U.S. patent application number 17/366937 was filed with the patent office on 2022-01-27 for packaging coated with an emulsion polymerized latex polymer.
The applicant listed for this patent is PPG Industries Ohio, Inc.. Invention is credited to Hanzhen Bao, John M. Dudik, Dary Duhamel, Qin Li, Kam Lun Lun, Edward R. Millero, JR., William H. Retsch, JR., Debra L. Singer.
Application Number | 20220025192 17/366937 |
Document ID | / |
Family ID | |
Filed Date | 2022-01-27 |
United States Patent
Application |
20220025192 |
Kind Code |
A1 |
Singer; Debra L. ; et
al. |
January 27, 2022 |
Packaging Coated with an Emulsion Polymerized Latex Polymer
Abstract
A package with a coating composition deposited on at least a
portion thereof is disclosed. The coating composition comprises:
(a) a latex polymer comprising the emulsion polymerization product
of (i) an emulsion monomer component comprising at least one
ethylenically unsaturated monomer polymerized in the presence of
(ii) a surfactant that is polymerizable with the at least one
ethylenically unsaturated monomer. Also disclosed is a method for
applying the coating composition to the package.
Inventors: |
Singer; Debra L.; (Wexford,
PA) ; Duhamel; Dary; (Stratford, GB) ; Lun;
Kam Lun; (Orpington, GB) ; Li; Qin; (Mason,
OH) ; Bao; Hanzhen; (Mason, OH) ; Dudik; John
M.; (Apollo, PA) ; Millero, JR.; Edward R.;
(Gibsonia, PA) ; Retsch, JR.; William H.; (Allison
Park, PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
PPG Industries Ohio, Inc. |
Cleveland |
OH |
US |
|
|
Appl. No.: |
17/366937 |
Filed: |
July 2, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15577941 |
Nov 29, 2017 |
11091656 |
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PCT/US2016/034276 |
May 26, 2016 |
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17366937 |
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62168040 |
May 29, 2015 |
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62168134 |
May 29, 2015 |
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International
Class: |
C09D 7/61 20060101
C09D007/61; C09D 5/02 20060101 C09D005/02; C09D 133/06 20060101
C09D133/06; C08K 5/42 20060101 C08K005/42; C08K 5/5333 20060101
C08K005/5333; C09D 123/08 20060101 C09D123/08; C09D 133/10 20060101
C09D133/10; C09D 133/12 20060101 C09D133/12; C09D 133/14 20060101
C09D133/14 |
Claims
1-22. (canceled)
23. A package with a coating composition deposited on at least a
portion thereof, wherein the coating composition comprises: (a) a
latex polymer comprising the emulsion polymerization product of:
(i) an emulsion monomer component comprising at least one
ethylenically unsaturated monomer reacted in the presence of (ii) a
surfactant reactive with the at least one ethylenically unsaturated
monomer; (b) a curing agent, wherein the curing agent comprises at
least one of a phenoplast, aminoplast, hydroxyalkyamide,
hydroxyalkylurea, and/or a combination thereof; and (c) a polar
polyolefin.
24. The package of claim 23, wherein the ethylenically unsaturated
monomers are free of styrene and/or epoxy group-containing
ethylenically unsaturated monomers.
25. The package of claim 23, wherein the coating composition is
substantially free of bisphenol A and bisphenol A diglycidyl ether
(BADGE).
26. The package of claim 23, wherein the coating composition does
not release formaldehyde upon curing.
27. The package of claim 23, wherein the polar polyolefin comprises
a polyethylene (meth)acrylic acid copolymer.
28. The package of claim 23, wherein the polar olefin is present in
the coating composition in amounts of from 5 to 50 percent by
weight based on resin solids weight of the coating composition.
29. The package of claim 23, wherein the latex polymer has an
average particle size of from 0.05 to 1.0 microns.
30. The package of claim 23, wherein the latex polymer has a weight
average molecular weight of from 100,000 to 800,000.
31. The package of claim 23, wherein: the latex polymer is present
in the coating composition in amounts of greater than 50 percent by
weight based on resin solids weight of the coating composition; the
curing agent is present in the coating composition in amounts of
from 5 to 40 percent by weight based on resin solids weight of the
coating composition; and the polar olefin is present in the coating
composition in amounts of from 5 to 50 percent by weight based on
resin solids weight of the coating composition.
32. The package of claim 23, wherein the package is a metal
can.
33. A package with a coating composition deposited on at least a
portion thereof, wherein the coating composition comprises: (a) a
latex polymer comprising the emulsion polymerization product of:
(i) an emulsion monomer component comprising at least one
ethylenically unsaturated monomer reacted in the presence of (ii) a
surfactant reactive with the at least one ethylenically unsaturated
monomer; (b) a curing agent, wherein the curing agent comprises at
least one of a phenoplast, aminoplast, hydroxyalkyamide,
hydroxyalkylurea, and/or a combination thereof; and (c) a
phosphorus acid.
34. The package of claim 33, wherein the ethylenically unsaturated
monomers are free of styrene and/or epoxy group-containing
ethylenically unsaturated monomers.
35. The package of claim 33, wherein the coating composition is
substantially free of bisphenol A and bisphenol A diglycidyl ether
(BADGE).
36. The package of claim 33, wherein the coating composition does
not release formaldehyde upon curing.
37. The package of claim 33, wherein the phosphorus acid is
phosphoric acid.
38. The package of claim 33, wherein the phosphorous acid is
present in the coating composition in amounts of from 0.1 to 1.0
percent by weight based on resin solids weight of the coating
composition.
39. The package of claim 33, wherein the latex polymer has an
average particle size of from 0.05 to 1.0 microns.
40. The package of claim 33, wherein the latex polymer has a weight
average molecular weight of from 100,000 to 800,000.
41. The package of claim 33, wherein: the latex polymer is present
in the coating composition in amounts of greater than 50 percent by
weight based on resin solids weight of the coating composition; the
curing agent is present in the coating composition in amounts of
from 5 to 40 percent by weight based on resin solids weight of the
coating composition; and the phosphorous acid is present in the
coating composition in amounts of from 0.1 to 1.0 percent by weight
based on resin solids weight of the coating composition.
42. The package of claim 33, wherein the package is a metal can.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims priority to U.S. Provisional
Patent Application Ser. No. 62/168,040, filed on May 29, 2015, the
entirety of which is incorporated by reference, and to U.S.
Provisional Patent Application Ser. No. 62/168,134, filed on May
29, 2015, the entirety of which is incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a package coated at least
in part with a coating comprising an emulsion polymerized latex
polymer prepared from a polymerizable surfactant and an emulsion
monomer, and optionally a phosphorus acid.
BACKGROUND OF THE INVENTION
[0003] The application of various polymeric coatings to metallic
substrates, including metal food and beverage containers, to retard
or inhibit corrosion is well established. 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 can lead to corrosion of the metal
container, which can then contaminate the food or beverage. This is
particularly true when the contents of the container are acidic in
nature, such as tomato-based products and soft drinks.
[0004] Certain coatings, particularly in the packaging industry,
must undergo extreme stresses in the course of preparation and use
of the packaging containers. In addition to flexibility, packaging
coatings may also need resistance to chemicals, solvents, and
pasteurization processes used in the packaging of beer and other
beverages, and may also need to withstand retort conditions
commonly employed in food packaging. In addition to corrosion
protection, coatings for food and beverage containers should be
non-toxic, and should not adversely affect the taste of the food or
beverage in the can. Resistance to "popping", "blushing" and/or
"blistering" may also be desired.
[0005] Bisphenol A ("BPA") contributes to many of the properties
desired in packaging coating products. The use of BPA and related
products such as bisphenol A diglycidyl ether ("BADGE"), however,
has recently come under scrutiny in the packaging industry.
Substantially BPA-free coatings having properties comparable to
coatings comprising BPA are therefore desired. The packaging
industry is also interested in eliminating or minimizing other
monomers, such as styrene, and components, such as formaldehyde, in
coatings.
SUMMARY OF THE INVENTION
[0006] The present invention provides a package with a coating
composition deposited on at least a portion thereof wherein the
coating composition comprises: [0007] (a) a latex polymer
comprising the emulsion polymerization product of [0008] (i) an
emulsion monomer component comprising at least one ethylenically
unsaturated monomer polymerized in the presence of [0009] (ii) a
surfactant that is polymerizable with the at least one
ethylenically unsaturated monomer.
[0010] The present invention also provides a method comprising:
[0011] (a) applying the coating composition described above to a
substrate prior to or after forming the substrate into a package;
and [0012] (b) heating the coated substrate to a temperature and
for a time sufficient to cure the coating composition.
DETAILED DESCRIPTION OF THE INVENTION
[0013] As used herein, the term "aliphatic group" means a saturated
or unsaturated linear or branched hydrocarbon group. The term
"alkyl group" means a saturated linear or branched hydrocarbon
group including, for example, methyl, ethyl, isopropyl, t-butyl,
heptyl, dodecyl, octadecyl, amyl, 2-ethylhexyl, and the like.
[0014] The term "alkenyl group" means an unsaturated linear or
branched hydrocarbon group with one or more carbon-carbon double
bonds such as vinyl group
##STR00001##
(meth)allyl group
##STR00002##
and (meth)acryl group
##STR00003##
[0015] The term "aromatic group" means a closed ring hydrocarbon
group with sigma bonds and delocalized pi electrons between carbon
atoms forming the ring and which can include heteroatoms.
[0016] A group that may be the same or different is referred to as
being "independently" something.
[0017] Substitution is anticipated on the alkyl, alkenyl and
aromatic groups of the compounds of the present invention. Thus,
when the term "group" is used to describe a chemical material, the
described chemical material includes the unsubstituted group and
that group substituted with O, N, Si, or S atoms. For example, the
phrase "alkyl group" is intended to include not only pure open
chain saturated hydrocarbon alkyl substituents, such as methyl,
ethyl, propyl, t-butyl, and the like, but also alkyl substituents
bearing further substituents known in the art, such as hydroxy,
alkoxy, alkylsulfonyl, halogen atoms, cyano, nitro, amino,
carboxyl, etc. Thus, "alkyl group" includes ether groups,
haloalkyls, nitroalkyls, carboxyalkyls, hydroxyalkyls, sulfoalkyls,
etc.
[0018] The term "crosslinker" or "curing agent" refers to a
molecule capable of forming a covalent linkage between polymers or
between two different regions of the same polymer.
[0019] The term "dispersed in aqueous medium" means that a polymer
or the resinous components of the coating composition used in the
practice of the invention can be mixed into aqueous medium to form
a stable mixture, that is, the mixture does not separate into
immiscible layers within an hour after mixing.
[0020] The term "aqueous medium" means water or a mixture of water
and organic solvent.
[0021] The term "resinous components" means the polymers,
crosslinkers and non-volatile organic components of the coating
composition that may be used in the practice of the invention.
[0022] The term "resin solids" means the non-volatile organic
components of the coating composition.
[0023] The term "food-contacting surface" refers to the surface of
a container such as an inner surface of a food or beverage
container that is in contact with, or intended for contact with, a
food or beverage product. By way of example, an interior surface of
a metal substrate of a food or beverage container, or a portion
thereof such as a can end or a can body, is a food-contacting
surface even if the interior metal surface is coated with a coating
composition.
[0024] The term "on", when used in the context of a coating applied
on a surface or substrate, includes both coatings applied directly
or indirectly to the surface or substrate. Thus, for example, a
coating applied to a primer layer overlying a substrate constitutes
a coating applied on the substrate.
[0025] Unless otherwise indicated, the term "polymer" includes both
homopolymers and copolymers (e.g., polymers of two or more
different monomers) and oligomers. Resin is used simultaneously
with polymer.
