U.S. patent application number 13/147839 was filed with the patent office on 2012-01-26 for hydroxyl functional oil polyols and coating compositions prepared from hydroxyl functional oil polyols.
Invention is credited to Gary P. Craun, Kenneth J. Gardner, Guy J. Stella, David J. Telford.
Application Number | 20120022186 13/147839 |
Document ID | / |
Family ID | 40885936 |
Filed Date | 2012-01-26 |
United States Patent
Application |
20120022186 |
Kind Code |
A1 |
Craun; Gary P. ; et
al. |
January 26, 2012 |
HYDROXYL FUNCTIONAL OIL POLYOLS AND COATING COMPOSITIONS PREPARED
FROM HYDROXYL FUNCTIONAL OIL POLYOLS
Abstract
Hydroxyl functional oil polyols are disclosed which can be used
to produce coating compositions and coated surfaces. In some
embodiments, the coating compositions are used to coat substrates
such as packaging materials and the like for the storage of food
and beverages. The hydroxyl functional oil polyols can be prepared
by reacting an epoxidized vegetable oil with a hydroxyl functional
material in the presence of an acid catalyst. Coating compositions
can be prepared by crosslinking the hydroxyl functional oil polyols
with a crosslinker.
Inventors: |
Craun; Gary P.; (Berea,
OH) ; Stella; Guy J.; (Cleveland Heights, OH)
; Gardner; Kenneth J.; (Independence, OH) ;
Telford; David J.; (Copley, OH) |
Family ID: |
40885936 |
Appl. No.: |
13/147839 |
Filed: |
March 2, 2010 |
PCT Filed: |
March 2, 2010 |
PCT NO: |
PCT/EP10/52577 |
371 Date: |
August 4, 2011 |
Current U.S.
Class: |
523/455 ;
427/386 |
Current CPC
Class: |
C09D 191/00 20130101;
C08L 75/00 20130101; C09D 191/00 20130101; C08L 67/00 20130101;
C08L 69/00 20130101; C08F 289/00 20130101; C09D 191/00 20130101;
C09D 151/00 20130101; C08L 61/24 20130101; C08L 61/06 20130101;
C08L 71/08 20130101; C08L 61/26 20130101; C08L 61/28 20130101; C08L
2666/14 20130101; C08L 2666/02 20130101; B32B 27/285 20130101; C08L
2666/18 20130101; C09D 191/00 20130101; C08L 71/02 20130101; C08G
65/14 20130101 |
Class at
Publication: |
523/455 ;
427/386 |
International
Class: |
C08K 5/09 20060101
C08K005/09; B05D 3/10 20060101 B05D003/10 |
Foreign Application Data
Date |
Code |
Application Number |
May 14, 2009 |
EP |
09160286.2 |
Claims
1. A coating composition comprising a hydroxyl functional oil
polyol prepared by a method comprising reacting an epoxidized
vegetable oil with a hydroxyl functional material in the presence
of an acid catalyst.
2. The coating composition of claim 1, wherein the epoxidized
vegetable oil comprises corn oil, cottonseed oil, grapeseed oil,
hempseed oil, linseed oil, wild mustard oil, peanut oil, perilla
oil, poppyseed oil, rapeseed oil, safflower oil, sesame oil, soy
bean oil, sunflower oil, canola oil, tall oil, a fatty acid ester,
monoglyceride or diglyceride of such oils, or a mixture
thereof.
3. The coating composition of claim 1, wherein the epoxidized
vegetable oil is derived from an unsaturated fatty acid
glyceride.
4. The coating composition of claim 1, wherein the epoxidized
vegetable oil is present in an amount from about 2 to about 98
parts based on the total weight of the hydroxyl functional oil
polyol.
5. The coating composition of claim 1, wherein the hydroxyl
functional material comprises propylene glycol, 1,3-propane diol,
ethylene glycol, neopentyl glycol, trimethylol propane, diethylene
glycol, a polyether glycol, benzyl alcohol, 2-ethyl hexanol, a
polyester, a polycarbonate, a hydroxyl functional polyolefin, or a
mixture thereof.
