U.S. patent application number 12/096845 was filed with the patent office on 2008-12-25 for dispensing devices and compositions therefor.
This patent application is currently assigned to RECKITT BENCKISER INC.. Invention is credited to Robert Zhong Lu.
Application Number | 20080313795 12/096845 |
Document ID | / |
Family ID | 38514945 |
Filed Date | 2008-12-25 |
United States Patent
Application |
20080313795 |
Kind Code |
A1 |
Lu; Robert Zhong |
December 25, 2008 |
Dispensing Devices and Compositions Therefor
Abstract
The present invention relates to improved toilet dispensing
devices for use in conjunction with a sanitary appliance,
particularly a toilet.
Inventors: |
Lu; Robert Zhong; (Montvale,
NJ) |
Correspondence
Address: |
NORRIS, MCLAUGHLIN & MARCUS
875 THIRD AVE, 18TH FLOOR
NEW YORK
NY
10022
US
|
Assignee: |
RECKITT BENCKISER INC.
Parsippany
NJ
|
Family ID: |
38514945 |
Appl. No.: |
12/096845 |
Filed: |
June 14, 2007 |
PCT Filed: |
June 14, 2007 |
PCT NO: |
PCT/GB07/02221 |
371 Date: |
August 19, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60816284 |
Jun 23, 2006 |
|
|
|
Current U.S.
Class: |
4/231 |
Current CPC
Class: |
C11D 7/20 20130101; C11D
3/1213 20130101; E03D 2009/024 20130101; A61L 9/05 20130101; C11D
17/0056 20130101; E03D 9/032 20130101 |
Class at
Publication: |
4/231 |
International
Class: |
E03D 9/02 20060101
E03D009/02 |
Claims
1. A cageless lavatory dispensing device comprising a hanger having
a hook end adapted to be suspended from a part of a sanitary
appliance, preferably the rim of a toilet bowl, and a compressed
solid block comprising titanium dioxide and at least one chemical
agent adapted to be suspended within the interior of the sanitary
appliance.
2. A device according to claim 1 which comprises a hanger having a
hook end, a stalk depending therefrom and a plate depending from
the stalk.
3. A device according to claim 1 which comprises a hanger having a
hook end, a stalk depending therefrom which includes a standoff
section and a plate depending from the stalk.
4. A device according to claim 2 wherein the compressed solid block
composition enrobes or encases part of the hanger.
5. A device according to claim 4 wherein the compressed solid block
composition enrobes or encases the plate.
6. A device according to claim 1 wherein the device further
includes an air treatment dispenser.
7. A device according to claim 1 wherein the compressed solid block
composition comprises titanium dioxide and further comprises one or
more chemical constituents such that when the block is immersed,
rinsed or washed with water, said chemical constituents are eluted
or dissolved into said water and forms a treatment composition
which provides a cleaning and/or sanitizing and/or disinfecting
benefit to the toilet or other sanitary appliance being treated
with the treatment composition.
8. The device according to claim 7 wherein the compressed solid
block comprises at least one surfactant.
9. A process for delivering a treatment composition to a sanitary
appliance, preferably, to the interior of a toilet bowl, which
process comprises: providing a cageless lavatory dispensing device
according to claim 1, suspending the compressed solid block within
the sanitary appliance, and, periodically flushing water about the
exterior of the compressed block to elute at least one chemical
constituent to form a treatment composition with said water which
treatment composition provides a cleaning and/or sanitizing and/or
disinfecting benefit to the sanitary appliance.
Description
[0001] The present invention relates to improvements to a
dispensing device. More particularly the present invention relates
to a device used to deliver a treatment composition to a sanitary
appliance, particularly to a toilet, which treatment composition
contains one or more chemical constituents e.g., coloring agents,
cleaning agents, disinfecting agents, anti-lime scale agents in the
form of a block. The treatment composition is formed by water
contacting the block of the device coming into contact with the one
or more chemical constituents; the block provides for the long term
release of the one or more active agents during sequential contacts
with water contacting the block of the toilet dispensing
device.
[0002] Since the advent of sanitary appliances and in particular
modern flush toilets, there has been a continuing need in the art
to provide effective ways to maintain these appliances in a
satisfactory condition between uses. The art is replete with
devices which are intended to be used as "in the bowl" (or ITB) or
"in the cistern" (or ITC) in order to provide a coloring and/or
cleaning and/or fragrancing and/or sanitizing effect to such
sanitary devices, particularly toilet bowls.
[0003] One common approach known to the art is to provide a device
which is at least immersed within the cistern or tank of a toilet,
which may be either placed wholly within the interior of the toilet
such as by placement at the bottom of a toilet tank so that the
entire device is wholly immersed in water when the tank is full, or
is at least partially immersed within the water present in a toilet
tank, such as wherein such a device is suspended from a part of the
toilet tank, such as a lip or rim of the tank. Such are generally
referred to as ITC devices.
