Note: Descriptions are shown in the official language in which they were submitted.
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COMPOSITIONS AND METHODS FOR MITIGATING CORROSION
OF APPLIED COLOR DESIGNS
Field of the Invention
The present invention relates to compositions and methods for mitigating
corrosion of applied color designs on a bottle, or on another glass or ceramic
item.
More specifically the composition or method of the present invention can
mitigate
corrosion even in the presence of a known corrosive agent. The composition and
methods of the invention employ one or more phosphates and one or more
phosphonates at a ratio that reduces or minimizes corrosion of an applied
color
design.
Background of the Invention
Many beverages sold outside North America come in reusable glass bottles.
By current estimates, annual worldwide production amounts to five billion
reusable
glass bottles. Many of these reusable glass bottles include an applied color
label
(ACL). An ACL is typically burned into the glass at the time of manufacture of
the
bottle. These labels are designed to be permanent for the useful life of the
bottle.
Reuse of a glass bottle with ACL requires that the bottle and label remain
aesthetically appealing for the duration of their life cycle. Currently,
ceramic colors
present the most commercially viable method of producing a label that will
withstand up to 50 reuses. Several companies have described non-ceramic
(resin/polymer or organic) based systems, but none these systems have yet
achieved
suitable durability. This lack of durability is quite understandable in light
of the
effect on the label of hot alkaline bottle washing processes. The cleaners
used in
bottle washing processes are designed to be aggressive on soils, but can also
attack
the ACL, eitlier organic or ceramic, causing deterioration and shortening the
useful
life of the label.
Label deterioration is undesirable because of the negative impact it has on
brand image, consumer appeal and quality of the beverage paclcage. When the
ACLs themselves appear `washed out' and bled, they are no longer aesthetically
appealing, forcing the bottles to be discarded before the end of their useful
lives.
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Therefore, there remains a need for a bottle washing composition that
minimizes attack on ACLs on glass bottles, while still providing adequate soil
removal.
Summary of the Invention
The present invention relates to the realization that a caustic cleaning
composition can be formed which significantly reduces or prevents
deterioration or
corrosion of an applied color design, such as an applied ceramic or applied
color
label, during cleaning operations, such as bottle washing. More specifically,
the
present invention is premised upon the realization that a highly caustic
cleaning
composition can be formed from materials that contain both phosphates and
phosphonates, known corrosive agents, providing effective cleaning properties
while
maintaining design or label integrity.
The present compositions and methods can also include one or more of a
suitable alkalinity source, such as sodium hydroxide or sodium carbonate; a
builder,
including those that are phosphorus-based; a sequestering agent, which can be
a
phosphonate; and an organic builder, such as gluconic acid, lactic acid,
citric acid,
salts of these acids, or combination thereof. The listed ingredients are but
examples
of suitable ingredients, and other suitable ingredients can be employed. The
present
methods and compositions can include surfactants such as alcohol ethoxylates,
polyoxyetheylene coco amines, EO-PO block copolymers, and capped alcohol
ethoxylates. Other surfactants may also be used.
Employing this chemistry provides an effective cleaning composition that
mitigates damage to the permanent applied ceramic designs or labels. Employing
this chemistry also provides useful methods and compositions for washing
bottles
that mitigates damage to the permanent applied ceramic labels. These cleaning
compositions and methods prolong the usable life of the bottle or other
ceramic ware
and contribute to the consumer perception of positive brand image.
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Brief Description of the Figures
Figure 1 is a diagram of a beverage plant, including a cold aseptic filling
plant, in which either carbonated or non-carbonated beverages can be prepared
and
bottled.
Figure 2 illustrates the intensity distribution (color intensity) for applied
color labels on bottles after various chemical treatments.
Figure 3 illustrates the surface roughness for an applied color label of a
bottle
washed with a conventional bottle wash composition compared to a control
bottle.
Figure 4 illustrates the surface roughness for an applied color label of a
bottle
washed with a bottle wash composition of the present invention compared to a
control bottle.
Figure 5 illustrates reduced glass corrosion by phosphate-containing
compositions according to the present invention.
Detailed Description of the Preferred Embodiment
Definitions
As used herein, the phrase "applied color design" refers to a design,
decoration, decorative element, or label that is applied in a fashion which is
intended
to be permanent while glass or ceramic ware (e.g. a bottle) is in circulation,
use,
and/or reuse. An applied color design can be a ceramic applied color design,
or a
non-ceramic applied color design (e.g. an organic applied color design).
Organic
applied color designs include thermoplastic non-ceramic, organics combined
with an
electrostatically applied organic coating, and LTV curing non-ceramic. Applied
ceramic designs include designs that are etched into the surface, embossed, or
pigmented. Certain applied color designs can also be applied to plastic
materials,
such as polyethylene terephthalate materials.
One type of applied color design is referred to herein as an "applied color
label" (ACL). An applied color label is a label that is applied in a fashion
whicll is
intended to be permanent while glass or ceramic ware (particularly a bottle)
is in
circulation, use, and/or reuse. An applied color label can be a ceramic
applied color
label, or a non-ceramic applied color label (e.g. an organic applied color
label).
Organic applied color labels include thermoplastic ACL non-ceramic, ACL
organics
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combined with an electrostatically applied organic coating, and LTV curing non-
ceramic ACL. Applied ceramic labels include labels that are etched into the
glass,
embossed, or pigmented. Some polyethylene terephthalate articles, such as
bottles,
also include applied color labels.
As used herein, the term "corrosion" refers to a degradation of an applied
color design or label through loss of color, removal of the design material,
roughening of the surface of the design, and the like. Corrosion in its
several
manifestations leads to a design or label that is no longer suitable for sale
or use.
Corrosion can lead to an unrecognizable label or design.
As used herein, the phrase "additive composition" refers to a composition
designed to boost, enhance, or otherwise improve cleaning power of an alkaline
or
caustic (or other) composition employed for washing glass or ceramic ware
having
an applied color design. As used herein, the phrase, "cleaning composition"
refers
to a composition including the major sources of caustic and/or surfactant for
a
mixture used in washing glass or ceramic ware having an applied color design.
The
mixture of the cleaning composition and additive composition is referred to
herein
as a "mixed composition" or "complete composition". A use composition refers
to
the cleaning and/or additive composition diluted to the concentrations
actually used
for washing or soaking bottles. Upon dilution, a concentrate composition
yields a
use composition.
As used herein, the phrase "washing" refers to washing bottles or washing
ceramic or glass objects having applied color designs or similar decorative
elements.
Washing includes both active spraying, scrubbing, or rinsing; and submersion
or
soaking in still or circulating fluid. Washing or cleaning includes washing or
cleaning wares such as painted china or coffee cups, glass or decorated
vitreous
enamel (e.g. vitreous enamel pans), decorated china, and the like.
As used herein, the phrase "bottle washing additive" refers to a composition
designed to boost, enhance, or otherwise improve cleaning power of an alkaline
or
caustic (or other) composition employed for bottle washing. The additive
compositions of the present invention are suitable as bottle washing
additives. As
used herein, the phrase, "bottle washing composition" refers to a composition
including the major sources of caustic and/or surfactant for a mixture used in
bottle
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washing. The mixture of the bottle washing composition and bottle washing
additive is referred to herein as a "complete bottle washing composition". A
use
composition refers to the bottle washing composition and/or the bottle washing
additive diluted to the concentrations actually used for washing or soaking
bottles.
Upon dilution, a concentrate composition yields a use composition.
As used herein, the phrase "bottle washing" refers to washing bottles, but can
also include washing ceramic or glass objects having applied color designs or
similar decorative elements. Washing includes both active spraying, scrubbing,
or
rinsing; and submersion or soaking in still or circulating fluid.
As used herein, weight percent, percent by weight, % by weight, 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.
As used herein, basic or alkaline pH refers to pH greater than 7, preferably
greater than 8 and up to about 14.
As used herein, the term "about" modifying the quantity of an ingredient in
the compositions of the invention or employed in the methods of the invention
refers
to variation in the numerical quantity that can occur, for example, through
typical
measuring and liquid handling procedures used for making concentrates or use
solutions in the real world; through inadvertent error in these procedures;
through
differences in the manufacture, source, or purity of the ingredients employed
to
make the compositions or carry out the methods; and the like. Whether or not
modified by the term "about", the claims include equivalents to the
quantities.
Methods and Compositions for Mitigating Corrosion of Applied Color Designs
The present invention relates to additive and/or cleaning compositions that
employ a phosphate and a phosphonate to provide cleaning or washing of glass
or
ceramic ware incorporating an applied color design without unacceptable
corrosion
of the design. The present invention also relates to methods of cleaning glass
or
ceramic ware employing such additive or cleaning compositions. In particular,
the
present use or concentrate additive or cleaning composition typically includes
phosphate and phosphonate at a weight ratio of phosphate to phosphonate
greater
than about 0.05:1 (1:20) and less than about 3:1, preferably about 2:1, such
as about
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1.9:1. Such ratios can be achieved in a concentrate additive composition with
a
phosphate at a level above about 0.5 wt-% and a phosphonate at a level above
about
0.25-0.35 wt-% and below about 80 wt-%. The present concentrate additive
compositions are typically diluted by about 100-fold to about 1000-fold to
form a
use composition. Thus, a use composition according to the present invention
typically contains a phosphate at a level above about 0.01 wt-% and a
phosphonate
at a level above about 0.005-0.007 wt-% and below about 0.2 wt-%.
An applied color design, particularly an applied color label, can withstand up
to about 50-100 or more or more washings with an alkaline cleaning composition
employing the present combinations of phosphate and phosphonate, compared to
only about 5 to about 20 washings with a conventional cleaning composition
with or
without a conventional additive.
Suitable phosphates build a bottle washing composition and can provide soil
dispersion, detergency, water hardness control, and the like to the present
additive or
cleaning composition. Such phosphates include a monomer of phosphoric acid, a
polymer of phosphoric acid, a salt of pliosphoric acid, or a combination
thereof; an
ortho phosphate, a meta phosphate, a tripolyphosphate, or a combination
thereof;
phosphoric acid; alkali metal, ammonium and alkanolammonium salts of
polyphosphates (e.g. sodium tripolyphosphate and other higher linear and
cyclic
polyphosphate species, pyrophosphates, and glassy polymeric meta-phosphates);
amino phosphates; nitrilotrismethylene phosphates; and the like; or a
combination
thereof. Preferred phosphates include phosphoric acid, and monomers, polymers,
and salts tliereof, and the like, or a combination thereof. The concentrate
additive
composition typically contains about 3 to about 30 % by weight phosphate,
preferably about 6 to about 15 % by weight, preferably about 10 % by weight.
Suitable phosphonates build and chelate in a bottle washing composition and
can provide hardness control, detergency, rinseability, scale prevention, and
the like
to the present additive or cleaning composition. Such phosphonates include a
wide
variety of phosphonic acids and phosphonate salts, such as organophosphonates.