6. The coating composition of claim 1, wherein the equivalent ratio
of hydroxyl functionality of the hydroxyl functional material to
oxirane functionality in the epoxidized vegetable oil is from about
0.2:1 to about 3:1.
7. The coating composition of claim 1, wherein the acid catalyst
comprises a strong acid, such as a sulfonic acid, a triflic acid, a
triflate salt of a metal of Group IIA, IIB, IIIA, IIIB or VIIIA of
the Periodic Table of Elements (according to the IUPAC 1970
convention), a mixture of said triflate salts, or a combination
thereof.
8. The coating composition of claim 1, wherein the reaction of the
epoxidized vegetable oil and the hydroxyl functional material is
conducted in the presence of a solvent.
9. The coating composition of claim 8, wherein the solvent
comprises a ketone, an aromatic solvent, an ester solvent, a
non-hydroxyl functional solvent, or a mixture thereof.
10. The coating composition of claim 1, wherein the hydroxyl
functional oil polyol of claim 1 is reacted with a crosslinker to
form the coating composition.
11. The coating composition of claim 10, wherein the crosslinker
comprises phenol-formaldehyde, melamine formaldehyde, urea
formaldehyde, benzoguanamine formaldehyde, a blocked isocyanate, or
a mixture thereof.
12. The coating composition of claim 11, further comprising a
hydroxyl functional acrylic copolymer, an acid functional acrylic
copolymer, a glycidyl functional acrylic copolymer, an acrylamide
functional acrylic copolymer, or a mixture thereof.
13. A coating composition prepared by a method comprising reacting
an epoxidized vegetable oil with a hydroxyl functional material in
the presence of an acid catalyst to form a hydroxyl functional oil
polyol, and crosslinking the hydroxyl functional oil polyol with a
crosslinker to form the coating composition.
14. A method of coating a substrate comprising: a) preparing a
coating composition by a method comprising reacting an epoxidized
vegetable oil with a hydroxyl functional material in the presence
of an acid catalyst to form a hydroxyl functional oil polyol; b)
mixing the hydroxyl functional oil polyol with a crosslinker to
form a mixture; c) applying the mixture to the substrate; and d)
crosslinking the mixture.
15. A substrate coated with the coating composition of claim 1.
16. A coating composition comprising a hydroxyl functional oil
polyol prepared by a method comprising reacting an epoxidized
vegetable oil with a hydroxyl functional material in the presence
of an acid catalyst to form a hydroxyl functional oil polyol,
wherein the equivalent ratio of hydroxyl functionality of the
hydroxyl functional material to oxirane functionality in the
epoxidized vegetable oil is from about 0.2:1 to about 3:1.
17. The hydroxyl functional oil polyol of claim 16, wherein the
hydroxyl functional material comprises propylene glycol,
1,3-propane diol, ethylene glycol, neopentyl glycol, trimethylol
propane, diethylene glycol, a polyether glycol, benzyl alcohol,
2-ethyl hexanol, a polyester, a polycarbonate, a hydroxyl
functional polyolefin, or a mixture thereof.
18. The hydroxyl functional oil polyol of claim 16, wherein the
acid catalyst comprises a strong acid, such as sulfonic acid, a
triflic acid, a triflate salt of a metal of Group IIA, IIB, IIIA,
IIIB or VIIIA of the Periodic Table of Elements (according to the
IUPAC 1970 convention), a mixture of said triflate salts, or a
combination thereof.
19. A coating composition prepared by crosslinking the hydroxyl
functional oil polyol of claim 16 with a crosslinker to form the
coating composition.
20. A method of coating a substrate comprising: a) preparing a
coating composition by a method comprising reacting an epoxidized
vegetable oil with a hydroxyl functional material in the presence
of an acid catalyst to form a hydroxyl functional oil polyol,
wherein the equivalent ratio of hydroxyl functionality to oxirane
functionality in the epoxidized vegetable oil is from about 0.2:1
to about 3:1; b) mixing the hydroxyl functional oil polyol with a
crosslinker to form a mixture; c) applying the mixture to the
substrate; and d) crosslinking the mixture.
21. A substrate coated with the coating composition of claim 20.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to hydroxyl functional oil
polyols, coating compositions formed from the hydroxyl functional
oil polyols, methods of coating substrates with the coating
compositions, and substrates coated with the coating
compositions.
