878, incorporated herein by reference to the extent that it
describes a thermoplastic polyurethane polymer.
[0065] Those having ordinary skill in the art will recognize that
the above list is a non-comprehensive listing of exemplary base
polymers. It will be appreciated that the scope of the present
invention is restricted by the claims only.
[0066] In certain embodiments base polymer comprises of a
thermoplastic polyamide. Such polyamide polymers are generally
known for example, nylon 66, nylon 6, nylon 610, and nylon 11,
nylon 12 and the like.
Stabilizing Agent
[0067] The aqueous dispersion may further comprise at least one or
more stabilizing agents to promote the formation of a stable
dispersion. The stabilizing agent may preferably be an external
stabilizing agent. The dispersion of the instant invention
comprises 1 to 50 percent by weight of one or more stabilizing
agents, based on the total weight of the solid content of the
dispersion. All individual values and subranges from 1 to 45 weight
percent are included herein and disclosed herein; for example, the
weight percent can be from a lower limit of 1, 3, 5, 10 weight
percent to an upper limit of 15, 25, 35, 45, or 50 weight percent.
For example, the dispersion may comprise from 1 to 25; or in the
alternative, from 1 to 35; or in the alternative, from 1 to 40; or
in the alternative, from 1 to 45 percent by weight of one or more
stabilizing agents, based on the total weight of the solid content
of the dispersion. In selected embodiments, the stabilizing agent
may be a surfactant, a polymer, or mixtures thereof. In certain
embodiments, the stabilizing agent can be a polar polymer, having a
polar group as either a comonomer or grafted monomer. In exemplary
embodiments, the stabilizing agent comprises one or more polar
polyolefins, having a polar group as either a comonomer or grafted
monomer. Exemplary polymeric stabilizing agents include, but are
not limited to, ethylene-acrylic acid (EAA) and
ethylene-methacrylic acid copolymers, such as those available under
the trademarks PRIMACOR.TM., commercially available from The Dow
Chemical Company, NUCREL.TM., commercially available from E.I.
DuPont de Nemours, and ESCOR.TM. commercially available from
ExxonMobil Chemical Company and described in U.S. Pat. Nos.
4,599,392, 4,988,781, and 5,938,437, each of which is incorporated
herein by reference in its entirety. Other exemplary polymeric
stabilizing agents include, but are not limited to, ethylene ethyl
acrylate (EEA) copolymer, ethylene methyl methacrylate (EMMA), and
ethylene butyl acrylate (EBA). Other ethylene-carboxylic acid
copolymer may also be used. Those having ordinary skill in the art
will recognize that a number of other useful polymers may also be
used.
[0068] In certain embodiments, the stabilizing agent may be a
functionalized polyolefin such as polypropylene or polyethylene
homopolymer or copolymer in which the polymer has been modified
with hydroxyl, amine, aldehyde, epoxide, ethoxylate, carboxylic
acid, ester, or anhydride groups. These functionalized polyolefins
such as polypropylene or polyethylene homopolymers and copolymers
are available, for example, from Clariant Corporation under the
tradenames LICOCENE 4351 and LICOCENE 6452, and from Baker
Petrolite, a subsidiary of Baker Hughes, Inc.
[0069] Other stabilizing agents that may be used include, but are
not limited to, long chain fatty acids, fatty acid salts, or fatty
acid alkyl esters having from 12 to 60 carbon atoms. In other
embodiments, the long chain fatty acid or fatty acid salt may have
from 12 to 40 carbon atoms.
[0070] Additional stabilizing agents that may be useful in the
practice of the present invention include, but are not limited to,
cationic surfactants, anionic surfactants, or non-ionic
surfactants. Examples of anionic surfactants include, but are not
limited to, sulfonates, carboxylates, and phosphates. Examples of
cationic surfactants include, but are not limited to, quaternary
amines. Examples of non-ionic surfactants include, but are not
limited to, block copolymers containing ethylene oxide and silicone
surfactants. Stabilizing agents useful in the practice of the
present invention can be either external surfactants or internal
surfactants. External surfactants are surfactants that do not
become chemically reacted into the base polymer during dispersion
preparation. Examples of external surfactants useful herein
include, but are not limited to, salts of dodecyl benzene sulfonic
acid and lauryl sulfonic acid salt. Internal surfactants are
surfactants that do become chemically reacted into the base polymer
during dispersion preparation. An example of an internal surfactant
useful herein includes 2,2-dimethylol propionic acid and its salts.
Additional surfactants that may be useful in the practice of the
present invention include cationic surfactants, anionic
surfactants, non-ionic surfactants, or combinations thereof.
Various commercially available surfactants may be used in
embodiments disclosed herein, including: OP-100 (a sodium
stearate), OPK-1000 (a potassium stearate), and OPK-181 (a
potassium oleate), each available from RTD Hallstar; UNICID 350,
available from Baker Petrolite; DISPONIL FES 77-IS and DISPONIL
TA-430, each available from Cognis; RHODAPEX CO-436, SOPROPHOR
4D384, 3D-33, and 796/P, RHODACAL BX-78 and LDS-22, RHODAFAC
RE-610, and RM-710, and SUPRAGIL MNS/90, each available from
Rhodia; and TRITON QS-15, TRITON W-30, DOWFAX 2A1, DOWFAX 3B2,
DOWFAX 8390, DOWFAX C6L, TRITON X-200, TRITON XN-455, TRITON H-55,
TRITON GR-5M, TRITON BG-10, and TRITON CG-110, each available from
The Dow Chemical Company, Midland, Mich.
[0071] Additional stabilizing agents which could be used are
solution or suspension polymers consisting of ethylenically
unsaturated monomers such as acrylic and/or methacrylic acid and
their (C.sub.1-C.sub.30) esters or amides;
acrylamide/methacrylamide and their N-substituted derivatives;
acrylonitrile; styrene and substituted styrene derivatives.
[0072] Exemplary polymeric stabilizing agents include, but are not
limited to, amphiphilic copolymer compositions, the copolymer
comprising the reaction product of (i) from 5 to 95 wt. % of one or
more hydrophilic monomers and (ii) from 5 to 95 wt. % of one or
more copolymerizable ethylenically unsaturated hydrophobic
monomers. These materials are water soluble or emulsifiable,
especially upon neutralization and can act as colloidal
stabilizers. Exemplary stabilizing agents, for example, include,
but are not limited to, butylacrylate and laurylmethacrylate.
[0073] Representative nonionic, water-soluble monomers suitable for
production of amphiphilic copolymer compositions, include, but are
not limited to, acrylamide, methacrylamide, N,N-dimethylacrylamide,
N,N-diethylacrylamide, N-isopropylacrylamide, N-vinylformamide,
N-vinylmethylacetamide, N-vinyl pyrrolidone, hydroxyethyl
methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate,
hydroxypropyl methacrylate, t-butylacrylamide, N
methylolacrylamide, alkyl(meth)acrylates such as
methyl(meth)acrylate, butyl acrylate and ethylacrylate, vinyl
monomers such as ethylene, styrene, divinylbenzene,
di-isobutylethylene, vinyl acetate and N-vinyl pyrrolidone, and
allyl monomers such as allyl (meth)acrylate.
[0074] Representative cationic, water-soluble monomers suitable for
production of amphiphilic copolymer compositions include, but are
not limited to, quaternary ammonium salts of amine functionalized
monomers such as acrylamide, methacrylamide,
N,N-dimethylacrylamide, N,N-diethylacrylamide,
N-isopropylacrylamide, N-vinylformamide, N-vinylmethylacetamide,
N-vinyl pyrrolidone, t-butylacrylamide, N-methylolacrylamide,
tributylammonium ethyl(meth)acrylate TBAEMA, DMAEMA, DMAPMAM,
diallyldimethylammonium chloride (DADMAC),
methylacrylamidopropyltrimethylammonium chloride (MAPTAC),
acrylamidopropyltrimethylammonium chloride (APTAC), N-vinyl
pyrrolidone, vinylimidazole, polyquaternium-11 and
polyquaternium-4.
[0075] "Anionic" or "acid-containing monomer" suitable for
production of amphiphilic copolymer compositions include, but are
not limited to, ethylenically unsaturated monomers containing
carboxylic acid, phosphonic acid, phosphinic acid, sulfinic acid
and sulfonic acid groups. Suitable examples include (meth)acrylic
acid, maleic acid, succinic acid, itaconic acid, vinyl phosphonic
acid and vinylsulfonic acid.
[0076] In an alternative embodiment, one or more stabilizing agents
may be based on resins such as polyester, epoxy resins, polyamide
resins, which might be reacted with acrylic resins or acrylic
monomers to form polyester acrylate, polyamide acrylates epoxy
resin acrylates.
[0077] Suitable polyester resins for producing stabilizing agents
may be obtained in accordance with conventional procedures well
known to those of ordinary skill in the art by reacting, for
example, a polybasic acid that contains at least two carboxyl
groups per polybasic acid molecule (e.g. an at least dibasic
polycarboxylic acid) with a polyhydric alcohol that contains at
least two hydroxyl groups in the polyhydric alcohol (e.g., at least
dihydric alcohol) in presence of a conventional esterification
catalyst at an elevated temperature with or without solvent
present. Alternatively alkyl esters of the polycarboxylic acids can
be reacted in presence of a conventional esterification catalyst at
an elevated temperature. One or more polymerizable double bonds may
be included into the polyester by employing a polybasic acid that
contains polymerizable double bonds and/or a polyhydric alcohol
that contains polymerizable double bonds.