As used herein, organic phosphonate or organophosphonate refers to organic
phosphonates lacking any amino or imino (e.g. nitrogen) moieties. The
phosphonic
acid or phosphonate can include a low molecular weight phosphonopolycarboxylic
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acid such as one having about 2-4 carboxylic acid moieties and about 1-3
phosphonic acid groups. Some examples of organic phosphonates include 1-
hydroxyethane-1,1-diphosphonic acid: CH3C(OH)[PO(OH)2]2; 1-phosphono-l-
methylsuccinic acid, phosphonosuccinic acid; 2-phosphonobutane-1,2,4- .
tricarboxylic acid; other similar organic phosphonates; and mixtures thereof.
Additional suitable phosphonates include phosphorus acid, H3P03, and its
salts.
Although not liniiting to the present uivention, it is believed that the
presence of one
or more organic phosphonates provides at least part of mitigation of corrosion
otherwise caused by phosphate or amino phosphonate.
As used herein, ainino phosphonate refers to phosphonates including amino
or imino (e.g. nitrogen) moieties. Although generally corrosive to glass and
applied
color designs, amino phosphonates can be employed in the compositions and
methods of the present invention, and corrosion caused by the amino
phosphonate
can be mitigated. Such amino phosphonates include: ethylene diamine
(tetramethylene phosphonates); nitrilotrismethylene phosphates;
diethylenetriamine
(pentamethylene phosphonates); aminotri(methylenephosphonic acid):
N[CH-)PO(OH)2]3; aminotri(methylenephosphonate), sodium salt:
Na+ O\
POCH2N[CH2PO(ONa)2]2
O F~
2-hydroxyethyliminobis(methylenephosphonic acid) HOCH2CH2N[CH2PO(OH)2]2;
diethylenetrianiinepenta(methylenephosphonic acid)
(HO)2POCH2N[CH2CH2N[CH2PO(OH)2]Z]2;
diethylenetriaminepenta(methylenephosphonate), sodium salt C9H(28-X)N3Na~O1sPs
(x=7); hexamethylenediarnine(tetrametliylenephosphonate), potassium salt
C1oH(2s-
,)N2KXO12P4 (x=6); bis(hexamethylene)triamine(pentaniethylenephosphonic acid)
(HO2-,)POCH2N[(CH2)6N[CH2PO(OH)2]2]2. These amino phosphonates commonly
contain alkyl or alkaline groups with less than 8 carbon atoms. Preferred
amino
phosphonates that can exhibit mitigated corrosion of glass or an applied color
design
include aminotri(methylenephosphonic acid), (N[CH2PO3H2]3), available from
Monsanto as DEQUESTO 2000 and also available as BriquestTM 301-50A, and Amino
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Tri (Methylene Phosphonic Acid) 50%, low ammonia from Albright & Wilson; and
their salts.
Phosphonic acids can be used in the fonn of water soluble acid salts,
particularly the alkali nletal salts, such as sodium or potassium; the
ammonium salts;
or the alkylol amine salts where the alkylol has 2 to 3 carbon atoms, such as
mono-,
di-, or triethanolamine salts. The phosphonic acid can be in the form of a
liquid or
powder alkali metal salt composition. If desired, nuxtures of the individual
phosphonic acids or their acid salts can also be used. A neutralized or
alkaline
phosphonate, or a combination of the phosphonate with an alkali source prior
to
being added into the mixture such that there is little or no heat or gas
generated by a
neutralization reaction when the phosphonate is added is preferred.
Preferred phosphonates include organic phosphonates. Preferred organic
phosphonates include phosphono butane tricarboxylic acid (PBTC) (such as that
sold under the trade name BayhibitTM AM) and hydroxy ethylene diphosphonic
acid
(I-iEDP) (such as that sold under the trade name Dequest 2010), and the like,
or a
combination thereof. The concentrate additive composition contains about 2 to
,
about 20 % by weight phosphonate, preferably about 4.5 to about 10 % by
weight,
preferably about 6 to about 7 % by weight, preferably about 6.8 % by weiglit.
If the present concentrate and cleaning compositions include an amino
phosphonate, they preferably also include an organic phosphonate.
Surprisingly,
although ainino phosphonates corrode glass and applied color design, a
composition
including both an amino phosplionate and an organic phosphonate exhibits
mitigated
corrosion of glass or applied color design. Such mitigation occurs even in the
absence of phosphate. In particular, a composition including ATMP,
amino(tri (methylenephosphonic acid)), (such as that sold under the trade name
Dequest 2000) plus an organic phosphonate mitigated corrosion of glass and/or
applied color design. Preferably the weight ratio of amino phosphonate to
organic
phosphonate is less than 4:1 (e.g. about 3.5:1); preferably less than 3:1
(e.g. about
2.3:1) or less than 2:1 (e.g. about 1.7:1 or 1.5:1); preferably about 1:1
(e.g. about
1.2:1 or 1.5:1).
Ratios of phosphate to phosphonate within a certain range provide mitigation
of corrosion or wear to the applied color design. Ratios of phosphate to
phosphonate
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of about 4:1 or greater (wt:wt) in a cleaning or additive composition did not
provide
effective mitigation of erosion or wear to the applied color design. A ratio
of
phosphate to phosphonate of about 1.9:1 in a cleaning or additive composition
provides effective mitigation of corrosion or wear to the applied color
design. The
ratio of phosphate to phosphonate can be as low as about 0.05:1, about 0.1:1,
about
0.2:1, about 0.3:1, about 0.4:1, about 0.5:1, about 0.6:1, about 0.7:1, about
0.8:1,
about 0.9:1, about 1:1, about 1.1:1, about 1.2:1, about 1.3:1, about 1.4:1,
about 1.5:1,
about 1.6:1, about 1.7:1, about 1.8:1, or about 1.9:1. The ratio of phosphate
to
phosphonate can be as high as about 2:1, about 2.2:1, about 2.4:1, about
2.6:1, about
2.8:1,about3:1,about3.2:1,orabout3.4:1.
Mitigation of corrosion or wear to the applied color design or label can be
monitored by known methods. For example, viewing the design can determine
whether it retains sufficient color, texture, sharpness, and/or overall
quality for a
salable product. A scale for grading color, texture, sharpness, and/or overall
quality
can aid in such a determination. The present application describes below
additional
methods for evaluating corrosion of an applied color design.
An additive of the present invention can be employed in washing glass or
ceramic ware (e.g. bottles) with applied color designs or labels to extend the
useful
life of the applied color design or label. For example, employing an additive
of the
present invention, an applied color design preferably retains salable quality
for at
least about 50, about 80, about 100, or more washings, preferably for more
than
about 75 washings.
In each embodiment, the present additive or cleaning composition can also
contain other ingredients, such as water, a chelating agent, a builder, or a
combination thereof. In a preferred embodiment, the composition includes one
or
more chelating or sequestering agents including the phosphonate, and the like.
In a
preferred embodiment, the composition also includes as builders 2 to 12 carbon
mono or di carboxylic acids, such as gluconic acid, lactic acid, citric acid,
and the
like, or a combination thereof. In concentrate compositions according to the
invention, the concentrations of each of the ingredients can vary over a range
that
will allow obtaining a use composition by a desired dilution. Preferably,
gluconic
acid is present at about 1.5 to about 20 wt-%. Preferably, lactic acid is
present at
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about 1 to about 20 wt-%. Preferably, citric acid is present at about 1 to
about 20
wt-%. In a more preferred embodiment, the concentrate additive or cleaning
composition of the invention includes about 7 wt-% gluconic acid, about 8 wt-%
phosphoric acid, about 4 wt-% HEDP, about 5 wt-% citric acid monohydrate,
about
4 wt-% lactic acid, and about 1 wt-% PBTC.
In each embodiment, the present additive or cleaning composition can also
contain one or more surfactants, such as an amphoteric surfactant, a noiuonic
surfactant, or a combination thereof. In one preferred embodiment, the
additive or
cleaning composition includes an amphoteric surfactant, such as a
polyoxyethylene
coco amine (e.g. such as those sold under the trade name BK 1057 or Chemeen C-
12G). In one preferred embodiment, the additive or cleaning composition
includes a
nonionic surfactant, such as an alcohol ethoxylate or an EO-PO block
copolymer.
Preferred alcohol ethoxylates include that sold under the trade name Plurafac
and
designated RA-40 and a butyl capped alcohol ethoxylate (e.g. one sold under
the
trade name DehyponTM LT-104). Preferred EO-PO block copolymers include those
sold under trade names such as Genepol with the designation PN 30. Preferably
an
EO-PO block copolymer is present at about 1 to about 20 wt-%. Preferably, an
alcohol ethoxylate is present at about 0.5 to about 10 wt%. In a more
preferred
embodinlent, the concentrate additive or cleaning composition of the invention
includes about 7 wt-% gluconic acid, about 8 wt-% phosphoric acid, about 4 wt-
%
HEDP, about 5 wt-% citric acid monohydrate, about 4 wt-% lactic acid, about 1
wt-
% PBTC, about 6 wt-% of an EO-PO block copolymer (e.g., Geiiepol PN 30), and
about 2 wt-% of an alcohol ethoxylate (e.g., Plurafac RA-40).
In certain embodiments an additive or cleaning composition according to the
present invention can include a source of alkalinity, sucli as hydroxide,
carbonate, or
a combination tliereof. Preferred sources of hydroxide include sources of
sodium
hydroxide, such as soda ash. An alkaline concentrate composition for
warewashing
can include 50% or more of the source of alkalinity. Compositions with these
high
levels of the source of alkalinity can often include only somewhat diniinished
levels
of components such as certain organic builders or certain phosplionates. For
example, some phosphonates are soluble to only about 1.5 to about 2 wt-% and
gluconic acid is soluble to only about 3 wt-% in the presence of 50% caustic.
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additive composition can advantageously contain higher concentrations of
components of limited solubility in highly alkaline cleaning compositions.
The present additive composition includes only levels of EDTA or NTA (in
their acid and/or salt forms) insufficient to cause corrosion of the applied
color
design. Preferably, the present additive composition includes no added EDTA,
e.g.
EDTA is absent or is present due to amounts found in components of the
additive
composition. Preferably, the level of EDTA is less than about 150 ppm,
preferably
less than about 100 ppm, preferably less than about 50 ppm.
The inventive additive or cleaning composition can be a concentrate or a use
composition. The present concentrate composition is typically employed at a
concentration of about 0.25 wt-% to about 0.5 wt-% to make a use composition.
However, the maximum amount that a concentrate composition can be diluted
ineed
be limited only by solubility or compatibility of its various components.
Thus, a
concentrate composition can be subjected to greater dilutions to form a use
composition. Maximum dilution of a concentrate composition typically employs
as
little as about 0.01 wt-% to about 0.1 wt-% of the concentrate. Alternatively,
the
minimum concentration or dilution of a concentrate composition is typically
limited
only by transport and handling considerations. That is, the concentrate is
typically
concentrated to an extent that provides easy and economical transport and
handling.
For example, convenience typically dictates dilution of a concentrate
composition to
concentrations of less than about 1 or 2 wt-%.
Diluting the inventive additive concentrate composition with water, with a
water and a concentrate bottle washing composition, or with a use bottle
washing
composition yields a composition suitable for using for washing bottles, glass
or
ceramic items having an applied color design. The additive composition can be
used
with various bottle washing compositions known to those of skill in the art.
These
include compositions employing sources of alkalinity and/or surfactants as
cleaners.