[0003] 2. Description of Related Art
[0004] Current art is primarily based on epoxy resin technology
cured with amino resins and phenolics. Coating compositions formed
from bisphenol A based epoxy resins have been used to coat
packaging and containers for foods and beverages. However, there is
a desire among some consumers and brand owners for coating
compositions free, or substantially free, of bisphenol A for
packaging and containers for food and beverages.
[0005] U.S. Pat. No. 5,728,796 discloses a process which reacts an
epoxide-containing compound with an aliphatic hydroxyl containing
compound in the presence of a sulfonic acid catalyst. This process
is used to form epoxy resins having high molecular weights.
[0006] U.S. Pat. No. 4,012,559 discloses a radiation curable
coating composition having an acrylic copolymer, a polyfunctional
compound having a molecular weight not greater than 2,000, and an
epoxidized vegetable oil. It is explained that the cured
compositions can be coated onto metal to form precoated metal
products.
[0007] Guo, et al., Rigid Polyurethane Foams Based on Soybean Oil,
Journal of Applied Polymer Science, Vol. 77, 467-473 (2000) teaches
the reaction of an epoxidized soybean oil with methanol to form an
epoxidized soybean oil polyol that is used to prepare polyurethane
foams for use in thermal insulation and packaging.
[0008] U.S. Patent Application Publication No. 2008/0302694
discloses a radiation curable coating composition having an
epoxidized vegetable oil oligomer prepared from the reaction of an
epoxidized vegetable oil and a hydroxyl functional acrylate or
hydroxyl functional methacrylate in the presence of a sulfonic acid
catalyst. This composition can be used as a coating for packaging
materials in food storage.
[0009] U.S. Pat. No. 4,212,781 discloses processes for modifying an
epoxy resin through a reaction with a copolymerizable monomer in
the presence of an initiator. A graft polymer is formed from the
epoxy resin by the grafting an addition polymer onto the aliphatic
backbone of the epoxy resin. It is disclosed that the process is
useful for making polymer blends for coating compositions.
[0010] There is a desire to produce packaging coatings that do not
contain bisphenol A or are substantially free of bisphenol A. The
hydroxyl functional oil polyols of the invention address this
desire and can be used in the preparation of coating compositions
suitable, inter alia, as packaging coatings for food and beverage
packaging and containers. They can be formulated to provide higher
solids for application and improved corrosion resistance compared
to some commercial epoxy coating systems.
SUMMARY OF THE INVENTION
[0011] The technology of the present invention has the capability
of providing better corrosion resistance and higher solids coatings
than some coatings of the current art. Higher solids allows broader
coating latitude in a single pass operation. The technology of the
present invention may also provide high molecular weight yet
un-gelled coating compositions that are excellent film formers.
[0012] The present invention includes processes for producing
hydroxyl functional oil polyols. Such processes can be performed in
a single reactor or in multiple reactors. In some embodiments of
the invention, a hydroxyl functional oil polyol is prepared by a
method comprising the step of reacting an epoxidized vegetable oil
with a hydroxyl functional material in the presence of an acid
catalyst.
[0013] The present invention also includes coating compositions
prepared from hydroxyl functional oil polyols. In some embodiments,
the coating compositions are prepared by a method comprising
reacting an epoxidized vegetable oil with a hydroxyl functional
material in the presence of an acid catalyst to form a hydroxyl
functional oil polyol, and crosslinking the hydroxyl functional oil
polyol with a crosslinker to form the coating composition.
[0014] The present invention further includes methods of coating a
substrate by mixing the hydroxyl functional oil polyol with a
crosslinker to form a mixture, applying the mixture to the
substrate, and crosslinking the mixture. Substrates coated with the
coating compositions are also included in the present invention. In
some embodiments, the substrate is a can or packaging.
DETAILED DESCRIPTION OF THE INVENTION
[0015] As used in the afore-discussed embodiments and other
embodiments of the disclosure and claims described herein, the
following terms generally have the meaning as indicated, but these
meanings are not meant to limit the scope of the invention if the
benefit of the invention is achieved by inferring a broader meaning
to the following terms.