[0078] Polyester acrylates as stabilizing agents may be formed via
in-situ polymerization of copolymerizable ethylenically unsaturated
monomers in presence of polyesters. Examples include ethylenically
unsaturated mono- or polyfunctional acids, ethylenically
unsaturated mono- or polyfunctional acid esters, amides, nitriles
as well as vinyl monomers and vinyl ester with a polyester in or
without presence of a reaction fluid. Polyester acrylates in
solvents can be dried according to suitable methods known to those
of ordinary skill in the art.
[0079] Suitable epoxy resins for producing stabilizing agents may
be obtained in accordance with conventional procedures well known
to those of ordinary skill in the art by reacting a polyepoxide
with a suitable polynucleophile. Suitable epoxides include, but are
not limited to, glycidyl ethers, and other epoxy group containing
molecules. Suitable polynucleophiles include, but are not limited
to, polyhydric phenols, and poly phenols, polythiols, aliphatic
polyalcohols or polybasic acids or polyamines. Exemplary suitable
epoxies, for example, include, but are not limited to, glycidyl
ether that contains at least two glycidyl ether groups per
polyglycidyl ether molecule (e.g. an at least diglycidyl ether)
with a polyhydric phenol that contains at least two hydroxyl groups
in the polyhydric polyphenol (e.g., at least dihydric phenol or a
diphenol) in presence of a conventional catalyst at an elevated
temperature with or without solvent present. Another class of epoxy
resins may be obtained in accordance with conventional procedures
well known to those of ordinary skill in the art by reacting, for
example, a polyglycidyl ether that contains at least two glycidyl
ether groups per polyglycidyl ether molecule (e.g. an at least
diglycidyl ether) with a polybasic acid that contains at least two
carboxyl groups per polybasic acid molecule (e.g. an at least
dibasic polycarboxylic acid) in presence of a conventional catalyst
at an elevated temperature with or without solvent present.
[0080] Epoxy acrylates for producing stabilizing agents may be
formed via in-situ polymerization of copolymerizable ethylenically
unsaturated monomers in presence of epoxy resins. Examples include,
but are not limited to, ethylenically unsaturated mono- or
polyfunctional acids, ethylenically unsaturated mono- or
polyfunctional acid esters, amides, nitriles as well as vinyl
monomers and vinyl ester with an epoxy resins in or without
presence of a reaction fluid. Alternatively a polymeric acid
functional acrylic resin can be reacted with an epoxy resin in the
presence of a suitable catalyst to form epoxy acrylate. Epoxy
acrylates in solvents can be dried according to suitable methods
known to those of ordinary skill in the art.
Neutralizing Agent
[0081] The stabilizing agent may be partially or fully neutralized
with a neutralizing agent. In certain embodiments, neutralization
of the stabilizing agent, such as a long chain fatty acid or EAA,
may be from 25 to 200 percent on a molar basis; or in the
alternative, it may be from 50 to 150 percent on a molar basis; or
in the alternative, it may be from 50 to 120 percent on a molar
basis; or in the alternative, it may be from 50 to 110 percent on a
molar basis. For example, for EAA, the neutralizing agent may be a
base, such as ammonium hydroxide or potassium hydroxide, for
example. Other neutralizing agents can include lithium hydroxide or
sodium hydroxide, for example. In another alternative, the
neutralizing agent may, for example, be a carbonate. In another
alternative, the neutralizing agent may, for example, be any amine
such as monoethanolamine, or 2-amino-2-methyl-1-propanol (AMP).
Amines useful in embodiments disclosed herein may include
diethanolamine, triethanolamine, and TRIS AMINO.TM. (each available
from Angus), NEUTROL.TM. TE (available from BASF), as well as
triisopropanolamine, diisopropanolamine, and
N,N-dimethylethanolamine (each available from The Dow Chemical
Company, Midland, Mich.). Other useful amines may include ammonia,
monomethylamine, dimethylamine, trimethylamine, monoethylamine,
diethylamine, triethylamine, mono-n-propylamine, butylamine,
dibutylamine, tributylamine, dimethyl benzyl amine, dimethyl
n-propylamine, N-methanol amine, N-aminoethylethanolamine,
N-methyldiethanolamine, monoisopropanolamine, N,N-dimethyl
propanolamine, 2-amino-2-methyl-1-propanol, 1,2-diaminopropane,
tris(hydroxymethyl)-aminomethane, ethylenediamine
N,N,N'N'-tetrakis(2-hydroxylpropyl) ethylenediamine, N,N,N',N'
tetramethylpropanediamine, 3-methoxypropyl amine, imino bis-propyl
amine and the like. In some embodiments, mixtures of amines or
mixtures of amines and surfactants may be used. In one embodiment,
the neutralizing agent may be a polymeric amine, e.g. diethylene
triamine. Those having ordinary skill in the art will appreciate
that the selection of an appropriate neutralizing agent depends on
the specific composition formulated, and that such a choice is
within the knowledge of those of ordinary skill in the art. In one
embodiment, amines with boiling points below 250.degree. C. may be
used as the neutralizing agents.
Fluid Medium
[0082] The aqueous dispersion further comprises a fluid medium. The
fluid medium may be any medium; for example, the fluid medium may
be water. The dispersion of the instant invention comprises 15 to
99 percent by volume of water, or in the alternative, a mixture of
water and one or more organic solvents, e.g. one or more water
miscible solvents, one or more water immiscible solvents, or
combinations thereof, based on the total volume of the dispersion.
In particular embodiments, the water content may be in the range of
from 30 to 75, or in the alternative from 35 to 65, or in the
alternative from 40 to 60 percent by volume, based on the total
volume of the dispersion. Water content of the dispersion may
preferably be controlled so that the solids content (one or more
base polymers plus stabilizing agent) is between about 1 percent to
about 99 percent by volume. In particular embodiments, the solids
range may be between about 15 percent and about 25 per cent. In
other particular embodiments, the solids range may be between 25
percent to about 70 percent by volume. In other particular
embodiments, the solids range is between about 35 percent to about
65 percent by volume. In certain other embodiments, the solids
range is between about 40 percent to about 60 percent by
volume.
Additional Components
[0083] The aqueous dispersion of the present invention may
optionally be blended with one or more binder compositions such as
acrylic latex, vinyl acrylic latex, styrene acrylic latex, vinyl
acetate ethylene latex, and combinations thereof; optionally one or
more fillers; optionally one or more additives such as catalysts,
wetting agents, defoamers, flow agents, release agents, slip
agents, anti-blocking agents, additives to mask sulfur staining,
pigment wetting/dispersion agents, anti-settling agents, UV
stabilizers, adhesion promoters; optionally one or more lubricants
such as fatty acid ester wax, silicon-based wax, fluorine-based
wax, polyethylene or any other similar polyolefin wax, carnauba
wax, lanolin wax or the like; optionally one or more corrosion
inhibitors such as aluminum, and zinc: optionally one or more
pigments, e.g. titanium dioxide, barium sulfate, mica, calcium
carbonate, silica, zinc oxide, milled glass, aluminum trihydrate,
talc, antimony trioxide, fly ash, and clay or the like; optionally
one or more co-solvents, e.g. glycols, glycol ether,
2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, alcohols, mineral
spirits, aromatic solvents and benzoate esters or the like;
optionally one or more dispersants, e.g. aminoalcohols, and
polycarboxylates; optionally one or more surfactants; optionally
one or more preservatives, e.g. biocides, mildewcides, fungicides,
algaecides, and combinations thereof; optionally one or more
thickeners, e.g. cellulosic based thickeners such as hydroxyethyl
cellulose, hydrophobically modified alkali soluble emulsions (HASE
thickeners such as UCAR POLYPHOBE TR-116) and hydrophobically
modified ethoxylated urethane thickeners (HEUR); or optionally one
or more additional neutralizing agents, e.g. hydroxides, amines,
ammonia, and carbonates; optionally one or more solvents or
coalescing agents.
[0084] In addition, the aqueous dispersion may be blended with one
or more dispersions, emulsions, suspensions, colloidal suspensions,
and the like.
Crosslinking Agent
[0085] The aqueous dispersion may further comprise at least one or
more crosslinking agents to promote crosslinking. The aqueous
dispersion of the instant invention comprises 1 to 50 percent by
weight of one or more cros slinking agents, based on the total
weight of the solid content of the dispersion. All individual
values and subranges from 1 to 50 weight percent are included
herein and disclosed herein; for example, the weight percent can be
from a lower limit of 1, 3, 5, 10. 15, 20 weight percent to an
upper limit of 10, 12, 15, 18, 20, 25, 30, 35, 40, 45, or 50 weight
percent. For example, the dispersion may comprise from 1 to 18; or
in the alternative, from 1 to 15; or in the alternative, from 1 to
12; or in the alternative, from 1 to 10; or in the alternative,
from 1 to 20; or in the alternative, from 1 to 30; or in the
alternative, from 1 to 40; or in the alternative, from 1 to 45; or
in the alternative, from 1 to 50 percent by weight of one or more
crosslinking agents, based on the total weight of the solid content
of the dispersion. In selected embodiments the crosslinking agent
may be, but is not limited to, phenol-formaldehyde resins,
amino-formaldehyde resins including but not limited to
urea-formaldehyde resins, melamine formaldehyde resins,
benzoguanamine formaldehyde resins, anhydride resins, epoxy group
containing resins, including but not limited to epoxy resins, epoxy
group containing polyester or acrylic resins and blocked isocyanate
resins, and combinations of two or more thereof, provided that the
combinations of such crosslinkers is compatible.
