(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

(19) World Intellectual Property

Organization
International Bureau

(43) International Publication Date (1()) International Publication Number

30 September 2004 (30.09.2004) PCT WO 2004/083310 Al

(51) International Patent Classification7 . C08L 91/06 CO, CR, CU, CZ, DE, DK, DM, DZ, BC, BE, EG, ES, Fl,
GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KB, KG,
(21) International Application Number: KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK,
PCT/US2004/007777 MN, MW, MX, MZ, NA, M, NO, NZ, 0M, PG, PH, PL, m,
RO. RU, SC, SD, SE, SG. SK, SL, sy, TJ, TM, TN, TR, TT, TZ,
[JA, UG, UZ, VC, VN, W, ZA, ZM, ZW.
(22) International Filing Date: 12 March 2004 (12.03.2004)
(84) Designated States (unless otherwise indicated, for every
(25) Filing Language: English kind of regional protection available): ARIPO (BW, GH,
GM, KB, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZM, ZW),
(26) Publication Language: English Eurasian (AM, AZ, BY, KG, KZ, MD, W, TJ, TM), European
(AT, BE, BG. CH, cy, CZ, DE, DK, BE, ES, H, FR, GB, GR,
(30) Priority Data: HO, 1B, IT, LU, MC, NL, PL, P'l*, RO, SE, Sl, SK, TR), OAPI
10/388,548 17 March 2003 (17.03.2003) US (BF, BJ, CE CG, Cl, CM, GA, GN, GQ, GW, ML, MR, NE,
SN, TD, TG).
(71) Applicant: HRD CORP. [US/US]•, P.O. Drawer 450267, Declarations under Rule 4.17:
Houston, TX 77245 (US). as to applicant's entitlement to apply for and he granted a

Published:

Rock Avenue, East Hanover, NJ 07936 (US). with international search report

(72) Inventors: HASSAN, Abbas; 2 Wedgewood Court, Sugariand, TX 77478 (US). BORSINGER, Gregory; 17 Pem- patent (Rule
4.17(ii))for all designations brooke Road, Chatham, NJ 07928 (US). as to the applicant's entitlement to claim the priority of
the earlier application (Rule 4.17(iii))for all designations
(74) Agent: ADAMS, Thomas, P.O. Box 340, 120 Eagle

(81) Designated States (unless otherwise indicated, for every For two-letter codes and other abbreviations, refer to the
"Guidkind of national protection available): AE, AG, AL, AM, ance Notes on Codes and Abbreviations " appearing at the
beginAT. AU, AZ, BA, BB, BG, BR, BW, BY, BZ, CA, CH, CN, ning of each regular issue of the PCT Gazette.

(54) Title: AQUEOUS WAX EMULSIONS AND THEIR COATING APLICATIONS

The effects of coating citrus fruit a

war:-based •rnulsion on •ne eiøht loss
 wo 2004/083310 PCT/US2004/007777

1
Day 0 Day 3 Day4 Day 7 Day 1 1 Day 12 Day 15
Treated with soy wax
Untreated

Dayo Dayg Day4 Day7 Day 1 1 Day 1 2 Day 1 5

Soy wax treatnnent 0.0% 2.9% 4.0% 6.2% 8.5% 10.9%

(57) Abstract: Waxes prepared from hydrogenated plant oils, such

as castor, palm, and soybean, are used Untreated 0.0% 2.9% 4.2% 6.8% 10.7% 12.8% to prepare water based emulsions.
The inventive waxes, obtained from naturally derived, renewable
resources, were emulsified under anionic, cationic and nonionic
conditions, producing emulsions having a solids content up to about 45% solids. When used to coat fibrous cellulosic articles, such
as paperboard, the emulsions' performance was similar to emulsions containing petroleum-derived waxes. The inventive waxes
have a low iodine value (between 2-5), and melting points between approximately 120-200 degrees F (Mettler Drop Point).

O These waxes comprise a triglyceride whose fatty acids are perdominantly stearic acid or ricinoleic acid. The inventive waxes arc
use as an alternative to petroleum-derived, or expensive naturally-occurring waxes in the manufacture of emulsions used in
coatings, polishes, adhesives. paper products, paperboard and other manufacturing operations.

AQUEOUS WAX EMULSIONS AND THEIR COATING APPLICATIONS

BACKGROUND OF THE INVENTION

5 1 . Field of the Invention

Emulsions prepared using a wax derived from vegetable sources are used
in a variety of applications, such as to coat fibrous cellulosic products, such as
paper and wood, to render them moisture-resistant, and could be used with
gypsum sheet goods. These emulsions are used as fruit coatings to improve
O moisture resistance. The emulsions comprise water, the vegetable wax and a surface-
active agent. The vegetable waxes, derived from sources such as castor oil, palm
or soybeans, comprise triglycerides with a melting point ranging about 1 36-200
degrees F. The solids content of the emulsions can be as high as 45% solids,
based on the total weight of the emulsion.
5
2. Description of Related Art
Wax based emulsions are used in numerous industrial applications, for
example, for coating fibrous cellulosic products, such as paper, corrugated cardboard,
kraft paper, boxboard and the like, to impart moisture resistance to o the product.
Wax emulsions usually comprise between about 1 5% to 40% (by weight) wax, and
with from about 5% to 25% surface-active agent added based on the weight of the
 wo 2004/083310 PCT/US2004/007777

wax. Emulsions are used in lieu of applying molten wax because of their ease of
handling, application and ability to formulate with other aqueous based ingredients.
Once prepared, an emulsion may remain stable (i.e., it will not separate into its
components) over a prolonged period of time. This stability facilitates factors such as
shipment of the emulsion from manufacturer to the end-user, storage, and its use in
particular applications By contrast, application of molten wax requires that the wax be
melted as needed, maintaining it in a molten state, and applying it in a molten state.
Wax emulsions are typically manufactured either in batch reactors or with
the use of a homogenizer. It is important that the equipment used to prepare
emulsions be capable of effecting agitation of the reactants to achieve thorough
mixing, and have proper temperature controls to maintain adequate heating and
cooling of the reagents and the products. In general, use of a homogenizer has
been known to effect a higher percentage of solids in the final emulsion product
5 than that obtained with emulsions prepared using mixing in conventional stirred
batch reactors. Both types of equipment have been used successfully to
manufacture the emulsions of the present invention.
It is desirable to utilize an emulsion that has as high a content of wax
solids as practical for certain applications. For example, where goods such as o paper
products, fruits or pharmaceuticals are treated with a wax, it is desirable to minimize
the drying time of the treated product, and one way to achieve this end is with the use
of an emulsion having a high wax solids content. In those instances where the
emulsions must be transported over long distances, reducing the volume amount helps
to reduce transportation costs. Water based
5 emulsions are also preferable to organic solvent based emulsions (or dispersions) of
wax, because of the potential to pollute the environment or adversely affect
health and safety.
Wax based emulsions are typically formulated to have a certain ionic charge,
usually to render the emulsion compatible with other ingredients to be
20 formulated with the wax emulsion at a later time. Wax emulsions can be either
anionic, nonionic or cationic depending upon the emulsifier, generally a
surfaceactive agent such as a surfactant, used to make the wax emulsion.
Waxes that are to be emulsified must have some functionality such as
carboxyl, acid or ester groups attached to the wax polymer. In the process of
25 emulsification these functional groups are saponified to render them more
hydrophilic, thus allowing the selected surfactant to form a micelle around the
 wo 2004/083310 PCT/US2004/007777

3
wax. Bases that are commonly used to saponify functional groups of the wax
include potassium hydroxide (KOH), sodium hydroxide (NaOH) and amines such
as ammonia, diethyl amine ("DEA") and other amine derivatives. For the
30 preparation of certain emulsion types, acids, such as glacial acetic acid or similar acids,
are utilized for functional group modification. The quantity of
 wo 2004/083310 PCT/US2004/007777

4
functional groups that need to be modified in order to form a stable emulsion
can vary depending on characteristics of the wax such as its molecular weight
and amount of chain branching. Generally, a wax with a minimum saponification
value of about 20-30 mg KOH/g wax can be readily emulsified.
5 The saponification value, or number, represents the quantity, in milligrams of KOH
which react with one gram of wax under elevated temperatures, and indicates the
amount of free carboxylic acid plus any esters which may be saponified. This value, and
the acid number, described below, provide an indication of the free carboxylic acid and
ester content of the wax. ASTM o DI 387 is an example of how a saponification number
is determined. The ASTM DI 386 represents a method to determine the acid number;
the quantity, in milligrams, of KOH necessary to neutralize one gram of wax, indicating
the amount of free carboxylic acid present.
A common first step in the emulsification process is to dissolve the wax
5 (by heating where necessary) and add sufficient base to saponify the desired number
of functional groups on the wax. Surfactant is then added and the emulsion is
allowed to form under good agitation. If a homogenizer is used in
manufacturing the emulsions the shearing action of the homogenizer also
affects the resulting particle size of the wax emulsion. The saponification of the
20 wax becomes less critical when emulsions are prepared using a homogenizer
because of the contributions of mechanical shearing of the wax. In general, the
most stable emulsions (generally having the smallest particle sizes) are
produced with a combination of saponification with good mixing.
Parameters that usually characterize the quality of the emulsion once it
25 has been formed include the clarity and stability of the emulsion. Stability is
generally measured as the degree of separation of the emulsion into its
component phases over time.
Hardness, defined by ASTM DI 321 and ASTM D-5, relates to the distance
(in tenths of a millimeter, dmm) that a specified needle penetrates a
30 wax under a given weight at a given temperature. A "'soft" wax has hardness
properties of > 10 mm of penetration, and are considered to be "less" useful,
while waxes having hardness values of < 10 mm penetration are considered to
be more useful in these preparations..
 wo 2004/083310 PCT/US2004/007777