[0016] Other than in the operating examples, or where otherwise
indicated, all numbers expressing quantities of ingredients,
reaction conditions, and so forth used in the specification and
claims are to be understood as being modified in all instances by
the term "about". Accordingly, unless indicated to the contrary,
the numerical parameters set forth in the following specification
and attached claims are approximations that may vary depending upon
the desired properties sought to be obtained by the present
invention. At the very least, and not as an attempt to limit the
application of the doctrine of equivalents to the scope of the
claims, each numerical parameter should be construed in light of
the number of significant digits and ordinary rounding approaches.
Notwithstanding that the numerical ranges and parameters setting
forth the broad scope of the invention are approximations, the
numerical values set forth in the specific examples are reported as
precisely as possible. Any numerical values, however, inherently
contain certain errors necessarily resulting from the standard
deviation found in their respective testing measurements. Unless
stated otherwise, all percentages, ratios and proportions herein
are by weight and particularly unless otherwise specifically
stated, the proportions of the components in the compositions
described are given in percentage pertaining to the total mass of
the mixture of these components.
[0017] Also herein, the recitations of numerical ranges by
endpoints include all numbers subsumed within that range (e.g., 1
to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).
[0018] Also herein, "a," "an," "the", "at least one", and "one or
more" are used interchangeably.
[0019] Also herein, the term "comprises" and variations thereof do
not have a limiting meaning where these terms appear in the
description and claims.
[0020] The terms "for example", "without limitation" and the like,
as well as the exemplary compounds, ranges, parameters and the like
disclosed throughout the application and claims are intended to
identify embodiments of the invention in a non-limiting manner
Other compounds, ranges, parameters and the like can be employed by
those skilled in the art without departing from the spirit and
scope of the invention.
[0021] The present invention includes substrates coated at least in
part with a coating composition of the invention and methods for
coating the substrates. The term "substrate" as used herein
includes, without limitation, cans, metal cans, packaging,
containers, receptacles, or any portions thereof used to hold,
touch or contact any type of food or beverage. Also, the terms
"substrate", "food can(s)", "food containers" and the like include,
for non-limiting example, "can ends", which can be stamped from can
end stock and used in the packaging of food and beverages.
[0022] The present invention includes methods for preparing
hydroxyl functional oil polyols and coating compositions having a
hydroxyl functional oil polyol by reacting an epoxidized vegetable
oil with a hydroxyl functional material in the presence of an acid
catalyst. The hydroxyl functional oil polyols can be used, inter
alia, in the preparation of packaging coatings. In some embodiments
of the invention, the hydroxyl functional oil polyols are
crosslinked with a crosslinker to form a coating composition for
food and beverage packaging and containers.
[0023] The epoxidized vegetable oil can be used alone or in
combination with other epoxidized vegetable oils. Epoxidized
vegetable oils can be prepared from vegetable oils by, for
non-limiting example, adding hydrogen peroxide and formic or acetic
acid to the vegetable oil, and then holding the mixture at an
elevated temperature until some or all of the carbon-carbon double
bonds are converted to epoxide groups.
[0024] Vegetable oils contain primarily glycerides which are
triesters of glycerol and fatty acids with varying degrees of
unsaturation. For non-limiting example, epoxidized vegetable oils
for use in the invention can be made from vegetable oils (fatty
acid triglycerides) such as without limitation, esters of glycerol
and fatty acids having an alkyl chain of about 12 to about 24
carbon atoms. Fatty acid glycerides which are triglycerides in
unsaturated glyceride oils are generally referred to as drying oils
or semidrying oils. Drying oils include, for non-limiting example,
linseed oil, perilla oil and combinations thereof, while semidrying
oils include, without limitation, tall oil, soy bean oil, safflower
oil and combinations thereof. Triglyceride oils in some embodiments
have identical fatty acid chains or alternatively have different
fatty acid chains attached to the same glycerol molecule. In some
embodiments, the oils have fatty acid chains containing
non-conjugated double bonds. In some embodiments, single double
bond or conjugated double bond fatty acid chains are used in minor
amounts. Double bond unsaturation in glycerides can be measured by
iodine value (number) which indicates the degree of double bond
unsaturation in the fatty acid chains. Unsaturated fatty acid
glyceride oils employed in some embodiments of the invention have
an iodine value greater than about 25 and alternatively between
about 100 and about 210.