The present additive compositions are compatible with a wide variety of
sources of
alkalinity including carbonate, liydroxide (e.g. caustic soda or soda ash),
their salts,
combinations thereof, and the like. The present additive compositions are
compatible with a wide variety of surfactants including amphoteric
surfactants,
nonionic surfactants, combinations thereof, and the like.
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Bottle, Glass, and Ceramic Washing
The present invention encompasses bottle washing compositions including
bottle washing additives, bottle washing detergents, bottle washing solutions,
as well
as the process of washing bottles. The present invention can be used in other
types
applications that benefit from the same protective properties provided. This
can
include any type of ware washing apparatus that may be used to clean glass of
any
type, dishes, china, etc, particularly if the glass or otlier ware includes an
applied
color design, label, or like decorative design. In one embodiment, a
composition of
the present invention can also be employed for washing polyethylene
terephthalate
bottles with applied color labels. The invention can also be used in consumer
applications such as detergents and detergent systems. The nature of the
invention
also extends to situations where chemistry similar to that used in ACLs is
utilized
for different applications that may also require cleaning and/or degreasing in
conjunction with protection, such as paint surfaces, etc.
A bottle washing apparatus will generally have a volume of water to which a
bottle washing composition with or without a bottle washing additive are
added. A
bottle washing composition typically includes a built detergent and/or an
alkalinity
source. A use bottle washing mixture can include a caustic soda concentration
of
about 1 to about 6 wt-%. In addition to the caustic soda, a bottle washing
composition typically includes a surfactant, preferably one that does not
promote
deterioration of an applied color design and in an amount effective to improve
soil
dispersion.
The bottle washing solution can be formed by adding the individual
components separately to the water in the bottle washer, or all of the
components
can be combined in the desired proportions and added to the water. The bottle
washing composition may include the caustic source or the caustic source can
be
purchased and charged in separately. Further, the bottle washing composition
can
be formulated as a liquid or a powder, or a solid.
In the method of the present invention, bottle washing includes contacting
the bottle or other glass or ceramic ware with an applied color design or
label with a
bottle washing composition according to the present invention or including an
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additive composition according to the present invention. Such contacting can
be
accomplished using a spray device or soaking tank or vessel to intimately
contact the
inside of the bottle with the cleaning composition for sufficient period of
time to
clean the container without unacceptably degrading the applied color design.
The container is then emptied of the amount of cleaning composition used.
After emptying, the container can then be commonly rinsed with potable water
or
sterilized water and again emptied. After rinsing, the container can be filled
with the
liquid beverage. The container is then sealed, capped or closed and then
packed for
shipment for ultimate sale.
Figure 1 shows a schematic for an embodiment of a bottle spraying/bottling
operation that can employ the method of the present invention. This figure
shows a
plant 100 that can sequentially contact beverage bottles with cleaning
composition.
In the figure, bottles 110 are passed through a cleaning tunnel 102. In the
cleaning
tunnel 102, the bottles can be contacted with the cleaning composition. The
cleaned
bottles 1 l0a then pass through a rinsing tunnel 103 and emerge as cleaned
rinsed
bottles 110b.
In the process, bulk cleaning composition and, optionally, additive
composition are added to a first holding tank 101. Commonly, the composition
is
maintained at a temperature of about 40-50 C in such a tank. To obtain the
effective use concentration of composition, make-up water 105 is combined with
the
concentrated cleaning and, optionally, additive composition into first tank
101. The
composition can be passed through a heater 108 to reach an elevated
temperature,
e.g., about 40-85 C.
The cleaning composition is sprayed within cleaning tunnel 102 into and
onto all surfaces of the bottle 110. An intimate contact between the
composition and
the bottle 110 is essential for cleaning to an adequate level. After contact
with the
composition and after dumping any excess composition from the bottles, the
cleaned
bottles 110 are then passed to a fresh water rinse tunnel 103. Fresh water 108
is
provided from a fresh water make-up into a spray rinsing tunnel 103. Excess
spray
drains from rinsing tunnel 103 to drain 106. Within the tunnel 103, cleaned
bottles
110a are thoroughly rinsed with fresh water. The complete removal of the
cleaning
composition from the bottles 110a is important for maintaining high quality of
the
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beverage product. The rinsed and sanitized bottles 110b are then removed from
the
rinsing tunnel.
The day tank 101, the sterilizing tunne1102 and the rinsing tunnel 103 are all
respectively vented to wet scrubber or vent l l la, 111 b or 111 c to remove
vapor or
fumes from the system components. The cleaning composition that has been
sprayed and drained from the bottles 1 l0a accumulates in the bottom of the
spray
tunnel 102 and is then recycled through recycle line and heater 107 into the
day tank
101.
The contact between the bottles and the cleaning composition is typically at a
temperature of greater than about 70 C. Cleaning of beverage containers
typically
employs about 0.1 to about 0.6 wt-% additive or cleaning composition with a
caustic
concentration of about 1.5 to about 3.5 wt-%, temperature of about 65 -85 C,
and a
contact time of typically more than about 15 min.
Builder
Detergent builders can optionally be included in the additive compositions of
the present invention for purposes including assisting in controlling mineral
hardness. Inorganic as well as organic builders can be used. The level of
builder
can vary widely depending upon the end use of the composition and its desired
physical form. Phosphate and phosphonate that can serve as builders are
described
herein above.
Suitable builders include non-phosphate builders. These can include phytic
acid, silicates, alkali metal carbonates (e.g. carbonates, bicarbonates, and
sesquicarbonates), sulphates, aluminosilicates, monomeric polycarboxylates,
homo
or copolymeric polycarboxylic acids or their salts in which the polycarboxylic
acid
includes at least two carboxylic radicals separated from each other by not
more than
two carbon atoms, citrates, succinates, and the like. Preferred builders
include
citrate builders, e.g., citric acid and soluble salts thereof, due to their
ability to
enhance detergency of a soap or detergent solution and their availability from
renewable resources and their biodegradability. Other preferred builders are
the
known polyaspartic acids and salts and derivatives thereof. Polyacetals
obtained by
reaction of dialdehydes with polyol carboxylic acids containing 5 to 7 carbon
atoms
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and at least three hydroxyl groups, for example as described in European
patent
application EP-A-0 280 223, are also suitable builders. Preferred polyacetals
are
obtained from dialdehydes, such as glyoxal, glutaraldehyde, terephthalaldehyde
and
mixtures thereof, and from polyol carboxylic acids, such as gluconic acid
and/or
glucoheptonic acid
Polycarboxylate Builders
Examples of low molecular weight polycarboxylates suitable as organic
cobuilders include: C4 -C20 -di-, -tri- and -tetracarboxylic acids, such as
succinic
acid, propanetricarboxylic acid, butanetetracarboxylic acid,
cyclopentanetetracarboxylic acid and alkyl- and alkenylsuccinic acids with C2 -
C16 -
alkyl- or -alkenyl radicals; C4 -C20 -hydroxy carboxylic acids, such as malic
acid,
tartaric acid, gluconic acid, glucaric acid, citric acid, lactobionic acid and
sucrosemono-, -di- and -tricarboxylic acids; aminopolycarboxylates, such as
nitrilotriacetic acid, methylglycinediacetic acid, alaninediacetic acid,
ethylenediaminetetraacetic acid and serinediacetic acid. Examples of
oligomeric or
polymeric polycarboxylates suitable as organic co-builders are: oligomaleic
acids as
described, for example, in EP-A-451 508 and EP-A-396 303; co- and terpolymers
of
unsaturated C4 -C8 -dicarboxylic acids, possible co-monomers which may be
present
being monoethylenically unsaturated monomers from group (i) in amounts of up
to
95% by weight, from group (ii) in amounts of up to 60% by weight, from group
(iii)
in amounts of up to 20% by weight. Examples of unsaturated C4 -C8 -
dicarboxylic
acids suitable in this case are maleic acid, fumaric acid, itaconic acid and
citraconic
acid. Maleic acid is preferred.
The group (i) includes monoethylenically unsaturated C3 -C8 -
monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid
and
vinylacetic acid. Preferably employed from group (i) are acrylic acid and
methacrylic acid. Group (ii) includes monoethylenically unsaturated C2 -C22
-
olefins, vinyl alkyl ethers with C1-C8 -alkyl groups, styrene, vinyl esters of
C1-C8 -
carboxylic acids, (meth)acrylamide and vinylpyrrolidone. Preferably employed
from group (ii) are C2 -C6 -olefins, vinyl alkyl ethers with C1-C4 -alkyl
groups, vinyl
acetate and vinyl propionate. Group (iii) includes (meth)acrylic esters of Cl -
C8 -
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alcohols, (meth)acrylnitrile, (meth)acrylamides of C1-C8 -amines, N-
vinylformamide and vinylimidazole.
If the polymers contain vinyl esters as monomers of group (ii) these can also
be partially or completely hydrolyzed to vinyl alcohol structural units.
Suitable co-
and terpolymers are disclosed, for example, in U.S. Pat. No. 3,887,806 and DE-
A 43
13 909.
Copolymers of dicarboxylic acids which are suitable and preferred as organic
cobuilders are the following: copolymers of maleic acid and acrylic acid in
the ratio
of 10:90 to 95:5 by weight, particularly preferably those in the ratio of from
30:70 to
90:10 by weight, with molecular weights of from 10,000 to 150,000; terpolymers
of
maleic acid, acrylic acid and a vinyl ester of a C1-C3 -carboxylic acid in the
ratio of
from 10 (maleic acid):90 (acrylic acid+vinyl ester) to 95 (maleic acid):5
(acrylic
acid+vinyl ester) by weight, it being possible for the ratio of acrylic acid
to vinyl
ester to vary in the range from 20:80 to 80:20 by weight, and particularly
preferably
terpolymers of maleic acid, acrylic acid and vinyl acetate or vinyl propionate
in the
ratio of from 20 (maleic acid):80 (acrylic acid+vinyl ester) to 90 (maleic
acid):10
(acrylic acid+vinyl ester) by weight, it being possible for the ratio of
acrylic acid to
the vinyl ester to vary in the range from 30:70 to 70:30 by weight; copolymers
of
maleic acid with C2 -C8 -olefins in the molar ratio from 40:60 to 80:20, with
copolymers of maleic acid with ethylene, propylene or isobutene in the molar
ratio
50:50 being particularly preferred.
Graft polymers of unsaturated carboxylic acids on low molecular weight
carbohydrates or hydrogenated carbohydrates, see U.S. Pat. No. 5,227,446, DE-A-
44
15 623, DE-A-43 13 909, are likewise suitable as organic cobuilders.
Suitable unsaturated carboxylic acids in this connection are, for example,
maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid,
methacrylic
acid, crotonic acid and vinylacetic acid, and mixtures of acrylic acid and
maleic
acid, which are grafted on in amounts of from 40 to 95% of the weight of the
component to be grafted.
It is additionally possible for up to 30% by weight, based on the component
to be grafted, of other monoethylenically unsaturated monomers to be present
for
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modification. Suitable modifying monomers are the abovementioned monomers of
groups (ii) and (iii).
