Note: Descriptions are shown in the official language in which they were submitted.
CA 02699537 2014-03-06
WO 2008/137853 PCT/US2008/062667
PRESSED, SELF-SOLIDIFYING, SOLID CLEANING COMPOSITIONS
AND METHODS OF MAKING THEM
Cross Reference to Related Applications
This application is being filed on 0$ May 2008, as a PCT International Patent
Application in the name of F,colab Inc., a U.S. national corporation,
applicant for the
designation of all countries except the US, and Roger L Stolte, Michael P.
Dziuk,
Melissa Meinke, Matthew C. Porter, and Michael E. Besse, all citizens of the
U.S.,
applicants for the designation of the US only, and claims priority to U.S.
Patent
Application No. 11/800,286, filed May 4, 2007, and U.S. Provisional Patent
Application No. 60/980,912, filed October 18, 2007.
Field of the Invention
The present invention relates to a method of making a solid cleaning
composition. The method can include pressing and/or vibrating a flowable solid
of a
self-solidifying cleaning composition. For a self-solidifying cleaning
composition,
pressing and/or vibrating a flowable solid determines the shape and density of
the
solid but is not required for forming a solid. The method can employ a
concrete
block machine for pressing and/or vibrating, The present invention also
relates to a
solid cleaning composition made by the method and to solid cleaning
compositions
including particles bound together by a binding agent.
Background of the Invention
The use of solidification technology and solid block detergents in
institutional and industrial operations was pioneered in the SOLID POWER
brand
technology claimed in Femholz et al., U.S. Reissue Patent Nos. 32,762 and
32,818.
This solidification technology and these solid cleaning compositions were
followed
by stable solid cleaning compositions including the proprietary E-Form binding
agent, a mixture of hydrated sequestrant and hydrated carbonate.
Conventional solid block or tablet compositions can be made at high pressure
in a tablet press, by casting a melted composition, and by extrusion. An
expensive
tablet press can apply its high pressures only to form tablet or puck sized
solids. A
tablet press is not suitable for making solid blocks. Casting requires melting
the
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
composition to form a liquid. Melting consumes energy and can destroy certain
desirable ingredients in some cleaning products. Extruding requires expensive
equipment and advanced technical know how.
There remains a need for additional methods for making solid cleaning
compositions and for compositions that can be made by these methods.
Summary of the Invention
The present invention relates to a method of making a solid cleaning
composition. The method can include pressing and/or vibrating a flowable solid
of a
self-solidifying cleaning composition. For a self-solidifying cleaning
composition,
pressing and/or vibrating a flowable solid determines the shape and density of
the
solid but is not required for forming a solid. The method can employ a
concrete
block machine for pressing and/or vibrating. The present invention also
relates to a
solid cleaning composition made by the method and to solid cleaning
compositions
including particles bound together by a binding agent.
The present method relates to a method of making a solid cleaning
composition. This method includes providing a flowable solid including water
and
alkalinity source, sequestrant, or mixture thereof. The method can include
mixing
the desired ingredients to form the flowable solid. The method also includes
placing
the flowable solid into a form. The method can include gently pressing the
flowable
solid in the form to produce the solid cleaning composition. The method can
include
vibrating the flowable solid in the form to produce the solid cleaning
composition.
The method can include both the gently pressing and the vibrating.
Gently pressing, vibrating, or a combination thereof can be done by a
concrete block machine, also known as a concrete products machine or masonry
product machine, or by a turntable press. The method of making a solid
cleaning
composition can include providing a flowable solid including water and
alkalinity
source, sequestrant, or mixture thereof. This embodiment of the method
includes
putting the flowable solid in a hopper or a drawer of a concrete block machine
and
operating the concrete block machine to produce uncured solid cleaning
composition. Curing the uncured composition produces the solid cleaning
composition. In an embodiment, the method includes putting the flowable solid
in a
drawer of a concrete block machine and vibrating the flowable solid in the
drawer.
2
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
The method also includes transferring the flowable solid from the drawer into
a
form. Once in the form, the method includes gently pressing the flowable solid
in
the form to produce the uncured solid cleaning composition, vibrating the
flowable
solid to produce the uncured solid cleaning composition, or combination
thereof.
The method then includes removing the uncured solid cleaning composition from
the form. Curing the uncured composition produces the solid cleaning
composition.
The gently pressing, the vibrating, or the combination thereof can produce an
uncured composition, the uncured composition including the flowable solid
compressed to provide sufficient surface contact between particles making up
the
flowable solid that the uncured composition will solidify into a stable solid
cleaning
composition. Gently pressing can include applying pressures of about 1 to
about
1000 psi to the flowable solid. In an embodiment, gently pressing can include
applying pressures of about 1000 to about 2000 psi to the flowable solid.
Vibrating
can occur at about 3000 to about 6000 rpm. Vibrating can occur at about 1500
to
about 3000 rpm. Vibrating can occur for about 1 to about 10 sec.
The present invention also relates to a solid cleaning composition. The solid
cleaning composition can include hydrated alkalinity source, hydrated
sequestrant, or
mixture thereof. The solid cleaning composition can include particles of
cleaning
composition including an interior and a surface. The surface can include a
binding
agent. In the solid cleaning composition, the surfaces of adjacent particles
can
contact one another to provide sufficient contact of binding agent on the
adjacent
particles to provide a stable solid cleaning composition. The solid cleaning
composition can be made by the method of the present invention.
Brief Description of the Figure
Figure 1 schematically illustrates an apparatus suitable for gently pressing
the
present compositions, a concrete block machine.
Figure 2 schematically illustrates another apparatus suitable for gently
pressing the present compositions, a turntable press.
3
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
Detailed Description of the Invention
Definitions
As used herein, the phrase "concrete block machine" refers to a machine that
forms concrete products (e.g., blocks or pavers) from concrete and that
includes
apparatus for pressing, vibrating, or combination thereof concrete (or the
present
flowable solid) in a form or mold. Such a machine is known in the product
literature
as a concrete product machine, concrete block machine, a masonry product
machine,
and the like.
Unless stated otherwise, as used herein, the term "psi" or "pounds per square
inch" refers to the actual pressure applied to the material (e.g., the present
flowable
solid) being pressed (e.g., gently pressed) or applied to the material in a
plurality of
forms. As used herein, psi or pounds per square inch does not refer to the
gauge or
hydraulic pressure measured at a point in the apparatus doing the pressing.
Gauge or
hydraulic pressure measured at a point in an apparatus is referred to herein
as "gauge
pressure".
As used herein, the term "phosphate-free" refers to a composition, mixture,
or ingredients that do not contain a phosphate or phosphate-containing
compound or
to which a phosphate or phosphate-containing compound has not been added.
Should a phosphate or phosphate-containing compound be present through
contamination of a phosphate-free composition, mixture, or ingredients, the
level of
phosphate shall be less than 0.5 wt %, may be less then 0.1 wt%, and can be
less
than 0.01 wt %.
As used herein, the term "phosphorus-free" refers to a composition, mixture,
or ingredients that do not contain phosphorus or a phosphorus-containing
compound
or to which phosphorus or a phosphorus-containing compound has not been added.
Should phosphorus or a phosphorus-containing compound be present through
contamination of a phosphorus-free composition, mixture, or ingredients, the
level
of phosphorus shall be less than 0.5 wt %, may be less then 0.1 wt%, and can
be less
than 0.01 wt %.
The term "functional material" or "functional additives" refers to an active
compound or material that affords desirable properties to the solid or
dissolved
composition. For example, the functional material can afford desirable
properties to
the solid composition such as enhancing solidification characteristics or
dilution
4
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
rate. The functional material can also, when dissolved or dispersed in an
aqueous
phase, provide a beneficial property to the aqueous material when used.
Examples
of functional materials include chelating/sequestering agent, alkalinity
source,
surfactant, cleaning agent, softening agent, buffer, anti-corrosion agent,
bleach
activators secondary hardening agent or solubility modifier, detergent filler,
defoamer, anti-redeposition agent, antimicrobials, rinse aid compositions, a
threshold agent or system, aesthetic enhancing agent (i.e., dye, perfume),
lubricant
compositions, additional bleaching agents, functional salts, hardening agents,
solubility modifiers, enzymes, other such additives or functional ingredients,
and the
like, and mixtures thereof. Functional materials added to a composition will
vary
according to the type of composition being manufactured, and the intended end
use
of the composition.
"Cleaning" means to perform or aid in soil removal, bleaching, microbial
population reduction, or combination thereof.
As used herein, a solid cleaning composition refers to a cleaning composition
in the form of a solid such as a powder, a flake, a granule, a pellet, a
tablet, a
lozenge, a puck, a briquette, a brick, a solid block, a unit dose, or another
solid form
known to those of skill in the art. The term "solid" refers to the state of
the detergent
composition under the expected conditions of storage and use of the solid
detergent
composition. In general, it is expected that the detergent composition will
remain in
solid form when exposed to temperatures of up to about 100 F and greater than
about 120 F.
As used herein, weight percent (wt-%), 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 total weight of the composition and multiplied
by 100.
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. The term about also
encompasses amounts that differ due to different equilibrium conditions for a
5
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
composition resulting from a particular initial mixture. Whether or not
modified by
the term "about", the claims include equivalents to the quantities.
The Present Solid Composition
The present invention relates to solid cleaning compositions and methods of
making them. The present method can include pressing, vibrating, or
combination
thereof (pressing and/or vibrating) a flowable solid of a self-solidifying
cleaning
composition to produce a solid, such as a block or puck. If just placed in a
form or
mold without having pressure or vibration applied to it, a flowable solid of a
self-
solidifying cleaning composition forms a crumbly (friable) solid. Gently
pressing
and/or vibrating the flowable solid in a mold or form produces a stable solid.
A
stable solid composition retains its shape under conditions in which the
composition
may be stored or handled. For a self-solidifying cleaning composition,
pressing
and/or vibrating a flowable solid determines the shape and density of the
stable
solid, but is not required for forming a solid.
The self-solidifying solid compositions include alkalinity source, chelating
agent, or combination thereof and water. Mixing of alkalinity source,
chelating
agent, or combination thereof with water and other desired cleaning agents
produces
a flowable solid (e.g., a flowable powder). Placing the flowable solid into a
form
(e.g., a mold or container) and gently pressing and/or vibrating the powder
produces
an uncured composition (e.g., a crumbly or friable solid) suitable for curing
into a
stable solid. Gently pressing refers to compressing the flowable solid in the
container that is effective to bring a sufficient quantity of particles (e.g.,
granules) of
the flowable solid into contact with one another. In the present method,
vibrating
refers to moving or imparting vibrational energy to the flowable solid in the
container that is effective to bring a sufficient quantity of particles (e.g.,
granules) of
the flowable solid into contact with one another. In the present method,
pressing and
vibrating refers to moving or imparting vibrational energy to and compressing
the
flowable solid in the container that is effective to bring a sufficient
quantity of
particles (e.g., granules) of the flowable solid into contact with one
another. A
sufficient quantity of particles (e.g. granules) in contact with one another
provides
binding of particles to one another effective for making a stable solid
composition.
6
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
In an embodiment, the uncured composition is a crumbly or friable solid that
can, for example, break into pieces if dropped from a person's hands onto the
floor.
After curing for, for example, about one day, the uncured composition has
become a
cured composition that is a solid, for example, block or puck. The cured
composition can be as hard as a rock.
The present solids can employ any of a variety of suitable binding agents.
For example, in an embodiment, the present solids include a carbonate hydrate
binding agent such as E-Form. The present solids can include a binding agent
based
on a hydrated chelating agent, such as a hydrated aminocarboxylate (e.g.,
HEDTA,
EDTA, MGDA, or the like) together with a carbonate hydrate. The present solids
can include a binding agent based on a hydrated carboxylate, such as a
hydrated
citrate salt or a hydrated tartrate salt. The present solids can include a
binding agent
based on a hydrated polycarboxylate or hydrated anionic polymer. Another
suitable
binding agent is hydrated sodium hydroxide (i.e., caustic). Conventional
caustic
compositions are provided in a plastic jar or capsule. In contrast, an
embodiment of
a solid block of a caustic composition made according to the present method
can be
provided as a dimensionally stable solid block without ajar or capsule.
The present examples disclose a variety of self-solidifying compositions that
can be made formed into a stable solid according to the method of the present
invention.
Making the Solid Cleaning Composition with a Concrete Block Machine or
Turntable Press
In an embodiment, the present composition can be vibrated and gently
pressed in an apparatus that can form a concrete block, concrete paver,
terrazzo tile,
concrete slab, concrete tile, kerbstone, large concrete block, or other shaped
concrete
product. One configuration of such an apparatus is known variously as a
concrete
block machine, a concrete product machine, a masonry product machine, or the
like.
Another configuration of such an apparatus is known variously as a hermetic
press,
tamping machine, brick press, turntable press, hydraulic press, or the like.
The method can include employing a concrete block machine to form the
solid cleaning composition. This embodiment of the method can include
providing
the present flowable solid. The method can include providing or putting the
7
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
flowable solid in a drawer of the machine. In an embodiment, the method can
include vibrating the flowable solid in the drawer. The method then includes
transferring the flowable solid from the drawer into a form. Once in the form,
the
flowable solid can be subjected to gently pressing the flowable solid in the
form to
produce the uncured solid cleaning composition. Once in the form, the flowable
solid can be subjected to vibrating the flowable solid to produce the uncured
solid
cleaning composition. Alternatively, once in the form, the flowable solid can
be
subjected to a combination of gentle pressing and vibrating. The uncured
composition can then be removed from the form. Once out of the form the
uncured
composition can be cured to produce the solid cleaning composition.
The concrete block machine can vibrate the composition in the mold or form
at about 200 to about 6000 rpm, about 200 to about 300 rpm, about 2500 to
about
3000 (e.g., 3100) rpm, about 1500 to about 3000 rpm, or about 3000 to about
6000
rpm.
The concrete block machine can vibrate the composition in the mold for
about 1 to about 10 sec or about 1 to about 6 sec.
The concrete block machine can press the content of the mold or form with a
force of about 1 to about 1000 psi (or in an embodiment, to about 2000 psi),
about 2
to about 300 psi, about 5 psi to about 200 psi, or about 10 psi to about 100
psi. In
certain embodiments, the present method employs pressures of less than or
equal to
about 300 psi, less than or equal to about 200 psi, or less than or equal to
about 100
psi. In certain embodiments, the present method can employ pressures as low as
greater than or equal to about 1 psi, greater than or equal to about 2,
greater than or
equal to about 5 psi, or greater than or equal to about 10 psi.
The concrete block machine can vibrate the composition in the mold (and
including the vibrating the form) at an excitation force (i.e., amplitude,
centrifugal
force) of, for example, about 2000 to about 6,500 lb, about 3000 to about 9000
lb,
about 4000 to about 13,000 lb, or about 5000 to about 15,000 lb. In certain
embodiments, the vibrational force can be about 2,000 lb, about 3,000 lb,
about
4,000 lb, about 5,000 lb, about 6,000 lb, about 7,000 lb, about 8,000 lb,
about 9,000
lb, about 10,000 lb, about 11,000 lb, about 12,000 lb, about 13,000 lb, about
14,000
lb, or about 15,000 lb.
8
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
In an embodiment, the method can include vibrating the drawer containing
flowable solid for about 1 to about 10 sec at about 200 to about 6,000 rpm. In
an
embodiment, the method can include vibrating the form containing flowable
solid
for about 1 to about 10 sec at about 200 to about 6,000 rpm. In an embodiment,
the
method can include such vibrating and also include pressing on the flowable
solid in
the form with a weight of about 100 to about 2000 lb.
The method employing the concrete products machine can include any of a
variety of additional manipulations useful for forming the solid cleaning
composition. The method can include putting the flowable solid into a hopper.
The
method can include flowing or transporting the flowable solid from the hopper
into
the drawer. The flowable solid can flow from the hopper under the force of
gravity
into the drawer. If the hopper is positioned directly above the drawer,
opening a
portal on the bottom of the hopper can allow flowable solid to drop into the
drawer.
Alternatively, the hopper can be positioned above a ramp and the flowable
solid can
flow down the ramp and into the drawer.
The method can include vibrating and/or agitating the flowable solid in the
hopper, as it flows or drops from the hopper into the drawer, in the drawer as
it is
flowing into the drawer, or once it is in the drawer.
The method includes transferring the flowable solid from the drawer into the
form. Transferring the flowable solid from the drawer into the form can be
accomplished by the force of gravity. For example, the drawer can be in a
position
(disposed) above the form. The bottom of the drawer can be configured to slide
out
or be moved laterally out from under the interior of the drawer. Thus, any
flowable
solid in the drawer will fall into the form, e.g., the cavity or cavities of
the form.
The method can include providing the drawer disposed above the form, the
drawer
including a panel disposed between an interior of the drawer and the form. The
method can include laterally moving the panel to a position not between the
interior
of the drawer and the form. Accordingly, the flowable solid drops into the
form.
The method can include vibrating the flowable solid in the form, as it flows
or drops from the drawer into the form, in the form as it is flowing into the
form, or
once it is in the form. The method can include pressing the flowable solid in
the
form (e.g., in the cavity or cavities of the form).
9
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
The pressed and/or vibrated flowable solid (e.g., the uncured composition)
can be removed from the form by any of a variety of methods. For example,
removing the uncured composition from the form can include raising the form
with
the uncured composition remaining on a pallet that had formed the bottom of
the
form. The method can also include moving the pallet horizontally away from the
drawer and form.