[0025] Naturally occurring vegetable oils for use in the invention
can be for non-limiting example, mixtures of fatty acid chains
present as glycerides, and include without limitation a
distribution of fatty acid esters of glyceride, where the fatty
acid distribution may be random but within an established range
that may vary moderately depending on the growing conditions of the
vegetable source. Soy bean oil is employed in some embodiments
which comprises approximately about 11% palmitic, about 4% stearic,
about 25% oleic, about 51% linolenic, and about 9% linoleic fatty
acids, where oleic, linoleic and linolenic are unsaturated fatty
acids. Unsaturated vegetable oils employed in some embodiments of
the invention include without limitation, glyceride oils containing
non-conjugated unsaturated fatty acid glyceride esters such as,
without limitation, linoleic and linolenic fatty acids.
[0026] Unsaturated glyceride oils include, without limitation, corn
oil, cottonseed oil, grapeseed oil, hempseed oil, linseed oil, wild
mustard oil, peanut oil, perilla oil, poppyseed oil, rapeseed oil,
safflower oil, sesame oil, soy bean oil, sunflower oil, canola oil,
tall oil, and mixtures thereof. Fatty acid glycerides for use in
the invention include, for non-limiting example, those which
contain linoleic and linolenic fatty acid chains, oils such as
without limitation, hempseed oil, linseed oil, perilla oil,
poppyseed oil, safflower oil, soy bean oil, sunflower oil, canola
oil, tall oil, grapeseed oil, rattonseed oil, corn oil, and similar
oils which contain high levels of linoleic and linolenic fatty acid
glycerides. Glycerides can contain lesser amounts of saturated
fatty acids in some embodiments. For non-limiting example, soy bean
oil can be employed which contains predominantly linoleic and
linolenic fatty acid glycerides. Combinations of such oils are
employed in some embodiments of the invention. Vegetable oils can
by fully or partially epoxidized by known processes, such as for
non-limiting example, using acids such as, without limitation,
peroxy acid for epoxidation of unsaturated double bonds of the
unsaturated vegetable oil. Unsaturated glyceride oils employed in
some embodiments include mono-, di-glycerides and mixtures thereof
with tri-glycerides or fatty acid esters of saturated and
unsaturated fatty acids.
[0027] In some embodiments, the epoxidized vegetable oil comprises
corn oil, cottonseed oil, grapeseed oil, hempseed oil, linseed oil,
wild mustard oil, peanut oil, perilla oil, poppyseed oil, rapeseed
oil, safflower oil, sesame oil, soy bean oil, sunflower oil, canola
oil, tall oil, a fatty acid ester, monoglyceride or diglyceride of
such oils, or a mixture thereof.
[0028] Commercially available sources of epoxidized vegetable oils
are used in some embodiments of the invention such as, for
non-limiting example, epoxidized soy oil sold under the trade
designations "VIKOLOX" and "VIKOFLEX 7170" available from Arkema,
Inc, "DRAPEX 6.8" available from Chemtura Corporation, and
"PLAS-CHECK 775" available from Ferro Corp. Other epoxidized
vegetable oils for use in the invention include, for non-limiting
example, epoxidized linseed oil sold under the trade designations
"VIKOFLEX 7190" available from Arkema, Inc. and "DRAPEX 10.4"
available from Chemtura Corporation, epoxidized cotton seed oil,
epoxidized carthamus oil and mixtures thereof. Epoxidized soy bean
oil is employed in some embodiments.
[0029] In some embodiments of the invention, the hydroxyl
functional material includes, without limitation, propylene glycol,
ethylene glycol, 1,3-propane diol, neopentyl glycol, trimethylol
propane, diethylene glycol, a polyether glycol, a polyester, a
polycarbonate, a polyolefin, a hydroxyl functional polyolefin, and
mixtures thereof. The hydroxyl functional material includes an
alcohol in some embodiments such as, without limitation, n-butanol,
2-ethyl hexanol, benzyl alcohol, and the like, alone, or in
combination with diols or polyols.