[0086] Crosslinking agent may be a compound, which reacts with a
reactive functional group contained in the dispersion formulation;
thereby facilitating their crosslinking. Such functional groups can
be present in both the base polymer as well as the stabilizing
agent.
[0087] For example, reactive functional groups include, but are not
limited to, acid groups such as carboxylic acid groups, free or in
the neutralized form, or any functional groups having another
active hydrogen by another component such as alcohol groups, amino
groups, epoxy groups, or the like.
[0088] Crosslinkable functional groups in the cross-linking agent
are groups capable of reacting with the reactive functional group
of the base polymer or the stabilizer. For example, a carbodiimide
group, an oxazoline group, an isocyanate group, an epoxy group, a
methylol group, an aldehyde group, an acid anhydride group, a
hydroxy group, an aziridinyl group or a silane group can be used in
a crosslinker.
[0089] Another possibility of crosslinking acid functional groups
is by use of multivalent metal ions by reaction of the
aforementioned acid groups with a multivalent metal ion containing
substance, such as zinc oxide.
[0090] Carboxylic acids could also be crosslinked in reactions with
multifunctional olefinic unsaturated substances under catalysis of
a strong acid. Multifunctional carbonates could also react with
carboxylic acids to give ester linkages with liberation of carbon
dioxide.
[0091] In the alternative, polyolefinic materials may be
crosslinked via free radical crosslinking, initiated by addition of
peroxides or via radiation, e.g., electron beam.
[0092] With respect to crosslinkable functional groups, one or more
may be present in a crosslinking agent. In the alternative, two or
more crosslinkable functional groups may be present in a single
molecule.
[0093] The cross-linking agent having the above described
crosslinkable functional group may be a waterdispersed or
waterdispersible or water-soluble substance. In one embodiment,
exemplary crosslinking agents include, but are not limited to, an
aqueous monomeric or polymeric substance, which contains two or
more oxazoline groups, carbodiimide groups, epoxy groups,
isocyanate groups, methylol groups etc. or several of these per
molecule.
[0094] An exemplary oxazoline crosslinking agent is an aqueous
polymer having two or more oxazoline groups in its molecules,
substances can be obtained by polymerizing an oxazoline
group-containing monomer and, as required, an ethylenic unsaturated
monomer. Alternatively an oxazoline crosslinking agent can also be
obtained by reaction between a nitrile group and an aminoethanol
group, dehydration of a hydroxylalkylamide group and the like.
[0095] Crosslinking agents having two or more carbodiimide groups
can be produced from diisocyanate compounds by a condensation
reaction accompanied by decarboxylation reaction of a diisocyanate
compound. Examples of the diisocyanate compound include, but are
not limited to, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane
diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate,
1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene
diisocyanate, hexanemethylene diisocyanate,
cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone
diisocyanate, dicyclohexylmethane-4,4'-diisocyanate,
methylcyclohexane diisocyanate, and tetramethylxylylene
diisocyanate and the like. These compounds may also be used as
mixtures.
[0096] Monofunctional isocyanates may be included to control the
resin molecular chain length such as phenyl isocyanate, tolyl
isocyanate, cyclohexylisocyanate, dimethylphenyl isocyanate,
butylisocyanate, and naphthyl isocyanate are useful.
[0097] Diisocyanate substances may be partially reacted with
aliphatic compounds, alicyclic compounds, or aromatic compounds
having a hydroxyl group, an imino group, an amino group, a carboxyl
group, a mercapto group, an epoxy group, and the like.
[0098] In the condensation reaction accompanied by decarboxylation
of a diisocyanate compound, a carbodiimidization catalyst can be
used. Usable as such a catalyst are, for example, phospholene
oxides such as
1-phenyl-2-phospholene-1-oxide,3-methyl-2-phospholene-1-oxide,
1-ethyl-2-phospholene-1-oxide, and 3-phospholene isomers
thereof.
[0099] In order to convert a carbodiimide group-containing polymer
into an aqueous polymer, a hydrophilic segment is provided in the
molecular structure of the carbodiimide group-containing polymer.
For example, an aqueous polymer containing a carbodiimide group can
be obtained by providing a hydrophilic segment having a functional
group which has reactivity with an isocyanate group. Usable as the
hydrophilic segment are: quaternary ammonium salts of dialkylamino
alkylamine (e.g., quaternary ammonium salts of
2-dimethylaminoethanol); quaternary salts of dialkylamino
alkylamine(e.g., 3-dimethylamino-n-propylamine); alkyl sulfonic
acid salts having at least one reactive hydroxyl group (e.g.,
sodiumhydroxypropanesulfonate); a mixture of polyethylene oxide or
polyethylene oxide, whose terminal is capped with an alkoxy group,
and a polypropylene oxide (e.g., polyethylene oxide whose terminal
position is capped with a methoxygroup or an ethoxy group)
[0100] As an aqueous cross-linking agent containing an epoxy group,
there are exemplified sorbitol polyglycidyl ether, glycerol
triglycidyl ether, polyglycerol polyglycidylether
trimethylolpropane triglycidyl ether, poly(ethyleneglycol)
diglycidyl ether, poly(propyleneglycol) diglycidyl ether, phenol
ethyleneoxide glycidyl ether, and lauryl alcohol ethyleneoxide
glycidyl ether or the like. In addition to the above, mentioned as
examples are: a water-soluble epoxy resin obtained by reacting a
carboxy compound, which is obtained through a reaction between a
polyoxyethylene polyol compound and an acid anhydride compound, and
an epoxy resin having two or more epoxy groups in its molecules;
and a self-emulsifiable epoxy resin composition obtained by mixing
the water-soluble epoxy resin and the epoxy resin having two or
more epoxy groups in its molecules. Such resins can be obtained for
example under the tradenames of XZ 92533.00, XZ 92598.00 and XZ
92446.00 from The Dow Chemical Company, Midland, Mich. Examples of
the anhydride compound include, but not particularly limited to,
preferably aromatic anhydrides such as phthalic anhydride,
trimellitic anhydride, and pyromellitic anhydride; and cyclic
aliphatic anhydrides such as maleic anhydride, succinic anhdyride,
tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride,
methyl nadic anhydride, alkenyl succinic anhdyride,
hexahydrophthalic anhydride, and methyl hexahydrophthalic
anhydride. There is no limitation on the epoxy resin having two or
more epoxy groups in its molecules, and all known epoxy resins with
an epoxy functionality of greater or equal to two can be used.
Examples are polyglycidyl ether obtained from epichlorohydrin and a
polyhydric compound such as, phenol novolac, and cresol novolac
bisphenol A, bisphenol F, bisphenol S, resorcinol, hydroquinone or
catechin; alkylene oxide-added bisphenol A; polyalcohols such as
polypropylene glycol, 1,6-hexanediol, trimethylol propane,
glycerin, cyclohexanedimethanol; and polyglycidyl ester and
polyglycidyl amine of polycarboxylic acids such as adipic acid,
phthalic acid, dimer acid and the like.
[0101] Aqueous cross-linking agent containing an isocyanate group
are, for example: polyisocyanate mainly containing at least one
member selected from the group consisting of an isocyanurate
group-containing polyisocyanate, an urethodione group-containing
polyisocyanate, an urethodione group/isocyanurate group containing
polyisocyanate, an urethane group containing polyisocyanate, an
allophanate group containing polyisocyanate, a biuret group
containing polyisocyanate, a carbodiimide group containing
polyisocyanate, and an uretodione group containing polyisocyanate,
each of which contains 1,6-hexamethylene diisocyanate and/or
isophorone diisocyanate as a raw material; and a self-emulsifiable
polyisocyanate obtained by reacting a hydrophilic surfactant having
at least one active hydrogen group which can react with an
isocyanate group or polyethylene ether alcohol containing at least
three poly-ethylene oxide units with fatty acid ester in which the
sum of the number of carbons of fatty acid and a hydroxyl
containing compound as raw materials is 8 or more and which has at
least one active hydrogen group which can react with an isocyanate
group. In addition to the above, an urethane group-containing
polyisocyanate obtained by reaction between
1,6-hexamethylenediisocyanate and/or an isophorone diisocyanate and
an active hydrogen group-containing compound or polyisocyanate
obtained by an allophanatization reaction, carbodiimidization
reaction, uretodionization reaction, and biuretization reaction of
these diisocyanate compounds can be mentioned.
[0102] Examples of suitable crosslinking agents containing an
aldehyde are waterdispersed or waterdispersible or water-soluble
phenol formaldehyde resins, amino formaldehyde resins or
combinations thereof.
[0103] Phenol formaldehyde crosslinking agents include, but are not
limited to, reaction products of aldehydes with phenols. Preferred
aldehdydes but not exclusive are formaldehyde and acetaldehyde. A
large variety of phenols can be used such as but not exclusive
phenol, cresol, p-phenylphenol, p-tert-butylphenol,
p-tert-amylphenol, cyclopentylphenol, cresylic acid, bisphenol-A,
bisphenol-F and the like and combinations thereof. Also acid
functional phenols could be used in making phenol formaldehyde
resins. The crosslinkers can be unetherified or etherified with
alcohols or polyols. These phenol formaldehyde resins may be
soluble or self-emulsifiable in water or can be stabilized by use
of colloid stabilizers such as polyvinyl alcohol.