5
The color of a particular wax preparation varies from batch to batch,
even of the same wax. Factors such as the rate of cooling of the wax, the
quantity
5 of occluded air, and the surface finish affect the overall color of a solidified wax
preparation. Generally, the color of a wax is determined on a molten wax preparation,
using either the ASTM DI 500 (Gardner) or the ASTM DI 56 (Seybolt) method. The
ASTM DI 500 method is generally used to measure dark-brown to off-white colors,
while the ASTM DI 56 is used for measurement o of off-white to pure white colors.
For applications such as coating of foods, or of pharmaceutical tablets, it
is desirable to use waxes that are characterized by having low penetration
hardness, and good color characteristics (towards the white end of the color
scale as opposed to the brown end).
1 5 Wax emulsions are often used by themselves, or in combination with other
ingredients when coated onto paper, paperboard, linerboard, or other paper
products to render it moisture resistant. Food items, such as fish, or vegetables
such as broccoli, for example, are often packaged and shipped in paper boxes
that are coated with wax. The wax coating helps to maintain the
20 strength and integrity of the package when it encounters a moist environment, such
as the presence of ice in the package, transportation in refrigerated vehicles, and
refrigerated storage environments. Other properties, such as the gloss, slip resistance
and printability on or of the finished paper product, depending on the end use
application, also are affected by a wax coating. Once 25 the wax coated packaging has
been used, it is generally discarded.
There is an increasing trend, both domestically and internationally, to
recycle paper products once the packaged item is used and the wax-coated
packaging has been disposed by the consumer. However, in the recycling
process the wax coating on the packaging tends to form what is known in the
30 industry as "stickies" and "tackies'% whose presence causes problems in the
recycling equipment. This problem has become so prevalent that in some
localities wax coated paper products are required to be excluded from the
recycling process. Consequently, the wax-coated articles are segregated, and
 wo 2004/083310 PCT/US2004/007777

6
instead of being recycled, are sent either to be incinerated or disposed of in
landfills. Alternate techniques have been proposed and used to rninilTlize wax
5 contamination of the recycling process, including the use of additives added to the
wax, (U.s. Pat. Nos. 6,255,375 and 6,273,993 to Michelman; U.S. Pat. No. 6,41
6,620 to Narancic et al.; and U.S. Pat. No. 6,053,439 to Locke et al.). None of
these approaches has been universally accepted as a solution to the problems
associated with wax in the recycling process.
Oil companies such as CITGO, ExxonMobil, Shell Oil and others are
among the commercial sources for waxes derived from petroleum Most of
these waxes are derived in the process of refining lube oil, where the wax is
separated from the lube oil stock and refined into various wax fractions,
including paraffins and microcrystalline waxes. Additional commercial sources
5 of waxes include formulators such as Astor Wax, IGI and Moore & Munger, who
supply wax for prior art applications; these axes are often either resold "as is" from the
oil companies, and/or formulated and repackaged to meet specific customer needs.
Other commercial suppliers, such as Michelman (Ohio) and ChemCore (New York),
often referred to as 'l emulsion houses" convert various waxes into emulsions which
are used for coating and other applications.
The prior art describes using petroleum-derived waxes and synthetic
waxes for incorporation into emulsions, but does not mention using vegetablederived
waxes in emulsions. Given that the world's oil supply is finite, and is being depleted,
there is a recognized and long-felt need to find alternatives to petroleum-derived
products, such as petroleum waxes, that are derived from limited natural resources
whose supply is being diminished. Because wax emulsions are frequently used in food
packaging applications, it is also desirable for the wax to have food grade properties for
safety. There is also a recognized and long-felt need to use materials in emulsions that
are naturally derived and can be easily recycled back into the environment without
long-term adverse effects; corrugated cartons having wax-based coatings and
adhesives, for example, are known to be difficult to recycle. Therefore, there is a need
for employing a wax, which has similar properties of petroleum derived or synthetic
waxes used in emulsion formulations. Due the large volume of waxes consurned in
these applications it is also preferred that the cornpositions be
 wo 2004/083310 PCT/US2004/007777

7
5 readily available. From both a supply and a natural resource viewpoint, it is preferred
that the compositions be obtained from a source that preferably is renewable, such as
from plant extracts. Thus it is desirable to have a wax that does not have to be
imported, and which can be produced at a cost that is competitive with that of
petroleum-derived waxes, such as the paraffins and o microcrystalline waxes.
There is a need for a wax that can be converted into anionic, cationic or
nonionic emulsions, has a relatively high melting point, low viscosity, has good
moisture barrier properties and is thermally stable. It is also desirable to have a
wax that can be obtained from a renewable source, such as plants, rather
5 than being petroleum based because of the previously discussed world's petroleum
supply. The waxes used in the present invention meet these requirements.
The present invention relates to emulsions prepared using a vegetable
wax comprising triglycerides, and having a melting point of from about 1 36-200 o
degrees F (50 — 95 degree C). These wax emulsions are used in a variety of
applications including coating paper and wood, in polish and cosmetic applications, in
inks, paints and adhesives; and in fruit coatings and in gypsum products to improve
moisture resistance.
The present invention relates to a family of waxes derived by
hydrogenating one or more vegetable oils. When hydrogenated to a high degree the
properties of the oils are modified and become wax — like, having high melting points,
low viscosities and good hardness. The waxes of the present invention are unique in
that they also possess a high degree of functional groups. By modifying a portion of the
functional groups on the present waxes they can be readily emulsified. Additionally it
has unexpectedly been discovered that the waxes of the present invention can also be
readily recycled due to the
 wo 2004/083310 PCT/US2004/007777

8
treated goods makes emulsions containing them suitable for use in textile
applications where the lubrication and or sizing properties of the wax may be
needed, such as in the process of fiber spinning and or fabric weaving, yet their
removal is desirable at a later stage such as dying or de-sizing. The
5 biodegradability of the novel waxes makes them particularly suitable for discharge
to waste treatment plants capable of handling natural organic materials.
Application of the novel vvax emulsions to fruit has also been shown to have
beneficial properties through their ability to reduce moisture loss and extend
produce shelf life.
The present invention describes natural waxes which are used to
formulate emulsions. The waxes are commercially available, high triglyceride
waxes, derived from the processing of natural oil-containing commodities such
as soybeans, palm, castor, canola and other crops from which oil can be
obtained. Vegetable oils having differing degrees of hydrogenation are used in
5 the food industry. For purposes of cooking oils, unsaturated oils are preferred. The
highly hydrogenated waxes employed in the present invention, while commercially
available, are not widely produced or used because of their limited applications in the
food industries. The waxes used in the present invention are commercially available.
Materials are processed and supplied by Archer Daniels Midland (Decatur Ill.)
designated by their product number 86-1 97- O, Cargill Incorporated (Wayzata, MN)
designated by their product number 800mrcsOOOOu and other sources under a generic
name 'hydrogenated soybean oil'. Palm oil wax was supplied by Custom Shortenings &
Oils (Richmond, VA) and was designated as their product Master Chef Stable Flake-P. A
mixture of hydrogenated castor oil and soy wax was also obtained from the Abitec
Group (Columbus, OH, a blender and formulator of vegetable oil derived waxes), sold
under the STEROTEXO trademark.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a wax composition that
can be formulated into water based wax emulsions.
7
 wo 2004/083310 PCT/US2004/007777

ability to further saponify the functional groups on the wax thereby rendering
the wax more hydrophilic. Yet another unexpected discovery is the ability of the
saponified waxes to help separate out inks and adhesive trash during the recycling
process due to the relatively low density of the waxes and their ability 5 to float and
carry the ink, adhesive and trash with the wax.
The wax emulsions are comprised primarily of water, a surface-active
agent (which will be either cationic, nonionic or anionic, depending upon the properties
desired for the particular emulsion) and either an acid or a base (often chosen from
KOH, NaOH, or one of a variety of amines. Other ingredients such o as biocides or
stabilizers may be added, as are well known to those versed in the art. Biocides, and/or
antimicrobial agents may be added to the emulsion, the choice of a particular biocide or
antimicrobial often being dependent upon the end use of the emulsion. Parabens such
as methyl or ethyl hydroxy parabenzoic acid, or quaternary ammonium compounds, are
among the biocides 5 which may be used, other compounds being known to those
skilled in the art.
Because the waxes used in the preparation of the present invention are
naturally occurring, readily available, generally regarded as safe and have relatively high
melting points with good hardness and color, they can be used in lieu of less desirable
synthetic waxes (often derived from petroleum, such as 20 polyethylene) or in lieu of
other less available naturally occurring waxes, such as, for example only, montan or
carnauba.
Additionally, the waxes employed in the present invention can be readily
removed from articles to which they have been applied, such as boxboard and
paper. This removal is effected under what are considered to be normal
25 conditions for paper recycling (dispersal in a warm alkaline aqueous mixture with
agitation), because these waxes have been readily modified. Further, the present
inventors have found that because of the relatively low density of the waxes
employed in the present invention, that separation of inks and other trash
during the paper recycling process are enhanced as the wax floats away from
30 the paper, carrying inks and other recycling trash with it for easy skimming and
removal in a paper recycling process. The ease of removal of these waxes from
Another object of the present invention is to provide a series of emulsions,
prepared using vegetable derived waxes, that are stable.
 wo 2004/083310 PCT/US2004/007777

