Note: Descriptions are shown in the official language in which they were submitted.
CA 02808962 2013-02-20
WO 2012/062372 PCT/EP2010/067312
PROCESS FOR CLEANING AND LABEL REMOVAL FOR BOTTLES
Field of the Invention
The present invention relates to a process for cleaning bottles. In more
detail, the present
invention is directed to an improved method for cleaning bottles comprising
the removal of bottle
labels in a bottle cleaning plant.
Back2round 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.
In known processes, returnable bottles for beverage are cleaned in bottle
cleaning machines
using additive containing sodium hydroxide, which has been heated to at least
85 C. Hot caustic
bottle cleaning of reusable glass, ceramic and plastic bottles at temperature
of at least 85 C is
involved with increased energy consumption.
Many of these reusable glass bottles are label that is adhered by an adhesive.
These labels need
to be removed at the cleaning process in a bottle cleaning plant. Further,
residues such as soil, mold,
dead yeast cells and there like needs to be removed during the cleaning
process of a bottle cleaning
plant.
Reuse of a glass bottle requires that the bottle remain aesthetically
appealing for the duration
of their life cycle. When the bottle 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. This
lack of durability is quite understandable in light of the effect on the hot
alkaline bottle washing
processes. The cleaners used in hot bottle washing processes at temperatures
of at least 85 C are
designed to be aggressive on soils, but can also attack the bottle causing
deterioration and shortening
the useful life of the bottle. Bottle deterioration is undesirable because of
the negative impact it has on
brand image, consumer appeal and quality of the beverage package.
_therefore, there remains a need for a bottle washing process that minimizes
energy
consumption, attack on glass bottle appearance, while still providing adequate
soil removal.
Summary of the Invention
The object addressed by the present invention is to provide a cleaning process
that minimizes
energy consumption for cleaning glass, ceramic, metal and/or plastic ware,
such as bottles, preferably
in a bottle cleaning plant, while still providing adequate soil removal and
excellent label removal
properties.
CA 02808962 2013-02-20
WO 2012/062372 2 PCT/EP2010/067312
According to the present invention, a process for washing and/or label removal
of glass,
ceramic or plastic ware with a liquid cleaning composition at a temperature
below 80 C, wherein the
liquid cleaning composition comprises active components in an amount of about
> 0.001 wt.-% to
about < 10 wt.-% and an alkaline source in an amount of about > 0.5 wt.-% to
about < 3.5 wt.-%,
wherein the active components comprising:
a) at least one sequestering agent selected from the group of a phosphonic
acid, phosphonate based
sequestering agent, and/or a polymer of monomers of monoethylenically
unsaturated C3-C8-
carboxylic acids or salts thereof;
b) at least one C4 to C18 hydroxymonocarboxylic acid or salt thereof;
wherein
the weight-% of the active components are based on the total weight of the
liquid cleaning
composition.
A solvent, preferably water, can be added add. 100 wt.-% to the cleaning
composition of the
invention. The solvent content, preferably water, of the cleaning composition
according to the
invention is simply determined by subtracting the amounts of all the usual
components from 100 wt.
%.
The weight amount (wt.-%) is calculated on the total weight amount of the
liquid cleaning
composition, if not otherwise stated. The total weight amount of all
components of the liquid cleaning
composition does not exceed 100 wt.-%.
The liquid cleaning composition may comprise the active components in an
amount of about >
0.003wt.-%, preferably of about > 0.006wt.-%, further preferred of about >
0.01wt.-%, in addition
preferred of about > 0.05 wt.-%, also preferred of about > 0. Iwt.-% or
further more preferred of about
> 0.5 wt.-%.
It has surprisingly found, that the process of the present invention can be
used for cleaning and
removal of labels of glass, ceramic, metal and/or plastic ware, such as
bottles, preferably in a bottle
cleaning plant, while still providing adequate soil removal and excellent
label removal properties, and
minimizes energy consumption. For example, bottle labels can be removed at
lower temperatures
compared to prior art in a soaking bath, preferably in a soaking bath of a
bottle cleaning plant that
containing the cleaning composition used in the process of the invention.
The active components can be added to the cleaning composition in the form of
an acid and/or
as a salt thereof.
The cleaning composition can be obtained by adding a liquid cleaning additive
that comprises
the active components.
The liquid cleaning additive that comprises the active components can be an
acid or alkaline
solution. The liquid cleaning additive can be a concentrated solution. The
concentrated liquid cleaning
additive can be further diluted by admixing a solvent, preferably water.
It should be understood that the active components, the liquid cleaning
additive and/or liquid
cleaning composition of the invention can be free of at least one additive,
preferably all additives,
3
selected from the group of dye, color transfer inhibitor, anti-redeposition
agents, optical brighteners, builder,
oil and water repellant agents, color fastness agents, starch/sizing agents,
fabric softening agents, anti-
microbials, fungicides, UV absorbers, thickeners, oxidizers, fragrances and/or
mixtures thereof.
It has been surprisingly found that a defined weight ratio of the active
components a) of at least one
sequestering agent to b) of at least one C4 to C18 hydroxymonocarboxylic acid
or salts thereof, used according
to the method of the invention provides an adequate soil removal and excellent
label removal properties at a
lower process temperature.
According to an embodiment of the present invention the weight ratio of the
active components a) of
at least one sequestering agent to b) of at least one C4 to C18
hydroxymonocarboxylic acid or salts thereof can
be in the range of about 6: 1 to about 1 : 6, preferably 5 : 1 to 1 : 5,
further preferred 4 : 1 to 1 : 4 and more
preferred 3 : 1 to 1 : 3.
The ratio of components as mentioned is the weight ratio, if not otherwise
indicated in the
specification.
The active components as used according to the method of the invention may
comprise in addition an
active component c) of at least one phosphoric acid based or phosphate-based
component. Exemplary, the
active component c) includes preferably phosphoric acid, sodium phosphate,
potassium phosphate,
pyrophosphoric acid, sodium pyrophosphate, potassium pyrophosphate, and
mixtures thereof.
The solvent, including water, is not considered as an active component.
The active components as used according to the method of the invention may
comprise in addition an
active component d) of at least one amphoteric alkoxylated C6 to C24 alcohol
amine surfactant containing 4 to
18 alkylene oxide units of ethylene oxide and/or propylene oxide or a salt
thereof.
The process of soil removal and excellent label removal properties at a lower
process temperature can
be improved by adding to the liquid cleaning composition an active component
of at least one non-endcapped
nonionic alkoxylated C6 to C14 alcohol surfactant containing about 1 to about
30 alkylene oxide units.
The addition of an active component of at least one alkyl endcapped nonionic
alkoxylated C8 to C18
alcohol surfactant containing 4 to 16 alkylene oxide units of ethylene oxide
and/or propylene oxide can further
improve soil removal and excellent label removal properties at a lower process
temperature of the process of
the invention.
According to an embodiment of the process of the invention, active components
can be used that
comprises in addition d) of at least one amphoteric alkoxylated C6 to C24
alcohol amine surfactant containing 4
to 18 alkylene oxide units of ethylene oxide and/or propylene oxide or a salt
thereof; and of at least one anti-
foaming agent, preferably select from the group of silicone based defoamer,
and/or of at least one alkyl
endcapped nonionic alkoxylated Cs to C18 alcohol surfactant containing 4 to 16
alkylene oxide units of
ethylene oxide and/or propylene oxide.
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The process according to the invention can be further optimized with respect
to the label removal
properties if active components are used, wherein the weight ratio of a) the
sequestering agent to b) the C4 to
C18 hydroxymonocarboxylic acid or salts thereof is in the range of about 5: 1
to about 1 : 5, preferably about 4
: 1 to 1 : 4, further preferred about 3 : 1 to about 1 : 3, and more preferred
about 2: 1 to about 1 : 2.
Improved soil removal and excellent label removal properties at a lower
process temperature can be
achieved according to the process of the invention, if the weight ratio of the
active components of c) the
phosphoric acid based or phosphate -based component to a) the sequestering
agent is about 10: 1 to about 1 :
10, preferably about 5 : Ito 1 : 5, further preferred about 3 : 1 to about 1 :
3, also preferred about 2 : Ito about
I : 2, and more preferred about 1.5 : Ito about 1.2 : 1.
According to an embodiment of the process of the invention it can be preferred
that the weight ratio of
the active components of d) the amphoteric surfactant to b) the C4 to C18
hydroxymonocarboxylic acid, or a
salt thereof is about 10: Ito about 1 : 10, preferably about 5 : 1 to 1: 5,
further preferred about 3 : 1 to about 1
: 3, also preferred about 2 : 1 to about 1 : 2, and more preferred about 1.7 :
1 to about 1.5 : I.