[0104] Amino formaldehyde crosslinking agents include, but are not
limited to, reaction products of aldehydes with amino or amido
group containing molecules. Exemplary aldehydes include, but are
not limited to, formaldehyde and acetaldehyde. A large variety of
amino or amido group containing molecules can be used such as but
not exclusive urea, melamine, benzoguanamine, acetoguanamine,
glycoluril and the like. Suitable amino crosslinking resins include
melamine-formaldehyde, urea-formaldehyde,
benzoguanamine-formaldehyde, acetoguanamine-formaldehyde,
glycoluril-formaldehyde resins. Also the methylol groups of an
amino formaldehyde resin can be partially or fully etherified with
at least one of the groups of monohydric aliphatic alcohols such as
methanol and/or n-butanol. These amino formaldehyde resins may be
soluble or self-emulsifiable in water or can be stabilized by use
of colloid stabilizers such as polyvinyl alcohol can be used to
stabilize the amino formaldehyde dispersions.
[0105] Commercially available amino-formaldehyde resins which are
water soluble or water dispersible and useful for the instant
purpose include Cymel.TM. 301, Cymel.TM. 303, Cymel.TM. 370, and
Cymel.TM. 373 (all being products of Cytec Surface Specialties,
Brussels, Belgium). Other aldehydes used to react with the amino
compound to form the resinous material are crotonic aldehyde,
acrolein, or compounds which generate aldehydes, such as
hexamethylene-tetramine, paraldehyde, and the like.
[0106] Another class of crosslinking agents for carboxylic acid
groups are water-soluble hydroxyalkylamide crosslinkers such as
Bis(N,N'-dihydroxyethyl)adipamide and the like. Such compounds are
commercially available under the tradename of PRIMID.TM.
crosslinker resins from EMS-PRIMID in Switzerland, for example
PRIIVIID.TM. XL-522, PRIMID.TM. SF-4510 and PRIMID.TM. QM-1260
[0107] The one or more cros slinking agents may be added to the
aqueous dispersion as part of the aqueous dispersion formulation
process; or in the alternative, the one or more crosslinking agents
may be added to the aqueous dispersion post dispersion formulation
process.
[0108] Depending on the type of food or beverage which is to be
contained in a coated container, and on required coating properties
it may be beneficial to combine several crossslinkers or some
crosslinkers may be more suited than others. Some crosslinkers may
not be suited for all applications. Some crosslinkers may require
the addition of catalysts for proper cure.
[0109] Crosslinkers will help to build thermoset networks which is
indicated by higher values of MEK Double Rubs compared to an
identical formulation not containing the crosslinker.
Forming the Dispersion
[0110] The aqueous dispersion can be formed by any number of
methods recognized by those having skill in the art. Dispersion
equipment can be operated in batch, semi-batch, or continuous mode.
Examples of mixers include rotor-stator, microfluidizer, high
pressure homogenizer, ultrasonic, impinging jet, Cowles.TM. blade,
planetary mixers, and melt kneading devices such as extruders.
[0111] In one embodiment, one or more base polymers, one or more
stabilizing agents are melt-kneaded in an extruder along with water
and optionally one or more neutralizing agents, such as ammonia,
potassium hydroxide, amine, or a combination of two or more, to
form a dispersion. In another embodiment, one or more base polymers
and one or more stabilizing agent are compounded, and then
melt-kneaded in an extruder in the presence of water, and
optionally one or more neutralizing agents thereby forming a
dispersion. In some embodiments, the dispersion is first diluted to
contain about 1 to about 20%, e.g., 1 to 5% or 1 to 3%, by weight
water and then, subsequently, further diluted to comprise greater
than about 25% by weight water. In one embodiment, further dilution
may be accomplished via a solvent.
[0112] Any melt-kneading means known in the art may be used. In
some embodiments, a kneader, a BANBURY.RTM. mixer, single-screw
extruder, or a multi-screw extruder, e.g. a twin screw extruder, is
used. A process for producing the dispersions in accordance with
the present invention is not particularly limited. For example, an
extruder, in certain embodiments, for example, a twin screw
extruder, is coupled to a back pressure regulator, melt pump, or
gear pump. Exemplary embodiments also provide a base reservoir and
an initial water reservoir, each of which includes a pump. Desired
amounts of base and initial water are provided from the base
reservoir and the initial water reservoir, respectively. Any
suitable pump may be used, but in some embodiments, for example, a
pump that provides a flow of about 150 cc/min at a pressure of 240
bar is used to provide the base and the initial water to the
extruder. In other embodiments, a liquid injection pump provides a
flow of 300 cc/min at 200 bar or 600 cc/min at 133 bar. In some
embodiments, the base and initial water are preheated in a
preheater.
[0113] One or more base polymers, in the form of pellets, powder,
or flakes, are fed from the feeder to an inlet of the extruder
where the resin is melted or compounded. One or more additional
components may optionally be fed simultaneously with one or more
base polymers into the extruder via the feeder; or in the
alternative, one or more additional components may be compounded
into one or more base polymers, and then fed into the extruder via
the feeder. In the alternative, additional one or more additional
components may optionally further be metered via an inlet prior to
the emulsification zone into the molten compound comprising one or
more base polymers. In some embodiments, the dispersing agent is
added to one or more base polymers through and along with the resin
and in other embodiments, the dispersing agent is provided
separately to the twin screw extruder. The resin melt is then
delivered from the mix and convey zone to an emulsification zone of
the extruder where the initial amount of water and base from the
water and base reservoirs are added through an inlet. In some
embodiments, dispersing agent may be added additionally or
exclusively to the water stream. In some embodiments, further
dilution water may be added via water inlet from water reservoir in
a dilution and cooling zone of the extruder. Typically, the
dispersion is diluted to at least 30 weight percent water in the
cooling zone. In addition, the diluted mixture may be diluted any
number of times until the desired dilution level is achieved. In
some embodiments, the dispersion is further cooled after exiting
the extruder by the use of a suitable heat exchanger. In other
embodiments, water is not added into the twin screw extruder but
rather to a stream containing the resin melt after the melt has
exited from the extruder. In this manner, steam pressure build-up
in the extruder is eliminated and the dispersion is formed in a
secondary mixing device such as a rotor stator mixer.
[0114] In another embodiment, the aqueous dispersion can be formed
in a continuous high shear mixer without the use of a melt kneading
extruder. In this embodiment, the first stream comprising one or
more liquid or molten base polymers is supplied to a continuous
high shear mixer from a suitable liquid pump for example, a syringe
pump, gear pump, or progressive cavity pump. The first stream is
flowed through a first conduit and merged continuously with a
second stream containing a continuous aqueous phase that is flowed
through a second conduit. The first and second streams are merged
into a disperser in the presence of a stabilizing agent with
optional neutralizing agent. The agents can be added to either the
first or second stream, or as a separate stream. A third stream
comprising water can be added downstream from the disperser. The
flow rates of the streams are adjusted to achieve a dispersion
having the desired amount of polymer phase and percent solids. The
disperser can be any one of a number of continuous inline mixers,
for example, an IKA high-shear mixer, Oakes rotor stator mixer,
Ross mixer, Silverson mixer, or centrifugal pump. The rpm setting
of the disperser can be used to help control the particle size of
the dispersed hydrophobic phase in the dispersion. The system can
be heated to provide the polymer and neutralizer components at a
suitable viscosity for pumping. Steam formation is reduced by
controlling the pressure through the use of a backpressure
regulator, gear pump, metering pump, or other suitable device near
the exit of the process. In some embodiments, the dispersion is
further cooled after exiting the disperser by the use of a suitable
heat exchanger.
[0115] In another embodiment, the aqueous dispersion can be formed
in a batch or semi-batch high shear mixer where the mixer may, for
example, be disposed within a pressurized tank to, for example,
reduce steam formation. All or at least a portion of the dispersion
is removed from the tank during processing, and optionally cooled
by the use of a suitable heat exchanger.
[0116] During the preparation of the aqueous dispersion, optionally
one or more fillers; optionally one or more additives such as
catalysts, wetting agents, defoamers, flow agents, release agents,
slip agents, anti-blocking agents, additives to mask sulfur
staining, pigment wetting/dispersion agents, anti-settling agents,
UV stabilizers, adhesion promoters; optionally one or more
lubricants such as fatty acid ester wax, silicon-based wax,
fluorine-based wax, polyethylene or any other similar polyolefin
wax, carnauba wax, lanolin wax or the like; optionally one or more
corrosion inhibitors such as aluminum, and zinc: optionally one or
more pigments, e.g. titanium dioxide, mica, calcium carbonate,
barium sulfate, silica, zinc oxide, milled glass, aluminum
trihydrate, talc, antimony trioxide, fly ash, and clay or the like;
optionally one or more dyes; optionally one or more co-solvents,
e.g. glycols, glycol ether, 2,2,4-trimethyl-1,3-pentanediol
monoisobutyrate, alcohols, mineral spirits, and benzoate esters or
the like; optionally one or more dispersants, e.g. aminoalcohols,
and polycarboxylates; optionally one or more surfactants;
optionally one or more defoamers; optionally one or more
preservatives, e.g. biocides, mildewcides, fungicides, algaecides,
and combinations thereof; optionally one or more thickeners, e.g.
cellulosic based thickeners such as hydroxyethyl cellulose,
hydrophobically modified alkali soluble emulsions (HASE thickeners
such as UCAR POLYPHOBE TR-116) and hydrophobically modified
ethoxylated urethane thickeners (HEUR); or optionally one or more
additional neutralizing agents, e.g. hydroxides, amines, ammonia,
and carbonates may be added to the aqueous dispersion formulation;
or in the alternative, may be added to the dispersion post
dispersion formulation process.