10
Another object of the present invention is to provide a wax based
emulsion which can be subsequently applied to articles such as paper,
5 paperboard, linerboard, other cellulosic articles and the like, to render them
moisture resistant for use in packaging for consumer and other industrial
applications.
Still another object of the present invention to provide a composition
that can be incorporated into wax based emulsion formulations as a substitute for o
petroleum-derived waxes currently used in many such formulations.
Another object of the present invention is to provide a composition that
when incorporated into wax based emulsion formulations, is compatible with
the other components of the formulations and forms a stable emulsion.
Still another object of the present invention is to provide a composition,
5 which when formulated into an emulsion used for coating paper or other cellulosic
goods, and which coating formulation is applied to an article for the purpose of
rendering the coating moisture resistant, the coating has coating performance
characteristics similar to that of a conventional wax based emulsion formulation
prepared utilizing petroleum-derived wax.
Yet another object of the present invention is to provide a composition
which can be derived from a renewable resource in place of non-renewable
petroleum based compositions.
Still another object of the present invention is to provide a
naturallyderived composition which is more economical to use, and thus can replace
other naturally occurring, but more expensive and less available waxes, such as
carnauba, in applications involving the coating of cellulosic goods and other products.
Still another object of the present invention is to provide a
naturallyderived composition which is more economical to use, and thus can
replace
30 other naturally occurring, but more expensive and less available waxes, such as
carnauba, in applications involving the coating of fruits in order to reduce
 wo 2004/083310 PCT/US2004/007777

11
moisture loss and extend the shelf life of produce.
Still another object of the present invention is to provide a composition
which can be derived from a renewable resource and which can be
economically produced.
5 Another object of the present invention is to provide a composition for use with food
packaging and coatings and vvhich has properties that are generally regarded as
safe by the Food and Drug Administration.
The present inventors have unexpectedly discovered that highly
hydrogenated oils such as palm and soybean can be converted into a wax that o can be
used effectively as substitutes for conventional petroleum and synthetic waxes in the
formulation of wax based emulsion compounds.
The present invention comprises highly hydrogenated vegetable oils
(derived from sources such as palm, soybean, corn, castor, canola or others)
that have wax-like properties and which can be formulated into water
emulsions
5 using conventional methods of emulsification, to produce emulsions having barrier
and coating characteristics similar to emulsion formulations containing petroleum-
derived waxes. The inventive waxes, obtained from naturally derived, renewable
resources, were emulsified under anionic, cationic and nonionic conditions, producing
emulsions having a solids content up to about 45% solids. The soy and palm waxes
consist essentially of a hydrogenated oil that comprises > 90% triglyceride, and whose
fatty acid components include palmitic acid and stearic acid, with stearic acid (C 18),
being the most predominant ( > 50%). The castor wax, by contrast, contains about 1 %
stearic acid, ricinoleic acid being its major component (approximately 90%). The wax
25 compositions have a low iodine value (between 2-5), and melting points between
approximately 1 20-1 85 degrees F (Mettler Drop Point). The wax compositions
of the present invention can also be used as an additive (as a coating) in the
manufacture of fibrous cellulosic products, such as wax coated boxes, which can
then be recycled more readily than boxes prepared using
30 conventional waxes. When used to coat fibrous cellulosic articles, such as
paperboard, the emulsions' performance was similar to emulsions containing
petroleum-derived waxes. The wax emulsions of the present invention can also
 wo 2004/083310 PCT/US2004/007777

12
be used by itself or in combination with other ingredients as a coating to reduce
moisture loss or to increase the shelf life of foodstuffs such as fruits or other
produce. The inventive waxes are used as an alternative to petroleum-derived,
5 or more expensive naturally-occurring waxes in the manufacture of emulsions used
in coatings, polishes, adhesives, paper products, paperboard and other
manufacturing operations.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 is a flow chart illustrating a process for the manufacture of
hydrogenated oils.
Fig. 2 illustrates the effects of coating citrus fruit with a soy wax-based
emulsion on weight loss.

5 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention relates to emulsions prepared using a wax
composition derived from plants, which can be used as an alternative to waxes derived
from petroleum. More particularly, the present invention describes wax to water
emulsions, prepared with a wax composition derived from plants. Because the waxes
used in the present invention can be economically produced from a renewable source,
they can also substitute for certain naturally occurring, but more expensive to produce,
waxes, coatings containing petroleum derived or synthetic waxes or properties from
less available naturally occurring waxes such as carnauba (see Table 3), in various
applications that will 25 be described herein.
Naturally occurring and synthetic waxes are extensively used in a wide
cross-section of industries including, for example but not limited to, cosmetics,
foodstuffs, tubricants, personal hygiene, pharmaceuticals, and polishes for
consumer and industrial use, such as floor polish. Additional uses include textile
30 softening and sizing, fruit coating, water based inks and paints, coating of
construction materials such as gypsum, particleboard, paper products such
as
 wo 2004/083310 PCT/US2004/007777

13
corrugated cardboard, boxboard, linerboard, laminates, and fertilizer coating.
The term wax is used to denote a broad class of organic ester and waxy compounds,
which span a variety of chemical structures and display a broad range of melting
temperatures. Often the same cornpound may be referred to as either a "wax," "fat"
or an "oil" depending on the ambient temperature. By whatever name it is called, the
choice of a wax for a particular application is often determined by whether it is a liquid
or solid at the temperature of the product with which it is to be used. Frequently it is
necessary to extensively purify and chemically modify a wax to make it useful for a
given purpose. Despite such efforts at modification, many of the physical
characteristics of waxes still prevent them from being used successfully or demand
that extensive, and oftentimes, expensive, additionai treatments be undertaken to
render them commercially useable.
Triglycerides are fatty acid esters of glycerol. As will be used herein, the
5 term "free fatty acid" will refer to a fatty acid that is not covalently bound through
an ester linkage to glycerol. The term "fatty acid component" will be used to
describe a fatty acid that is covalently bound through an ester linkage to glycerol.
Naturally occurring carboxylic acids ("fatty acids") and their derivatives,
O most commonly the glyceryl derivatives in which all three hydroxy groups of the
glycerol molecule are esterified with a carboxylic acid, are used commercially.
The carboxylic acids may be saturated or unsaturated. The tri-substituted
glycerols (triglycerides, also referred to as triacylglycerols) are major components
of most animal and plant fats, oils and waxes. When all three
5 hydroxy groups of a glycerol molecule have been esterified with the same fatty acid,
it is referred to as a monoacid triglyceride. Whether one refers to triglycerides as
"waxes,' "fats, " or "oils" depends upon the chain lengths of the esterified acids and
their degree of saturation or unsaturation as well as the ambient temperature at
which the characterization is made. Generally, the O greater the degree of saturation
and the longer the chain length of the esterified acids, the higher will be the melting
point of the triglyceride.
Many commercially utilized triglycerides and free fatty acids are obtained
preferably from plant sources, including soybean, canola, cottonseed, corn,
 wo 2004/083310 PCT/US2004/007777

14
cranbe, linseed, palm, peanut, safflower, soy and sunflower oils. The
triglycerides are used after they have been refined using methods known to
5 those skilled in the art, such as, but not limited to, the solvent extraction of plant
biomass using aliphatic solvents to obtain plant triglycerides. Subsequent
additional purification may involve distillation, fractional crystallization,
degumming, bleaching and steam stripping. The triglycerides obtained are
partially or fully hydrogenated. Furthermore, fatty acids may be obtained by
O hydrolysis of natural triglycerides (e.g., alkaline hydrolysis followed by purification
methods known in the art, including distillation and steam stripping) or by
synthesis from petrochemical fatty alcohols. Free fatty acids, triglycerides and
the like may also be obtained from commercial sources, such as Cargill, Archer
Daniels Midland and Central Soya.
5 In the present invention. the free fatty acids and fatty acid components of the
triglycerides are saturated, and have various chain lengths. The free fatty acids
and fatty acid components of the triglycerides may be unsaturated, provided
that the coating composition will be a solid at the temperature at which the
coating is used. The properties of the free fatty acid/triglyceride
O mixture, such as melting point, varies as a function of the chain length and degree of
saturation of the free fatty acids and the fatty acid components of the triglycerides. For
example, as the degree of saturation decreases, the melting point decreases. Similarly,
as the chain length of the fatty acids decreases, the melting point decreases. Preferred
free fatty acids are saturated fatty acids, 5 such as palmitic acid, oleic acid, stearic acid,
arachidic acid and behenic acid. Stearic acid (a CIB saturated fatty acid) is further
preferred. Ricinoleic acid ((9Z, 1 2R)-1 2-Hydroxy-9-octadecenoic acid) is a hydroxy,
unsaturated CIB fatty acid. Ricinoleic acid is the major component of castor oil and
castor 'uvax, which contain minor concentrations of oleic, linoleic and palmitic acids, as
will be described further below.
The iodine value ("I.V."), also referred to as the iodine number, is a
measure of the degree of saturation or unsaturation of a compound. The iodine
value measures the amount of iodine absorbed in a given time by a compound or
mixture. When used in reference to an unsaturated material, such as a vegetable oil,
the IV is thus a measure of the unsaturation, or the nunnber of 5 double bonds, of that
compound or mixture.
 wo 2004/083310 PCT/US2004/007777

15
Vegetable oils or animal fats can be synthetically hydrogenated, using
methods known to those skilled in the art, to have low or very low iodine values. Fats
naturally composed primarily of saturated triglycerides (such as palm oil or fractionated
fats) can be used alone or in blend formulations with o adhesives/laminants to achieve
an enhanced water tolerance for composite materials (US Patent 6,277,310), The major
components of plant oils are triacylglycerols.
Saturated triglycerides having a low iodine value (ranging from iodine
values of about O - about 70, with an iodine value of about O — about 30 being
5 preferred) may be produced by hydrogenation of a commercial oil, such as oils of
soybean, soy stearine, stearine, corn, cottonseed, rape, canola, sunflower, palm, palm
kernel, coconut, crambe, linseed, peanut, fish and tall oil; or from fats, such as animal
fats, including lard and tallow, and blends thereof. These oils may also be produced from
genetically engineered plants to obtain low IV oil with a high percentage of fatty acids.
Fats are commonly fractionated by a process known as "winterization" ,
wherein the mixture is chilled for a period of time which is long enough to allow the
harder fractions of the fats to crystallize. This chilling is followed by filtration, with the
harder fractions being retained on a filter cake. These harder fractions have a lower
iodine value and, therefore, a melting point that is higher than the melting point of the
fat from which it has been separated. Hence, winterization can also be used as a source
for lower IV fats.
The winterization process is generally used to fractionate animal fats, and
can thus produce a variety of animal fat fractions, having differing iodine values and
consequently, differing chemical properties. These fractions can be blended with fatty
acids and free fatty acids obtained from other sources, such as plant
or vegetable extracts referred to above.
Wax based emulsions are routinely used in the manufacture of
corrugated cartons, boxes and the like. They are also used in diverse areas, such
as floor polish, textile softening and sizing, fruit coating, cosnnetic formulations,
water
5 based inks and paints, gypsum manufacture and fertilizer coating. In many of these
applications the moisture vapor barrier properties of the wax are critical to
performance. It has been shown that the waxes of the present invention have
comparable moisture vapor barrier properties to that of paraffin wax (See Table
 wo 2004/083310 PCT/US2004/007777