[0026] Acrylic and methacrylic monomers and polymers are designated
as (meth)acrylic monomers and polymers.
[0027] Molecular weights are on a number average or weight average
basis as indicated and are determined by gel permeation
chromatography using tetrahydrofuran as a solvent and using
polystyrene standards.
[0028] As used herein, unless otherwise expressly specified, all
numbers such as those expressing values, ranges, amounts or
percentages may be read as if prefaced by the word "about", even if
the term does not expressly appear. Singular encompasses plural and
vice versa. For example, although reference is made herein to "a"
polymeric surfactant, "an" emulsion polymerized latex or "an"
emulsion polymerized latex polymer, "a" latex, "a" latex polymer,
"an" emulsion monomer, "a" phosphorus acid, one or more of each of
these and any other components can be used. "Including", "for
example", "such as" and like terms means including, for example,
such as, but not limited to.
[0029] The term "reactive surfactant" or "polymerizable surfactant"
means any surfactant that has the ability to react with the
emulsion monomer component, such as, for example, by formation of a
covalent bond. Typically, the reaction between the polymerizable
surfactant and the latex particle surface is sufficiently strong to
prevent separation and migration therebetween.
[0030] The term "non-reactive surfactant" means a surfactant that
is adsorbed (as opposed to fixed or reacted) onto the surface of
the latex particle. During high-speed metal can coating operations,
non-reactive surfactants are typically desorbed or stripped off of
the latex particle surface.
[0031] The term "emulsion monomer component" means one or more
ethylenically unsaturated monomer(s) that are reactive with the
polymerizable surfactant using emulsion polymerization
techniques.
[0032] The term "emulsion polymerization" means free radical
polymerization of ethylenically unsaturated monomer(s) and
surfactant dispersed in aqueous medium.
[0033] The term "latex" or "latex polymer" means the polymer
resulting from emulsion polymerization.
[0034] The polymerizable surfactant used in the preparation of the
emulsion polymerized latex polymer can be any surfactant containing
an alkenyl group capable of polymerizing with the emulsion monomer
component; that is, the surfactant has at least one moiety that can
undergo polymerization with at least one ethylenically unsaturated
monomer. The polymerizable surfactant can be polymeric and may have
an ionic and nonionic portion. The ionic portion can be, for
example, an acid salt, an amine salt and the like. Suitable acid
salt functionality can include, for example, phosphonate
functionality, sulfonate functionality, and/or carboxylate
functionality. The nonionic portion can be aliphatic or aromatic.
It may be desired to use a polymerizable surfactant having a
nonionic portion that is generally resistant to hydrolysis.
Suitable polymerizable surfactants can also be solely nonionic or
solely ionic. The polymerizable surfactant can have a weight
average molecular weight ("Mw") of at least 200, such as at least
400 or at least 500 or as high as 5,000 or lower, such as 2,000 or
lower or 1,000 or lower. The Mw can be, for example, 250 to 850,
such as 500 to 700.
[0035] The polymerizable surfactant used according to the present
invention becomes polymerized into the polymeric matrix during
latex formation. This distinguishes the present invention from use
of surfactants that are not capable of reacting with the emulsion
monomers; such surfactants are therefore able to "move around" in
the latex, such as by migrating to the surface of the coating. This
migration is highly undesirable, particularly for packaging
applications. In contrast, the polymerizable surfactants of the
present invention polymerize into the latex, which minimizes the
ability of the surfactant to migrate after cure of the coating.
This makes the present coatings particularly suitable for packaging
coatings, as the migration of surfactant into food or beverage or
personal care products is minimized.
[0036] The polymerization of the surfactant into the latex may also
contribute to the flexibility of coatings made from the present
latex, although the inventors do not wish to be bound by this. For
example, coatings used according to the present invention can have
a flexibility as identified by wedge bend testing of 90% or greater
or 95% or greater. This is further described in the example
section, below.
[0037] Like non-reactive surfactants, reactive or polymerizable
surfactants are molecules that typically have a hydrophobic
segment, such as C.sub.8 to C.sub.50 alkyl, and a hydrophilic
segment(s) such as an ionic salt group and/or poly(oxyethylene)
groups (ethoxy hydrophobicity). The hydrophobic segment
preferentially absorbs onto the surface of the latex particle
during and following particle polymerization. The hydrophilic group
extends into the normally aqueous solution phase and thereby
provides a steric barrier against particle coagulation. Unlike
their non-reactive counterparts, reactive surfactants contain a
reactive group, typically an alkenyl group, on the hydrophobic
segment that is capable of covalently bonding to the latex surface.
The length and composition of the hydrophobic segment of the
reactive surfactant is selected to substantially correspond to the
surface chemistry and the rheological needs of the latex particle.
The ionic groups may be anionic or cationic. Suitable anionic
functional groups include, for example, sulfonate, phosphonate, and
carboxylate ions. Suitable cationic functional groups include, for
example, ammonium ions. A representative ionic reactive surfactant
for such a reaction is MAXEMUL.TM. 6106 (available from Uniquema),
which has both phosphonate and ethoxy hydrophilicity, and a nominal
C.sub.18 alkyl chain with an alkenyl reactive group. Another
representative reactive surfactant with ionic groups and with
ethoxy hydrophilicity is Reasoap SR10 containing sulfonate and
ethoxy hydrophilicity and a C.sub.15 to C.sub.18 alkyl chain with
an allyl functional group.
[0038] The hydrophilicity of nonionic reactive surfactants is
typically that provided by poly(oxyethylene) groups.
[0039] Examples of alkenyl-functional nonionic surfactants are
ethoxylated unsaturated fatty alcohol esters such as the methyl
ester of ethoxylated oleic alcohol, specifically, MAXEMUL 5110 that
contains 24 units of ethylene oxide and MAXEMUL 5112 that contains
32 units of ethylene oxide. Other examples are nonyl phenoxy
poly(ethyleneoxy) crotanate, nonyl phenoxy poly(ethyleneoxy)
fumarate, nonyl phenoxy poly(ethyleneoxy) acrylate, and nonyl
phenoxy poly(ethyleneoxy) methacrylate.
[0040] Further alkenyl-functional nonionic surfactants include
cetyl polyethoxylated methacrylate (CEM), stearyl polyethoxylated
(meth)acrylate, arachidyl polyethoxylated (meth)acrylate, behenyl
polyethoxylated methacrylate (BEM), melissyl polyethoxylated
(meth)acrylate and lacceryl polyethoxylated (meth)acrylate, where
the polyethoxylated portion of the monomer comprises about 5 to
about 250, such as about 15 to about 40, and about 15 to about 60
ethylene oxide repeating units.
Structurally, the polymerizable surfactant typically is of the
structure:
##STR00004##
where R.sub.1 is independently H, C.sub.1 to C.sub.30 alkyl
group,
##STR00005##
where R.sub.4 is C.sub.1 to C.sub.30 alkyl,
[0041] A is
Ar,
##STR00006##
[0042] or
[0043] Ar is a divalent aromatic group,
[0044] m is 0 to 1,
[0045] R.sub.2 is H, an alkyl group containing at least 8 carbon
atoms,
[0046] n is 0 to 30,
[0047] p is 0 to 1,
[0048] q is 2 to 250,
[0049] R.sub.3 is --C.sub.2H.sub.4--, including mixtures with
--C.sub.3H.sub.7--, and
[0050] X is an ionic salt group or an alkyl group.
[0051] More specifically, the polymerizable surfactant can be of
the above structure, where
[0052] R.sub.1 is independently H or CH.sub.3,
[0053] A is --CH.sub.2--O--CH.sub.3,
[0054] m is 1,
[0055] R.sub.2 is an alkyl group containing at least 8 carbon
atoms,
[0056] n is 1,
[0057] p is 1,
[0058] R.sub.3 is --C.sub.2H.sub.4--,
[0059] q is 2 to 30, and
[0060] X is sulfonate or phosphonate.
[0061] Also, the polymerizable surfactant can be of the above
structure, where
[0062] R.sub.1 is independently H or CH.sub.3,
[0063] A is [0064] R.sub.4
##STR00007##
[0064] where R.sub.4 is an alkyl group having at least 8 carbon
atoms,
[0065] m is 1,
[0066] n is 0,
[0067] p is 1,
[0068] R.sub.3 is --C.sub.2H.sub.4--,
[0069] q is 2 to 40, and
[0070] X is sulfonate or phosphonate.
[0071] Further, the polymerizable surfactant can be of the above
structure, where
[0072] R.sub.1 is independently H or CH.sub.3,
[0073] A is --CH.sub.2--O--,
[0074] m is 1,
[0075] R.sub.2 is an alkyl group having at least 8 carbon
atoms,
[0076] n is 1,
[0077] p is 1,
[0078] R.sub.4 is --C.sub.2H.sub.4--,
[0079] q is 2 to 40, and
[0080] X is sulfonate or phosphonate.
[0081] In addition, the polymerizable surfactant can be of the
above structure, where
[0082] R.sub.1 is independently H or C.sub.1 to C.sub.30 alkyl,
[0083] m is 0,
[0084] R.sub.2 is H,
[0085] n is 6 to 10,
[0086] p is 1,
[0087] q is 5 to 40,
[0088] R.sub.3 is --C.sub.2H.sub.4--, and
[0089] X is C.sub.1 to C.sub.4 alkyl.
[0090] The polymerizable surfactant is present in the coating
composition in amounts of 0.1 to 25, such as 0.5 to 15 percent by
weight based on resin solids weight of the emulsion monomer
component and the polymerizable surfactant.
[0091] The nonionic surfactants are typically used in combination
with anionic surfactants to provide stable latexes. Examples of
anionic surfactants are those mentioned above as well as
non-reactive anionic surfactants. Examples of non-reactive anionic
surfactants include alkali metal and ammonium salts of long chain
alkyl sulfates, sulfonates and sulfosuccinates; alkali metal and
ammonium phosphate esters and alkali metal and ammonium alkyl
phenoxy polyethoxysulfates, sulfonates or phosphates in which the
alkyl group contains 4 to 18 carbon atoms and the oxyethylene units
range from 6 to 60. Examples of specific anionic surfactants
include sodium lauryl sulfate, sodium cetyl sulfate, sodium dioctyl
sulfosuccinate and ammonium nonyl phenoxy (polyethoxy).sub.6-60
sulfonate. When used, the non-reactive surfactant is present in the
coating composition in amounts of 0.1 to 5.0, such as 0.5 to 3.0
percent by weight based on resin solids weight of polymerizable
surfactant and emulsion monomer.
[0092] The polymerizable surfactant is used in conjunction with the
emulsion monomer component comprising at least one ethylenically
unsaturated monomer. According to the present invention, use of a
keto aldehyde monomer can be specifically excluded. The emulsion
monomer component can be free of styrene and/or epoxy
group-containing ethylenically unsaturated monomer.
[0093] The emulsion monomer component can be a mixture of monomers
and/or oligomers that are capable of free radical initiated
polymerization in aqueous medium.
[0094] Suitable ethylenically unsaturated monomers and/or oligomers
for inclusion in the ethylenically unsaturated monomer component
include, for example, ethylenically unsaturated alkyl
(meth)acrylates, epoxy-containing ethylenically unsaturated
monomers and various vinyl monomers. Examples of ethylenically
unsaturated acid are acrylic and methacrylic acid. If used, they
are typically present in amounts of up to 10, such as 3 to 8
percent by weight based on weight of the emulsion monomer
component.