[0030] In some embodiments, the hydroxyl functional material is
present in an amount from about 2:98 to about 98:2 in a weight
ratio of hydroxyl functional material to epoxidized vegetable oil,
and alternatively from about 5:95 to about 40:60. In some
embodiments, the equivalent ratio of hydroxyl functionality of
hydroxyl functional material to oxirane functionality in the
epoxidized vegetable oil is from about 0.1:1 to about 3:1. In some
embodiments, the equivalent ratio of hydroxyl functionality to
oxirane functionality in the epoxidized vegetable oil is from about
0.2:1 to about 3:1. In some embodiments, the equivalent ratio of
hydroxyl functionality to oxirane functionality in the epoxidized
vegetable oil is about 0.2:1.
[0031] The acid catalyst employed to facilitate the reaction of the
epoxidized vegetable oil with the hydroxyl functional material can
be a strong acid catalyst in some embodiments of the invention such
as, for non-limiting example, one or more sulfonic acids or another
strong acid (an acid with a pKa about 3 or less), a triflic acid, a
triflate salt of a metal of Group IIA, IIB, IIIA, IIIB or VIIIA of
the Periodic Table of Elements (according to the IUPAC 1970
convention), a mixture of said triflate salts, or a combination
thereof. In some embodiments, the amount of the acid catalyst can
range from about 1 ppm to about 10,000 ppm, and alternatively from
about 10 ppm to about 1,000 ppm, based on the total weight of the
reaction mixture. Catalysts include, for non-limiting example, the
Group IIA metal triflate catalysts such as without limitation
magnesium triflate, the Group IIB metal triflate catalysts such as
without limitation zinc and cadmium triflate, the Group IIIA metal
triflate catalysts such as without limitation lanthanum triflate,
the Group IIIB metal triflate catalysts such as without limitation
aluminum triflate, and the Group VIIIA metal triflate catalysts
such as without limitation cobalt triflate, and combinations
thereof. The amount of the metal triflate catalyst can range, for
non-limiting example, from about 10 to about 1,000 ppm,
alternatively from about 10 to about 200 ppm, based on the total
weight of the reaction mixture. Some embodiments of the invention
employ a metal triflate catalyst in the form of a solution in an
organic solvent. Examples of solvents include, without limitation,
water, alcohols such as n-butanol, ethanol, propanol, and the like,
as well as aromatic hydrocarbon solvents, cycloaliphatic polar
solvents such as, for non-limiting example, cycloaliphatic ketones
(e.g. cyclohexanone), polar aliphatic solvents, such as, for
non-limiting example, alkoxyalkanols, 2-methoxyethanol, non
hydroxyl functional solvents, and mixtures thereof.
[0032] In some embodiments, the epoxidized vegetable oil and
hydroxyl functional material are heated in the presence of an acid
catalyst to a temperature of about 50 to about 200.degree. C.
Optionally, a solvent can be included in the synthesis of the
epoxidized vegetable oil and hydroxyl functional material to help
control viscosity. In some embodiments, the solvent includes, for
non-limiting example, a ketone such as, without limitation, methyl
amyl ketone, an aromatic solvent such as, without limitation,
xylene or Aromatic 100, an ester solvent or other non-hydroxyl
functional solvent, and mixtures thereof. About 0 to about 90% of a
solvent based on the total weight reaction mixture is employed in
various embodiments of the invention, and alternatively about 5 to
about 30% is employed. After about 2 to about 3 hours, >90% of
the epoxide groups are consumed in some embodiments. Solvents
selected from those described above as well as other solvents
including, without limitation, hydroxyl functional solvents can be
added upon cooling. In some embodiments, it is desirable to have a
final NV (non-volatile content by weight) of about 30 to about
80.
