Title of Invention

A METHOD FOR LUBRICATING THE PASSAGE OF A CONTAINER ALONG A CONVEYOR

Abstract The passage of a container along a conveyor is lubricated by applying to the container or conveyor a composition comprising a water-miscible silicone material wherein the composition has good wetting to polyethylene terephthalate surfaces. The compatibility of the lubricating composition with polyethylene terephthalate is increased because the wetting of the composition to polyethylene terephthalate is improved.
Full Text WO 2007/040677 PCT/US2006/023299
SILICONE LUBRICANT WITH GOOD WETTING ON PET SURFACES
FIELD OF THE INVENTION
This invention relates to conveyor lubricants and to a method for conveying
articles. The invention also relates to conveyor systems and containers wholly or
5 partially coated with such lubricant compositions.
BACKGROUND
In commercial container filling or packaging operations, the containers
typically are moved by a conveying system at very high rates of speed. Dilute
aqueous lubricant compositions are typically applied to the conveyor or containers
U) using spray or pumping equipment. These lubricant compositions permit high-speed
operation of the conveyor and limit marring of the containers or labels. One problem
that can occur with thermoplastic beverage containers made from polyethylene
icrcphthalatc (PET) is environmental stress cracking. Stress cracking in polymers is
the- development of cracks normal to an applied stress as a result of stress promoted
1.1 chemical degradation. Typically amorphous polymers are more susceptible to stress
cracking. In the case of PET, it is the amorphous regions of a beverage container
such as the center of the base of a PET bottle that are most susceptible to stress
cracking. When stress cracks penetrate through the wall of a PET bottle, the bottle
fails either by leaking or bursting. Because of environmental stress cracking, bottles
?.o filled with carbonated drinks are at risk for failure, especially at elevated
temperatures (e.g., warmer weather, elevated storage temperatures, etc.). The risk of
environmental stress cracking is exacerbated by the presence of materials which are
incompatible with PET. Materials that, when in contact with PET increase the rate
of occurrence of environmental stress cracking are considered incompatible with
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PET while materials that result in no increase in environmental stress cracking are
considered compatible with PET. The failure rate of PET bottles is greater for
bottles that have been contacted with alkaline water than for bottles that have been
contacted with deionized water, thus it can be stated that the presence of alkalinity
decreases the compatibility of aqueous compositions with PET bottles.
It is often the case that water used in the preparation of conveyor lubricant
compositions contains alkalinity. For example, the alkalinity of water used for
dilution of conveyor lubricants in bottling plants typically ranges between about 10
ppm and 100 ppm, expressed as ppm of CaCOs (calcium carbonate), with occasional
values above 100 ppm. According to the International Society of Beverage
Technologists web site, it is strongly recommended to keep the total alkalinity level
(expressed as CaCOg) below 50 mg/L (equivalent to 50 ppm as CaC03) in the water
used to dilute lubricant concentrate compositions (lube make up water) in order to
minimize the risk of stress crack failure. It is therefore important for conveyor
lubricant compositions to show good compatibility with PET beverage bottles in the
case that the dilution water contains alkalinity, particularly in the case that the
dilution water exhibits alkalinity levels above 50 ppm and up to and in excess of 100
ppm, measured as CaC03.
Silicone based lubricants are preferred lubricants for PET bottles because
they provide improved lubrication properties and significantly increased conveyor
efficiency. Silicone containing lubricant compositions are described, for example in
US Patent 6,495,494 (Li et. al) which is incorporated by reference herein in its
entirety. However, aqueous silicone based lubricants may be considered to be less
compatible with PET than other types of lubricants such as phosphate ester based
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lubricants. For example, conventional aqueous silicone lubricant compositions
generally show a relatively higher incidence of stress cracking under conditions of
high alkalinity. There has therefore been an unmet need in the field of conveyor
lubrication which is an aqueous silicone conveyor lubricant that exhibits good
compatibility with PET, particularly in the case that the lubricant contains alkalinity,
for example from the dilution water.
It is against this background that the present invention has been made.
SUMMARY OF THE INVENTION
Surprisingly, it has been discovered that a silicone based lubricant with
improved wetting characteristics increases the compatibility of the silicone based
lubricant with PET. Accordingly, the present invention provides, in one aspect, a
method for lubricating the passage of a container along a conveyor comprising
applying a composition of a water-miscible silicone material to at least a portion of
the container contacting surface of the conveyor or to at least a portion of the
conveyor-contacting surface of the container, wherein the contact angle between the
lubricant composition and container is less than about 60 degrees. The present
invention provides, in another aspect, a method for lubricating the passage of a
container along a conveyor comprising applying a composition of a water-miscible
silicone material to at least a portion of the container contacting surface of the
conveyor or to at least a portion of the conveyor-contacting surface of the container,
wherein the lubricant forms a substantially contiguous coating which covers greater
than about 30% of the surface when coated and dried onto polyethylene
let ephthalate film with a wet coating thickness of about 14 microns. The present
invention provides, in another aspect, a method for lubricating the passage of a
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container along a conveyor comprising applying a composition of a water-miscible
silicone material to at least a portion of the container contacting surface of the
conveyor or to at least a portion of the conveyor-contacting surface of the container,
wherein the lubricant composition has a foam profile of greater than about 1.1. The
invention also provides conveyor lubricant compositions comprising a water-
miscible silicone material and a wetting agent present in an amount effective to
provide a contact angle of less than 60 degrees between the lubricant composition
and a container surface. The present invention provides, in another aspect, a
lubricant concentrate composition comprising a water-miscible silicone material and
a wetting agent present in an amount effective to provide a contact angle of less than
60 degrees between the diluted lubricant composition and a container surface when
one part of the lubricant concentrate is diluted with between 100 and 1000 parts of
water and/or hydrophilic diluent. These and other aspects of this invention will be
evident upon reference to the following detailed description of the invention.
DETAILED DESCRIPTION
Definitions
For the following defined terms, these definitions shall be applied, unless a
different definition is given in the claims or elsewhere in this specification.
All numeric values are herein assumed to be modified by the term "about,"
whether or not explicitly indicated. The term "about" generally refers to a range of
numbers that one of skill in the art would consider equivalent to the recited value
(i.e., having the same function or result). In many instances, the term "about" may
include numbers that are rounded to the nearest significant figure.
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Weight percent, percent by weight, % by weight, wt. %, and the like are
synonyms that refer to the concentration of a substance as the weight of that
substance divided by the weight of the composition and multiplied by 100.
The recitation of numerical ranges by endpoints includes all numbers
subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80,4 and 5).
As used in this specification and the appended claims, the singular forms "a,"
"an," and "the" include plural referents unless the content clearly dictates otherwise.
Thus, for example, reference to a composition containing "a compound" includes a
mixture of two or more compounds. As used in this specification and the appended
claims, the term "or" is generally employed in its sense including "and/or" unless
the content clearly dictates otherwise.
Compositions
The invention provides a lubricant coating that reduces the coefficient of
friction of coated conveyor parts and containers and thereby facilitates movement of
containers along a conveyor line. The present invention provides in one aspect, a
method for
lubricating the passage of a container along a conveyor comprising applying a
composition of a watcr-miscible silicone material to at least a portion of the
container contacting surface of the conveyor or to at least a portion of the conveyor-
contacting surface of the container, wherein the composition exhibits good wetting
to PET. Typically lubricant compositions according to the present invention will
contain in addition to the water-miscible silicone material an agent or agents for the
improvement of the wetting of the composition to PET. Lubricant compositions of
the present invention may also include, in addition to silicone and wetting agents,
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waler-miscible lubricants that do not significantly improve the wetting of the
lubricant to PET.
It has been found, surprisingly, that the "compatibility" with PET of
conveyor
lubricant compositions containing silicone can be significantly improved by
improving the wetting of the lubricant composition to the PET surface. That is, PET
beverage bottles which have been contacted with a silicone conveyor lubricant
composition which has good wetting to PET show a lower bottle failure rate upon
storage in a hot and humid environment than a similar silicone conveyor lubricant
composition which has poor wetting to PET. Prior art silicone conveyor lubricant
compositions exhibit poor wetting on PET surfaces. The use of these products in the
situation of alkalinity and high temperature and humidity poses a risk for
environmental stress cracking of PET bottles.
The wetting behavior of lubricant compositions can be observed by
preparing a coating of the lubricant composition onto PET film. By this method, a
puddle of lubricant composition is spread across the film surface using a wire wound
bar in an action that is referred to as "drawing down" or "handspreading." The
thickness of the wet coating prepared by hand spreading is determined by the gauge
thickness of the wire wound on the bar. As the thickness of the wire increases, so do
the sizes of gaps between wire wraps and so does the thickness of the resulting
coating. For example, a bar wrapped with 150 micron diameter wire will deposit a
coating approximately 14 microns thick and a bar wrapped with 300 micron
diameter wire will deposit a coating approximately 27 microns thick under similar
conditions. Once the coating has been prepared by handspreading, the stability of the
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coating is dependent upon the wetting behavior. Coating compositions that have
poor wetting are observed to de-wet the surface instantly, beading up to give isolated
droplets of the coating composition. Coating compositions that have good wetting
remain as contiguous, substantially uninterrupted films without showing a tendency
to de-wet the surface or to bead up. Coating compositions that have intermediate
wetting properties typically give contiguous films which may have imperfections
including dc- wet spots and areas of non-uniform thickness.
The wetting behavior of lubricant compositions can be quantified by
measuring the contact angle of the lubricant composition with PET. It is well known
to characterize the wetting behavior of liquids on solids by measuring the contact
angle.
The lower the contact angle between a liquid and a solid, the better a liquid
will wet the surface of the solid. The contact angle 9 of a liquid on a solid is
dependent upon the solid-liquid interfacial tension YSL, the solid-vapor interfacial
tension YSV ("surface energy of solid"), and the liquid-vapor interfacial tension YLV
("surface tension of a liquid") by the well known Young's equation:
COSO-'(YSV-YSL)/YLV
The contact angle is smaller as cos G increases. Therefore from Young's
equation best wetting is achieved by making YSL and YLV as small as possible. This
can be accomplished by use of wetting agents. For the special case of conveyor
lubricant compatibility with polyethylene terephthalate, Ysv is a property of
polyethylene terephthalate and is not changeable by modifying the properties of the
lubricant composition. It might be thought that it is effective merely to achieve a
much lower the surface tension (YLV) of the lubricant composition, and that addition
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of any surfactant that is capable to lower the surface tension would be sufficient to
improve the wetting of the lubricant composition to the polymer surface. Actually it
is equally if not more important that the wetting agent lower the interfacial energy
between the polymer surface and the liquid lubricant composition (ysi,)- Lowering
the interfacial energy between the polyethylene terephthalate surface and the liquid
lubricant composition may also diminish the reactivity of the polymer with water in
the hydrolysis reaction, and increase the degree of crazing. According to Volynskii
(Volynskii, A. L., & Bakeev, N. F. (1995). Solvent Crazing of Polymers, Studies in
Polymer Science 13. New York, NY: Elsevier), solvent crazing of polymers under
stress results from suppression of the coagulation of oriented polymer fibrils due to
the presence of surface active liquid environments. The surface activity of the liquid
environment increases as ysi, decreases. Whether for the benefit of improving the
wetting and the areal coverage of the lubricant composition as it dries, increasing the
surface activity of the lubricant composition with respect to the polymer surface, or
to promote crazing, it is believed important to select wetting agents on the basis of
lowering the contact angle between the lubricant composition and the polymer
surface rather than simply on the basis of lowering the surface tension of the liquid
lubricant composition.
The contact angle is typically measured by recording an image of a test
liquid on the surface of the test solid, then measuring the intersecting angle between
the liquid-air interface and the liquid-solid interface.
While we do not wish to be bound by theory, there are several possible
explanations for why improving the wetting of silicone lubricants improves the
compatibility with PET. The simplest explanation is that by preventing the lubricant
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composition from beading up, the feature of good wetting is preventing the
concentration of alkaline residue, for example in water spots. By distributing
alkaline compounds evenly across the bottle, the better wetting lubricant
compositions are preventing localized attack of concentrated alkaline species.
Another possible reason for the lowering of burst rates with better wetting
lubricant compositions is that surface active agents in the lubricant stabilize the
polymer against chemical attack. When filled bottles expand under pressure in a
process commonly referred to as "creep," virgin, previously unexposed polymer
surface is created. By stabilizing the newly generated surface area, the reaction of
the polymer in those areas with water in the ester hydrolysis reaction may be
reduced.
The lowering of burst rates may also be related to the development of
microscopic crazes on the surface of the bottle. Typically, as the wetting behavior of