Suitable as grafting base are degraded polysaccharides, such as acidically or
enzymatically degraded starches, inulins or cellulose, reduced (hydrogenated
or
reductively aminated) degraded polysaccharides, such as mannitol, sorbitol,
aminosorbitol and glucamine, and polyalkylene glycols with molecular weights
of
up to 5,000 such as polyethylene glycols, ethylene oxide/propylene oxide or
ethylene oxide/butylene oxide block copolymers, random ethylene
oxide/propylene
oxide or ethylene oxide/butylene oxide copolymers, alkoxylated mono- or
polyhydric C1-C22 -alcohols, see U.S. Pat. No. 4,746,456.
Preferably employed from this group are grafted degraded or degraded
reduced starches and grafted polyethylene oxides, employing from 20 to 80% by
weight of monomers, based on the grafting component, in the graft
polymerization.
A mixture of maleic acid and acrylic acid in the ratio of from 90:10 to 10:90
by
weight is preferably employed for the grafting.
Polyglyoxylic acids suitable as organic cobuilders are described, for
example, in EP-B-001 004, U.S. Pat. No. 5,399,286, DE-A-41 06 355 and EP-A-656
914. The end groups of the polyglyoxylic acids may have various structures.
Polyamidocarboxylic acids and modified polyamidocarboxylic acids suitable
as organic cobuilders are disclosed, for example, in EP-A-454 126, EP-B-511
037,
WO 94/01486 and EP-A-581 452.
Also preferably used as organic cobuilders are polyaspartic acid or
cocondensates of aspartic acid with other amino acids, C4 -C25 -mono- or -
dicarboxylic acids and/or C4 -C25 -mono- or -diamines. Polyaspartic acids
prepared
in phosphorus-containing acids and modified with C6 -C22 -mono- or -
dicarboxylic
acids or with C6 -C22 -mono- or -diamines are particularly preferably
employed.
Condensation products of citric acid with hydroxy carboxylic acids or
polyhydroxy compounds which are suitable as organic cobuilders are disclosed,
for
example, in WO 93/22362 and WO 92/16493. Carboxyl-containing condensates of
this type normally have molecular weights of up to 10,000, preferably up to
5,000.
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Surfactants
The surfactant or surfactant admixture 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
for use
in the process and products of this invention can depend on the conditions of
final
utility, including method of manufacture, physical product form, use pH, use
temperature, foam control, and soil type.
A preferred surfactant system of the invention can be selected from
amphoteric species of surface-active agents, which offer diverse and
comprehensive
commercial selection, low price; and, most important, excellent detersive
effect --
meaning surface wetting, soil penetration, soil removal from the surface being
cleaned, and soil suspension in the detergent solution. Despite this
preference the
present composition can include one or more of nonionic surfactants, anionic
surfactants, cationic surfactants, the sub-class of nonionic entitled semi-
polar
nonionics, or those surface-active agents which are characterized by
persistent
cationic and anionic double ion behavior, thus differing from classical
amphoteric,
and which are classified as zwitterionic surfactants.
Generally, the concentration of surfactant or surfactant mixture useful in
compositions or methods of the present invention fall in the range of from
about
0.5% to about 40% by weight of the composition, preferably about 2 to about 15
wt-
%. 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.
Preferred surfactants for the compositions of the invention include non or
low foaming surfactants including amphoteric surfactants, such as dicarboxylic
coconut derivative sodium salts, and nonionic surfactants, such as alcohol
ethoxylates and EO-PO block copolymers.
A typical listing of the classes and species of surfactants useful herein
appears in U.S. Pat. No. 3,664,961 issued May 23, 1972, to Norris.
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Nonionic Surfactant
Nonionic surfactants useful in the invention are generally characterized by
the presence of an organic liydrophobic 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 hydrogen atom can be condensed
with ethylene oxide, or its polyhydration adducts, or its mixtures with
alkoxylenes
such as propylene oxide to form a nonionic surface-active agent. The length of
the
llydrophilic 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 Rhone-Poulenc and Triton manufactured by Union Carbide.
3. Condensation products of one mole of a saturated or unsaturated,
straight or branched chain alcoliol 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 mixtures of alcohols in the above delineated carbon range or it 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
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 for
specialized embodiments. All of these ester moieties have one or more reactive
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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 etliylene 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
are 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.
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 are 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
R
b (C2H4)n (OA)m OH
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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)õOH]Z
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(C3H60)õ(CaH40),,,H wherein Y is the residue of organic compound having from
about 1 to 6 carbon atoms and one reactive h.ydrogen 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[(C3H6Oõ(C2H40),,,H]X wherein Y is the residue of an organic compound having
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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Additional conjugated polyoxyalkylene surface-active agents which are
advantageously used in the compositions of this invention correspond to the
formula: P[(C3H60)õ(C2H40),,,H]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.
In 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 R2CONR1Z 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 glycityl 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 C6-C18 fatty alcohols and C6-C18 mixed ethoxylated
and propoxylated fatty alcohols are suitable surfactants for use in the
present
compositions, particularly those that are water soluble. Suitable ethoxylated
fatty
alcohols include the C10-C18 ethoxylated fatty alcohols with a degree of
ethoxylation
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
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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
galactoside.) 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 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 R7 is independently hydrogen, C1-
C4
alkyl, C1-C4 hydroxyalkyl, or -(CZH4O)XH, where x is in the range of from 1 to
3.
Preferred nonionic surfactants for the compositions of the invention include
alcohol 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
Heuring on
Dec. 30, 1975. Further examples are given in "Surface Active Agents and
Detergents" (Vol. I and II by Schwartz, Perry and Berch).
Semi-Polar Nonionic Surfactants
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 bottlewashing systems. However, within compositional
embodiments
of this invention designed for high foam cleaning methodology, semi-polar
nonionics would have immediate utility. The semi-polar nonionic surfactants
include the amine oxides, phosphine oxides, sulfoxides and their alkoxylated
derivatives.
13. Amine oxides are tertiary amine oxides corresponding to the general
formula:
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R2
1 4 1
R-(OR )-N-im- 0
R3
wherein the arrow is a conventional representation of a semi-polar bond; and,
R1, R2,
and R3 may be aliphatic, aromatic, heterocyclic, alicyclic, or combinations
thereof.
Generally, for amine oxides of detergent interest, Rl is an alkyl radical of
from about
8 to about 24 carbon atoms; R2 and R3 are alkyl or hydroxyalkyl of 1-3 carbon
atoms
or a mixture thereof; R2 and R3 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,
etradecyldimethylamine
oxide, pentadecyldimethylarnine oxide, hexadecyldimethylamine oxide,
heptadecyldimethylamine oxide, octadecyldimethylaine oxide,
dodecyldipropylamine oxide, tetradecyldipropylamine 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:
2
R
Ri P-)0O
R3
wherein the arrow is a conventional representation of a semi-polar bond; and,
R' is
an alkyl, alkenyl or hydroxyalkyl moiety ranging from 10 to about 24 carbon
atoms
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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, methylethyltetradecylphosphone oxide,
dimethylhexadecylphosphine oxide, diethyl-2-hydroxyoctyldecylphosphine oxide,
bis(2-hydroxyethyl)dodecylphosphine oxide, and
bis(hydroxymethyl)tetradecylphosphine oxide. Semi-polar nonionic surfactants
useful herein also include the water soluble sulfoxide compounds which have
the
structure:
R
I
S)WO
12
R
wherein the arrow is a conventional representation of a semi-polar bond; and,
Rl 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 R2 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 Surfactants
Also useful in the present invention are surface active substances which are
categorized as anionics because the charge on the hydrophobe is negative; or
surfactants in which the hydrophobic section of the molecule carries no charge
unless the pH is elevated to neutrality or above (e.g. carboxylic acids).
Carboxylate, sulfonate, sulfate and phosphate are the polar (hydrophilic)
solubilizing
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groups found in anionic surfactants. 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 is well understood, anionics are excellent detersive surfactants and are
therefore, favored additions to heavy duty detergent compositions. Generally,
however, anionics have high foam profiles which limit their use alone or at
high
concentration levels in cleaning systems such as bottlewashers that require
strict
foam control. 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 known chemical classes and additional sub-groups,
which
are 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
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
ethoxysulfates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide
ether
sulfates, the C5 -C17 acyl-N-(C1-C4 alkyl) and -N-(C1-C2 hydroxyalkyl)
glucamine
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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 detergent 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.
Anionic carboxylate surfactants suitable for use in the present compositions
include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate
surfactants and the soaps (e.g. alkyl carboxyls). Secondary soap surfactants
(e.g.
alkyl carboxyl surfactants) useful in the present compositions include those
which
contain a carboxyl unit connected to a secondary carbon. The secondary carbon
can
be in a ring structure, e.g. as in p-octyl benzoic acid, or as in alkyl-
substituted
cyclohexyl carboxylates. The secondary soap surfactants typically contain no
ether
linkages, no ester linkages and no hydroxyl groups. Further, they typically
lack
nitrogen atoms in the head-group (amphiphilic portion). Suitable secondary
soap
surfactants typically contain 11-13 total carbon atoms, although more carbons
atoms
(e.g., up to 16) can be present.
Other anionic detergents 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 liydroxyalkane-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.
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.
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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.
Cationic Surfactants
Surface active substances are classified as cationic if the charge on the
liydrotrope portion of the molecule is positive. Surfactants in which the
hydrotrope
carries no charge unless the pH is lowered close to neutrality or lower, but
which are
then cationic (e.g. alkyl amines), are also included in this group. In theory,
cationic
surfactants may be synthesized from any combination of elements containing an
"onium" structure RnX+Y- and could include compounds other than nitrogen
(ammonium) such as phosphorus (phosphonium) and sulfur (sulfonium). In
practice, the cationic surfactant field is dominated by nitrogen containing
compounds, probably because synthetic routes to nitrogenous cationics are
simple
and straightforward and give high yields of product, which can make them less
expensive.
Cationic surfactants preferably include, more preferably refer to, compounds
containing at least one long carbon chain hydrophobic group and at least one
positively charged nitrogen. The long carbon chain group may be attached
directly
to the nitrogen atom by simple substitution; or more preferably indirectly by
a
bridging functional group or groups in so-called interrupted alkylamines and
amido
amines. Such functional groups can make the molecule more hydrophilic and/or
more water dispersible, more easily water solubilized by co-surfactant
mixtures,
and/or water soluble. For increased water solubility, additional primary,
secondary
or tertiary amino groups can be introduced or the amino nitrogen can be
quatemized
with low molecular weight alkyl groups. Further, the nitrogen can be a part of
branched or straight chain moiety of varying degrees of unsaturation or of a
saturated or unsaturated heterocyclic ring. In addition, cationic surfactants
may
contain complex linkages having more than one cationic nitrogen atom.
The surfactant compounds classified as amine oxides, amphoterics and
zwitterions are tliemselves typically cationic in near neutral to acidic pH
solutions
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and can overlap surfactant classifications. Polyoxyethylated cationic
surfactants
generally behave like nonionic surfactants in alkaline solution and like
cationic
surfactants in acidic solution.
The simplest cationic amines, amine salts and quaternary ammonium
compounds can be schematically drawn thus:
Rt
R R
R-N. l R-N H+X R-N+-RX
R I II
x ~11
in which, R represents a long alkyl chain, R', R", and R"' may be either long
alkyl
chains or smaller alkyl or aryl groups or hydrogen and X represents an aiiion.