16
5).
Emulsions are used at varying concentration and addition levels depending
on the application. In fruit coating applications for example the wax may
comprise a majority of the formulation that often also includes shellac to give
gloss to the fruit. In paper applications, or for use with other fibrous cellulosic
products, wax based emulsions can be used neat, i.e., without dilution, or may
5 be diluted if incorporated into a coating or sizing formulation. The ionic charge that is
desirable is usually related to the application. In textiles, for example, cationic wax
emulsions have a greater affinity to the fiber or fabric than anionic or non-ionic
emulsions, and cationic emulsions are generally used to aid in wax pick up of the fiber /
fabric. Surfactants, or surface-active agents, also called emulsifiers, can include nonyl
phenol ethoxylates and other ethoxylates available from commercial suppliers.
Examples include alcohol ethoxylates, alkylamine ethoxylates, alkylphenol ethoxylates,
octylphenol ethoxylates and the like. Other surfactants, such as a number of fatty acid
esters may be employed; for example, but not limited to, glycerol esters,
polyethyleneglycol esters and sorbitan esters and also amidated fatty esters such as
tallow amine.
Nonionic surfactants which can be employed include nonylphenyl
ethoxylates, such as sold under the IGEPAL@ trademark (Rhodia, Inc., Cranbury
NJ), such as IGEPALOCO-630 (CAS No. 6841 2-54-4) or POLYSTEP O F-3
(Stepan Co., Northfield, IL); alkylphenol ethoxylates; octylphenol ethoxylates,
such as [GEPAL@ CA series compounds; decyl phenol ethoxylates; oleyl alcohol
ethoxylates; NONIDET NP-40 (CAS No. 901 6-45-9) and the like. TOMADOL@
25-3/25-9 combination to HLB 10.5 (Tomah Chemical Corp. Milton, WI, a
mixture of ethoxylated linear alcohol nonionic surfactants) or TERGITOL@ 1 5-
S5/1 5-S-9 combination to HLB 1 0.5 (Dow Chemical, Midland Ml) are other
nonionic surfactants which may be employed..
5 Generally, the surfactant to be used will have a specific range of HLB values, and
other surfactants with similar properties can be substituted therefor.
Cationic surfactants include imidazolines, diethyl amine, or
ethoxylated amines, such as tallow amine TAM-5 or TAM-1 5. The surfactant to
 wo 2004/083310 PCT/US2004/007777

17
be used will have a specific range of HLB values, and other surfactants with
similar 1 0 properties can be substituted therefor.
Certain surfactants, used for removal of ink from paper, include those of
the ANTAROX@ (Rhodia Inc., Cranbury NJ) group. These compounds include nonionic
dispersants, ethylene oxide-propylene oxide copolymers, nonylphenolethylene oxide-
propylene oxides, and poloaxomers. Companies such as ONDEO 1 5 Nalco of
Naperville, Illinois also supply custom blended surfactants tailored to meet the ink
removal and repulping needs of specific customers.
The present invention relates to emulsions prepared using a vegetable
wax comprising triglycerides, and having a melting point of from about 1 36-200
degrees F. The present invention employs a hydrogenated triglyceride where
20 the iodine value is close to zero thereby rendering the triglyceride more thermally
stable. The triglycerides can be chosen from those having an iodine value of
between O — 30, but a triglyceride having an iodine value of between 2-5 is
preferred.
The wax emulsions are comprised primarily of water, a surface-active
25 agent (which will be either cationic, nonionic or anionic, depending upon the
properties desired for the particular emulsion) and either an acid or a base
(often chosen from KOH, NaOH, or one of a variety of amines, as previously
described.
Other ingredients such as biocides or other stabilizers can be added to the
emulsions, and these agents are known to those skilled in the art. Biocides,
30 and/or antimicrobial agents may be added to the emulsion, the choice of a particular
biocide or antimicrobial often being dependent upon the end use of the
emulsion. Parabens such as methyl or ethyl hydroxy parabenzoic acid, or
quaternary ammonium compounds, are among the biocides which may be used,
other compounds are known to those skilled in the art. Buffering agents and
thickeners, also known to those skilled in the art, nnay be added to the
5 emulsions of the present invention. Common preservatives such as formaldehyde are
sometimes used and the subject of regulatory agencies such as the Food and
Drug Administration and Environmental Protection Agency.
 wo 2004/083310 PCT/US2004/007777

18
Because the waxes used in the preparation of the present invention are
naturally occurring, readily available, generally regarded as safe and have o relatively
high melting points with good hardness and color, they can be used in lieu of less
desirable synthetic waxes (often derived from petroleum, such as polyethylene) or in
lieu of other less available naturally occurring waxes, such as, for example only,
montan or carnauba.
The present invention is a natural wax for use in wax based emulsion
5 formulations. The product is a commercially available high triglyceride wax derived
from the processing of natural oil-containing commodities such as soybeans, palm,
castor, canola and other crops from which oil can be obtained. The waxes used in the
present invention are a palm oil wax and a soybean wax and combihations of these
with castor wax prepared from hydrogenated oil. The materials are processed and
supplied by Cas Chem (Bayonne, NJ), Archer Daniels Midland (Decatur Ill.) designated
by their product number 86-1 97- O; Cargill Incorporated (Wayzata, Mn) designated by
their product number 800mrcsOOOOu; and other sources under a generic name
'hydrogenated soybean oil'. Palm oil wax was supplied by Custom Shortenings & Oils
(Richmond, Va) and was designated as their product Master Chef Stable FlakeP. The
soybean wax is also distributed by Marcus Oil and Chemical Corp., Houston, TX
under the designation Marcus Nat 155; these waxes can also be used as food
additives.
The properties of the soy and palm waxes are summarized in Tables 1
and 2, where it can be seen that these waxes have IV's of between 5 and 2,
respectively.
The soybean oil wax has a melting point, as measured by Mettler Drop
Point, of between 1 55-1 60 degrees F, while that of the palm oil wax is
between 1 36-142 degrees F.
The palm and soy waxes are further characterized by having a viscosity
5 of between 1 0-200 cps at a temperature of 210 degrees F,
The palm and soy waxes each comprise 98 % triglyceride by weight with
trace amounts of fatty acids. The triglyceride can be saponified through the addition of
a base such as KOH to yield a saponification value. Saponification values will vary
depending mainly upon the chain length of the fatty acid, which o itself is a function of
 wo 2004/083310 PCT/US2004/007777

19
the source of the vegetable wax. For hydrogenated soy and palm wax the
saponification value is usually in the 180 — 200 mg KOH/g range (Tables 1 and 2).
When the palm and soy waxes were analyzed for their fatty acid content
using known methods of Gas Liquid Chromatography ("GLC"), the soybean wax
5 was found to comprise between 82-94 % stearic acid (C18:o) and between 3-1 4 %
palmitic acid (C16:o). By comparison, the palm oil wax comprises approximately
55 % stearic acid (C 18-0), 39.5 % palmitic acid (C 16-0), myristic acid
(C14:o) and approximately 1 .0 % oleic acid (C18-1).
Castor wax is derived from castor oil in much the same was as the soy
and palm waxes are prepared from their respective oils. Castor oil is a natural oil
obtained from the seed of the castor plant. It is unique among all fats and oils in that it
is the only commercially important oil comprised of approximately 90% ricinoleic acid
((9Z,1 2R)-1 2-Hydroxy-9-octadecenoic acid, a hydroxy, unsaturated C 18 fatty acid
having a double bond in the 9-1 0 position and a hydroxyl group on the 12th carbon).
The fatty acid composition of castor oil is described as 87% ricinoleic acid, 7% oleic acid,
3% linoleic acid, 2% palmitic acid, 1 % stearic acid, and trace amounts of dihydrostearic
acid (The Merck Index , 1 edition, 2001, Merck & Co. Inc, Whitehouse Station NJ). India,
China and Brazil are the primary sources of castor oil. Scientific and historical records
reveal that regardless of origin, its chemical nature and composition are remarkably
uniform.
Castor wax, also referred to as hydrogenated castor oil, is catalytically
hydrogenated castor oil (hydrogenation of castor oil in the presence of a nickel
catalyst). Castor wax is a hard, brittle wax that is extremely insoluble in water
and in commonly used organic solvents, known to those skilled in the art. The
5 wax has a melting point of about 84 — 88 degrees C (approximately 183 — 1 85
degrees F.) , nd is characterized by having an acid number of 2-3 (mg KOH/g), a
saponification number of about 1 74-1 86 (mg KOH/g), and an iodine number of
3-4 (Table 3).
Castor wax has been used in the preparation of coatings that are either
O water —repellant, or resistant to oils, petroleum and petroleum derivatives. While a
major use of castor wax is in manufacturing greases, it is also used in paper coatings for
food packaging and cosmetic applications, and derivatives of castor wax are used as
surfactants and plastics additives. Note the difference in stearic acid contents among
 wo 2004/083310 PCT/US2004/007777

20
these waxes, the palm and soy waxes having 1 5 between 84-92% stearic acid, while
about 1 % stearic acid is present in castor wax.
Although the present invention has been described with a certain degree
of particularity, it is to be understood that the examples below are merely for
purposes of illustrating the present invention, the scope of the present
invention
20 intended to be defined by the claims.