lubricants on PET improves, the amount of crazing increases. The presence of crazes
in the amorphous PET regions of the bottle may mitigate macroscopic cracking and
failure by either dissipating the attack of alkaline hydrolysis or by making more
tortuous the path of a propagating crack tip. When tested on carbonated beverage
bottles in a stress test at 100 F and 85% relative humidity, inventive lubricant
compositions showed relatively more crazing than either deionized water or
comparative example formulations. Using a visual crazing test where bottles with
no visible signs of crazing are scored 0 and bottles with pronounced crazing are
scored 10, lubricant compositions of the present invention typically gave crazing
values above about 4, compared to water and comparative example compositions
which gave crazing values less than about 4.
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Regardless of the mechanism, the present invention has been observed to
reduce stress cracking in PET bottles when compared to prior art compositions,
based on the wetting properties of the invention. The wetting properties can be
measured in a variety of ways including contact angle and by coating the
compositions onto PET sheets. The contact angles of compositions of the present
invention with PET are generally below about 60 degrees, while the contact angles
of prior art and comparative compositions are above 60 degrees. Accordingly,
compositions of the present invention having improved wetting properties have
contact angles below about 60 degrees, below about 50 degrees, or below about 40
degrees. When coated as a thin film onto PET sheets and dried, inventive lubricant
compositions cover greater than about 30% of the PET surface area that was
originally wetted in the coating process, while prior art and comparative examples
generally cover less than 10% of the originally wetted surface. Accordingly, when
coated as a thin film onto PET sheets and dried, compositions of the present
invention cover greater than about 30%, greater than about 50%, or greater than
about 70% of the PET surface area that was originally wetted in the coating process.
Inventive lubricant compositions also give relatively more foam than either
dcionized water or comparative example formulations. Using a foam profile test
where the foam profile measured 60 seconds after ten inversions of a graduated
cylinder is the ratio of the volume of liquid plus foam to liquid originally present,
inventive compositions gave foam profile values greater than about 1.1 compared to
prior art and comparative example compositions which generally gave foam profile
values less than 1.1. Accordingly, when evaluated using a foam profile test where
the foam profile measured 60 seconds after ten inversions of a graduated cylinder is
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the ratio of the volume of liquid, compositions of the present invention give foam
profile values greater than about 1.1, greater than about 1.3, or greater than about
Lubricant compositions of the present invention comprise wetting agents in
amounts sufficient to impart good wetting properties of the composition to PET.
Accordingly, compositions of the present invention have greater than about 0.01 wt.
% of wetting agent, greater than about 0.02 wt. % wetting agent, or greater than
about 0.04 wt. % wetting agent.
It may be desirable to provide compositions of the present invention in the
form of concentrates that can be diluted with water at the point of use to give use
compositions. Inventive lubricant concentrate compositions comprise a water-
miscible silicone material and a wetting agent present in an amount effective to
provide a contact angle of less than 60 degrees between the diluted lubricant
composition and a container surface when one part of the lubricant concentrate is
diluted with between 100 and 1000 parts of water plus hydrophilic diluent.
Accordingly, lubricant concentrate compositions comprise greater than about 1.0 wt.
% of wetting agent, greater than about 2.0 wt. % wetting agent, or greater than about
4.0 wt. % wetting agent.
The wetting behavior of lubricants is relevant to the lubricant as it is applied,
cither to the PET bottle directly or to any other surface where it may come in contact
with PET bottles, including the conveyor belt. This includes lubricants which consist
of a lubricant concentrate that is diluted with water at the point of use in any ratio of
lubricant concentrate to water, and it includes lubricants which are applied without
dilution.
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The silicone material and wetting agents are "water-miscible", that is, they
arc sufficiently water-soluble or water-dispersible so that when added to water at the
desired use level they form a stable solution, emulsion, or suspension. The desired
use level will vary according to the particular conveyor or container application, and
according to the type of silicone and wetting agent employed.
A variety of water-miscible silicone materials can be employed in the
lubricant compositions, including one or more of the group consisting of silicone
emulsions (such as emulsions formed from methyl(dimethyl), higher alkyl and aryl
silicones; and functionalized silicones such as chlorosilanes; amino-, methoxy-,
epoxy- and vinyl-substituted siloxanes; and silanols). Suitable silicone emulsions
include E2175 high viscosity polydimethylsiloxane (a 60% siloxane emulsion
commercially available from Lambent Technologies, Inc.), E2140
polydimethylsiloxane (a 35% siloxane emulsion commercially available from
! .arnbcnt Technologies, Inc.), E21456 FG food grade intermediate viscosity
polydimethylsiloxane (a 35% siloxane emulsion commercially available from
Lambent Technologies, Inc.), HV490 high molecular weight hydroxy-terminated
dimethyl silicone (an anionic 30-60% siloxane emulsion commercially available
from Dow Coming Corporation), SM2135 polydimethylsiloxane (a nonionic 50%
siloxane emulsion commercially available from GE Silicones) and SM2167
polydimethylsiloxane (a cationic 50% siloxane emulsion commercially available
from GE Silicones). Other water-miscible silicone materials include finely divided
silicone powders such as the TOSPEARL™ series (commercially available from
Toshiba Silicone Co. Ltd.); and silicone surfactants such as SWP30 anionic silicone
surfactant, WAXWS-P nonionic silicone surfactant, QUATQ-400M cationic
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silicone surfactant and 703 specialty silicone surfactant (all commercially available
from Lambent Technologies, Inc.).
Polydimethylsiloxane emulsions are preferred silicone materials. Generally
the concentration of the active silicone material useful in the present invention
exclusive of any dispersing agents, water, diluents, or other ingredients used to
emulsify the silicone material or otherwise make it miscible with water falls in the
range of about 0.0005% to about 5.0%, about 0.001% to about 1.0%, or about
0.002% to about 0.50%. In the case that the lubricant composition is provided in the
form of a concentrate, the concentration of active silicone material useful in the
present invention exclusive of any dispersing agents, water, diluents, or other
ingredients used to emulsify the silicone material or otherwise make it miscible with
water falls in the range of about 0.05% to about 20%, about 0.10% to about 5%, or
about 0.2% to about 1.0%.
As used herein, a wetting agent is a surface active agent or a mixture of one
or more surface active agents that imparts good wetting when added to a lubricant
composition. By good wetting it is meant the contact angle between the lubricant
composition and PET is below about 60 degrees or increases the areal coverage of
the lubricant concentration upon coating and drying on PET film is greater than
about 30%>. The wetting agent or wetting admixture of wetting agents of the present
invention can be selected from water soluble or water dispersible nonionic, semi-
polar nonionic, anionic, cationic, amphoteric, or zwitterionic surface-active agents;
or any combination thereof. The particular surfactant or surfactant mixture chosen
tor use in the process and products of this invention can depend on the conditions of
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final utility, including method of manufacture, physical product form, use pH, use
temperature, and foam control.
Generally, the concentration of wetting agent or wetting agent mixture useful
in lubricant use compositions of the present invention fall in the range of from about
0.01.% to about 0.5 wt. % of the wetting agent or agents, by weight of the
composition, about 0.02% to about 0.30 wt. % of the wetting agent, or about 0.04%
to about 0.15 wt. % of the wetting agent. These percentages can refer to percentages
of the commercially available surfactant composition, which can contain solvents,
dyes, odorants, and the like in addition to the actual surfactant. In this case, the
percentage of the actual surfactant chemical can be less than the percentages listed.
These percentages can refer to the percentage of the actual surfactant chemical. In
the case that the lubricant composition is provided in the form of a concentrate, the
concentration of wetting agent or wetting agent mixture useful in the concentrate
compositions of the present invention fall in the range of from about 1 % to about
50% of the wetting agent or agents, by weight of the composition, about 2% to about
30% of the wetting agent, or about 4% to about 20 wt. % of the wetting agent.
Nonionic Surfactant Wetting Agents
Nonionic surfactant wetting agents useful in the invention are generally
characterized by the presence of an organic hydrophobic group and an organic
hydrophilic group and are typically produced by the condensation of an organic
aliphatic, alkyl aromatic or polyoxyalkylene hydrophobic compound with a
hydrophilic alkaline oxide moiety which in common practice is ethylene oxide or a
polyhydration product thereof, polyethylene glycol. Practically any hydrophobic
compound having a hydroxyl, carboxyl, amino, or amido group with a reactive
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hydrogen atom can be condensed with ethylene oxide, or its polyhydration adducts,
or its compositions with alkoxylenes such as propylene oxide to form a nonionic
surface-active agent. The length of the hydrophilic polyoxyalkylene moiety which
is condensed with any particular hydrophobic compound can be readily adjusted to
yield a water dispersible or water soluble compound having the desired degree of
balance between hydrophilic and hydrophobic properties. Useful nonionic
surfactants in the present invention include:
1. Block polyoxypropylene-polyoxyethylene polymeric compounds
based upon propylene glycol, ethylene glycol, glycerol, trimethylolpropane, and
ethylenediamine as the initiator reactive hydrogen compound. Examples of
polymeric compounds made from a sequential propoxylation and ethoxylation of
initiator are commercially available under the trade names Pluronic® and Tetronic®
manufactured by BASF Corp.
Pluronic® compounds are difunctional (two reactive hydrogens) compounds
formed by condensing ethylene oxide with a hydrophobic base formed by the
addition of propylene oxide to the two hydroxyl groups of propylene glycol. This
hydrophobic portion of the molecule weighs from about 1,000 to about 4,000.
Ethylene oxide is then added to sandwich this hydrophobe between hydrophilic
groups, controlled by length to constitute from about 10% by weight to about 80%
by weight of the final molecule.
Tetronic® compounds are tetra-functional block copolymers derived from the
sequential addition of propylene oxide and ethylene oxide to ethylenediamine. The
molecular weight of the propylene oxide hydrotype ranges from about 500 to about
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7,000; and, the hydrophile, ethylene oxide, is added to constitute from about 10% by
weight to about 80% by weight of the molecule.
2. Condensation products of one mole of alkyl phenol wherein the alkyl
chain, of straight chain or branched chain configuration, or of single or dual alkyl
constituent, contains from about 8 to about 18 carbon atoms with from about 3 to
about 50 moles of ethylene oxide. The alkyl group can, for example, be represented
by diisobutylene, di-amyl, polymerized propylene, iso-octyl, nonyl, and di-nonyl.
These surfactants can be polyethylene, polypropylene, and polybutylene oxide
condensates of alkyl phenols. Examples of commercial compounds of this
chemistry are available on the market under the trade names Igepal® manufactured
by Hhone-Poulenc and Triton® manufactured by Union Carbide.
3. Condensation products of one mole of a saturated or unsaturated,
straight or branched chain alcohol having from about 6 to about 24 carbon atoms
with from about 3 to about 50 moles of ethylene oxide. The alcohol moiety can
consist of an alcohol having a specific number of carbon atoms within this range. Examples
of like commercial surfactant are available under the trade names Neodol®
manufactured by Shell Chemical Co. and Alfonic® manufactured by Vista Chemical
Co.
4. Condensation products of one mole of saturated or unsaturated,
straight or branched chain carboxylic acid having from about 8 to about 18 carbon
atoms with from about 6 to about 50 moles of ethylene oxide. The acid moiety can
consist of mixtures of acids in the above defined carbon atoms range or it can consist
of an acid having a specific number of carbon atoms within the range. Examples of
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commercial compounds of this chemistry are available on the market under the trade
names Nopalcol® manufactured by Henkel Corporation and Lipopeg® manufactured
by Lipo Chemicals, Inc.
In addition to ethoxylated carboxylic acids, commonly called polyethylene
glycol esters, other alkanoic acid esters formed by reaction with glycerides, glycerin,
and polyhydric (saccharide or sorbitan/sorbitol) alcohols have application in this
invention for specialized embodiments, particularly indirect food additive
applications. All of these ester moieties have one or more reactive hydrogen sites on
their molecule which can undergo further acylation or ethylene oxide (alkoxide)
addition to control the hydrophilicity of these substances.
Examples of nonionic low foaming surfactants include:
5. Compounds from (1) which are modified, essentially reversed, by
adding ethylene oxide to ethylene glycol to provide a hydrophile of designated
molecular weight; and, then adding propylene oxide to obtain hydrophobic blocks
on the outside (ends) of the molecule. The hydrophobic portion of the molecule
weighs from about 1,000 to about 3,100 with the central hydrophile including 10%
by weight to about 80% by weight of the final molecule. These reverse Pluronics®
arc manufactured by BASF Corporation under the trade name Pluronic® R
surfactants.
Likewise, the Tetronic® R surfactants are produced by BASF Corporation by
the sequential addition of ethylene oxide and propylene oxide to ethylenediamine.
The hydrophobic portion of the molecule weighs from about 2,100 to about 6,700
with the central hydrophile including 10% by weight to 80% by weight of the final
molecule.
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6. Compounds from groups (1), (2), (3) and (4) which are modified by
"capping" or "end blocking" the terminal hydroxy group or groups (of multi-
functional moieties) to reduce foaming by reaction with a small hydrophobic
molecule such as propylene oxide, butylene oxide, benzyl chloride; and, short chain
fatty acids, alcohols or alkyl halides containing from 1 to about 5 carbon atoms; and
mixtures thereof. Also included arc reactants such as thionyl chloride which convert
terminal hydroxy groups to a chloride group. Such modifications to the terminal
hydroxy group may lead to all-block, block-heteric, heteric-block or all-heteric
nonionics.
Additional examples of effective low foaming nonionics include:
7. The alkylphenoxypolyethoxyalkanols of U.S. Pat No. 2,903,486
issued September 8, 1959 to Brown et al. and represented by the formula