It can be further preferred for the process of the invention that the weight
ratio of the active
components off) the alkyl endcapped nonionic surfactant to e) the non-
endcapped nonionic surfactant is about
: Ito about I : 10, preferably about 5 : Ito 1 : 5, further preferred about 4
: Ito about 1 : 4, also preferred
about 3 : 1 to about 1 : 3, and more preferred about 2.6 : 1 to about 2.3 : 1.
It should be understood that the active components, the liquid cleaning
additive and/or liquid cleaning
composition of the invention can be free of the component c) of at least one
phosphoric acid based or
phosphate -based component.
It should be understood that the active components, the liquid cleaning
additive and/or liquid cleaning
composition of the invention can be free of the component d) of at least at
least one amphoteric alkoxylated (,
to C24 alcohol amine surfactant containing 4 to 18 alkylene oxide units of
ethylene oxide and/or propylene
oxide or a salt thereof.
It should be understood that the active components, the liquid cleaning
additive and/or liquid cleaning
composition of the invention can be free of at least one non-endcapped
nonionic alkoxylated C6 to C24 alcohol
surfactant containing about 1 to about 30 alkylene oxide units.
It should be understood that the active components, the liquid cleaning
additive and/or liquid cleaning
composition of the invention can be free of at least one alkyl endcapped
nonionic alkoxylated C8 to Ci8 alcohol
surfactant containing 4 to 16 alkylene oxide units of ethylene oxide and/or
propylene oxide.
It should be understood that the active components, the liquid cleaning
additive and/or liquid cleaning
composition of the invention can be free of the component c) of at least one
phosphoric acid based or
phosphate-based component and d) of at least at least one amphoteric
alkoxylated C6 to C24
CA 2808962 2017-08-24
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alcohol amine surfactant containing 4 to 18 alkylene oxide units of ethylene
oxide and/or propylene oxide or a
salt thereof.
It should be understood that the active components, the liquid cleaning
additive and/or liquid cleaning
composition of the invention can be free of the component c) of at least one
phosphoric acid based or
phosphate-based component and d) of at least at least one amphoteric
alkoxylated C6 to C24 alcohol amine
surfactant containing 4 to 18 alkylene oxide units of ethylene oxide and/or
propylene oxide or a salt thereof
and c) of at least one non-endcapped nonionic alkoxylated C6 to C24 alcohol
surfactant containing about 1 to
about 30 alkylene oxide units and/or of at least one alkyl endcapped nonionic
alkoxylated Cg to C18 alcohol
surfactant containing 4 to 16 alkylene oxide units of ethylene oxide and/or
propylene oxide.
It should be understood that the active components, the liquid cleaning
additive and/or liquid cleaning
composition of the invention can be free of the component d) of at least at
least one amphoteric alkoxylated Co
to C/4 alcohol amine surfactant containing 4 to 18 alkylene oxide units of
ethylene oxide and/or propylene
oxide or a salt thereof and e) of at least one non-endcapped nonionic
alkoxylated C6 to C24 alcohol surfactant
containing about 1 to about 30 alkylene oxide units and/or of at least one
alkyl endcapped nonionic
alkoxylated C8 to C18 alcohol surfactant containing 4 to 16 alkylene oxide
units of ethylene oxide and/or
propylene oxide.
It should be understood that the active components, the liquid cleaning
additive and/or liquid cleaning
composition of the invention can be free of the component c) of at least one
phosphoric acid based or
phosphate-based component and d) of at least at least one amphoteric
alkoxylated C6 to C/4 alcohol amine
surfactant containing 4 to 18 alkylene oxide units of ethylene oxide and/or
propylene oxide or a salt thereof, d)
of at least at least one amphoteric alkoxylated C6 to C24 alcohol amine
surfactant containing 4 to 18 alkylene
oxide units of ethylene oxide and/or propylene oxide or a salt thereof and e)
of at least one non-endcapped
nonionic alkoxylated Co to C24 alcohol surfactant containing about I to about
30 alkylene oxide units and/or of
at least one alkyl endcapped nonionic alkoxylated C8 to C18 alcohol surfactant
containing 4 to 16 alkylene
oxide units of ethylene oxide and/or propylene oxide.
The active components used in the process of the invention may be added in
form of a concentrate or
in a diluted form to an alkaline solution to provide the liquid cleaning
composition. A concentrated liquid
cleaning additive can be diluted with a solvent, preferably water, to its
diluted form. The diluted liquid
cleaning additive can be added to an alkaline solution to obtain the liquid
cleaning composition.
It can be preferred to preprocess glass, ceramic or plastic bottle, preferably
glass and/or
ceramic bottles, with an alkaline solution for cleaning residues such as soil,
mold, dead yeast cells and
the like, and thereafter with the liquid cleaning composition for cleaning
and/or label removal at a temperature
below 80 C. As an alternative, right from the start a liquid cleaning
composition can be used in the process of
CA 2808962 2017-08-24
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the invention for cleaning residues such as soil, mold, dead yeast cells and
there like of glass, ceramic or
plastic ware and label removal at a process temperature below 80 C.
Suitable bottle cleaning plants that can be used in the process of the
invention are for example a
single-end-bottle washer Or a double-end-bottle washer.
According to an embodiment of the invention a concentrated liquid cleaning
additive may comprises
a) about? l wt.-% to about <30 wt.-%, preferably about > 2 wt.-% to about
<20 wt.-%, more
preferred about? 5 wt.-% to about < 15 wt.-% of a gluconic acid or a salt
thereof,
b) about > 1 wt.-% to about < 10 wt.-%, preferably about? 3 wt.-% to about
<8 wt.-%, more
preferred about? 4 wt.-% to about < 6 wt.-% of a phosphonic acid or a salt
thereof, or a
polymer of monomers of monoethylenically unsaturated Cs-Cs-carboxylic acids or
salts
thereof,
c) about > 0 wt.-% to about <20 wt.-%, preferably about? 5 wt.-% to about <
15 wt.-%, more
preferred about? 6 wt.-% to about < 10 wt.-% of a phosphoric acid or a salt
thereof,
d) about? 0 wt.-% to about <20 wt.-%, preferably about? 3 wt.-% to about <
15 wt.-%, more
preferred about? 5 wt.-% to about < 10 wt.-% of at least one amphoteric
alkoxylated C6 to C24
alcohol amine surfactant containing 4 to 18 alkylene oxide units of ethylene
oxide and/or
propylene oxide, preferably an amphoteric alkoxylated C12 to C14 alcohol amine
surfactant
containing 10 to 14 alkylene oxide units, or a salt thereof;
e) about? 0 wt.-% to about <40 wt.-%, preferably about? 1 wt.-% to about <
35 wt.-%, further
preferred about? 10 wt.-% to about < 30 wt.-%, more preferred about? 15 wt.-%
to about <
25 wt.-% of at least one alkyl endcapped nonionic alkoxylated Cs to C18
alcohol surfactant
containing 4 to 16 alkylene oxide units of ethylene oxide and/or propylene
oxide, preferably
an butyl endcapped nonionic alkoxylated C12 to C18 alcohol surfactant
containing 8 to 10
alkylene oxide units of ethylene oxide; and/or at least one non-endcapped
nonionic
alkoxylated Cs to C18 alcohol surfactant containing 4 to 16 alkylene oxide
units of ethylene
oxide and/or propylene oxide, preferably at least one non-endcapped nonionic
alkoxylated C12
to C14 alcohol surfactant containing 2 to 4 units of ethylene oxide and 3 to 5
units propylene
oxide; and
a solvent, preferably water, is added add. 100 wt.-%; wherein the weight-% of
the components
of the concentrated liquid cleaning additive are based on the total weight of
the concentrated
liquid cleaning additive and does not exceed 100 wt.-%.
Alternatively, the liquid cleaning additive can be presented in a diluted
form. A diluted liquid cleaning
additive that can be used in the process of the invention comprises about?
0.01wt.-% to about < 10 wt.-%,
preferably about? 0.05 wt.-% to about < 5 wt.-%, further preferred about?
0.1wt-% to about <2 wt.-%, also
CA 2808962 2017-08-24
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preferred about > 0.15 wt.-% to about < 1 wt.-%, in addition preferred about >
0.2 wt.-% to about < 0.5 wt.-%,
furthermore preferred about > 0.25wt.-% to about <0.5 wt.-%, and more
preferred about? 0.3wt.-% to about <
0.4 wt.-% of the concentrated additive and at least one solvent, preferably
water, is added add. 100 wt.-%.
Alkaline Solution
According to the process of the present invention a liquid cleaning
composition comprising an alkaline
source can be used having a pH in the range of about? 10 pH, preferably? 12 pH
and more preferred? 13 pH
to < 14 pH.