In short, the method can employ a drawer and form that are components of a
concrete block machine. The concrete block machine can vibrate the flowable
solid
in the drawer; transfer the flowable solid from the drawer into a form, gently
press
the flowable solid in the form to produce the uncured solid cleaning
composition,
vibrate the flowable solid to produce the uncured solid cleaning composition,
or
combination thereof; and remove the uncured solid cleaning composition from
the
form (i.e., move the form off of the uncured composition).
In an embodiment, the method can be carried out with the apparatus known
as a hermetic press, tamping machine, brick press, turntable press, hydraulic
press,
or the like. This embodiment of the method can be carried out as described
above
for the concrete block machine. This embodiment can also include the following
variations from the use of the concrete block machine. This embodiment of the
method can include providing the present flowable solid. The method can
include
providing or putting the flowable solid in a mold of the machine. Putting the
flowable solid in the mold can be accomplished by an auger that feeds the
solid into
the mold. Putting the flowable solid in the mold can include vibrating the
flowable
solid in a drawer and transferring the flowable solid from the drawer into the
mold.
The mold can be subjected to negative pressure or suction to settle the
flowable solid
in the mold.
The method employing the turntable press can include any of a variety of
additional manipulations useful for forming the solid cleaning composition.
The
method can include putting the flowable solid into a hopper. The method can
include flowing or transporting the flowable solid from the hopper into the
mold.
The flowable solid can flow from the hopper (e.g., down a chute) under the
force of
gravity into the mold. The flowable solid can be moved from the hopper to the
mold
by an auger. The method can include vibrating and/or agitating the flowable
solid in
the hopper. The method can include vibrating the flowable solid in the mold,
as it
CA 02 699537 2014-03-06
WO 2008/137853 PCT/US2008/062667
flows or drops into the mold, in the mold as it is flowing into the mold, or
once it is
in the mold. The method can include gently pressing the flowable solid in the
mold
(e.g., in the cavity or cavities of the form). Gently pressing can employ
hydraulic
pressure and a ram. The apparatus can be employed to apply a pressure of up to
2000 psi. In an embodiment, the apparatus can apply a maximum pressure of 1740
psi.
The pressed and/or vibrated flowable solid (e.g., the uncured composition)
can be removed from the mold by any of a variety of methods. The uncured solid
can be removed from the mold by lifting the mold and recovering the solid from
a
platform. The turntable can rotate to move another mold under the hydraulic
ram.
In an embodiment, such an apparatus can provide the functions of a hermetic
press, tamping, wet molding, and vibration.
Concrete Block Machine
Suitable concrete block machines include those manufactured by, for
example, Columbia, Besser, Masa, Omag, or Quadra and having model numbers
TM TM -rm TM
such as Columbia Model 15, 21, or 22; Besser SuperPae, BeseoPac, or VibraPac;
or
MasiamExtra-Targe XL 6Ø These machines can produce, for example, 6-10 blocks
of solid cleaning composition each weighing 1.5-3 kg in a single operation.
Referring now to Figure 1, a concrete block machine 100 can include a
drawer 1 configured to receive the flowable solid and to drop the flowable
solid into
a form 3. The form 3 can define one or a plurality of cavities 5 configured to
provide the desired shape of the solid cleaning composition. For example, the
form
3 can define cavity 5 with open top 7, form sides 9, and pallet 11.
Drawer 1 can include drawer sides 13 and bottom panel 15. Bottom panel 15
can be configured to be moved from beneath drawer sides 13. For example,
bottom
panel 15 can slideably engage drawer sides 13 so that bottom panel 15 be slid
our
from under drawer interior 17 defined by drawer sides 13. Concrete block
machine
100 can be configured to position drawer 1 containing the present flowable
solid (not
shown) over form 3. Concrete block machine 100 can be configured to slide
bottom
panel 15 out from under drawer interior 17. When drawer 1 containing the
present
flowable solid is positioned over form 3 and bottom panel 15 is slid out from
under
drawer interior 17, the flowable solid drops into cavity or cavities 5.
11
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
Concrete block machine 100 can also include vibration system 19. Vibration
system 19 can include drawer vibrator 21. Drawer vibrator 21 can be configured
to
vibrate drawer 1 and any flowable solid it contains. Drawer vibrator 21 can
impart
vibrational energy to the flowable solid in the drawer. Drawer vibrator 21 can
be
configured to vibrate drawer 1 and its contents at a preselected frequency
(rpm) and
a preselected amplitude (centrifugal force). Vibration system 19 can include
form
vibrator 23. Form vibrator 23 can be configured to vibrate form 3 and any
flowable
solid it contains. Form vibrator 23 can impart vibrational energy to the
flowable
solid in the form. Drawer vibrator 23 can be configured to vibrate form 3 and
its
contents at a preselected frequency (rpm) and a preselected amplitude
(centrifugal
force).
Concrete block machine 100 can also include pressing system 25. Pressing
system 25 can be configured to press flowable solid in the cavity or cavities
5 of
form 3. Pressing system can include, for example, a shoe or shoes 27
configured to
be moved down onto flowable solid in cavity or cavities 5. Pressing system 25
can
be configured to press upon the flowable solid in the cavity or cavities 5 of
form 3 at
a preselected pressure (psi).
Concrete block machine 100 can also include optional drawer transport 29
configured to move the drawer 1 with respect to the form 3. For example,
drawer
transport 29 can be configured to move drawer 1 from under a hopper 31 to over
form 3. Alternatively, drawer 1 and hopper 31 can both be positioned over form
3.
In such an embodiment, the drawer transport 29 may be absent of may be
configured
to move drawer 1 from over form 3, for example, for maintenance or other
purposes.
Hopper 31 can be configured to contain sufficient flowable solid for
repeatedly
filling the drawer 1 and the cavity or cavities 5.
Concrete block machine 100 can also include form transport 33 configured to
move the form 3 with respect to the drawer 1. For example, form transport 33
can
be configured to move form 3 from under drawer 1 to a position at the exterior
of
machine 100. For example, form transport 33 can be configured to raise form
sides
9 while leaving uncured solid composition on pallet 11. Pallet 11 can then be
moved
to the exterior of the machine 100 so that the uncured solid composition can
be
removed from the machine.
12
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
Turntable Press
Suitable concrete block machines include those manufactured by, for
example, Schauer & Haeberle, Masa, or the like and having model names such as
Multi-System-Press 970, RECORD Power WP-06 4D, UN1-2000, W'KP 1200 S, or
the like. These machines can produce, for example, 6-10 blocks of solid
cleaning
composition each weighing 1.5-3 kg in a single operation.
Referring now to Figure 2, a turntable press 200 can include a hopper 201
with chute 203 configured to receive the flowable solid and to drop the
flowable
solid into a mold 205. The mold 205 can define one or a plurality of chambers
207
configured to provide the desired shape of the solid cleaning composition.
Turntable
press 200 can include hopper vibrator 209 and/or mold vibrator 211 to vibrate
the
hopper and/or the mold, respectively, and any flowable solid that they might
contain.
Turntable press 200 can impart vibrational energy to the flowable solid in the
hopper 201. Hopper vibrator 209 can be configured to vibrate hopper 201 and
its
contents at a preselected frequency (rpm) and a preselected amplitude
(centrifugal
force). Mold vibrator 211 can impart vibrational energy to the flowable solid
in the
mold 205. Mold vibrator 211 can be configured to vibrate mold 205 and its
contents
at a preselected frequency (rpm) and a preselected amplitude (centrifugal
force).
Turntable press 200 can also include press 213. Press 213 can be configured
to press flowable solid in the mold 205 and any chamber or chambers 207 that
might
be in the mold 205. Press 213 can include, for example, a ram 215 configured
to be
moved down onto flowable solid in mold 205 and any chamber or chambers 207.
Press 213 can be configured to press upon the flowable solid in the mold 205
and
any chamber or chambers 207 at a preselected pressure (psi).
Turntable press 200 can also include turntable 217 configured to move the
mold 205. For example, turntable 217 can be configured to move mold 205 from
under chute 203 to a position under ram 215, and then, for example, to a
unloading
position 219, where the turntable pressed solid 221 can be removed from the
apparatus.
Additional Methods for Pressing and/or Vibrating
The present solid composition can be made by an advantageous method of
pressing and/or vibrating the solid composition. The method of pressing and/or
13
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
vibrating the composition includes mixing the desired ingredients in the
desired
proportions, for example, with a ribbon or other known blender to form the
flowable
solid. In an embodiment, the method then includes forming the solid cleaning
composition from the mixed ingredients by placing the flowable solid in a
mold,
pressing and/or vibrating the flowable solid in the mold to form an uncured
composition, and recovering the composition from the mold. The uncured
composition can be removed from the mold and then allowed to cure.
Pressing can employ low pressures compared to conventional pressures used
to form tablets or other conventional solid cleaning compositions. For
example,
successful pressing and/or vibrating can be achieved by placing a board on the
top of
the mold and in contact with the flowable solid in the mold and tapping on the
board
(or other piece of wood, or a piece of metal or plastic) with a common claw
hammer.
By way of further example, in an embodiment, the present method employs a
pressure on the solid of only less than or equal to about 1000 psi. In certain
embodiments, the present method employs pressures of less than or equal to
about
300 psi, less than or equal to about 200 psi, or less than or equal to about
100 psi. In
certain embodiments, the present method can employ pressures as low as greater
than or equal to about 1 psi, greater than or equal to about 2, greater than
or equal to
about 5 psi, or greater than or equal to about 10 psi. In certain embodiments,
the
present method can employ pressures of about 1 to about 1000 psi, about 2 to
about
300 psi, about 5 psi to about 200 psi, or about 10 psi to about 100 psi. Such
pressing
is referred to herein as "gentle pressing." In an embodiment, gently pressing
can
include applying pressures of about 1000 to about 2000 psi to the flowable
solid.
Gentle pressing can be accomplished by any of a variety of apparatus. Suitable
apparatus for gentle pressing include a press with a lever, which can employ
hydraulic cylinder or a screw press.
In an embodiment, the ingredients are packed in the mold by a method
including vibrating. This embodiment includes forming the solid cleaning
composition from the mixed ingredients by placing the flowable solid in a
mold,
vibrating the mold containing the flowable solid, vibrating the flowable solid
in the
mold, vibrating the flowable solid before or as it is put into the mold, or
combination
thereof to form the uncured composition, and recovering the pressed and/or
vibrated
composition from the mold.
14
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
Vibrating can include any of a variety of methods for imparting vibrational
energy to the mold of the mixed ingredients. For example, vibrating can
include
vibrating a plurality of molds containing the mixed ingredients on a platform.
For
example, vibrating can include inserting a vibrating probe into the mixed
ingredients
in the mold. For example, vibrating can include placing a vibrating surface or
object
onto the mixed ingredients in the mold.
Vibrating can also include vibrating the flowable solid before or as the
flowable solid is placed in the mold. The flowable solid can be stored or
provided as
a quantity sufficient for producing hundreds or thousands of pounds of solid
cleaning
composition. For example, an amount of flowable solid sufficient to fill
several
molds or forms can be placed in a container (e.g., a drawer) and vibrated in
the
container. The flowable solid can be vibrated as it is moved (e.g., dropped)
from the
container into the mold or form.
Vibrating effective for forming the present solids includes vibrating at about
200 to about 6000 rpm, about 200 to about 300 rpm, about 2500 to about 3000
(e.g.,
3100) rpm, about 1500 to about 3000 rpm, or about 3000 to about 6000 rpm.
Vibrating can be conducted for about 1 to about 10 sec or about 1 to about 6
sec. Suitable apparatus for vibrating the composition includes a concrete
block
machine or concrete products machine.
In certain embodiments, the vibration can be quantified as the amount of
vibrational energy ¨ centrifugal force - applied to the flowable solid, mold
or form,
and moving parts of the apparatus. In certain embodiments, the amount of
vibrational force is about 100 lb, about 200 lb, about 300 lb, about 400 lb,
about 500
lb, about 600 lb, about 700 lb, about 800 lb, about 900 lb, or about 1,000. In
certain
embodiments, the amount of vibrational force is about 2,000 lb, about 3,000
lb,
about 4,000 lb, about 5,000 lb, about 6,000 lb, about 7,000 lb, about 8,000
lb, about
9,000 lb, about 10,000 lb, about 11,000 lb, about 12,000 lb, about 13,000 lb,
about
14,000 lb, or about 15,000 lb. In certain embodiments, the amount of
vibrational
force is about 100 lb, about 200 lb, about 300 lb, about 400 lb, about 500 lb,
about
600 lb, about 700 lb, about 800 lb, about 900 lb, about 1,000, about 1,500 lb,
about
2,000 lb, about 3,000 lb, about 4,000 lb, about 5,000 lb, about 6,000 lb,
about 7,000
lb, about 8,000 lb, about 9,000 lb, about 10,000 lb, about 11,000 lb, about
12,000 lb,
about 13,000 lb, about 14,000 lb, or about 15,000 lb. Employing a concrete
products
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
machine, the amount of vibrational force applied to the flowable solid, mold
or form,
and moving parts of the machine can be about 2000 to about 6,500 lb, about
3000 to
about 9000 lb, about 4000 to about 13,000 lb, or about 5000 to about 15,000
lb.
The mold can be coated with a release layer to ease release of the solid
composition from the mold.
The method can operate on any of a variety of compositions. The
composition can be, for example, a flowable powder or a paste. Suitable
flowable
powders include a powder and a wetted powder. The method can operate on a
composition that can flow or be dropped into and fill the mold and that forms
a
suitable binding agent.
In certain embodiments, it is possible to make the present solid compositions
by methods that do not employ gentle pressing, but that employ higher
pressures,
such as up to 2500 psi, up to 3000 psi, up to 3500 psi, up to 4000 psi, up to
4500 psi,
or less than 5000 psi.
The Present Method Employs Advantageously Gentle Pressing
The method of the present invention can produce a stable solid without the
high pressure compression employed in conventional tableting. A conventional
tableting press applies pressures of at least about 5000 psi and even about
30,000-
100,000 psi or more to a solid to produce a tablet. In contrast, the present
method
employs pressures on the solid of only less than or equal to about 1000 psi,
in an
embodiment less than or equal to 2000 psi. In certain embodiments, the present
method employs pressures of less than or equal to about 300 psi, less than or
equal to
about 200 psi, or less than or equal to about 100 psi. In certain embodiments,
the
present method can employ pressures as low as greater than or equal to about 1
psi,
greater than or equal to about 2, greater than or equal to about 5 psi, or
greater than
or equal to about 10 psi. The solids of the present invention are held
together not by
mere compression but by a binding agent produced in the flowable solid and
that is
effective for producing a stable solid.
The method of the present invention can produce a stable solid in any of a
variety of sizes, including sizes larger than can be produced in a tableting
press. A
conventional tableting press can make only smaller solid products, for
example,
those smaller than a hockey puck (or smaller than about 600 g). The present
method
16
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
has been employed to produce a solid block weighing about 3 kg to about 6 kg,
with
a volume of, for example, 5 gal, or having dimensions of; for example, 6x6
inches or
a paver-like slab 12 inches square. The present method employs a binding
agent, not
pressure, to provide a large stable solid.
The method of the present invention can produce a stable solid without
employing a melt and solidification of the melt as in conventional casting.
Forming
a melt requires heating a composition to melt it. The heat can be applied
externally
or can be produced by a chemical exotherm (e.g., from mixing caustic (sodium
hydroxide) and water). Heating a composition consumes energy. Handling a hot
melt requires safety precautions and equipment. Further, solidification of a
melt
requires cooling the melt in a container to solidify the melt and form the
cast solid.
Cooling requires time and/or energy. In contrast, the present method can
employ
ambient temperature and humidity during solidification or curing of the
present
compositions. Caustic compositions made according to the present method
produce
only a slight temperature increase due to the exotherm. The solids of the
present
invention are held together not by solidification from a melt but by a binding
agent
produced in the flowable solid and that is effective for producing a stable
solid.
The method of the present invention can produce a stable solid without
extruding to compress the mixture through a die. Conventional processes for
extruding a mixture through a die to produce a solid cleaning composition
apply
high pressures to a solid or paste to produce the extruded solid. In contrast,
the
present method employs pressures on the solid of less than or equal to about
1000
psi or even as little as 1 psi. The solids of the present invention are held
together not
by mere compression but by a binding agent produced in the flowable solid and
that
is effective for producing a stable solid.
Any of a variety of flowable solids can be used in the method of the present
invention. For example, in an embodiment, the flowable solid has a consistency
similar to wet sand. Such a flowable solid can be compressed in a person's
hand,
like forming a snowball. However, immediately after forming it, a forceful
impact
(dropping or throwing) would return a hand compacted ball of the flowable
solid to
powder and other smaller pieces. In an embodiment, a flowable solid contains
little
enough water that compressing the powder at several hundred psi does not
squeeze
17
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
liquid water from the solid. In certain embodiments, the present flowable
solid can
be a powder or a wetted powder.
Embodiments of the Present Solid Cleaning Compositions
Binding Agent
A solid cleaning composition can be maintained as a solid by a portion or
component of the composition that acts as a binding agent. The binding agent
can
be dispersed throughout the solid cleaning composition to bind the detergent
composition together to provide a solid cleaning composition. In an
embodiment,
the binding agent is inorganic and can be a source of alkalinity. Examples of
such
inorganic alkaline binding agents include sodium hydroxide, sodium carbonate
or
ash, sodium metasilicate, or a mixture thereof. The solid cleaning composition
can
include about 10 to about 80 wt-% binding agent or about 1 to about 40 wt-%
binding agent, and sufficient water to provide hydration for solidification.
