Title of Invention

SILICONE CONVEYOR LUBRICANT WITH STOICHIOMETRIC AMOUNT OF AN ACID

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 comprises a stoichiometric amount of an organic acid. The compatibility of the lubricating composition with polyethylene terephthalate is increased because of the presence of a stoichiometric amount of acid.
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SILICONE CONVEYOR LUBRICANT WITH
STOICHIOMETRIC AMOUNT OF AN ACID
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
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
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
terephthalate (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
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
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

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of occurrence of environmental stress cracking are considered incompatible with
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 CaCC>3 (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 CaCOs) 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
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compatible with PET than other types of lubricants such as phosphate ester based
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
greater than a stoichiometric amount of an organic acid increases the compatibility
of the silicone based lubricant with PET. By stoichiometric it is meant an amount of
acid such that there is at least about one equivalent of available, unneutralized acid
in the composition for each two equivalents of alkaline compounds present in water
used for preparing the lubricant mixture. Water with 50 ppm alkalinity as calcium
carbonate contains 0.001 equivalents of alkalinity per kg. In the case that the water
alkalinity is equivalent to about 50 ppm CaC03, a stoichiometric amount of acid is
therefore an amount of acid such that there will be greater than about 0.0005
equivalents of available, unneutralized acid per kilogram of the lubricant
composition before reaction with alkalinity present in the water used to prepare the
composition. 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 comprising one or more acid
compounds in an amount sufficient to provide at least one equivalent of available,
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unneutralized acid for every two equivalents of alkalinity in water used to prepare
the 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 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 wherein the lubricant composition
comprises greater than about 0.0005 equivalents of available, unneutralized acid per
kilogram of the lubricant composition before reaction with alkalinity present in the
water used to prepare the composition. 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 comprising
one or more acid compounds in an amount sufficient to provide a pH of less than
about 6.4 when the lubricant concentrate is diluted with water comprising greater
than about 50 ppm alkalinity as CaC03 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 invention provides, in another aspect, conveyor
lubricant compositions comprising a water-miscible silicone material and greater
than about 0.0005 equivalents of available, unneutralized acid per kilogram of the
lubricant composition before reaction with alkalinity present in the water used to
prepare the composition. The present invention provides, in another aspect, a
lubricant concentrate composition comprising a water-miscible silicone material and
greater than about 0.05 equivalents of unneutralized acid per kg of the lubricant
concentrate composition. These and other aspects of this invention will be evident
upon reference to the following detailed description of the invention.
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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.
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
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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 composition
comprises one or more acid compounds in an amount sufficient to provide at least
one equivalent of available, unneutralized acid for every two equivalents of
alkalinity in water used to prepare the lubricant composition. The available
unneutralized acid comes from one or more acid compounds present in the lubricant
composition. The concentration of available, unneutralized acid before reaction
with alkalinity present in the water used to prepare the composition can be
determined by preparing a composition with deionized water and titrating the acid to
approximately pH 8.3, or by calculating the concentration of acid present in a
composition diluted with deionized water using formulation data. For example, if
the lubricant concentrate of Example 1 was diluted with deionized water instead of
water containing 168 ppm sodium bicarbonate, there would be 0.0034 equivalents of
succinic acid per kg of the use composition and 0.0009 equivalents of sodium
hydroxide per kg of the use composition, and therefore 0.0025 equivalents of
available, unneutralized succinic acid per kg of the use composition before reaction
with alkalinity present in the water. The total alkalinity of the water used to dilute
the lubricant concentrate composition can be determined by an acid base titration.
For example, 1000 g of the water used to dilute the lubricant concentrate
composition can be titrated to approximately pH 4.3 using 0.1 N HC1 solution. In
this case, the ppm alkalinity as CaC03 per mL of titrant can be calculated according
to:
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alkalinity as CaC03 per 1.0 mL of titrant =
(LP mL) x (0.1 equivalent/1000 mL) x (50 g CaCCh/equivalent)
1000 g
= 0.005 g CaCO3/1000 g = 50 ppm as CaC03 per mL of titrant.
The total alkalinity of the water used to dilute the lubricant concentrate
composition in the Examples herein can be calculated by formulation. For example,