The cleaning composition can be obtained by adding the active components to an
alkaline solution.
The alkaline solution or liquid cleaning composition that can be used in the
process of the invention
comprises about > 0.5wt.-% to about <3.5 wt.-%, preferably about? lwt.-% to
about < 3 wt.-%, further
preferred about > 1.25 wt.-% to about < 2.75 wt.-%, also preferred about > 1.3
wt.- to about <2.5 wt.-%, in
addition preferred about? 1.5 wt.-% to about < 2.3 wt.-%, furthermore
preferred about? 1.7 wt.-% to about <
2.25 wt.-%, and more preferred about? 1.5 wt.-% to about <2.0 wt.-%, of an
alkaline source, preferably
sodium hydroxide, and at least one solvent, preferably water, is added add.
100 wt.-%; wherein the weight-%
of the alkaline source are based on the total weight of the alkaline solution
or liquid cleaning composition.
Liquid Cleaning Composition
The liquid cleaning composition can be obtained by adding the active
components or a liquid cleaning
additive, preferably a concentrated and more preferred a diluted liquid
cleaning additive, to an alkaline
solution. Thus, the liquid cleaning composition can be an alkaline solution
containing the active components.
According to the process of the present invention the pH of the liquid
cleaning composition used in the
process of the invention is in the range of about? 10 pH, preferably? 12 pH
and more preferred? 13 pH to <
14 pH. The use of an alkaline liquid cleaning composition ensures an excellent
soil removable as necessary in
a bottle cleaning process.
In a common bottle cleaning plant for washing of and label removal from glass,
ceramic or plastic
ware the process temperature of the cleaning solution of the soaking bath is
of about 85 C. According to the
present invention the process temperature of the cleaning solution of a
soaking bath of about 85 C can be
lowered to temperatures of below 80 C, that saves energy.
Further, the use of the liquid cleaning composition allows running the bottle
cleaning and labeling
removal process at lower temperatures. The process of the invention saves
energy compared to standard
cleaning conditions as used in a bottle cleaning plant for bottle cleaning and
label removal at? 85 C.
The process of the invention allows washing, such as cleaning and label
removal, of glass, ceramic or
plastic ware, preferably bottle cleaning and label removal in a bottle
cleaning plant, at
CA 2808962 2017-08-24
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process temperatures, preferably of the liquid cleaning solution, in the range
of about > 30 C to <780 C,
further preferred in the range of about > 40 C to < 77 C, also preferred in
the range of about > 50 C to <750
C, furthermore preferred in the range of about? 550 C to < 70 C and more
preferred in the range of about?
60 C to < 65 C.
As already mentioned before, the label removal may take place preferably in a
soaking bath
comprising the liquid cleaning composition at temperatures in the range of
about? 30 C to < 78 C, further
preferred in the range of about? 40 C to < 77 C, also preferred in the range
of about? 50 C to < 75 C,
furthermore preferred in the range of about? 55 C to < 70 C and more
preferred in the range of about? 60
C to < 65 C.
The label removal time obtained using the liquid cleaning composition in the
process of the invention
can be in the range of? 60 seconds to <480 seconds, preferably of? 120 seconds
to < 420 seconds, further
preferred of? 150 seconds to < 390 seconds and furthermore preferred of? 180
seconds to < 360 seconds.
The label removal time obtained using the process of the invention fulfils the
demand for label
removal time required in an automated cleaning and label removal process for
bottles.
The liquid cleaning composition can comprises about > 0.003 wt.- to about <
0.035 wt.-%, preferably
about? 0.01 wt.-% to about < 0.03 wt.-%, more preferred about? 0.014 wt.-% to
about < 0.022 wt.-% of a
phosphonic acid or a salt thereof, or a polymer of monomers of
monoethylenically unsaturated C3-C8-
carboxylic acids or salts thereof, preferably polyacrylic acid or a salt
thereof.
Further, the cleaning composition can comprises about? 0.003 wt.-% to about <
0.105 wt.-%,
preferably about? 0.007 wt.-% to about < 0.070 wt.-%. more preferred about?
0.01 wt.-% to about < 0.053
wt.-% of a gluconic acid or a salt thereof.
It can be preferred that the cleaning composition may comprises about? 0 wt.-%
to about < 0.07 wt.-
%, preferably about? 0.01 wt.-% to about <0.053 wt.-%, more preferred about?
0.021 wt-% to about < 0.035
wt.-% of a phosphoric acid or a salt thereof.
The liquid cleaning composition can comprises about > 0 wt.-% to about <0.07
wt.-%, preferably
about? 0.01 wt.-% to about < 0.053 wt.-%, more preferred about? 0.017 wt.-% to
about < 0.035 wt.-% of at
least one amphoteric alkoxylated Coto C24 alcohol amine surfactant containing
4 to 18 alkylene oxide units of
ethylene oxide and/or propylene oxide, preferably an amphoteric alkoxylated
C12 to C14 alcohol amine
surfactant containing 10 to 14 alkylene oxide units, or a salt thereof.
According to an preferred embodiment, the liquid cleaning composition
comprises about? 0 wt.-% to
about < 0.14 wt.-%, preferably about? 0.003 wt.-% to about < 0.123 wt.-%,
further preferred about?
0.035wt.-% to about < 0.0105 wt.-%, more preferred about? 0.052 wt.-% to about
< 0.088 wt.-% of at least
one alkyl endcapped nonionic alkoxylated C8 to C18 alcohol surfactant
containing 4 to 16 alkylene oxide units
of ethylene oxide and/or propylene oxide, preferably an butyl endcapped
nonionic alkoxylated C12 to
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C18 alcohol surfactant containing 8 to 10 alkylene oxide units of ethylene
oxide; and/or at least one non-
endcapped nonionic alkoxylated C8 to C18 alcohol surfactant containing 4 to 16
alkylene oxide units of
ethylene oxide and/or propylene oxide, preferably at least one non-endcapped
nonionic alkoxylated C12 to
C14 alcohol surfactant containing 2 to 4 units of ethylene oxide and 3 to 5
units propylene oxide.
The liquid cleaning composition may comprises about > 0.5 wt.-% to about < 3.5
wt.-%, preferably
about > lwt.-% to about <3 wt.-%, further preferred about? 1.25 wt.-% to
about? 2.75 wt.-%, also preferred
about? 1.3 wt.-% to about < 2.5 wt.-%, in addition preferred about > 1.5 wt.-%
to about < 2.3 wt.-%,
furthermore preferred about > 1.7 wt.-% to about < 2.25 wt.-%, and more
preferred about > 1.5 wt.-% to about
<2.0 wt.-%, of an alkaline source, preferably sodium hydroxide.
To the liquid composition a solvent, preferably water, can be added add. 100
wt.-%. The weight-% of
the components of the liquid composition are based on the total weight of the
liquid cleaning composition and
does not exceed 100 wt.-%.
More preferred, the liquid cleaning composition that can be used in the
process of the invention may
comprise:
a) about? 0.003 wt.-% to about <0.035 wt.-%, preferably about? 0.01 wt.-% to
about < 0.03 wt.-%,
more preferred about? 0.014 wt.-% to about? 0.022 wt.-% of a phosphonic acid
or a salt thereof, or a
polymer of monomers of monoethylenically unsaturated C3-C8- carboxylic acids
or salts thereof, preferably
polyaerylie acid or a salt thereof,
b) about? 0.003 wt.-% to about < 0.105 wt.-%, preferably about? 0.007 wt.-% to
about < 0.070 wt.-
%, more preferred about 20.01 wt.-% to about < 0.053 wt.- of a gluconic acid
or a salt thereof,
c) about? 0 wt.-% to about <0.07 wt.-%, preferably about > 0.01 wt.-% to about
< 0.053 wt.-%, more
preferred about? 0.021 wt.- to about < 0.035 wt.-% of a phosphoric acid or a
salt thereof,
d) about? 0 wt.-% to about <0.07 wt.-%, preferably about? 0.01 wt.-% to about?
0.053 wt.-%, more
preferred about? 0.017 wt.-% to about? 0.035 wt.-% of at least one amphoteric
alkoxylated C to C24 alcohol
amine surfactant containing 4 to 18 alkylene oxide units of ethylene oxide
and/or propylene oxide, preferably
an amphoteric alkoxylated C12 to C14 alcohol amine surfactant containing 10 to
14 alkylene oxide units, or a
salt thereof;
e) about? 0 wt.-% to about <0.14 wt.-%, preferably about > 0.003 wt.-% to
about < 0.123 wt.-%,
further preferred about? 0.035wt.- to about <0.0105 wt.-%, more preferred
about 20.052 wt.-% to about?