in which R is an alkyl group of 8 to 9 carbon atoms, A is an alkylene chain of 3 to 4
carbon atoms, n is an integer of 7 to 16, and m is an integer of 1 to 10.
The polyalkylene glycol condensates of U.S. Pat. No. 3,048,548 issued
August 7, 1962 to Martin et al. having alternating hydrophilic oxyethylene chains
and hydrophobic oxypropylene chains where the weight of the terminal hydrophobic
chains, the weight of the middle hydrophobic unit and the weight of the linking
hydrophilic units each represent about one-third of the condensate.
The defoaming nonionic surfactants disclosed in U.S. Pat. No. 3,382,178
issued May 7 1968 to Lissant et al. having the general formula Z[(OR)nOH]z
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wherein Z is alkoxylatable material, R is a radical derived from an alkaline oxide
which can be ethylene and propylene and n is an integer from, for example, 10 to
2,000 or more and z is an integer determined by the number of reactive
oxyalkylatable groups.
The conjugated polyoxyalkylene compounds described in U.S. Pat. No.
2,677,700, issued May 4, 1954 to Jackson et al. corresponding to the formula
Y(("3II60)n(C2H40)mH wherein Y is the residue of organic compound having from
about 1 to 6 carbon atoms and one reactive hydrogen atom, n has an average value
of at least about 6.4, as determined by hydroxyl number and m has a value such that
the oxyethylene portion constitutes about 10% to about 90% by weight of the
molecule.
The conjugated polyoxyalkylene compounds described in U.S. Pat. No.
2,674,619, issued April 6, 1954 to Lundsted et al. having the formula
Y|(C3H from about 2 to 6 carbon atoms and containing x reactive hydrogen atoms in which x
has a value of at least about 2, n has a value such that the molecular weight of the
polyoxypropylene hydrophobic base is at least about 900 and m has value such that
the oxyethylene content of the molecule is from about 10% to about 90% by weight.
Compounds falling within the scope of the definition for Y include, for example,
propylene glycol, glycerine, pentaerythritol, trimethylolpropane, ethylenediamine
and the like. The oxypropylene chains optionally, but advantageously, contain small
amounts of ethylene oxide and the oxyethylene chains also optionally, but
advantageously, contain small amounts of propylene oxide.
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WO 2(107/040677 PCT/US2006/023299
Additional conjugated polyoxyalkylenc surface-active agents which are
advantageously used in the compositions of this invention correspond to the
formula: P[(C3H60)n(C2H40)mH]x wherein P is the residue of an organic compound
having from about 8 to 18 carbon atoms and containing x reactive hydrogen atoms
in which x has a value of 1 or 2, n has a value such that the molecular weight of the
polyoxyethylene portion is at least about 44 and m has a value such that the
oxypropylene content of the molecule is from about 10% to about 90% by weight.
Jn either case the oxypropylene chains may contain optionally, but advantageously,
small amounts of ethylene oxide and the oxyethylene chains may contain also
optionally, but advantageously, small amounts of propylene oxide.
8. Polyhydroxy fatty acid amide surfactants suitable for use in the
present compositions include those having the structural formula R^ONR'Z in
which: Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy,
propoxy group, or a mixture thereof; R2 is a C5 -C31 hydrocarbyl, which can be
straight-chain; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain
with at least 3 hydroxyls directly connected to the chain, or an alkoxylated
derivative (preferably ethoxylated or propoxylated) thereof. Z can be derived from a
reducing sugar in a reductive amination reaction; such as a glycidyl moiety.
9. The alkyl ethoxylate condensation products of aliphatic alcohols with
from about 0 to about 25 moles of ethylene oxide are suitable for use in the present
compositions. The alkyl chain of the aliphatic alcohol can either be straight or
branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
10. The ethoxylated Ce-Cig fatty alcohols and CVCig mixed ethoxylated
and propoxylated fatty alcohols are suitable surfactants for use in the present
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WO 2(iH ,7040677 PCI7US2006/023299
compositions, particularly those that are water soluble. Suitable ethoxylated fatty
alcohols include the Cio-Cig ethoxylated fatty alcohols with a degree of cthoxylation
of from 3 to 50.
11. Suitable nonionic alkylpolysaccharide surfactants, particularly for use
in the present compositions include those disclosed in U.S. Pat. No. 4,565,647,
Llenado, issued Jan. 21, 1986. These surfactants include a hydrophobic group
containing from about 6 to about 30 carbon atoms and a polysaccharide, e.g., a
polyglycoside, hydrophilic group containing from about 1.3 to about 10 saccharide
units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g.,
glucose, galactose and galactosyl moieties can be substituted for the glucosyl
moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc.
positions thus giving a glucose or galactose as opposed to a glucoside or
gaiactosidc.) The intersaccharide bonds can be, e.g., between the one position of the
additional saccharide units and the 2-, 3-, 4-, and/or 6-positions on the preceding
saccharide units.
12. Fatty acid amide surfactants suitable for use in the present
compositions include those having the formula: R6CON(R7)2 in which R6 is an alkyl
group containing from 7 to 21 carbon atoms and each R; is independently hydrogen,
(VC4 alkyl, C]-C4 hydroxyalkyl, or -(C^R^xii, where x is in the range of from 1
to 3.
13. A useful class of non-ionic surfactants include the class defined as
alkoxylated amines or, most particularly, alcohol alkoxylated/aminated/alkoxylated
surfactants. These non-ionic surfactants may be at least in part represented by the
general formulae:
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WO 2007/040677 PCT/US2006/023299
R20-CPO)sN--(EO)tH,
R;i) (PO)sN (EO)tH(RO)tH, and
R?-°-N(EO)tH;
in which R20 is an alkyl, alkenyl or other aliphatic group, or an alkyl-aryl group of
from 8 to 20, preferably 12 to 14 carbon atoms, EO is oxyethylenc, PO is
oxypropylene, s is 1 to 20, preferably 2-5, t is 1-10, preferably 2-5, and u is 1-10,
preferably 2-5. Other variations on the scope of these compounds may be
represented by the alternative formula:
R20-_ (PO)v-N[(EO)wHj L(EO)zH]
in which R20 is as defined above, v is 1 to 20 (e.g., 1, 2, 3, or 4 (preferably 2)), and w
and /. are independently 1-10, preferably 2-5.
These compounds are represented commercially by a line of products sold by
Huntsman Chemicals as nonionic surfactants. A preferred chemical of this class
includes Surfonic™ PEA 25 Amine Alkoxylate.
Preferred nonionic surfactants for the compositions of the invention include
aicohol alkoxylates, EO/PO block copolymers, alkylphenol alkoxylates, and the like.
The treatise Nonionic Surfactants, edited by Schick, M.J., Vol. 1 of the
Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 is an excellent
reference on the wide variety of nonionic compounds generally employed in the
practice of the present invention. A typical listing of nonionic classes, and species
of these surfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin and
I Jeuring on Dec. 30, 1975. Further examples are given in "Surface Active Agents
and Detergents" (Vol. 1 and II by Schwartz, Perry and Berch).
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WO 20117/040677 PCT/US2006/023299
Semi-Polar Nonionic Surfactant Wetting Agents
The semi-polar type of nonionic surface active agents are another class of
nonionic surfactant useful in compositions of the present invention. Generally,
semi-polar nonionics are high foamers and foam stabilizers, which can limit their
application in conveyor lubricant compositions. However, within compositional
embodiments of this invention designed for high foam applications, semi-polar
nonionics would have immediate utility. The semi-polar nonionic surfactants
include the amine oxides, phosphine oxides, sulfoxides and their alkoxylated
derivatives.
14. Amine oxides are tertiary amine oxides corresponding to the general
formula:

wherein the arrow is a conventional representation of a semi-polar bond; and, R1, R2,
and R" may be aliphatic, aromatic, heterocyclic, alicyclic, or combinations thereof.
Generally, for amine oxides of detergent interest, R1 is an alkyl radical of from about
8 to about 24 carbon atoms; R2and R3 are alkyl or hydroxyalkyl of 1-3 carbon atoms
or a mixture thereof; R' and R can be attached to each other, e.g. through an oxygen
or nitrogen atom, to form a ring structure; R4 is an alkaline or a hydroxyalkylene
group containing 2 to 3 carbon atoms; and n ranges from 0 to about 20.
Useful water soluble amine oxide surfactants are selected from the coconut
or tallow alkyl di-(lower alkyl) amine oxides, specific examples of which are
dodecyldimethylamine oxide, tridecyldimethylamine oxide,
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WO 2007/040677 PCT/US2006/023299
tctradccyldimcthylamine oxide, pentadecyldiraethylamine oxide,
hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,
octadecyldimethylamine oxide, dodecyldipropylamine oxide,
tettadecyldipropylaminc oxide, hexadecyldipropylamine oxide,
tetradecyldibutylamine oxide, octadecyldibutylamine oxide, bis(2-
hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecoxy-l-
hydroxypropylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-
trioctadecyldimethylamine oxide and 3-dodecoxy-2-hydroxypropyldi-(2-
hydroxyethyl)amine oxide.
Useful semi-polar nonionic surfactants also include the water soluble
phosphine oxides having the following structure:

wherein the arrow is a conventional representation of a semi-polar bond; and, R1 is
an alkyl, alkenyl or hydroxyalkyl moiety ranging from 10 to about 24 carbon atoms
in chain length; and, R2 and R3 are each alkyl moieties separately selected from alkyl
or hydroxyalkyl groups containing 1 to 3 carbon atoms.
Examples of useful phosphine oxides include dimethyldecylphosphine oxide,
dimethyltetradecylphosphine oxide, methylethyltetradecylphosphine oxide,
dimethylhexadccylphosphine oxide, diethyl-2-hydroxyoctyldecylphosphine oxide,
biK(2-hydroxyethyl)dodecylphosphine oxide, and
bis(hydroxyrnethyl)tetradecylphosphine oxide. Semi-polar nonionic surfactants
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WO 2007/040677 PCMJS2006/023299
useful herein also include the water soluble sulfoxide compounds which have the
structure:

wherein the arrow is a conventional representation of a semi-polar bond; and, R is
an alkyl or hydroxyalkyl moiety of about 8 to about 28 carbon atoms, from 0 to
about 5 ether linkages and from 0 to about 2 hydroxyl substituents; and R is an
alkyl moiety consisting of alkyl and hydroxyalkyl groups having 1 to 3 carbon
atoms.
Useful examples of these sulfoxides include dodecyl methyl sulfoxide; 3-
hydroxy tridecyl methyl sulfoxide; 3-methoxy tridecyl methyl sulfoxide; and 3-
hydroxy-4-dodecoxybutyl methyl sulfoxide.
Preferred semi-polar nonionic surfactants for the compositions of the
invention include dimethyl amine oxides, such as lauryl dimethyl amine oxide,
myristyl dimethyl amine oxide, cetyl dimethyl amine oxide, combinations thereof,
and the like.
Anionic Surfactant Wetting Agents
Also useful in the present invention are surface active substances which are
categorized as anionics because the charge on the hydrophobe is negative.
Carboxylate, sulfonate, sulfate and phosphate are the polar (hydrophilic) solubilizing
groups found in anionic surfactants. Preferred anionic surfactant wetting agents are
those in which the hydrophobic section of the molecule carries a charge at pH values
at neutrality or below, less preferred are those in which the hydrophobic section of
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WO 20(17/040677 PCT/US2006/023299
the molecule carries no charge unless the pH is elevated to neutrality or above (e.g.
carboxylic acids). Of the cations (counter ions) associated with these polar groups,
sodium, lithium and potassium impart water solubility; ammonium and substituted
ammonium ions provide both water and oil solubility; and, calcium, barium, and
magnesium promote oil solubility.
As those skilled in the art understand, anionics are excellent detersive
surfactants and are therefore, favored additions to give lubricant compositions which
provide improved detergency. Generally, however, anionics have high foam profiles
which limit their use alone or at high concentration levels in conveyor lubricants
where low foam profiles are preferred. Anionics are very useful additives to
preferred compositions of the present invention. Further, anionic surface active
compounds are useful to impart special chemical or physical properties other than
detergency within the composition. Anionics can be employed as gelling agents or
as part of a gelling or thickening system. Anionics are excellent solubilizers and can
be used for hydrotropic effect and cloud point control.
The majority of large volume commercial anionic surfactants can be
subdivided into five major chemical classes and additional sub-groups known to
those of skill in the art and described in "Surfactant Encyclopedia", Cosmetics &
Toiletries, Vol. 104 (2) 71-86 (1989). The first class includes acylamino acids (and
salts), such as acylgluamates, acyl peptides, sarcosinates (e.g. N-acyl sarcosinates),
taurates (e.g. N-acyl taurates and fatty acid amides of methyl tauride), and the like.
The second class includes carboxylic acids (and salts), such as alkanoic acids (and
alkanoates), ester carboxylic acids (e.g. alkyl succinates), ether carboxylic acids, and
the like. The third class includes phosphoric acid esters and their salts. The fourth
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WO 2007/040677 PCT/US2006/023299
class includes sulfonic acids (and salts), such as isethionates (e.g. acyl isethionates),
alkylaryl sulfonates, alkyl sulfonates, sulfosuccinates (e.g. monoesters and diesters
of sulfosuccinate), and the like. The fifth class includes sulfuric acid esters (and
salts), such as alkyl ether sulfates, alkyl sulfates, and the like.
Anionic sulfate surfactants suitable for use in the present compositions
include the linear and branched primary and secondary alkyl sulfates, alkyl
cthoxysulfates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether
sulfates, the C5 -Cn acyl-N-(C] -C4 alkyl) and -N-(Ci -C2 hydroxyalkyl) glucamine
sulfates, and sulfates of alkylpolysaccharides such as the sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
Examples of suitable synthetic, water soluble anionic surfactant compounds
include the ammonium and substituted ammonium (such as mono-, di- and
triethanolamine) and alkali metal (such as sodium, lithium and potassium) salts of
the alkyl mononuclear aromatic sulfonates such as the alkyl benzene sulfonates
containing from about 5 to about 18 carbon atoms in the alkyl group in a straight or
branched chain, e.g., the salts of alkyl benzene sulfonates or of alkyl toluene, xylene,
cumene and phenol sulfonates; alkyl naphthalene sulfonate, diamyl naphthalene
sulfonate, and dinonyl naphthalene sulfonate and alkoxylated derivatives.
Other anionic surfactants suitable for use in the present compositions include
olefin sulfonates, such as long chain alkene sulfonates, long chain hydroxyalkane
sulfonates or mixtures of alkenesulfonates and hydroxyalkane-sulfonates. Also
included are the alkyl sulfates, alkyl poly(ethyleneoxy) ether sulfates and aromatic
poly(ethyleneoxy) sulfates such as the sulfates or condensation products of ethylene
oxide and nonyl phenol (usually having 1 to 6 oxyethylene groups per molecule.
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Resin acids and hydrogenated resin acids are also suitable, such as rosin,
hydrogenated rosin, and resin acids and hydrogenated resin acids present in or
derived from tallow oil.
The particular salts will be suitably selected depending upon the particular
formulation and the needs therein.
Further examples of suitable anionic surfactants are given in "Surface Active
Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of
such surfactants are also generally disclosed in U.S. Pat. No. 3,929,678, issued Dec.
30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23.
Care should be taken to avoid the use of wetting agents that might promote
environmental stress cracking in plastic containers when evaluated using the PET
Stress Crack Test set out below. The tendency of wetting agents to promote
environmental stress cracking can be evaluated using the PET Stress Crack Test set
out below. Examples of preferred wetting agents include fatty amines, alcohol
ethoxylates and mixtures thereof. Examples of particularly preferred lubricant use
compositions include those having from about 0.001 wt. % to about 0.02 wt. % of a
water-misciblc silicone material from about 0.01 wt. % to about 0.05 wt. % of a fatty
amine compound, and from about 0.02 wt. % to about 0.10 wt. % of an alcohol
ethoxylate compound. Examples of particularly preferred lubricant concentrate
compositions include those having from about 0.10 wt. % to about 2 wt. % of a
water-miscible silicone material from about 1.0 wt. % to about 20 wt. % of fatty
amine compound, and from about 2 wt. % to about 40 wt. % of an alcohol
eihoxylate compound. Particularly preferred lubricant compositions are
substantially aqueous, that is, they comprise greater than about 99 wt. % of water.
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WO 2(1(17/040677 PCT/US2006/023299
Lubricant compositions of the present invention can be applied as is or may
be diluted before use. It may be desirable to provide compositions of the present
invention in the form of concentrates that can be diluted with water at the point of
use to give use compositions. If diluted, preferred ratios for dilution at the point of
use range from about 1:100 to 1:1000 (parts of concentrate: parts of water). In the
case that lubricant compositions are provided in the form of concentrates, it is
particularly preferred to select silicone materials and wetting agents that form stable
compositions at 100 to 1000 times the concentration of the use composition.
In the case that the silicone material is a silicone emulsion, the wetting agent
or agents preferably are selected from those that will not cause the silicone emulsion
to coagulate or separate, either in the use composition or in the concentrate if the
composition is provided in the form of a concentrate.
The lubricant compositions can contain functional ingredients if desired. For
example, the compositions can contain hydrophilic diluents, antimicrobial agents,
stabilizing/coupling agents, detergents and dispersing agents, anti-wear agents,
viscosity modifiers, sequestrants, corrosion inhibitors, film forming materials,
antioxidants or antistatic agents. The amounts and types of such additional
components will be apparent to those skilled in the art.
Water-miscible Lubricants
A variety of water-miscible lubricants can be employed in the lubricant
compositions, including hydroxy-containing compounds such as polyols (e.g.,
glycerol and propylene glycol); polyalkylene glycols (e.g., the CARBOWAX™
series of polyethylene and methoxypolyethylene glycols, commercially available
from Union Carbide Corp.); linear copolymers of ethylene and propylene oxides
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WO 20(17/040677 PCT/US2006/023299
(e.g., UCON™ 50-HB-100 water-soluble ethylene oxide:propylene oxide
copolymer, commercially available from Union Carbide Corp.); and sorbitan esters
(e.g., TWEEN™ series 20, 40, 60, 80 and 85 polyoxyethylene sorbitan monooleates
and SPAN™ series 20, 80, 83 and 85 sorbitan esters, commercially available from
ICT Surfactants). Other suitable water-miscible lubricants include phosphate esters,
amines and their derivatives, and other commercially available water-miscible
lubricants that will be familiar to those skilled in the art. Derivatives (e.g., partial
esters or ethoxylates) of the above lubricants can also be employed. For applications
involving plastic containers, care should be taken to avoid the use of water-miscible
lubricants that might promote environmental stress cracking in plastic containers
when evaluated using the PET Stress Crack Test set out below. Preferably the water-
miscible lubricant is a polyol such as glycerol or a linear copolymer of ethylene and
propylene oxides.
Hydrophilic Diluents
Suitable hydrophilic diluents include alcohols such as isopropyl alcohol,
polyols such as ethylene glycol and glycerine, ketones such as methyl ethyl ketone,
and cyclic ethers such as tetrahydrofuran. For applications involving plastic
containers, care should be taken to avoid the use of hydrophilic diluents that might
promote environmental stress cracking in plastic containers when evaluated using
the PET Stress Crack Test set out below.
Antimicrobial Agents
Anti-microbial agents can also be added. Some useful anti-microbial agents
include disinfectants, antiseptics, and preservatives. Some non-limiting examples
include phenols including halo- and nitrophenols and substituted bisphenols such as
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WO 2007/040677 PCT/US2006/023299
4-hexylresorcinol, 2-benzyl-4-chlorophenol and 2,4,4'-trichloro-2-hydroxydiphenyl
ether, organic and inorganic acids and its esters and salts such as dehydroacetic acid,
peroxycarboxylic acids, peroxyacetic acid, methyl p-hydroxy benzoic acid, cationic
agents such as quaternary ammonium compound, phosphonium compounds such as
tetrakishydroxymethyl phosphonium sulphate (THPS), aldehydes such as
glutaraldehyde, antimicrobial dyes such as acridines, triphenylmethane dyes and
quinines and halogens including iodine and chlorine compounds. The antimicrobial
agents can be used in amounts to provide the desired antimicrobial properties. In
some examples, the amount can range from 0 to about 20 wt.-% of the total
composition, hydrophilic
Stabilizing/Coupling Agents
In a lubricant concentrate, stabilizing agents, or coupling agents can be
employed to keep the concentrate homogeneous, for example, under cold
temperature. Some of the ingredients may have the tendency to phase separate or
form layers due to the high concentration. Many different types of compounds can
be used as stabilizers. Examples are isopropyl alcohol, ethanol, urea, octane
sulfonate, glycols such as hexylene glycol, propylene glycol and the like. The
stabilizing/coupling agents can be used in an amount to give desired results. This