PREPARATION OF EXAMPLES

Example 1 . Preparation and Evaluation of Nonionic Emulsions Comprising Soy 25

Wax and Prepared Using a Homogenizer.
For the purpose of illustrating the invention a nonionic emulsion was
prepared utilizing Marcus Nat 1 55 Wax (Soybean wax). The emulsion was
prepared using two atmospheric vessels, one to melt the wax and emulsifiers
blend and the other to heat the water to temperature. Once melted and the
30 water brought up to temperature, the wax-emulsifiers blend is combined with the
heated water at the appropriate temperature. The mixture is homogenized
using an APV / Goullin Homogenizer, an apparatus that is typically used in both
the chemical and dairy industries. After homogenizing, the product can be cooled by a
heat exchanger or other vessel. The homogenizer allows for more aggressive mixing
and a higher solids emulsion than can be obtained using 5 standard mixing techniques.

Ingredients addition (grams)

Marcus NAT 1 55 wax (Soy) 20.0 gm 30.0 gm 40.0 gm

Nonionic Surfactant 5.0 gm
(Target HLB 1 1 so-1 2.0)
Potassium Hydroxide (45% KOH) 0.01 gm 0.01 gm 0.01 gm
Water to 25% solids 35% solids 45%solids

5 Procedure
1 ) Charge water and set agitation for good movement without vortex.
 wo 2004/083310 PCT/US2004/007777

21
2 Heat water charge to 70-80 degrees C.
3 Charge Marcus NAT 1 55 Wax
4 Add Nonionic Surfactant.
0 5) Add Potassium Hydroxide (45% KOH).
6) Hold the mixture at 70-80 degrees C for 30 minutes.
7) Maintain agitation and cool to 50 degrees C.
8) Discharge through homogenizer set at 3000 psi (secondary
500/primary 2500)
5 (Note that the emulsion temperature and viscosity will be increased during discharge
from the homogenizer).
9) Cool material to 30-35 degrees C by use of a heat exchanger or a
second vessel
(Viscosity of emulsion will be reduced by cooling to 30-35 degrees C).

In this Example, the nonionic surfactant employed was IGEPAL O CO-

630
(Rhodia Inc, Cranbury, NJ). The surfactants are chosen such that the
surfactant possesses an HLB in the range of 1 1-1 2, or as indicated as the
"target HLB". The HLB properties of surfactants are known to those skilled in the
art, and will not be discussed further. Therefore, other surfactants having the
desired 5 characteristics can be used instead of IGEPAL@ CO-630. Examples of
such alternate surfactants have been described previously in this specification.
The resulting emulsions were milk colored and stable. When viewing the
emulsion on a glass slide it appeared uniform to the eye, and only minor
amounts of non-emulsified wax particles were observed.
10

Exam le 2. Pre aration and Evaluation of Cationic Emulsions Com risin So

Wax.
For the purpose of illustrating the invention a cationic emulsion was
prepared utilizing Marcus Nat 1 55 Wax (Soy-based). The emulsion was
 wo 2004/083310 PCT/US2004/007777

22
1 5 prepared using two atmospheric vessels, one to melt the wax and emulsifiers blend
and the other to heat the water to temperature. Once melted and the water brought
up to temperature, the wax- emulsifiers mixture is combined together with the heated
water at temperature. This technique for emulsification is commonly known to those
versed in the art as a wax to water technique, and utilizes a standard mixing
technique to prepare the emulsion

The reagents used were:

Marcus NAT 1 55 Wax (Soy) 30.0 gm
Cationic Surfactant
25 Tallow Amine Ethoxylate (TAM-5)
Glacial Acetic Acid
Water 61 .6 gm

Final water charge to 35% Solids

Procedures
1) Melt Marcus 1 55 Wax, cationic surfactant at 60-70 degrees C.
2) Heat 1 st water charge to 55-65 degrees C.
3) After 1 st water charge is at temperature, add Glacial Acetic Acid 5
to the melt from step 1 .
4) Transfer molten wax, cationic surfactant and acid mixture to
heated water.
5) After all material is transferred, mix 30 minutes.
6) Cool to 30-35 degrees C.
[0 7) Add water to achieve a final concentration of 35% solids.
The resulting emulsions were milk colored and stable. When viewing the
emulsion on a glass slide it appeared uniform with only minor amounts of non
emulsified wax particles observed.
15
Example 3. Preparation and Evaluation of Nonionic Emulsions Comprising Soy
Wax.
 wo 2004/083310 PCT/US2004/007777

23
For the purpose of illustrating the invention a nonionic emulsion was
prepared utilizing Marcus Nat 1 55 Wax (Soy-based). The emulsion was prepared
20 using two atmospheric vessels, one to melt the wax and emulsifiers blend and the
other to heat the water to temperature. Once melted and the water brought up
to temperature, the wax emulsifiers mixture is combined together with the
heated water at temperature. As in Example 2, this technique for emulsification
is commonly known to those versed in the art as a wax to water technique
25
Ingredients
Marcus NAT 1 55 Wax (Soy) 20.0 gm
Nonionic Surfactant (Target HLB 10.5)
Potassium Hydroxide (45% KOH) 0.05 gm
30
Water to 25% Solids
Procedures
1) Charge water and set agitation for good movement without vortex.
2) Heat water charge to 70-80 degrees C. 3)
Charge Marcus NAT 1 55 wax.
5 4) Add Nonionic Surfactant.
5) Add Potassium Hydroxide (45% KOH).
6) Hold at 70-80 degrees C for 30 minutes.
7) Cool to 30-35 degrees C as soon as possible and maintain good
agitation.
In this Example, the nonionic surfactant used was IGEPAL O CO-630
(Rhodia). The resulting emulsions were milk colored and stable. When viewing
the emulsion on a glass slide it appeared uniform with only minor amounts of
wax particles observed.
15

Exam le 4. Pre aration and Evaluation of Cationic Emulsions Com risin a So

Wax and Castor Wax Blend.
 wo 2004/083310 PCT/US2004/007777

24
Certain end use applications, such as floor polishes, textiles, coatings
and inks, for wax emulsions often require the wax emulsions to be made
with a wax
20 having a higher melting point than waxes used in applications such as cosmetics.
For the purpose of illustrating the invention, a cationic emulsion was prepared utilizing
Marcus NAT 1 80 Wax, which is a blend of 30% casto lr wax and 70% soy wax. The
castor and soy waxes were prepared by hydrogenating castor oil and soy oil to a low
iodine value similar to the soy wax preparations 25 already described herein. The
blended castor and soy wax is characterized by the following properties:

Acid Value 1 .0 max mg/g

Iodine value 5.0 max cg/g
Melt point 1 80-1 85 F (82-85 C)
30 1 85-1 95 (mg/g)
Saponification Value

The material as described above is also available from Abitec Performance

Products under the trademark STEROTEX@ K and is typically used in the
pharmaceutical industry to coat tablets.
The emulsion was prepared using two atmospheric vessels, one to melt 5
the wax and emulsifiers blend and the other to heat the water to temperature. Once
melted and the water brought up to temperature, the wax / emulsifiers / alkali is
combined together with the water at temperature. This technique for
emulsification is commonly known to those versed in the art as a wax to water
technique

Ingredients 2

Marcus NAT 180 Wax 30.0 gm 30.0 gm

Cationic Surfactant
Tallow Amine Ethoxylate (TAM-5)
5 Tallow Amine Ethoxylate (TAM-1 5)
Glacial Acetic Acid
Water
 wo 2004/083310 PCT/US2004/007777

25

Final water charge to 35% Solids 35% Solids

Procedures
1 ) Melt Marcus NAT 180 Wax, and the cationic surfactant, at 85-90

degrees C.

2) Heat 1 st water charge to 90-95 degrees C.

st
3) After 1 water charge is at temperature, add Glacial Acetic Acid to the
melt from step 1 .
4) Transfer molten wax, cationic surfactant and acid mixture to heated
water.
5) After all material transferred, mix 30 minutes.
6) Cool to 30-35 degrees C.
7) Add sufficient water to adjust the solids content to 35% solids.

The resulting emulsions were milk colored and stable. When viewing the
ennulsion on a glass slide it appeared uniform with only minor amounts of wax 5
particles observed.

Example 5. Preparation and Evaluation of Nonionic Emulsions Comprising a Soy.