0.088 wt.-% of at least one alkyl endcapped nonionic alkoxylated C8 to C18
alcohol surfactant containing 4 to
16 alkylene oxide units of ethylene oxide and/or propylene oxide, preferably
an butyl endcapped nonionic
alkoxylated Cp to C18 alcohol surfactant containing 8 to 10 alkylene oxide
units of ethylene oxide; and/or at
least one non-endcapped nonionic alkoxylated C8 to C18 alcohol surfactant
containing 4 to 16 alkylene oxide
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units of ethylene oxide and/or propylene oxide, preferably at least one non-
endcapped nonionic alkoxylated
Cl2 to C14 alcohol surfactant containing 2 to 4 units of ethylene oxide and 3
to 5 units propylene oxide;
f) about > 0.5 wt.-% to about <3.5 wt.-%, preferably about > lwt.-% to about
<3 wt.-%, further
preferred about > 1.25 wt.-% to about < 2.75 wt.-%, also preferred about? 1.3
wt- % to about < 2.5 wt.-%, in
addition preferred about? 1.5 wt.-% to about < 2.3 wt.-%, furthermore
preferred about? 1.7 wt.-% to about <
2.25 wt.-%, and more preferred about? 1.5 wt.-% to about <2.0 wt.-%, of an
alkaline source, preferably
sodium hydroxide; and
g) a solvent, preferably water, is added add. 100 wt.-%; wherein the weight-%
of the components are
based on the total weight of the liquid cleaning composition and does:not
exceed 100 wt.-%.
Subsequently components of the active components, the liquid cleaning
additive, the alkaline solution
as well as of the liquid cleaning composition that can be used in the process
of the invention are described in
more detail.
Sequestrants
The active components, the liquid cleaning additive and/or liquid cleaning
composition used in the
process of the invention includes a) at least one sequestering agent selected
from the group of a phosphonic
acid, phosphonate based sequestering agent, and/or a polymer of monomers of
monoethylenically unsaturated
C3-Cs-carboxylic acids or salts thereof. In general, a sequestrant is a
molecule capable of coordinating (i.e.,
binding) the metal ions commonly found in natural water to prevent the metal
ions from interfering with the
action of the other detersive ingredients of a cleaning composition. Some
sequestering agents can also function
as a threshold agent when included in an effective amount.
A variety of phosphonic acid or phosphonate based sequestering agents can be
used including, for
example, organic phosphonatc, condensed phosphonate, mixture thereof, or the
like. Such sequestrants arc
commercially available. Suitable condensed phosphonates include sodium and
potassium orthophosphonate,
sodium and potassium pyrophosphonate, sodium and potassium tripolyphosphonate,
sodium
hexametaphosphonate, preferably of tripolyphosphonate.
Sodium salts of condensed phosphonates are preferred to the corresponding
potassium salts. The
sequestrant includes an organic phosphonate, such as an organic -phosphonic
acid or alkali metal salts thereof.
Some examples of suitable organic phosphonic acids including their
corresponding phosphonates include:
-hydroxyethane- 1, 1 -diphosphonic acid:
CH3C(OH)[PO(OH)212;
aminotri(methylenephosphonic acid) :
N[CH2P0(OH)2]3;
aminotri(methylenephosphonate), sodium salt;
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2-hydroxyethyliminobis(methylenephosphonic acid):
HOCH2CH2N[CH2P0(OH)2]2;
diethylenetriaminepenta(methylenephosphonic acid):
(H0)2POCH2N[CH2CH2N[CH2P0(OH)2] 21 2;
diethylenetriaminepenta(methylene-phosphonate), sodium salt:
C9H(28.$)N3Nas015P5 (x=7);
hexamethylenediamine(tetramethylenephosphonate), potassium salt:
CioH(28.)N2K,012P4 (x=6);
bis(hexamethylene)triamine(pentamethylenephosphonic acid):
(1-102)POCH2N(CH2)6N[CH2P0(OH)212]2; and phosphorus acid H3P03; and other
similar organic phosphonates,
and mixtures thereof.
2-hydroxyethyliminobis(methylenephosphonic acid):
HOCH2CH2N[CH2PO(OH)2]2;
diethylenetriaminepenta(methylenephosphonic acid):
(H0)2POCH2NICH2CH2NICH2P0(OH)21 21 2;
diethylenetriaminepenta(methylenephosphonate), sodium salt:
4...1111 28-x)N Na(j x1
hexamethylenediamine(tetramethylenephosphonate), potassium salt:
C]oli(28.$)N2Ks012P4 (x=6);
bis(hexamethylene)triamine(pentamethylenephosphonic acid):
(H02)POCH2N[CH2)6N[CH2P0(OH)2]212; and phosphorus acid H3P03: and other
similar organic
phosphonates, and mixtures thereof.
Other sequestrant agents can be used selected from the group of salts of acid
substituted polymers of
monomers of monoethylenically unsaturated C3-Cs-carboxylic acid, preferably
from salts of C3-C4-
monocarboxylic acid, acrylate, methacrylate, salts of polyitaconate, salts of
polymaleate, and mixtures thereof
, most preferred is a polyacrylate; and/or the sequestrant can be selected
from the group of acid substituted
polymers of monomers of monoethylenically unsaturated C3-C8-carboxylic acid,
preferably from a C3-C4-
monocarboxylic acid, acrylic acid, methacrylic acid, polyitaconic acid,
polymaleic acid, and mixtures thereof,
most preferred is a polyactylic acid or a salt thereof. Suitable polyacrylic
acid polymers are SokalanTM. for
example Sokalan CP 5 and/or Sokalan CP 10, obtainable from BASF.
The polymers tend to be water-soluble or at least colloidally dispersible in
water. The molecular
weight of these polymers may vary over a broad range although it is preferred
to use polymers haying an
average molecular weights (Mw) ranging from > 1 ,000 up to < 1 ,000, 000,
preferably > 2.000 up to <
800,000, further preferred > 2.500 up to <500, 000, also preferred > 3,000 up
to <250, 000, more preferred >
3,500 up to 100, 000, especially preferred > 4,000 up to <50, 000 and in
particular preferred > 4,500 up to <
10, 000.
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The polymers or copolymers, either the acid-substituted polymers or other
added polymers may be
prepared by either addition or hydrolytic techniques. Thus, maleic anhydride
copolymers are prepared by the
addition polymerization of malcic anhydride and another comonomer such as
styrene. Preferably salts of acid
substituted polymers of monomers of acrylate, methacrylate, salts of
polyitaconic acid, salts of polymaleic
acid, and mixtures thereof. In particular preferred are salts of polyacrylic
acid.
The low molecular weight acrylic acid polymer may be prepared by addition
polymerization of acrylic
acid or its salts either with itself or other vinyl comonomers.
Alternatively, such polymers may be prepared by the alkaline hydrolysis of low
molecular weight
acrylonitrile homopolymers or copolymers.
More preferred can he the use of a sequestrant in the process of the invention
such as a homo
polyacrylic acid and/or a homo polyacrylate. Most preferred is the use of a
homo polyacrylic acid and/or a
homo polyacrylate having a Mw ranging from? 1,000 up to < 1,000, 000,
preferably > 2.000 up to <800,000,
further preferred > 2.500 up to < 500, 000, also preferred > 3,000 up to <
250, 000, more preferred? 3,500 up
to < 100, 000, especially preferred > 4,000 up to <50, 000 and in particular
preferred > 4,500 up to < 10, 000.
It should be understood that other sequestrants, with the exception of at
least one sequestering agent
selected from the group of a phosphonic acid, phosphonatc based sequestering
agent, and/or a polymer of
monomers of monoethylenically unsaturated C3-Cs-carboxylic acids or salts
thereof, are optional.
Phosphates
The active components, the liquid cleaning additive and/or liquid cleaning
composition used in the
process of the invention may comprise at least one phosphate or phosphoric
acid. Phosphates or phosphoric
acid 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 phosphoric acid, or a combination thereof; an ortho phosphate, a
meta phosphate, a tripolyphosphatc,
or a combination thereof; phosphoric acid; alkali metal, ammonium and
alkanolammonium salts of
polyphosphates, for example 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 thereof, and the like, or a combination thereof.
Chelant Component
The active components, the liquid cleaning additive and/or liquid cleaning
composition used in the
process of the invention includes a) at least one C4 to C18
hydroxymonocarboxylic acid or salts thereof. A
chelant component exhibits soil removal properties when used for example at
alkaline conditions. The chelant
component is provided for tying up metals in the soil to assist in cleaning
and detergency. The chelant
component can be provided as part of the composition. A concentrated liquid
cleaning additive can comprise
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the chelant component in an amount of > 1 wt.- to about < 30 wt.-%, preferably
about? 2 wt.-% to about <20
wt.-%, more preferred about? 5 wt.-% to about < 15 wt.-%. It should be
understood that the chelant
component can include mixturcs of different chelants.