in Example 1 the ppm alkalinity as CaC03 of water containing 168 ppm NaHC03
can be calculated according to:
alkalinity as CaC03 =
(0.168 g NaHCCVlOOO g) x (50 g CaC03/equivalent)
84 g NaHC03/cquivalent
= 0.100 g CaCO3/1000 g = 100 ppm alkalinity as CaC03
Lubricant compositions according to the present invention will contain in
addition to the water-miscible silicone material unneutralized acid compounds.
Lubricant compositions of the present invention may also optionally include, in
addition to silicone and unneutralized acid compounds, water-miscible lubricants,
wetting agents that improve the wetting of the lubricant to PET, and other functional
ingredients.
Ester bonds as are present in PET are well known to hydrolyze under
conditions of either acid or base catalysis. It is expected that the overall rate of ester
bond hydrolysis would be at a minimum at approximately neutral pH, where both
hydronium ions and hydroxide ions are present at minimum concentrations.
Surprisingly it has been found that the "compatibility" of a silicone emulsion based
conveyor lubricant composition prepared with water containing bicarbonate
alkalinity is not improved when the lubricant composition has approximately
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neutral pH, but instead is improved when the lubricant composition has at least a
stoichiometric amount of unneutralized acid, in which case the pH is less than about
6.4. For example, addition of sufficient acid to adjust the pH of a conveyor lubricant
use composition down to 7.20 did not result in a decrease in the failure rate of
carbonated PET bottles contacted with the lubricant composition relative to a control
composition with pH equal to 8.20. By stoichiometric it is meant an amount of acid
such that there is at least about one equivalent of available, unneutralized acid in the
composition for every two equivalents of alkaline compounds present in water used
for preparing the lubricant composition. In the case that the water used for preparing
the lubricant composition comprises alkalinity equivalent to 50 ppm as CaC03, a
stoichiometric amount of acid is an amount of acid such that there will be about
0.0005 equivalents or more of available, unneutralized acid in the lubricant
composition before reaction with alkaline compounds present in the water used to
prepare the composition. The compatibility of lubricant use compositions is
improved even more in the case that there are two times or four times a
stoichiometric amount of acid.
While we do not wish to be bound by theory, it is believed that neutralizing
alkalinity to neutral pH does not improve the compatibility because the pH can
subsequently increase upon complete or partial evaporation of the lubricant
composition and consequent loss of carbon dioxide. It is believed that sufficient
acid is required in order to substantially oppose upward shifts in system pH that can
occur by evaporative loss of carbon dioxide. As used herein, "system" refers to the
liquid lubricant composition as it contacts the PET bottle, the residue that is left on
the bottle after evaporation and all forms intermediate between starting liquid and
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final residue. According to the well known Henderson - Hasselbach equation, the
pH of an acid solution is equal to the pKa value of the acid when it is half
neutralized, that is when there are equimolar concentrations of the acid and the
conjugate base in solution. Bicarbonate anion is the conjugate base of carbonic acid,
H2CO3. The pKa value for the first ionization of carbonic acid is often quoted as
approximately 6.4 (Weast, R. C, Editor (1976) CRC Handbook, 57th Edition,
Cleveland OH: Chemical Rubber Publishing Company). This value is in fact
misleading because it incorporates the equilibrium constant between dissolved
carbon dioxide and carbonic acid, and the pKa value of 6.4 is better described as the
acidity constant of carbon dioxide, not carbonic acid (Cotton, F. A. and Wilkinson,
G (1980) Advanced Inorganic Chemistry, Fourth Edition, New York, NY: John
Wiley and Sons). Thus at about pH 6.4, bicarbonate anion exists in a complex
equilibrium with carbonic acid and dissolved carbon dioxide. When there is
provided a stoichiometric amount of available unneutralized acid, that is, at least
about one equivalent of available, unneutralized acid in the composition for every
two equivalents of bicarbonate anion present in the water used for preparing the
lubricant before reaction, at equilibrium the concentration of acid species (primarily
dissolved carbon dioxide) will be greater than approximately the concentration of
bicarbonate anion and the pH of the buffered system will be less than or equal to
approximately 6.4. More preferably, when there are provided two times a
stoichiometric amount of available unneutralized acid, that is, two equivalents of
available, unneutralized acid in the composition for every two equivalents of
bicarbonate anion present in the water used for preparing the lubricant before
reaction there will be a much lower concentration of bicarbonate ion at equilibrium.
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In this case if even if complete loss of C02 from the system occurs, there will remain
only the conjugate base of the provided acid and further loss of C02 from
unneutralized bicarbonate anion to give more basic and potentially more PET
incompatible anions such as carbonate and hydroxide ions is prevented. Even more
preferably, there is provided three times a stoichiometric amount of available
unneutralized acid, that is, three equivalents of available, unneutralized acid in the
composition for every two equivalents of alkalinity present in the water used for
preparing the lubricant before reaction. In this case, if complete loss of CO2 from
the system occurs, there will be a mixture of the added acid and its conjugate base.