[0095] Suitable alkyl(meth)acrylates include, but are not limited
to, methyl (meth)acrylate, ethyl(meth)acrylate,
propyl(meth)acrylate, isopropyl (meth)acrylate,
butyl(meth)acrylate, isobutyl(meth)acrylate, pentyl(meth)acrylate,
isoamyl(meth)acrylate, hexyl(meth)acrylate,
2-ethylhexyl(meth)acrylate, cyclohexyl(meth)acrylate,
decyl(meth)acrylate, isodecyl(meth)acrylate, benzyl (meth)acrylate,
lauryl(meth)acrylate, isobornyl(meth)acrylate, octyl(meth)acrylate
and nonyl(meth)acrylate.
[0096] The alkyl (meth)acrylates are typically present in amounts
of up to 100, such as 20 to 80 percent by weight based on weight of
the emulsion monomer component.
[0097] Hydroxyalkyl (meth)acrylates can also be used. Examples
include hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate
(HEMA) and hydroxypropyl(meth)acrylate (HPMA).
[0098] The hydroxyalkyl (meth)acrylates are typically present in
amounts of up to 30 percent, such as 5 to 15 percent by weight
based on weight of the emulsion monomer component.
[0099] Difunctional (meth)acrylate monomers may be used in the
monomer mixture as well. Examples include ethylene glycol
di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, allyl
methacrylate, and the like. If present, the difunctional
(meth)acrylate monomers are present in amounts of up to 5 percent,
such as 0.1 to 2 percent by weight based on weight of the emulsion
monomer component.
[0100] Also, epoxy-containing ethylenically unsaturated monomers
such as glycidyl (meth)acrylate can be present in the ethylenically
unsaturated monomer component. If present, it is present in amounts
of up to 30, such as 1 to 20 percent by weight based on weight of
the ethylenically unsaturated monomer component.
[0101] Suitable vinyl monomers include vinyl aromatic monomers,
styrene, methyl styrene, alpha-methylstyrene, halostyrene, vinyl
toluene, vinyl naphthalene, and mixtures thereof. The ethylenically
unsaturated monomer component may be free of styrene monomers.
Other vinyl monomers include vinyl ester, vinyl acetate, vinyl
propionate, vinyl butyrate and vinyl stearate. The vinyl monomers,
if used, are typically present in amounts of up to 70 percent, such
as 10 to 60 percent by weight based on total weight of the emulsion
monomer component.
[0102] Other suitable polymerizable ethylenically unsaturated
monomers include acrylonitrile, acrylamide, methacrylamide,
methacrylonitrile, N-isobutoxymethyl acrylamide, N-butoxymethyl
acrylamide, conjugated butadiene and isoprene, and mixtures
thereof, and which may be present in amounts of up to 30, such as 3
to 20 percent by weight based on total weight of the emulsion
monomer component.
[0103] The emulsion monomer component can be present in amounts of
75 to 99.9, such as 85 to 99.5 percent by weight based on weight of
the ethylenically unsaturated monomer component and the reactive
polymerizable surfactant.
[0104] The coating composition can optionally contain polyolefin
base polymers functionalized with a polar group such as an acid
group, such as polypropylene or polyethylene homopolymer or
copolymer in which the polymer has been modified with carboxylic
acid.
[0105] 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.
[0106] The base polymers mentioned above comprise 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.
[0107] The polar polyolefin polymer such as an ethylene-acrylic
acid (EAA) or ethylene-methacrylic acid copolymer can be present
with the reactive surfactant when the ethylenically unsaturated
monomer component is polymerized in the presence of the reactive
surfactant, or alternatively, all or a portion thereof may be added
to the coating composition after polymerization of the
ethylenically unsaturated monomer component. The polar polyolefin
is typically at least partially neutralized with ammonia or an
organic amine.
[0108] The polar polyolefin provides enhanced flexibility to the
cured coating, which is particularly desirable in coatings for
metal can ends and for can bodies that are formed by a deep drawing
process. The polar polyolefins are typically present in the coating
composition in amounts of 5 to 50, such as 20 to 40 percent by
weight based on total weight of resin solids.
[0109] The emulsion polymerized latex of the present invention can
be prepared according to methods known in the art. For example, the
ethylenically unsaturated monomer component can be emulsified with
the polymerizable surfactant in aqueous medium and the emulsion fed
into pre-heated aqueous medium with an initiator.
[0110] With regard to the conditions of the emulsion
polymerization, the ethylenically unsaturated monomer component can
be polymerized in aqueous medium with a water-soluble free radical
initiator in the presence of the reactive surfactant.
[0111] The temperature of polymerization is typically from
0.degree. C. to 100.degree. C., such as 70.degree. C. to 90.degree.
C. The pH of the aqueous medium is usually maintained at a pH of 5
to 12.
[0112] The free radical initiator can be selected from one or more
water-soluble peroxides which are known to act as free radical
initiators. Examples include hydrogen peroxide and t-butyl
hydroperoxide. Redox initiator systems well known in the art (e.g.,
t-butyl hydroperoxide, erythorbic acid, and ferrous complexes) can
also be employed. Persulfate initiators such as ammonium persulfate
or potassium persulfate can be used but may lead to poor water
resistance properties of the cured coating.
[0113] Further examples of polymerization initiators which can be
employed include polymerization initiators which thermally
decompose at the polymerization temperature to generate free
radicals. Examples include both water-soluble and water-insoluble
species. Further examples of free radical initiators that can be
used include persulfates, such as ammonium or alkali metal
(potassium, sodium or lithium) persulfate; azo compounds such as
2,2'-azo-bis(isobutyronitrile),
2,2'-azo-bis(2,4-dimethylvaleronitrile), and
1-t-butyl-azocyanocyclohexane; hydroperoxides such as t-butyl
hydroperoxide, hydrogen peroxide, t-amyl hydroperoxide, methyl
hydroperoxide, and cumene hydroperoxide; peroxides such as benzoyl
peroxide, caprylyl peroxide, di-t-butyl peroxide, ethyl
3,3'-di(t-butylperoxy) butyrate, ethyl 3,3'-di(t-amylperoxy)
butyrate, t-amylperoxy-2-ethyl hexanoate, and t-butylperoxy
pivilate; peresters such as t-butyl peracetate, t-butyl
perphthalate, and t-butyl perbenzoate; as well as percarbonates,
such as di(1-cyano-1-methylethyl)peroxy dicarbonate; perphosphates,
and the like; and combinations thereof.
[0114] Polymerization initiators can be used alone or as the
oxidizing component of a redox system, which also may include a
reducing component such as ascorbic acid, malic acid, glycolic
acid, oxalic acid, lactic acid, thioglycolic acid, or an alkali
metal sulfite, more specifically a hydrosulfite, hyposulfite or
metabisulfite, such as sodium hydrosulfite, potassium hyposulfite
and potassium metabisulfite, or sodium formaldehyde sulfoxylate,
and combinations thereof.
[0115] The initiator and accelerator can be used in proportion from
about 0.001% to 5% each, based on the weight of monomers and
reactive surfactant to be copolymerized.
[0116] Chain transfer agents can be used to control polymer
molecular weight, if desired.
[0117] The polymerization reaction of the ethylenically unsaturated
monomer component in the presence of the reactive surfactant may be
conducted as a batch, intermittent, or continuous operation. While
all of the polymerization ingredients may be charged initially to
the polymerization vessel, better results normally are obtained
with proportioning techniques.
[0118] Typically, the reactor is charged with an appropriate amount
of water, free radical initiator and optionally a portion of
reactive surfactant. The reactor is then heated to the free radical
initiation temperature and then charged with the emulsified
ethylenically unsaturated monomer component. Only water, initiator,
reactive surfactant, and some portion of the ethylenically
unsaturated monomer component may be initially charged to the
vessel. There may also be some water-miscible solvent present.
After this initial charge is allowed to react for a period of time
at polymerization temperature, the remaining emulsified
ethylenically unsaturated monomer component can be added
incrementally with the rate of addition being varied depending on
the polymerization temperature, the particular initiator being
employed, and the type and amount of monomers being polymerized.
After all the monomer component has been charged, a final heating
is carried out to complete the polymerization. The reactor is then
cooled and the latex recovered.
[0119] The average particle size of the latex particles can be 0.05
micron, or greater such as at 0.08 micron or greater or 0.1 micron
or greater, and can be up to 1.0 micron or less, such as 0.5 micron
or less or 0.2 micron or less. The average particle size can range,
for example, from 0.05 to 1.0 micron, such as 0.1 to 0.5 micron,
0.1 to 0.2 micron, or 0.08 to 0.2 micron. The Mw of these particles
as measured by gel permeation chromatography in tetrahydrofuran can
be, for example, 50,000 or greater, such as 100,000 or greater or
400,000 or greater, and can be 1,000,000 or less, such as 800,000
or less or 650,000 or less. The average Mw of these particles can
range, for example, from 50,000 to 1,000,000, such as 100,000 to
800,000 or 400,000 to 650,000. Higher Mw may increase flexibility
and/or resistance of the film coating. Any values within these
broad ranges are also within the scope of the present invention, as
are higher or lower numbers. Theoretical Tg values (Fox Equation)
for the latex can be as low as -20.degree. C. or greater, such as
5.degree. C. or greater or 25.degree. C. or greater and as high as
100.degree. C. or lower, such as 80.degree. C. or lower or
40.degree. C. or lower. The Tg can range, for example, from
-20.degree. C. to 100.degree. C., such as 25.degree. C. to
80.degree. C. or 5.degree. C. to 40.degree. C.
[0120] The coating compositions used according to the present
invention can comprise, for example, 10 percent by weight of the
latex polymer or greater, such as 20 percent by weight or greater
or 50 percent by weight or greater, and as much as 100 percent by
weight or less, such as 95 percent by weight or less or 90 percent
by weight or less; the amount of latex polymer can range, for
example, from 10 to 100 percent by weight, such as 20 to 95 percent
by weight or 50 to 95 percent by weight, with weight percent based
on the total resin solids weight of the coating composition.
[0121] It has been discovered that coating compositions using the
aforementioned latexes that contain reactive functional groups such
as hydroxyl and carboxylic acid may be formulated using one or more
optional curing agents (i.e., crosslinking resins, sometimes
referred to as "crosslinkers"). The choice of particular
crosslinker typically depends on the reactive functional group of
the latex polymer and particular product being formulated.
[0122] Any of the well known curing resins for packaging coatings
can be used. For example, phenoplast, and aminoplast curing agents
may be used.
[0123] Phenoplast resins include the condensation products of
aldehydes with phenols. Formaldehyde and acetaldehyde are
particularly suitable aldehydes. Various phenols can be employed
such as phenol, cresol, p-phenylphenol, p-tert-butylphenol,
p-tert-amylphenol, and cyclopentylphenol.
[0124] Aminoplast resins are the condensation products of aldehydes
such as formaldehyde, acetaldehyde, crotonaldehyde, and
benzaldehyde with amino or amido group-containing substances such
as urea, melamine, and benzoguanamine.
[0125] Examples of suitable crosslinking resins include, without
limitation, benzoguanamine-formaldehyde resins,
melamine-formaldehyde resins, esterified melamine-formaldehyde, and
urea-formaldehyde resins. One specific example of a useful
crosslinker is a highly alkylated melamine-formaldehyde resin
commercially available from Allenex under the trademark of CYMEL
303.
[0126] The crosslinker, when present, may be selected from
hydroxyalkylamide materials and hydroxyalkylurea materials.
Hydroxyalkylamides are typically of the structure:
##STR00008##
[0127] wherein R.sup.10 and R.sup.11 each, independently, represent
an electron withdrawing group, such as carbonyl;
[0128] Y.sup.1, Y.sup.2, Y.sup.3 and Y.sup.4 each, independently,
represent a C.sub.1 to C.sub.3 alkylene group; and
[0129] X represents a C.sub.2 to C.sub.6 alkylene group.
[0130] Suitably, each of Y.sup.1, Y.sup.2, Y.sup.3 and Y.sup.4
represent an ethylene group.