Suitable C4 to C18 hydroxymonocarboxylic acid or corresponding salt compounds
include, but are not
limited to, citric acid; propionic acid; gluconic acid; glycolic acid;
glucoheptanoic acid; succinic acid; lactic
acid; methyllactic acid; 2- hydroxybutanoic acid; mandelic acid; atrolactic
acid; phenyllactic acid; glyeric acid;
2,3, 4-trihydroxybutanoic acid; alpha hydroxylauric acid; benzillic acid;
isocitric acid; citramalic acid; agaricic
acid; quinic acid; uronic acids, including glucuronic acid, glucuronolactonic
acid, galaturonic acid, and
galacturonolactonic acid; hydroxypyruvic acid; ascorbic acid; and tropic acid.
Preferred
hydroxymonocarboxylic acid compounds include citric acid; propionic acid;
gluconic acid; glycolic acid;
glucoheptanoic acid; and succinic acid. Suitable hydroxydicarboxylic acid
compounds include, but are not
limited to, tartronic acid ; malic acid; tartaric acid; arabiraric acid;
ribaric acid; xylaric acid; lyxaric acid;
glucaric acid; galactaric acid; mannaric acid; gularic acid; allaric acid;
altraric acid; idaric acid; and talaric
acid. Preferred hydroxydicarboxylic acid compounds include tartaric acid as
well as ethylene diamine
tetraacetic acid. However, most preferred is gluconic acid or a salt thereof,
such as sodium gluconate.
Additional chelants can be used in the process of the present invention.
Exemplary chelants that can be
used in addition according to the invention include pentasodium salt of
diethylenetriamine pentaacetic acid
(available under the name Versenex 80), sodium glucoheptonate, ethylene
diamine tetraacetic acid (EDTA),
salts of ethylene diamine tetraacetic acid, hydroxyethyl ethylene diamine
triacetic acid (HEDTA), salts of
hydroxyethyl ethylene diamine triacetic acid, nitrilotriacetic acid (NTA),
salts of nitrilotriacetic acid,
diethanolglycine sodium salt (DEG), ethanoldiglycine disodium salt (EDG),
tetrasodium N,N-
bis(carboxylatomethyl)-L-glutamate (GLDA), and mixtures thereof, Exemplary
salts of ethylene diamine
tetraacetic acid include disodium salts, tetrasodium salts, diammonium salts,
and tisodium salts. An
exemplary salt of hydroxyethyl ethylene diamine triacetic acid is the
trisodium salt.
Suitable chelant that can be used in addition in the process of the invention
are iminodisuccinatc,
preferably the sodium salt of iminoclisuccinate, hydroxyethylidene
diphosphonic acid and/or tetrasodium N,N-
bis(carboxylatomethyl)-L-glutamate (GLDA).
It should be understood that the chelant component can include mixtures of
different chelants.
However, other chelants, with the exception of C4 to Ci8hydroxymonocarboxylic
acid or salts thereof, are
optional.
Acids
The active components, the liquid cleaning additive and/or liquid cleaning
composition used
in the process of the invention may comprises an acid or a salt thereof.
Exemplary inorganic acids that
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can be used include mineral acids such as sulfuric acid, nitric acid,
hydrochloric acid, and phosphoric
acid.
Exemplary organic acids that can be used include carboxylic acids including
monocarboxylic acids
and polycarboxcylic acids such as dicarboxcylic acids. Exemplary carboxylic
acids include aliphatic and
aromatic carboxylic acids. Exemplary aliphatic carboxylic acids include acetic
acid, formic acid, halogen-
containing carboxylic acids such as chloroacetic carboxylic acid, and modified
carboxylic acids containing
side groups such - OH, - R, - OR, -(E0)x, - (P0)x, - NH2, and ¨ NO2 wherein R
is a CI to C10 alkyl group.
Exemplary aromatic carboxylic acids include benzoic carboxylic acid, salicylic
carboxylic acid, and aromatic
carboxylic acid modified to include as a side group at least one of halogen, -
OH, - R, - OR, -(E0)x, - (PM, -
NH2, and -NO2 wherein R is a Ci to CI() alkyl group. Additional exemplary
organic acids include oxalic acid,
phthlaic acid, sebacic acid, adipic acid, citric acid, maleic acid, and
modified forms thereof containing side
groups including halogen, -OH, - R, OR, -(E0),, - (PO), - NH2, and -NO2
wherein R is a CI to C10 alkyl
group. It should be understood that the subscript 'x refers to repeating
units.
The active components, the liquid cleaning additive and/or liquid cleaning
composition can comprise
at least one acid or a corresponding salt thereof. It should be understood
that the addition of acid or a
corresponding salt thereof to the active components, the liquid cleaning
additive and/or liquid cleaning
composition can be omitted.
Surfactant
The active components, the liquid cleaning additive and/or liquid cleaning
composition used in the
process of the invention may comprises at least one surfactant. The surfactant
can be selected from the group
of nonionic surfactant, cationic surfactant, anionic surfactant, amphoteric
surfactant and mixtures thereof.
More preferred are surfactant, which are biodegradable.
The additional surfactant component can be used for enhancing the cleaning
properties of the liquid
cleaning composition. The surfactant component can be used in the process of
the invention to reduce surface
tension and wet the soil particulate to allow penetration of the use solution
and separation of the soil as well as
removal of a bottle label.
It should be understood that the addition of a surfactant to the active
components, the liquid cleaning
additive and/or liquid cleaning composition is optional.
Nonionic Surfactants
Exemplary nonionic surfactants that can be used in the active components, the
liquid cleaning additive
and/or liquid cleaning composition for the process of the invention are
alkoxylated, preferably ethoxylated or
ethoxylated and propoxylated, fatty acid alkyl esters preferably containing 1
to 4 carbon atoms in the alkyl
chain, more particularly the fatty acid methyl esters.
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The nonionic low alkoxylated alcohol surfactants can be used to reduce surface
tension, wet the soil
particulate to allow penetration of the use solution, separation of the soil
and enhance the bottle label removal.
The alkoxylated alcohol surfactants mentioned above includes end caped
alkoxylated alcohol
surfactants.
Exemplary nonionic low alkoxylated alcohol surfactants that can be used are
alkoxylated alcohols
containing 1 to 4 ethylene oxide groups (1-4E0), I to 4 butylene oxide groups
(1-4B0), 1 to 4 propylene oxide
groups (1-4P0), end caped alkoxylated alcohol surfactants thereof or mixtures
thereof.
Most preferred are nonionic surfactants d) of at least one amphoteric
alkoxylated C6 to C24 alcohol
amine surfactant containing 4 to 18 alkylene oxide units of ethylene oxide
and/or propylene oxide or a salt
thereof.
Advantageously low alkoxylated alcohols that can be useful used in addition in
the process according
to the invention are particularly primary and/or branched alcohols, preferably
containing 8 to 18 carbon atoms,
and containing 1 to 4 ethylene oxide groups (1-4E0), 1 to 4 butylene oxide
groups (1-4B0), Ito 4 propylene
oxide groups (1-4P0), end caped alkoxylated alcohol surfactants thereof or may
contain a mixture. The
alcohol radical may be linear, branched, or may contain a mixture.
Exemplary nonionic higher alkoxylated alcohol surfactants that can be useful
in the active
components, the liquid cleaning additive and/or liquid cleaning composition
according to the invention are
alkoxylated alcohols containing 5 to 40 ethylene oxide groups (5-40E0),
butylene oxide groups (5-40B0),
propylene oxide groups (5-40P0), preferably 6 to 30 ethylene oxide groups (6-
30E0), butylene oxide groups
(6-30B0), propylene oxide groups (6-30P0), further preferred 7 to 20 ethylene
oxide groups (7-20E0),
butylene oxide groups (7-20B0), propylene oxide groups (7-20P0), more
preferred 8 to 10 ethylene oxide
groups (8-10E0), butylene oxide groups (8-10B0), propylene oxide groups (8-
10P0), and most preferred 8
ethylene oxide groups (8E0), butylene oxide groups (8B0), propylene oxide
groups (8P0) groups, end caped
alkoxylated alcohol surfactants thereof, or mixtures thereof.