Surprisingly, the presence of three or more equivalents of available, unneutralized
acid in the composition has been found to give greatly improved PET compatibility,
in spite of the presence of excess acid in the case that carbon dioxide is not lost from
the system or in the case the composition is prepared with water that is free from
alkalinity.
Regardless of the mechanism, the present invention has been observed to
reduce stress cracking in PET bottles when compared to prior art and comparison
compositions, based on the presence of a stoichiometric amount of an organic acid.
Accordingly, compositions of the present invention comprise at least a
stoichiometric amount of acid and comprise, for every two equivalents of alkalinity
in water used to prepare the composition, at least about one equivalent, at least about
two equivalents, or at least about three equivalents of acid, before reaction with
alkalinity in the water used to prepare the composition.
In the case that the water alkalinity is equivalent to about 50 ppm CaC03, a
stoichiometric amount of acid is an amount of acid such that there will be about
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0.0005 equivalents or more of available, unneutralized acid per kilogram of the
mixture in the lubricant mixture before reaction with alkalinity. Accordingly,
compositions of the present invention comprise available, unneutralized acid in an
amount at least about 0.0005 equivalents per kilogram, at least about 0.001
equivalents per kilogram, or at least about 0.002 equivalents per kilogram of
composition.
In compositions that comprise a stoichiometric amount of acid, that is, at
least about one equivalent of available, unneutralized acid for every two equivalents
of alkalinity, the concentration of the conjugate acid of bicarbonate anion will be
present in a concentration greater than approximately the concentration of
bicarbonate anion, in which case the composition pH will be less than approximately
the carbon dioxide/bicarbonate pKa value which is approximately 6.4. Accordingly,
when prepared with water containing greater than about 50 ppm alkalinity as
CaCO.3, compositions of the present invention have pH less than about 6.4, less than
about 6.0, or less than about 5.
Lubricant compositions of the present invention can be applied undiluted 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. Inventive lubricant concentrate compositions
comprise a water-miscible silicone material and an amount of available,
unneutralized acid effective to provide at least about 0.0005 equivalents of available,
unneutralized acid per Kg in a lubricant composition that results from diluting one
pail of the lubricant concentrate with between 100 and 1000 parts of water and/or
hydrophilic diluent. Accordingly, lubricant concentrate compositions comprise at
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least about 0.05 equivalents per liter, at least about 0.1 equivalents per liter, or at
least about 0.2 equivalents per liter of available, unneutralized acid.
The silicone material and acid are "water-miscible", that is, they are
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.
The present invention includes one or more water-miscible silicone
materials. A variety of water-miscible silicone materials can be employed in the
lubricant compositions, including 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 Lambent 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 Corning 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
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(commercially available from Toshiba Silicone Co. Ltd.); and silicone surfactants
such as SWP30 anionic silicone surfactant, WAXWS-P nonionic silicone surfactant,
QUATQ-400M cationic 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 wt. % to about 5.0 wt. %, preferably 0.001 wt. % to about 1.0
wt. %, and more preferably 0.002 wt. % to about 0.50 wt. %. 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 wt. % to about
20 wt. %, preferably 0.10 wt. % to about 5 wt. %, and more preferably 0.2 wt. % to
about 1.0 wt. %.
The present invention includes one or more acid compounds. Preferred acids
for this invention have pKa values between about 2.0 and about 6.4, that is, they are
relatively weaker acids. It is believed that the pKa value must be below about 6.4,
that is, sufficiently strong that bicarbonate anion will be substantially protonated.
The pKa value is not required to be lower than that of carbonic acid which is
approximately 3.6, again owing to the complex equilibrium between dissolved
carbon dioxide, carbonic acid, and bicarbonate anion. Acids with pKa values above
about 2.0 are preferred because acids with lower pKa values, i.e. stronger acids, will
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result in objectionably low pH for lubricant concentrate compositions and for
lubricant use compositions that have been prepared with water free from alkalinity.
The pKa value is important because it determines the pH of the concentrated lube
composition and the diluted use lubricant composition. Using acids that are too
strong (that is, have low pKa values below about 2.0) will result in undesirably low
pi 1 in the concentrated lubricant composition and in lubricant compositions that
have been diluted with water that does not contain alkalinity. Relatively higher pH
of the lubricant concentrate is valuable because it reduces the corrosivity of the
composition and makes the composition less hazardous to manufacture, package,
transport and store. Relatively higher pH of the use composition makes the
composition less corrosive and more compatible with dispensing equipment and
conveyor equipment. Examples of inorganic acids with pKa values between 2.5 and
about 6.4 include dialkyl phosphoric acid compounds, disodium dihydrogen
pyrophosphate (Na2H2P207), and nitrous acid. Useful organic acids include
carboxylic acids and anilinium salts. Preferred organic acids are carboxylic acid