amount can range, for example, from about 0 to about 30 wt.-% of the total
composition.
Detergents/Dispersing Agents
Detergents of dispersing agents may also be added. Some examples of
detergents and dispersants include alkylbenzenesulfonic acid, alkylphenols,
carboxylic acids, alkylphosphonic acids, and their calcium, sodium, and magnesium
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WO 2007/040677 PCT/IJS2006/023299
salts, polybutenylsuccinic acid derivatives, silicone surfactants, fluorosurfactants,
and molecules containing polar groups attached to an oil-solubilizing aliphatic
hydrocarbon chain.
Some examples of suitable dispersing agents include triethanolamine,
alkoxylated fatty alkyl monoamines and diamines such as coco bis (2-
hydroxyethy])amine, polyoxyethylene(5-)coco amine, polyoxyethylene(15)coco
amine, tallow bis(-2hydroxyethyl)amine, polyoxyethylene(15)amine,
polyoxyethylenc(5)oleyl amine and the like.
The detergent and/or dispersants can be used in an amount to give desired
results. This amount can range, for example, from about 0 to about 30 wt.-% of the
total composition.
Anti-wear Agents
Anti-wear agents can also be added. Some examples of anti-wear agents
include zinc dialkyl dithiophosphates, tricresyl phosphate, and alkyl and aryl
disulfides and polysulfides. The anti-wear and/or extreme pressure agents are used
in amounts to give the desired results. This amount can range, for example, from 0
to about 20 wt.-% of the total composition.
Viscosity Modifiers
Viscosity modifiers can also be used. Some examples of viscosity modifiers
include pour-point depressants and viscosity improvers, such as polymethacrylates,
polyisobutylcnes polyacrylamides, polyvinyl alcohols, polyacrylic acids, high
molecular weight polyoxyethylenes, and polyalkyl styrenes. The modifiers can be
used in amounts to provide the desired results. In some embodiments, the viscosity
modifiers can range for 0 to about 30 wt.-% of the total composition.
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WO 2007/040677 PCT/US2006/023299
Sequestrants
In addition to the aforementioned ingredients, it is possible to include other
chemicals in the lubricant concentrates. For example, where soft water is unavailable
and hard water is used for the dilution of the lubricant concentrate, there is a
tendency for the hardness cations, such as calcium, magnesium, and ferrous ions, to
reduce the efficacy of the surfactants, and even form precipitates when coming into
contact with ions such as sulfates, and carbonates. Sequestrants can be used to form
complexes with the hardness ions. A sequestrant molecule may contain two or more
donor atoms which are capable of forming coordinate bonds with a hardness ion.
Sequestrants that possess three, four, or more donor atoms are called tridentate,
tctradentate, or polydentate coordinators. Generally the compounds with the larger
number of donor atoms are better sequestrants. The preferable sequestrant is
ethylene diamine tetracetic acid (EDTA), such as Versene products which are
Na2EDTA and Na^EDTA sold by Dow Chemicals. Some additional examples of
other sequestrants include: iminodisuccinic acid sodium salt, trans-1,2-
diaminocyclohexane tetracetic acid monohydrate, diethylene triamine pentacetic
acid, sodium salt of nitrilotriacetic acid, pentasodium salt of N-hydroxyethylene
diamine triacetic acid, trisodium salt of N,N-di(beta-hydroxyethyl)glycine, sodium
salt of sodium glucoheptonate, and the like.
Corrosion Inhibitors
Useful corrosion inhibitors include polycarboxylic acids such as short chain
carboxylic diacids, triacids, as well as phosphate esters and combinations thereof.
Useful phosphate esters include alkyl phosphate esters, monoalkyl aryl phosphate
esters, dialkyl aryl phosphate esters, trialkyl aryl phosphate esters, and mixtures
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WO 2007/040677 PCT/US2006/023299
thereof such as Emphos PS 236 commercially available from Witco Chemical
Company. Other useful corrosion inhibitors include the triazoles, such as
benzotriazole, tolyltriazole and mercaptobenzothiazole, and in combinations with
phosphonates such as 1-hydroxyethylidene-l, 1-diphosphonic acid, and surfactants
such as oleic acid diethanolamide and sodium cocoamphohydroxy propyl sulfonate,
and the like. Useful corrosion inhibitors include polycarboxylic acids such as
dicarboxylic acids. The acids which are preferred include adipic, glutaric, succinic,
and mixtures thereof. The most preferred is a mixture of adipic, glutaric and succinic
acid, which is a raw material sold by BASF under the name SOKALAN™ DCS.
Preferred lubricant compositions may also contain a stoichiometric amount
of an organic acid. Lubricant compositions that comprise a stoichiometric amount of
an organic acid and have improved compatibility with PET are disclosed in
assignee's copending patent application, titled SILICONE CONVEYOR
LUBRICANT WITH STOICHIOMETRIC AMOUNT OF AN ORGANIC ACID,
filed September 22, 2005 with attorney docket number 2264US01, which
application is incorporated herein by reference. Compositions which comprise both a
stoichiometric amount of acid and wetting agent sufficient to lower the contact angle
to less than about 60 degrees may exhibit a synergistic effect, that is, the overall
reduction of the failure rate for PET bottles may be greater than the sum of the
reduction of the failure rate for either a stoichiometric amount of acid or wetting
agent alone.
Preferred lubricant compositions may be foaming, that is, they may have a
foam profile value greater than about 1.1 when measured using a Foam Profile Test.
Conveyor lubricants that contain silicone and foam are heretofore unknown.
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Lubricant compositions which exhibit foam profile values greater than about 1.1
may be advantageous because they offer a visual indication of the presence of
lubricant, because foam allows movement of lubricant to areas of the conveyor that
are not wetted directly by nozzles, brushes, or other means of application, and
because foam enhances contact of the lubricant composition with the package being
conveyed. Lubricant compositions preferably have a foam profile value that is
greater than about 1.1, more preferably greater than about 1.3, and most preferably
greater than about 1.5, when evaluated using the Foam Profile Test described below.
The lubricant compositions preferably create a coefficient of friction (COF)
i that is less than about 0.20, more preferably less than about 0.15, and most
preferably less than about 0.12, when evaluated using the Short Track Conveyor
Test described below.
A variety of kinds of conveyors and conveyor parts can be coated with the
lubricant composition. Parts of the conveyor that support or guide or move the
> containers and thus are preferably coated with the lubricant composition include
belts, chains, gates, chutes, sensors, and ramps having surfaces made of fabrics,
metals, plastics, composites, or combinations of these materials.
The lubricant composition can also be applied to a wide variety of containers
including beverage containers; food containers; household or commercial cleaning
i product containers; and containers for oils, antifreeze or other industrial fluids. The
containers can be made of a wide variety of materials including glasses; plastics
(e.g., polyolefins such as polyethylene and polypropylene; polystyrenes; polyesters
such as PET and polyethylene naphthalate (PEN); polyarnides, polycarbonates; and
mixtures or copolymers thereof); metals (e.g., aluminum, tin or steel); papers (e.g.,
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WO 2(107/040677 PCT/US2006/023299
untreated, treated, waxed or other coated papers); ceramics; and laminates or
composites of two or more of these materials (e.g., laminates of RET, PEN or
mixtures thereof with another plastic material). The containers can have a variety of
sizes and forms, including cartons (e.g., waxed cartons or TETRAPACK™ boxes),
cans, bottles and the like. Although any desired portion of the container can be
coated with the lubricant composition, the lubricant composition preferably is
applied only to parts of the container that will come into contact with the conveyor
or with other containers. For some such applications the lubricant composition
preferably is applied to the conveyor rather than to the container.
The lubricant composition can be a liquid or semi-solid at the time of
application. Preferably the lubricant composition is a liquid having a viscosity that
will permit it to be pumped and readily applied to a conveyor or containers, and that
will facilitate rapid film formation whether or not the conveyor is in motion. The
lubricant composition can be formulated so that it exhibits shear thinning or other
pseudo-plastic behavior, manifested by a higher viscosity (e.g., non-dripping
behavior) when at rest, and a much lower viscosity when subjected to shear stresses
such as those provided by pumping, spraying or brushing the lubricant composition.
This behavior can be brought about by, for example, including appropriate types and
amounts of thixotropic fillers (e.g., treated or untreated fumed silicas) or other
rheology modifiers in the lubricant composition.
Methods of Application
The lubricant coating can be applied in a constant or intermittent fashion.
Preferably, the lubricant coating is applied in an intermittent fashion in order to
minimize the amount of applied lubricant composition. It has been discovered that
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WO 2(107/040677 PCT/US2006/023299
the compositions of the present invention may be applied intermittently and
maintain a low coefficient of friction in between applications, or avoid a condition
known as "drying". Specifically, compositions of the present invention may be
applied for a period of time and then not applied for at least 15 minutes, at least 30
minutes, or at least 120 minutes or longer. The application period may be long
enough to spread the composition over the conveyor belt (i.e. one revolution of the
conveyor belt). During the application period, the actual application may be
continuous, i.e. lubricant is applied to the entire conveyor, or intermittent, i.e.
lubricant is applied in bands and the containers spread the lubricant around. The
lubricant is preferably applied to the conveyor surface at a location that is not
populated by packages or containers. For example, it is preferable to apply the
lubricant spray upstream of the package or container flow or on the inverted
conveyor surface moving underneath and upstream of the container or package.
In some embodiments, the ratio of application time to non-application time
may be 1:10, 1:30, 1:180, and 1:500 where the lubricant maintains a low coefficient
of friction in between lubricant applications.
In some embodiments, the lubricant maintains a coefficient of friction below
about 0.2, below about 0.15, and below about 0.12.
In some embodiments, a feedback loop may be used to determine when the
coefficient of friction reaches an unacceptably high level. The feedback loop may
trigger the lubricant composition to turn on for a period of time and then optionally
turn the lubricant composition off when the coefficient of friction returns to an
acceptable level.
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WO 2007/040677 PCT/US2006/023299
The lubricant coating thickness preferably is maintained at at least about
0.0001 mm, more preferably about 0.001 to about 2 mm, and most preferably about
0.005 to about 0.5 mm.
Application of the lubricant composition can be carried out using any
suitable technique including spraying, wiping, brushing, drip coating, roll coating,
and other methods for application of a thin film.
The lubricant compositions can if desired be evaluated using a Contact
Angle Measurement Test, a Surface Tension Test, a Coating Test, a Short Track
Conveyor Test, a Foam Profile Test, and a PET Stress Crack Test.
Contact Angle Measurement Test
For the present invention, the contact angle of lubricant use compositions
was measured using an FTA 200 Dynamic Contact Angle Analyzer available from
First Ten Angstroms, Portsmouth, VA. A droplet of use composition was applied to
Melinex 516 uncoated polyethylene terephthalate film using a 1 inch 22 gauge
needle and the contact angle measured 10 seconds after applying the drop to the
film. Melinex 516 film is a product of Dupont Teijin Films and is available in sheets
from GE Polymershapes, Huntersville, NC.
Surface Tension Test
The surface tension of lubricant compositions was measured using a K12
Microbalancc Surface Tensiometer available from Kriiss USA, Charlotte, NC.
According to this method, the surface tension force resisting advancement of a
platinum
Wilhelmy plate into a sample of the conveyor lubricant mixture was measured
directly
38