Advantageously higher alkoxylated alcohols useful in the composition of the
invention are particularly
linear and/or branched alcohols, preferably containing 8 to 18 carbon atoms,
and 5 to 40 ethylene oxide groups
(5-40E0), butylene oxide groups (5-40B0), propylene oxide groups (5-40P0),
preferably 6 to 30 ethylene
oxide groups (6-30E0), butylene oxide groups (6-30B0), propylene oxide groups
(6-30P0), further preferred
7 to 20 ethylene oxide groups (7-20E0), butylene oxide groups (7-20B0),
propylene oxide groups (7-20P0),
more preferred 8 to 10 ethylene oxide groups (8-10E0), butylene oxide groups
(8-10B0), propylene oxide
groups (8-10P0), and most preferred 8 ethylene oxide groups (8E0), butylene
oxide groups (8B0), propylene
oxide groups (8P0), end capped alkoxylated alcohol surfactants thereof, or may
contain a mixture. The alcohol
radical may be linear, branched, or may contain a mixture.
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Particularly preferred are higher alkoxylated alcohols, preferably alcohol
ethoxylates with linear or branched
radicals of alcohols with 12 to 18 carbon atoms, e.g. from coco-, palm-,
tallow- or oleyl alcohol, containing 8
to 18 carbon atoms, and 5 to 40 ethylene oxide groups (5-40E0), butylene oxide
groups (5-40B0), propylene
oxide groups (5-40P0), preferably 6 to 30 ethylene oxide groups (6-30E0),
butylene oxide groups (6-30B0),
propylene oxide groups (6-30P0), further preferred 7 to 20 ethylene oxide
groups (7-20E0), butylene oxide
groups (7-20B0), propylene oxide groups (7-20P0), more preferred 8 to 10
ethylene oxide groups (8-10E0),
butylene oxide groups (8-10B0), propylene oxide groups (8-10P0), and most
preferred 8 ethylene oxide
groups (8E0), butylene oxide groups (8B0), propylene oxide groups (8P0), end
capped alkoxylated alcohol
surfactants thereof, or may contain a mixture. However, most preferred is
isotridecyl alcohol in the
composition of the invention with 6E0 to 14E0, 6P0 to 14P0, 6B0 to 14B0,
preferably 7E0 to 10E0, 7P0
to 10P0, 7B0 to 10B0, and most preferred 8E0, 8P0, 8B0, or may contain a
mixture.
According to the present invention higher alkoxylated alcohols can be used
with 5E0, 6E0, 7E0,
8E0, 9E0, 10E0, 11E0, 12E0, 13E0, 14E0, 15E0, 16E0,17E0, 18E0, 19E0, 20E0,
21E0, 22E0, 23E0,
24E0 or 25E0, 5P0, 6P0, 7P0, 8P0, 9P0, 10P0, 11PO, 12P0, 13P0, 14P0, 15P0,
16P0.17P0, 18P0,
19P0, 20P0, 21P0, 22P0, 23P0, 24P0 or 25P0, 5B0, 6B0, 7B0, 8B0, 9B0, 10B0,
IIBO, 12B0, 13B0,
14B0, 15B0, 16B0,17B0, 18B0, 19B0, 20B0, 21B0, 22B0, 23B0, 24B0 or 25B0, end
capped
alkoxylated alcohol surfactants thereof, or may contain a mixture.
Exemplary higher alkoxylated alcohols with 5E0 to 40E0, preferably 6E0 or
30E0, further preferred
7E0 to 20E0, more preferred 8E0 to 10E0 and most preferred 8E0; 5P0 to 40P0,
preferably 6P0 or 30P0,
further preferred 7P0 to 20P0, more preferred 8P0 to 10P0 and most preferred
8P0; 5B0 to 40B0,
preferably 6B0 or 30B0, further preferred 7B0 to 20B0, more preferred 8B0 to
10B0 and most preferred
8B0 include C12-C14-alcohols; C9-Ci!-alcohols, C13-C15-alcohols, C12-Cis-
alcohols, end capped alkoxylated
alcohol surfactants thereof, and mixtures thereof, as well as mixtures of C12-
C14-alcohols and Co-Cis -alcohols,
end capped alkoxylated alcohol surfactants thereof, and most preferred is a
C13-alcohol.
In addition to these nonionic surfactants, fatty alcohols containing more than
12 EO, 12 PO, 12 BO
may also be used. Examples of such fatty alcohols are tallow fatty alcohol
containing 14 DO, 25 EO, 30 EO or
40 EO, 14 PO, 25 PO, 30 PO or 40 PO, 14 BO, 25 BO, 30 BO or 40 BO and end
capped alkoxylated alcohol
surfactants thereof.
The degrees of 5E0 to 40E0, 5P0 to 40P0, 5B0 to 40B0 preferably 6E0 or 30E0,
6P0 or 30P0,
6B0 or 30B0,further preferred 7E0 to 20E0, 7P0 to 20P0, 7B0 to 20B0.more
preferred 8E0 to 10 BO.
8P0 to 10 PO, 8B0 to 10 BO and most preferred 8E0, 8P0, 8B0 alkoxylation
mentioned are statistical mean
values, which for a special product, may be either a whole number or a
fractional number. However, more
preferred, the degrees of 5E0 to 40E0, 5P0 to 40P0, 5B0 to 40B0 preferably 6E0
or 30E0, 6P0 or 30P0,
6B0 or 30B0 further preferred 7E0 to 20E0, 7P0 to 20P0 , 7B0 to 20B0, more
preferred 8E0 to 10 EO,
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8P0 to 10 PO, 8B0 to 10 BO and most preferred 8E0, 8P0, 8B0 alkoxylation
mentioned may be either a
whole number or a fractional number. Most preferred, the degrees of 5E0 to
40E0, 5P0 to 40P0, 5B0 to
40B0, preferably 6E0 or 30E0, 6P0 or 30P0, 6B0 or 30B0, further preferred 7E0
to 20E0, 7P0 to 20P0,
7B0 to 20B0, more preferred 8E0 to 10 E0, 8P0 to 10P0, 8B0 to 10B0 and most
preferred 8E0, 8P0,
8B0. The alkoxylation grade mentioned may be a whole number.
Preferred higher alkoxylated alcohols have a narrow homolog distribution
(narrow range ethoxylates,
NRE).
Further surfactants include alkoxylated long chain fatty acid amides where the
fatty acid has 8-20
carbon atoms and the amide group is alkoxylated with 1-20 ethylene oxide,
propylene oxide and/or butylenes
oxide units.
A further class of nonionic surfactants, which can be used as ingredients in a
active components, the
liquid cleaning additive and/or liquid cleaning composition according to the
invention, is that of the alkyl
polyglycosides (APG). Suitable alkyl polyglycosides satisfy the general
Formula RO(G)z where R is a linear
or branched, particularly 2-methyl -branched, saturated or unsaturated
aliphatic radical containing 8 to 22 and
preferably 12 to 18 carbon atoms and G stands for a glyeose unit containing 5
or 6 carbon atoms, preferably
glucose. The degree of oligomerization z is a number between 1.0 and 4.0 and
preferably between 1.1 and 1.4.
Silicone containing nonionic surfactants, such as the ABIL B8852 or Silwet
7602, can also be used.
An exemplary silicone -containing surfactant is silicone polybutane.
Examples of amine oxide surfactants include: dimethylciodecylarnine oxide,
dimethyltetradecylamine
oxide; ethylmethyltetradecylamine oxide, cetyldimethylamine oxide,
dimethylstearylamine oxide,
cetylethylpropylamine oxide, diethyldodecylamine oxide, d iethyltetradecyl
amine oxide, dipropyldodecylamine
oxide, lauryl dimethyl amine oxide, bis- (2-hydroxyethyl) dodecylamine oxide,
bis- (2-hydroxyethyl)-3-
dodecoxy-1- hydroxypropyl amine oxide, (2-hydroxypropyl) methyltetradecylamine
oxide, dimethyloleyamine
oxide, dimethyl- (2-hydroxydodecyl) amine oxide, and the corresponding decyl,
hexadecyl and octadecyl
homologs of the above compounds.
Additional nitrogen-containing surfactants include ethoxylated primary alkyl
arnines where the alkyl
group has 10-20 carbon atoms and the amine is ethoxylated with 2-20 ethylene
oxide units.
Additionally, non-ionic surfactants derived from the condensation of ethylene
oxide with the product
resulting from the reaction of propylene oxide and ethylene diamine are also
useful. For example, there are
compounds containing from 40% to 80% of polyoxyethylenc by weight and having a
molecular weight from
5,000 to 11,000 resulting from the reaction of ethylene oxide groups with a
hydrophobic base constituted of
the reaction product from ethylene diamine and excess propylene oxide wherein
the base has a molecular
weight on order of 2,500-3,000.