In an embodiment, the binding agent is formed by mixing alkali metal
carbonate, alkali metal bicarbonate, and water. The alkali metal carbonate can
be or
include soda ash (i.e., sodium carbonate). The alkali metal bicarbonate can be
or
include sodium bicarbonate. The alkali metal bicarbonate component can be
provided by adding alkali metal bicarbonate or by forming alkali metal
bicarbonate
in situ. The alkali metal bicarbonate can be formed in situ by reacting the
alkali
metal carbonate with an acid. The amounts of alkali metal carbonate, alkali
metal
bicarbonate, and water can be adjusted to control the rate of solidification
of the
detergent composition and to control the pH of aqueous detergent composition
obtained from the solid cleaning composition. The rate of solidification of
the
detergent composition can be increased by increasing the ratio of alkali metal
bicarbonate to alkali metal carbonate, or decreased by decreasing the ratio of
alkali
metal bicarbonate to alkali metal carbonate.
In certain embodiments, the solid cleaning composition contains about 10 to
about 80 wt-% alkali metal carbonate or about 1 wt-% to about 40 wt-% alkali
metal
bicarbonate and sufficient water to provide at least a monohydrate of
carbonate and a
monohydrate of bicarbonate.
In other embodiments, binding agent includes alkaline carbonate, water, and
a sequestering agent. For example, the composition can include an alkali metal
salt
18
CA 02699537 2014-03-06
WO 2008/137853
PCIYUS2008/062667
of an organophosphonate at about 1 to about 30 wt-%, e.g., about 3 to about 15
wt-%
of a potassium salt; water at about 5 to about 15 wt-%, e.g., about 5 to about
12 wt-
%; and alkali metal carbonate at about 25 to about 80 wt-%, e.g., about 30 to
about
55 wt-%. For example, the composition can include an alkali metal salt of an
aminocarboxylate at about Ito about 30 wt-%, e.g., about 3 to about 20 wt-% of
a
potassium salt; water at about 5 to about 15 wt-%, e.g,., about 5 to about 12
wt-%;
and alkali metal carbonate at about 25 to about 80 wt-%, e.g., about 30 to
about 55
wt-%, A single E-form hydrate binder forms as this material solidifies. The
solid
detergent includes a major proportion of carbonate monohydrate, a portion of
non-
hydrated (substantially anhydrous) 011rali metal carbonate and the E-form
binder
including a fraction of the carbonate material, an amount of the
organophosphonate
and water of hydration.
The present invention relates to a solid composition including a binding
agent (e.g. the E-form binding agent), a source of alkalinity in addition to
the binding
agent, and additional cleaning agents. The E-form binding agent includes
sequestrant and source of alkalinity with advantageous stability. It is
described in
U.S. Patents including 6,177,392; 6,150,324,6,156,715, 6,258,765.
In an embodiment, the solid cleaning composition includes sodium carbonate
(Na2CO3), sodium hydroxide (NaOH), sodium metasilicate, amino carboxylate, or
a
mixture thereof for solidification of the solid composition. The composition
can
include, for example, about 10 to 80 wt-% of sodium carbonate, sodium
hydroxide,
sodium metasilicate, aminocarboxylate, or a mixture thereof. The solid
cleaning
composition can also include an amount of an organic phoaphonate sequestrant
effective to aid solidification. The phosphonate can be a potassium salt. The
solid
cleaning composition can include about 10 to about 40 wt-% sodium carbonate or
about 20 to about 40 wt-% sodium carbonate. In an embodiment, the solid
cleaning
composition can include about 20 to about 40 wt-% sodium carbonate and about
15
to about 40 wt-% sodium hydroxide.
In some embodiments, the solid cleaning composition includes a substantial
portion of sodium hydroxide. The resulting solid can include a matrix of
hydrated
solid sodium hydroxide with the detergent ingredients in the hydrated matrix.
In
such a caustic solid, or in other hydrated solids, the hydrated chemicals are
reacted
19
CA 02699537 2014-03-06
WO 2008/137853
PCT/US2008/062667
with water and the hydration reaction can be run to substantial completion.
The
sodium hydroxide also provides substantial cleaning in warewashing systems and
in
other use loci that require rapid and complete soil removal. Certain
embodiments
contain at least about 30 wt-% of an alkali metal hydroxide in combination
with
water of hydration. For example, the composition can contain about 30 to about
50
wt-% of an alkali metal hydroxide.
The following patents disclose various combinations of solidification,
binding and/or hardening agents that can be utilized in the solid cleaning
compositions of the present invention:
7,153,820; 7,094,746; 7,087,569;7,037,886; 6,831,054;
6,730,653; 6,660,707; 6,653,266; 6,583,094; 6,410,495; 6,258,765; 6,177,392;
6,156,715; 5,858,299; 5,316,688; 5,234,615; 5,198,198; 5,078,301; 4,595,520;
4,680,134; RE32,763; and RE32818.
In other embodiments, binding agent includes a sequestering agent and,
optionally, carbonate. For example, the composition can include an alkali
metal salt
of an organophosphonate at about Ito about 30 wt-%, e.g., about 3 to about 15
wt-%
of a potassium salt.
For example, the composition can include an alkali metal salt of an
aminocarboxylate at about 1 to about 30 wt-%, e.g., about 3 to about 20 wt-%
of a
pOtassiinn salt. For example, the composition can include an alkali metal salt
of
carboxylic acid at about Ito about 30 wt-%, e.g., about 3 to about 20 wt-% of
a
potassium salt. Suitable carboxylic acid salts include citrate and other
carboxylates
with 2 or 3 carboxyl groups. In an embodiment, the carboxylate salt can be
acetate.
These compositions can also include, for example, water at about 5 to about 15
wt-
%, e.g., about 5 to about 12 wt-%; and alkali metal carbonate at about 2$ to
about 80
wt-%, e.g., about 30 to about 55 wt-%.
In an embodiment, the binding agent is inorganic and can be a source of
alkalinity. Additional examples of such inorganic alkaline binding agents
include
hipolyphosphate hexahydmteõ orthosilicate (e.g., sodium orthosilicate), or
mixture
thereof. The solid cleaning composition can include about 10 to about 80 wt-%
binding agent or about 1 to about 40 wt-% binding agent, and sufficient water
to
provide hydration for solidification.
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
The composition can include two binding agents, a primary binding agent
and a secondary binding agent. The term "primary binding agent" refers to the
binding agent that is the primary source for causing the solidification of the
detergent
composition. The term "secondary binding agent" refers to the binding agent
that
acts as an auxiliary binding agent in combination with another primary binding
agent. The secondary binding agent can, for example, enhance or accelerate
solidification of the composition.
Embodiments of Carboxvlate/Sulfonate Co- and Ter-Polymer Containing Binding
Agents
An embodiment of the present invention is a binding agent that includes a
carboxylate/sulfonate co- or ter-polymer, alkalinity source (e.g., a carbonate
salt),
and water. Suitable carboxylate/sulfonate co- and ter-polymers include a
carboxylate/sulfonate copolymer of molecular weight of about 11,000, such as
copolymers of (meth)acrylate and 2-a.crylamido-2-methyl propane sulfonic acid
(AMPS) and a terpolymer including (meth)acrylate, AMPS and a vinyl ester,
vinyl
acetate or alkyl substituted acrylamide having a molecular weight of about
4,500 to
about 5,500. In an embodiment, the detergent composition includes about 1 to
about
15 wt-% carboxylate/sulfonate co- or ter-polymer, about 2 to about 50% water,
less
than about 40% builder, about 20 to about 70 wt-% alkalinity source (e.g., a
carbonate salt), and about 0.5 to about 10 wt-% surfactant.
The binding agent can include a carboxylate/sulfonate co- or ter-polymer,
alkalinity source (e.g., a carbonate salt, such as sodium carbonate (soda
ash)), and
water for forming solid compositions. Suitable component concentrations for
the
binding agent range include about 1 to about 15 wt-% of carboxylate/sulfonate
co- or
ter-polymer, about 2 to about 20 wt-% water, and about 20 to about 70 wt-%
alkalinity source (e.g., a carbonate salt). Suitable component concentrations
for the
binding agent include about 2 to about 13 wt-% carboxylate/sulfonate co- or
ter-
polymer, about 2 to about 40 wt-% water, and about 25 to about 65 wt-%
alkalinity
source (e.g., a carbonate salt). Additional suitable component concentrations
for the
binding agent range from about 6 about 13 wt-% carboxylate/sulfonate co- or
ter-
polymer, about 2 to about 20 wt-% water, and about 45 to about 65 wt-%
alkalinity
source (e.g., a carbonate salt).
21
CA 02699537 2014-03-06
WO 2008/137853
PCT/US2008/062667
Examples of suitable polycarboxylic acid polymer include
carboxylate/sulfonate co- and ter-polymers including (meth)acrylic acid units
and
acrylaruido alkyl or aryl sulfonate units. The terpolymer can also include one
or
more units that is a vinyl ester, a vinyl acetate, or substituted acrylamide,
Suitable
copolymers include (meth)acrylic acid and AMPS in at about 50 wt-% each and
with
a molecular weight of about 11,000.
Suitable terpolymers can include about 10 to about 84 wt-% (meth)acrylic
acid units, greater than 11 to about 40 wt-% acrylamido alkyl or aryl
sulfonate units,
and about 5 to about 50 wt-% of one or more units that is a vinyl ester, vinyl
acetate,
or substituted acrylamide and with an average molecular weight of about 3000
to
about 25,000, about 4000 to about 8000, or, preferably, about 4,500 to about
5,500.
Suitable (meth)acrylic acids and salts include acrylic acid, methacrylic acid
and
sodium salts thereof. Suitable vinyl dicarboxylic acids and anhydrides thereof
such
as for example maleic acid, fiunaric acid, itaconic acid and their anhydrides,
may
also be used in place of all, or part of, the (meth)acrylic acid and salt
component. 2-
acrylamido-2-methyl propane sulfonic acid (AMPS) is the preferred substituted
acrylamido sulfonate. Hindered amines such as t-butyl acrylamide, t-octyl
acrylamide and dimethylacrylamide are the preferred (alkyl) substituted
acrylamides.
Suitable vinyl esters include ethyl acrylate, hydroxy ethyl methacryl ate
hydroxy
propyl acrylate and cellosolve acrylate, A suitable terpolymer contains about
57 wt-
% (raeth)acrylic acid or salt units, about 23 wt-% AMPS, and about 20 wt-% of
a
vinyl ester, vinyl acetate or alkyl substituted acrylamide, and an average
molecular
weight of about 4500 to about 5500. Suitable terpolymers are described in U.S.
Patent No. 4,711,725.
A suitable commercially available carboxylate/sulfonate copolymer is
Acume72100, available from Rohm & Haas LLC, Philadelphia, PA. A suitable
commercially available carboxylate/sulfonate terpolymer is Acumer 3100,
available
from RoInn & Haas LLC, Philadelphia, PA.
Embodiments of Carboxylate Containing Binding Agents
In the solid of the present invention, the binding agent can include a salt of
straight chain saturated mono-, di-, and tri - carboxylic acid. In an
embodiment, the
binding ascot includes a straight chain saturated carboxylic acid salt,
alkalinity
22
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
source (e.g., a carbonate salt), and water. The straight chain saturated
carboxylic
acid salt can be a salt of a mono-, di-, or tri- carboxylic acid.
The binding agent can include a straight chain saturated mono-, di-, or tri-
carboxylic acid salt, sodium carbonate (soda ash), and water for forming solid
compositions. Suitable component concentrations for the binding agent range
from
about 1% and about 15 wt-% of a saturated straight chain saturated mono-, di-,
or tri-
carboxylic acid salt, about 2% and about 20 wt-% water, and about 20% and
about
70 wt-% sodium carbonate. Suitable component concentrations for the binding
agent range from about 1% and about 12% of a salt of a saturated straight
chain
saturated mono-, di-, or tri- carboxylic acid, about 5% and about 40 wt-%
water, and
about 45% and about 65 wt-% sodium carbonate. Additional suitable component
concentrations for the binding agent range from about 1% and about 10% of a
salt of
a saturated straight chain saturated mono-, di-, or tri- carboxylic acid,
about 5% and
about 20 wt-% water, and about 50% and about 60 wt-% sodium carbonate.
Examples of suitable salts of straight chain saturated monocarboxylic acids
include salts of acetic acid and salts of gluconic acid. Examples of suitable
salts of
straight chain saturated dicarboxylic acids include: salts of tartaric acid,
salts of
malic acid, salts of succinic acid, salts of glutaric acid, and salts of
adipic acid. An
example of a suitable salt of a straight chain saturated tricarboxylic acid is
a salt of
citric acid.
In an embodiment, the solid detergent composition can include a salt of a
straight chain saturated mono-, di-, or tri- carboxylic acid, water, builder,
alkalinity
source (e.g., a carbonate salt), and surfactant. In an embodiment, the solid
detergent
composition includes about 1 to about 15 wt-% straight chain saturated mono-,
di-,
or tri- carboxylic acid salt or about 1 to about 10 wt-% straight chain
saturated
mono-, di-, or tri- carboxylic acid salt. In an embodiment, the solid
detergent
composition includes about 2 to about 20 wt-% water or about 5 to about 40 wt-
%
water. In an embodiment, the solid detergent composition includes less than
about
40 wt-% builder or less than about 30 wt-% builder. In an embodiment, the
solid
detergent composition includes about 20 to about 70% sodium carbonate or about
45
to about 65 wt-% sodium carbonate. In an embodiment, the solid detergent
composition includes about 0.5 to about 10 wt-% surfactant or about 1 to about
5 wt-
% surfactant.
23
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
Embodiments of Aminocarboxvlate Containing Binding Agents
An embodiment of the present invention is a binding agent that includes a
biodegradable aminocarboxylate, alkalinity source (e.g., a carbonate salt),
and water.
The biodegradable aminocarboxylate, alkalinity source (e.g., a carbonate
salt), and
water interact to form a hydrate solid. Another embodiment of the present
invention
is a detergent composition that includes a biodegradable aminocarboxylate,
water,
builder, alkalinity source (e.g., a carbonate salt), and a surfactant. The
detergent
composition can include about 2 to about 20% biodegradable aminocarboxylate,
about 2 to about 20 wt-% water, less than about 40 wt-% builder, about 20 to
about
70 wt-% alkalinity source (e.g., a carbonate salt), and about 0.5 to about 10
wt-%
surfactant.
The binding agent can include an aminocarboxylate, alkalinity source (e.g., a
carbonate salt, such as sodium carbonate (soda ash)), and water for forming
solid
compositions. Suitable component concentrations for the binding agent range
from
about 1 to about 20 wt-% of an aminocarboxylate, about 2 to about 20 wt-%
water,
and about 20 to about 70 wt-% alkalinity source (e.g., a carbonate salt).
Suitable
component concentrations for the binding agent include about 2 to about 18 wt-
%
aminocarboxylate, about 2 to about 40 wt-% water, and about 25 about 65 wt-%
alkalinity source (e.g., a carbonate salt). Additional suitable component
concentrations for the binding agent include about 3 about 16 wt-%
aminocarboxylate, about 2 about 20 wt-% water, and about 45 about 65 wt-%
alkalinity source (e.g., a carbonate salt).
Examples of suitable aminocarboxylates include biodegradable
aminocarboxylates. Examples of suitable biodegradable aminocarboxylates
include:
ethanoldiglycine, e.g., an alkali metal salt of ethanoldiglycine, such at
disodium
ethanoldiglycine (Na2EDG);
methylgylcinediacetic acid, e.g., an alkali metal salt of
methylgylcinediacetic acid,
such as trisodium methylgylcinediacetic acid;
iminodisuccinic acid, e.g., an alkali metal salt of iminodisuccinic acid, such
as
iminodisuccinic acid sodium salt;
N,N-bis (carboxylatomethyl)-L-glutamic acid (GLDA), e.g., an alkali metal salt
of
N,N-bis (carboxylatomethyl)-L-glutamic acid, such as iminodisuccinic acid
sodium
salt (GLDA-Nas);
24
CA 02699537 2014-03-06
WO 2008/137853 PCT/US2008/062667
(S-S]-ethylertediaminedisuceinic acid (EDDS), e.g., an alkali metal salt of [S-
SJ-
ethylenedituninedisuccinie acid, such as a sodium salt of ES-S1-
ethylenediaminedisuccinic acid;
3-hydroxy-2,2'-iminodisuccinic acid (BIDS), e.g., an alkali metal salt of 3-
hydroxy-
2,2'-iminodisuccinic acid, such as tetrasodiurn 3-hydroxy-2,2'-
iminodisuccinate.
Examples of suitable commercially available biodegradable aminocarboxylates
include, but are not limited to: VersenAIBIDA (52%), available from Dow
Chemical, Midland, MI; TriloiiiM (40% MGDA), available from BASF Corporation,
Charlotte, NC; IDS, available from Lanxess, Leverkusen, Germany, Dissolvine GL-
38 (38%), available from Akin Nobel, Tarrytown, NJ; Octaquest (37%), available
from; and RIDS (50%), available from hmospee Performance Chemicals (Octal
Performance Chemicals), Edison, NJ.
Embodiments of Polycarboxylate Containing Binding Agents
An embodiment of the present invention is a binding agent that includes a
polycarboxylic acid polymer, alkalinity source (e.g., a carbonate salt), and
water.
Suitable polycarboxylic acid polymers include a polyacrylic acid polymer
having a
molecular weight of about 1,000 to about 100,000, a modified polyacrylic acid
polymer having a molecular weight of about 1,000 to about 100,000, or a
polymaleic
acid polymer having a molecular weight of about 500 to about 5,000. In an
embodiment, the detergent composition includes about 1 to about 15 wt-%
polycarboxylic acid polymer, about 2 to about 50% water, less than about 40%
builder, about 20 to about 70 wt-% alkalinity source (e.g., a carbonate salt),
and
about 0.5 to about 10 wt-% surfactant.