[0004] A further common approach known to the art is to provide a
device which is suspended from the rim of the toilet bowl and which
is placed at or near the interior sidewall of the toilet bowl. Such
are generally referred to as ITB devices. Such a device is designed
to typically dispense a treatment composition to the interior of a
toilet when a gel or block compositions is contacted with flushing
water, or alternately, dispensing a fragrancing composition to the
toilet bowl which is intended to counteract or mask malodors.
Typically such devices include a hanger portion which is used to
suspend a cage portion from the rim of the toilet bowl, such that
the cage portion is positioned within the path of flowing water
which is dispensed with each flush operation of the toilet. The
cage portion typically comprises a plurality of holes or apertures
which permit for the flush water to both enter and to exit the cage
portion of the device. Typically a solid block composition or a gel
composition is present within the cage. The solid block composition
and/or gel composition typically comprises one or more cleaning
constituents, e.g., one or more surfactants which provide a good
cleaning and/or foaming benefit. Often the solid block composition
and/or gel composition comprises a fragrance constituent as well
which is provided to provide some degree of malodor suppression.
For most such devices, the use of a cage is essential as in the
case of a gel compositions, as gels are not self supporting and
would not be useful without the physical supporting structure
provided by the cage. With regard to solid block compositions, such
compositions are notoriously prone to weakening and softening over
time and most are known to sell or sag over their lifetime,
particularly when approaching the end of their useful service life.
The cage acts then as a porous receptacle and support for said
blocks which would otherwise prematurely soften or disintegrate and
fall into the toilet bowl and be flushed away before their
composition is substantially consumed.
[0005] While the use of a cage is beneficial, the use of a cage is
not without attendant problems. The use of a cage requires
increased material costs, and additional manufacturing steps.
Further as such ITB devices are typically single use type devices,
once the gel or block composition is consumed or otherwise
exhausted, the consumer discards the entire ITB device which is
wasteful and contributes to the problems associated with proper
garbage disposal. With regard to costs, in most conventional rim
suspended lavatory devices comprising a hanger portion and a cage
portion, the bulk of the material is typically used to form the
cage. As such cages are typically fabricated from a synthetic
polymer, such requires specific molding operations in order to form
the rim suspended lavatory device, and to fill the cage with the
solid block composition and/or gel composition prior to use and or
sale.
[0006] Known to the art are rim suspended lavatory devices which
are lavatory blocks of paradichlorobenzene which provide no
cleaning benefit, but provide only a fragrancing benefit. Such
blocks typically erode per sublimation of the paradichlorobenzene
and/or by contact with flush water. Such rim suspended are lavatory
blocks of paradichlorobenzene are typically packaged as a solid
block or cake having extending from one side a loop of bendable
wire. A portion of the bendable wire is embedded within the
paradichlorobenzene block. The consumer is required to form the
wire into a hanger appropriate to the particular geometry of their
toilet so that the paradichlorobenzene block is positioned with the
interior of the toilet bowl.
[0007] Apart from the foregoing, while the elimination of a cage
from a conventional, rim suspended lavatory device would be
beneficial such are not believed to be known. This is due to the
fact that surfactant containing solid block compositions are known
to soften quickly and this in turn eliminates any reasonable
prospect of a useful service life when used in conjunction with a
toilet absent the support provided by the cage.
[0008] Thus, while certain known-art dispensing devices provide
beneficial malodor treatment effects, there is nonetheless a real
and continuing need in the art to provide still further improved
devices which can provide to a sanitary appliance a useful
treatment benefit, preferably a useful cleaning benefit.
[0009] The present invention, in its various aspects, provides a
lavatory dispensing device useful for the delivery of at least one
treatment composition, preferably a cleaning composition and/or a
sanitizing composition to a sanitary appliance, e.g. a toilet bowl.
The device can be used either as an ITC type device, or an ITB type
device for a sanitary appliance such as a urinal, toilet tank or
toilet bowl. In certain preferred embodiments the device according
to the invention is used as an ITB type device. In certain
alternate preferred embodiments the device according to the
invention is used as an ITC type device.
[0010] According to a first aspect of the invention there is
provided a cageless lavatory dispensing device comprising a hanger
and a compressed solid block comprising one or more chemical
constituents for use with a sanitary appliance.
[0011] According to a second aspect of the invention there is
provided a cageless lavatory dispensing device comprising a hanger
having a hook end adapted to be suspended from a part of a sanitary
appliance, particularly the rim of a toilet bowl, and a compressed
solid block comprising at least one chemical agent adapted to be
suspended within the interior of the sanitary appliance. The
dimensions and configuration of the cageless lavatory dispensing
device are such that the solid block comprising the one or more
chemical constituents are preferably positioned within the path of
flushing water which is released or dispensed by the sanitary
appliance.
[0012] According to a third aspect of the invention there is
provided a cageless lavatory dispensing device comprising a hanger
having a part adapted to be suspended from a part of a sanitary
appliance, and a compressed solid block comprising one or more
chemical constituents, wherein the device is adapted to be
suspended within the interior of the toilet bowl.