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Suitable nonionic surfactants include the polyoxyethylene -polyoxypropylene
condensates, which are
sold by BASF under the trade name'Pluronic', polyoxyethylene condensates of
aliphatic alcohols/ethylene
oxide condensates having from 1 to 30 moles of ethylene oxide per mole of
coconut alcohol; ethoxylated long
chain alcohols sold by Shell Chemical Co. under the trade name 'Neodol',
polyoxyethylene condensates of
sorbitan fatty acids, alkanolamides, such as the monoalkoanolamides,
dialkanolamides and the ethoxylated
alkanolamides, for example coconut monoethanolamide, lauric isopropanolamide
and lauric diethanolamide;
and amine oxides for example dodecyldimethylamine oxide.
Further exemplary non-ionic surfactants include alkylphenol alkoxylates, and
amine oxides such as
alkyl dimethylamine oxide or bis (2- hydroxyethyl) alkylamine oxide.
The additional nonionic surfactants can be provided in the active components
and/or the liquid
cleaning additive as used in the process of the invention in an amount of? 0
wt.-% to about < 40 wt-%,
preferably about? 1 wt.-% to about < 35 wt.-%, further preferred about? 10 wt.-
q0 to about <30 wt.-%, more
preferred about? 15 wt.-% to about < 25 wt.-%, based on the total weight
amount of the liquid cleaning
additive or liquid cleaning composition.
Most preferred is the use of at least one alkyl endcapped nonionic alkoxylated
C8 to C18 alcohol
surfactant containing 4 to 16 alkylene oxide units of ethylene oxide and/or
propylene oxide, preferably an
butyl endcapped nonionic alkoxylated C12 to C18 alcohol surfactant containing
8 to 10 alkylene oxide units of
ethylene oxide; and/or at least one non-endcapped nonionic alkoxylated C8 to
C18 alcohol surfactant containing
4 to 16 alkylene oxide units of ethylene oxide and/or propylene oxide,
preferably at least one non-endcapped
nonionic alkoxylated C12to C14 alcohol surfactant containing 2 to 4 units of
ethylene oxide and 3 to 5 units
propylene oxide.
It should be understood that the addition of a nonionic surfactant to the
active components, the liquid
cleaning additive ancUor liquid cleaning composition of the invention is
optional.
Anionic Surfactants
The active components, the liquid cleaning additive and/or liquid cleaning
composition that can be
used in a process according to the invention is preferably free of an anionic
surfactant.
Exemplary anionic surfactants that can be used include organic carboxylates,
organic sulfonates,
organic sulfates, organic phosphates and the like, particularly linear
alkylaryl sulfonates, such as
alkylarylcarboxylates, alkylarylsulfonates, alkylarylphosphates, and the like.
These classes of anionic
surfactants are known within the surfactant art as linear alkyl benzyl
sulfonates (LABS), alpha olefin
sulfonates (AOS), alkyl sulfates, and secondary alkane sulfonates.
The anionic surfactants can be provided in the active components and/or the
liquid cleaning additive as
used in the process of the invention in an amount of? 0 wt.-% to <40 wt.-%,
preferably? 0.1 wt.-% to < 35
CA 2808962 2017-08-24
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wt.-%, further preferred > 0.5 wt.-% to < 32 wt.-%, and more preferred 1.0 wt.-
% to 30 wt.-%, based on the
weight of all components of the total composition.
It should be understood that the addition of an anionic surfactant to the
active components, the liquid
cleaning additive and/or liquid cleaning composition of the invention is
optional.
Cationic Surfactants
The presence of the nonionic surfactants enables the use of low levels of
higher foaming cationic
surfactants, while keeping the foaming at an acceptable level. In a preferred
embodiment of the invention, the
active components, the liquid cleaning additive and/or liquid cleaning
composition also comprises a cationic
surfactant.
Suitable cationic surfactants include quaternary ammonium compounds having the
formula of RR'R"
R"NX, where R, R', R" and R" are each a Ci-C24 alkyl, aryl or arylalkyl group
that can optionally contain
one or more P, 0, S or N heteroatoms, and X is F, CI, Br, I or an alkyl
sulfate. Additional preferred cationic
surfactants include ethoxylated and/or propoxylated alkyl amines, diamines, or
triamines.
Each of R, R', R" and R" can independently include, individually or in
combination, substituents
including 6 to 24 carbon atoms, preferably 14 to 24 carbon atoms, and more
preferably, 16 to 24 carbon atoms.
Each of R, R', R" and R" can independently be linear, cyclic, branched,
saturated, or unsaturated, arid
can include heteroatoms such as oxygen, phosphorous, sulfur, or nitrogen. Any
two of R, R', R" and R" can
form a cyclic group. Any one of three of R, R', R" and R" can independently
can be hydrogen. X is preferably
a counter ion and preferably a non-fluoride counter ion. Exemplary counter
ions include chloride, bromide,
methosulfate, ethosulfate, sulfate, and phosphate.
In an embodiment, the quaternary ammonium compound includes alkyl ethoxylated
and/or
propoxylatecl quaternary ammonium salts (or amines).
Preferably, the alkyl group contains between about 6 and about 22 carbon atoms
and can be saturated
and/or unsaturated. The degree of alkoxylation is preferably between about 2
and about 20, and/or the degree
of propoxylation is preferably between about 0 and about 30.
In an embodiment, the quaternary ammonium compound includes an alkyl group
with about 6 to about
22 carbon atoms and a degree of alkoxylation between about 2 and about 20.
The cationic surfactants can be provided in the active components and/or the
liquid cleaning additive
as used in the process of the invention in an amount of >0 wt.-% to < 40 wt.-
%, preferably >0.1 wt.-% to < 35
wt.-%, further preferred >0.5 wt.-% to < 32 wt.-%, and more preferred 1.0 wt.-
% to 30 wt.-%, based on the
weight of all components of the total composition.
It should be understood that the addition of a cationic surfactant to the
active components, the liquid
cleaning additive and/or liquid cleaning composition of the invention is
optional.
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Amphoteric Surfactants
The active components, the liquid cleaning additive and/or liquid cleaning
composition according to
the invention can be free of amphoteric surfactants. Examples of suitable
amphoteric surfactants include
capryloamphopropionate, disodium lauryl B-iminodipropionate, and
cocoamphocarboxypropionate, and
disodium octylimino dipropionate.
Most preferred is the use of an amphoteric surfactant d) of at least one
amphoteric alkoxylated C6 to
C24 alcohol amine surfactant containing 4 to 18 alkylene oxide units of
ethylene oxide and/or propylene oxide
or a salt thereof, in the process of the invention.
The amphoteric surfactants can be provided in the liquid cleaning additive
and/or the liquid cleaning
composition in an amount of ?-0 wt.-% to about <20 wt.-%, preferably about >3
wt.-% to about < 15 wt.-%,
more preferred about >5 wt.-% to about < 10 wt.-%, based on the weight of the
liquid cleaning additive and/or
liquid cleaning composition.
It should be understood that the addition of an amphoteric surfactant to the
active components, the
liquid cleaning additive and/or liquid cleaning composition of the invention
is optional.
Foam Inhibitor
The active components, the liquid cleaning additive and/or liquid cleaning
composition as used in the
process of the invention may contain at least one foam inhibitor. Suitable
foam inhibitors are, for example,
organopolysiloxanes and mixtures thereof with microfine, optionally silanised
silica and also paraffins, waxes,
microcrystalline waxes and mixtures thereof with silanised silica or bis-fatty
acid alkylenediamides such as
bis-stearyl ethylenediamide. The amount of foam inhibitors of the active
components and/or the liquid
cleaning additive as used in the process of the invention can be of >0 wt.-%
to about < 20 wt.-%, preferably
about >3 wt.-% to about < 15 wt.-%, more preferred about >5 wt.-% to about <
10 wt.-%, based on the total
weight of the cleaning additive or liquid cleaning composition.
Mixtures of various foam inhibitors, for example mixtures of silicones,
paraffins or waxes, arc also
used with advantage. It should be understood that the addition of a foam
inhibitor to the liquid cleaning
additive and/or cleaning composition as used in the process of the invention
is optional.
Alkaline Source
The source of alkalinity can be any source of alkalinity that is compatible
with the other components
of the cleaning composition and that will provide the desired pH.
Exemplary sources of alkalinity include alkali metal hydroxides, alkali metal
salts, phosphates,
amines, and mixtures thereof.
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Exemplary alkali metal hydroxides include sodium hydroxide, potassium
hydroxide, and lithium
hydroxide. Exemplary alkali metal salts include sodium carbonate, trisodium
phosphate, potassium carbonate,
and mixtures thereof. Most preferred is the use of sodium hydroxide as
alkaline source.
The source of alkalinity, preferably an alkali metal hydroxide, may be added
to the composition in a
variety of forms, dissolved in an aqueous solution or a combination thereof.
Alkali metal hydroxides are
commercially available as pellets or beads or as an aqueous solution.