compounds. Particularly preferred acids are di- or poly- functional organic
compounds. By di- or poly- functional it is meant that the organic compound
contains, in addition to one carboxylic acid group, one or more of a second
functional moiety selected from the group including carboxylic acid, ketone,
aldehyde, ester, carbonate, urea, amide, ether, amine, ammonium, and hydroxyl
groups. The importance of a second functional group on the carboxylic acid
compound molecule is it minimizes the volatility and odor of the acid. Particularly
preferred acids are sufficiently non-volatile so as to not provide an objectionable
odor. Useful carboxylic acid compounds in the present invention include formic,
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acetic, propionic, hydroxy acetic, lactic, malonic, maleic, succinic, glutaric, adipic,
hydroxy succinic, malic, fumaric, itaconic, citric, and gluconic acids, and carboxylic
acid functional polymers such as homopolymers and copolymers of acrylic acid,
methacrylic acid, maleic acid, and itaconic acid, and mixtures thereof. In
compositions of the present invention, carboxylic acid compounds can also act as
corrosion inhibitors. A preferred acid is a mixture of adipic, glutaric and succinic
acid commercially available from BASF under the trade name SOKALAN™ DCS.
In preferred compositions of the present invention, particularly concentrate
compositions, it might be desirable to partially neutralize acids. By partially
neutralizing acids in lubricant compositions of the present invention, the pH of the
lubricant concentrate and the pH of the lubricant use composition that has been
prepared using water with low alkalinity can be increased. Relatively higher pH of
the lubricant concentrate is valuable because it reduces the corrosivity of the
composition and makes the composition less hazardous to manufacture, package,
transport and store. Relatively higher pH of the use composition makes the
composition less corrosive and more compatible with dispensing equipment and
conveyor equipment. In the case that acid compounds are partially neutralized, it is
important that there remains at least about one equivalent of available, unneutralized
acid in the mixture for each equivalent of alkaline compounds in the mixture, where
the alkaline compounds originate from water used to prepare the mixture.
In preferred compositions of the present invention, organic acids may be
present as peracids. Typically peracid compounds are in equilibrium with hydrogen
peroxide and organic acids. By providing organic acids in the form of peracids, the
pH of the lubricant concentrate can be increased.
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Care should be taken to avoid the use of acids that might promote
environmental stress cracking in plastic containers when evaluated using the PET
stress Crack Test Set out below. Examples of preferred acids include acetic, lactic,
succinic, glutaric, adipic, and citric acid and partially neutralized compositions
thereof. Examples of particularly preferred lubricant compositions include those
having from about 0.001 to about 0.02% of a water-miscible silicone material and
from about 0.01 to about 0.10% of a mixture of citric acid and dihydrogen citrate
anion.
Examples of particularly preferred lubricant concentrate compositions
include those having from about 0.10% to about 2% of a water-miscible silicone
material and about 4% to about 20% of a mixture of citric acid and dihydrogen
citrate anion.
Particularly preferred lubricant compositions are substantially aqueous that
is, they comprise greater than about 99% of water.
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 acids that
form stable compositions at 100 to 1000 times the concentration of the use
composition.
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Preferred lubricant compositions may also contain a wetting agent. Lubricant
compositions that comprise a wetting agent and have improved compatibility with
PET are disclosed in assignee's copending patent application, titled SILICONE
LUBRICANT WITH GOOD WETTING ON PET SURFACES, filed on September
22, 2005, with attorney docket number 2259US01, which application is incorporated
herein by reference in its entirety. 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.
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 CARBOWAXTM
series of polyethylene and methoxypolyethylene glycols, commercially available
from Union Carbide Corp.); linear copolymers of ethylene and propylene oxides
(e.g., UCONTM 50-FJB-100 water-soluble ethylene oxide:propylene oxide
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copolymer, commercially available from Union Carbide Corp.); and sorbitan esters
(e.g., TWEENTM series 20, 40, 60, 80 and 85 polyoxyethylene sorbitan
monooleates and SPANTM series 20, 80, 83 and 85 sorbitan esters, commercially
available from ICI 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
4-hexylresorcinol, 2-benzyl-4-chlorophenol and 2,4,4 -trichloro-2'-hydroxydiphenyl
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ether, organic and inorganic acids and its esters and salts such as dehydroacetic acid,
peroxycarboxylic acids, peroxyacetic acid, peroctanoic acid, methyl p-hydroxy
benzoic acid, cationic agents such as quaternary ammonium compound,
phosphonium compounds such as tetrakishydroxymethyl phosphonium sulphate
(TUPS), aldehydes such as glutaraldehyde, antimicrobial dyes such as acridines,
triphenylmethane dyes and quinines, halogens including iodine and chlorine
compounds and oxidizers such as ozone, and hydrogen peroxide. 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.
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, cthanol, urea, octane sulfonate, glycols such as
hcxylene 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
salts, polybutenylsuccinic acid derivatives, silicone surfactants, fluorosurfactants,