The binding agent can include a polycarboxylic acid polymer, alkalinity
Source (e.g., a carbonate salt, such as sodium carbonate (soda ash)), and
water for
forming solid compositions. Suitable component concentrations for the binding
agent range include about 1 to about 15 wt-% of polycarboxylic acid polymer,
about
2 to about 20 wt-% water, and about 20 to about 70 wt-% alkalinity source
(e.g., a
carbonate salt). Suitable component concentrations for the binding agent
include
about 2 to about 12 wt-% polycarboxylic acid polymer, about 2 to about 40 wt-%
water, and about 25 to about 65 wt-% alkalinity source (e.g., a carbonate
salt).
Additional suitable component concentrations for the binding agent range front
CA 02699537 2014-03-06
WO 2008/137853 PCT/US2008/062667
about 5 about 10 wt-% polycarboxylic acid polymer, about 2 to about 20 wt-%
water, and about 45 to about 65 wt-% alkalinity source (e.g., a carbonate
salt).
Examples of an suitable polycarboxyfic acid polymer include: polyacrylic
acid polymers, polyacrylic acid polymers modified by a fatty acid end group
("modified polyacrylic acid polymers"), and polyntaleic acid polymers.
Examples of
suitable polyacrylic acid polymers and modified polyacrylic acid polymers
include
those having a molecular weight of about 1,000 to about 100,000. Examples of
suitable polymaleic acid polymers include those having a molecular weight of
about
500 to about 5,000. A suitable commercially available polyacrylic acid
polymers is
Acusor445N, available from Rohm & Haas LLC, Philadelphia, PA. An example of
-
suitable commercially available modified polyacrylic acid polymer is
AlcosperseTM
325, available from Alco Chemical, Chattanooga, TN. Examples of suitable
commercially available polymaleic acid polymers include: BelclenTe'1200,
available
from Houghton Chemical Corporation, Boston, MA and AquatreaVAR-801,
available from Alco Chemical, Chattanooga, TN.
Embodiments of Inulin Containing Binding Agents
The solid cleaning composition according to the present invention can
include an effective amount of one or more binding agents which contain no
phosphorus or aminocarboxylate-based compounds. A suitable binding agent
includes inulin. Inulins are naturally-occurring oligosaccharides. Inulins are
chlorine-compatible and biodegradable. A representative structure is presented
below.
26
CA 02699537 2014-03-06
WO 2008/137853 PCT/US2008/062667
HO
HO
r---1OH OH
0
HO
6,, OH
OH
OH
HO \
HO N 0
OH-'*() H9AA
I OH
innomorr
OH
Intilins for use as binding agents include derivatized inulins. Derivatized
inulins are modified to be further substituted at a varying number of the
available
hydroxyls, with alkyl, alkoxy, carboxy, and carboxy alkyl moieties, for
example.
Typically, suitable inulin binding agents have molecular weights >1000.
Often, suitable inulin binding agents have molecular weights >2000. An example
of
a suitable inulin binding agent is carboxymethyl jail& available from. Solutia
Inc.
Ttvi
under the tradename DEQUEST. DEQUBST PB 11625 is a 20% solution of
carboxymethyl inulin, sodium salt, having a MW >2000.
In general, an effective amount of binding agents is considered an amount
that enables solidification oldie warewashing composition. An suitable
effective
amount of binding agent is in a range of 5 to 15% by weight of the warewashing
composition. The binding agent is initially provided into the warewashing
composition in a hydrated form. Typically, the hydrated binding agent is
prepared in
an aqueous solution for use in the warewashing composition.
Possible Mechanism
Although not limiting to the present invention, it is believed that the actual
solidification mechanism of the binding agent occurs through ash hydration, or
the
interaction of the sodium carbonate with water. The straight chain saturated
mono-,
27
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
di-, or tri- carboxylic acid salt, the aminocarboxylate, or the
polycarboxylate can be
considered a solidification modifier. The solidification modifier can control
the
kinetics and thermodynamics of the solidification process and provide a
binding
agent in which additional functional materials may be bound to form a
functional
solid composition. The solidification modifier may stabilize the carbonate
hydrates
and the functional solid composition by acting as a donor and/or acceptor of
free
water. By controlling the rate of water migration for hydration of the ash,
the
solidification modifier may control the rate of solidification to provide
process and
dimensional stability to the resulting product. The rate of solidification is
significant
because if the binding agent solidifies too quickly, the composition may
solidify
during mixing and stop processing. If the binding agent solidifies too slowly,
valuable process time is lost.
The solidification modifier can also provide dimensional stability to the end
product by ensuring that the solid product does not swell. If the solid
product swells
after solidification, various problems may occur, including but not limited
to:
decreased density, integrity, and appearance; and inability to dispense or
package the
solid product. A solid product is considered to have dimensional stability if
the solid
product has a growth exponent of less than about 3%, less than about 2%, and
more
less than about 1.5%.
The solidification modifier can be combined with water prior to
incorporation into the solid composition and can be provided as a solid
hydrate or as
a solid salt that is solvated in an aqueous solution, e.g., in a liquid
premix. In an
embodiment, the solidification modifier is in a water matrix when added to the
detergent composition for the detergent composition to effectively solidify.
In
general, an effective amount of solidification modifier considered an amount
that
effectively controls the kinetics and thermodynamics of the solidification
system,
which can occur through controlling the rate and movement of water.
The binding agent and resulting solid detergent composition may also
exclude phosphorus or nitilotriacetic acid (NTA) containing compounds, to make
the solid detergent composition more environmentally acceptable. Phosphorus-
free
refers to a composition, mixture, or ingredients to which phosphorus-
containing
compounds are not added. Should phosphorus-containing compounds be present
through contamination of a phosphorus-free composition, mixture, or
ingredient, the
28
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
level of phosphorus-containing compounds in the resulting composition is less
than
about 0.5 wt %, less than about 0.1 wt%, and often less than about 0.01 wt %.
NTA-
free refers to a composition, mixture, or ingredients to which NTA-containing
compounds are not added. Should NTA-containing compounds be present through
contamination of an NTA-free composition, mixture, or ingredient, the level of
NTA
in the resulting composition shall be less than about 0.5 wt %, less than
about 0.1
wt%, and often less than about 0.01 wt %. When the binding agent is NTA-free,
the
binding agent and resulting solid detergent composition is also compatible
with
chlorine, which functions as an anti-redeposition and stain-removal agent.
E-Form Solids
In an aspect, E-form binding agent can be part of a solidified mixture of
organic sequestrant including a phosphonate, an aminocarboxylic acid, or
mixtures
thereof; a carbonate or other source of alkalinity, and water. At least a
portion of the
components of the mixture, including organic sequestrant, alkalinity source,
and
water, during solidification, complex to form at least a portion of a binding
agent.
As the mixture solidifies, the binding agent forms to bind and solidify the
components of the mixture. The solidified mixture can optionally include
additional
functional materials, and the additional functional materials are bound within
the
solidified mixture by the formation of the binding agent.
Formation of the binder can increase the stability of the source of alkalinity
and water. In certain embodiments, the stabilized source of alkalinity within
the
solidified mixture has a higher decomposition temperature than the source of
alkalinity would have when it is not within the solidified mixture. In certain
embodiments, the solidified composition has a melting transition temperature
in the
range of 120 C to 160 C. However, other embodiments may have a melting
transition temperature outside of this range.
Some embodiments of the cleaning composition include one or more sources
of alkalinity. The source of alkalinity can be an alkali metal salt, which can
enhance
cleaning of a substrate or improve soil removal performance of the
composition.
Additionally, in some embodiments the alkali metal salts can provide for the
formation of an additional binder complex or binding agent including: alkali
metal
salt; organic sequestrant including a phosphonate, an axninocarboxylic acid,
or
29
CA 02 699537 2014-03-06
WO 2008/137853 PCT1US2008/062667
mixtures thereof; and water. We refer to such binder complexes as "E-Form"
hydrates. Such E-Form hydrates are discussed in detail in the following U.S.
Patents
and Patent Applications: U.S. Patent Nos. 6,177,392 B1; 6,150,324; and
6,156,715;
and 6,258,765. The binding agent
can include the organic sequestrant and the source of alkalinity. For example,
the
binding agent can have a melting transition temperature in the range of about
120 C
to 160 C.
Some examples of alkali metal salts include alkali metal carbonates,
silicates,
phosphonates, arninocarboxylates, sulfates, borates, or the like, and mixtures
thereof.
Suitable alkali metal salts include alkali metal carbonates, such as sodium or
potassium carbonate, bicarbonate, sesquicarbomde, mixtures thereof, and the
like;
for example, sodium carbonate, potassium carbonate, or mixtures thereof. The
composition can include in the range of 0 to about 80 wt-%, about 15 to about
70 wt-
% of an alkali metal salt, for example, about 20 to about 60 wt-%.
The basic ingredients in the solid composition, and the ranges of molecular
equivalents, are shown in the following Table 1:
Table 1: Composition Mole Ratios of Base Materials (based on composition
total weight)
Range of Molar Equivalents in the Composition
Component
Organic Sequestrant 1 mole per moles 1 mole per moles 1 mole per moles
of sotute of of source of of source of
(Phosphonate or
alkalinity and alkalinity and alkalinity and
arninocarboxylate
water as listed water as listed water as listed
or mixture thereof)
below , below below
10 or less moles
per mole of
8 or less moles,
20 or less moles organic
e.g., 7 or less
e
per mole of sequestrant, .g,.,
Source of Alkalinity moles per mole of
organic about 3 to about
sequestrant 10 moles per organic
sequestrant
mole of organic
sequestrant
Water 50 or less moles 20 or less moles 5 to 15
moles per
per mole of per mole of mole of organic
organic organic sequestrant
sequestrant sequestrant
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
The weight percent of the components will vary, depending upon the
particular compounds used, due to the differences in molecular weight of
various
usable components.
Source of Alkalinity
The solid cleaning composition according to the invention includes an
effective amount of one or more alkaline sources to enhance cleaning of a
substrate
and improve soil removal performance of the composition. In general, an
effective
amount of one or more alkaline sources should be considered as an amount that
provides a use composition having a pH of at least about 8. When the use
composition has a pH of between about 8 and about 10, it can be considered
mildly
alkaline, and when the pH is greater than about 12, the use composition can be
considered caustic. In general, it is desirable to provide the use composition
as a
mildly alkaline cleaning composition because it is considered to be more safe
than
the caustic based use compositions.
The solid cleaning composition can include an alkali metal carbonate and/or
an alkali metal hydroxide. Suitable metal carbonates that can be used include,
for
example, sodium or potassium carbonate, bicarbonate, sesquicarbonate, mixtures
thereof. Suitable alkali metal hydroxides that can be used include, for
example,
sodium, lithium, or potassium hydroxide. An alkali metal hydroxide can be
added to
the composition in the form of solid beads, dissolved in an aqueous solution,
or a
combination thereof. Alkali metal hydroxides are commercially available as a
solid
in the form of prilled solids or beads having a mix of particle sizes ranging
from
about 12-100 U.S. mesh, or as an aqueous solution, as for example, as a 50 wt-
%
and a 73 wt-% solution.
The solid cleaning composition can include a sufficient amount of the
alkaline source to provide the use composition with a pH of at least about 8.
The
source of alkalinity is preferably in an amount to enhance the cleaning of a
substrate
and improve soil removal performance of the composition. In general, it is
expected
that the concentrate will include the alkaline source in an amount of at least
about 5
wt-%, at least about 10 wt-%, or at least about 15 wt-%. The solid cleaning
composition can include between about 10 wt-% and about 80 wt-%, preferably
between about 15 wt-% and about 70 wt-%, and even more preferably between
about
31
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
20 wt-% and about 60 wt-% of the source of alkalinity. The source of
alkalinity can
additionally be provided in an amount to neutralize the anionic surfactant and
can be
used to assist in the solidification of the composition.
In order to provide sufficient room for other components in the concentrate,
the alkaline source can be provided in the concentrate in an amount of less
than
about 60 wt-%. In addition, the alkaline source can be provided at a level of
less
than about 40 wt-%, less than about 30 wt-%, or less than about 20 wt-%. In
certain
embodiments, it is expected that the solid cleaning composition can provide a
use
composition that is useful at pH levels below about 8. In such compositions,
an
alkaline source can be omitted, and additional pH adjusting agents can be used
to
provide the use composition with the desired pH. Accordingly, it should be
understood that the source of alkalinity can be characterized as an optional
component.
For compositions including carboxylate as a component of the binding agent,
the solid cleaning composition can include about 75 wt-%, less than about 60
wt-%,
less than about 40 wt-%, less than about 30 wt-%, or less than about 20 wt-%.
The
alkalinity source may constitute about 0.1 to about 90 wt-%, about 0.5 to
about 80
wt-%, or about 1 to about 60 wt-% of the total weight of the solid detergent
composition.
Secondary Alkalinity Sources
An E-Form solid of the present invention can include effective amounts of
one or more inorganic detergents or alkaline sources to enhance cleaning of a
substrate and improve soil removal performance of the composition. As
discussed
above, in embodiments including an alkali metal salt, such as alkali metal
carbonate,
the alkali metal salt can act as an alkalinity source. The composition may
include a
secondary alkaline source separate from the source of alkalinity, and that
secondary
source can include about 0 to 75 wt-%, about 0.1 to 70 wt-% of, 1 to 25 wt-%,
or
about 20 to 60 wt-%, or 30 to 70 wt-% of the total composition.
Additional alkalinity sources can include, for example, inorganic alkalinity
sources, such as an alkali metal hydroxide or silicate, or the like. Suitable
alkali
metal hydroxides include, for example, sodium or potassium hydroxide. An
alkali
metal hydroxide may be added to the composition in a variety of forms,
including for
32
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
example in the form of solid beads, dissolved in an aqueous solution, or a
combination thereof. Alkali metal hydroxides are commercially available as a
solid
in the form of prilled solids or beads having a mix of particle sizes ranging
from
about 12-100 U.S. mesh, or as an aqueous solution, as for example, as a 50 wt-
%
and a 73 wt-% solution.
Examples of useful alkaline metal silicates include sodium or potassium
silicate (with a M20:Si02 ratio of 1:2.4 to 5:1, M representing an alkali
metal) or
metasificate.
Other sources of alkalinity include a metal borate such as sodium or
potassium borate, and the like; ethanolamines and amines; and other like
alkaline
sources.
Organic Sequestrant
Suitable organic sequestrant includes organic phosphonate, aminocarboxylic
acid, or mixtures thereof.
Organic Phosphonate
Appropriate organic phosphonates include those that are suitable for use in
forming the solidified composition with the source of alkalinity and water.
Organic
phosphonates include organic-phosphonic acids, and alkali metal salts thereof.
Some examples of suitable organic phosphonates include:
1-hydroxyethane-1,1-diphosphonic acid: CH3C(OH)[130(OH)2]2;
aminotri(methylenephosphonic acid): N[CH2P0(011)2]3;
aminotri(methylenephosphonate), sodium salt
Na+
POCH2N[CH2P0(0Na)2]2
2-hydroxyethyliminobis(methylenephosphonic acid): HOCH2CH2N[CH2P0(OH)2]2;
diethylenetriaminepenta(methylenephosphonic acid):
(H0)2POCH2N[CH2CH2N[CH2P0(OH)2]212;
diethylenetriaminepenta(methylenephosphonate), sodium salt: C9H(28-
x)1131=Tax0i5P5
(x=7); hexamethylenediamine(tetramethylenephosphonate), potassium salt: C10l-
1(28-
x)N2Kx004 (x=6);
33
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
bis(hexamethylene)triamine(pentamethylenephosphonic acid):
(H02)POCH2NRCH2)61sTECH2P0(0102M2; and
phosphorus acid H3P03; and other similar organic phosphonates, and mixtures
thereof.
These materials are well known sequestrants, but have not been reported as
components in a solidification complex material including an source of
alkalinity.
Suitable organic phosphonate combinations include ATMP and DTPMP. 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
suitable.
Aminocarboxylic Acid
The organic sequestrant can also include aminocarboxylic acid type
sequestrant. Appropriate aminocarboxylic acid type sequestrants include those
that
are suitable for use in forming the solidified composition with the source of
alkalinity and water. Aminocarboxylic acid type sequestrant can include the
acids,
or alkali metal salts thereof. Some examples of aminocarboxylic acid materials
include amino acetates and salts thereof. Some examples include the following:
N-hydroxyethylaminodiacetic acid;
hydroxyethylenediaminetetraacetic acid, nitrilotriacetic acid (NTA);
ethylenediaminetetraacetic acid (EDTA);
N-hydroxyethyl-ethylenediarninetriacetic acid (HEDTA);
diethylenetriaminepentaacetic acid (DTPA); and
alanine-N,N-diacetic acid;
and the like; and mixtures thereof.
In an embodiment, the organic sequestrant includes a mixture or blend
including two or more organophosphonate compounds, or including two or more
aminoacetate compounds, or including at least one organophosphonate and an
aminoacetate compound.
Useful aminocarboxylic acids include, for example,
n-hydroxyethyliminodiacetic acid, nitrilotriacetic acid (NTA),
34
CA 02699537 2014-03-06
WO 2008/137853
PCT/1JS2008/062667
ethylenediaminetetraacetic acid (EDTA), N-hydroxyethyl-ethylenediaminetriacdic
acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), and the Wm.
Useful aminocarboxylic acid materials containing little or no NTA and no
phosphorus include: N-hydroxyethylaminodiacetic acid,
ethylenediaminetetraae.etic
acid (EDTA), hydroxyethylenediaminetetntacelic acid,
diethylenetriaminepenta.acetic
acid, N-hydroxyethyl-ethylenediarninetriacetic acid (HEDTA),
diethylenetriaminepentaacetic acid (DTPA), and other similar acids having an
amino
group with a carboxylic acid substituent.