The alkaline solution or the liquid cleaning composition can comprise the
source of alkalinity,
preferably sodium hydroxide, in an amount of about > 0.5wt.-% to about < 3.5
wt.-%, preferably about >lwt.-
% to about <3 wt.-%, further preferred about >1.25 wt.-% to about <2.75 wt.-%,
also preferred about >1.3
wt.-% to about <2.5 wt.-%, in addition preferred about >1.5 wt.-% to about <
2.3 wt.-%, furthermore preferred
about >1.7 wt.-% to about <2.25 wt.-%, and more preferred about >1.5 wt.-% to
about < 2.0 wt.-%; wherein
the weight-% of the alkaline source are based on the total weight of the
alkaline solution or liquid cleaning
composition.
Use of Cleaning Composition
The cleaning composition as used in the process of the invention can be used
for cleaning hard and/or
soft surfaces, preferably glass, ceramic, metal and/or plastic ware.
Preferably, the cleaning composition as
used in the process of the invention can be used for cleaning bottles. More
preferred, the cleaning composition
as used in the process of the invention can be used for cleaning glass,
ceramic, metal and/or plastic ware,
preferably bottles, in a bottle cleaning plant.
Bottle labels are removed in soaking bath containing the cleaning composition
of the invention.
Suitable cleaning plants are a single-end-bottle washer or double-end bottle
washer.
Most preferred is the use of the cleaning solution of the invention, to clean
and to remove labels of
glass, ceramic, metal and/or plastic ware, especially glass, ceramic and/or
plastic bottles, in an automated
processing.
Figures
Fig.1 shows the label removal time of glass bottles achieved in a bottle
cleaning plant using a liquid
cleaning solution at different temperatures,
Fig.2 shows the label removal time of glass plates using a liquid cleaning
solution at different temperatures.
Examples
The following examples El to E5 of the liquid cleaning additive are used to
illustrate the improved cleaning
and label removal effect at lower temperatures.
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Example El - additive
Liquid cleaning additive Wt.-% %
phosphoric acid 75% 10.0
gluconic acid 50% 10.0
phosphonic acid 50% 11.0 sequestering agent
fatty alcohol C12-18 9 EO-butyl capped 17.0 endcapped nonionic
surfactant
fatty alcohol C12-14 2 E0 ¨ 4P0 7.0 non endcapped nonionic
surfactant
PEG Coco amine 12E0 8.0 amphoteric surfactant
distilled water Add. 100 wt.-%
Example E2 - surfactant free liquid cleaning additive
Liquid cleaning additive Wt.-% %
phosphoric acid 75% 10.0
gluconic acid 50% 10.0
phosphonic acid 50% 11.0
distilled water add. 100 wt-%
Example E3 - defoamer free liquid cleaning additive
Liquid cleaning additive Wt.-% %
phosphoric Acid 75% 10.0
gluconic Acid 50% 10.0
fatty alcohol C12-14 2 E0 ¨ 4P0 7.0 non cndcapped nonionic
surfactant
PEG Coco amine 12E0 8.0 amphoteric surfactant
distilled water add. 100 wt.-%
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Example E4 - sequestrant free liquid cleaning additive
Liquid cleaning additive Wt.-% %
phosphoric acid 75% 10.0
gluconic acid 50% 10.0
fatty alcohol C12-18 9 EO-butyl capped 17.0 endcapped nonionic
surfactant
fatty alcohol C12-14 2E0 ¨4 PO 7.0 non endcapped nonionic
surfactant
PEG Coco amine 12E0 8.0 amphoteric surfactant
distilled water add. 100 wt.-%
Example E5 ¨ only sequestrant
Liquid cleaning additive Wt.-% %
gluconic acid 50% 10.0
posphonic acid 50% 11.0 sequestering agent
distilled water Add. 100 wt.-%
Label removal test
Background:
This test method has been developed to evaluate the label removal performance
of different caustic
additives for bottle washing. The label removal test is a measurement for the
cleaning efficacy of an additive.
It can be applied for polyethylene terephthalate (PET) and for glass bottles.
Equipment:
- 700 ml mineral water glass bottles with a plane outer surface to which a
MifareTM Standard Paper Label
with a Casein ST 50 KF adhesive is attached
- uncoated glass plates of 19 cm x 10 cm or uncoated glass 330 ml glass
bottles
- Analytical balance capable of weighing to the 0.0001 place
- Casein ST 50 KF adhesive obtainable from the company Tuermerleim GmbH in
Ludwigshafen/Rhein,
Germany (glass plates)
- Mifare Standard Paper Label with Label size: 85.60 +/- 0.12mm x 53.98 +/-
0.05mm, total thickness: 0.30
+/- 0.03mm and weight: 0.20 g +/- 0.05 g
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- Roll coater / Hand coater
- double-walled vessel of 5000 ml inner volume
Procedure:
Label removing device for glass plates:
The label removing device is composed of an oscillating motor (wind screen
wiper motor
obtained from a car "Opel Record") where a glass plate can be fixed in a
clamping tool in a vertically
position for testing. The speed of the oscillating motor has been set so that
it moves forward and
backward every second. The testing solution is heated in a double-walled
vessel. The vessel is
connected to a thermostat, which regulates the required temperature.
Label removing device for mineral water glass bottles:
The700 ml mineral water glass bottles with a plane outer surface to which a
Mifare Standard
Paper Label with a Casein ST 50 KF adhesive was attached are processed in a
Fontana RME SEN
cleaning plant with a capacity of 45.000 bottles per hour. The soaking bath
for label removal was
filled up with a cleaning composition as used in the process of the invention
and described below.
Glass plates labeling:
The glass plates are degreased with acetone and dried at room temperature. A
label is applied
to the glass plates with a hand coater using the Casein ST 50 KF adhesive. The
adhesive film should
be very thin (100 vim). The labels are dried for 3 days at room temperature.
Bottle labeling:
The mineral bottles are degreased with acetone and dried at room temperature.
A label is
applied to the glass plates with a hand coater using the Casein ST 50 KF
adhesive. The adhesive film
should be very thin (100 m). The labels are dried for 3 days at room
temperature.
Liquid cleaning solution:
The various cleaning solution are obtained by mixing 2000 ml of a 2 wt.-% NaOH
alkaline
solution with 4 ml of the liquid cleaning additive of examples El or 7 ml of
the liquid cleaning
additive of examples El to E5.
After that, the cleaning solutions as used for label removal of glass bottles
according to Fig. 1
are heated in a soaking bath of the Fontana RME SEN to the required
temperature of 65 C and 80 C
(see Fig. 1) and the cleaning process is started. The time is measured for
each glass bottle with respect
to the used cleaning solution until the label is completely removed (= label
removal time [see]). For
each cleaning solution and temperature, the test is repeated 3 times.
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For the glass plates label test the liquid cleaning composition in the double-
walled vessel is
brought to the temperature of 60 C (see Fig. 2). Subsequently, a labeled
glass plate is fixed with a
clamping tool and the glass plate is introduced into the cleaning solution so
that the label is completely
dipped into the cleaning solution and the oscillating motor is started. The
time is measured for each
glass plate with respect to the used cleaning solution until the label is
completely removed (= label
removal time [sec]). For each cleaning solution and temperature, the test is
repeated 3 times.
Results:
Figure 1 clearly shows that the label removal performance for 700 ml mineral
water glass
bottles with a plane outer surface to which a Mifare Standard Paper Label with
a Casein ST 50 KF
adhesive is attached using 7 ml of an additive of example El added to a 2000
ml caustic solution of
2.0 wt.-% NaOH processed at a process temperature of 65 C provides the same
label removal time as
compared to 4 ml of the same additive of example El added to 2000 ml of a 2.0
wt.-% NaOH caustic
solution at a cleaning temperature of 800 C. Thus, Fig. 1 demonstrates that
the process of the present
invention provides good cleaning and label removal characteristics at lower
temperatures.
Figure 2 shows that the label removal for glass plates using 7 ml of an
additive of example E2,
E3, E4 and E5 to a 2000 ml caustic solution of 2.0 wt.-% NaOH at a process
temperature of 60 C
provides improved label removal time of between 120 sec to 140 sec. Thus, Fig.
2 shows that the
process of the present invention provides good cleaning and label removal
characteristics at lower
process temperatures.
As used herein, the term "about'' 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 used to make the
compositions or carry out the
methods; and the like. The term "about" also encompasses amounts that differ
due to different
equilibrium conditions for a composition resulting from a particular initial
mixture. Whether or not
modified by the term "about", the claims include equivalents to the
quantities.
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 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. 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 to various specific and preferred embodiments and
techniques. However,
it should be understood that many variations and modifications may be made
while remaining within
the spirit and scope of the invention.