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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-
hydroxyethyl)amine, polyoxyethylene(5-)coco amine, polyoxyethylene(15)coco
amine, tallow bis(-2hydroxyethyl)amine, polyoxyethylene(15)amine,
polyoxyethy1ene(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,
polyisobutylenes 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 from 0 to about 30 wt.-% of the total composition.
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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,
tetradentate, 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 Na4EDTA 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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thereof such as Emphos PS 236 commercially available from Witco Chemical
Company. Other useful corrosion inhibitors include the triazoles, such as
bcnzotriazole, 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 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 arc heretofore unknown.
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)
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.
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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
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); polyamides, polycarbonates; and
mixtures or copolymers thereof); metals (e.g., aluminum, tin or steel); papers (e.g.,
untreated, treated, waxed or other coated papers); ceramics; and laminates or
composites of two or more of these materials (e.g., laminates of PET, 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
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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
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
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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.
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 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
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First Ten Angstroms, Portsmouth, VA. A droplet of use composition was applied to
Melincx 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.
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
RKXNORD™ 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
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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.
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 to 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
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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
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 the 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 100 ppm added alkalinity)
A solution of deionized water containing 100 ppm alkalinity as CaCCh was
prepared by dissolving 0.168 g of sodium bicarbonate in lOOOg of deionized water.
The ratio of unneutralized acid equivalents to equivalents of base from the alkaline
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water was 0 to 1.00. 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 B
(silicone plus water-miscible lubricant)
A lubricant composition was prepared which contained 125 ppm Lambent
E2140FG 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 ratio of unneutralized acid
equivalents to equivalents of base from the alkaline water was 0 to 1.00. The
contact angle of the lubricant composition on PET film was determined to be 64
degrees and the pH of the lubricant composition was 8.7. 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
silicone plus water-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
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water does not cause a significant improvement in the proportion of failed bottles in
the PET compatibility test relative to alkaline water alone.
COMPARATIVE EXAMPLE C
(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 ratio of unneutralized
acid equivalents from the lubricant concentrate composition to equivalents of base
from the alkaline water was 0 to 1.00. 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 the proportion of failed bottles in the PET compatibility
test relative to alkaline water alone.
EXAMPLE 1
(Silicone lubricant plus succinic acid/sodium succinate)
A lubricant concentrate composition was prepared by adding 5 g Lambent E-
2140FG, 7.9 g succinic acid, 2.7 g of a 50% solution of NaOH, and 1.7g of an 18%
solution of Pluronic F-108 poly(ethylene oxide-propylene oxide) block copolymer to
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82.7 g deionized water. A lubricant composition was prepared by diluting 1.0 g of
the lubricant concentrate composition with 399 g of a solution of 168 ppm sodium
bicarbonate in deionizcd water. The resulting lubricant composition contained 125
ppm Lambent E2140FG silicone emulsion, 7.6 ppm Pluronic F108, 198 ppm
succinic acid, 34 ppm sodium hydroxide, and 168 ppm sodium bicarbonate
(equivalent to 100 ppm alkalinity as CaCOs). The ratio of unneutralized acid
equivalents from the lubricant concentrate composition to equivalents of base from
the alkaline water was 1.25 to 1.00. The pH of the lubricant composition was 4.23.
The silicone lubricant composition was tested for PET compatibility whereupon
after 28 days of storage under conditions of 100 F and 85% relative humidity, 8 of
96 bottles had failed (8%). The crazing score for the unfailed bottles in this test was
1.8. What this example shows is that including approximately 1.25 equivalents of
unneutralized acid for every equivalent of alkalinity in lube dilution water is capable
to reduce the failure rate of bottles in the PET compatibility test relative to a silicone
plus watcr-miscible lubricant composition.
EXAMPLE 2
(Silicone lubricant plus glutaric acid/sodium glutarate)
A lubricant concentrate composition was prepared by adding 5 g Lambent E-
2140FG, 14.1g glutaric acid, 4.3 g of a 50% solution of NaOH, and 1.7g of an 18%