[0117] During the preparation of the aqueous dispersion, one or
more stabilizing agents may also be added to the aqueous dispersion
formulation; or in the alternative, may be added to the dispersion
post dispersion formulation process.
[0118] Optionally during the dispersion of the one or more base
polymers another polymer dispersion or emulsion may be used as a
portion of the aqueous phase of the dispersion. Examples include,
but are not limited to, acrylic, epoxy, polyester, polyurethane,
polyolefin, polyamide and the like containing dispersions,
emulsions, suspensions, colloidal suspensions.
Coating Applications and Forming Coated Containers or Closure
Devices
[0119] The aqueous dispersion may be used, for example, in
container, e.g. can, coating application, or closure device coating
application. Such coated container devices include, but are not
limited to, cans such as beverage cans, food cans; aerosol
containers such as those for non-food products, e.g. hair spray,
hair dye, or color spray lacquers; drums; kegs; pails; decorative
tins; open trays; tubes, bottles, monoblocs, and the like. The
coated closure devices include, but are not limited to, caps, lids
such as thin aluminum foil based lids for yogurt and butter
containers, or crown corks; closures for glass jars and bottles
such as roll-on closures, vacuum closures, pilfer-proof closures,
easy peel lids for can closures, and easy open end or conventional
ends for cans. Cans may be 2 piece cans or 3 piece cans. Beverage
cans include, but are not limited to, beer cans, carbonated soft
drink cans, energy drink cans, isotonic drink cans, water cans,
juice cans, tea cans, coffee cans, milk cans, and the like. Food
cans, include, but are not limited to, vegetable cans, fruit cans,
meat cans, soup cans, ready meal cans, fish cans, edible oil cans,
sauce cans and the like. Such cans may have any shapes; for
example, such can may have a cylindrical shape, cubical, spherical,
semi-spherical, bottle shape, elongated cubical shape, shallow or
tall shape, round or rectangular shape or any other suitable shape.
The coated container devices according to the instant invention may
be formed via any conventional method. For example, the coated
container device may be formed via stamping, drawing, redrawing,
wall ironing, bending, beading, embossing, debossing, flanging,
necking, stretching, blow-stretching and any other suitable
conventional method. Such methods are generally known to those
having ordinary skill in the art. The aqueous dispersion may, for
example, be applied to a metal substrate, e.g. metal sheet or metal
foil, and then the coated substrate may be formed into a coated
container device or a coated closure device. In the alternative,
the metal substrate may be formed into a container device or a
closure device, and then the container device or the closure device
is coated with one or more aqueous dispersions to form the coated
container device or coated closure device. The coating may be
applied via any method; for example, via roller coating, spray
coating, powder coating, dip coating, electrodeposition coating,
printing, wash coating, flow coating, curtain coating.
[0120] The one or more aqueous dispersions applied to the at least
one surface of the metal substrate may be dried via any
conventional drying method. Such conventional drying methods
include but, are not limited to, air drying, convection oven
drying, hot air drying, and/or infrared oven drying. During the
drying process, cros slinking of one or more base polymers,
stabilizing agents, or combinations thereof, involving one or more
the crosslinking agents, may occur. Additional cure might occur by
radiation cure, e.g. electron-beam cure. The one or more aqueous
dispersions applied to the at least one surface of the metal
substrate may be dried at any temperature; for example, it may be
dried at a temperature in the range of equal or greater than the
melting point temperature of the base polymer; or in the
alternative, it may be dried at a temperature in the range of less
than the melting point of the base polymer. The one or more aqueous
dispersions applied to the at least one surface of the metal
substrate may be dried at a temperature in the range of about
60.degree. F. (15.5.degree. C.) to about 700.degree. F.
(371.degree. C.) for a period of less than about 40 minutes, for
example, less than 20 minutes, or less than 10 minutes, or less
than 5 minutes, or less than 2 minutes, or less than 1 minute, or
less than 20 seconds. All individual values and subranges from
about 60.degree. F. (15.5.degree. C.) to about 700.degree. F.
(371.degree. C.) are included herein and disclosed herein; for
example, the one or more aqueous dispersions applied to the at
least one surface of the metal substrate may be dried at a
temperature in the range of about 60.degree. F. (15.5.degree. C.)
to about 500.degree. F. (260.degree. C.) for a period of less than
about 40 minutes, for example, less than 20 minutes, or less than
10 minutes, or less than 5 minutes, or less than 2 minutes, or less
than 1 minute, or in the alternative, the one or more aqueous
dispersions applied to the at least one surface of the metal
substrate may be dried at a temperature in the range of about
60.degree. F. (15.5.degree. C.) to about 450.degree. F.
(232.2.degree. C.) for a period of less than about 40 minutes, for
example, less than 20 minutes, or less than 10 minutes, or less
than 5 minutes, or less than 2 minutes, or less than 1 minute. The
temperature of the one or more aqueous dispersions applied to the
at least one surface of the metal substrate may be raised to a
temperature in the range of equal or greater than the melting point
temperature of the base polymer for a period of less than about 40
minutes. All individual values and subranges from less than about
40 minutes are included herein and disclosed herein; for example,
the temperature of the one or more aqueous dispersions applied to
the at least one surface of the metal substrate may be raised to a
temperature in the range of equal or greater than the melting point
temperature of the base polymer for a period of less than about 20
minutes, or in the alternative, the temperature of the one or more
aqueous dispersions applied to the at least one surface of the
metal substrate may be raised to a temperature in the range of
equal or greater than the melting point temperature of the base
polymer for a period of less than about 5 minutes, or in another
alternative, the temperature of the one or more aqueous dispersions
applied to the at least one surface of the metal substrate may be
raised to a temperature in the range of equal or greater than the
melting point temperature of the base polymer for a period in the
range of about 0.5 to 300 seconds. In another alternative, the
temperature of the one or more aqueous dispersions applied to the
at least one surface of the metal substrate may be raised to a
temperature in the range of less than the melting point temperature
of the base polymer for a period of less than 40 minutes. All
individual values and subranges from less than about 40 minutes are
included herein and disclosed herein; for example, the temperature
of the one or more aqueous dispersions applied to the at least one
surface of the metal substrate may be raised to a temperature in
the range of less than the melting point temperature of the base
polymer for a period of less than about 20 minutes, or in the
alternative, the temperature of the one or more aqueous dispersions
applied to the at least one surface of the metal substrate may be
raised to a temperature in the range of less than the melting point
temperature of the base polymer for a period of less than about 5
minutes, or in another alternative, the temperature of the one or
more aqueous dispersions applied to the at least one surface of the
metal substrate may be raised to a temperature in the range of less
than the melting point temperature of the base polymer for a period
in the range of about 0.5 to 300 seconds.
[0121] The coated metal substrate may further be coated with one or
more conventional coating compositions, or it may further be
laminated to one or more other layers. Such conventional coating
compositions are generally known to person of ordinary skill in the
art, and they may include, but are not limited to, epoxy resin
coating compositions, acrylate based coating compositions, and
polyester based coating compositions. The lamination process is
generally known, and exemplary lamination layers may include, but
are not limited to, polyester laminates, polyolefin based laminates
such as polypropylene laminates.
[0122] The one or more aqueous dispersions applied to at least one
surface of a metal substrate, for example a pre-coated substrate,
as one or more crosslinked coating layers may have a cross cut
adhesion rating of at least 3B; for example, 5B, measured according
to ASTM-D 3359-08. The one or more aqueous dispersions applied to
at least one surface of a metal substrate as one or more
crosslinked coating layers may a methyl ethyl ketone (MEK) double
rub rating of at least 10. The one or more aqueous dispersions
applied to at least one surface of a metal substrate as one or more
crosslinked coating layers may have a wedge bend pass rating of at
least 90 percent, measured via a Gardner "COVERALL" Bend Tester IG
1125.
Examples
[0123] The following examples illustrate the present invention but
are not intended to limit the scope of the invention. The examples
of the instant invention demonstrate that the one or more aqueous
dispersions applied to at least one surface of a metal substrate
provide for improved coating layer flexibility as well as coating
layer adhesion to the metal substrate.
Preparation of Inventive Aqueous Dispersion A
[0124] Aqueous dispersion A was prepared according to the following
procedures based on the formulation components listed in Table I.
PRIMACOR.TM. 1410 (CAS No. 9010-77-9), ethylene acrylic-acid
copolymer having acrylic acid content of approximately in the range
of 9 to 10 weight percent and a melt index of approximately in the
range of 1.3 to 1.6 g/10 minutes (ASTM D 1238, 190 deg C./2.16 Kg),
available from The Dow Chemical Company, as the base polymer, and
PRIMACOR.TM. 5980i (CAS No. 9010-77-9), ethylene acrylic-acid
copolymer having acrylic acid content of approximately in the range
of 19.5 to 21.5 weight percent and a melt index of approximately
300 g/10 minutes (ASTM D 1238, 190 deg C./2.16 Kg), available from
The Dow Chemical Company, as the stabilizing agent were fed into a
25 mm diameter twin screw extruder by means of a controlled rate
feeder where they were forwarded and melted. The extruder
temperature profile was ramped up to approximately 160.degree. C.
prior to the addition of the initial water and AMP-95,
amino-2-methyl-1-propanol (95%) (CAS No. 124-68-5), as the
neutralizing agent, and subsequently, it was cooled back down to a
temperature below 100.degree. C. by the end of the extruder after
the dilution water was added. The extruder speed was approximately
450 rpm. Amine base and water were mixed together and fed to the
extruder at the initial water introduction point. The dilution
water was fed via a second pump, and it was introduced into the
dilution zone of the extruder. The initial water and dilution water
streams were optionally pre-heated to the extruder temperature. At
the extruder outlet, a back-pressure regulator was used to adjust
to a suitable pressure inside the extruder barrel to reduce steam
formation at the operating temperature. The resulting dispersions
were cooled and filtered through a 200 micron filter.