WO 2007/040677 PCT/US2006/023299
and the surface tension is reported mN/m (equivalent to dyne/cm).
Coating Test
A wet coating of lubricant composition was prepared by pipetting
approximately 4 mL of lubricant composition onto an approximately 90 square inch
sample of Melinex 516 uncoated polyethylene terephthalate film and spreading the
puddle across the film surface by hand using a number 6 Mayer bar (available from
RD Specialties, Webster NY). The thickness of the wet coating was approximately
14 microns. The wet film was observed for wetting properties and defects in the wet
coating including beading up and localized de-wetting. The coating was allowed to
dry under ambient conditions and the properties of the dried film noted including
contiguity and percent surface coverage.
Short Track Conveyor Test
A conveyor system employing a motor-driven 83 mm wide by 6.1 meter
long REXNORD1M LF polyacetal thermoplastic conveyor belt was operated at a belt
speed of 30.48 meters/minute. Four 20 ounce filled PET beverage bottles were
lassoed and connected to a stationary strain gauge. The force exerted on the strain
gauge during belt operation was recorded using a computer. A thin, even coat of the
lubricant composition was applied to the surface of the belt using conventional
lubricant spray nozzles which apply a total of 4 gallons of lubricant composition per
hour. The belt was allowed to run for 25 to 90 minutes during which time a
consistently low drag force was observed. The coefficient of friction (COF) was
calculated by dividing the drag force (F) by the weight of the four 20 ounce filled
PUT beverage bottles (W): COF = F/W.
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WO 2007/040677 PCT/US2006/023299
Foam Profile Test
According to this test, 200 mL of room temperature lubricant composition in
a stoppered 500 mL glass graduated cylinder was inverted 10 times. Immediately
after the tenth inversion, the total volume of liquid plus foam was recorded. The
stoppered cylinder was allowed to remain stationary, and 60 seconds after the last
inversion of the cylinder the total volume of liquid plus foam was recorded. The
foam profile value is the ratio of the total volume of liquid plus foam at 60 seconds
divided by the original volume.
PET Stress Crack Test
Compatibility of lubricant compositions with PET beverage bottles was
determined by charging bottles with carbonated water, contacting with lubricant
composition, storing at elevated temperatures and humidity for a period of 28 days,
and counting the number of bottles that either burst or leaked through cracks in the
base portion of the bottle. Standard twenty ounce "Global Swirl" bottles (available
from Constar International) were charged successively with 658 g of chilled water at
0 lo 5 C, 10.6 g of citric acid, and 10.6 g of sodium bicarbonate. Immediately after
addition of sodium bicarbonate, the charged bottle was capped, rinsed with
deionized water and stored at ambient conditions (20 - 25 C) overnight. Twenty four
bottles thus charged were dipped in lubricant working composition up to the seam
which separates the base and sidewall portions of the bottle and swirled for
approximately five seconds, then placed in a standard bus pan (part number
4034039, available from Sysco, Houston TX) lined with a polyethylene bag.
Additional lubricant working composition was poured into the bus pan around the
bottles so that the total amount of lubricant composition in the pan (carried in on
40

WO 2007/040677 PCT/IIS2006/023299
bottles and poured in separately) was equal to 132 g. The lubricant composition was
not foamed for this test. For each lubricant tested, a total of four bus pans of 24
bottles were used. Immediately after placing bottles and lubricant into bus pans, the
bus pans were removed to a humidity chamber under conditions of 100 F and 85%
relative humidity. Bins were checked on a daily basis and number of failed bottles
(burst or leak of liquid through cracks in the bottle base) was recorded. At the end of
28 days, the amount of crazing on the base region of bottles that did not fail during
humidity testing was evaluated. A visual crazing score was given to bottles where 0
= no crazing is evident, the bottle base remains clear; and 10 = pronounced crazing
to s he extent that the base has become opaque.
EXAMPLES
The invention can be better understood by reviewing the following
examples.
The examples are for illustration purposes only, and do not limit the scope of the
invention.
COMPARATIVE EXAMPLE A
(Deionized water with 200 ppm added alkalinity)
A solution of deionized water containing 200 ppm alkalinity as CaC03 was
prepared by dissolving 0.336g of sodium bicarbonate in lOOOg of deionized water.
The contact angle of the solution on PET film was determined to be 67 degrees. The
wetting behavior of the solution was evaluated by the coating test described above.
Upon coating, the solution beaded up immediately giving isolated drops which dried
to give water spots which covered approximately 5% of the film surface. The foam
profile value for the solution measured as described above was 1.0. The alkaline
41

WO 2(107/040677 PCT/US2006/023299
water solution was tested for PET compatibility as described above. After 28 days of
storage under conditions of 100 F and 85% relative humidity, 20 of 96 bottles had
failed (21%). The visual crazing score for the unfailed bottles in this test was 1.7.
COMPARATIVE EXAMPLE B
(silicone lubricant)
A solution of deionized water containing 2000 ppm alkalinity as CaC03 was
prepared by dissolving 3.36 g of sodium bicarbonate in lOOOg of deionized water. A
lubricant composition was prepared by adding 5.0 g of a 10% dilution of Lambent
E2140FG silicone emulsion with water and 200 g of 2000 ppm alkaline water to
1795 g of deionized water. The lubricant composition contained 250 ppm Lambent
E2140FG silicone emulsion and 336 ppm sodium bicarbonate (equivalent to 200
ppm alkalinity as CaC03). The contact angle of the lubricant composition on PET
film was determined to be 64 degrees, and the surface tension of the composition
was 38.7 dynes/cm. The wetting behavior of the lubricant composition was'
evaluated by the coating test described above. Upon coating, the composition
beaded up immediately giving isolated drops which dried to give water spots which
covered approximately 5% of the film surface. The foam profile value for the
composition measured as described above was 1.0. The silicone lubricant
composition was tested for PET compatibility whereupon after 28 days of storage
under conditions of 100'F and 85% relative humidity, 22 of 96 bottles had failed
(23%). The visual crazing score for the unfailed bottles in this test was 2.1. What
this comparative example shows is that addition of silicone lubricant to alkaline
water does not cause a significant change in the proportion of failed bottles in the
PET compatibility test relative to alkaline water alone.
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WO 2007/040677 PCT/US2006/023299
EXAMPLE 1
(silicone lubricant plus alcohol ethoxylate wetting agent)
A lubricant composition was prepared by adding 8.0 g of a 10% aqueous
solution of Surfonic L 24-7 surfactant (available from Huntsman Chemical, Houston
TX) to 992 g of the silicone lubricant composition of Comparative Example B. The
lubricant composition contained 248 ppm Lambent E2140FG silicone emulsion, 800
ppm of Surfonic L 24-7, and 333 ppm sodium bicarbonate (equivalent to 200 ppm
alkalinity as OaCO.-)). The contact angle of the lubricant composition on PET film
was determined to be 24 degrees, and the surface tension of the composition was
28.3 dynes/cm. The wetting behavior of the lubricant composition was evaluated by
the coating test described above. Upon coating, the composition gave a uniform film
with approximately 10 pin head size spots where the liquid had partially de wet the
surface. When dried, the coating was slightly hazy, with about 16 spots about 1 cm
in diameter where the composition had partially de wet the film. Around each defect
was a diffuse hazy halo. The dried coating covered approximately 95% of the
surface. The foam profile value for the composition measured as described above
was 1.9. The silicone plus alcohol ethoxylate composition lubricant was tested for
P'l 85% relative humidity, 14 of 96 bottles had failed (15%). The visual crazing score
for the unfailed bottles in this test was 6.8. What this example shows is that addition
of an alcohol ethoxylate wetting agent to a silicone lube improves the wetting of the
lubricant composition to a PET surface and gives a reduction in the failure rate of
bottles in the PET compatibility test compared to a silicone lubricant without
wetting agent.
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WO 2007/040677 PCT/US2006/023299
EXAMPLE 2
(silicone lubricant plus silicone wetting agent)
A lubricant composition was prepared by adding 5.2 g of a 10% aqueous
solution of Silwet 1.-11 surfactant (available from GE Silicones, Friendly, WV) to
1000 g of the silicone lubricant composition of Comparative Example B. The
lubricant composition contained 249 ppm Lambent E2140FG silicone emulsion, 517
ppm of Silwet L-77, and 334 ppm sodium bicarbonate (equivalent to 200 ppm
alkalinity as CaCOs). The contact angle of the lubricant composition on PET film
was determined to be 49 degrees. The surface tension of the composition was 23.6
dynes/cm. The wetting behavior of the lubricant composition was evaluated by the
coating test described above. Upon coating, the composition gave a film with
approximately 100 spots of about 0.5 cm diameter where the liquid had de wet the
surface. When dried, the coating was hazy, with about 100 de wet spots about 0.7
cm in diameter. Around each defect was a diffuse hazy halo. The dried coating
covered approximately 50% of the surface. The foam profile value for the
composition measured as described above was 1.1. The silicone plus silicone
wetting agent lubricant composition was tested for PET compatibility whereupon
after 28 days of storage under conditions of 100 F and 85% relative humidity, 14 of
96 bottles had failed (15%). The visual crazing score for the unfailed bottles in this
test was 6.3. What this example shows is that addition of a silicone surfactant
wetting agent to a silicone lube improves the wetting of the lubricant composition to
a PET surface and gives a reduction in the failure rate of bottles in the PET
compatibility test compared to a silicone lubricant without wetting agent.
44

WO 2(107/040677 PCT/US2006/023299
EXAMPLE 3
(silicone lubricant plus nonyl phenol ethoxylate wetting agent)
A lubricant composition was prepared by adding 8.0 g of a 10% aqueous
solution of Surfonic N95 surfactant (available from Huntsman Chemical, Houston
TX) to 992 g of the silicone lubricant composition of Comparative Example B. The
lubricant composition contained 249 ppm Lambent E2140FG silicone emulsion, 800
ppm of Silwet L-77, and 334 ppm sodium bicarbonate (equivalent to 200 ppm
alkalinity as CaC03). The contact angle of the lubricant composition on PET film
was determined to be 15 degrees. The surface tension of the composition was 42.4
dynes/cm. The wetting behavior of the lubricant composition was evaluated by the
coating test described above. Upon coating, the composition gave a substantially
uniform film with no defects or de wet spots. When dried, the coating was slightly
hazy, with non-uniform gradations of haziness. The dried coating covered
approximately 99% of the surface. The foam profile value for the composition
measured as described above was 1.8. The silicone plus nonyl phenol ethoxylate
wetting agent lubricant composition was tested for PET compatibility whereupon
after 28 days of storage under conditions of 100F C and 85% relative humidity, 10
of 96 bottles had failed (10%). The visual crazing score for the unfailed bottles in
this test was 7.8. What this example shows is that addition of a nonyl phenol
ethoxylate wetting agent to a silicone lube improves the wetting of the lubricant
composition to a PET surface and gives a reduction in the failure rate of bottles in
the PET compatibility test compared to a silicone lubricant without wetting agent.
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WO 2007/040677 PCT/US2006/023299
EXAMPLE 4
(silicone lubricant plus fatty amine plus alcohol ethoxylate wetting agent)
An acidified fatty amine solution was prepared by adding 29 g of glacial
acetic acid and 80.0g of Duomeen OL (available from Akzo Nobel Surface
Chemistry LLC, Chicago, TL) to 691 g of deionized water. A lubricant concentrate
composition was prepared by adding 15 g of Lambent E2140FG silicone emulsion,
24 g of Surfonic L 24-7 surfactant, and 150 g of acidified fatty amine solution to 111
« of deionized water. A lubricant composition was prepared by adding 5.0 g of the
lubricant concentrate composition to a solution of 0.336 g of sodium bicarbonate in
1 OOOg of deionized water. The lubricant composition contained 250 ppm Lambent
H2140FG silicone emulsion, 250 ppm of Duomeen OL, 400 ppm of Surfonic L 24-7,
and 336 ppm sodium bicarbonate (equivalent to 200 ppm alkalinity as CaC03). The
contact angle of the lubricant composition on PET film was determined to be 32
degrees. The surface tension of the composition was 28.0 dynes/cm. The wetting
behavior of the lubricant composition was evaluated by the coating test described
above. Upon coating, the composition gave a film with approximately 50 pencil
eraser size dc wet spots which dried to give an imperfect film which covered
approximately 80% of the PET surface. The foam profile value for the composition
measured as described above was 1.8. The lubricant composition was tested for
PET compatibility as described above whereupon after 28 days of storage under
conditions of 100 F and 85% relative humidity, 7 of 96 bottles had failed (7%). The
visual crazing score for the unfailed bottles in this test was 4.1. What this example
shows is that addition of a wetting agent comprising a mixture of acidified fatty
amine and alcohol ethoxylate compounds to a silicone lube improves the wetting of
46