Wax and Castor Wax Blend.
Nonionic emulsions are extremely versatile due to their wide range of
o compatibility and the availability of readily available and relatively innocuous
surfactants with which they can be prepared. To test whether a blend of
vegetable oil derived waxes could be emulsified in a nonionic formulation, the
soy-castor wax formulation, described in Example 4, was formulated into an
emulsion as follows:
5
Ingredients
Marcus NAT 1 80 Wax 20.0 gm
Nonionic Surfactant (Target HLB 1 0.5)
 wo 2004/083310 PCT/US2004/007777

26
Potassium Hydroxide (45% KOH) 0.05 gm

Water to 25% Solids

Procedures
1 ) Charge water and set agitation for good movement without vortex.
2) Heat water charge to 90-95 degrees C.
3) Charge Marcus NAT 1 80 wax.
4) Charge Nonionic Surfactant(s).
5) Charge Potassium Hydroxide (45% KOH).
6) Hold mixture at 90-95 degrees C for 30 minutes.
7) Cool to 30-35 degrees C as soon as possible and maintain good agitation.
In this Example, the nonionic surfactant employed was IGEPAL O CO-630 (Rhodia).
Among the other nonionic surfactants that could be utilized include:
TOMADOL@ 25-3/25-9 combination to HLB 10.5 (Tomah Chemical Corp.) or
TERGITOLO 1 5-S-5/1 5-S-9 combination to HLB 10.5 (Dow Chemical,
Midland

The resulting emulsions were milk colored and stable. When viewing the
emulsion on a glass slide it appeared uniform with only minor amounts of wax
particles observed.

o Example 6. Preparation and Evaluation of Nonionic Emulsions Comprising a Soy Wax

and Castor Wax Blend and Prepared Using a Homogenizer.
The use of a homogenizer (as used in Example 1) for the preparation of
an emulsion generally allows for a higher solids loading of the emulsion than
can be obtained using conventional stirring techniques, such as those
employed in
5 Examples 4 and 5 above. To test whether a stable emulsion could be prepared
using a blend of castor and soy waxes, an emulsion was prepared as follows:
 wo 2004/083310 PCT/US2004/007777

27
Ingredients

Marcus NAT 180 Wax 20.0 gm 30 gm 40

gm
Nonionic Surfactant (Target HLB 1 1 .0-1 2.O) 5.0 gm 5 gm 5 gm
Potassium Hydroxide (45% KOH) 0.01 gm 0.01 gm 0.01
gm

Water to 35% 45%

solids solids solids
Procedure
1 ) Charge water and set agitation for good movement without vortex.
2 Heat water charge to 90-95 degrees C.
3 Charge Marcus NAT 1 80 Wax.
4 Charge Nonionic Surfactant(s).
5 Charge Potassium Hydroxide (45% KOH).
6 Hold at 85-90 degrees C for 30 minutes.
7 Maintain agitation and cool to 50 degrees C.
8 Discharge through homogenizer set at 3000 psi (secondary 500/primary
5 2500)
(Note emulsion temperature and viscosity will be increased).
9) Cool material to 30-35 degrees C by use of heat exchange or second vessel
(Viscosity of emulsion will be reduced by cooling to 30-35 degrees C).

In this Example, the nonionic surfactant used was IGEPAL@ CO-630

(Rhodia). The resulting emulsions were milk colored and stable. When viewing
the emulsion on a glass slide it appeared uniform with only minor amounts of
wax particles observed.
5
Example 7. Moisture Vapor Transmission Rate ("M VTR")
 wo 2004/083310 PCT/US2004/007777

28
Moisture transmission is an important property of wax-based coatings.
The MVTR indicates how rapidly moisture would penetrate the wax coating and
degrade the properties of the substrate. It is desirable to have a low MVTR in
10 cartons containing produce, where excessive moisture would cause spoilage of the
fruits or vegetables. Poultry is often shipped in freezer boxes, which are generally wax
coated corrugated boxes (kraft paper coated with wax) that are packed with poultry
(or other food item) and then rapidly chilled, often by immersion in a ice/water bath..
If the paper were not protected from the water, the strength of the box would
degrade, making the use of these kinds of boxes impractical.
In this experiment MVTR was tested by a modified ASTM D3833 method.
The modification required the use of clamps to assure adhesion of the
linerboard to the aluminum cup.
Coatings were made using a wet film applicator (Bird type) with a 1 .5 to
5 mil gap depending on the viscosity of the test wax. The coating, the 4 inch
wide applicator and sheets of lh inch thick plate glass were placed into a 200 to
250 degrees F oven for 1 0-1 5 minutes. The glass was removed from the oven
and strips of the linerboard (unbleached kraft paper, as known to those skilled
in the art) were placed onto the glass. A volume of the specific coating
5 was placed at one end of the linerboard, the applicator applied to the linerboard
and the hot molten coating drawn by hand to coat the linerboard, which was
then allowed to solidify at ambient temperature. Each sample was tested to
assure a coat weight in the range of 5.6 to 6.2 lbl/1 000 square feet.
The results are summarized in Table 5, which illustrates that while the
[ 0 coating weights were comparable; the soybean oil wax composition resulted in
MVTR levels comparable to that of the control preparation. Although the
evaluations were not conducted with application of the wax as an emulsion,
the results are indicative of the ability of the wax coating to reduce moisture
transmission.
15
Example 8. Evaluation of Emulsions Comprising Vegetable Wax as a Fruit Coating.
Wax emulsions are often used to coat food products to reduce their
moisture loss during transportation, storage, and delivery to the ultimate
 wo 2004/083310 PCT/US2004/007777

29
20 consumer, and thus help preserve products, such as citrus fruit. To test the novel
emulsion's effectiveness in reducing moisture loss in citrus fruit, an emulsion
was prepared according to the following formulation and procedure, the
emulsion then used to coat fruit, which was subsequently monitored for
weight loss over a period of time.
25 Fifteen (1 5) grams of Marcus Oil & Chemical (Houston, TX) NAT 1 55 Wax (soy wax)
was placed in a 400 ml SORVALLO (Norwalk, Conn.) stainless steel chamber and melted
on an electric hot plate until clear. To the molten wax was added 1 gm of POLYSTEP O F-
5 nonylphenol ethoxylated (1 2 moles Ethylene Oxide) (Stepan Company Northfield, Ill.)
and 1 gm of a 30% KOH solution. The mix was kept molten and agitated for 30 min.
Separately, 50 gm tap water was heated to boiling. The boiling water was added to the
hot molten
wax mixture and immediately inserted into a SORVALL O Omni-mixer
homogenizer equipped with a SORVALL@ model no. 1 71 83 rotor-knife agitator. The
mixer speed was set to 0.5. After Imin 30 sec. the chamber was placed in cold tap
water and allowed to cool while still under agitation. Following 5 cooling to ambient
temperature the resulting emulsion appeared fluid and opaque. This emulsion was
designated Soy Wax Emulsion #1 .
Twenty-three (23) grams of Soy Wax Emulsion #1 was added to 230
grams of tap water and mixed until uniform. This diluted emulsion was
designated as Coating #1 . Citrus fruit, specifically lemons, were purchased
1 0 from a local vendor. Three of the lemons were then immersed in Coating #1 for 30
seconds, then removed and placed atop beakers where they were allowed to dry. After
8 hours, three uncoated lemons, designated as Untreated Control Lemons and the three
coated lemons, designated as Treated Lemons, were weighed and this weight was
designated as the initial weight (WI) for the 5 experiment.
The lemons were placed in a cool (temperature between approximately
65 70 degrees F) dry room and weighed periodically. The average results for the three
Untreated Control and three Treated Lemons are shown in Fig. 2. After 1 2 days the
Untreated Control Lemons showed signs of spoilage and were no longer weighed.
The Treated Lemons showed no signs of spoilage after 15 days, whereupon the
experiment was terminated. The weight of each lemon during this period was
 wo 2004/083310 PCT/US2004/007777

30
recorded, and designated as W X, where X is the weight of the lemon on a particular
day. The difference between the experimental weight (WX) and the initial weight (WI)
was the weight loss, which was then calculated as a percent of the initial weight,
and the per cent of weight loss plotted as a function of time.
The data in Fig. 2 shows that the novel emulsion was able to reduce
moisture loss of the Treated Lemons from 12.8% to 9.2%, thereby effecting a
28% reduction in weight loss.
Example 9. Repulping Tests.
To test the feasibility of repulping the wax-coated paper samples, one
and one half liter (1 .51) of hot (approximately 120 degrees F) tap water was
placed in the chamber of an OSTERIZERO Model 6641 Blender (Registered
5 Trademark of Sunbeam Corp. Ft. Lauderdale, FL). To this was added 3.98 grams of
sodium carbonate. The blender was set on low speed and run for one minute to
dissolve the sodium carbonate. The aqueous solution had a pH of approximately 10.
Then 5 grams of wax coated linerboard sample (prepared as described in Example 7
above) was added to the water. The blender was run for o ten minutes and then
stopped briefly to determine whether sample pieces had stuck to the sides of the lid,
and if so, such pieces were removed from the lid, and added back to the water in the
blender. The blender was then turned back on for an additional 10 minutes to
complete the blending cycle. Immediately upon completion, 500 ml was poured off
and diluted with an additional 500 ml
5 of hot (approximately 1 20 degrees F) water. The diluted solution was poured into a
quart jar. The samples were then subjectively compared to the Control Wax sample
(Control wax used was CITGO BLEND-KOTE O 467, a paraffin wax derived from
petroleum, CITGO Petroleum Corporation, Tulsa, OK), the number and size of particles
present in the liquid being determined as described in Table 4.
The results of this evaluation are shown in Table 4. The Marcus Oil palm
wax had the best repulping results, the linerboard sample treated with it producing
almost no particles evident and the coating all but disappearing into the repulping
solution. The MVTR of this preparation (Table 6), although higher than the control, is
considered low and within the acceptable range for most food packaging applications.
 wo 2004/083310 PCT/US2004/007777

31
The soybean wax sample produced fewer small particles than the
control wax but many more particles than the palm wax in the repulping experiment.
The CITGO control wax, as expected, had a very large number of small particles
evident.
Although the repulping tests in this Example were conducted using a
molten wax, the results are indicative of results that would be achieved had the
coating been applied in the form of an emulsion (as will be shown in Example
10, below).

5 Example 10. Renulping and Wet Strength Testing of Emulsion-Coated

Paperboard.
Samples of corrugated paperboard were obtained, coated with a soy
wax emulsion, and the repulpability of the emulsion-coated paperboard was
determined.
The test emulsion was prepared using the following formulation:

Ingredient
Marcus Nat 1 80 Wax (mixture comprising
70% hydrogenated soy wax and
5 30% hydrogenated castor oil wax).
POLYSTEP@ F-3 ethoxylated nonyl phenol surfactant
(Stepan Chemical, Chicago, IL)
KOH (50% solution) 0.025 gm Water 50 gm.