The
amine salts and quaternary ammonium compounds are preferred for practical use
in
this invention due to their high degree of water solubility.
The majority of large volume commercial cationic surfactants can be
subdivided into four known major classes and additional sub-groups, which are
described in "Surfactant Encyclopedia", Cosmetics & Toiletries, Vol. 104 (2)
86-96
(1989). The first class includes alkylamines and their salts. The second class
includes alkyl imidazolines. The third class includes ethoxylated amines. The
fourth class includes quaternaries, such as alkylbenzyldimethylammonium salts,
alkyl benzene salts, heterocyclic ammonium salts, tetra alkylammonium salts,
and
the like. Cationic surfactants are known to have a variety of properties that
can be
beneficial in the present compositions. These desirable properties can include
detergency in compositions of or below neutral pH, antimicrobial efficacy,
tliickening or gelling in cooperation with other agents, and the like.
Cationic surfactants useful in the compositions of the present invention
include those having the formula Rl ,,, R2XYLZ wherein each Rl is an organic
group
containing a straight or branched alkyl or alkenyl group optionally
substituted with
up to three phenyl or hydroxy groups and optionally interrupted by up to four
of the
following structures:
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O O R1 O H
-C-O- -C-N- -C-N-
O O Rl O H
-C-O- -C-N- -C-N-
or an isomer or mixture of these structures, and which contains from about 8
to 22
carbon atoms. The Rl groups can additionally contain up to 12 ethoxy groups. m
is
a number from 1 to 3. Preferably, no more than one R' group in a molecule has
16
or more carbon atoms when m is 2 or more than 12 carbon atoms when m is 3.
Each
Ra is an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms or a
benzyl group with no more than one R2 in a molecule being benzyl, and x is a
number from 0 to 11, preferably from 0 to 6. The remainder of any carbon atom
positions on the Y group are filled by hydrogens.
Y is can be a group including, but not limited to:
+ N
-N C~+
~ N
+
-N-(C2H40) p p=about 1 to 12
(C2H40)-N+-(C2H40) p=about 1 to 12
p l P
-P .-S
I I
CN + + N+
s N J
O
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or a mixture thereof. Preferably, L is 1 or 2, with the Y groups being
separated by a
moiety selected from Rl and R2 analogs (preferably alkylene or alkenylene)
having
from 1 to about 22 carbon atoms and two free carbon single bonds when L is 2.
Z is
a water soluble anion, such as a halide, sulfate, methylsulfate, hydroxide, or
nitrate
anion, particularly preferred being chloride, bromide, iodide, sulfate or
methyl
sulfate anions, in a number to give electrical neutrality of the cationic
component.
Amphoteric Surfactants
Amphoteric, or ampholytic, surfactants contain both a basic and an acidic
hydrophilic group and an organic hydrophobic group. These ionic entities may
be
any of anionic or cationic groups described herein for other types of
surfactants. A
basic nitrogen and an acidic carboxylate group are the typical functional
groups
employed as the basic and acidic hydrophilic groups. In a few surfactants,
sulfonate,
sulfate, phosphonate or phosphate provide the negative charge.
Amphoteric surfactants can be broadly described as derivatives of aliphatic
secondary and tertiary amines, in which the aliphatic radical may be straight
chain or
branched and wherein one of the aliphatic substituents contains from about 8
to 18
carbon atoms and one contains an anionic water solubilizing group, e.g.,
carboxy,
sulfo, sulfato, phosphato, or phosphono. Amphoteric surfactants are subdivided
into
two known major classes, which are described in "Surfactant Encyclopedia"
Cosmetics & Toiletries, Vol. 104 (2) 69-71 (1989). The first class includes
acyl/dialkyl etllylenediamine derivatives (e.g. 2-alkyl hydroxyethyl
imidazoline
derivatives) and their salts. The second class includes N-alkylamino acids and
their
salts. Some amphoteric surfactants can be envisioned as fitting into both
classes.
Amphoteric surfactants can be synthesized by known methods. For example,
2-alkyl hydroxyethyl imidazoline is synthesized by condensation and ring
closure of
a long chain carboxylic acid (or a derivative) with dialkyl ethylenediamine.
Commercial amph.oteric surfactants are derivatized by subsequent hydrolysis
and
ring-opening of the imidazoline ring by alkylation -- for example with
chloroacetic
acid or ethyl acetate. During alkylation, one or two carboxy-alkyl groups
react to
form a tertiary amine and an ether linkage with differing alkylating agents
yielding
different tertiary amines.
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Long chain imidazole derivatives having application in the present invention
generally have the general formula:
(MONO)ACETATE (DI)PROPIONATE AMPHOTERIC
SULFONATE
CH2COOE) CH2CHZCOOD OH
RCONHCH2CH2NEDH RCONHCH2CH2 I~CH2CH2COOH CH2CHCH2SO30iVa0 III CH2CH2OH
CHZCH2OH RCONHCH2CH2N
1~1 CHzCHZOH
Neutral pH - Zwitterion
wlierein R is an acyclic hydrophobic group containing from about 8 to 18
carbon
atoms and M is a cation to neutralize the charge of the anion, generally
sodium.
Commercially prominent imidazoline-derived amphoterics that can be employed in
the present compositions include for example: Cocoamphopropionate,
Cocoa.inphocarboxy-propionate, Cocoamphoglycinate, Cocoamphocarboxy-
glycinate, Cocoamphopropyl-sulfonate, and Cocoamphocarboxy-propionic acid.
Preferred amphocarboxylic acids are produced from fatty imidazolines in which
the
dicarboxylic acid fiulctionality of the amphodicarboxylic acid is diacetic
acid and/or
dipropionic acid.
The carboxymethylated compounds (glycinates) described herein above
frequently are called betaines. Betaines are a special class of amphoteric
discussed
herein below in the section entitled, Zwitterion Surfactants.
Long chain N-alkylamino acids are readily prepared by reaction RNH2, in
which R=C$-C18 straight or branched chain alkyl, fatty amines with halogenated
carboxylic acids. Alkylation of the primary amino groups of an amino acid
leads to
secondary and tertiary amines. Alkyl substituents may have additional amino
groups that provide more than one reactive nitrogen center. Most commercial N-
alkylamine acids are alkyl derivatives of beta-alanine or beta-N(2-
carboxyethyl)
alanine. Examples of commercial N-alkylamino acid ampholytes having
application
in this invention include alkyl beta-amino dipropionates, RN(C2H4COOM)2 and
RNHC2H4COOM. In these R is preferably an acyclic hydrophobic group containing
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from about 8 to about 18 carbon atoms, and M is a cation to neutralize the
charge of
the anion.
Preferred amphoteric surfactants include those derived from coconut
products such as coconut oil or coconut fatty acid. The more preferred of
these
coconut derived surfactants include as part of their structure an
ethylenediamine
moiety, an alkanolamide moiety, an amino acid moiety, preferably glycine, or a
combination tlzereof; and an aliphatic substituent of from about 8 to 18
(preferably
12) carbon atoms. Such a surfactant can also be considered an alkyl
amphodicarboxylic acid. These amphoteric surfactants can include chemical
structures represented as: C12-alkyl-C(O)-NH-CH2-CH2-N+(CH2-CH2-CO2Na)2-
CH2-CH2-OH or C12-alkyl-C(O)-N(H)-CH2-CHZ-N+(CH2-CO2Na)Z-CH2-CH2-OH.
Disodium cocoampho dipropionate is one most preferred amphoteric surfactant
and
is commercially available under the tradename MiranolTM FBS from Rhodia Inc.,
Cranbury, N.J. Another most preferred coconut derived amphoteric surfactant
with
the chemical name disodium cocoampho diacetate is sold under the tradename
MiranolTM C2M-SF Conc., also from Rhodia Inc., Cranbury, N.J.
A typical listing of amphoteric classes, and species of these surfactants, is
given in U.S. Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30,
1975.
Further examples are given in "Surface Active Agents and Detergents" (Vol. I
and II
by Schwartz, Perry and Berch).
Zwitterionic Surfactants
Zwitterionic surfactants can be thought of as a subset of the amphoteric
surfactants. Zwitterionic surfactants can be broadly described as derivatives
of
secondary and tertiary amines, derivatives of heterocyclic secondary and
tertiary
amines, or derivatives of quatemary ammonium, quaternary phosphonium or
tertiary
sulfonium compounds. Typically, a zwitterionic surfactant includes a positive
charged quaternary ammoniuin or, in some cases, a sulfonium or phosphonium
ion;
a negative charged carboxyl group; and an alkyl group. Zwitterionics generally
contain cationic and anionic groups which ionize to a nearly equal degree in
the
isoelectric region of the molecule and which can develop strong" inner-salt"
attraction between positive-negative charge centers. Examples of such
zwitterionic
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synthetic surfactants include derivatives of aliphatic quaternary ammonium,
phosphonium, and sulfonium compounds, in which the aliphatic radicals can be
straight chain or branched, and wherein one of the aliphatic substituents
contains
from 8 to 18 carbon atoms and one contains an anionic water solubilizing
group,
e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Betaine and
sultaine
surfactants are exemplary zwitterionic surfactants for use herein.
A general formula for these compounds is:
(~)x
I+ 3 -
R-Y-CH2-R-Z
wherein R' contains an alkyl, alkenyl, or hydroxyalkyl radical of from 8 to 18
carbon
atoms having from 0 to 10 etliylene oxide moieties and from 0 to 1 glyceryl
moiety;
Y is selected from the group consisting of nitrogen, phosphorus, and sulfur
atoms;
R2 is an alkyl or monohydroxy alkyl group containing 1 to 3 carbon atoms; x is
1
when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorus atom, R3 is
an
alkylene or hydroxy alkylene or hydroxy alkylene of from 1 to 4 carbon atoms
and Z
is a radical selected from the group consisting of carboxylate, sulfonate,
sulfate,
phosphonate, and phosphate groups.
Examples of zwitterionic surfactants having the structures listed above
include: 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-l-carboxylate; 5-
[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1-sulfate; 3-[P,P-
diethyl-P-3,6,9-trioxatetracosanephosphonio]-2-hydroxypropane-1-phosphate; 3-
[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropyl-amrnonio]-propane-l-phosphonate;
3 -(N,N-dimethyl-N-hexadecylammonio)-propane-l-sulfonate; 3 -(N,N-dimethyl-N-
hexadecylammonio)-2-hydroxy-propane-l-sulfonate; 4-[N,N-di(2(2-hydroxyethyl)-
N(2-hydroxydodecyl)ammonio]-butane-l-carboxylate; 3-[S-ethyl-S-(3-dodecoxy-2-
hydroxypropyl)sulfonio]-propane-l-phosphate; 3-[P,P-dimethyl-P-
dodecylphosphonio] -propane- 1 -phosphonate; and S[N,N-di(3-hydroxypropyl)-N-
hexadecylammonio]-2-hydroxy-pentane-l-sulfate. The alkyl groups contained in
said detergent surfactants can be straight or branched and saturated or
unsaturated.