[0033] In some embodiments, the hydroxyl functional oil polyol is
mixed with a crosslinker to form a curable coating composition. In
some embodiments, the mixture further includes a hydroxyl
functional acrylic copolymer, an acid functional acrylic copolymer,
a glycidyl functional acrylic copolymer, an acrylamide functional
acrylic copolymer, or a mixture thereof. A non-limiting list of
crosslinkers for use in the invention includes benzoguanamine,
benzoguanamine formaldehyde, glycoluril, melamine formaldehyde, a
phenolic crosslinker, phenol formaldehyde, urea formaldehyde, an
isocyanate, a blocked isocyanate, and mixtures thereof. In various
embodiments, the crosslinker to hydroxyl functional oil polyol
ratio is about 1:99 to about 90:10, and alternatively about 5:95 to
about 60:40. Optionally, to the mixture of the hydroxyl functional
oil polyol and crosslinker a cure catalyst can be added to enhance
cure. Cure catalysts include, for non-limiting example, dodecyl
benzene sulfonic acid, p-toluene sulfonic acid, and the like, as
well as mixtures thereof. In some embodiments, other polymers that
may blended into the coating composition, such as without
limitation, polyethers, polyesters, polycarbonates, polyurethanes
and the like, as well as mixtures thereof. Cure conditions for
packaging coatings in some embodiments are about 10 to about 60
seconds at about 500.degree. F. to about 600.degree. F., and
alternatively about 1 minute to about 20 minutes at about
250.degree. F. to about 500.degree. F. In some embodiments,
additives commonly used in formulating thermally cured coatings are
employed, such as without limitation, solvents and slip aids.
[0034] The hydroxyl functional oil polyols and the coating
compositions of the invention can include conventional additives
known to those skilled in the art, such as without limitation, flow
agents, surface active agents, defoamers, anti-cratering additives,
lubricants, heat-release additives, and cure catalysts.
[0035] The hydroxyl functional oil polyols can be used to form
thermally curable coating compositions. It is thought that the
hydroxyl functionality of the hydroxyl functional oil polyol is
reactive with conventional crosslinkers, such as melamine and
phenolic materials. Hydroxyl functional compounds that are also
(meth)acrylate functional are not preferred materials for the
preparation of hydroxyl functional oil polyols for thermal
curing.
[0036] In some embodiments of the invention, one or more coating
compositions are applied to a substrate, such as for non-limiting
example, cans, metal cans, packaging, containers, receptacles, can
ends, or any portions thereof used to hold or touch any type of
food or beverage. In some embodiments, one or more coatings are
applied in addition to the coating compositions of the present
invention, such as for non-limiting example, a prime coat may be
applied between the substrate and the coating composition.
[0037] The coating compositions can be applied to substrates in any
manner known to those skilled in the art. In some embodiments, the
coating compositions are sprayed or roll coated onto a
substrate.
[0038] For some applications, solvent borne polymeric solutions can
contain, for non-limiting example, between about 20% and about 60%
by weight polymer solids. Organic solvents are utilized in some
embodiments to facilitate roll coating or other application methods
and such solvents can include, without limitation, n-butanol,
2-butoxy-ethanol-1, xylene and other aromatic solvents and ester
solvents, and mixtures thereof. In some embodiments, n-butanol is
used in combination with 2-butoxy-ethanol-1. The coating
compositions of the present invention can be pigmented and/or
opacified with known pigments and opacifiers in some embodiments.
For many uses, including food use for non-limiting example, the
pigment can be zinc oxide, carbon black, or titanium dioxide. The
resulting coating compositions are applied in some embodiments by
conventional methods known in the coating industry. Thus, for
non-limiting example, spraying, rolling, dipping, and flow coating
application methods can be used for both clear and pigmented films.
In some embodiments, after application onto a substrate, the
coating composition is thermally cured at temperatures in the range
of about 130.degree. C. to about 250.degree. C., and alternatively
higher for time sufficient to effect complete curing as well as
volatilizing any fugitive components.
EXAMPLES
[0039] The invention will be further described by reference to the
following non-limiting examples. It should be understood that
variations and modifications of these examples can be made by those
skilled in the art without departing from the spirit and scope of
the invention.
Example 1
Preparation of Hydroxyl Functional Oil Polyol
[0040] 11.0 grams of propylene glycol, 112.0 grams of epoxidized
soy bean oil, 30.9 grams of methyl amyl ketone and 0.036 grams of
Nacure A-218 (available from King Industries) were stirred under
nitrogen and warmed to 150.degree. C. The initial exotherm was
controlled at <155.degree. C., and the mixture was held at
150.degree. C. for about 2 hours then cooled. Oxirane titration
indicated >99.9% conversion of the epoxide groups.