solution of Pluronic F-108 poly(ethylene oxide-propylene oxide) block copolymer to
74.9 g deionizcd water. A lubricant composition was prepared by diluting 1.0 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 125
ppm Lambent E2140FG silicone emulsion, 7.6 ppm Pluronic F108, 353 ppm
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glutaric acid, 54 ppm NaOH, and 168 ppm sodium bicarbonate (equivalent to 100
ppm alkalinity as CaC03). The ratio of unneutralized acid equivalents from the
lubricant concentrate composition to equivalents of base from the alkaline water was
2.00 to 1.00. The pH of the lubricant composition was 4.25. The silicone lubricant
composition was tested for PET compatibility whereupon after 28 days of storage
under conditions of 100 F and 85% relative humidity, 0 of 96 bottles had failed
(0%). The crazing score for the unfailed bottles in this test was 2.3. What this
example shows is that including approximately two equivalents of unneutralized
acid for every equivalent of alkalinity in lube dilution water is capable to reduce the
failure rate of bottles in the PET compatibility test relative to a silicone plus water-
miscible lubricant composition.
EXAMPLE 3
(Silicone lubricant plus citric acid/sodium citrate)
A lubricant concentrate composition was prepared by adding 2.5 g Lambent
E-2140FG, 14. lg of 50% citric acid, 2.2 g of a 50% solution of NaOH, 0.84 g of an
18% solution of Pluronic F-108 poly(ethylene oxide-propylene oxide) block
copolymer, and 2.85 g of 35% hydrogen peroxide solution to 74.9 g dcionized water.
A lubricant composition was prepared by diluting 2.0 g of the lubricant concentrate
composition with 398 g of a solution of 168 ppm sodium bicarbonate in deionized
water. The resulting lubricant composition contained 125 ppm Lambent E-2140FG
silicone emulsion, 353 ppm citric acid, 54 ppm NaOH, 7.6 ppm Pluronic F-108
polyethylene oxide-propylene oxide) block copolymer, 50 ppm H202, and 168 ppm
sodium bicarbonate (equivalent to 100 ppm alkalinity as CaC03). The ratio of
unneutralized acid equivalents from the lubricant concentrate composition to
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equivalents of base from the alkaline water was 2.08 to 1.00. The silicone lubricant
composition was tested for PET compatibility as described above. After 28 days of
storage under conditions of 100 F and 85% relative humidity, 0 of 96 bottles had
failed (0%). The crazing score for the unfailed bottles in this test was 1.4. What this
example shows is that including approximately two equivalents of unneutralized
acid for every equivalent of alkalinity in lube dilution water is capable to reduce the
failure rate of bottles in the PET compatibility test relative to a silicone plus water-
mi scible 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 andDelrin track was 0.13.
EXAMPLE 4
(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
1.0 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 H202, and 168 ppm
sodium bicarbonate (equivalent to 100 ppm alkalinity as CaCOs). The ratio of
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unneutralized 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
PKT 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
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.
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COMPARATIVE EXAMPLE D
(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 ratio of unneutralized acid equivalents to equivalents of base from the alkaline
water was 0 to 1.00. 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 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 E
(Silicone plus water-miscible lubricant)
A lubricant concentrate composition was prepared by adding 5 g Lambent E-
2140FG, 1.7g of an 18% solution of Pluronic F-108 polyethylene oxide-propylene
oxide) block copolymer,.5.7 g of 35% hydrogen peroxide, and 0.4g of 1% citric acid
solution to 87.2 g deionized water. A lubricant composition was prepared by
diluting 2.0 g of the lubricant concentrate composition with 398 g of a solution of
336 ppm sodium bicarbonate in deionized water. The resulting lubricant
composition contained 250 ppm Lambent E2140FG silicone emulsion, 15.0 ppm
Pluronic F108, 0.2 ppm citric acid, and 336 ppm sodium bicarbonate (equivalent to
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200 ppm alkalinity as CaC03). The ratio of unneutralized acid equivalents from the
lubricant concentrate composition to equivalents of base from the alkaline water was
0.001 to 1.00. The pH of the lubricant composition was 8.20. The silicone lubricant
composition was tested for PET compatibility whereupon after 28 days of storage
under conditions of 100 F and 85% relative humidity, 45 of 288 bottles had failed
(16%). What this comparative example shows is that addition of a mixture of
silicone plus water-miscible lubricant to alkaline water does not cause a significant
improvement in the proportion of failed bottles in the PET compatibility test relative
to alkaline water alone.
COMPARATIVE EXAMPLE F
(Silicone lubricant plus adipic acid)
A lubricant concentrate composition was prepared by adding 5 g Lambent E-
2140FG, 1.7g of an 18% solution of Pluronic F-108 poly(ethylene oxide-propylene
oxide) block copolymer, 5.7 g of 35% hydrogen peroxide, and 1.0 g of adipic acid to
87.8 g deionized water. A lubricant composition was prepared by diluting 2.0 g of
the lubricant concentrate composition with 398 g of a solution of 334 ppm sodium
bicarbonate in deionized water. The resulting lubricant composition contained 250
ppm Lambent E2140FG silicone emulsion, 15.3 ppm Pluronic F108, 50 ppm adipic
acid, and 334 ppm sodium bicarbonate (equivalent to 200 ppm alkalinity as CaCOs).
The ratio of unneutralized acid equivalents from the lubricant concentrate
composition to equivalents of base from the alkaline water was 0.17 to 1.00. The
pH of the lubricant composition was 7.20. The silicone lubricant composition was