The zwitterionic surfactant suitable for use in the present compositions
includes a betaine of the general structure:
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R R R~
I+ - +
RI
-N-CH2-CO2 R-S-CH2-CO2 RI-P-CH2 C02
R ft IRIII
These surfactant betaines typically do not exhibit strong cationic or anionic
characters at pH extremes nor do they show reduced water solubility in their
isoelectric range. Unlike "externaP" quaternary ammonium salts, betaines are
compatible with anionics. Examples of suitable betaines include coconut
acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C12-14
acylamidopropylbetaine; C8-14 acylamidohexyldiethyl betaine; 4-C14-16
acylmethylamidodiethylammonio-l-carboxybutane; C 16-18
acylamidodimethylbetaine; C12-16 acylamidopentanediethylbetaine; and C12-16
acylmethylamidodimethylbetaine.
Sultaines useful in the present invention include those coinpounds having the
formula (R(R')2 N+ R2SO3-, in which R is a C6 -C18 hydrocarbyl group, each Rl
is
typically independently C1-C3 alkyl, e.g. methyl, and R2 is a C1-C6
hydrocarbyl
group, e.g. a C1-C3 alkylene or hydroxyalkylene group.
A typical listing of zwitterionic classes, and species of these surfactants,
is
given in U.S. Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30,
1975.
Further examples are given in "Surface Active Agents and Detergents" (Vol. I
and II
by Schwartz, Perry and Berch).
Surfactants
The surfactants described hereinabove can be used singly or in combination
in the practice and utility of the present invention. In particular, the
nonionics and
anionics can be used in combination. The semi-polar nonionic, cationic,
amphoteric
and zwitterionic surfactants can be employed in combination with nonionics or
anionics. The above examples are merely specific illustrations of the numerous
surfactants which can find application within the scope of this invention. The
foregoing organic surfactant compounds can be formulated into any of the
several
commercially desirable composition forms of this invention having disclosed
utility.
Said compositions are washing or presoak treatments for food or other soiled
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surfaces in concentrated form which, when dispensed or dissolved in water,
properly
diluted by a proportionating device, and delivered to the target surfaces as a
solution,
gel or foam will provide cleaning. Said cleaning treatments consisting of one
product; or, involving a two product system wherein proportions of each are
utilized.
Said product is typically a concentrate of liquid or emulsion.
Additional Ingredients
The additive composition of the invention can also include any number of
additional ingredients. Specifically, the composition of the invention can
include
stabilizing agents, wetting agents, hydrotropes as well as pigments or dyes
among
any number of constituents which can be added to the composition. Such
additional
ingredients can be preformulated with the additive composition of the
invention or
added to the system simultaneously, or even after, the addition of the
additive
composition. The composition of the invention can also contain any number of
other constituents as necessitated by the application, which are known and
which
can facilitate the activity of the present invention.
Stabilizing Agents
Chelating agents or sequestrants generally useful as stabilizing agents in the
present compositions include acrylic and polyacrylic acid-type stabilizing
agents,
phosphonic acid, and phosphonate-type chelating agents among others. Preferred
phosphate, polyphosphate, phosphonic acid, and otlier phosphonate sequestrants
and
chelating agents are described hereinabove. The chelating agent or
sequestering
agent can effectively complex and remove undesired ions from inappropriate
interaction with active ingredients thus increasing cleaning agent
performance. Both
organic and inorganic chelating agents may be used. Inorganic phosphate and
phosphonate chelating agents are described hereinabove. Organic chelating
agents
include both polymeric and small molecule chelating agents. Polymeric
chelating
agents commonly include polyanionic compositions such as polyacrylic acid
compounds. The concentration of chelating agent useful in the present
invention
generally ranges from about 0.01 to about 20 wt-%, preferably from about 0.1
to
about 10 wt-%, most preferably from about 0.5 to about 5 wt-%.
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Wetting or Defoaming Agents
Also useful in the composition of the invention are wetting and defoaming
agents. Wetting agents function to increase the penetration activity of the
additive
composition of the invention. Wetting agents which can be used in the
composition
of the invention include any of those constituents known to raise the surface
activity
of the composition of the invention.
Along these lines surfactants, and especially nonionic surfactants, can also
be
useful in the present invention. Nonionic surfactants which can be useful in
the
present invention are those which include ethylene oxide moieties, propylene
oxide
moieties, as well a mixtures thereof, and ethylene oxide-propylene oxide
moieties in
either heteric or block formation. Additionally useful in the present
invention are
nonionic surfactants which include an alkyl ethylene oxide compounds, alkyl
propylene oxide compounds, as well as mixtures thereof, and alkyl ethylene
oxide-
propylene oxide compounds where the ethylene oxide propylene oxide moiety is
either in heteric or block formation. Further useful in the present invention
are
nonionic surfactants having any mixture or combination of ethylene oxide-
propylene
oxide moieties linked to a alkyl chain where the ethylene oxide and propylene
oxide
moieties can be in any randomized or ordered pattern and of any specific
length.
Nonionic surfactants useful in the present invention can also include
randomized
sections of block and heteric ethylene oxide propylene oxide, or ethylene
oxide-
propylene oxide.
Generally, the concentration of nonionic surfactant used in a composition of
the present invention can range from about 0 wt-% to about 20 wt-% of the
composition.
The composition used in the methods of the invention can also contain
additional ingredients as necessary to assist in defoaming.
Generally, defoamers wliich can be used in accordance with the invention
include silica and silicones; aliphatic acids or esters; alcohols; sulfates or
sulfonates;
amines or amides; halogenated compounds such as fluorochlorohydrocarbons;
vegetable oils, waxes, mineral oils as well as their sulfated derivatives;
fatty acid
soaps such as alkali, alkaline earth metal soaps; and phosphates and phosphate
esters
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such as alkyl and alkaline diphosphates, and tributyl phosphates among others;
and
mixtures thereof.
Especially preferable, are those antifoaming agents or defoamers which are
appropriate for the application of the method of the invention. To this end,
one of
the more effective antifoaming agents includes silicones. Silicones such as
dimethyl
silicone, glycol polysiloxane, methylphenol polysiloxane, trialkyl or
tetralkyl
silanes, hydrophobic silica defoamers and mixtures tliereof can all be used in
defoaming applications. Commercial defoamers commonly available include
silicones such as Ardefoam from Armour Industrial Chemical Company which is a
silicone bound in an organic emulsion; Foam Kill or Kresseo available from
Krusable Chemical Company which are silicone and non-silicone type defoamers
as
well as silicone esters; and Anti-Foam A and DC-200 from Dow Corning
Corporation which are both food grade type silicones among others. These
defoamers can be present at a concentration range from about 0.01 wt-% to 5 wt-
%,
preferably from about 0.01 wt-% to 2 wt-%, and most preferably from about 0.01
wt-% to about 1 wt-%.
Hydrotrope
The additive composition of the invention or employed in the methods of the
invention may also include a hydrotrope coupler or solubilizer. Such materials
can
be used to ensure that the composition remains phase stable and in a single
highly
active aqueous form. Such hydrotrope solubilizers or couplers can be used at
compositions which maintain phase stability but do not result in unwanted
compositional interaction.
Representative classes of hydrotrope solubilizers or coupling agents include
an anionic surfactant such as an alkyl sulfate, an alkyl or alkane sulfonate,
a linear
alkyl benzene or naphthalene sulfonate, a secondary alkane sulfonate, alkyl
ether
sulfate or sulfonate, an alkyl phosphate or phosphonate, dialkyl sulfosuccinic
acid
ester, sugar esters (e.g., sorbitan esters) and a C8-10 alkyl glucoside.
Preferred coupling agents for use in the rinse agents of the invention include
n-octane sulfonate and aromatic sulfonates such as an alkyl benzene sulfonate
(e.g.,
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sodium xylene sulfonate or naphthalene sulfonate). Generally, any number of
surfactants may be used consistent with the purpose of this constituent.
Anionic surfactants useful with the invention include alkyl carboxylates,
linear alkylbenzene sulfonates, paraffin sulfonates and secondary n-alkane
sulfonates, sulfosuccinate esters and sulfated linear alcohols.
Zwitterionic or amphoteric surfactants useful with the invention include beta-
N-alkylaminopropionic acids, n-alkyl-beta-iminodipropionic acids, imidazoline
carboxylates, n-alky-Iletaines, amine oxides, sulfobetaines and sultaines.
Nonionic surfactants useful in the context of this invention are generally
polyether (also known as polyalkylene oxide, polyoxyalkylene or polyalkylene
glycol) compounds. More particularly, the polyether compounds are generally
polyoxypropylene or polyoxyethylene glycol compounds. Typically, the
surfactants
useful in the context of this invention are synthetic organic polyoxypropylene
(PO)-
polyoxyethylene (EO) block copolymers. These surfactants have a diblock
polymer
including an EO block and a PO block, a center block of polyoxypropylene units
(PO), and having blocks of polyoxyethylene grated onto the polyoxypropylene
unit
or a center block of EO with attached PO blocks. Further, this surfactant can
have
further blocks of either polyoxyethylene or polyoxypropylene in the molecule.
The
average molecular weight of useful surfactants ranges from about 1000 to about
40,000 and the weight percent content of ethylene oxide ranges from about 10-
80%
by weight.
Also useful in the context of this invention are surfactants including alcohol
alkoxylates having EO, PO and BO blocks. Straight chain primary aliphatic
alcohol
alkoxylates can be particularly useful as sheeting agents. Such alkoxylates
are also
available from several sources including BASF Wyandotte where they are known
as
"Plurafac" surfactants. A particular group of alcohol alkoxylates found to be
useful
are those having the general formula R-(EO),,,--(PO)õ wherein m is an integer
of
about 2-10 and n is an integer from about 2-20. R can be any suitable radical
such
as a straight chain alkyl group having from about 6-20 carbon atoms.
Other useful nonionic surfactants of the invention include capped aliphatic
alcohol alkoxylates. These end caps include but are not limited to methyl,
ethyl,
propyl, butyl, benzyl and chlorine. Preferably, such surfactants have a
molecular
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weight of about 400 to 10,000. Otlier useful nonionic surfactants are
alkylpolyglycosides.
Another useful nonionic surfactant of the invention is a fatty acid alkoxylate
wherein the surfactant includes a fatty acid moiety with an ester group
including a
block of EO, a block of PO or a mixed block or heteric group. The molecular
weights of such surfactants range from about 400 to about 10,000, a preferred
surfactant has an EO content of about 30 to 50 wt-% and wherein the fatty acid
moiety contains from about 8 to about 18 carbon atoms.
Similarly, alkyl phenol alkoxylates have also been found useful in the
invention. Such surfactants can be made from an alkyl phenol moiety having an
alkyl group with 4 to about 18 carbon atoms, can contain an ethylene oxide
block, a
propylene oxide block or a mixed ethylene oxide, propylene oxide block or
heteric
polymer moiety. Preferably such surfactants have a molecular weight of about
400
to about 10,000 and have from about 5 to about 20 units of etliylene oxide,
propylene oxide or mixtures thereof.
The concentration of hydrotrope useful in the present invention generally
ranges from about 0.1 to about 20 wt-%, preferably from about 0.5 to about 10
wt-
%, most preferably from about 1 to about 4 wt-%.
Thickening or Gelling Agents
Thickeners useful in the present invention include those which do not leave
contaminating residue on the surface of bottles or bottle washing apparatus.