[0131] Suitably, X represents a butylene group.
[0132] The crosslinker material may comprise a commercially
available beta-hydroxyalkylamide crosslinker, such as, for example,
PRIMID XL-552, i.e., N,N,N',N'-tetrakis(2-hydroxypropyl)adipamide,
and PRIMID QM-1260 (available from EMS Chemie).
[0133] The crosslinker material may comprise a hydroxyalkylurea
material. Suitable hydroxyalkylureas are those of the
structure:
##STR00009##
[0134] wherein R.sub.2 is a substituted or unsubstituted C.sub.1 to
C.sub.36 alkyl group, an aromatic group, the residue of an
isocyanurate, biuret, allophanate, glycoluril, benzoguanamine
and/or polyether amine; wherein each R.sub.1 is independently a
hydrogen, an alkyl having at least 1 carbon atom, or a hydroxy
functional alkyl having 2 or more carbon atoms and at least one
R.sub.1 is hydroxyalkyl having 2 or more carbon atoms; and n is 2
to 6.
[0135] The level of curing agent (i.e., crosslinker) required will
depend on the type of curing agent, the time and temperature of the
bake, and the molecular weight of the polymer. If used, the
crosslinker is typically present in amounts of 2 to 50, such as 5
to 40 percent by weight. These weight percentages are based upon
the total weight of the resin solids in the coating
composition.
[0136] Optionally the coating composition may contain a phosphorus
acid. It has been surprisingly discovered that use of phosphorus
acid in the coatings of the present invention allow for cure using
a significantly reduced amount of crosslinker, such as those based
on formaldehyde, i.e., phenolplast and aminoplast, or even without
the use of crosslinker at all, thereby resulting in a composition
that is free of formaldehyde, that is, release of formaldehyde
during curing. The phosphorus acid can be used in any amount, such
as 0.01 wt % or greater, 0.05 wt % or greater or 0.1 wt % or
greater and can be used in amounts less than 5 wt %, less than 1 wt
% or less than 0.05%, based on total solid such as resin solids
weight of the coating. The phosphorus acid can be phosphoric acid
used in an amount ranging from 0.1 to 1.0 percent by weight, based
on the total weight of resin solids of the coating composition.
[0137] The phosphorus acid used in the present invention can be a
phosphinic acid (H.sub.3PO.sub.2), a phosphonic acid
(H.sub.3PO.sub.3) and/or a phosphoric acid (H.sub.3PO.sub.4). The
phosphoric acid can be in the form of an aqueous solution, for
example, an 85 percent by weight aqueous solution, or can be 100
percent phosphoric acid or super phosphoric acid. The phosphorus
acid can also be diluted in a water miscible solvent. The amount of
phosphorous acid in weight percent used in the present invention
reflects the amount of acid itself, and not the combined amount of
acid and solvent, if used.
[0138] A coating composition of the present invention may also
include other optional polymers that do not adversely affect the
coating composition or a cured coating composition resulting
therefrom. Such optional polymers are typically included in a
coating composition as a filler material, although they can be
included to provide desirable properties. One or more optional
polymers can be included in a sufficient amount to serve an
intended purpose, but not in such an amount to adversely affect a
coating composition or a cured coating composition resulting
therefrom.
[0139] Such additional polymeric materials can be non-reactive, and
hence, simply function as fillers. Such optional non-reactive
filler polymers include, for example, polyesters, acrylics,
polyamides and polyethers. Alternatively, such additional polymeric
materials can be reactive with other components of the composition
(e.g., the curing agent). If desired, reactive polymers can be
incorporated into the compositions of the present invention, to
provide additional functionality for various purposes, such as
crosslinking. Examples of such reactive polymers include, for
example, hydroxyl-functional polyesters and acrylic polymers. If
present, these additional polymeric materials are present in
amounts up to 20 percent by weight based on weight of resin solids
of the coating composition.
[0140] A coating composition of the present invention may also
include other optional ingredients that do not adversely affect the
coating composition or a cured coating composition resulting
therefrom. Such optional ingredients are typically included in a
coating composition to enhance composition esthetics, to facilitate
manufacturing, processing, handling, and application of the
composition, and to further improve a particular functional
property of a coating composition or a cured coating composition
resulting therefrom.
[0141] Such optional ingredients include, for example, catalysts,
lubricants, anticorrosion agents, flow control agents, thixotropic
agents, dispersing agents, antioxidants, adhesion promoters, light
stabilizers, and mixtures thereof. Each optional ingredient is
included in a sufficient amount to serve its intended purpose, but
not in such an amount to adversely affect a coating composition or
a cured coating composition resulting therefrom. If present, these
optional ingredients are present in amounts up to 10 percent by
weight based on weight of resin solids of the coating
composition.
[0142] As used herein, the term "colorant" means any substance that
imparts color and/or other opacity and/or other visual effect to
the composition. The colorant can be added to the coating in any
suitable form, such as discrete particles, dispersions, solutions
and/or flakes. A single colorant or a mixture of two or more
colorants can be used in the coatings of the present invention.
Suitable colorants are listed in U.S. Pat. No. 8,614,286, column 7,
line 2 through column 8, line 65, which is incorporated by
reference herein. Particularly suitable for packaging coatings are
those approved for food contact, such as titanium dioxide; iron
oxides, such as black iron oxide; carbon black; ultramarine blue;
phthalocyanines, such as phthalocyanine blue and phthalocyanine
green; chromium oxides, such as chromium green oxide; graphite
fibrils; ferried yellow; quindo red; and combinations thereof, and
those listed in Article 178.3297 of the Code of Federal
Regulations, which is incorporated by reference herein.
[0143] In general, the colorant can be present in any amount
sufficient to impart the desired visual and/or color effect. The
colorant may comprise from 1 to 65 weight percent of the coatings
in the present invention, such as from 3 to 40 weight percent or 5
to 35 weight percent, with weight percent based on the total weight
of the coating composition.
[0144] In certain embodiments, the compositions used in the
practice of the invention, are substantially free, may be
essentially free and may be completely free of bisphenol A and
derivatives or residues thereof, including bisphenol A ("BPA") and
bisphenol A diglycidyl ether ("BADGE"). Such compositions are
sometimes referred to as "BPA non intent" because BPA, including
derivatives or residues thereof are not intentionally added but may
be present in trace amounts because of unavoidable contamination
from the environment. The compositions can also be substantially
free and may be essentially free and may be completely free of
Bisphenol F and derivatives or residues thereof, including
bisphenol F and bisphenol F diglycidyl ether ("BPFG"). The term
"substantially free" as used in this context means the compositions
contain less than 1000 parts per million (ppm), "essentially free"
means less than 100 ppm and "completely free" means less than 20
parts per billion (ppb) of any of the above mentioned compounds,
derivatives or residues thereof.
[0145] As previously discussed, the coating composition of the
invention can include water and may further include one or more
optional organic solvents. Typically, the coating composition
includes up to 40, such as 10 to 40 percent by weight organic
solvent based on total weight of organic solvent and water.
[0146] The coating composition typically has a total solids content
of from about 10 to about 70, such as about 20 to about 50 percent
by weight based on weight of the coating composition.
[0147] Specifically, the coating composition has a resin solids
content of 5 to 65, such as 15 to 45 percent by weight, the
percentage by weight being based on total weight of the coating
composition.
[0148] The coatings described herein are particularly suitable for
use as a packaging coating. The application of various
pretreatments and coatings to packaging is well established. Such
treatments and/or coatings, for example, can be used in the case of
metal cans, wherein the treatment and/or coating may be used, for
example, to retard or inhibit corrosion, provide a decorative
coating, provide ease of handling during the manufacturing process,
and the like. Coatings can be applied to the interior of such cans
to prevent the contents from contacting the metal of the container.
Contact between the metal and a food or beverage, for example, can
lead to corrosion of a metal container, which can then contaminate
the food or beverage. This is particularly true when the contents
of the can are acidic in nature. The coatings applied to the
interior of metal cans also help prevent corrosion in the headspace
of the cans, which is the area between the fill line of the product
and the can lid; corrosion in the headspace is particularly
problematic with food products having a high salt content. Coatings
can also be applied to the exterior of metal cans. Certain coatings
of the present invention are particularly applicable for use with
coiled metal stock, such as the coiled metal stock from which the
ends of cans are made ("can end stock"), and end caps and closures
are made ("cap/closure stock"). Since coatings designed for use on
can end stock and cap/closure stock are typically applied prior to
the piece being cut and stamped out of the coiled metal stock, they
are typically flexible and extensible. For example, such stock is
typically coated on both sides. Thereafter, the coated metal stock
is punched. For can ends, the metal is then 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. A similar procedure is done for
"easy open" can ends. For easy open can ends, a score substantially
around the perimeter of the lid allows for easy opening or removing
of the lid from the can, typically by means of a pull tab. For caps
and closures, the cap/closure stock is typically coated, such as by
roll coating, and the cap or closure stamped out of the stock; it
is possible, however, to coat the cap/closure after formation.
Coatings for cans subjected to relatively stringent temperature
and/or pressure requirements may desirably also be resistant to
cracking, popping, corrosion, blushing and/or blistering.
[0149] Accordingly, the present invention is directed to a package
coated at least in part with any of the coating compositions
described above. A "package" is anything used to contain another
item, particularly for shipping from a point of manufacture to a
consumer, and for subsequent storage by a consumer. A package will
be therefore understood as something that is sealed so as to keep
its contents free from deterioration until opened by a consumer.
The manufacturer will often identify the length of time during
which the food or beverage will be free from spoilage, which
typically ranges from several months to years. Thus, the present
"package" is distinguished from a storage container or bakeware in
which a consumer might make and/or store food; such a container
would only maintain the freshness or integrity of the food item for
a relatively short period. A package according to the present
invention can be made of metal or non-metal, for example, plastic
or laminate, and be in any form. An example of a suitable package
is a laminate tube. Another example of a suitable package is metal
can. The term "metal can" includes any type of metal can, container
or any type of receptacle or portion thereof that is sealed by the
food/beverage manufacturer to minimize or eliminate spoilage of the
contents until such package is opened by the consumer. One example
of a metal can is a food can; the term "food can(s)" is used herein
to refer to cans, containers or any type of receptacle or portion
thereof used to hold any type of food and/or beverage. The term
"metal can(s)" specifically includes food cans and also
specifically includes "can ends" including "E-Z open ends", which
are typically stamped from can end stock and used in conjunction
with the packaging of food and beverages. The term "metal cans"
also specifically includes metal caps and/or closures such as
bottle caps, screw top caps and lids of any size, lug caps, and the
like. The metal cans can be used to hold other items as well,
including, but not limited to, personal care products, bug spray,
spray paint, and any other compound suitable for packaging in an
aerosol can. The cans can include "two-piece cans" and "three-piece
cans" as well as drawn and ironed one-piece cans; such one-piece
cans often find application with aerosol products. Packages coated
according to the present invention can also include plastic
bottles, plastic tubes, laminates and flexible packaging, such as
those made from PE, PP, PET and the like. Such packaging could
hold, for example, food, toothpaste, personal care products and the
like.
[0150] The coating can be applied to the interior and/or the
exterior of the package. For example, the coating can be rollcoated
onto metal used to make a two-piece food can, a three-piece food
can, can end stock and/or cap/closure stock. The coating can be
applied to a coil or sheet by roll coating; the coating is then
cured by heating or radiation and can ends are stamped out and
fabricated into the finished product, i.e. can ends. The coating
can be applied as a rim coat to the bottom of the can; such
application can be by roll coating. The rim coat functions to
reduce friction for improved handling during the continued
fabrication and/or processing of the can. The coating can be
applied to caps and/or closures; such application can include, for
example, a protective varnish that is applied before and/or after
formation of the cap/closure and/or a pigmented enamel post applied
to the cap, particularly those having a scored seam at the bottom
of the cap. Decorated can stock can also be partially coated
externally with the coating described herein, and the decorated,
coated can stock used to form various metal cans. This is within
the scope of the "package" according to the present invention.