Preparation of Inventive Aqueous Dispersion B
[0125] Aqueous dispersion B was prepared according to the following
procedures based on the formulation components listed in Table I.
PRIMACOR.TM. 1321 (CAS No. 9010-77-9), ethylene acrylic-acid
copolymer having acrylic acid content of approximately in the range
of 6 to 7 weight percent and a melt index of approximately in the
range of 2.2 to 2.8 g/10 minutes, available from The Dow Chemical
Company, as the base polymer, and HDPE 30460M (CAS No. 26211-73-8),
a high density polyethylene with a density of approximately in the
range of 0.958 to 0.962 g/cm.sup.3 and a melt index of
approximately in the range of 24 to 36 g/1 minutes, available from
The Dow Chemical Company, as additional base polymer, and
PRIMACOR.TM. 5980i (CAS No. 9010-77-9), ethylene acrylic-acid
copolymer having acrylic acid content of approximately in the range
of 19.5 to 21.5 weight percent and a melt index of approximately in
the range of 300 g/10 min (ASTM D 1238, 190 deg C./2.16 Kg),
available from The Dow Chemical Company, as the stabilizing agent
were fed into a 25 mm diameter twin screw extruder by means of a
controlled rate feeder where they were forwarded and melted. The
extruder temperature profile was ramped up to approximately
160.degree. C. prior to the addition of the initial water and
AMP-95, amino-2-methyl-1-propanol (95%) (CAS No. 124-68-5), as the
neutralizing agent, and subsequently, it was cooled back down to a
temperature below 100.degree. C. by the end of the extruder after
the dilution water was added. The extruder speed was approximately
450 rpm. Amine base and water were mixed together and fed to the
extruder at the initial water introduction point. The dilution
water was fed via a second pump, and it was introduced into the
dilution zone of the extruder. The initial water and dilution water
streams were optionally pre-heated to the extruder temperature. At
the extruder outlet, a back-pressure regulator was used to adjust
to a suitable pressure inside the extruder barrel to reduce steam
formation at the operating temperature. The resulting dispersions
were cooled and filtered through a 200 micron filter.
Preparation of Inventive Aqueous Dispersion C
[0126] Aqueous dispersion C was prepared according to the following
procedures based on the formulation components listed in Table I.
PRIMACOR.TM. 1321 (CAS No. 9010-77-9), ethylene acrylic-acid
copolymer having acrylic acid content of approximately in the range
of 6 to 7 weight percent and a melt index of approximately in the
range of 2.2 to 2.8 g/10 minutes (ASTM D 1238, 190 deg C./2.16 Kg)
available from The Dow Chemical Company, as the base polymer, and
PRIMACOR.TM. 5980i (CAS No. 9010-77-9), ethylene acrylic-acid
copolymer having acrylic acid content of approximately in the range
of 19.5 to 21.5 weight percent and a melt index of approximately
300 g/10 minutes (ASTM D 1238, 190 deg C./2.16 Kg), available from
The Dow Chemical Company, as the stabilizing agent were fed into a
25 mm diameter twin screw extruder by means of a controlled rate
feeder where they were forwarded and melted. The extruder
temperature profile was ramped up to approximately 160.degree. C.
prior to the addition of the initial water and DMEA, 2-dimethyl
amino ethanol (100%) (CAS No. 108-01-0), as the neutralizing agent,
and subsequently, it was cooled back down to a temperature below
100.degree. C. by the end of the extruder after the dilution water
was added. The extruder speed was approximately 450 rpm. Amine base
and water were mixed together and fed to the extruder at the
initial water introduction point. The dilution water was fed via a
second pump, and it was introduced into the dilution zone of the
extruder. The initial water and dilution water streams were
optionally pre-heated to the extruder temperature. At the extruder
outlet, a back-pressure regulator was used to adjust to a suitable
pressure inside the extruder barrel to reduce steam formation at
the operating temperature. The resulting dispersions were cooled
and filtered through a 200 micron filter.
Preparation of Inventive Aqueous Dispersion D
[0127] Dispersion D was prepared in a manner similar to dispersion
A, but with the formulation components listed in Table I.
Preparation of Supplemental Inventive Aqueous Dispersions S1-28
[0128] Supplemental Inventive Dispersions S1-28 were prepared in a
manner similar to dispersion A, but with the formulation components
listed in Table I.
Preparation of Coatings Based on Formulations with Melamine
Formaldehyde Crosslinker
[0129] Dispersions A-D were mixed with Cymel.TM. 327 (CAS No.
9003-08-1), melamine formaldehyde resin, available from Cytec
Surface Specialties, Brussels, Belgium as a crosslinking agent in a
beaker using a IKA RW 16 electrical stiffing agitator at level 5
with a R-1302 stirrer at room temperature, approximately 25.degree.
C., for about one minute to yield the finished formulation. The
mixture is allowed to sit until bubbles dissipate. The details of
the coating formulations based on the combination of aqueous
dispersions A-D and Cymel.TM. 327, as crosslinking agent, are
reported in Table II.
Preparation of Coatings Based on Formulations with Phenolic
Crosslinker
Inventive Formulation Example 5:
[0130] Step 1: Preparation of the phenolic crosslinker blend
dispersion: [0131] 20 g of XZ 95320.02 experimental epoxy curing
agent, 20 g of Phenodur.TM. PR 401 phenolic resin and 0.75 g of
dimethyl ethanol amine were mixed under stirring with an IKA RE-166
electric stirring agitator and a propeller-blade stirrer at about
2000 rpm. Then 18.0 g of water was added slowly under stirring
until a phase inversion occurred. The resulting emulsion had a
solids content of 41.1%. [0132] XZ 95320.02 experimental epoxy
curing agent is available from The Dow Chemical Company. Midland
Mich. Phenodur.TM. PR 401 phenolic resin is available from Cytec
Surface Specialties, Brussels, Belgium [0133] Step 2: Preparation
of the final formulation
[0134] 25.46 g of the inventive dispersion D are mixed with 4.44 g
of the phenolic crosslinker dispersion of above in a beaker using
an IKA RW 16 electrical stirring agitator at level 5 with a R-1302
stirrer at room temperature, approximately 25.degree. C., for about
one minute to yield the finished formulation. [0135] Step 3: A tin
plate panel, provided by Rasselstein, having grade TS-245 standard
finish, with approximately 10 cm to 20 cm size was cleaned with
acetone, and then dried. About 3 grams of the coating formulation
was applied to the tin plate panel via a 30 micron spiral drawdown
bar thereby coating one surface of the tin plate panel.
Subsequently, the panel was placed into a convection oven to be
cured at 200.degree. C. for 3 minutes. The coating was slightly
hazy. The details of the coating formulation are listed in Table
III.
Inventive Formulation Example 6:
[0135] [0136] Preparation of coatings with acrylic resin
composition [0137] Step 1: Dimethyl amino ethanol was mixed with
water to form a 50% aqueous solution. [0138] Step 2: 2.14 g of the
aqueous dimethyl amino ethanol solution (50%) of step 1 were slowly
added to 4.65 gr of PRIMAL.TM. E 3203 acrylic emulsion in a beaker
using a IKA RW 16 electrical stiffing agitator at level 5 with a
R-1302 stirrer at room temperature, approximately 25.degree. C.,
for about one minute. A high viscosity dispersion was obtained.
[0139] Step 3: PRIMID.TM. XL 552 crosslinker was dissolved in water
to form a 50% aqueous solution. [0140] Step 4: 6.72 g of the
resulting mixture of step 2 were mixed with 24.48 of dispersion D
in a beaker using a IKA RW 16 electrical stirring agitator at level
5 with a R-1302 stirrer at room temperature, approximately
25.degree. C., for about one minute. Then 2 g of the PRIMID.TM.
XL-552 solution (50%) of step 3 was added using a IKA RW 16
electrical stirring agitator at level 5 with a R-1302 stirrer at
room temperature, approximately 25.degree. C., for about one
minute. [0141] PRIIVIAL.TM. E-3203 is available from The Dow
Chemical Company, Midland, Mich.; PRIMID.TM. XL 552 is available
from EMS Chemie, Donat; Switzerland.
[0142] A tin plate panel, provided by Rasselstein, having grade
TS-245 standard finish, with approximately 10 cm to 20 cm size was
cleaned with acetone, and then dried. About 3 grams of the coating
formulation was applied to the tin plate panel via a 30 micron
spiral drawdown bar thereby coating one surface of the tin plate
panel. Subsequently, the panel was placed into a convection oven to
be cured at 200.degree. C. for 3 and 6 minutes. The details of the
coating results are listed in Table IV.