That is,
preferred thickeners or gelling agents do not include components incompatible
with
glass bottles and the bottle washing apparatus.
Generally, thickeners which may be used in the present invention include
natural gums such as xanthan gum. Also useful in the present invention are
cellulosic polymers, such as carboxymethyl cellulose. Generally, the
concentration
of thickener employed in the present compositions or methods will be dictated
by
the desired viscosity within the final composition. However, as a general
guideline,
the viscosity of thickener within the present composition ranges from about
0.1 wt-
% to about 1.5 wt-%, preferably from about 0.1 wt-% to about 1.0 wt-%, and
most
preferably from about 0.1 wt-% to about 0.5 wt-%.
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Polyol
The bottle washing additive composition of the invention can also include a
polyol. The polyol advantageously provides additional stability and
hydrotrophic
properties to the composition. Propylene glycol and sorbitol are preferred
polyols.
Dyes/Odorants
Various dyes, odorants including perfunies, and other aesthetic enhancing
agents may also be included in the bottle washing additive comp )sition. The
dye
advantageously provides visibility of the product in a package, dispenser,
and/or
lines of the bottlewasher, as for example, Direct Blue 86 (Miles), Fastusoff
Blue
(Mobay Chemical Corp.), Acid Orange 7 (American Cyanamid), Basic Violet 10
(Sandoz), Acid Yellow 23 (GAF), Acid Yellow 17 (Sigma Chemical), Sap Green
(Keyston Analine and Chemical), Metanil Yellow (Keystone Analine and
Chemical), Acid Blue 9(Hilton Davis), Sandolan Blue/Acid Blue 182 (Sandoz),
Hisol Fast Red (Capitol Color and Chemical), Fluorescein (Capitol Color and
Chemical), Acid Green 25 (Ciba- Geigy ), and the like. A wide variety of dyes
are
suitable.
Fragrances or perfumes that may be included in the compositions include, for
example, terpenoids sucli as citronellol, aldehydes sucli as amyl
cinnainaldehyde, a
j asmine such as C 1 S-j astnine or j asmal, vanillin, and the like.
The present invention may be better understood with reference to the
following exaniples. These examples are intended to be representative of
specific
embodiments of the iiivention, and are not intended as limiting the scope of
the
invention.
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Examples
Example 1- Formulas for Liquid Additive Compositions
Table 1- Additive formulas that failed to mitigate corrosion of a ceramic
applied
color label.
Ingredient Control Control Control Control Control Control
#1 #2 #3 #4 #5 #6
Water 67 67 79 79 51 66
ATMP 3 3 4
HEDP 4 4 4
PBTC 1 1 2 1
Phosphoric Acid 15 15 0 0 23 15
Gluconic Acid 5 5 8 8 5 7
Lactic Acid 4 4 4
Citric Acid 6 6 5
Polyoxyethylene coco 2 2 8
amine
EO-PO block 6 6 8
copolymer
Alcohol ethoxylate 2 2
Phosphate:Phosphonate 5 5 0 0 4.1 3.8
Ratio
ACL Label Attacked? YES YES YES YES YES YES
Quantities are in wt-%
Sodium carbonate was employed at 15,000 ppni (1.5 wt-%) and caustic soda
at 25,000 ppm (2.5 wt-%) in the use cleaning composition created from the
concentrate additive compositions described in Table 1. EDTA was added to the
cleaning compositions for controls #2, #3, and #4 separately from the additive
composition to yield concentrations of EDTA in the cleaning compositions of
533
ppm, 500 ppm, and 1000 ppm, respectively. The additive concentrate composition
was diluted 1:400 to make the use composition. Control #7 exposed the applied
color design to only caustic and carbonate, and the design was attacked.
Control #8
exposed the applied color design to only water, and the design was not
attaclced.
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Control #15 exposed the applied color design to only caustic, and the design
was
attacked.
Table 2 - Additive formulas that mitigated corrosion of a ceramic applied
color
label.
Ingredient Test #9 Test#10 Test #11 Test#12 Test#13 Test #14
Water 73 73 63 73 65 79
HEDP 4 4 4 4 4 4
PBTC 1 1 1 1 1 1
Phosphoric Acid 8 8 8 8
Gluconic Acid 7 7 5 7 7 8
Lactic Acid 4 4 4 4 4 4
Citric Acid 5 5 5 5 5 6
Polyoxyethylene coco 3
amine
Butyl capped alcohol 15
ethoxylate
EO-PO block copolyrner 6
Alcohol ethoxylate 2
Phosphate:Phosphonate 1.9 1.9 0 1.9 1.9 0
Ratio
ACL Label Attack? NO NO NO NO NO NO
Quantities are in wt-%
Sodium carbonate was employed at 15,000 ppm (1.5 wt-%) and caustic soda
at 25,000 ppm (2.5 wt-%) in the use cleaning composition created from the
concentrate additive compositions described in Table 2. The additive
concentrate
composition was typically diluted 1:400 to make the use composition, and in
test
#12 was diluted 1:200.
For purposes of testing, the additive composition was mixed with a caustic
composition with or without added carbonate to achieve conditions of carbonate
concentrations typically found in a bottle washing use composition. Caustic
soda,
and other basic mixtures, absorb carbon dioxide from the atmosphere to achieve
carbonate concentrations as large as about 1.5 wt-%.
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Materials
The following materials present exaniples of materials suitable for preparing
the compositions of the present invention. Dequest 2000: Amino tri (methylene-
phosphonic acid), 50 % (Solutia Inc.). Dequese2010: 1-Hydroxyethylene-1,1-
diphosphonic acid, 60 % (Solutia Inc.). Bayhibit AM, 2-phosphono-1,2,4-
butanetricarboxylic acid, 50 % (Miles Mobay/Bayer). Phosphoric acid, 75 %
(Albright and Wilson, Monsanto, FMC). Gluconic acid, 50 % (PMP Fermentation
Products). Lactic Acid: 2-hydroxypropanoic acid, 80 % (Archer Daniels
Midland).
Citric acid, anhydrous granular, 100 %, (A.E. Stanley). BK 1057,
Polyoxyethylene
(12) cocoamine, 98-100 % (Chemax). LT-104, Butyl-capped alcohol ethoxylate,
100
% (Henkel.). Genepol PN 30, EO-PO block copolymer (Hoechst Celanese).
Plurafac RA-40, linear alcohol ethoxylate (BASF). Tetra sodium EDTA, ethylene
diamine tetra acetic acid-sodium salt, 100 % pwd, 40 % solution (BASF). Sodium
carbonate, pwd various densities and particles sizes (North American
Chemical).
Sodium hydroxide, beads, 50% solution (Oxychem).
Example 2 - - Formula With the Inventive Mixture of Phosphate and
Phosphonate
Exhibits Reduced Corrosion of an Applied Color Label in Bottle Washin~
An additive coniposition according to the present invention was tested and
quantitatively evaluated for its effect on applied ceraniic labels on bottles.
Test Method
To be able to simulate conditions in a bottle washing apparatus, a simple
laboratory soak test method was employed to duplicate the soaking portion of
the
bottle washing cycle. The testing for was done using virgin bottles with
applied
ceramic labels, all being the same type of bottle and label (Carib' Beer
bottles). The
bottles (typically 3 bottles per wash or additive composition) were submerged
in 4
liters of the solution being tested for 24 hours at 75 C. A solution of 0.25%
Stabilon SF and 500 ppm EDTA represented conventional bottle washing
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compositions. A bottle not treated by submersion was employed as a control.
After
submersion, the test bottles were rinsed with warm tap water, followed by
distilled
water, and set aside to dry.
The appearance of the test and control labels were then quantitatively
evaluated using a surface roughness method, statistical software in Image Pro-
Plus,
and a NikonTM SMZ-U Stereo-microscope. A uniform light intensity was
established
using a double arm halogen light source by positioning each arm at
approximately
0 and 180 , respectively. This insured a spatially non-biased color
illumination,
independent of light intensity. The bottle was then placed on the stereoscope
stage
at a set angle and position to ensure a standardized image collection. Uniform
intensity was checked by applying a best fit equalization to the image; this
then
allowed for any non-uniform liaht natterns to be seen prior to data
collection.
Images were then collected using the SONYTM DXC-970MD digital camera in a 24
bit
color format and images were converted to 8-bit gray scale inlages. From this
format a monochromatic shade distribution could be analyzed with a histogram
and
line plot analysis.
Results
The analysis of unwashed, new control applied color labels, labels treated
with an additive composition according to the present invention, and labels
treated
with a conventional bottle washing coniposition are illustrated in Figures 2-4
and
Table 3. The data represent values of and variation in intensity of color in
the label.
Table 3 - Grey scale intensity, standard deviation, and range for unwashed
control
labels, labels treated with an additive composition of the present invention,
and a
conventional bottle washing composition.
Measurement Control Inventive Conventional
Additive Bottle Washing
Composition Composition
Mean 97.91 95.01 147.61
Standard Deviation 8.74 9.72 18.81
Raiige, Minimum - Maximum 83-174 71-146 89-223
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I The analysis of the applied color label treated with the conventional
washing
composition, 0.25% Stabilion SF with 500 ppm EDTA, showed a significant change
in color intensity compared to the control (Figure 2, Table 3). The control
sample,
an untreated surface, had an average intensity level of 97.91 with a standard
deviation of 8.74 (on a scale of 256 levels of gray). The conventional washing
composition averaged a 147.61 intensity level with a standard deviation of
16.16.
This shift to a higher value on the gray scale spectrum indicates a bleaching
of the
label, since 255 is equivalent to a completely white background, and zero
represents
a completely black background. In addition to the peak shift, the distribution
found
after treatment with the conventional washing composition was significantly
broadened, with a range (2 standard deviations) of 115 to 180. This 64 unit
range is
an indication of greater variation of the label material caused by the
conventional
wash composition, which is consistent with bleaching and degradation of the
label.
As seen in Figure 2, the untreated, control label showed a narrow distribution
(36
intensity unit range), as well as a higher average frequency, which correlates
witli
the low level of visible bleaching in the sample.
The inventive additive composition resulted in applied color labels having
quality similar to that of the untreated, new control label. As seen in Figure
2 and
Table 3, like the control label, the label treated with the inventive
composition
showed a narrow distribution (36 intensity unit range), as well as a higher
average
frequency. Both of these values correlate with the low level of visible
bleaching in
the label treated with the inventive composition.
Analysis of surface roughness was performed using a component of the
Image Pro Plus analysis software that obtains a plot based on the intensity
values of
a single line within an image. The intensity of each pixel is then related to
surface
roughness based on the intensity of each neighboring pixel. The range of
intensity
values thus determines the degree in change over the entire line with the
standard
deviation a relative measure of how widely values are dispersed from the
average
value. For this analysis, the assumption was made that the spatial variation
is
primarily a result of the roughness of the surface. Therefore, the line
standard
deviation can be used as a relative measure of the surface roughness.