Examples of suitable biodegradable aminocarboxylates include:
ethanoldiglycine, e.g., an alkali metal salt of ethanoldiglycine, such at
disoditun
ethanoldiglycine (NazEDG);
methylgylcinediacetic acid, e.g., an alkali metal salt of
methylgylcinediacetic acid,
such as trisodium rnethylikylcinediacetic acid;
iminodisuccinic acid, e.&, an alkali metal salt of iminodisuccinic acid, such
as
iminodisuccinic acid sodium salt;
NN-bis (carboxylatomethyl.)-L-glutamic acid (GLDA), e.g., an alkali metal salt
of
N,N-bis (carboxylatomethyl)-L-glutamic acid, such as iminodisuccinic acid
sodium
salt (GLDA-Nas);
[S-S]-ethylenediaminedisuccinic acid (EDDS), e.g., an alkali metal salt of [S-
SJ-
ethylenediaminedisuccinic acid, such as a sodium salt of [S-Si-
ethylenediaminedisuccinic acid;
3-hydroxy-2,2'-iminodisuccinic acid (BIDS), e.g., an alkali metal salt of 3-
hydroxy-
2,2'-imiuodisucµinic acid, such as tetrasodium 3-hydroxy-2,2'-
iminodisuccinate.
Examples of suitable commercially available biodegradable aminocarboxylates
include: Versene HEEDA (52%), available from Dow Chemical, Midland, MI; Triton
M (40% MGDA), available from BASF Corporation, Charlotte, NC; IDS, available
from Lanxess, Leverkusen, Germany; DissolvinTGL-38 (38%), available from Alma
Nobel, Tarrytown, NJ; OctaquerZi(37%), available from; and HMS (50%),
available
from bmospec Performance Chemicals pad Performance Chemicals), Edison, NT.
Water
A solid cleaning composition can include water. Water can be independently
added to the detergent composition or can be provided in the composition as a
result
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
of its presence in an aqueous material that is added to the composition.
Typically,
water is introduced into the detergent composition to provide the detergent
composition with a desired flowability prior to solidification and to provide
a desired
rate of solidification.
In general, it is expected that water is present as a processing aid and can
be
removed or become water of hydration. It is expected that water can be present
in
the solid composition. In certain embodiments of the solid cleaning
composition,
water can be present at about 0 to about 10 wt-%, about 0.1 to about 10 wt-%,
about
2 to about 10 wt-%, about 1 to about 5 wt-%, or about 2 to about 3 wt-%. In
certain
embodiments of the solid cleaning composition, water can be present at about
25 to
about 40 wt-%, about 27 to about 20 wt-%, or about 29 wt-% to about 31 wt-%.
Water can be provided, for example, as deionized water or as softened water.
When preparing a carboxylate containing composition by pressing and/or
vibrating, water may be present at about 5 to about 25 wt-%, about 7 to about
20 wt-
%, or about 8 to about 15 wt-%.
Embodiments of the Present Compositions
Some examples of representative constituent concentrations for embodiments
of the present compositions can be found in Tables A and B, in which the
values are
given in wt-% of the ingredients in reference to the total composition weight.
In
certain embodiments, the proportions and amounts in Tables A and B can be
modified by "about".
= 36
CA 02699537 2010-03-09
WO 2008/137853 PCT/US2008/062667
Table A
Ingredient wt..% wt-04 wt..% m-0/.
Carbonate Salt 10-70 40-70 40-70 10-20
Bicarbonate Salt 3 3 3 --
(optional)
Sequestrant 1-80 5-80 5-50 1-4
Surfactant 0-5 4-5 4-5 --
Builder 0.5-45 0.5-25 3-35 40-50
Secondary 3-8 3-8 3-8 2-5
Alkalinity Source
Water 0-34 0-34 1-5
Sodium Hydroxide 0-40 -- 30-40
_
37
Table B
Ingredient Wt-% wt-% wt-% wt-% wt-% wt-% wt-%
Carbonate 53 40-60 50-60 9-40 46-53 0-10 66
(44
amino carboxylate (e.g.,
0-11 0-10 5-16 0-44 0-22 0-20
12 (44
biodegradable)
citrate 14-25 10-26 20 , 0-
2 0-35
Hydroxide salt 17-37 0-5
polymer polycarboxylate 1 1 1 0-2 0-1
5
Sulfonated polymer 6-13
0
phosphonate 5-13 5-12
(44
UJ
Cie
"A
= Water 8 0-25 0-10 0-3
0
secondary alkalinity 3 3 3 1-20 0-3 0-
0.5 4
0
0
tripolyphosphate 0-50 0-25
0
polyol 0-4
Surfactant 5 3-5 3-5 3.5-4.5 0-45
8
1-d
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
Additives
Solid cleaning compositions made according to the invention may further
include additional functional materials or additives that provide a beneficial
property, for example, to the composition in solid form or when dispersed or
dissolved in an aqueous solution, e.g., for a particular use. Examples of
conventional additives include one or more of each of salt, alkalinity source,
surfactant, detersive polymer, cleaning agent, rinse aid composition,
softener, pH
modifier, source of acidity, anti-corrosion agent, secondary hardening agent,
solubility modifier, detergent builder, detergent filler, defoamer, anti-
redeposition
agent, antimicrobial, rinse aid composition, threshold agent or system,
aesthetic
enhancing agent (i.e., dye, odorant, perfume), optical brightener, lubricant
composition, bleaching agent or additional bleaching agent, enzyme,
effervescent
agent, activator for the source of alkalinity, other such additives or
functional
ingredients, and the like, and mixtures thereof.
Adjuvants and other additive ingredients will vary according to the type of
composition being manufactured, and the intended end use of the composition.
In
certain embodiments, the composition includes as an additive one or more of
source
of alkalinity, surfactant, detergent builder, cleaning enzyme, detersive
polymer,
antimicrobial, activators for the source of alkalinity, or mixtures thereof.
Metal Protecting Silicate
We have found that an effective amount of an alkaline metal silicate or
hydrate thereof can be employed in the compositions and processes of the
invention
to form a stable solid warewashing detergent that can have metal protecting
capacity.
The silicates employed in the compositions of the invention are those that
have
conventionally been used in warewashing formulations. For example, typical
alkali
metal silicates are those powdered, particulate or granular silicates which
are either
anhydrous or preferably which contain water of hydration (5 to 25 wt%,
preferably
15 to 20 wt% water of hydration). These silicates can be sodium silicates and
have a
Na20:Si02 ratio of about 1:1 to about 1:5, respectively, and typically contain
available bound water in the amount of from 5 to about 25 wt%. In general, the
silicates of the present invention have a Na20:Si02 ratio of 1:1 to about
1:3.75,
preferably about 1:1.5 to about 1:3.75 and most preferably about 1:1.5 to
about
39
CA 02699537 2014-03-06
WO 2008/137853 PCT/US2008/062667
1:2.5. A silicate with a Na20:Si02 ratio of about 1:2 and about 16 to 22 wt%
water
of hydration is suitable.
For example, such silicates are available in powder form as GD Silicate and
TM
in granular form as Britesil H-20, from PQ Corporation. These ratios may be
obtained with single silicate compositions or combinations of silicates which
upon
combination result in the preferred ratio. The hydrated silicates at preferred
ratios, a
Na20:Si02 ratio of about 1:1.5 to about 1:2.5 have been found to provide the
optimum metal protection and rapidly forming solid block detergent. The amount
of
silicate used in forming the compositions of the invention tend to vary
between 10
and 30 wt%, preferably about 15 to 30 wt% depending on degree of hydration.
Hydrated silicates are preferred.
Suitable silicates for use in the present compositions include sodium
silicate,
anhydrous sodium metasilicate, and anhydrous sodium silicate.
Solid Matrix Composition
Ingredient wt-% wt-%
Alkali metal salt of an
1-30 3-15
Organo-Phosphonate
Water 5-15 5-12
Alkali metal silicate
(e.g., hydrated silicate, 12-25 15-30
5 to 25 % water)
Alkali Metal Carbonate 25-80 30-55
Surfactant 0 to 25 0.1-20
Salt
In some embodiments, salts, for example acidic salts, can be included as pH
modifiers, sources of acidity, effervescing aids, or other like uses. Some
examples
of salts for use in such applications include sodium bisulfate, sodium
acetate,
sodium bicarbonate, citric acid salts, and the like and mixtures thereof. The
composition can include in the range of 0.1 to 50 wt-% such material. It
should be
understood that agents other than salts that act as pH modifiers, sources of
acidity,
effervescing aids, or like, can also be used in conjunction with the
invention.
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
Active Oxygen Compounds
The active oxygen compound acts to provide a source of active oxygen, but
can also act to form at least a portion of the solidification or binding
agent. The
active oxygen compound can be inorganic or organic, and can be a mixture
thereof.
Some examples of active oxygen compound include peroxygen compounds, and
peroxygen compound adducts that are suitable for use in forming the binding
agent.
Many active oxygen compounds are peroxygen compounds. Any peroxygen
compound generally known and that can function, for example, as part of the
binding agent can be used. Examples of suitable peroxygen compounds include
inorganic and organic peroxygen compounds, or mixtures thereof.
Inorganic Active Oxygen Compound
Examples of inorganic active oxygen compounds include the following types
of compounds or sources of these compounds, or alkali metal salts including
these
types of compounds, or forming an adduct therewith:
hydrogen peroxide;
group 1 (IA) active oxygen compounds, for example lithium peroxide,
sodium peroxide, and the like;
group 2 (IIA) active oxygen compounds, for example magnesium peroxide,
calcium peroxide, strontium peroxide, barium peroxide, and the like;
group 12 (BB) active oxygen compounds, for example zinc peroxide, and the
like;
group 13 (MA) active oxygen compounds, for example boron compounds,
such as perborates, for example sodium perborate hexahydrate of the formula
Na2[Br2(02)2(OH)41 = 6H20 (also called sodium perborate tetrahydrate and
formerly
written as NaB03=4H20); sodium peroxyborate tetrahydrate of the formula
Na2Br2(02)2ROHM=4H20 (also called sodium perborate Iiihydrate, and formerly
written as NaB03=3H20); sodium peroxyborate of the formula Na2P32(02)2(01)41
(also called sodium perborate monohydrate and formerly written as NaB03=H20);
and the like; e.g., perborate;
group 14 (IVA) active oxygen compounds, for example persilicates and
peroxycarbonates, which are also called percarbonates, such as persilicates or
peroxycarbonates of alkali metals; and the like; e.g., percarbonate, e.g.,
persilicate;
41
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
group 15 (VA) active oxygen compounds, for example peroxynitrous acid
and its salts; peroxyphosphoric acids and their salts, for example,
perphosphates; and
the like; e.g., perphosphate;
group 16 (VIA) active oxygen compounds, for example peroxysulfuric acids
and their salts, such as peroxymonosulfuric and peroxydisulfuric acids, and
their
salts, such as persulfates, for example, sodium persulfate; and the like;
e.g.,
persulfate;
group Vila active oxygen compounds such as sodium periodate, potassium
perchlorate and the like.
Other active inorganic oxygen compounds can include transition metal
peroxides; and other such peroxygen compounds, and mixtures thereof.
In certain embodiments, the compositions and methods of the present
invention employ certain of the inorganic active oxygen compounds listed
above.
Suitable inorganic active oxygen compounds include hydrogen peroxide, hydrogen
peroxide adduct, group DIA active oxygen compounds, group VIA active oxygen
compound, group VA active oxygen compound, group VITA active oxygen
compound, or mixtures thereof. Examples of such inorganic active oxygen
compounds include percarbonate, perborate, persulfate, perphosphate,
persilicate, or
mixtures thereof. Hydrogen peroxide presents an example of an inorganic active
oxygen compound. Hydrogen peroxide can be formulated as a mixture of hydrogen
peroxide and water, e.g., as liquid hydrogen peroxide in an aqueous solution.
The
mixture of solution can include about 5 to about 40 wt-% hydrogen peroxide or
5 to
50 wt-% hydrogen peroxide.
In an embodiment, the inorganic active oxygen compounds include hydrogen
peroxide adduct. For example, the inorganic active oxygen compounds can
include
hydrogen peroxide, hydrogen peroxide adduct, or mixtures thereof. Any of a
variety
of hydrogen peroxide adducts are suitable for use in the present compositions
and
methods. For example, suitable hydrogen peroxide adducts include percarbonate
salt, urea peroxide, peracetyl borate, an adduct of H202 and polyvinyl
pyrrolidone,
sodium percarbonate, potassium percarbonate, mixtures thereof, or the like.
Suitable
hydrogen peroxide adducts include percarbonate salt, urea peroxide, peracetyl
borate, an adduct of H202 and polyvinyl pyrrolidone, or mixtures thereof.
Suitable
42
. _
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
hydrogen peroxide adducts include sodium percarbonate, potassium percarbonate,
or
mixtures thereof, e.g., sodium percarbonate.
Organic Active Oxygen Compound
Any of a variety of organic active oxygen compounds can be employed in the
compositions and methods of the present invention. For example, the organic s
active oxygen compound can be a peroxycarboxylic acid, such as a mono- or di-
peroxycarboxylic acid, an alkali metal salt including these types of
compounds, or an
adduct of such a compound. Suitable peroxycarboxylic acids include CI-Cu
peroxycarboxylic acid, salt of CI-Cu peroxycarboxylic acid, ester of CI-Cu
peroxycarboxylic acid, diperoxycarboxylic acid, salt of diperoxycarboxylic
acid,
ester of diperoxycarboxylic acid, or mixtures thereof.
Suitable peroxycarboxylic acids include C1-C10 aliphatic peroxycarboxylic
acid, salt of C1-C10 aliphatic peroxycarboxylic acid, ester of C1-C10
aliphatic
peroxycarboxylic acid, or mixtures thereof; e.g., salt of or adduct of
peroxyacetic
acid; e.g., peroxyacetyl borate. Suitable diperoxycarboxylic acids include C4-
C10
aliphatic diperoxycarboxylic acid, salt of C4-C10 aliphatic diperoxycarboxylic
acid,
or ester of C4-C10 aliphatic diperoxycarboxylic acid, or mixtures thereof;
e.g., a
sodium salt of perglutaric acid, of persuccinic acid, of peradipic acid, or
mixtures
thereof.
Organic active oxygen compounds include other acids including an organic
moiety. Suitable organic active oxygen compounds include perphosphonic acids,
perphosphonic acid salts, perphosphonic acid esters, or mixtures or
combinations
thereof.
Active Oxygen Compound Adducts
Active oxygen compound adducts include any generally known and that can
function, for example, as a source of active oxygen and as part of the
solidified
composition. Hydrogen peroxide adducts, or peroxyhydrates, are suitable. Some
examples of source of alkalinity adducts include the following: alkali metal
percarbonates, for example sodium percarbonate (sodium carbonate
peroxyhydrate),
potassium percarbonate, rubidium percarbonate, cesium percarbonate, and the
like;
ammonium carbonate peroxyhydrate, and the like; urea peroxyhydrate,
peroxyacetyl
43
CA 02699537 2014-03-06
WO 2008/137853
PCT/US2008/062667
borate; an adduct of H2O2 polyvinyl pyrrolidone, and the hire, and mixtures of
any of
the above.
Chelating/Sequestering Agents
Other chelating/sequestering agents, in addition to the phosphonate or
aminocarboxylic acid sequestrant discussed above, can be added to the
composition
and are useful for their sequestering properties. In general, a
chelatinglsequestming
agent 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. The
chelating/sequestering agent may also function as a threshold agent when
included in
an effective amount In certain embodiments, a cleaning composition includes
about
0.1-70 wt-% or about 5-60 wt-%, of a chelating/sequestering agent Examples of
chelating/sequestering agents include aminocarboxylic acids, condensed
phosphates,
polymeric polycarboxylates, and the like.
Examples of condensed phosphates include sodium and potassium
orthophosphate, sodium and potassium pyrophosphate, sodium and potassium
tripolyphosphate, sodium hexametaphosphate, and the hie. A condensed phosphate
may also assist, to a limited extent, in solidification of the composition by
fixing the
free water present in the composition as water of hydration.
Water conditioning polymers can be used as non-phosphorus containing
builders. Suitable water conditioning polymers include, but are not limited
to:
polycarboxylates. Suitable polycarboxylates that can be used as builders
and/or
water conditioning polymers include, but are not limited to: those having
pendant
carboxylate (-0O2) groups such as polyacrylic acid, maleic acid, maleiefolefin
copolymer, sulfonated copolymer or terpolymer, acrylic/maleic copolymer,
polymethacrylic acid, acrylic acid-ruethacrylic acid copolymers, hydrolyzed
polyacrylarnide, hydrolyzed polymethacrylamide, hydrolyzed polyamide-
methacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed
polymethacrylonitrile, and hydrolyzed aerylonitrile-methacrylonitrile
copolymers.
For a further discussion of chelating agents/sequestrants, see Kirk-Cnhmer,
Encyclopedia of Chemical Technology, Third Edition, volume 5, pages 339-366
and
volume 23, pages 319-320.
44
CA 02699537 2014-03-06
WO 2008/137853 PCT/US2008/062667
These materials may also be used at substoichiometric levels to function as
crystal modifiers
In an embodiment, organic sequestrants include amino tri(methylene
phosphonie) acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
diethylesetriaminepenta(methylene phosphonic) acid, alanine-N,N-diacetic acid,
diethylenetrinninepentaacelic acid, or alkali metal salts thereof or mixtures
thereof
In this embodiment, alkali metal salts include sodium, potassium, calcium,
magnesium, or mixtures thereof. The organic segues-aunt can include one or
more of
1-hydroxyethylidene-1,1-diphosphonic acid; or
diethylenetriaminepenta(methylene
phosphonic) acid; or alanine-N,N-diacetic acid; or
diethylenetriarninepentaacetic
acid.