tested for PET compatibility whereupon after 28 days of storage under conditions of
100 F and 85% relative humidity, 21 of 120 bottles had failed (18%). The crazing
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score for the unfailed bottles in this test was 2.4. What this comparative example
shows is that neutralization of alkalinity to approximately pH 7 in a silicone
lubricant composition did not reduce the failure rate of bottles in the PET
compatibility test relative to a silicone lubricant composition or to alkaline water
alone.
EXAMPLE 5
(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 80.0g 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 solution, 8.0 g
of Surfonic L 24-7 surfactant, 6.5 g of 88% lactic acid, and 2.5g of Lambent
E2140FG 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
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 ratio of
unneutralized acid equivalents from the lubricant concentrate composition to
equivalents of base from the alkaline water was 1.59 to 1.00. 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
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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.
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.
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WJIAT IS CLAIMED IS:
1 - A method for lubricating the passage of a container along a conveyor,
comprising
a. providing a lubricant concentrate composition comprising
i. from about 0.05% to about 20% of a water-miscible silicone
material; and
ii. one or more acid compounds in an amount sufficient to
provide at least one equivalent of available, unneutralized acid for
every two equivalents of alkalinity in water used to dilute the lubricant
concentrate;
b. diluting the lubricant concentrate with water in a ratio of one part
lubricant concentrate to 100 to 1000 parts water to form a lubricant use
composition; and
c. applying the lubricant use 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.
2. The method of claim 1, wherein the water used to dilute the lubricant
concentrate composition comprises greater than about 50 ppm alkalinity as CaC03.
3. 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.
4. The method of claim 1, wherein the lubricant concentrate composition
further comprises one or more functional ingredients selected from the group of
water-miscible lubricants, wetting agents, hydrophilic diluents, antimicrobial agents,
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stabilizing/coupling agents, detergents/ dispersing agents, anti-wear agents, viscosity
modifiers, sequestrants, corrosion inhibitors and mixtures thereof.
5. The method of claim 1, wherein the pH of the lubricant use composition is
less than about 6.4.
6. The method of claim 1, wherein the container comprises one or more
polymers selected from the group of polyethylene terephthalate, polyethylene
naphthalate, arid bisphenol A carbonate.
7. The method of claim 1, wherein the lubricant concentrate composition
comprises one or more acid compounds in an amount sufficient to provide at least
two equivalents of available, unneutralized acid for every two equivalents of
alkalinity in water used to dilute the lubricant concentrate composition.
8. The method of claim 1, wherein the lubricant concentrate composition
comprises one or more acid compounds in an amount sufficient to provide at least
three equivalents of available, unneutralized acid for every two equivalents of
alkalinity in water used to dilute the lubricant concentrate composition.
9. The method of claim 1, wherein the lubricant use 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.
10. The method of claim 1, wherein the lubricant concentrate composition
comprises one or more organic carboxylic acid compounds selected from the group
consisting of acetic, lactic, succinic, glutaric, adipic, and citric acid and mixtures
thereof.
11. A method for lubricating the passage of a container along a conveyor,
comprising:
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a. providing a lubricant concentrate composition comprising
i. from about 0.05% to about 20.0% of a water-miscible silicone
material; and
ii. greater than about 0.05 equivalents of acid per Kg of the
lubricant concentrate composition before reaction with alkalinity in water
used to prepare the lubricant use composition;
b. diluting the lubricant concentration composition with water to form a
lubricant use composition; and
c. applying the lubricant use 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.
12. The method of claim 11, wherein the water used to dilute the lubricant
concentrate composition comprises greater than about 50 ppm alkalinity as CaC03.
13. The method of claim 11, wherein the silicone material is selected from the
group consisting of silicone emulsion, finely divided silicone powder, and silicone
surfactant.
14. The method of claim 11, wherein the lubricant composition further
comprises one or more functional ingredients selected from the group of water-
miscible lubricants, wetting agents, hydrophilic diluents, antimicrobial agents,
stabilizing/coupling agents, detergents/ dispersing agents, anti-wear agents, viscosity
modifiers, sequestrants, corrosion inhibitors and mixtures thereof.
15. The method of claim 11, wherein the container comprises one or more
polymers selected from the group of polyethylene terephthalate, polyethylene
naphthalate, and bisphenol A carbonate.
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16. The method of claim 11, wherein the lubricant concentrate composition
comprises greater than about 0.1 equivalents of acid per Kg of the concentrate
composition before reaction with alkalinity in water used to prepare the use
composition.
17. The method of claim 11, wherein the lubricant concentrate composition
comprises greater than about 0.15 equivalents of acid per Kg of the concentrate
composition before reaction with alkalinity in water used to prepare the use
composition.