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Such an analysis is illustrated in Figures 3 and 4. These line graphs
represent the surface roughness as a measurement of intensity. From the data
illustrated in Figure 3, the min/max intensity values for the conventional
washing
composition are 89-223 with an absolute value of 134. When compared to the
control bottle, which scored a min/max of 83-174 and a absolute value of 91,
treatment with the conventional composition yields a label that is 32% rougher
than
the new, untreated, control label. In contrast, the inventive additive
composition
yields a label that is smoother than the control label. Figure 4 illustrates
that using
the inventive additive achieved a min/max of 71-146 and absolute value of 75.
That
is, using the inventive additive results in a surface that is 18% smoother
than the
control.
In addition to the range of surface roughness, the specific variance in the
line
is also shown in Figures 3 and 4. The specific variance also indicates a more
severe
level of surface roughness caused by the conventional bottle washing
composition,
which exhibits a standard deviation of 18.81. The control, untreated label and
the
label treated with the inventive additive composition yielded standard
deviations of
8.74 and 9.72, respectively. The control and inventive additive labels had
standard
deviations less than half caused by treatment with the conventional washing
composition.
Conclusions
The results demonstrated that the additive composition of the present
invention did not have a detrimental iinpact of an applied color label. A
correlation
was observed between both visible color deterioration seen in the sample and
the
control. A correlation was also observed that indicated that an increase in
color
stability, which was reflected in a more non-variant surface (smooth) based on
a
decreased color variance. In contrast, a conventional bottle washing
composition
caused both a change in color intensity, which indicated bleaching or whiting
of the
label, as well as an increase in surface intensity variance, which again is
indicative
of a non-uniform surface.
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Example 3 - Phosphate Containing Additive Compositions Reduce Glass
Corrosion
Table 4 - Phosphate-free additive formulas used as controls in this Example.
Ingredient Control Control Control Control Control Control
#16 #17 #18 #19 #20 #21
Water 73 53 90 95 98 99
Potassium Iodide 0.3 0.3
HEDP (60%) 10 10 1 0.5 0.25 0.13
PBTC (50%) 1.5 1.5 1 0.5 0.25 0.13
ATMP (50%) 20
Gluconic Acid (50%) 15 15 8 4 2 1
Phosphoric Acid 0 0 0 0 0 0
Phosphate: 0 0 0 0 0 0
Phosphonate Ratio
Glass Corroded? No No No No No No
Quantities are in wt-%.
Table 5 - Phosphate containing additive formulas that mitigated corrosion of a
ceramic applied color label and cleaned the bottle.
Ingredient Test #22 Test #23 Test #24 Test #25 Test #26
Water 56 45 94 97 98
Potassium Iodide 0.3 0.3
HEDP (60%) 10 10 0.5 0.25 0.13
PBTC (50%) 1.5 1.5 0.5 0.25 0.13
ATMP (50%) 17
Gluconic Acid (50%) 15 15 4 2 1
Phosphoric Acid (75%) 18 12 1.5 0.7 0.4
Phosphate: 2:1 0.6:1 2:1 2:1 2:1
Phosphonate Ratio
Glass Corroded? No No No No No
Quantities are in wt-%.
Methods
Glass Corrosion Testiniz
For glass corrosion testing the bottle washing compositions were made up as:
0.25% Bottle Wash Additive 9.5 g
1.50% Na2CO3 57.0 g
5% of 50% NaOH Solution 195.0
Tap Water 3543.5 g
Total 3800 g
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The bottle washing composition was prepared in a 4 liter stainless steel
beaker. The beaker was covered with two layers of plastic wrap secured with
binders. The beakers were preheated in a 75 C oven.
Two glass bottles were selected and coded for each control or test
composition. The bottles were rinsed with DI water and placed in <122 F oven
to
dry for several hours or overnight, then they were removed and cooled. The
bottles
were weiglied to the nearest tenth of a milligram and the weight recorded.
The marked bottles were placed in their respective preheated bottle wash
composition. The plastic wrap was recovered and secured with binders. The
beakers were placed back into the 75 C oven and leave for 24 hours. At the end
of
24 hours, the beakers were removed from the oven and cooled for 1.5 hours. The
bottles were then removed from the wash compositions and rinsed with warm tap
water. The bottles were placed into 1% phosphoric acid solution for 0.5 hours
to
remove residues. The bottles were removed from the phosphoric acid, rinsed
with
DI water, and dried in a<122 F oven. On the next day, the bottles were
removed
from the oven to cool. When cooled, the bottles were weighed to the nearest
tenth
of a milligram and this post-treatment weight was recorded.
The % weight loss for the bottle was determined from the equation:
(Original Bottle Wt - Final Bottle Wt)/Original Bottle Wt* 100.
Cleaning Efficacy Testing
For cleaning efficiency testing the bottle washing compositions were made
up as:
0.25% Bottle Wash Additive 9.5 g
1.50% Na2CO3 57.0 g
5% of 50% NaOH Solution 195.0
Tap Water 3543.5 g
Total 3800 g
The bottle washing composition was prepared in a 4 liter stainless steel
beaker. The beakers were preheated in a 75 C oven with stirring.
Two glass bottles were selected and coded for each control or test
composition. Bottles were obtained from a local bottler and were soiled with a
clay
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and dirt. Soiled bottles were sorted and those with similar soiling were
grouped
together and used as pairs.
When the cleaning compositions reached 75 C, the two selected (coded)
bottles were placed into their respective solutions and allowed to soak for 10
minutes. The composition was mildly stirred to dissipate heat from bottom of
beaker. After 10 minutes, the bottles were removed from the composition and
rinsed
with light to medium flow of lukewarm water for 20 seconds.
The bottles were then allowed to air dry and then visually rated for
cleanliness against each other. The visual rating scale ranked the bottles
from 1 to
10. The bottles had been photographed before washing, and the washed bottles
were
compared to the photographs of the unwashed bottles. A control bottle washed
with
a caustic wash composition without additive typically had about 80% of the
total
mass of soil removed. Such a bottle generally was rated 2 or 3 on the visual
ranking
scale. A bottle that had had some 98% of the mass of soil removed typically
ranlced
8 or 9 on the visual ranking scale. A bottle with about 90% of the mass of
soil
removed typically rated about a 5 on the visual ranking scale. The visible
ranking
scale has proven reproducible and useful for determining bottle cleanliness.
Results
Phosphate-containing compositions according to the present invention had
some cleaning activity and, surprisingly, reduced corrosion of the glass
(Table 6).
Also surprising, the control compositions lacking phosphate cleaned more
effectively than the test compositions. The control compositions lacking
phosphate
also reduced corrosion of the glass (Table 6).
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Table 6 - Phosphate containing compositions according to the present invention
clean with only acceptable levels of glass corrosion.
Composition Average Percent Average Cleaning Grade
Weight Loss (maximum is 10)
Control #16 0.0030 5
Control #17 0.0384 6
Test #22 0.0557 2
Test #23 0.0188 3
Another study evaluated glass corrosion by control compositions #18-21 and
test compositions #24-26. These results are illustrated in Figure 5. Bottle
washing
with caustic and no additive caused by far the greatest loss of mass of glass.
Control
#18 caused the greatest reduction in glass corrosion. Controls #19, #20, and
#21
caused intermediate reductions in glass corrosion. Surprisingly, adding an
agent
known to cause corrosion of glass, phosphoric acid, to the additive resulted a
greater
reduction in glass corrosion; compare controls #19-21 to tests #24-26 (Figure
5).
Conclusions
The phosphate-containing compositions according to the present invention
reduce glass corrosion. Surprisingly, control compositions lacking phosphate
exhibited greater cleaning and also reduced glass corrosion.
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Example 4 - Phosphate-Free Formulas of Liquid Additive Compositions
Reduce Glass Corrosion
Table 7 - Control phosphate-free additive formulas that reduce glass corrosion
but
clean only poorly, and test formulas that reduce glass corrosion and clean.
Ingredient Control #27 Control #28 Test #29 Test #30
Water 67 54 53 35
Potassium Iodide 0.25 0.25 0.3 0.3
HEDP (60%) 6.5 6.5 10 10
PBTC (50%) 1 1 1.5 1.5
ATMP (50%) 0 0 20 20
Gluconic Acid (50%) 15 10 15 15
Citric Acid Monohydrate 5.5 5.5 0 0
Lactic Acid 5 5 0 0
Polyoxyethylene coco amine 0 3 0 3
Alcohol ethoxylate 0 15 0 15
Glass Corroded? No No No No
Bottle Cleaned No No Yes Yes
Quantities are in wt-%.
Table 8 - Additional phosphate containing compositions that mitigate glass
corrosion.
Ingredient Control #31 Test #32 Test #33 Test #34 Test #35
Water 67 22 39 32 29
Potassium Iodide 0.25 0.25 0.25 0.25 0.25
HEDP (60%) 6.5 0 6.5 9.9 9.9
PBTC (50%) 1 0 1 1.5 1.5
ATMP (50%) 0 26 26 26 13
Phosphoric Acid 0 17 12 5.5 12
Gluconic Acid (50%) 48 15 15 15 15
Citric Acid Monohydrate 5.5 10 0 5 10
Lactic Acid 4.6 9.2 0 4.6 9.2
Phosphate:Phosphonate 0 - 2:1 1:1 1.3:1
Ratio
Glass Corroded? No Yes No No No
Bottle Cleaned No Yes Yes Yes Yes
Quantities are in wt-%.
Methods
Glass corrosion and cleaning efficacy were tested by the methods described
in Example 3.
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Results
The phosphate-free compositions according to the present invention cleaned
the bottles with high scores on the visual rating test and reduced corrosion
of the
glass. In contrast, control compositions with lower levels of phosphonate
neither
cleaned nor corroded the glass. These results are shown in Table 9.
Surprisingly,
the control compositions did not clean the bottles even at the levels of
phosphonate
they employ.
Table 9 - Amino phosphonate containing compositions according to the present
invention clean without unacceptably corroding glass.
Composition Average Percent Average Cleaning Grade
Weight Loss (maximum is 10)
Control #27 0.0056 1
Control #28 0.0048 0.5
Test #29 0.0384 6
Test #30 0.0396 7
Table 10 - Compositions containing phosphate and amino phosphonate mitigate
glass corrosion.
Composition Average Percent
Weight Loss
Control #31 0.0021
Test #32 0.23
Test #33 0.12
Test #34 0.12
Test #35 0.023
Conclusions
The amino phosphonate containing compositions according to the present
invention mitigate glass corrosion and clean.
It should be noted that, as used in this specification and the appended
claims,
the singular forms "a," "an," and "the" include plural referents unless the
content
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clearly dictates otherwise. Thus, for example, reference to a composition
containing
"a compound" includes a mixture of two or more compounds. It should also be
noted that the term "or" is generally employed in its sense including "and/or"
unless
the content clearly dictates otherwise.
It should also be noted that, as used in this specification and the appended
claims, the phrase "adapted and configured" describes a system, apparatus, or
other
structure that is constructed or configured to perform a particular task or
adopt a
particular configuration to. The phrase "adapted and configured" can be used
interchangeably with other similar phrases such as arranged and configured,
constructed and arranged, adapted, constructed, manufactured and arranged, and
the
like.
All publications and patent applications in this specification are indicative
of
the level of ordinary skill in the art to which this invention pertains.
The invention has been described with reference to various specific and
preferred embodiments and techniques. However, it sliould be understood that
many
variations and modifications may be made while remaining within the spirit and
scope of the invention.