For compositions including a cazboxylate as a component of the binding
agent, suitable levels of addition for builders that can also be chelating or
sequestering agents are about 0.1 to about 70 wt-%, about 1 to about 60 wt-%,
or
about 1.5 to about 50 wt-%. The solid detergent can include about 1 to about
60
wt-%, about 3 to about 50 wt-%, or about 6 to about 45 wt-% of the builders.
Additional ranges of the builders include about 3 to about 20 wt-%, about 6 to
about
15 wt-%, about 25 to about 50 wt-%, or about 35 to about 45 wt-%.
Glass and Metal Corrosion Inhibitors
The solid detergent composition can include a metal corrosion inhibitor in an
amount up to about 50 wt-%, about Ito about 40 wt-%, or about 3 to about 30 wt-
%.
The corrosion inhibitor is included in the solid detergent composition in an
amount
sufficient to provide a use solution that exhibits a rate of corrosion and/or
etching of
glass that is less than the rate of corrosion and/or etching of glass for an
otherwise
identical use solution except for the absence of the corrosion inhibitor. It
is expected
that the use solution will include at least about 6 parts per million (ppm) of
the
corrosion inhibitor to provide desired corrosion inhibition properties. It is
expected
that larger amounts of corrosion inhibitor can be used in the use solution
without
deleterious effects. It is expected that at a certain point, the additive
effect of
increased corrosion and/or etching resistance with increasing corrosion
inhibitor
concentration will be lost, and additional corrosion inhibitor will simply
increase the
cost of using the solid detergent composition. The use solution can include
about 6
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
ppm to about 300 ppm of the corrosion inhibitor or about 20 ppm to about 200
ppm
of the corrosion inhibitor. Examples of suitable corrosion inhibitors include,
but are
not limited to: a combination of a source of aluminum ion and a source of zinc
ion,
as well as an alkaline metal silicate or hydrate thereof.
The corrosion inhibitor can refer to the combination of a source of aluminum
ion and a source of zinc ion. The source of aluminum ion and the source of
zinc ion
provide aluminum ion and zinc ion, respectively, when the solid detergent
composition is provided in the form of a use solution. The amount of the
corrosion
inhibitor is calculated based upon the combined amount of the source of
aluminum
ion and the source of zinc ion. Anything that provides an aluminum ion in a
use
solution can be referred to as a source of aluminum ion, and anything that
provides a
zinc ion when provided in a use solution can be referred to as a source of
zinc ion. It
is not necessary for the source of aluminum ion and/or the source of zinc ion
to react
to form the aluminum ion and/or the zinc ion. Aluminum ions can be considered
a
source of aluminum ion, and zinc ions can be considered a source of zinc ion.
The
source of aluminum ion and the source of zinc ion can be provided as organic
salts,
inorganic salts, and mixtures thereof. Suitable sources of aluminum ion
include, but
are not limited to: aluminum salts such as sodium aluminate, aluminum bromide,
aluminum chlorate, aluminum chloride, aluminum iodide, aluminum nitrate,
aluminum sulfate, aluminum acetate, aluminum formate, aluminum tartrate,
aluminum lactate, aluminum oleate, aluminum bromate, aluminum borate,
aluminum potassium sulfate, aluminum zinc sulfate, and aluminum phosphate.
Suitable sources of zinc ion include, but are not limited to: zinc salts such
as zinc
chloride, zinc sulfate, zinc nitrate, zinc iodide, zinc thiocyanate, zinc
fluorosilicate,
zinc dichromate, zinc chlorate, sodium zincate, zinc gluconate, zinc acetate,
zinc
benzoate, zinc citrate, zinc lactate, zinc formate, zinc bromate, zinc
bromide, zinc
fluoride, zinc fluorosilicate, and zinc salicylate.
The applicants discovered that by controlling the ratio of the aluminum ion to
the zinc ion in the use solution, it is possible to provide reduced corrosion
and/or
etching of glassware and ceramics compared with the use of either component
alone.
That is, the combination of the aluminum ion and the zinc ion can provide a
synergy
in the reduction of corrosion and/or etching. The ratio of the source of
aluminum
ion to the source of zinc ion can be controlled to provide a synergistic
effect In
46
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
general, the weight ratio of aluminum ion to zinc ion in the use solution can
be at
least about 6:1, can be less than about 1:20, and can be about 2:1 and about
1:15.
An effective amount of an alkaline metal silicate or hydrate thereof can be
employed in the compositions and processes of the invention to form a stable
solid
detergent composition having metal protecting capacity. The silicates employed
in
the compositions of the invention are those that have conventionally been used
in
solid detergent formulations. For example, typical alkali metal silicates are
those
powdered, particulate or granular silicates which are either anhydrous or
preferably
which contain water of hydration (about 5% to about 25 wt-%, about 15% to
about
20 wt-% water of hydration). These silicates are preferably sodium silicates
and
have a Na20:Si02 ratio of about 1:1 to about 1:5, respectively, and typically
contain
available water in the amount of from about 5% to about 25 wt-%. In general,
the
silicates have a Na20:Si02 ratio of about 1:1 to about 1:3.75, about 1:1.5 to
about
1:3.75 and most about 1:1.5 to about 1:2.5. A silicate with a Na20:Si02 ratio
of
about 1:2 and about 16% to about 22 wt-% water of hydration, is most
preferred.
For example, such silicates are available in powder form as GD Silicate and in
granular form as Britesil H-20, available from PQ Corporation, Valley Forge,
PA.
These ratios may be obtained with single silicate compositions or combinations
of
silicates which upon combination result in the preferred ratio. The hydrated
silicates
at preferred ratios, a Na20:Si02 ratio of about 1:1.5 to about 1:2.5, have
been found
to provide the optimum metal protection and rapidly form a solid detergent.
Hydrated silicates are preferred.
Silicates can be included in the solid detergent composition to provide for
metal protection but are additionally known to provide alkalinity and
additionally
function as anti-redeposition agents. Suitable silicates include, but are not
limited
to: sodium silicate and potassium silicate. The solid detergent composition
can be
provided without silicates, but when silicates are included, they can be
included in
amounts that provide for desired metal protection. The composition can include
silicates in amounts of at least about 1 wt-%, at least about 5 wt-%, at least
about 10
wt-%, and at least about 15 wt-%. In addition, in order to provide sufficient
room
for other components in the composition, the silicate component can be
provided at a
level of less than about 20 wt-%, less than about 25 wt-%, less than about 20
wt-%,
or less than about 15 wt-%.
47
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
Organic Surfactants or Cleaning Agents
The composition can include at least one cleaning agent which can be a
surfactant or surfactant system. A variety of surfactants can be used in a
cleaning
composition, including anionic, nonionic, cationic, and zwitterionic
surfactants,
which are commercially available from a number of sources. Nonionic agents are
suitable. For a discussion of surfactants, see Kirk-Otluner, Encyclopedia of
Chemical Technology, Third Edition, volume 8, pages 900-912. For example, the
cleaning composition includes a cleaning agent in an amount effective to
provide a
desired level of cleaning, which can be about 0-20 wt-% or about 1.5-15 wt-%.
Anionic surfactants useful in the present cleaning compositions, include, for
example, carboxylates such as alkylcarboxylates (carboxylic acid salts) and
polyalkoxycarboxylates, alcohol ethoxylate carboxylates, nonylphenol
ethoxylate
carboxylates, and the like; sulfonates such as allcylsulfonates,
alkylbenzenesulfonates, alkylarylsulfonates, sulfonated fatty acid esters, and
the like;
sulfates such as sulfated alcohols, sulfated alcohol ethoxylates, sulfated
allcylphenols, alkylsulfates, sulfosuccinates, allcylether sulfates, and the
like; and
phosphate esters such as allcylphosphate esters, and the like. Suitable
anionics are
sodium allcylarylsulfonate, alpha-olefin sulfonate, and fatty alcohol
sulfates.
Nonionic surfactants useful in cleaning compositions, include those having a
polyallcylene oxide polymer as a portion of the surfactant molecule. Such
nonionic
surfactants include, for example, chlorine-, benzyl-, methyl-, ethyl-, propyl-
, butyl-
and other like alkyl-capped polyethylene glycol ethers of fatty alcohols;
polyallcylene
oxide free nonionics such as alkyl polyglycosides; sorbitan and sucrose esters
and
their ethoxylates; alkoxylated ethylene diamine; alcohol alkoxylates such as
alcohol
ethoxylate propoxylates, alcohol propoxylates, alcohol propoxylate ethoxylate
propoxylates, alcohol ethoxylate butoxylates, and the like; nonylphenol
ethoxylate,
polyoxyethylene glycol ethers and the like; carboxylic acid esters such as
glycerol
esters, polyoxyethylene esters, ethoxylated and glycol esters of fatty acids,
and the
like; carboxylic amides such as diethanolamine condensates, monoallcanolamine
condensates, polyoxyethylene fatty acid amides, and the like; and polyalkylene
oxide
block copolymers including an ethylene oxide/propylene oxide block copolymer
such as those commercially available under the trademark PLURONIC
48
CA 02699537 2014-03-06
WO 2008/137853
ACT/US2008/062667
(BASF-Wyandotte), and the like; ethoxylated amines and ether amines
commercially
available from Tomah Corporation and other like nonionic compounds. Silicone
11.4
surfactants such as the ABM, B8852 (Goldsclunidt) can also be used.
Cationic surfactants useful for inclusion in a cleaning composition for fabric
softening or for reducing the population of one or more microbes include
amines
such as primary, secondary and tertiary monoamines with C6.24 alkyl or alkenyl
chains, ethoxylated alicylamines, alkoxylates of ethylenediamine, imidazolcs
such as
a 1-(2-hydroxyethyl)-2-imidazoline, a 2-alkyl-1-(2-hydroxyethyl)-2-
imidazoline, and
the like; and quaternary ammonium salts, as for example, alkylquaternary
ammonitnn chloride surfactants such as n-alkyl(C6-C24)dimethylbenzyl
aramonitan
chloride, n-tetradecyldimethylbenzylarnmonium chloride monohydrate, a
naphthalene-substituted quaternary ammonium chloride such as dimethyl-l-
naphthyhriethylarnmonium chloride, and the tile; and other his cationic
surfactants.
Antimicrobials
Antimicrobial agents are chemical compositions that can be used in a solid
functional material that alone, or in combination with other components, act
to
reduce or prevent microbial contamination and deterioration of commercial
products
material systems, surfaces, etc. In some aspects, these materials fall in
specific
classes including phenolics, halogen compounds, quaternary ammonium
compounds, metal derivatives, amines, alkanol amines, nitro derivatives,
analides,
organosulfur and sulfur-nitrogen compounds and miscellaneous compounds.
It should also be understood that the source of alkalinity used in the
formation of compositions embodying the invention also act as antimicrobial
agents,
and can even provide sanitizing activity. In fact, in some embodiments, the
ability of
the source of alkalinity to act as an antimicrobial agent reduces the need for
secondary antimicrobial agents within the composition. For example,
percathonate
compositions have been demonstrated to provide excellent antimicrobial action.
Nonetheless, some embodiments incorporate additional antimicrobial agents.
The given antimicrobial agent, depending on chemical composition and
concentration, may simply limit further proliferation of numbers of the
microbe or
may destroy all or a portion of the microbial population. The terms "microbes"
and
"microorganisms" typically refer primarily to bacteria, virus, yeast, spores,
and
49
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
fungus microorganisms. In use, the antimicrobial agents are typically formed
into a
solid functional material that when diluted and dispensed, optionally, for
example,
using an aqueous stream forms an aqueous disinfectant or sanitizer composition
that
can be contacted with a variety of surfaces resulting in prevention of growth
or the
killing of a portion of the microbial population. A three log reduction of the
microbial population results in a sanitizer composition. The antimicrobial
agent can
be encapsulated, for example, to improve its stability.
Common antimicrobial agents include phenolic antimicrobials such as
pentachlorophenol, orthophenylphenol, a chloro-p-benzylphenol, p-chloro-m-
xylenol. Halogen containing antibacterial agents include sodium
trichloroisocyanurate, sodium dichloro isocyanate (anhydrous or dihydrate),
iodine-
poly(vinylpyrolidinone) complexes, bromine compounds such as 2-bromo-2-
nitropropane-1,3-diol, and quaternary antimicrobial agents such as
benzalkonium
chloride, didecyldimethyl ammonium chloride, choline diiodochloride,
tetramethyl
phosphonium tribromide. Other antimicrobial compositions such as hexahydro-
1,3,5-tris(2-hydroxyethyl)-s-triazine, dithiocarbamates such as sodium
dimethyldithiocarbamate, and a variety of other materials are known in the art
for
their anti-microbial properties. In some embodiments, an antimicrobial
component,
such as TAED can be included in the range of 0.001 to 75 wt-% of the
composition,
about 0.01 to 20 wt-%, or about 0.05 to about 10 wt-%.
If present in compositions, the additional antimicrobial agent can be about
0.01 to about 30 wt-% of the composition, 0.05 to about 10 wt-%, or about 0.1
to
about 5 wt-%. In a use solution the additional antimicrobial agent can be
about
0.001 to about 5 wt-% of the composition, about 0.01 to about 2 wt-%, or about
0.05
to about 0.5 wt-%.
Activators
In some embodiments, the antimicrobial activity or bleaching activity of the
composition can be enhanced by the addition of a material which, when the
composition is placed in use, reacts with the active oxygen to form an
activated
component. For example, in some embodiments, a peracid or a peracid salt is
formed. For example, in some embodiments, tetraacetylethylene diamine can be
included within the composition to react with the active oxygen and form a
peracid
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
or a peracid salt that acts as an antimicrobial agent. Other examples of
active
oxygen activators include transition metals and their compounds, compounds
that
contain a carboxylic, nitrile, or ester moiety, or other such compounds known
in the
art. In an embodiment, the activator includes tetraacetylethylene diamine;
transition
metal; compound that includes carboxylic, nitrile, amine, or ester moiety; or
mixtures thereof.
In some embodiments, an activator component can include in the range of
0.001 to 75 % by wt. of the composition, about 0.01 to about 20, or about 0.05
to
about 10% by wt of the composition.
In an embodiment, the activator for the source of alkalinity combines with
the active oxygen to form an antimicrobial agent.
The solid composition typically remains stable even in the presence of
activator of the source of alkalinity. In many compositions would be expected
to
react with and destabilize or change the form of the source of alkalinity. In
contrast,
in an embodiment of the present invention, the composition remains solid; it
does
not swell, crack, or enlarge as it would if the source of alkalinity were
reacting with
the activator.
In an embodiment, the composition includes a solid block, and an activator
material for the active oxygen is coupled to the solid block. The activator
can be
coupled to the solid block by any of a variety of methods for coupling one
solid
cleaning composition to another. For example, the activator can be in the form
of a
solid that is bound, affixed, glued or otherwise adhered to the solid block.
Alternatively, the solid activator can be formed around and encasing the
block. By
way of further example, the solid activator can be coupled to the solid block
by the
container or package for the cleaning composition, such as by a plastic or
shrink
wrap or film.
Rinse Aid Functional Materials
Functional materials of the invention can include a formulated rinse aid
composition containing a wetting or sheeting agent combined with other
optional
ingredients in a solid made using the complex of the invention. The rinse aid
component of the present invention can include a water soluble or dispersible
low
foaming organic material capable of reducing the surface tension of the rinse
water
51
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
to promote sheeting action and to prevent spotting or streaking caused by
beaded
water after rinsing is completed. This is often used in warewashing processes.
Such
sheeting agents are typically organic surfactant-like materials having a
characteristic
cloud point. The cloud point of the surfactant rinse or sheeting agent is
defined as
the temperature at which a 1 wt-% aqueous solution of the surfactant turns
cloudy
when warmed.
There are two general types of rinse cycles in commercial warewashing
machines, a first type generally considered a sanitizing rinse cycle uses
rinse water at
a temperature of about 180 F, about 80 C or higher. A second type of non-
sanitizing
machines uses a lower temperature non-sanitizing rinse, typically at a
temperature of
about 125 F, about 50 C or higher. Surfactants useful in these applications
are
aqueous rinses having a cloud point greater than the available hot service
water.
Accordingly, the lowest useful cloud point measured for the surfactants of the
invention is approximately 40 C. The cloud point can also be 60 C or higher,
70 C
or higher, 80 C or higher, etc., depending on the use locus hot water
temperature and
the temperature and type of rinse cycle.
Suitable sheeting agents, typically include a polyether compound prepared
from ethylene oxide, propylene oxide, or a mixture in a homopolymer or block
or
heteric copolymer structure. Such polyether compounds are known as
polyalkylene
oxide polymers, polyoxyalkylene polymers or polyalkylene glycol polymers. Such
sheeting agents require a region of relative hydrophobicity and a region of
relative
hydrophilicity to provide surfactant properties to the molecule. Such sheeting
agents
have a molecular weight in the range of about 500 to 15,000. Certain types of
(P0)(E0) polymeric rinse aids have been found to be useful containing at least
one
block of poly(P0) and at least one block of poly(E0) in the polymer molecule.
Additional blocks of poly(E0), poly PO or random polymerized regions can be
formed in the molecule.