The wax was melted by immersion in a water bath set to 205 degrees F,
the emulsion prepared by adding the KOH solution, surfactant and 50 grams of hot
water into a SORVALLO Mixer (mix speed set to 2) and agitating for 1 5 min followed by
rapid cooling in a tap water bath while continuing to agitate. 5 The resultant emulsion
was a stable, pourable milky emulsion. POLYSTEP@ F-3@ is a nonionic surfactant
having an HLB in the range of 1 0-1 2.
 wo 2004/083310 PCT/US2004/007777

32
Paperboard, specifically a corrugated box (200# 'C' flute, Kraft
corrugated with edge crush of 321b/in) was cut into pieces, each piece being 3
cm by 8 cm, and the pieces weighed. The weighed pieces were dried in an o
oven set at 90 degrees C for 30 min to dry.
Six pieces (three designated A, treated and three designated C, control)
were dipped in the emulsion for 5 min. The pieces appeared completely
saturated. Three other pieces of paperboard (designated B, untreated) were
kept as untreated samples. The six treated pieces (A and C) were removed from
the emulsion and were allowed to drain. All samples were placed into an
5 oven set to 90 degrees C for 1 hour. Weights were recorded as follows:

Sample Initial Weight Weight after applying Wax Pick

Weight after Drying emulsion & Dry Up
corrugated

o A - treated 4.3g 4.0g 4.9g o.9g

B- 4. 1 g

untreated 3.8g blank 0.0g

C - control 4. 1 g 3.7g 4.5g o.8g

To replicate repulping conditions, each of the dried samples were mixed with 80
5 ml tap water, 3 ml POLYSTEP@ F-3 and KOH added to produce a pH of
approximately 9. The samples were heated to 60 degrees C and mixed in a SORVALL O
mixer set to #3 speed for 5 min. Each sample was filtered through a paper filter (20
micron pore size), rinsed with warm tap water (3 rinses, each rinse approximately
200ml). The rinsed pulp was placed in an oven at 90 o degrees C for 8 hr to dry.
Once dried, 3 gm of pulp from each sample was taken and mixed with 40
ml of xylene (a known solvent for Marcus NAT 180 wax). The xylene soaked pulp
was placed in an oven at 80 degrees C for 30 min and then mixed well and
allowed to settle for 30 min. Thirteen (1 3) gm of supernatant xylene
5 was decanted from each beaker, placed in a weighed beaker, then on a hot plate
and the solvent allowed to volatize. The Control samples (samples of emulsion
 wo 2004/083310 PCT/US2004/007777

33
coated corrugated paperboard) were prepared and put through xylene
extraction without first having been repulped.
The results, shown below, indicate that the wax was removed from the
paper as a result of the washing with warm alkaline water and surfactant. The
control indicates the approximate amount of wax that would have been
present had it not been removed in the repulping process.

5 SAMPLE Residual after drying

A - treated (wax)

B - untreated (no wax)

C - Control (wax) 0.3g

The treated samples
were observed to be noticeably stiffer than the untreated samples. To test whether
the emulsion coating affected the wet strength properties of corrugated board,
additional treated and untreated samples were prepared as described in this Example
above, but not subjected to the repulping conditions. All samples were immersed in
room temperature
5 water for 1 min, the samples then placed on a scale and a 3/8 inch diameter rod
placed perpendicular to the paper and the force needed to crush the
corrugated board was measured.
The results, shown below, indicate that the novel emulsions aid in
increasing the crush strength for wet corrugated board.

Sample Crush strength (grams)

Treated > 1000
Untreated 100-120
5 Example 1 1 . RepulQing of Wax and Newsprint.
The paper stock used in this evaluation was the US News, a paper
lcnown in the industry to be manufactured using a high percentage of
secondary fiber. Because the paper is manufactured using a high content of
 wo 2004/083310 PCT/US2004/007777

34
recycled paper, wax-coated paper stock is often mixed with uncoated paper
stock. Unless the
O wax is removed, the wax causes problems in the reprocessed paper. Among the
problem are spotting of the paper, and effects on the gloss, and printability of the paper.
The following evaluation shows that the waxes of the present invention
can be readily dispersed under normal repulping conditions and also illustrate the 5
additional benefit resulting from saponifying the triglyceride wax into a soap, thereby
further aiding repulping.
A 10 % solids paper solids stock (1 0 gm paper and 90 gm water) was
made by using a high-speed mixer. This paper stock was used as the control pulp
stock. A series of mixtures was prepared by adding either an emulsion o prepared with
one of the vegetable waxes, or by addition of a surfactant known to be effective in
removing ink from paper. The emulsions or surfactant were added to a concentration
of either 0.5% or 1 .0%, based on the weight of the bath (i.e., based on the total
weight of the paper stock). Each emulsion was added from a product comprising 30%
active, while the surfactant was added
5 from a stock comprising 45% actives (ethylene oxide and propylene oxide).

The following mixtures were made and evaluated for ink removal:
A. Control (no additives),
B. 1 Marcus NAT 1 55 (Soy wax) Direct Emulsion product comprising 30%
solids (final concentration of actives = 0.3%).
C. 0.5% Marcus NAT 1 55 (Soy wax) Direct Emulsion product comprising 30%
solids (final concentration of actives = 0.15%).
D. 1 Marcus NAT 180 (Soy wax-castor oil wax blend) Direct Emulsion product
comprising 30% solids (final concentration of actives = 0.3%).
E. 0.5% Marcus NAT 180 (Soy wax-castor oil wax blend) Direct Emulsion product
comprising 30% solids (final concentration of actives = O. 15%).
F. 1 De-inking Surfactant (45% actives, Ethylene oxide and propylene oxide).

In this Example, the de-inking surfactant was Nalco D12221 , a propylene

oxide alcohol ethoxylated supplied by ONDEO Nalco of Naperville, Illinois. This
 wo 2004/083310 PCT/US2004/007777

35
surfactant had been developed specifically for deinking applications. The
mixtures were stirred for 10 minutes. As will be described further in this
Example, the mixtures containing emulsions prepared with the waxes
necessitated adjusting the pH of the reaction mixture to pH 7.5 to 8.0, using
5 a sodium hydroxide solution. The paper slurries were then washed to float the ink off
of the paper, and the paper samples examined for whiteness using the Hunter
Whiteness scale, as known to those skilled in the art.
The results, shown below, indicate that both of the NAT waxes
outperformed the de-inking surfactant (Nalco D12221 ) at the lower o concentrations
(0.5%). However, samples made with the NAT 180 wax (70% hydrogenated soy wax and
30% hydrogenated castor wax) required the processing temperature to be raised to 1
60-175 degrees F to improve the solubility of the base wax.

A second series of experiments was performed to determine if the NAT

5 SAMPLE Whites Numbers 5 waxes performed better than
(Hunter
Whiteness) the control de-inking surfactant
Control because of a greater rate of ink
41
removal from the paper. In this
0.5% NAT 1 55 63 experiment, samples
0.5% NAT 1 80 64 containing the inventive
1 .0% NAT 1 55 65 wax compositions effected ink

1 .0% NAT 1 80 removal within the first 5

62
minutes of processing compared
De-Inking Surfactant 52
to the de-inking surfactant
(Nalco D12221 ) which required 8 minutes of processing to obtain its' best
results.
The emulsions used in the mixtures described above were prepared with
emulsions made using a pH of 6-7 during the emulsification process.
An emulsion was prepared using the Marcus NAT 155 (Soy) using a pH of
approximately 7.8 during the emulsification process, and a sample of this emulsion
tested for its ability to remove ink from newsprint as described earlier in this Exarnple.
These data showed the best results were obtained using an 5 emulsion which was
 wo 2004/083310 PCT/US2004/007777

36
prepared with the process pH between 6.0-7.0, and adding alkali during the de-inking
slurry process to adjust the pH to 7.5-8.0.

Example 12. Effects of pH and Temperature on Repulpability of Paper Stock.

In this Example, a stock paper with no finish applied was employed (a o
finish is a starch and or starch and clay based coating typically applied to writing
paper). The paper stock is commonly referred to in the gift-wrapping industry as #1
white wrapping tissue and has a basis weight of 10 lbs per 1 000 square feet of paper.
Its source was Federal Paper Board Company, Inc., (Montvale, NJ).
5 Replicate samples of this paper stock were treated with an emulsion prepared with
the Marcus NAT 1 80 (soy wax-castor oil wax blend, comprising 30% solids and
prepared using IGEPAL@ CO-630 nonionic surfactant), such that the samples had a
final concentration of 0.5%, 1 .0%, and 1 .5% add-on of solids. No additional surfactant
was added to the repulped mix and the pH for the samples measured between 7.5
and 8.0. The coated paper stock was air dried at 250 degrees F. After drying, the
coated paper stock was re-pulped using a high-speed blender, and compared with a
control sample of untreated stock.
The results of this study showed that samples treated with the lower
level (0.5%) of wax achieved a pulp at a normal viscosity within 20 minutes, compared
to the control (untreated paper stock) that required 42 minutes. Sodium hydroxide
was added to raise the pH to 7.5-8.0, and no additional heat was applied. A process
temperature of 1 70-1 80 degrees F was achieved, the heat being generated from the
high speed mixing of the reaction mixtures. The sample prepared with a high level of
NAT 1 80 wax (1 .5%) showed a process time of 1 8 minutes.
 wo 2004/083310 PCT/US2004/007777

37
These results indicated that emulsions containing the NAT 180 (soy wax-
castor wax blend) or NAT 1 55 (soy) waxes would aid in the re-pulping process, when
present on the paper at a low level (between 0.5 1 .5%) with the pH adjusted to
convert the natural wax to a mild soap. The degree of 5 change, as shown in the
differences in the time needed to effect a pulp, is considered to be significant.
Obviously, many modifications and variations of the present invention
are possible in light of the above teachings. It is therefore to be understood that
within the scope of the appended claims, the invention may be practiced o otherwise
than as specifically described.
wo 2004/083310 PCT/US2004/007777
38

Table 1 : Typical properties of Hydrogenated Soybean Oil

(Archer Daniels Midland (Decatur Ill.) designate by its prod. no. 86-1 97- O)
Property Lvpical analysis
Lovibond Red Color 2.0 max
Saponification 1 80 mgKOH/g
Viscosity 60SUS @ 210F
Hardness (needle penetration) 2dmm @77F

% FFA Max.* 0.10 max

Flavor Min. Characteristic
P. V. Mil eq/kg/max. 1 .0max
8.0 min
Specific gravity (H20 1) 0.92
% Moisture max. 0.05 max
2.0 max
Iron (ppm) 0.3 max
Soap (ppm) 3.0 max.
Nickel (ppm) 0.02 max
Copper (ppm) 0.05 max.
Phosphorous (ppm) 15.0 Max
Residual Citric Acid (ppm) 15.0 max
Mettler Drop Point (F) 155-1 60

Typical Fatty Acid Composition (by GLC)

3.0 max
3-14

82-94
wo 2004/083310 PCT/US2004/007777
39

C20:o 5 max
* FFA: Free Fatty Acids. ** F.l.: Flavorlndex no. of carbon atoms:no.
of double bonds (e.g., 18:2 refers to linoleic acid palmitic acid (1 6:0),
stearic acid (1 8:0), oleic acid (1 8: 1 ), arachidic acid (20:0) and behenic
acid (22:0)

Table 2: Typical properties of Hydrogenated Palm Oil

(Custom Shortenings & Oils (Richmond, Va) product Master Chef Stable
Flake-P.)