Inventive Formulation Example 7:
[0143] 1.74 g of XZ 92546.00 experimental epoxy novolac emulsion at
57.5% nv were mixed with 31.47 g of inventive dispersion D in a
beaker using a IKA RW 16 electrical stiffing agitator at level 5
with a R-1302 stirrer at room temperature, approximately 25.degree.
C., for about one minute to yield the finished formulation.
[0144] A tin plate panel, provided by Rasselstein, having grade
TS-245 standard finish, with approximately 10 cm to 20 cm size was
cleaned with acetone, and then dried. About 3 grams of the coating
formulation was applied to the tin plate panel via a 30 micron
spiral drawdown bar thereby coating one surface of the tin plate
panel. Subsequently, the panel was placed into a convection oven to
be cured at 200.degree. C. for 3 minutes. The details of the
coating results are listed in Table V.
Preparation of a Tinplate Panel Coated with a Polyester Resin
Formulation
[0145] 23.28 g of Dynapol.TM. 952 polyester and 3.98 g of SFC
112/65 from SI group were mixed with 43.23 g of a mixture of 52
parts by weight Solvesso.TM. 100 aromatic solvent and 48 parts by
weight of Dowanol.TM. PMA glycol ether in a sealed glass bottle,
which was rotating on an array of rotating bars at room temperature
for 72 hours. Then 0.181 g of phosphoric acid (25% in Downanol.TM.
glycol ether) were added and the glass was rotated for additional
24 hrs. Dynapol is a trademark of Evonik. Solves so is a trademark
of ExxonMobil, Dowanol is a trademark of The Dow Chemical
Company.
[0146] A tin plate panel, provided by Rasselstein, having grade
TS-245 standard finish, with approximately 10 cm to 20 cm size was
cleaned with acetone, and then dried. About 3 grams of the coating
formulation was applied to the tin plate panel via a 30 micron
spiral drawdown bar thereby coating one surface of the tin plate
panel. Subsequently, the panel was placed into a convection oven to
be cured at 200.degree. C. for 10 minutes. The coating had a
thickness of 3.9 microns and 15 MEK DR.
Coating Application on a Pre-Coated Panel
[0147] The tin plate panel, coated with the polyester based
formula, of above was used with out further cleaning. About 3 grams
of the inventive coating formulation 4 was coated onto the
polyester coating via a 30 micron spiral drawdown bar.
Subsequently, the panel was placed into a convection oven to be
cured for 3 minutes at 200.degree. C.
The coated tin plate panels were tested for coating thickness,
wedge bend, MEK DR (methyl ethyl ketone double rub) cross cut
adhesion before sterilization, and cross cut adhesion and blush
after sterilization in water according to the procedures described
below. The results are reported in Table VI.
Coating Application of Uncoated Panels
[0148] A tin plate panel, provided by Rasselstein, having grade
TS-245 standard finish, with approximately 10 cm to 20 cm size was
cleaned with acetone, and then dried. About 3 grams of the
inventive coating formulations 1-3 were applied individually to the
tin plate panel via a 30 micron spiral drawdown bar thereby coating
one surface of the tin plate panel. Subsequently, the panel was
placed into a convection oven to be cured. The curing conditions
are reported in Table VII.
[0149] The coated tin plate panels were tested for coating
thickness, wedge bend, MEK DR (methyl ethyl ketone double rub)
cross cut adhesion before sterilization, and cross cut adhesion and
blush after sterilization according to the procedures described
below. The results are reported in Table VII.
Comparative Experiment
[0150] A tin plate panel, provided by Rasselstein, having grade
TS-245 standard finish, with approximately 10 cm to 20 cm size was
cleaned with acetone, and then dried. About 3 grams of an inventive
dispersion listed in Table IVwas applied to the tin plate panel via
a 30 micron spiral drawdown bar thereby coating one surface of the
tin plate panel. Subsequently, the panel was placed into a
convection oven to be cured. The curing conditions and testing
results are reported in Table VIII.
[0151] The coated tin plate panels were tested for coating
thickness, wedge bend, MEK DR (methyl ethyl ketone double rub)
cross cut adhesion before sterilization, and cross cut adhesion and
blush after sterilization in water according to the procedures
described below.
Test Methods
[0152] Test methods include the following:
Cross-Cut Adhesion
[0153] Cross-cut adhesion is measured according to ASTM-D 3359-08,
Measuring adhesion by tape test, Method B, using an Erichsen
cross-cut tester EPT 675R. This method provides the procedure for
assessing the adhesion of coating films to metallic substrates by
applying and removing a tape (grade: TESA 4124 clear) over the cuts
made in the film. Place the center of a piece of tape over the grid
and in the area of the grid smooth into place by a finger. To
ensure good contact with the film rub the tape firmly. Within
90.+-.30 seconds of application, remove the tape by seizing the
free end and rapidly (not jerked) pulling it off at as close to an
angle of 180 degrees as possible. Inspect the grid area for removal
of coating from the substrate or from a previous coating using the
illuminated magnifier. Rate the adhesion in accordance with the
following scale.
TABLE-US-00001 5B The edges of the cuts are completely smooth; none
of the squares of the lattice is detached. 4B Small flakes of the
coating are detached at intersections; less than 5% of the area is
affected. 3B Small flakes of the coating are detached along the
edges and at intersections of cuts. The area affected is 5-15% of
the lattice. 2B The coating has flaked along the edges and on parts
of the squares. The area affected is 15-35% of the lattice. 1B The
coating has flaked along the edges of cuts in large ribbons and
whole squares have detached. The area affected is 35-65% of the
lattice. 0B Flaking and detachment is worse than 1B
Sterilization in Water
[0154] The coated panels were immersed in water in a pressurizable
metal container, and placed into a Steriliser Automat V where it
was retorted at 129.degree. C. for 30 minutes. Subsequently, the
pressurized container was placed into a containment vessel with
cold water, and the temperature of pressurized container was
lowered to a temperature in the range of less than 50.degree. C.
before opening. The panels were removed, and dried. The blush
appearance was then rated. Blush is called a whitish appearance of
the coating. If the coating does not show any blush, then the
rating is no blush; otherwise, it will be rated as very slight
blush, slight blush, blush or strong blush.
Sterilization in Lactic Acid
[0155] The coated panels were immersed in 2% lactic acid solution
in a pressurizable metal container, and placed into a Steriliser
Automat V where it was retorted at 121.degree. C. for 30 minutes.
Subsequently, the pressurized container was placed into a
containment vessel with cold water, and the temperature of
pressurized container was lowered to a temperature in the range of
less than 50.degree. C. before opening. The panels were removed,
and dried. The blush appearance was then rated. Blush is called a
whitish appearance of the coating. If the coating does not show any
blush, then the rating is no blush; otherwise, it will be rated as
very slight blush, slight blush, blush or strong blush.
MEK Double Rub
[0156] The flat end of a hemispherical hammer having a weight of
1230.+-.10 g was used. A normal tissue "VILEDA 3168" was bound
around the hammer end. It was soaked with methyl ethyl ketone
(MEK). The hammer was brought into contact with the coating, and
moved forth-and-back over the whole coating, wherein one movement
forth-and-back over the whole coating is considered one double rub.
No additional pressure was applied onto the hammer. After every 10
double rubs, the tissue was re-soaked. The double rub step was
repeated until the coating was rubbed off, i.e. at least a portion
of the metal substrate was exposed. In the event that the double
rub step reached 100 double rubs, the testing was terminated, and
100 double rubs were reported as the final results.
Wedge Bend
[0157] Wedge bend was measured via Gardner "COVERALL" Bend Tester
IG 1125. The apparatus used for this test consists of two parts to
convert it to a bending machine. A steel rod (mandrel) is mounted
at the front of the base. The coated test panel of 100 mm width was
flexed over the 3 mm rod mandrel; thus, the coating appears on the
outside of the bend. The flexed panel was inserted in the wedge
mandrel. The impactor, i.e. a metal weight, was raised to 7 inches
height, and then dropped. The impactor is retrieved on its first
bounce, and secured. The cylindrical fold in the panel was squeezed
into a conical shape. The edge of the coated panel was rubbed with
a solution of copper sulfate (mixture of 10 grams of copper
sulfate, 90 grams of water and 3 grams of sulfuric acid). Anywhere
the coating had been cracked; dark spots appeared, indicating
failure. The length of the intact area along the length of the
wedge bend, which is 100 mm, was measured in millimeters and
expressed as percent pass.
Coating Thickness
[0158] Coating thickness was measured according to ASTM-D 1186-01,
Non-destructive measurement of dry film thickness of non magnetic
coatings applied to a ferrous base, using a PERMASCOPE D-211D,
coating thickness gauge. The standard panel without any coating was
used for calibration. The thickness of the coating of the coated
panels were the average of 10 measurements, wherein each
measurement of the thickness of the coating of the coated panels
was measured using a probe for ferrous materials relative to the
thickness of the coating of the standard panel, i.e. zero. The
measured thickness was reported in microns.
Degree of Neutralization
[0159] The percent neutralization was the calculated amount of
acrylic acid groups in the resin melt that are neutralized by the
base.
Particle Size Measurement
[0160] The particle size was measured by a Coulter LS-230 particle
size analyzer (Beckman Coulter Corporation).
Measurement Percent Solids
[0161] The percent solid was measured using a microwave solids
analyzer.
[0162] The present invention may be embodied in other forms without
departing from the spirit and the essential attributes thereof,
and, accordingly, reference should be made to the appended claims,
rather than to the foregoing specification, as indicating the scope
of the invention.