Particularly useful polyoxypropylene polyoxyethylene block copolymers are
those including a center block of polyoxypropylene units and blocks of
polyoxyethylene units to each side of the center block. Such polymers have the
formula shown below:
(E0)õ-(P0),õ-(E0)õ
52
CA 02699537 2014-03-06
WO 2008/137853
PCT/US2008/062667
wherein n is an integer of 20 to 60, each end is independently an integer of
10 to
130. Another useful block copolymer are block copolymers having a center block
of
polyoxyetb.ylene units and blocks of polyoxypropylerne to each side of the
center
block. Such copolymers have the formula:
(130)a-(B0)10-(P0)0
wherein m is an integer of 15 to 175 and each end are independently integers
of
about 10 to 30. The solid timetional materials of the invention can often use
a
hydrotrope to aid in maintaining the solubility of sheeting or wetting agents.
1-1ydrotropes can be used to modify the aqueous solution creating increased
solubility
for the organic material. Suitable hydrotropt% are low molecular weight
aromatic
sulfonate materials such as xylene sulfonates and diallcyldiphenyl oxide
sulfonate
materials.
In an embodiment, compositions according to the present invention provide
desirable rinsing properties in ware washing without employing a separate
rinse
agent in the rinse cycle. For example, good rinsing occurs using such
compositions
in the wash cycle when rinsing employs just soft water.
Additional Bleaching Agents
Additional bleaching agents for use in inventive formulations for lightening
or whitening a substrate, include bleaching compounds capable of liberating an
active halogen species, such as C12, Br2, I, C102, ar02, IO, -ocr, -OW andVor,
-
or, under conditions typically encountered during the cleansing process.
Suitable
bleaching agents for use in the present cleaning compositions include, for
example,
chlorine-containing compounds such as a chlorite, a hypochlorite, chloramine.
Suitable halogen-releasing compounds include the alkali metal
dichloroisocyanurates, chlorinated trisodium phosphate, the alkali metal
hypochlorites, alkali metal chlorites, monochloramine and dichloramine, and
the
like, and mixtures thereof. Encapsulated chlorine sources may also be used to
enhance the stability of the chlorine source in the composition (see, for
example,
U.S. Patent Nos. 4,618,914 and 4,830,773)
A bleaching agent may also be an additional peroxygen or
active oxygen source such as hydrogen peroxide, perborates, for example sodium
perborate mono and tetrahydrate, sodium carbonate peroxyhydrate, phosphate
53
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
peroxyhydrates, and potassium permonosulfate, with and without activators such
as
tetraacetylethylene diamine, and the like, as discussed above.
A cleaning composition may include a minor but effective additional amount
of a bleaching agent above that already available from the stabilized source
of
alkalinity, e.g., about 0.1-10 wt-% or about 1-6 wt-%. The present solid
compositions can include bleaching agent in an amount of about 0.1 to about 60
wt-
%, about 1 to about 20 wt-%, about 3 to about 8 wt-%, or about 3 to about 6 wt-
%.
Secondary Hardening Agents/Solubility Modifiers.
The present compositions may include a minor but effective amount of a
secondary hardening agent, as for example, an amide such stearic
monoethanolamide
or lauric diethanolamide, or an alkylamide, and the like; a solid polyethylene
glycol,
or a solid EO/PO block copolymer, and the like; starches that have been made
water-
soluble through an acid or alkaline treatment process; various inorganics that
impart
solidifying properties to a heated composition upon cooling, and the like.
Such
compounds may also vary the solubility of the composition in an aqueous medium
during use such that the cleaning agent and/or other active ingredients may be
dispensed from the solid composition over an extended period of time. The
composition may include a secondary hardening agent in an amount of about
5-20 wt-% or about 10-15 wt-%.
Detergent Fillers
A cleaning composition may include an effective amount of one or more of a
detergent filler which does not perform as a cleaning agent per se, but
cooperates
with the cleaning agent to enhance the overall processability of the
composition.
Examples of fillers suitable for use in the present cleaning compositions
include
sodium sulfate, sodium chloride, starch, sugars, C1-C10 allcylene glycols such
as
propylene glycol, and the like. A filler such as a sugar (e.g. sucrose) can
aid
dissolution of a solid composition by acting as a disintegrant. A detergent
filler can
be included in an amount up to about 50 wt-%, of about 1 to about 20 wt-%,
about 3
to about 15 wt-%, about 1 to about 30 wt-%, or about 1.5 to about 25 wt-%.
54
=
CA 02699537 2014-03-06
WO 2008/137853
PCT/US2008/062667
Defoarning Agents
An effective amount of a defoaming agent for reducing the stability of foam
may also be included in the present cleaning compositions. The cleaning
composition can include about 0.0001-5 wt-% of a defoaming agent, e.g., about
0.01-3 wt-%. The defoaming agent can be provided in an amount of about 0.0001%
to about 10 wt-%, about 0.001% to about 5 wt-%, or about 0.01% to about 1.0 wt-
%
Examples of defoaming agents suitable for use in the present compositions
include silicone compounds such as silica dispersed in polydiraethylsiloxane,
EOPPO
block copolymers, alcohol alkoxylates, fatty amides, hydrocarbon waxes, fatty
acids,
fatty esters, fatty alcohols, fatty acid soaps, ethoxylates, rnixteral oils,
polyethylene
glycol esters, alkyl phosphate esters such as monostearyl phosphate, and the
like. A
discussion of defoaming agents may be found, for example, in U.S. Patent No.
3,048,548 to Martin et al., U.S. Patent No. 3,334,147 to Brunelle et al., and
U.S.
Patent No. 3,442,242 to Rue et al.
Anti-redeposition Agents
A cleaning composition may also include an anti-redeposition agent capable
of facilitating sustained suspension of soils in a cleaning solution and
preventing the
removed soils from being redeposited onto the substrate being cleaned.
Examples of
suitable anti-redeposition agents include fatty acid amides, fluorocarbon
surfactants,
complex phosphate esters, styrene maleic anhydride copolymers, and cellulosic
derivatives such as hydroxyediyl cellulose, hydroxypropyl cellulose, and the
like. A
cleaning composition may include about 0.5 to about 10 wt-%, e.g., about Ito
about
5 wt-%, of an anti-redeposition agent.
Optical Brighteners
Optical brightener is also referred to as fluorescent whitening agents or
fluorescent brightening agents provide optical cornpensAtion for the yellow
cast in
fabric substrates. With optical brighteners yellowing is replaced by light
emitted
from optical brighteners present in the area commensurate in scope with yellow
color. The violet to blue light supplied by the optical brighteners combines
with
other light reflected from the location to provide a substantially complete or
CA 02699537 2014-03-06
WO 2008/137853 PCr/1JS2008/062667
enhanced bright white appearance. This additional light is produced by the
brightener through fluoresceuce. Optical brighteners absorb light in the
ultraviolet
range 275 through 400 ran. and emit light in the ultraviolet blue spectrum 400-
500
nra.
Fluorescent compounds belonging to the optical brightener family are
typically aromatic or aromatic heterocyclic materials often containing
condensed
ring system. An important feature of these compounds is the presence of an
uninterrupted chain of conjugated double bonds associated with an aromatic
ring.
The number of such conjugated double bonds is dependent on substituents as
well as
the planarity of the fluorescent part of the molecule. Most brightener
compounds are
derivatives of stilbene or 4,4'-diamino stilbene, biphenyl, five membered
heterocycles (triazoles, oxazoles, imiclazoles, etc.) or six membered
heterocycles
(cumarins, naphthalamides, triazines, etc.). The choice of optical brighteners
for use
in detergent compositions will depend upon a number of factors, such as the
type of
detergent, the nature of other components present in the detergent
composition, the
temperature of the wash water, the degree of agitation, and the ratio of the
material
washed to the tub size. The brightener selection is also dependent upon the
type of
material to be cleaned, e.g., cottons, synthetics, etc. Since most laundry
detergent
products are used to clean a variety of fabrics, the detergent compositions
should
contain a mixture of brighteners which are effective for a variety of fabrics.
It is of
course necessary that the individual components of such a brightener mixture
be
compatible.
Optical brighteners useful in the present invention are commercially
available and will be appreciated by those skilled in the art. Commercial
optical
brighteners which may be useful in the present invention can be classified
into
subgroups, which include, but are not necessarily limited to, derivatives of
stilbene,
pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiophene-5,5-
dioxide, azoles, 5- and 6-membered-ring heterocycles and other miscellaneous
agents. Examples of these types of brighteners are disclosed in "The
Production and
Application of Fluorescent Brightening Agents", M. Zahradnik, Published by
John
Wiley & Sons, New York (1982),
56
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
Stilbene derivatives which may be useful in the present invention include,
but are not necessarily limited to, derivatives of bis(triazinyl)amino-
stilbene;
bisacylamino derivatives of stilbene; triazole derivatives of stilbene;
oxadiazole
derivatives of stilbene; oxaz,ole derivatives of stilbene; and styryl
derivatives of
stilbene.
For laundry cleaning or sanitizing compositions, suitable optical brighteners
include stilbene derivatives, which can be employed at concentrations of up to
1 wt-
%.
Stabilizing Agents
The solid detergent composition may also include a stabilizing agent.
Examples of suitable stabilizing agents include, but are not limited to:
borate,
calcium/magnesium ions, propylene glycol, and mixtures thereof. The
composition
need not include a stabilizing agent, but when the composition includes a
stabilizing
agent, it can be included in an amount that provides the desired level of
stability of
the composition. Suitable ranges of the stabilizing agent include up to about
20 wt-
%, about 0.5 to about 15 wt-%, or about 2 to about 10 wt-%.
Dispersants
The solid detergent composition may also include a dispersant. Examples of
suitable dispersants that can be used in the solid detergent composition
include, but
are not limited to: maleic acid/olefin copolymers, polyacrylic acid, and
mixtures
thereof. The composition need not include a dispersant, but when a dispersant
is
included it can be included in an amount that provides the desired dispersant
properties. Suitable ranges of the dispersant in the composition can be up to
about
20 wt-%, about 0.5 to about 15 wt-%, or about 2 to about 9 wt-%.
Enzymes
Enzymes that can be included in the solid detergent composition include
those enzymes that aid in the removal of starch and/or protein stains.
Suitable types
of enzymes include, but are not limited to: proteases, alpha-amylases, and
mixtures
thereof. Suitable proteases that can be used include, but are not limited to:
those
derived from Bacillus lichenifonnix, Bacillus lenus, Bacillus alcalophilus,
and
57
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
Bacillus amyloliquefacins. Suitable alpha-amylases include Bacillus subtilis,
Bacillus amyloliquefaciens, and Bacillus licheniformis. The composition need
not
include an enzyme, but when the composition includes an enzyme, it can be
included
in an amount that provides the desired enzymatic activity when the solid
detergent
composition is provided as a use composition. Suitable ranges of the enzyme in
the
composition include up to about 15 wt-%, about 0.5 to about 10 wt-%, or about
1 to
about 5 wt-%.
Thickeners
The solid detergent compositions can include a rheology modifier or a
thickener. The rheology modifier may provide the following functions:
increasing
the viscosity of the compositions; increasing the particle size of liquid use
solutions
when dispensed through a spray nozzle; providing the use solutions with
vertical
cling to surfaces; providing particle suspension within the use solutions; or
reducing
the evaporation rate of the use solutions.
The rheology modifier may provide a use composition that is pseudo plastic,
in other words the use composition or material when left undisturbed (in a
shear
mode), retains a high viscosity. However, when sheared, the viscosity of the
material is substantially but reversibly reduced. After the shear action is
removed,
the viscosity returns. These properties permit the application of the material
through
a spray head. When sprayed through a nozzle, the material undergoes shear as
it is
drawn up a feed tube into a spray head under the influence of pressure and is
sheared
by the action of a pump in a pump action sprayer. In either case, the
viscosity can
drop to a point such that substantial quantities of the material can be
applied using
the spray devices used to apply the material to a soiled surface. However,
once the
material comes to rest on a soiled surface, the materials can regain high
viscosity to
ensure that the material remains in place on the soil. Preferably, the
material can be
applied to a surface resulting in a substantial coating of the material that
provides the
cleaning components in sufficient concentration to result in lifting and
removal of
the hardened or baked-on soil. While in contact with the soil on vertical or
inclined
surfaces, the thickeners in conjunction with the other components of the
cleaner
minimi7e dripping, sagging, slumping or other movement of the material under
the
effects of gravity. The material should be formulated such that the viscosity
of the
58
CA 02699537 2014-03-06
WO 2008/137853
PCT/US2008/062667
material is adequate to maintain contact substantial quantities of the film of
the
material with the soil for at least a minute, five minutes or more.
Examples of suitable thickeners or theology modifiers are polymeric
thickeners including, but not limited to: polymers or natural polymers or gums
derived from plant or animal sources. Such materials may be polysaccharides
such
as large polysaccharide molecules having substantial thickening capacity.
Thickeners or theology modifiers also include clays.
A substantially soluble polymeric thicken= can be used to provide increased
viscosity or increased conductivity to the use compositions. Examples of
polymeric
thickeners for the aqueous compositions of the invention include, but are not
limited
to: carboxylated vinyl polymers such as polyacrylic acids and sodium salts
thereof,
ethoxylated cellulose, polyacrylamide thickeners, cross-linked, xanthan
compositions, sodium alginate and algin products, hydroxypropyl cellulose,
hydrroryethyl cellulose, and other similar aqueous thickeners that have some
substantial proportion of water solubility. Examples of suitable commercially
available thickeners include, but are not limited to: Acusol, available from
Rohm &
Haas Company, Philadelphia, PA; and Carbopol, available from B.F. Goodrich,
Charlotte, NC.
Examples of suitable polymeric thickeners include, but not limited to:
polysaccharides. An example of a suitable commercially available
polysaccharide
includes, but is not limited to, Diutan,Iviavailable from Kelco Division of
Merck, San
Diego, CA. Thickeners for use in the solid detergent compositions further
include
polyvinyl alcohol thickeners, such as, fully hydrolyzed (greater than 98.5 mol
acetate
replaced with the ¨OH function).
An example of a suitable polysaccharide includes, but is not limited to,
xanthans. Such xanthan polymers are preferred due to their high water
solubility,
and great thickening power. Xanthan is an extracellular polysaccharide of
Xanthomonas campestras. Xanthan may be made by fermentation based on corn
sugar or other corn sweetener by-products. Xanthan includes a poly beta-(1-4)-
D-
Glucopyranosyl backbone chain, similar to that found in cellulose. Aqueous
dispersions of xanthan gum and its derivatives exhibit novel and remarkable
theological properties. Low concentrations of the gum have relatively high
viscosities which permit it to be used economically. Xanthan gum solutions
exhibit
59
CA 02699537 2014-03-06
WO 2008/137853
PCT/US2008/062667
high pseudo plasticity, i.e. over a wide range of concentrations, rapid shear
thinning
occurs that is generally understood to be instantaneously reversible. Non-
sheared
materials have viscosities that appear to be independent of the pH and
independent
of temperature over wide ranges. Preferred xanthan materials include
crosslinkcd
xanthan materials. )(afghan polymers can be crosslinked with a variety of
known
covalent reacting crosslinlcing agents reactive with the hydroxyl
functionality of
large polysaccharide molecules and can also be crosslinked using divalent,
trivalent
or polyvalent metal ions. Such crosslinked xanthan gels are disclosed in U.S.
Patent
No. 4,782,901. Suitable crosslinking
agents for xanthan materials include, but are not limited to: metal cations
such as
A1+3, Fe+3, Sb+3, Zr+4 and other transition metals. Examples of suitable
commercially available xanthans include, but are not limited to: KELTROLO,
ICELZAN AR, KELZ.ANO D35, KBLZAN S, ICEIZANO KZ, available from
Kelco Division of Merck, San Diego, CA. Known organic crosslinking agents can
also be used. A preferred crosslinked xanthan is KELZAN AR, which provides a
pseudo plastic use solution that can produce large particle size mist or
aerosol when
sprayed.
Dyes/Odorants
Various dyes, odorants including perfumes, and other aesthetic enhancing
agents may also be included in the composition. Dyes may be included to alter
the
appearance of the composition, as for example, Direct Blue 86 (Miles),
Fastusol
Blue (Mobay Chemical Corp.), Acid Orange 7 (American Cyanamid), Basic Violet
10 (Sandoz), Acid Yellow 23 (GAF), Acid Yellow 17 (Sigma Chemical), Sap Green
(1Ceyston Analine and Chemical), Metanil Yellow (Keystone &online 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.
Fragrances or perfumes that may be included in the compositions include, for
example, terpenoids such as citronellol, aldehydes such as amyl
cin.namalclehyde, a
jasmine such as Cl S-jasmine or jasmal, vanillin, and the like.
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
Embodiments of Solids
A solid cleaning composition as used in the present disclosure encompasses a
variety of forms including, for example, solids, pellets, blocks, and tablets,
but not
powders. It should be understood that the term "solid" refers to the state of
the
detergent composition under the expected conditions of storage and use of the
solid
cleaning composition. In general, it is expected that the detergent
composition will
remain a solid when provided at a temperature of up to about 100 F or greater
than
120 F.
In certain embodiments, the solid cleaning composition is provided in the
form of a unit dose. A unit dose refers to a solid cleaning composition unit
sized so
that the entire unit is used during a single washing cycle. When the solid
cleaning
composition is provided as a unit dose, it can have a mass of about 1 g to
about 50 g.
In other embodiments, the composition can be a solid, a pellet, or a tablet
having a
size of about 50 g to 250 g, of about 100 g or greater, or about 40 g to about
11,000
g.