WO 2(107/040677 PCT/US2006/023299
the lubricant composition to a PET surface and gives a reduction in the failure rate
of bottles in the PET compatibility test compared to a silicone lubricant without
wetting agent.
COMPARATIVE EXAMPLE C
(Deionized water with 100 ppm added alkalinity)
A solution of deionized water containing 100 ppm alkalinity as CaC03 was
prepared by dissolving 0.168 g of sodium bicarbonate in lOOOg of deionized water.
The wetting behavior of the solution was evaluated by the coating test described
above. Upon coating, the solution beaded up immediately giving isolated drops
which dried to give water spots which covered approximately 5% of the film
surface. The alkaline water solution was tested for PET compatibility as described
above. After 28 days of storage under conditions of 100 F and 85% relative
humidity, 19 of 120 bottles had failed (16%). The visual crazing score for the
unfailed bottles in this test was 1.4.
COMPARATIVE EXAMPLE D
(silicone plus water-miscible lubricant)
A lubricant composition was prepared which contained 125 ppm Lambent
K2140FG silicone emulsion, 7.5 ppm Pluronic F108 poly(ethylene oxide-propylene
oxide) block copolymer, 5.0 ppm methyl paraben, and 168 ppm sodium bicarbonate
(equivalent to 100 ppm alkalinity as CaCOs). The contact angle of the lubricant
composition on PET film was determined to be 64 degrees. The wetting behavior of
the lubricant composition was evaluated by the coating test described above. Upon
coating, the composition beaded up immediately giving isolated drops which dried
to give water spots which covered approximately 5% of the film surface. The
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WO 2007/040677 PO7US2006/023299
silicone plus watcr-miscible lubricant composition was tested for PET compatibility
whereupon after 28 days of storage under conditions of 100 F and 85% relative
humidity, 9 of 48 bottles had failed (19%). What this comparative example shows is
that addition of a composition of silicone plus water-miscible lubricant to alkaline
water does not cause a significant improvement in wetting of the composition to a
PET surface and does not cause a significant improvement in the proportion of
failed bottles in the PET compatibility test relative to alkaline water alone.
COMPARATIVE EXAMPLE E
(commercial silicone lubricant)
A commercial lubricant composition was prepared which contained 2500
ppm of Dicolube TPB (product of Johnson Diversey) and 168 ppm sodium
bicarbonate (equivalent to 100 ppm alkalinity as CaC03). The contact angle of the
lubricant composition on PET film was determined to be 72 degrees. The wetting
behavior of the lubricant composition was evaluated by the coating test described
above. Upon coating, the composition beaded up immediately giving isolated drops
which dried to give water spots which covered less than 5% of the film surface. The
commercial lubricant composition was tested for PET compatibility whereupon after
28 days of storage under conditions of 100 F and 85% relative humidity, 7 of 48
bottles had failed (15%). What this comparative example shows is that addition of a
composition of a commercial silicone lubricant to alkaline water does not cause a
significant improvement in wetting of the composition to a PET surface and does
not cause a significant improvement in the proportion of failed bottles in the PET
compatibility test relative to alkaline water alone.
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WO 2(107/040677 PCT/IJS2006/023299
EXAMPLE 5
(silicone lubricant plus fatty amine plus alcohol ethoxylate wetting agent)
An acidified fatty amine solution was prepared by adding 29 g of glacial
acetic acid and 80.0g of Duomeen OL (available from Akzo Nobel Surface
Chemistry LLC, Chicago, IL) to 691 g of deionized water. A lubricant concentrate
composition was prepared by adding 25.0 g of acidified fatty amine composition,
8.0 g of Surfonic L 24-7 surfactant, and 2.5 g of Dow Corning HV-490 silicone
emulsion to 64.5 g of deionized water. A lubricant composition was prepared by
adding 5.0 g of the lubricant concentrate composition to a solution of 0.168 g of
sodium bicarbonate in 1 OOOg of deionized water. The lubricant composition
contained 125 ppm Dow Corning HV-490 silicone emulsion, 125 ppm of Duomeen
01,, 400 ppm of Surfonic L 24-7, and 168 ppm sodium bicarbonate (equivalent to
100 ppm alkalinity as CaCC^). The contact angle of the lubricant composition on
PET film was determined to be 29 degrees. The wetting behavior of the lubricant
composition was evaluated by the coating test described above. Upon coating, the
composition gave a continuous coating with about 40 de wet areas about 0.5 to 1 cm
in diameter. The wet coating covered about 80 - 90% of the PET surface. Upon
drying, the composition gave a substantially continuous film which covered
approximately 70% of the PET surface. The foam profile value for the composition
measured as described above was 1.8. The lubricant composition was tested for
PET compatibility as described above whereupon after 28 days of storage under
conditions of 100E and 85% relative humidity, 9 of 96 bottles had failed (9%). The
visual crazing score for the unfailed bottles in this test was 7.5. What this example
shows is that addition of a composition of a wetting agent comprising a mixture of
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WO 2007/040677 PCT/US2006/023299
acidified fatty amine and alcohol ethoxylate compounds to a silicone lubricant
causes an improvement in wetting of the composition to a PET surface and an
improvement in the proportion of failed bottles in the PET compatibility test relative
to a silicone plus water-miscible lubricant composition.
EXAMPLE 6
(Silicone lubricant plus citric acid/sodium citrate plus alcohol ethoxylate wetting
agent)
A lubricant concentrate composition was prepared by adding 2.5g of Dow
Corning HV-490 silicone emulsion, 7.0g citric acid, 2.1 g of a 50% solution of
NaOH, 2.0 g of Tomadol 91-8 alcohol ethoxylate, and 2.85g of a 35% solution of
H2O2 to 83.6 g deionized water. A lubricant composition was prepared by diluting
! .0 g of the lubricant concentrate composition with 399 g of a solution of 168 ppm
sodium bicarbonate in deionized water. The resulting lubricant composition
contained 63 ppm Dow Corning HV-490 silicone emulsion, 175 ppm citric acid, 26
ppm NaOH, 50 ppm Tomadol 91-8 alcohol ethoxylate, 25 ppm H2O2, and 168 ppm
sodium bicarbonate (equivalent to 100 ppm alkalinity as CaCCh). The ratio of
unneutralizcd acid equivalents from the lubricant concentrate composition to
equivalents of base from the alkaline water was 1.00 to 1.00. The pH of the
lubricant composition was 5.94. The contact angle of the lubricant composition on
PET film was determined to be 58 degrees. The wetting behavior of the lubricant
composition was evaluated by the coating test described above. Upon coating, the
composition beaded up immediately and dried to give spots which covered less than
5% of the PET surface. The foam profile value for the composition measured as
described above was 1.3. The silicone lubricant composition was tested for PET
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WO 2007/040677 PCT/US2006/023299
compatibility as described, except that 20 oz "Contour" bottles available from
Southeastern Container Corp. (Enka, NC) were substituted for 20 ounce "Global
Swirl" bottles. After 28 days of storage under conditions of 100 F and 85% relative
humidity, 1 of 96 bottles had failed (1%). The crazing score for the unfailed bottles
: in this test was 3.4. What this example shows is that including approximately one
equivalent of unneutralized acid for every equivalent of alkalinity in lube dilution
water and decreasing the contact angle of the lubricant composition to less than
about 60 degrees is capable to reduce the failure rate of bottles in the PET
compatibility test relative to a silicone plus water-miscible lubricant composition. In
) a separate test, 20 g of the lubricant concentrate composition was diluted with 10 Kg
of city water and the coefficient of friction using the Short Track Conveyor Test
described above. The coefficient of friction between 4 20 ounce "Global Swirl"
bottles and Delrin track was 0.11.
EXAMPLE 7
i (silicone lubricant plus fatty amine plus alcohol ethoxylate wetting agent
plus lactic acid)
An acidified fatty amine solution was prepared by adding 29 g of glacial
acetic acid and 80.Og of Duomecn OL (available from Akzo Nobel Surface
Chemistry LLC, Chicago, IL) to 691 g of deionized water. A lubricant concentrate
i composition was prepared by adding 25.0 g of acidified fatty amine solution, 8.0 g
of Surfonic L 24-7 surfactant, 6.5 g of 88% lactic acid, and 2.5g of Lambent
K2140FG silicone emulsion to 58.0 g of deionized water. A lubricant composition
was prepared by adding 5.0 g of the lubricant concentrate composition to a solution
of 0.168 g of sodium bicarbonate in lOOOg of deionized water. The lubricant
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WO 2(107/040677 PCT/1JS2006/023299
composition contained 125 ppm Lambent E2140FG silicone emulsion, 125ppm of
Duomeen OL, 400 ppm of Surfonic L 24-7, 286 ppm lactic acid, and 168 ppm
sodium bicarbonate (equivalent to 100 ppm alkalinity as CaCOs). The contact angle
of the lubricant composition on PET film was determined to be 39 degrees. The
wetting behavior of the lubricant composition was evaluated by the coating test
described above. Upon coating, the composition gave a film with approximately 30
pencil eraser size de wet spots which dried to give an imperfect film which covered
approximately 75% of the PET surface. The foam profile value for the composition
measured as described above was 1.7. The lubricant composition was tested for PET
compatibility as described, except that 20 oz "Contour" bottles available from
Southeastern Container Corp. (Enka, NC) were substituted for 20 ounce "Global
Swirl" bottles. After 28 days of storage under conditions of 100 F and 85% relative
humidity, 0 of 96 bottles had failed (0%). The visual crazing score for the unfailed
bottles in this test was 7.6. What this example shows is that addition of a wetting
agent comprising a mixture of acidified fatty amine and alcohol ethoxylate
compounds and a stoichiometric amount of organic acid to a silicone lubricant
composition causes an improvement in wetting of the composition to a PET surface
and an improvement in the proportion of failed bottles in the PET compatibility test
relative to a silicone plus water-miscible lubricant composition.
EXAMPLES 8 -14 AND COMPARATIVE EXAMPLES F -1
Twelve lubricant formulations were prepared according to the formulas of
Table 1. These lubricant compositions were evaluated using the Contact Angle
Measurement Test, the Coating Test, and the Foam Profile Test. Comparative
Examples F, G, H and I have poor wetting to PET film, generally exhibiting contact
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WO 2007/040677 P(TAJS2006/023299
angles greater than about 60 degrees using the Contact Angle Measurement Test and
areal coverages less than about 30% using the Coating Test. Examples 8-14
(Invention) show good wetting, generally exhibiting contact angles less than about
60 degrees using the Contact Angle Measurement Test and areal coverages greater
than about 30% using the Coating Test.