[0151] The packages of the present invention can be coated with any
of the compositions described above by any means known in the art,
such as spraying, roll coating, dipping, flow coating and the like;
the coating may also be applied by electrocoating when the
substrate is conductive. The appropriate means of application can
be determined by one skilled in the art based upon the type of
package being coated and the type of function for which the coating
is being used. The coatings described above can be applied over the
substrate as a single layer or as multiple layers with multiple
heating stages between the application of each layer, if desired.
After application to the substrate, the coating composition may be
cured by any appropriate means.
[0152] The coatings described herein can be applied to any
packaging substrates, which can be metallic or non-metallic.
Metallic substrates include tin, steel, tin-plated steel, chromium
passivated steel, galvanized steel, aluminum, aluminum foil, coiled
steel or other coiled metal. Non-metallic substrates including
polymeric, plastic, polyester, polyolefin, polyamide, cellulosic,
polystyrene, polyacrylic, polyethylene naphthalate), polypropylene,
polyethylene, nylon, EVOH, polylactic acid, other "green" polymeric
substrates, poly(ethyleneterephthalate) ("PET"), polycarbonate,
polycarbonate acrylobutadiene styrene ("PC/ABS"), polyamide, glass,
paper, cardboard, textiles, leather, both synthetic and natural,
and the like. The substrate can be one that has been already
treated in some manner, such as to impart visual and/or color
effect.
[0153] The coatings can be applied to a dry film thickness of 0.04
mils or greater, such as 0.1 mil or greater or 0.7 mil or greater
and up to 4 mils or less, such as 2 mils or less or 1.3 mils or
less, with suitable ranges from 0.04 mils to 4 mils, such as 0.1 to
2 or 0.7 to 1.3 mils. For some applications, the coatings can be
applied to a dry film thickness of 0.1 mils or greater, 0.5 mils or
greater, 1.0 mils or greater, 2.0 mils or greater, 5.0 mils or
greater, or even thicker. For packaging coatings, the dry film
thickness can be, for example, 1.0 to 20 microns. The coatings of
the present invention can be used alone, or in combination with one
or more other coatings. For example, the coatings of the present
invention can comprise a colorant or not and can be used as a
primer, basecoat, and/or top coat. For substrates coated with
multiple coatings, one or more of those coatings can be coatings as
described herein. For example, a coating such as described herein
can be spray applied as a top coat over a roller applied basecoat
of a different composition for improvements in organoleptic
performance.
EXAMPLES
[0154] The following examples are intended to illustrate the
present invention and are not intended to limit the invention in
any way.
Latex Preparation Examples
[0155] Latex A Made with Polymerizable Surfactant
[0156] A total of 14 grams of MAXEMUL 6106 (anionic surfactant
commercially available from Croda) was added to an Erlenmeyer flask
with 421 grams of deionized water and stirred well. A total of 98
grams of hydroxyethyl methacrylate, 349 grams of styrene, 644 grams
of ethyl acrylate and 22 grams of methacrylic acid were added in
order to the Erlenmeyer while mixing well. It was mixed until the
monomer emulsion showed no separation upon standing. This is
referred to below as the monomer premix.
[0157] A total of 1431 grams of deionized water was placed into a
5-liter, 4-neck round bottom flask equipped with a stirrer,
water-cooled reflux condenser, two addition funnels and a
thermocouple. The water was heated to 80.degree. C. with stirring
and under a nitrogen gas blanket. A total of 15 grams of the
monomer premix was added to the reactor over 2 minutes. A total of
0.5 grams of ammonium persulfate dissolved in 5 grams of water was
then added over 1 minute to the reactor. After 20 minutes, 4 grams
of ammonium persulfate dissolved in 419 grams of water were added
to the flask.
[0158] The remaining 1554 grams of the monomer premix and 4.4 grams
of ammonium persulfate dissolved in 419 grams of water were added
simultaneously to the flask over 150 minutes. At the end of the
monomer feed the reaction was maintained at 80.degree. C. for an
additional 60 minutes. An aliquot of 4.5 grams of t-butyl
peroctoate thinned with 22 grams of Dowanol PM (commercially
available from Dow) were added over 5 minutes as a chase initiator
to the reactor. The reaction was held with stirring for an
additional 60 minutes at 80.degree. C. It was then allowed to cool
to <40.degree. C. A total of 11 grams of dimethylethanolamine in
34 grams of water was added over about 5 minutes. The contents of
the flask were filtered and filled out into a suitable container.
The final latex had a measured solids of 33%, a surface weighted
mean particle size of 121 nm, a Brookfield Viscosity of 33
centipoise (#4@60 rpm) and a bluish-white appearance. Unless
otherwise indicated, viscosity is measured at 20.degree. C.
[0159] Latex B Made with Polymerizable Surfactant
[0160] A total of 14 grams of MAXEMUL 6106 was added to an
Erlenmeyer flask with 421 grams of deionized water and stirred
well. A total of 45 grams of glycidyl methacrylate, 279 grams of
styrene, 550 grams of ethyl acrylate and 18 grams of methacrylic
acid were added on order to the Erlenmeyer while mixing well. It
was mixed until the monomer emulsion showed no separation upon
standing. This is the monomer premix.
[0161] A total of 1145 grams of deionized water was placed into a
5-liter, 4-neck round bottom flask equipped with a stirrer,
water-cooled reflux condenser, two addition funnels and a
thermocouple. The water was heated to 80.degree. C. with stirring
and under a nitrogen gas blanket. A total of 12 grams of the
monomer premix was then added to the reactor over 2 minutes. A
total of 0.39 grams of ammonium persulfate dissolved in 4 grams of
water was added over 1 minute to the reactor. After 20 minutes, 4
grams of ammonium persulfate dissolved in 335 grams of water were
added to the flask.
[0162] The remaining 1227 grams of the monomer premix and 3.5 grams
of ammonium persulfate dissolved in 335 grams of water were added
simultaneously to the flask over 150 minutes. At the end of the
monomer feed the reaction was maintained at 80.degree. C. for an
additional 60 minutes. An aliquot of 3.6 grams of t-butyl
peroctoate thinned with 18 grams of Dowanol PM were added over 5
minutes as a chase initiator to the reactor. The reaction was held
with stirring for an additional 60 minutes at 80.degree. C. It was
then allowed to cool to <40.degree. C. A total of 9 grams of
dimethylethanolamine in 28 grams of water was added over about 5
minutes. The contents of the flask were filtered and filled out
into a suitable container. The final latex had a measured solids of
33%, a surface weighted mean particle size of 109 nm, a Brookfield
Viscosity of 36 centipoise (#4@60 rpm) and a bluish-white
appearance.
[0163] Latex C Made with Polymerizable Surfactant
[0164] A total of 11 grams of MAXEMUL 6106 was added to an
Erlenmeyer flask with 337 grams of deionized water and stirred
well. A total of 45 grams of glycidyl methacrylate, 279 grams of
methyl methacrylate, 550 grams of ethyl acrylate and 18 grams of
methacrylic acid were added on order to the Erlenmeyer while mixing
well. It was mixed until the monomer emulsion showed no separation
upon standing. This is the monomer premix.
[0165] A total of 1147 grams of deionized water was placed into a
5-liter, 4-neck round bottom flask equipped with a stirrer,
water-cooled reflux condenser, two addition funnels and a
thermocouple. The water was heated to 80.degree. C. with stirring
and under a nitrogen gas blanket. A total of 12 grams of the
monomer premix was then added to the reactor over 2 minutes. A
total of 0.39 grams of ammonium persulfate dissolved in 4 grams of
water was added over 1 minute to the reactor. After 20 minutes, 3.5
grams of ammonium persulfate dissolved in 335 grams of water were
added to the flask.
[0166] The remaining 1227 grams of the monomer premix and 3.5 grams
of ammonium persulfate dissolved in 335 grams of water were added
simultaneously to the flask over 150 minutes. At the end of the
monomer feed the reaction was maintained at 80.degree. C. for an
additional 60 minutes. An aliquot of 3.6 grams of t-butyl
peroctoate thinned with 18 grams of Dowanol PM were added over 5
minutes as a chase initiator to the reactor. The reaction was held
with stirring for an additional 60 minutes at 80.degree. C. It was
then allowed to cool to <40.degree. C. A total of 7 grams of
dimethylethanolamine in 22 grams of water was added over about 5
minutes. The contents of the flask were filtered and filled out
into a suitable container. The final latex had a measured solids of
33%, a surface weighted mean particle size of 111 nm, a Brookfield
Viscosity of 32 centipoise (#4@60 rpm) and a bluish-white
appearance.
[0167] Latex D Made with Ionic Polymerizable Surfactant
[0168] A total of 5.6 grams of MAXEMUL 6106 was added to an
Erlenmeyer flask with 153 grams of deionized water and stirred
well. A total of 23 grams of glycidyl methacrylate, 139 grams of
methyl methacrylate, 221 grams of ethyl acrylate, 22 grams of
methacrylic acid and 40 grams of hydroxyethyl methacrylate were
added in order to the Erlenmeyer while mixing well. The contents
were mixed until the monomer emulsion showed no sign of separation
upon standing. This is the monomer premix.
[0169] A total of 724 grams of deionized water was placed into a
3-liter, 4-neck round bottom flask equipped with a stirrer,
water-cooled reflux condenser, two addition funnels and a
thermocouple. The water was heated to 80.degree. C. with stirring
and under a nitrogen gas blanket. A total of 6 grams of the monomer
premix was added to the reactor over 2 minutes. A total of 0.2
grams of ammonium persulfate dissolved in 2 grams of water was then
added over 1 minute to the reactor.
[0170] After stirring the reaction for 20 minutes, the remaining
599 grams of the monomer premix and 1.8 grams of ammonium
persulfate dissolved in 167 grams of water were added
simultaneously to the flask over 150 minutes. At the end of the
monomer feed the reaction was maintained at 80.degree. C. for an
additional 60 minutes. An aliquot of 1.8 grams of t-butyl
peroctoate dissolved in 9 grams of Dowanol PM were added over 5
minutes as a chase initiator to the reactor. The reaction was held
with stirring for an additional 60 minutes at 80.degree. C. It was
then allowed to cool to <40.degree. C. A total of 9 grams of
dimethylethanolamine in 28 grams of water was added over about 5
minutes. The contents of the flask were filtered and filled out
into a suitable container. The final latex had a measured solids of
30%, a Z-average particle size of 175 nm, a Brookfield Viscosity of
20 centipoise (#4@60 rpm) and a bluish-white appearance.
[0171] Latex E Made with Ionic Polymerizable Surfactant
[0172] A total of 4.6 grams of Adeka Reasoap SR-10 was added to an
Erlenmeyer flask with 153 grams of deionized water and stirred
well. A total of 23 grams of glycidyl methacrylate, 139 grams of
methyl methacrylate, 221 grams of ethyl acrylate, 22 grams of
methacrylic acid and 40 grams of hydroxyethyl methacrylate were
added in order to the Erlenmeyer while mixing well. The contents
were mixed until the monomer emulsion showed no sign of separation
upon standing. This is the monomer premix.
[0173] A total of 722 grams of deionized water was placed into a
3-liter, 4-neck round bottom flask equipped with a stirrer,
water-cooled reflux condenser, two addition funnels and a
thermocouple. The water was heated to 80.degree. C. with stirring
and under a nitrogen gas blanket. A total of 6 grams of the monomer
premix was added to the reactor over 2 minutes. A total of 0.2
grams of ammonium persulfate dissolved in 2 grams of water was then
added over 1 minute to the reactor.