In other embodiments, the solid cleaning composition is provided in the form
of a multiple-use solid, such as, a block or a plurality of pellets, and can
be
repeatedly used to generate aqueous detergent compositions for multiple
washing
cycles. In certain embodiments, the solid cleaning composition is provided as
a
solid having a mass of about 5 g to 10 kg. In certain embodiments, a multiple-
use
form of the solid cleaning composition has a mass of about 1 to 10 kg. In
further
embodiments, a multiple-use form of the solid cleaning composition has a mass
of
about 5 kg to about 8 kg. In other embodiments, a multiple-use form of the
solid
cleaning composition has a mass of about 5 g to about 1 kg, or about 5 g and
to
500g.
Packaging System
In some embodiments, the solid composition can be packaged. The
packaging receptacle or container may be rigid or flexible, and composed of
any
material suitable for containing the compositions produced according to the
invention, as for example glass, metal, plastic film or sheet, cardboard,
cardboard
composites, paper, and the like.
61
CA 02699537 2014-03-06
WO 2008/137853
PCITUS2008/062667
Advantageously, since the composition is processed at or near ambient
temperatures, the temperature of the processed mixture is low enough so that
the
mixture may be formed directly in the container or other packaging system
without
structurally damaging the material. As a result, a wider variety of materials
may be
used to manufacture the container than those used for compositions that
processed
and dispensed under molten conditions.
Suitable packaging used to contain the compositions is manufactured from a
flexible, easy opening film material.
Dispensin2 of the Processed Compositions
The cleaning composition made according to the present invention can be
dispensed in any suitable method generally known. The cleaning composition can
be dispensed from a spray-type dispenser such as that disclosed in U.S. Patent
Nos,
4,826,661, 4,690,305, 4,687,121, 4,426,362 and in U.S. Patent Nos. Re 32,763
and
32,818. Briefly, a
spray-type dispenser functions by impinging a water spray upon an exposed
surface
of the solid composition to dissolve a portion of the composition, and then
immediately directing the concentrate solution including the composition out
of the
dispenser to a storage reservoir or directly to a point of use. When used, the
product
is removed from the package (cg.) film and is inserted into the dispenser. The
spray
of water can be made by a nozzle in a shape that conforms to the solid shape.
The
dispenser enclosure can also closely fit the detergent shape in a dispensing
system
that prevents the introduction and dispensing of an incorrect detergent. The
aqueous
concentrate is generally directed to a use locus.
In some embodiments, the compositions hereof will be formulated such that
during use in aqueous cleaning operations the wash water will have a pH of
between
about 1 and about 14, about 6.5 to about 11, or 7-10.5. Techniques for
controlling
pH at recommended usage levels include the use of buffers, alkali, acids,
etc., and
are well known to those skilled in the art.
In an embodiment, the present composition can be dispensed by immersing
either intermittently or continuously in water. The composition can then
dissolve,
for example, at a controlled or predetermined rate. The rate can be effective
to
maintain a concentration of rlissolved cleaning agent that is effective for
cleaning
62
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
In an embodiment, the present composition can be dispensed by scraping
solid from the solid composition and contacting the scrapings with water. The
scrapings can be added to water to provide a concentration of dissolved
cleaning
agent that is effective for cleaning.
Methods Employing the Present Compositions
It is contemplated that the cleaning compositions of the invention can be
used in a broad variety of industrial, household, health care, vehicle care,
and other
such applications. Some examples include surface disinfectant, ware cleaning,
laundry cleaning, laundry cleaning or sanitizing, vehicle cleaning, floor
cleaning,
surface cleaning, pre-soaks, clean in place, and a broad variety of other such
applications.
The present invention can be better understood with reference to the
following examples. These examples are intended to be representative of
specific
embodiments of the invention, and are not intended as limiting the scope of
the
invention.
63
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
EXAMPLES
Example 1 - - MakinE Pressed Solid Compositions
Table 1 ¨ Embodiments of Solid Cleaning Compositions of the Present Invention
wt_cy.
Ingredient A Al B C D D1 E
Carbonate Salt 52 50-70 68 47 40 0-50 13
Bicarbonate Salt 2.9 2.9
Sequestrant 32 5-25 6.7 5.6 49 33-80 2.0
Surfactant 4.6 4.6 3.7 3.7 3.6 3.6
Builder 3.1 0.5-3.1 7 25 -- -- 43
Secondary Alkalinity
3 3 44 3.7 7.7 7.7 3.0
Source
Coated Bleach 3.3 8.5 --
Water 0-34 2.2 2.2 --
Sodium Hydroxide -- 37
As used in the table above, the compositions can include as sequestrants
DTPA, HEDP, NTA, or the like; as builder citric acid, sodium polyacrylate,
tripolyphosphate, or the like; as secondary alkalinity source sodium
metasilicate,
hydroxide salt, or the like. Each of compositions A-E were made as pressed
solids. The ingredients were mixed for a sufficient time to mix the
ingredients
without excess drying. Suitable mixing times included about 5 (e.g., 4) to
about 30
minutes.
Composition A, Al, D, D1, and E formed a pressed solid when mixed for 4,
15, and 30 minutes and pressed at 24, 59, 120, and 610 psi. The pressed solid
was a
2, 4 or 6 lb block.
Compositions B and C formed a pressed solid when pressed at 24, 59, and
120 psi. The pressed solid was a 2, 4 or 6 lb block.
The compositions in the tables below can be made by the method of the
present invention. For example, the flowable solid can be placed in a small
cup
(e.g., a specimen
64
Table 2¨ Embodiments of Solid Cleaning Compositions of the Present Invention
0
Cwt.%) t..)
o
o
Go
Ingredient F G H I J K L M N OP QR
-4
Go
Carbonate 53 63-67 42-53 51 56-57 53-59 55-57 54 14
or 9 30 25 40 52 u,
biodegradable
10 10 26* 20 5-16 0-10 0-10
30 43 20*
amino carboxylate
citrate 14-25 10 10 2
20 13-23 13-23 2
Hydroxide salt 2 0-1 1 37
18
n
polymer
1 2-4 4-5 1 7-9 1 1 1 4
polycarboxylate
0
I.)
61
l0
Sulfonated
ko
6-12 7-13
polymer
cA ui
Ul
"A
phosphonate 5
10 13 I.)
0
H
0
I
0
UJ
I
Water 8 4 3-4 , 0-10 4
0
l0
secondary
3 3 3-4 3 3 3 3 1
20 10 3
alkalinity
tripolyphosphate 40
50
_
polyol
4 4
1-d
n
Surfactant 5 3 3-5 5 5 3-5 5 5
cp
t..)
o
o
Go
5
O-
t..)
-4
(wt-%)
0
= t..)
Ingredient S T U V W X
Y Z AA =
o
Go
Carbonate 67 46 66 13 9
30 , 25 40
(...)
-4
Go
biodegradable amino
u,
12
30 43 (...)
. carboxylate
. .
phosphonate 7 6 ,
gluconate 50
Hydroxide salt 10* 8* 25 37 37
18
polymer
n
5 2 2
polycarboxylate
0
I.)
phosphonate 5 , 5 .
10 13 ko
ko
o Lo
IV
Water 2 2 0-10
0
H
0
I
secondary alkalinity 3 0-20 1 1
20 10 0
UJ
0
. tripolyphosphate 7 25 40 40
50 ko
Surfactant 3.5 3.5
4 4
1-d
n
1-i
cp
t..)
o
o
Go
O-
o
t..)
o
o
-4
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
cup) and pressed gently by hand. After sitting several hours (e.g., overnight
or 24
hours) the composition has cured to a stable solid composition.
Example 2 - - Makin2 Pressed Solid Compositions with a Concrete Block
Machine
In this example, stable solid block compositions were made by gentle
pressing and/or vibrating using a concrete block machine.
A self-solidifying carbonate-based cleaning composition was subjected to
pressing and vibration in a Besser Vibrapac concrete block machine. The
ingredients for the composition were mixed in 1000 lb batches. Standard
pallets of
forms (e.g., shoes) for making concrete pavers were employed. Each pallet
included
forms for 10 pavers. A total of 92 pallets were filled with mixed ingredients
under
various conditions, including those employed to set up the machine for working
with
a self-solidifying carbonate-based composition rather than concrete.
The machine was operated with vibration for feeding the composition and,
optionally, finishing the block. Feed vibration refers to vibration while
filling the
drawer, which is then moved over the pallet of forms to fill the forms.
Finishing
vibration refers to vibration while the shoes press the flowable solid into
the mold
cavities. Feed vibration was at 2800 rpm and an amplitude of 1000 (the
maximum).
Finishing vibration was at 3000 rpm and an amplitude of 1000 when used. Stable
solid blocks were formed with and without finishing vibration. The flowable
solid
was pressed in the molds with a total weight/pressure/force of about 100 lbs.
The
forms (e.g., shoes) were not heated or were heated to 115 to 150 F during
vibrating
and/or pressing. A block was determined to be suitable if, when pushed out of
the
form, the block retained its shape.
After the settings for the machine were set for making blocks of the self-
solidifying carbonate-based composition, 910 blocks were made with only 32
blocks
that did not solidify to form a stable solid block. Nearly all of these blocks
weighed
4.2 to 5.1 pounds, a few weighed as little as 4.1 pounds or up to nearly 5.2
pounds.
Example 3- - Pressed Solid Compositions are Dimensionally Stable
The experiments detailed below demonstrate that the solid compositions
according to the present invention were dimensionally stable.
67
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
Materials and Methods
Compositions AB, AC, and AD (Table 3) were compositions of the present
invention including a straight chain saturated mono-, di-, or tri- carboxylic
acid salt
in the binding agent. Compositions AE, AF, AG, AH, Al, and Al (Table 3) were
compositions of the present invention including an aminocarboxylate in the
binding
agent. Compositions AK, AL, and AM (Table 3) were compositions of the present
invention including a polycarboxylate in the binding agent.
The ingredients except the straight chain saturated mono-, di-, or tri-
carboxylic acid salt, the amino carboxylate, or polycarboxylate were premixed
to
form a powder premix. The straight chain saturated mono-, di-, or Ili-
carboxylic
acid salt, the amino carboxylate, or polycarboxylate and water were premixed
to
form a liquid premix. The powder premix and the liquid premix were then mixed
together to form the flowable solid and subjected to gentle pressing as
described
above. For compositions AK and AM, the liquid premix included the sodium
hydroxide.
Control composition CA (Table 3) was similarly prepared as a control
lacking the mono-, di-, or tri- carboxylic acid salts, the aminocarboxylates,
and the
polycarboxylates.
Versene HEIDA, 52%: a Na2EDG, disodium ethanoldiglycine, available
from Dow Chemical, Midland, MI. Trilon M, 40%: a trisodium
methylgylcinediacetic acid trisodium salt solution, available from BASF
Corporation, Charlotte, NC. IDS: an iminodisuccinic acid sodium salt solution,
available from Lanxess, Leverkusen, Germany. DissolvineGL-38, 38%: a GLDA-
Na4, tetrasodium N,N-bis (carboxylatomethyl)-L-glutamate, available from Akzo
Nobel, Tarrytown, NJ. Octaquest, 37%: a EDDS, [S-S]-ethylenediaminedisuccinic
acid; and tetrasodium 3-hydroxy-2,2'-iminodisuccinate, available from Innospec
Performance Chemicals (Octel Performance Chemicals), Edison, NJ. HIDS, 50%: a
tetrasodium 3-hydroxy-2,2'-iminodisuccinate, available from Nippon Shokubai,
Osaka, Japan.
Dimensional Stability Test for Gently Pressed Solid Cleaning Compositions
A batch of solid cleaning composition according to the present invention
weighing about 50 grams was made by gentle pressing and including in the
binding
68
=
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
agent a straight chain saturated mono-, di-, or tri- carboxylic acid salt, an
aminocarboxylate, or a polycarboxylic acid polymer. Each batch of solid
cleaning
composition was made by pressing the flowable solid in a die at a gauge
pressure of
about 1000 psi (about 425 psi on the solid in the form) for about 20 seconds
to form
a puck of the solid cleaning composition. The diameter and height of the
solids were
measured and recorded. The pucks were maintained at room temperature for one
day and then placed in an oven at a temperature of about 120 F. After the
pucks
were removed from the oven, their diameters and heights were measured and
recorded. They were considered to exhibit dimensional stability if there was
less
than about 2% swelling, or growth.
=
69
=
Table 3 ¨ Embodiments of Solid Cleaning Compositions of the Present Invention
0
(wt-%)
t..)
o
o
Go
Ingredient AB AC AD AE AF AG All , Al Al AK
AL AM CA
(...)
-4
Go
Sodium
u,
55 55 52 54 55 57 59 53 53 56
57 57 57 (...)
carbonate
Sodium
3 3 3 3 3 3 3 3 3
3 3 3 3
bicarbonate
Anhydrous
sodium 3 3 3 3 3 3 3 3 3
3 3 3 3
0
metasilicate
0
Builder 20 20 20 20 20 20 20 20 20 20
20 20 20 "
61
l0
l0
polymer Hydroxide
1 1 1 1 1 1 1 1 1 1.3
1.3 1 -..., ui
polycarboxylate Salt
o "A
IV
0
Nonionic
H
3.5 3.5 3.5 3.5 2 2 3.5 3.5 3.5 3.5
3.5 3.5 3.5 0
,
surfactant
0
u.)
1
Defoamer 1 1 11 1 1 1 1 1 1
1 1 1
.
0
l0
Water 8.8 13 7.6 9.5 8.5 3.8
3.8 2. 8 11 .
Sodium citrate Polyacrylic
5.2 HEIDA 7.8 7.3
dihydrate acid
Modified
Sodium tartrate
1-d
1.4 MGDA 2.2 polyacrylic
9 n
dihydrate acid
cp
t..)
o
Sodium acetate 9.4 IDS 5 Polymaleic
7.1 =
acid
O-
c.,
t..)
c.,
c.,
-4
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
71
=
44
co
(:;)1
<4 up
c-4
n p
<4
CA 02699537 2010-03-09
WO 2008/137853
PCT/US2008/062667
(wt-%)
Ingredient AN AO AP AQ AR AS AT AU AV
Sodium carbonate 56 57 56 54 54 54. 54 52 55
Sodium bicarbonate 3 3 3 3 3 3 3 3 3
Anhydrous sodium
3 3 3 3 3 3 3 3 3
metasilicate
Sodium Citrate 10 20 20 10 10 13 10 20 20
iminodisuccinate 10
polymer
1 1 1 1 1 1 1 1 1
polycarboxylate
Nonionic surfactant 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5
Defoamer 1 1 1 1 1 1 1 1 1
Water 4.3 4.3 1 4.3
Hydroxide Salt 1.3 1.4 0.7 1.3
Carboxylate/sulfonate
6 12 6 7.8
copolymer
Carboxylate/sulfonate
2.2 2
terpolymer
Polymethacrylate 4.9 3.6
Results
The results of the testing of dimensional stability for solid compositions of
the present invention and control compositions are reported in Table 5 below.
A
negative percent increase in size represents a decrease in size.
The compositions of the present invention are dimensionally stable with
increases in size that are significantly less than 2%, with most increases
less than
1%. The control composition is not and increased in size by 2.7% and 8.2% in
diameter and height, respectively. This indicates that the binding agent of
the
present composition participates in providing dimensional stability to the
present
gently pressed solid cleaning compositions.
72
CA 02699537 2010-03-09
WO 2008/137853 PCT/US2008/062667
Table 5 - Results of dimensional stability testing for solid compositions of
the
invention.
Initial After Heating
Composition % Increase
(mm) (mm)
Diameter 45.17 45.33 0.3
AB
Height 19.15 19.17 0.1
Diameter 44.69 44.86 0.4
AC
Height 21.03 21.07 0.1
Diameter 45.38 45.46 0.1
AD
Height 20 20.08_ 0.4
Diameter 45.51 45.82 0.7
AE
Height 19.14 19.4 _ 1.4
Diameter 44.77 45.08 0.7
AF
Height 19.37 19.61 1.2
Diameter 44.75 44.75 0
AG
Height 19.87 19.89 0.1
Diameter 44.7 44.76 0.1
AH _
Height 19.87 20.02 0.7
Diameter 44.69 44.96 0.6
Al
Height 19.24 19.08 -0.8
Diameter 44.94 45.08 , 0.3
A.1
Height 19.74 19.99 1.3
Diameter 44.69 44.96 , 0.6
AK
Height 20.64 20.87 1.1
Diameter 44.69 44.71 0
AL
Height 19.76 19.64 -0.6
Diameter 45.03 45.44 0.9
AM
Height 19.66 19.89 1.2
73
CA 02699537 2014-03-06
WO 2008/137853 PCT/US2008/062667
=
Initial After Heating
Composition % Increase
(mm) (mm)
Diameter 44.69 44.99 0.7
AN
Height 18.7 19 1.6
Diameter , 44.81 45.2 0.9
AO
Height 19.21 19.48 1.4
Diameter 44.67 45.2 1.2
AP
Height 19.68 19.93 1.3
Diameter 44.81 45 _ 0.4
AQ
Height 19.58 19.78 1.0
Diameter 44.90 45.01 0.2
AR
Height 19.48 19.58 0.5
Diameter 44.76 44.92 0.3
AS
Height 17.35 17.32 0.2
Diameter 44.93 45.08 0.3
AT
Height , 19.24 19.35 0.6
Diameter 44.81 44.79 0
AU
Height 19.15 19.17 0.1
Diameter 44.82 44.87 0.1
AV
Height 19,40 19.37 0.1
Diameter 44.77 46 2.7
CA (control)
Height 19.38 20.96 8.2
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 with reference to various specific and
preferred embodiments and techniques. The scope of the claims should not be
74
CA 02 699537 2 014-03-0 6
WO 2008/137853 PCT/US2008/062667
limited by the preferred embodiments set forth in the examples, but should be
given the broadest interpretation consistent with the description as a whole,