Table 1
Example F Example G Example H Example I
(Comp.) (Comp.) (Comp.) (Comp.) Example 7 Example 8
Sodium Bicarbonate, 168 334 334 334 331 331
Lambent E2140FG 125
Dicolube TPB 5000 5000
Lubodrivc FP 5000
5000
Composition of Example 2 from US Patent 6495494 5000 _ 800 800
Sulfonic 1.24-7



Rhtxlafac RA-600

NaOH
Harlox 12 (30% lauryl dimethyl amine N-oxide)
Glucopon 425 N (50% alklyl polyglucoside)


Tomadol91-8
Antarox HL-240


4gof8%TomahPA-1618 22
contact angle 68 69 64 70
22
wet coating coverage dry coating coverage 99% about 95%
foam profile value 1.0 1.0 1.0 1.0 1.6 1.6
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WO 2007/040677 PCT/US2006/023299

Example 9 Example 10 Example 11 Example
12 Example 13 Example
14
Sodium Bicarbonate 331 332 332 332 329 332
lambent E2140FG 125 125 125 124 125
Dicolube TPB -- -
Lubodrive FP

Composition of Example 2 from US Patent 6495494 5000
Surfonic L 24-7 800
Rhodafac RA-600 800
NaOH 130
Barlox 17, (30% lauryl dimethyl amine N-oxide)
3750
Glucopon 425 N (50% alklyl polyglucoside)
1600
Tomadol 91-8
792
Antarox BL-240 792
4 R of 8% Toman PA 1618 800
contact angle 25 41 37 32 19 21
wet coating coverage about 100% about 100% about 100% about 90% about 100% about 50%
dry coating coverage about 95% about 95% about 95% about 80% about 80% about 30%
foam profile value 1.8 1.9 2.0 1.6 1.3 1.3
Various modifications and alterations of this invention will be apparent to
those skilled in the art without departing from the scope and spirit of the invention,
and are intended to be within the scope of the following claims.

WO 2007/040677 PCT/US2006/023299
WHAT IS CLAIMED IS:
1. A method for lubricating the passage of a container along a conveyor,
comprising applying a lubricant composition to at least a portion of the container-
contacting surface of the conveyor or to at least a portion of the conveyor-contacting
surface of the container, the lubricant composition comprising from about 0.0005
wt. % to about 5.0 wt. % of a water-miscible silicone material wherein the contact
angle between the lubricant composition and container is less than about 60 degrees.
2. The method of claim 1, wherein the silicone material is selected from the
group consisting of silicone emulsion, finely divided silicone powder, and silicone
surfactant.
3. The method of claim 1, wherein the lubricant composition further comprises
one or more functional ingredients selected from the group of water-miscible
lubricants, hydrophilic diluents, antimicrobial agents, stabilizing/coupling agents,
detergents/ dispersing agents, anti-wear agents, viscosity modifiers, sequestrants,
corrosion inhibitors, and mixtures thereof.
4. The method of claim 1, wherein the lubricant composition comprises from
about 0.002 wt. % to about 0.5 wt. % of a water-miscible silicone material.
5. The method of claim 1, wherein the container comprises one or more
polymers selected from the group of polyethylene terephthalate, polyethylene
naphthalate, and bisphenol A carbonate.
6. The method of claim 1, wherein the contact angle between the lubricant
composition and polyethylene terephthalate is less than about 50 degrees.
7 The method of claim 1, wherein the contact angle between the lubricant
composition and polyethylene terephthalate is less than about 40 degrees.
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WO 2007/040677 PCT/US2006/023299
8. The method of claim 1, wherein the lubricant composition is applied for a
period of time and off for a period of time and the ratio of applied time to off time is
at least 1:1.
9. The method of claim 1, wherein the lubricant composition further comprises
from about 0.01 wt. % to about 0.50 wt. % of at least one wetting agent.
10. The method of claim 1, wherein the lubricant composition further comprises
from about 0.02 wt. % to about 0.30% of at least one wetting agent.
11. The method of claim 9, wherein the wetting agent is selected from the group
consisting of a fatty amine, an alcohol ethoxylate and mixtures thereof.
12. A method for lubricating the passage of a container along a conveyor,
comprising applying a lubricant composition to at least a portion of the container-
contacting surface of the conveyor or to at least a portion of the conveyor-contacting
surface of the container, the lubricant composition comprising from about 0.0005%
to about 5.0% of a water-miscible silicone material wherein the lubricant
composition forms a substantially contiguous coating which covers greater than
about 30% of the surface when coated and dried onto polyethylene terephthalate
film with a wet coating thickness of about 14 microns.
13. The method of claim 12, wherein the silicone material is selected from the
group consisting of silicone emulsion, finely divided silicone powder, and silicone
surfactant.
1.4. The method of claim 12, wherein the lubricant composition further
comprises one or more functional ingredients selected from the group of water-
miscible lubricants, hydrophilic diluents, antimicrobial agents, stabilizing/coupling
56

WO 2007/040677 PCT/US2006/023299
agents, detergents/ dispersing agents, anti-wear agents, viscosity modifiers,
sequestrants, corrosion inhibitors, and mixtures thereof.
15. The method of claim 12, wherein the lubricant composition comprises from
about 0.002 wt. % to about 0.5 wt. % of a water-miscible silicone lubricant.
16. The method of claim 12, wherein the container comprises one or more
polymers selected from the group of polyethylene terephthalate, polyethylene
naphthalate, and bisphenol A carbonate.
17. The method of claim 12, wherein the lubricant composition forms a
substantially contiguous coating which covers greater than about 50% of the surface
when coated and dried onto polyethylene terephthalate film with a wet coating
thickness of about 14 microns.
18. The method of claim 12, wherein the lubricant composition forms a
substantially contiguous coating which covers greater than about 70% of the surface
when coated and dried onto polyethylene terephthalate film with a wet coating
thickness of about 14 microns.
19. The method of claim 12, wherein the lubricant composition is applied for a
period of time and off for a period of time and the ratio of applied time to off time is
at least 1:1.
20. The method of claim 12, wherein the lubricant composition further
comprises from about 0.01 wt. % to about 0.50 wt. % of at least one wetting agent.
21. The method of claim 12, wherein the lubricant composition comprises from
about 0.02 wt. % to about 0.30 wt. % of at least one wetting agent.
22. The method of claim 20, wherein the wetting agent is selected from the
group consisting of a fatty amine, an alcohol ethoxylate, and mixtures thereof.
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23. A method for lubricating the passage of a container along a conveyor,
comprising applying a lubricant composition to at least a portion of the container-
contacting surface of the conveyor or to at least a portion of the conveyor-contacting
surface of the container, the lubricant composition comprising from about 0.0005
wt. % to about 5.0 wt. % of a water-miscible silicone material wherein the foam
profile for the composition is greater than about 1.1.
24. The method of claim 23, wherein the silicone material is selected from the
group consisting of silicone emulsion, finely divided silicone powder, and silicone
surfactant.
25. The method of claim 23, wherein the lubricant composition further
comprises one or more functional ingredients selected from the group of water-
miscible lubricants, hydrophilic diluents, antimicrobial agents, stabilizing/coupling
agents, detergents/ dispersing agents, anti-wear agents, viscosity modifiers,
sequestrants, corrosion inhibitors and mixtures thereof.
26. The method of claim 23, wherein the lubricant composition comprises from
about 0.002 wt. % to about 0.5 wt. % of a water-miscible silicone material.
27. The method of claim 23, wherein the container comprises one or more
polymers selected from the group of polyethylene terephthalate, polyethylene
naphthalate, and bisphenol A carbonate.
28. The method of claim 23, wherein the foam profile for the composition is
greater than about 1.3.
29. The method of claim 23, wherein the foam profile for the composition is
greater than about 1.5.
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WO 2007/040677 PCT/US2006/023299
59
30. The method of claim 23, wherein the lubricant composition is applied for a
period of time and off for a period of time and the ratio of applied time to off time is
at least 1:1.
31. The method of claim 23, wherein the lubricant composition further
comprises from about 0.01 wt. % to about 0.50 wt. % of at least one wetting agent.
32. The method of claim 23, wherein the lubricant composition further
comprises from about 0.02 wt. % to about 0.30 wt. % of at least one wetting agent.
33. The method of claim 23, wherein the wetting agent is selected from the
group consisting of a fatty amine, an alcohol ethoxylate, and mixtures thereof.

The passage of a container along a conveyor is lubricated by
applying to the container or conveyor a composition comprising a
water-miscible silicone material wherein the composition has
good wetting to polyethylene terephthalate surfaces. The
compatibility of the lubricating composition with polyethylene
terephthalate is increased because the wetting of the
composition to polyethylene terephthalate is improved.

Documents:

01151-kolnp-2008-abstract.pdf

01151-kolnp-2008-claims.pdf

01151-kolnp-2008-correspondence others.pdf

01151-kolnp-2008-description complete.pdf

01151-kolnp-2008-form 1.pdf

01151-kolnp-2008-form 2.pdf

01151-kolnp-2008-form 3.pdf

01151-kolnp-2008-form 5.pdf

01151-kolnp-2008-international publication.pdf

01151-kolnp-2008-international search report.pdf

01151-kolnp-2008-pct priority document notification.pdf

01151-kolnp-2008-pct request form.pdf

1151-KOLNP-2008-(02-11-2012)-CORRESPONDENCE.pdf

1151-KOLNP-2008-(07-08-2013)-ABSTRACT.pdf

1151-KOLNP-2008-(07-08-2013)-AMANDED PAGES OF SPECIFICATION.pdf

1151-KOLNP-2008-(07-08-2013)-CLAIMS.pdf

1151-KOLNP-2008-(07-08-2013)-CORRESPONDENCE.pdf

1151-KOLNP-2008-(07-08-2013)-FORM-1.pdf

1151-KOLNP-2008-(07-08-2013)-FORM-2.pdf

1151-KOLNP-2008-(07-08-2013)-OTHERS.pdf

1151-KOLNP-2008-(07-08-2013)-PETITION UNDER RULE 137.pdf

1151-KOLNP-2008-(12-08-2013)-CORRESPONDENCE.pdf

1151-KOLNP-2008-(12-08-2013)-PA.pdf

1151-KOLNP-2008-(17-04-2014)-ANNEXURE TO FORM 3.pdf

1151-KOLNP-2008-(17-04-2014)-CORRESPONDENCE.pdf

1151-KOLNP-2008-(17-04-2014)-OTHERS.pdf

1151-KOLNP-2008-(17-04-2014)-PETITION UNDER RULE 137.tif

1151-kolnp-2008-form 18.pdf


Patent Number 265802
Indian Patent Application Number 1151/KOLNP/2008
PG Journal Number 12/2015
Publication Date 20-Mar-2015
Grant Date 18-Mar-2015
Date of Filing 18-Mar-2008
Name of Patentee ECOLAB INC.
Applicant Address ECOLAB CENTER 370 N, WABASHA STREET ST.PAUL, MINNESOTA 55102
Inventors:
# Inventor's Name Inventor's Address
1 MORRISON, ERIC, D. 938 DELAWARE AVENUE, WEST ST., PAUL, MN 55118
2 MAN, VICTOR, F. 1410 CARLING DRIVE, APT. 207, ST. PAUL, MN 55108
3 BESSE, MICHAEL E. 7450 WINNETKA HEIGHT DRIVE, GOLDEN VALLEY, MN 55427
4 JOHNSON, RICHARD, D 78 TENTH STREET EAST, APT. 2901 ST. PAUL, MN 55101
PCT International Classification Number C10M 173/02
PCT International Application Number PCT/US2006/023299
PCT International Filing date 2006-06-16
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 11/233,596 2005-09-22 U.S.A.