Property Typical analysis

Lovibond Red Color 4.0 max
%Free Fatty Acids Max. 0.10 max
Flavor Min. Bland
Iodine Value. by R.I. 5.0 max
Mettler Drop Point 1 36-1 42
Saponification 185 mgKOH/g
Viscosity 65 SUS @210 F
Hardness (needle penetration) 2-3 dmm @ 77F
Typical Fatty Acid Composition (by
GLC)
C8:o * 0.3% max
c 1 0:0 0.3 max
c 1 2:0 0.5% max
C 14:0 1 .1 % max
39.5% min

53.0% min

1 .0% max
wo 2004/083310 PCT/US2004/007777
40

0.5% max
*number of carbon atoms:nurnber of double bonds (e.g., 1 refers to
linoleic acid)
Table 3. Properties of Castor Oil and Carnauba Waxes.

Product / Color Acid Iodin Saponifi Melting Hardnes

Typical (Gardne Value e point s
-cation
Properties (mg Value O
Celsiu (dmnn)
Value
KOH/g
1 500) (mg s ASTM
KOH/g) (ASTM
D-1 27)

Hydrogenated 7 2-3 3-4 1 74-1 8 84-85 2-4

Castor Oil 6
(I-ICC)) or
Castor Wax

Carnauba wax
2-5 78 - 88 83-85 1-2
 wo 2004/083310 PCT/US2004/007777
41

Table 4: Repulping Evaluation

Wax Sample Control Marcus Marcus Nat

CITGO Palm 1 55
BLENDKOTE Oil Soy Wax
467 Wax
Sample Coating Weight 5.7 5.7 5.8
1b/ 1 000sqft
Repulping test results 3 0.5 2
No particles evident
1 = small number of small
particles evident
2= Moderate number of
small particles evident
(less than control wax)
3= Very large number of small
particles are evident
(Control wax)
Table 5: MVTR Evaluation (ASTM D3833)

Wax Sample Control Marcus Palm Marcus Nat

CITGO Oil Wax 1 55
O
BLENDKOTE Soy Wax
467
Sample Coating 5.8 5.6 5.7
Weight
1b/ 1000sqft
MVTR 8.6 ± 0.9 1 0. O ±

(Grams/ 100 sq inches

in 24 hours)
CLAIMS:

1. A water-wax emulsion, comprising:

 wo 2004/083310 PCT/US2004/007777
42

about to about 50%, based on the total weight of the emulsion, of a

hydrogenated vegetable wax, the wax being characterized by having an iodine
value of less than about 10, and a melting point of between 120 to about 200
degrees F (Mettler drop point); about 50% to about 90% by weight water, based
on the total weight of the emulsion; about to about 25% by weight of a surface-
active agent, based on the total weight of the emulsion; and about 0.02% to
about 2.5% of an acid or base, based on the total weight of the emulsion.

2. The emulsion as described in claim 1, wherein the wax is chosen

from the group consisting of castor, soybean, palm, corn, cottonseed, rape,
canola, sunflower, palm kernel, coconut, cranbe, linseed and peanut.

3. The emulsion as described in claim 2, wherein the wax is chosen

from the group consisting of castor, palm and soybean, or a combination
thereof.

4. The emulsion as described in claim 3, wherein the wax comprises a

fatty acid chosen from the group consisting of stearic acid, ricinoleic acid, oleic
acid and palmitic acid.

5. The emulsion as described in claim 4, wherein the fatty acid is

stearic acid.

6. The emulsion as described in claim 4, wherein the fatty acid is

ricinoleic acid.

7. The emulsion as described in claim 2, wherein the emulsion

comprises between about 55% and about 75% water, based on the total weight
of the emulsion and between about 20% to about 45% solids, based on the
weight of the emulsion

& The emulsion as described in claim 7, wherein the surface active agent
is chosen from the group consisting of cationic and nonionic surfactants.
 wo 2004/083310 PCT/US2004/007777
43

9. The emulsion as described in claim 7, wherein the emulsion is

applied to fibrous cellulosic products in a quantity effective to render the fibrous
cellulosic products moisture resistant.

10. The emulsion as described in claim 9, wherein the treated fibrous

cellulosic products are characterized by an increase in their crush strength.

11. The emulsion as described in claim 10, wherein the treated fibrous
cellulosic products are characterized by an increase in their wet crush strength.

12. The emulsion as described in claim 9, wherein the applied

emulsion is removed from the moisture resistant fibrous cellulosic products by
treating the moisture resistant fibrous cellulosic products with a warm, alkaline,
aqueous mixture.

13. The emulsion as described in claim 7, which when added to a

warm, alkaline, aqueous mixture including fibrous cellulosic products containing
ink, removes the ink from the fibrous cellulosic products.

14. The emulsion as described in claim 13, wherein the emulsion is

added to the warm, alkaline, aqueous mixture in an amount ranging from about
0.1% to about 1% of the weight of the bath.

1 5. The emulsion as described in claim 7, wherein the emulsion is

applied to fruits in a quantity effective to retard the rate of moisture loss from
the fruit.
wo 2004/083310
pCT/lJS2004/007777

PCT/US2004/007777
2/2
 Figure 2
The effects of coating citrus fruit
with a soy wax-based emulsion on weight loss

CumuDatfive Weight Loss of Lemons

Day O Day 3 Day4 Day 7 Day 1 1 Day 12 Day 15

Treated with soy wax
Untreated
Dayo Day3 Day4 Day7 Day 1 Day 12 Day 1 5
1
Soy wax treatment 0.0% 2.9% 4.0% 6.2% 8.5% 10.9%

Untreated 0.0% 2.9% 4.2% 6.8% 10.7% 12.8%

"ternational Application No
INTERNATIONAL SEARCH REPORT
T/US2004/007777
BE

fpc 7 cd8t9å%d

According to International Patent Classification (IPC) or to both national classification and IPC

B. FIELDS SEARCHED

Minimum documentation searched (classification system followed by classification symbols)

IPC 7 A61K COU C08F COD

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched
 wo 2004/083310
Electronic data base consulted during the international search (name of data base and, where practical, search terms used)

EPO-1nternal , PAJ, WPI Data

C. DOCUMENTS CONSIDERED TO BE RELEVANT

Category Citation of document, with indication, where appropriate, of the relevant passages
0 Relevant to claim No.

WO 87/04070 A (RESEARCH CORP) 16 July 1-15

1987 (1987-07-16) page 5, line 29 - page 6, l
ine 11; cl alms 1-25; examples 1-3 page 2,
line 1 - 1 page 3, line 1 - line 16
GB 915 759 A (DU PONT)
16 January 1963 (1963-01-16) page 4, l
ine 104 - line 106; claim 1 ; examples 2- 1-15
4, 10; table 2
US 5 403 392 A (CRAIG DANIEL H) 4 April
1995 (1995-04-04) col umn 6, line 20 line
21; claim 1 ; example 11 1-15

X
Further documents are listed in the continuation of box C.Patent family members are listed in annex.

0
Special categories of cited documents :
later document published after the international filing date
document defining the general state of the art which is not or cited priority to understand date and not the in principle conflict or with theoty the
application underlying butthe considered to be of particular relevance invention
earlier document but published on or after the international document of particular relevance; the claimed invention filing date
cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve
an inventive step when the document Is taken alone which is cited to establish the publication date of another document of
particular relevance: the claimed Invention citation or other special reason (as specified) cannot be considered to involve an inventive
step when the document referring to an oral disclosurer use, exhibition or document is combined with one or more other such docu
— other means ments, such combination being obvious to a person skilled document published prior to the international filing date but
in the art.
later than the priority date claimed document member of the same patent family

Date of the actual completion of the international search Date of mailing of the intemational search report

23 June 2004 05/07/2004

Name and mailing address of the ISA Authorized officer
European Patent Office, P.B. 5818
Patentlaan 2 NL - 2280 HV Rijswijk
Tel. (+31-70) 340-2040, TX, 31 651 epo
nl, Fax: (+31-70) 340-3016
olde Scheper, B
Form PCT/lSA/210 (second sheet) (January 2004)
 ernational Application No
t
INTERNATIONAL SEARCH REPORT
Information on patent family members T/US2004/007777
Patent document Publication Patent family Publication
cited in search report date member(s) date
 wo 8704070 16-07-1987 0321457 Al 28-06-1989
8704070 Al 16 ¯07-1987 US
5023108 A 11-06-1991

Form PCT/lSA!210 (patent family annex) (January 2004)