[0174] After stirring the reaction for 20 minutes, the remaining
598 grams of the monomer premix and 1.8 grams of ammonium
persulfate dissolved in 167 grams of water were added
simultaneously to the flask over 150 minutes. At the end of the
monomer feed the reaction was maintained at 80.degree. C. for an
additional 60 minutes. An aliquot of 1.8 grams of t-butyl
peroctoate dissolved in 9 grams of Dowanol PM were added over 5
minutes as a chase initiator to the reactor. The reaction was held
with stirring for an additional 60 minutes at 80.degree. C. It was
then allowed to cool to <40.degree. C. A total of 9 grams of
dimethylethanolamine in 28 grams of water was added over about 5
minutes. The contents of the flask were filtered and filled out
into a suitable container. The final latex had a measured solids of
29%, a volume weighted mean particle size of 145 nm, a Brookfield
Viscosity of 22 centipoise (#4@60 rpm) and a bluish-white
appearance.
[0175] Latex F Made with Mixed Non-Polymerizable Surfactant and
Non-Ionic Polymerizable Surfactant
[0176] A total of 5.7 grams of sodium dioctyl sulfosuccinate at 75%
solids (AOT-75 from Cytec Solvay Group) and 11.4 grams of MAXEMUL
5010 was added to an Erlenmeyer flask with 323 grams of deionized
water and stirred well. A total of 47 grams of glycidyl
methacrylate, 279 grams of methyl methacrylate, 485 grams of ethyl
acrylate, 45 grams of methacrylic acid, and 36 grams of
hydroxyethyl acrylate were added in order to the Erlenmeyer while
mixing well. The contents were mixed until the monomer emulsion
showed no separation upon standing. This is the monomer premix.
[0177] A total of 1003 grams of deionized water was placed into a
5-liter, 4-neck round bottom flask equipped with a stirrer,
water-cooled reflux condenser, two addition funnels and a
thermocouple. The water was heated to 80.degree. C. with stirring
and under a nitrogen gas blanket. A total of 0.39 grams of ammonium
persulfate dissolved in 3.9 grams of water was then added over 1
minute to the reactor. A total of 12 grams of the monomer premix
was then added to the reactor over 2 minutes.
[0178] After stirring the reaction for 20 minutes, the remaining
1219 grams of the monomer premix and 3.5 grams of ammonium
persulfate dissolved in 335 grams of water were added
simultaneously to the flask over 150 minutes. At the end of the
monomer feed the reaction was maintained at 80.degree. C. for an
additional 60 minutes. An aliquot of 0.9 grams of t-butyl
peroctoate dissolved in 4.5 grams of Dowanol PM were added over 5
minutes as a chase initiator to the reactor. The reaction was held
with stirring for an additional 60 minutes at 80.degree. C. It was
then allowed to cool to <40.degree. C. A total of 18 grams of
dimethylethanolamine in 55 grams of water was added over about 5
minutes. The contents of the flask were filtered and filled out
into a suitable container. The final latex had a measured solids of
35%, a volume weighted mean particle size of 292 nm, a Brookfield
Viscosity of 28 centipoise (#4@60 rpm) and a bluish-white
appearance.
[0179] Latex G Made with Mixed Ionic and Non-Ionic Polymerizable
Surfactants
[0180] A total of 10.7 grams of MAXEMUL 6106 and 3.6 grams of
MAXEMUL 5010 was added to an Erlenmeyer flask with 288 grams of
deionized water and stirred well. A total of 4 grams of ethylene
glycol dimethacrylate, 262 grams of methyl methacrylate, 454 grams
of ethyl acrylate, 42 grams of methacrylic acid, and 74 grams of
hydroxyethyl acrylate were added in order to the Erlenmeyer while
mixing well. The contents were mixed until the monomer emulsion
showed no separation upon standing. This is the monomer premix.
[0181] A total of 1364 grams of deionized water was placed into a
5-liter, 4-neck round bottom flask equipped with a stirrer,
water-cooled reflux condenser, two addition funnels and a
thermocouple. The water was heated to 80.degree. C. with stirring
and under a nitrogen gas blanket. A total of 11 grams of the
monomer premix was then added to the reactor over 2 minutes. A
total of 0.37 grams of ammonium persulfate dissolved in 3.7 grams
of water was then added over 1 minute to the reactor.
[0182] After stirring the reaction for 20 minutes, the remaining
1126 grams of the monomer premix and 3.3 grams of ammonium
persulfate dissolved in 314 grams of water were added
simultaneously to the flask over 150 minutes. At the end of the
monomer feed the reaction was maintained at 80.degree. C. for an
additional 60 minutes. An aliquot of 3.3 grams of t-butyl
peroctoate dissolved in 17 grams of Dowanol PM were added over 5
minutes as a chase initiator to the reactor. The reaction was held
with stirring for an additional 60 minutes at 80.degree. C. It was
then allowed to cool to <40.degree. C. A total of 17 grams of
dimethylethanolamine in 52 grams of water was added over about 5
minutes. The contents of the flask were filtered and filled out
into a suitable container. The final latex had a measured solids of
30%, a volume weighted mean particle size of 121 nm, a Brookfield
Viscosity of 42 centipoise (#4@60 rpm) and a bluish-white
appearance.
[0183] Latex H Made with Ionic Polymerizable Surfactant
[0184] A total of 11.4 grams of MAXEMUL 6106 was added to an
Erlenmeyer flask with 323 grams of deionized water and stirred
well. A total of 47 grams of glycidyl methacrylate, 279 grams of
methyl methacrylate, 485 grams of ethyl acrylate, 45 grams of
methacrylic acid and 36 grams of hydroxyethyl acrylate were added
in order to the Erlenmeyer while mixing well. The contents were
mixed until the monomer emulsion showed no sign of separation upon
standing. This is the monomer premix.
[0185] A total of 989 grams of deionized water was placed into a
3-liter, 4-neck round bottom flask equipped with a stirrer,
water-cooled reflux condenser, two addition funnels and a
thermocouple. The water was heated to 80.degree. C. with stirring
and under a nitrogen gas blanket. A total of 12 grams of the
monomer premix was added to the reactor over 2 minutes. A total of
0.4 grams of ammonium persulfate dissolved in 4 grams of water was
then added over 1 minute to the reactor.
[0186] After stirring the reaction for 20 minutes, the remaining
1214 grams of the monomer premix and 3.5 grams of ammonium
persulfate dissolved in 335 grams of water were added
simultaneously to the flask over 150 minutes. At the end of the
monomer feed the reaction was maintained at 80.degree. C. for an
additional 60 minutes. An aliquot of 3.6 grams of t-butyl
peroctoate dissolved in 18 grams of Dowanol PM were added over 5
minutes as a chase initiator to the reactor. The reaction was held
with stirring for an additional 60 minutes at 80.degree. C. It was
then allowed to cool to <40.degree. C. A total of 18 grams of
dimethylethanolamine in 55 grams of water was added over about 5
minutes. The contents of the flask were filtered and filled out
into a suitable container. The final latex had a measured solids of
34%, a Z-average particle size of 130 nm, a Brookfield Viscosity of
40 centipoise (#4@60 rpm) and a bluish-white appearance.
[0187] Latex I Made with Ionic Polymerizable Surfactant
[0188] A total of 18.6 grams of Adeka Reasoap SR-10 was added to an
Erlenmeyer flask with 323 grams of deionized water and stirred
well. A total of 46 grams of glycidyl methacrylate, 277 grams of
methyl methacrylate, 482 grams of ethyl acrylate, 44 grams of
methacrylic acid and 35 grams of hydroxyethyl acrylate were added
in order to the Erlenmeyer while mixing well. The contents were
mixed until the monomer emulsion showed no sign of separation upon
standing. This is the monomer premix.
[0189] A total of 989 grams of deionized water was placed into a
3-liter, 4-neck round bottom flask equipped with a stirrer,
water-cooled reflux condenser, two addition funnels and a
thermocouple. The water was heated to 80.degree. C. with stirring
and under a nitrogen gas blanket. A total of 12 grams of the
monomer premix was added to the reactor over 2 minutes. A total of
0.4 grams of ammonium persulfate dissolved in 4 grams of water was
then added over 1 minute to the reactor.
[0190] After stirring the reaction for 20 minutes, the remaining
1214 grams of the monomer premix and 3.5 grams of ammonium
persulfate dissolved in 341 grams of water were added
simultaneously to the flask over 150 minutes. At the end of the
monomer feed the reaction was maintained at 80.degree. C. for an
additional 60 minutes. An aliquot of 3.6 grams of t-butyl
peroctoate dissolved in 18 grams of Dowanol PM were added over 5
minutes as a chase initiator to the reactor. The reaction was held
with stirring for an additional 60 minutes at 80.degree. C. It was
then allowed to cool to <40.degree. C. A total of 18 grams of
dimethylethanolamine in 55 grams of water was added over about 5
minutes. The contents of the flask were filtered and filled out
into a suitable container. The final latex had a measured solids of
33%, a Z-average particle size of 139 nm, a Brookfield Viscosity of
50 centipoise (#4@60 rpm) and a bluish-white appearance.
Polyethylene-Acrylic Acid Dispersions
[0191] Dispersion J of Ionic Polyethylene-Acrylic Acid Copolymer in
Water--50% Neutralization (TN)
[0192] A total of 600 grams of Primacor 5980i (from Dow Chemical
Co.) was added to a 3-liter, 4-neck round bottom flask equipped
with a stirrer, water-cooled reflux condenser and a thermocouple. A
total of 20 grams of propylene glycol, 1305 grams of water and 74
grams of dimethylethanolamine were added to the flask and the
contents were heated slowly to 92.degree. C. with stirring and
under a nitrogen gas blanket. The contents were held at 92.degree.
C. for two hours, at which time the contents were cooled to less
than 60.degree. C. with stirring. The contents were then filtered
through a 5-micron bag into a suitable container. The final
dispersion had a measured solids of 27% and a viscosity of 3333
centipoise (#4@60 rpm).
[0193] Dispersion K of Ionic Polyethylene-Acrylic Acid Copolymer in
Water--50% TN
[0194] A total of 700 grams of Primacor 5980i was added to a
5-liter, 4-neck round bottom flask equipped with a stirrer,
water-cooled reflux condenser and a thermocouple. A total of 35
grams of propylene glycol, 2678 grams of water and 87 grams of
dimethylethanolamine were added to the flask and the contents were
heated slowly to 92.degree. C. with stirring and under a nitrogen
gas blanket. The contents were held at 92.degree. C. for two hours,
at which time the contents were cooled to less than 60.degree. C.
with stirring. The contents were then filtered through a 5-micron
bag into a suitable container. The final dispersion had a measured
solids of 20%.
Latex--Ionic Polyethylene-Acrylic Acid Copolymer Blends
[0195] Blend L: 85% Latex H--15% Dispersion J Blend (85 to 15 Resin
Solids Weight Ratio
[0196] A total of 471 grams of Latex H was placed into a 3-liter,
4-neck round bottom flask equipped with a stirrer, water-cooled
reflux condenser and a thermocouple. The contents of the flask were
heated to 70.degree. C. with stirring under a nitrogen gas blanket.
A total of 127 grams of Dispersion J was added dropwise to the
contents of the flask over 30 minutes. The contents of the flask
were then allowed to stir for 60 minutes at 70.degree. C. and then
cooled to less than 40.degree. C. The contents of the flask were
then filtered and poured into a suitable container. The final blend
had a solids content of 33%.
[0197] Blend M: 85% Latex I--15% Dispersion J Blend
[0198] A total of 566 grams of Latex I was placed into a 3-liter,
4-neck round bottom flask equipped with a stirrer, water-cooled
reflux condenser and a thermocouple. The contents of the flask were
heated to 70.degree. C. with stirring under a nitrogen gas blanket.