19. The method of claim 11, 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 11, wherein the lubricant concentrate composition
comprises one or more organic carboxylic acid compounds selected from the group
consisting of consisting of acetic, lactic, succinic, glutaric, adipic, and citric acid and
mixtures thereof.
21. A lubricant concentrate composition comprising from about 0.05% to about
20% of a water-miscible silicone material selected from the group consisting of
silicone emulsion, finely divided silicone powder, and silicone surfactant and greater
than about 0.05 equivalents of unneutralized acid per kg of the concentrate
composition wherein the acid is selected from the group consisting of consisting of
acetic, lactic, succinic, glutaric, adipic, and citric acid and mixtures thereof.
22. The lubricant concentrate composition of claim 21 comprising greater than
about 0.1 equivalents of unneutralized acid per kg of the concentrate composition.
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43
23. The lubricant concentrate composition of claim 21 comprising greater than
about 0.15 equivalents of unneutralized acid per kg of the concentrate composition.

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
comprises a stoichiometric amount of an organic acid. The
compatibility of the lubricating composition with polyethylene
terephthalate is increased because of the presence of a
stoichiometric amount of acid.

Documents:

01152-kolnp-2008-abstract.pdf

01152-kolnp-2008-claims.pdf

01152-kolnp-2008-correspondence others.pdf

01152-kolnp-2008-description complete.pdf

01152-kolnp-2008-form 1.pdf

01152-kolnp-2008-form 2.pdf

01152-kolnp-2008-form 3.pdf

01152-kolnp-2008-form 5.pdf

01152-kolnp-2008-international publication.pdf

01152-kolnp-2008-international search report.pdf

01152-kolnp-2008-pct priority document notification.pdf

01152-kolnp-2008-pct request form.pdf

1152-KOLNP-2008-(02-11-2012)-CORRESPONDENCE.pdf

1152-KOLNP-2008-(12-06-2013)-ANNEXURE TO FORM 3.pdf

1152-KOLNP-2008-(12-06-2013)-CLAIMS.pdf

1152-KOLNP-2008-(12-06-2013)-CORRESPONDENCE.pdf

1152-KOLNP-2008-(12-06-2013)-FORM-1.pdf

1152-KOLNP-2008-(12-06-2013)-OTHERS.pdf

1152-KOLNP-2008-(12-06-2013)-PETITION UNDER RULE 137-1.pdf

1152-KOLNP-2008-(12-06-2013)-PETITION UNDER RULE 137.pdf

1152-KOLNP-2008-(27-09-2013)-CORRESPONDENCE.pdf

1152-KOLNP-2008-(27-09-2013)-PA.pdf

1152-KOLNP-2008-FORM 18.pdf


Patent Number 261141
Indian Patent Application Number 1152/KOLNP/2008
PG Journal Number 24/2014
Publication Date 13-Jun-2014
Grant Date 06-Jun-2014
Date of Filing 18-Mar-2008
Name of Patentee ECOLAB INC.
Applicant Address ECOLAB CENTER 370 N, WABASHA STREET ST.PAUL, MINNESOTA
Inventors:
# Inventor's Name Inventor's Address
1 MORRISON, ERIC, D. 938 DELAWARE AVENUE, WEST ST., PAUL, MN 55118
2 HEL, ROBERT, D.P. 2224 30TH AVENUE, BALDWIN, W1 54002
3 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/US2006/023300
PCT International Filing date 2006-06-16
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 11/233,568 2005-09-22 U.S.A.