Example 2
Preparation of Hydroxyl Functional Oil Polyol
[0041] 50.9 grams of diethylene glycol and 150 grams of epoxidized
soy bean oil were added to a 1 liter flask. 0.02 grams of Nacure
A-218 (available from King Industries) was added to the flask at
20.degree. C. and the mixture was stirred under nitrogen and warmed
to 160 .degree. C. The initial exotherm was controlled at <165
.degree. C., and the mixture was held at 160 .degree. C. for about
3 hours. Oxirane titration indicated >99.9% conversion of the
epoxide groups. 50.3 grams of butyl cellosolve was added on cool
down to give 80% NV.
Example 3
Preparation of Hydroxyl Functional Oil Polyol
[0042] 50.0 grams of neopentyl glycol and 150 grams of epoxidized
soy bean oil were added to a 1 liter flask. 0.02 grams of Nacure
A-218 (available from King Industries) was added to the flask at
20.degree. C. and the mixture was stirred under nitrogen and warmed
to 160.degree. C. The initial exotherm was controlled at
<165.degree. C., and the mixture was held at 160.degree. C. for
about 3 hours. Oxirane titration indicated >99.9% conversion of
the epoxide groups. 50.3 grams of butyl cellosolve was added on
cool down to give 80% NV.
Example 4A
Preparation of Hydroxyl Functional Oil Polyol
[0043] 185.500 grams of propylene glycol, 812.450 grams of
epoxidized soy bean oil and 0.206 grams of Nacure A-218 (available
from King Industries) were stirred under nitrogen and warmed to
150.degree. C. (141 grams of propylene glycol remained as unreacted
solvent). The initial exotherm was controlled at <155.degree.
C., and the mixture was held at 150.degree. C. for about 2 hours
then cooled. Oxirane titration indicated >99.9% conversion of
the epoxide groups.
Example 5
Preparation of Hydroxyl Functional Oil Polyol
[0044] 150.0 grams of epoxidized soy bean oil, 36.8 grams of
trimethylol propane, and 46.7 grams of methyl amyl ketone were
added to a 1 liter flask. 0.02 grams of Nacure A218 (available from
King Industries) was added to the flask at 20.degree. C. and the
mixture was stirred under nitrogen and warmed to 150.degree. C. The
initial exotherm was controlled to 153.degree. C., and the mixture
was held at 150.degree. C. for about three hours, then cooled.
Oxirane titration indicated >99.9% conversion of the epoxide
groups.
Example 6
Preparation of Glycidyl Functional Acrylic Copolymer
[0045] 1253 grams of butyl cellosolve was charged to a five liter
glass flask and heated and stirred under nitrogen to 110.degree. C.
A mixture of 450 grams of glycidyl methacrylate, 525 grams of butyl
acrylate, 525 grams of methyl methacrylate, and 75 grams of
tertiary butyl peroctoate was added over a period of three hours,
while the flask contents were maintained at 110.degree. C. An
additional 197 grams of butyl cellosolve was then added to the
flask, while the temperature was allowed to fall to 95.degree. C. A
mixture of 150 grams of butyl cellosolve and 25 grams of tertiary
butyl peroctoate was then added over 30 minutes. The flask was then
held at 95.degree. C. for 60 minutes, and then cooled.
Example 7
Preparation of Coating Composition
[0046] A blend was made consisting of 76.14 pounds of the resin
from Example 5; 57.9 pounds of the resin from Example 6; 85.7
pounds of RSO199, a phenolic resin available from Cytec Industries;
17.04 pounds of Santolink EP560, a phenolic resin available from
Cytec Industries; 10.7 pounds of Cymel 27-809, a benzoguanamine
resin available from Cytec Industries; 6.06 pounds of Lanco Glidd
TPG 087, a dispersion of carnauba wax in solvent available from
Lubrizol Advanced Materials; 4.6 pounds of a dispersion consisting
of 30 parts of MPP-620XF, a polyethylene wax available from Micro
Powders, Inc, in 70 parts of butyl cellosolve; 0.387 pounds of
Coroc A-620-A2, an acrylic flow agent available form Cook
Composites and Polymers; and 16.4 pounds of butyl cellosolve.
* * * * *