A total of 130 grams of Dispersion J was added dropwise to the
contents of the flask over 30 minutes. The contents of the flask
were then allowed to stir for 60 minutes at 70.degree. C. and then
cooled to less than 40.degree. C. The contents of the flask were
then filtered and poured into a suitable container. The final blend
had a solids content of 34%.
[0199] Blend N: 83% Latex F--17% Dispersion J Blend
[0200] A total of 501 grams of Latex F was placed into a 3-liter,
4-neck round bottom flask equipped with a stirrer, water-cooled
reflux condenser and a thermocouple. The contents of the flask were
heated to 70.degree. C. with stirring under a nitrogen gas blanket.
A total of 130 grams of Dispersion J was added dropwise to the
contents of the flask over 30 minutes. The contents of the flask
were then allowed to stir for 60 minutes at 70.degree. C. and then
cooled to less than 40.degree. C. The contents of the flask were
then filtered and poured into a suitable container. The final blend
had a solids content of 34%.
Hybrid Latexes
[0201] Latex O:
[0202] A total of 5.5 grams of MAXEMUL 6106 was added to an
Erlenmeyer flask with 154 grams of deionized water and stirred
well. A total of 6 grams of benzoin, 230 grams of methyl
methacrylate, 216 grams of ethyl acrylate and 14 grams of glycidyl
methacrylate were added in order to the Erlenmeyer while mixing
well. The contents were mixed until the monomer emulsion showed no
sign of separation upon standing. This is the monomer premix.
[0203] A total of 1011 grams of Dispersion K along with 159 grams
of water were placed into a 5-liter, 4-neck round bottom flask
equipped with a stirrer, water-cooled reflux condenser, a
thermocouple and two addition funnels. The contents of the flask
were heated to 70.degree. C. with stirring under a nitrogen gas
blanket. The monomer premix described above and 4.6 grams of 35%
hydrogen peroxide dissolved in 92 grams of water were added
simultaneously in two separate streams to the flask over 150
minutes. At the end of the monomer feed the reaction was maintained
at 70.degree. C. for 30 minutes. An aliquot of 0.8 grams of 35%
hydrogen peroxide dissolved in 16 grams of water was added over 20
minutes as a chase initiator to the reactor. The reaction was held
with stirring for an additional 60 minutes at 80.degree. C. A
second aliquot of 0.8 grams of 35% hydrogen peroxide in 16 grams of
water was added over 20 minutes. The reaction was held for another
hour at 70.degree. C. and was then allowed to cool to less than
40.degree. C. The contents of the flask were filtered and filled
out into a suitable container. The final latex had a measured
solids of 35%.
[0204] Latex P:
[0205] A total of 691 grams of Dispersion K along with 213 grams of
water, 0.7 grams of Adeka Reasoap SR-10 and 4 grams of benzoin
dispersed in 2 grams of butyl Cellosolve were placed into a
3-liter, 4-neck round bottom flask equipped with a stirrer,
water-cooled reflux condenser, a thermocouple and two addition
funnels. The contents of the flask were heated to 70.degree. C.
with stirring under a nitrogen gas blanket. The monomer premix
consisting of a blend of 165 grams of methyl methacrylate, 154
grams of ethyl acrylate and 10 grams of glycidyl methacrylate was
placed in an addition funnel. A total of 3 grams of 35% hydrogen
peroxide dissolved in 99 grams of water was placed in a second
addition funnel. The monomer mixture and the hydrogen peroxide
mixture were added simultaneously in two separate streams to the
flask over 120 minutes. At the end of the monomer feed the reaction
was maintained at 70.degree. C. for 30 minutes. An aliquot of 0.6
grams of 35% hydrogen peroxide dissolved in 11 grams of water was
added over 20 minutes as a chase initiator to the reactor. The
reaction was held with stirring for an additional 60 minutes at
80.degree. C. A second aliquot of 0.6 grams of 35% hydrogen
peroxide in 11 grams of water was added over 20 minutes. The
reaction was held for another hour at 70.degree. C. and was then
allowed to cool to less than 40.degree. C. The contents of the
flask were filtered and filled out into a suitable container. The
final latex had a measured solids of 34% and a viscosity of 56
centipoise (#4@60 rpm).
[0206] Latex Q:
[0207] A total of 572 grams of Dispersion K along with 155 grams of
water, 0.6 grams of AOT-75, 2 grams of MAXEMUL 5010 and 3 grams of
benzoin dispersed in 3 grams of butyl Cellosolve were placed into a
3-liter, 4-neck round bottom flask equipped with a stirrer,
water-cooled reflux condenser, a thermocouple and two addition
funnels. The contents of the flask were heated to 70.degree. C.
with stirring under a nitrogen gas blanket. The monomer premix
consisting of a blend of 132 grams of methyl methacrylate, 124
grams of ethyl acrylate and 8 grams of glycidyl methacrylate was
placed in an addition funnel. A total of 3 grams of 35% hydrogen
peroxide dissolved in 79 grams of water was placed in a second
addition funnel. The monomer mixture and the hydrogen peroxide
mixture were added simultaneously in two separate streams to the
flask over 120 minutes. At the end of the monomer feed the reaction
was maintained at 70.degree. C. for 30 minutes. An aliquot of 0.5
grams of 35% hydrogen peroxide dissolved in 9 grams of water was
added over 20 minutes as a chase initiator to the reactor. The
reaction was held with stirring for an additional 60 minutes at
80.degree. C. A second aliquot of 0.5 grams of 35% hydrogen
peroxide in 9 grams of water was added over 20 minutes. The
reaction was held for another 90 minutes at 70.degree. C. and was
then allowed to cool to less than 40.degree. C. The contents of the
flask were filtered and filled out into a suitable container. The
final latex had a measured solids of 33% and a viscosity of 80
centipoise (#4@60 rpm).
[0208] Latex R:
[0209] A total of 572 grams of Dispersion K along with 154 grams of
water, 1.9 grams of grams of MAXEMUL 5010 and 3 grams of benzoin
dispersed in 3 grams of butyl Cellosolve were placed into a
3-liter, 4-neck round bottom flask equipped with a stirrer,
water-cooled reflux condenser, a thermocouple and two addition
funnels. The contents of the flask were heated to 70.degree. C.
with stirring under a nitrogen gas blanket. The monomer premix
consisting of a blend of 132 grams of methyl methacrylate, 124
grams of ethyl acrylate and 8 grams of glycidyl methacrylate was
placed in an addition funnel. A total of 3 grams of 35% hydrogen
peroxide dissolved in 79 grams of water was placed in a second
addition funnel. The monomer mixture and the hydrogen peroxide
mixture were added simultaneously in two separate streams to the
flask over 120 minutes. At the end of the monomer feed the reaction
was maintained at 70.degree. C. for 30 minutes. An aliquot of 0.5
grams of 35% hydrogen peroxide dissolved in 9 grams of water was
added over 20 minutes as a chase initiator to the reactor. The
reaction was held with stirring for an additional 60 minutes at
80.degree. C. A second aliquot of 0.5 grams of 35% hydrogen
peroxide in 9 grams of water was added over 20 minutes. The
reaction was held for another 90 minutes at 70.degree. C. and was
then allowed to cool to less than 40.degree. C. The contents of the
flask were filtered and filled out into a suitable container. The
final latex had a measured solids of 34% and a viscosity of 180
centipoise (#4@60 rpm).
[0210] Latex S Made with Ionic Polymerizable Surfactant
[0211] A total of 8 grams of MAXEMUL 6106 was added to an
Erlenmeyer flask with 168 grams of deionized water and stirred
well. A total of 139 grams of methyl methacrylate, 240 grams of
ethyl acrylate, 27 grams of methacrylic acid and 40 grams of
hydroxyethyl methacrylate were added in order to the Erlenmeyer
while mixing well. The contents were mixed until the monomer
emulsion showed no sign of separation upon standing. This is the
monomer premix.
[0212] A total of 708 grams of deionized water was placed into a
5-liter, 4-neck round bottom flask equipped with a stirrer,
water-cooled reflux condenser, two addition funnels and a
thermocouple. The water was heated to 80.degree. C. with stirring
and under a nitrogen gas blanket. A total of 0.2 grams of ammonium
persulfate dissolved in 20 grams of water was added over 1 minute
to the reactor. A total of 6 grams of the monomer premix was then
added to the reactor over 2 minutes.
[0213] After stirring the reaction for 20 minutes, the remaining
616 grams of the monomer premix and 1.8 grams of ammonium
persulfate dissolved in 176 grams of water were added
simultaneously to the flask over 150 minutes. At the end of the
monomer feed the reaction was maintained at 80.degree. C. for an
additional 60 minutes. An aliquot of 0.5 grams of ammonium
persulfate dissolved in 2.3 grams of water were added over 5
minutes as a chase initiator to the reactor. The reaction was held
with stirring for an additional 60 minutes at 80.degree. C. It was
then allowed to cool to <40.degree. C. A total of 11 grams of
dimethylethanolamine in 33 grams of water was added over about 5
minutes. The contents of the flask were filtered and filled out
into a suitable container. The final latex had a measured solids of
29.5%, a Z-average particle size of 124 nm, a Brookfield Viscosity
of 76 centipoise (#4@60 rpm) and a bluish-white appearance.
Coating Examples
[0214] The properties of the coatings were tested via the following
methods. Results are also shown in Tables 1-2. The acetic acid
sterilization test was performed on all the coatings. The results
are shown in Tables A-B.
[0215] Test Methods
[0216] Test Panel Preparation: The coating samples were applied
onto an ETP panel using a wire wound bar coater to give a 7-9
g/square meter dried coating weight. The substrates were cleaned by
MEK before application. The coated panels were stoved in a conveyor
oven with 3 controllable heating zones at the following temperature
settings: zone 1 145.degree. C.; zone 2 220.degree. C.; zone 3
220.degree. C. at a conveyor speed setting of 2.30 to give a time
of 6 minutes.
[0217] MEK Rub Test: The number of reciprocating rubs required to
remove the coating was measured using a ball of cotton wool soaked
in methyl ethyl ketone (MEK).
[0218] Wedge Bend Test: A 10 cm.times.4 cm coated panel was bent on
a 6 mm steel rod to form a U-shaped strip 10 cm long and 2 cm wide.
The U-shaped strip was then placed onto a metal block with a built
in tapered recess. A 2 kg weight was dropped onto the recessed
block containing the U-shaped strip from a height of 60 cm in order
to from a wedge. The test piece was then immersed in a copper
sulphate (CuSO.sub.4) solution acidified with hydrochloric acid
(HCl) for 2 minutes, followed by rinsing with tap water. The sample
was then carefully dried by blotting any residual water with tissue
paper. The length of coating without any fracture was measured. The
result was quoted in mm passed. The wedge bends were tested in
triplicate and the average value was quoted. That is, the results
indicate the mm of the 100 mm coating surface that remained in-tact
or unbroken upon deformation. A result of 98 therefore means that
only 2 mm of the coating out of 100 mm cracked upon
deformation.
[0219] Acetic Acid Sterilization: This test was used to determine
if the coatings are compatible for use in beverage containers. The
coating samples were applied onto aluminum can plate using a wire
wound bar coater to give a 7-9 g/square meter dried coating weight.
The substrates were cleaned by MEK before application. The coated
panels were stoved in a conveyor oven with the following settings:
zone 1 145.degree. C.; zone 2 215.degree. C.; zone 3 215.degree. C.
and conveyor setting 3.30 to give a through time of 4 minutes.