TABLE-US-00002 TABLE I Average Additional Initial Dilution Particle
Base Neutralizing Water Water Size Aqueous Base Polymer Stabilizing
Polymer Agent Rate Rate Diameter Dispersion (g/min) Agent (g/min)
(g/min) (ml/min) (ml/min) (ml/min) (microns) A PRIMACOR .TM.
PRIMACOR .TM. None AMP-95 .TM. 33 130 0.4 1410 5980i (12.4) (49)
(21) B PRIMACOR .TM. PRIMACOR .TM. HDPE AMP-95 .TM. 12 160 0.8 1321
(18.8) 5980i 30460M (8.5) (25) (6.2) C PRIMACOR .TM. PRIMACOR .TM.
None DMEA (7.2) 25 95 1.2 1321 5980i (35) (15) D PRIMACOR .TM.
PRIMACOR .TM. None DMEA 33 120 0.3 1410 5980i (11.2) (47.6) (20.4)
S1 109MFR Exp PRIMACOR .TM. none DMEA 20.6 80 2.1 polypropylene
5980i (7.55) (52.9) (22.7) S2 109MFR Exp PRIMACOR .TM. EPOLENE .TM.
DMEA 19 80 2.0 polypropylene 5980i E-25 (6.08) (52.9) (17.0) (5.7)
S3 D118.01 PRIMACOR .TM. EPOLENE .TM. DMEA 24.68 80 8.85
polypropylene 5980i E-25 (7.79) (47.3) (22.7) (5.7) S4 PRIMACOR
.TM. PRIMACOR .TM. None AMP-95 .TM. 30 102 0.7 1321 5980i (13.5)
(42) (18) S5 PRIMACOR .TM. PRIMACOR .TM. HDPE DMEA (3.1) 17 50 1.3
1321 5980i 30460M (25.7) (7.5) (3.8) S6 PRIMACOR .TM. PRIMACOR .TM.
HDPE DMEA (5.8) 17 35 1.7 1321 5980i 30460M (26.9) (7.5) (4.0) S7
PRIMACOR .TM. PRIMACOR .TM. None DMEA 32 94 1.2 1410 5980i (11.4)
(45.8) (19.3) S8 PRIMACOR .TM. PRIMACOR .TM. None DMEA 30 115 0.9
1410 5980i (15.2) (45) (15) S9 PRIMACOR .TM. PRIMACOR .TM. None
DMEA (13) 29 100 0.3 1410 5980i (30) (30) S10 PRIMACOR .TM.
PRIMACOR .TM. None DMEA (9.8) 50 160 0.3 1430 5980i (80) (20) S11
PRIMACOR .TM. PRIMACOR .TM. None DMEA (9.8) 49 173 0.3 1430 5990
(80) (20) S12 PRIMACOR .TM. PRIMACOR .TM. None DMEA (6.8) 20 55 1.5
3150 5980i (29) (20) S13 PRIMACOR .TM. PRIMACOR .TM. None AMP-95
.TM. 30 114 0.55 3440 5980i (10.4) (42) (18) S14 PRIMACOR .TM.
PRIMACOR .TM. None AMP-95 .TM. 30 102 0.35 3460 5980i (8.6) (48)
(12) S15 HDPE PRIMACOR .TM. None AMP-95 .TM. 20 220 1.0 30460M (35)
5980i (19.4) (35) S16 HDPE PRIMACOR .TM. None DMEA (10) 17 64 0.8
DMDA-8965 5980i (30) (20) S17 6D43 PRIMACOR .TM. LICOCENE .TM. DMEA
24.7 110 1.0 polypropylene 5980i 6452 (9.64) (79.4) (25.5) (8.5)
S18 6D43 PRIMACOR .TM. LICOCENE .TM. DMEA 14.31 80 0.84
polypropylene 5980i 6452 (6.35) (52.9) (17.0) (5.7) S19 6D43
PRIMACOR .TM. LICOCENE .TM. DMEA 12.84 75 2.48 polypropylene 5980i
(5.7) and 6452 (4.01) (61) behenic acid (5.7) (3.0) S20 6D43
PRIMACOR .TM. LICOCENE .TM. DMEA 13.02 83 1.45 polypropylene 5980i
6452 (4.99) (52.9) (11.3) (11.3) S21 6D43 PRIMACOR .TM. none AMP-95
.TM. 19.97 85 2.57 polypropylene 5980i (22.7) (6.07) (52.9) S22
6D43 PRIMACOR .TM. none 28% 16.79 70 3.67 polypropylene 5990
Ammonia (52.9) (22.7) (5.13) S23 6D43 PRIMACOR .TM. none 1,2 14.93
70 2.29 polypropylene 5980i diaminopropane (52.9) (22.7) (2.72) S24
6D43 NUCREL .TM. none DMEA (6.6) 17.87 90 1.06 polypropylene 2806
(22.7) (52.9) S25 6D43 NUCREL .TM. none 1,2 14.88 80 1.37
polypropylene 2806 diaminopropane (52.9) (22.7) (2.93) S26 6D43
PRIMACOR .TM. EPOLENE .TM. DMEA 18.98 80 1.98 polypropylene 5980i
E-25 (6.05) (52.9) (17.0) (5.7) S27 6D43 PRIMACOR .TM. PRIMACOR
.TM. DMEA 14.33 80 2.59 polypropylene 5980i 3340 (5.3) (52.9)
(17.0) (5.7) S28 6D43 PRIMACOR .TM. EXXELOR .TM. DMEA 23.25 80 1.6
polypropylene 5980i PO1020 (7.75) (47.3) (22.7) (5.7)
TABLE-US-00003 TABLE II Total Weight nv [%]* of Crosslinking of
Coating nv [%]* of Crosslinking Crosslinking Dispersion Agent
Formulation nv [%]* of Formulation Dispersion Dispersion Agent
Agent Weight [grams] Weight [grams] [grams] formulation 1 A 33.3
Cymel .TM. 327 90 30.03 0.58 30.61 34.4 2 B 29.3 Cymel .TM. 327 90
34.13 0.58 34.71 30.3 3 C 29.6 Cymel .TM. 327 90 33.78 0.58 34.36
30.6 4 D 28.6 Cymel .TM. 327 90 33.22 0.56 33.78 29.6 *nv =
non-volatiles or solid content
Phenolic Crosslinker Cured
TABLE-US-00004 [0163] TABLE III cross cut Total cross cut adhesion
coating cross cut adhesion wedge loss after blush after cure
thickness adhesion loss after blush after bent sterilization
sterilization Coated Formulation condition average loss before
sterilization sterilization [% MEK in lactic in lactic Substrate
Example [.degree. C./min] [microns] sterilization in water in water
pass] DR acid acid 10 5 200/3 5.9 5B 5B no blush 100% 100 5B no
blush
Blend with Acrylic Resin
TABLE-US-00005 TABLE IV cross cut cross cut adhesion Coating cross
cut adhesion loss after cure thickness adhesion loss after blush
after wedge sterilization blush after Coated Inventive condition
average loss before sterilization sterilization bent MEK in lactic
sterilization Substrate Dispersion [.degree. C./min] [microns]
sterilization in water in water [% pass] DR acid lactic 11 6 200/3
5.4 5B 5B no blush 100% 100 5B slight blush 12 6 200/6 5.9 5B 5B no
blush 100 100 5B very slight blush
Blend with Epoxy
TABLE-US-00006 TABLE V cross cut cross cut adhesion Coating cross
cut adhesion wedge loss after blush after cure thickness adhesion
loss after blush after bent sterilization sterilization Coated
Inventive condition average loss before sterilization sterilization
[% MEK in lactic in lactic Substrate Dispersion [.degree. C./min]
[microns] sterilization in water in water pass] DR acid acid 13 7
200/3 5.5 5B 5B no blush 100% 100 5B slight blush
Overcoated Polyester Coated Panel
TABLE-US-00007 [0164] TABLE VI Total cross cut coating cross cut
adhesion cure thickness adhesion loss after blush after wedge
Coated Formulation condition average loss before sterilization
sterilization bent MEK Substrate Example [.degree. C./min]
[microns] sterilization in water in water [% pass] DR 9 4 200/3 8.0
5B 5B no blush 100% 63
TABLE-US-00008 TABLE VII Crosscut Crosscut Coating Adhesion
Adhesion Loss Blush Cure Thickness Loss Before After After Wedge
Coated Formulation Condition Average Sterilization in Sterilization
in Sterilization Bent MEK Substrate Example [.degree. C./min]
[microns] Water Water in Water [% pass] DR 1 1 200/3 4.4 5B 5B no
blush 100% 56 2 2 200/3 3.9 5B 5B no blush 100% 30 3 3 200/3 5.6 5B
5B no blush 100% >100 4 1 150/5 4.3 5B 5B no blush 100% 99 5 2
150/5 3.9 5B 5B no blush 100% 50 6 3 150/5 5.2 4B 4B no blush 100%
>100
Comparative Example
TABLE-US-00009 [0165] TABLE VIII cross cut Coating cross cut
adhesion cure thickness adhesion loss after blush after wedge
Coated Formulation condition average loss before sterilization
sterilization bent MEK Substrate Example [.degree. C./min]
[microns] sterilization in water in water [% pass] DR 7 A 150/5 5.0
5B 5B no blush 100% 23 8 D 200/3 5.0 5B 5B Slight blush 100% 27
* * * * *