[0220] The coated panels were immersed in a deionized water
solution comprising 5% acetic acid inside a Kilner jar and
sterilized for 30 minutes at 100.degree. C. in an autoclave. After
this time, the coated panels were quickly removed while still hot
and rinsed with cold tap water. The portion of the coated panel
immersed in acetic acid, was assessed for extent of damage. Five
aspects were graded by visual assessment on a scale where 0=no
damage and 5=severe damage/defect: [0221] (A) Gloss surface
modification [0222] (B) Extent of blushing wherein the coating
turns hazy due to water trapped in the coating [0223] (C) Extent of
color wherein the coating turns into another color [0224] (D)
Coating adhesion loss (assessed by making a cross hatch on the
coating and taping with Scotch 610 tape) [0225] (E) Blistering of
the coating
Sample Preparation and Testing for Examples 1-10
Coating Example 1
[0226] 20 g of coating sample 1 were prepared by adding 3.95 g of
deionized water and 2.60 g of a mix of butanol and pentanol in a 3
to 1 ratio (i.e. 1.95 g of butanol and 0.65 g of pentanol) to 13.45
g of latex S, made as described above. The mixtures were stirred
manually. No PRIMID XL-552 was used in this coating.
Coating Examples 2-5
[0227] 20 g of coating samples 2-5 were prepared by adding 0.18 g
of PRIMID XL-552 to 13.26 g of latex S in an amount shown in Table
1. This mixture was stirred manually; then 3.96 g of deionized
water and 2.60 g of the butanol/pentanol (3/1) mix were added.
Formulation of the coatings was completed using the components and
amounts also shown in Table 1.
Coating Examples 6-10
[0228] 20 g of coating samples 6-10 were prepared by adding a 10%
solution of phosphoric acid drop by drop and PRIMID XL-552 to 13.26
g of latex S in an amount shown in Table 2. This mixture was
stirred manually; then 3.91 g of deionized water and 2.60 g of the
butanol/pentanol (3/1) mix were added. Formulation of the coatings
was completed using the components and amounts also shown in Table
2.
TABLE-US-00001 TABLE 1 Coating Examples 1-5 and Test Results
Coating Coating Coating Coating Coating 1 2 3 4 5 Latex S 13.45
13.26 13.07 12.70 12.36 PRIMID XL-552.sup.1 0.00 0.18 0.36 0.72
1.06 2-butoxyethanol/ 2.60 2.60 2.60 2.60 2.60 pentanol (3/1)
Deionized water 3.95 3.96 3.96 3.98 3.99 Total 20.00 20.00 20.00
20.00 20.00 Results MEK Rubs 6 12 15 7 13 Wedge Bend 96.3 95.3 97.3
97.3 93 .sup.1Hydroxyalkylamide.
TABLE-US-00002 TABLE 2 Coating Examples 6-10 and Test Results
Coating Coating Coating Coating Coating 6 7 8 9 10 Latex S 13.26
13.26 12.98 12.70 12.70 PRIMID XL-552 0.17 0.17 0.41 0.66 0.66
Phosphoric acid* 0.08 0.15 0.11 0.08 0.15 2-butoxyethanol/ 2.60
2.60 2.60 2.60 2.60 pentanol (3/1) Deionized water 3.91 3.88 3.89
3.91 3.87 Total 20.02 20.06 20.00 19.95 19.99 Results MEK Rubs 6 10
10 80 27 Wedge Bend 81.7 77.3 81.7 80.3 79 *10 weight % of
0-phosphoric acid in deionized water and neutralized at 50% by
dimethylethanolamine (DMAE).
TABLE-US-00003 TABLE A Results of Acetic Acid Sterilization Test on
Coatings 1-5 Coating 1 Coating 2 Coating 3 Coating 4 Coating 5 5% A
2 1 0-1 0-1 1 Acetic B 2-3 2 1-2 1-2 1-2 acid C 0 0 0 0 0 D 2 3 3
1-2 2 E 3 5 5 5 5
TABLE-US-00004 TABLE B Results of Acetic Acid Sterilization Test on
Coatings 6-10 Coating 6 Coating 7 Coating 8 Coating 9 Coating 10 5%
A 0-1 0-1 0-1 0 0-1 Acetic B 2 1 1 0-1 0-1 acid C 0 0 0 0 0 D 0-1 0
1 0 1 E 2 5 5 0 1
[0229] The above examples demonstrate that coatings made from a
latex polymer prepared with a polymerizable surfactant and an
emulsion monomer are suitable for use on packaging but that the use
of a phosphorus acid in combination with an adapted crosslinker in
the latex stabilized by polymerizable surfactant results in a
notable improvement of the chemical resistance of the film formed.
Moreover, with the appropriate choice of surfactant and the amount
of added phosphoric acid and crosslinker, an excellent flexibility
of the coatings is also demonstrated; such flexibility is
particularly desired for packaging applications.
Sample Preparation and Testing for Examples 11-20
[0230] Sample Preparation: Ten latex polymers were examined for use
as a coating for the lids of metal beverage cans. The latex
polymers were varied based on polymer type and the surfactant
type.
[0231] Each latex polymer was placed into an appropriately sized
container. To the container was added enough deionized water to
bring the final solids of the formulated polymer to 29%. The
mixture was agitated using an overhead air supplied stirrer
attached with a paddle blade. While the mixture was under
agitation, 10% on polymer weight solids of ethylene glycol
mono-2-ethylhexyl ether (purchased from Eastman as Ektasolve EEH)
was added and allowed to incorporate. After the addition of the
Ektasolve EEH, 4% on solids of the phenolic crosslinker HRJ-13078
(purchased from SI Group) was added and allowed to incorporate.
After the addition of the crosslinker, 0.1% on solids of a blocked
dodecylbenzene sulfonic acid (purchased from King Industries as
NACURE 5925) was added and held under agitation until the resulting
mixture became homogenous.
[0232] The resulting mixtures (Examples 11-20) were drawn down on
0.0088'' zirconium treated aluminum substrate with wire wound rods
to a wet film thickness of 27 microns. The films were baked for 10
seconds in a 290.degree. C. conveyor oven. The substrate reached a
peak metal temperature of 450.degree. F. (232.degree. C.).
[0233] Testing Methods: After baking, the resulting coatings were
checked for MEK solvent resistance as described above.
[0234] The final coatings were also evaluated using various
simulant soak tests in order to determine the coatings' resistance
to the different solutions.
[0235] The "Acetic Acid" test uses a boiling 3% acetic acid
solution. The solution is prepared by mixing 90 grams of glacial
acetic acid (product of Fisher Scientific) into 3000 grams of
deionized water. Coated strips are partially immersed into the
boiling acetic acid solution for 30 minutes.
[0236] The "Dowfax" test uses a boiling 0.17% solution of Dowfax
2A1 (product of Dow Chemical). The solution is prepared by mixing
5.65 g of Dowfax 2A1 into 3000 grams of deionized water. Coated
strips are partially immersed into the boiling Dowfax solution for
10 minutes.
[0237] The "Joy" test uses a 1% solution of Ultra Joy dishwashing
liquid. The solution is prepared by mixing 30 g of Ultra Joy into
3000 grams of deionized water. Coated strips are partially immersed
into a 180.degree. F. (82.degree. C.) Joy solution for 10
minutes.
[0238] The "Water Retort" test uses coated strips that are placed
into a wide-mouth quart sized mason jar. The coated strips are
partially immersed using deionized water. The mason jar is then
sealed using a piece of heavy-duty aluminum foil. The sealed mason
jar is placed into an autoclave (such as an EZ11 Plus from
Tuttnauer) and allowed to reach 250.degree. F. (121.degree. C.) and
held at that temperature for 30 minutes.
[0239] After the individual tests are completed, the coated strips
are then rinsed and cooled in deionized water, dried, and
immediately rated for blister, blush and adhesion as described
below.
[0240] Blister resistance is a Pass/Fail test. Each panel was
visually inspected for the presence of blistering. Blistering is
evidenced by the formation of bubbles in the coating during the
Acetic Acid, Dowfax, and Water Retort tests. A Pass rating is given
if there is no detectable blistering of the coating.
[0241] Blush resistance measures the ability of a coating to resist
attack by various testing solutions. When the coated film absorbs
test solution, it generally becomes cloudy or looks white. Blush is
measured visually using a scale of 1-10 where a rating of "10"
indicates no blush and a rating of "0" indicates complete whitening
of the film. The coated panel tested is 2.times.4 inches
(5.times.10 cm) and the testing solution covers half of the panel
being tested so you can compare blush of the exposed panel to the
unexposed portion.
[0242] Immediately after measuring the Blush resistance, the
adhesion of the coated panels were checked using ASTM D3359 Method
B "Standard Test Methods for Measuring Adhesion by Tape Test". The
adhesive tape used is Scotch Packaging Tape 610. The crosshatch
pattern of cuts is made over the liquid/air interface on the coated
panel. The results are recorded as Pass/Fail. Any amount of coating
removal by the adhesive tape is considered as a Fail.
[0243] The panels for the Wedge Bend test were made using a
BYK-Gardner "Coverall" Bend and Impact Tester. A 2.times.4 inch
(5.times.10 cm) coated test panel is first bent double over the
1/8'' rod so that the coated surface is on the outside. The bent
panel is placed between the parts of the hinge. The impact tool,
flat face down, is dropped from a height needed to deliver 40
inch-pounds of impact force onto the upper part of the hinge. The
impacted test panel will have a wedge shape where one end of the
coated metal impinged upon itself and a 1/8 inch space remained on
the opposite end.
[0244] After completing the wedge bend, the panels are submerged in
a copper sulfate solution (70% water, 20% copper sulfate, 10%
hydrochloric acid) for 15 seconds. The panels are then removed from
the solution, rinsed with deionized water, dried, and immediately
rated. The copper sulfate solution will etch any area of the panel
where the coating has cracked and failed. The etched wedge bent
panels were then examined through a microscope at 20.times. power
to determine how far from the impinged end along the bent radii did
the coating crack. Wedge Bend results are reported as the
percentage of cracked area versus total length of the wedge bent
panel.
[0245] The results of the testing are reported in Table 3.
TABLE-US-00005 TABLE 3 Wedge Bend (Average Soak Tests Polymer of 3
Acetic Acid Dowfax Joy Water Retort Ex. Latex Surfactant Type MEK
Tests) Blush Adh Blister Blush Adh Blister Blush Adh Blush Adh
Blister 11 D Maxemul 6106 Latex 11 27 8 F F 8 F P 9 F 9 P P 12 L
Maxemul 6106 Blend 100 16 7 P F 8 P P 8 P 8 P P 13 O Maxemul 6106
Hybrid 84 21 6 P P 9 P P 9 P 8 P P 14 E Reasoap SR10 Latex 32 29 7
P F 8 P P 9 P 9 P P 15 M Reasoap SR10 Blend 100 21 6 P F 8 P P 8 P
6 P P 16 P Reasoap SR10 Hybrid 44 18 6 P P 8 P P 9 P 8 P P 17 F
AOT-75 / Latex 61 25 8 P P 8 P P 8 P 9 P P Maxemul 5010 18 N AOT-75
/ Blend 100 25 4 P P 7 P P 7 P 4 P P Maxemul 5010 19 Q AOT-75 /
Hybrid 63 25 4 P P 9 P P 9 P 8 P P Maxemul 5010 20 R Maxemul 5010
Hybrid 100 20 4 P P 9 P P 9 P 9 P P
[0246] Whereas particular embodiments of this invention have been
described above for purposes of illustration, it will be evident to
those skilled in the art that numerous variations of the details of
the present invention may be made without departing from the
invention as defined in the appended claims.
[0247] Although various embodiments of the invention have been
described in terms of "comprising", embodiments consisting
essentially of or consisting of are also within the scope of the
present invention.
* * * * *