[0013] In accordance with a fourth aspect of the invention there is
provided a cageless lavatory dispensing device comprising a hanger
adapted to be suspended from the rim of a sanitary appliance,
particularly a toilet bowl, and block comprising at least one or
more chemical constituents adapted to be suspended within the
interior of the toilet bowl, wherein the block composition is long
lasting.
[0014] According to a fifth aspect of the invention there is
provided a process for delivering a treatment composition to a
sanitary appliance, especially preferably, to the interior of a
toilet bowl, which process comprises: providing a cageless lavatory
dispensing device comprising a hanger adapted to be suspended from
a part of a sanitary appliance, and a compressed block comprising
at least one or more chemical constituents adapted to be suspended
within the sanitary appliance, and, periodically flushing water
about the exterior of the compressed block to elute at least one
chemical constituent to form a treatment composition with said
water which treatment composition is used to treat a part of the
sanitary appliance.
[0015] According to a sixth aspect of the invention there is
provided a process for delivering a treatment composition to a to
the interior of a toilet bowl, which process comprises: providing a
cageless lavatory dispensing device comprising a hanger adapted to
be suspended from a part of a toilet bowl, preferably the rim
thereof, where the device further comprises a compressed block
comprising at least one chemical constituent, said compressed block
adapted to be suspended within the interior of the toilet bowl,
and, periodically flushing water about the exterior of the
compressed block to elute or release at least one chemical
constituent so to form treatment composition with the water which
is used to treat at least the interior of the toilet bowl.
[0016] According to a seventh aspect of the invention there is
provided a cageless lavatory dispensing device comprising a hanger
having a part thereof adapted to be suspended from a part of a
sanitary appliance, particularly from a part a toilet cistern or
toilet tank, and a compressed solid block comprising one or more
chemical constituents, wherein the device is adapted to be
suspended within the interior of said cistern or tank.
[0017] In accordance with a eighth aspect of the invention there is
provided a cageless lavatory dispensing device comprising a hanger
adapted to be suspended from the rim of a sanitary appliance,
particularly a part of a toilet cistern or toilet tank such as from
a part of a rim of a toilet cistern or toilet tank comprising at
one or more chemical constituents adapted to be suspended within
the interior of said cistern or tank, wherein the block composition
is long lasting.
[0018] According to a ninth aspect of the invention there is
provided a cageless lavatory dispensing device comprising a hanger
having a part thereof adapted to be suspended from a part of a
sanitary appliance, particularly from a part a toilet cistern or
toilet tank, and a compressed solid block comprising one or more
chemical constituents which necessarily includes titanium
dioxide.
[0019] According to a tenth aspect of the invention there is
provided a process for delivering a treatment composition to a
sanitary appliance, especially preferably, to the interior of a
toilet cistern or toilet tank, which process comprises: providing a
cageless lavatory dispensing device comprising a hanger adapted to
be suspended from the rim of a sanitary appliance, particularly a
part of a toilet cistern or toilet tank such as from a part of a
rim of a toilet cistern or toilet tank, and a compressed block
comprising one or more chemical constituents adapted to be
suspended within the said cistern or tank, and, periodically
immersing the exterior of the compressed block in the water within
the cistern or tank so to elute at least one chemical constituent
to form a treatment composition with the water which is used to
treat a part of the sanitary appliance.
[0020] According to a eleventh aspect of the invention there is
provided a process for delivering a treatment composition to a to
the interior of a toilet bowl, which process comprises: providing a
cageless lavatory dispensing device to the interior of a toilet
cistern or tank comprising a hanger adapted to be suspended from a
part of the toilet cistern or tank, preferably from a part of the
rim thereof, where said device further comprises a compressed block
comprising at least one chemical constituent adapted to be
suspended within the water within the cistern or tank so to elute
at release at least one chemical constituent an to form a treatment
composition therefrom which is used to treat at least the toilet
cistern or tank, and preferably to also treat the interior of the
toilet bowl when the treatment composition formed is used to flush
the toilet bowl.
[0021] In accordance with a still further aspect of the invention
there is provided as a vendible article, a cageless lavatory
dispensing device comprising a hanger and a compressed solid block
comprising one or more chemical constituents for use with a
sanitary appliance, particularly a toilet.
[0022] These and other aspects of the invention will be more
evident from a reading of the following specification.
[0023] Broadly defined, the present invention provides a cageless
lavatory dispensing device comprising a hanger and a compressed
solid block comprising one or more chemical constituents for use
with a sanitary appliance but which block composition necessarily
comprises titanium dioxide, as well as methods for its use of the
cageless lavatory dispensing device in the treatment of sanitary
appliances, particularly toilets.
[0024] The inventors have surprisingly found that notwithstanding
the existing prejudice in the prior art which dictates the use of
cages to support and contain lavatory treatment blocks, that it has
been discovered by the inventors that it is now possible to
fabricate cageless lavatory dispensing devices which comprise a
hanger and a compressed solid block composition depending from the
hanger which solid block compositions comprise one or more chemical
constituents, preferably at least a surfactant composition, which
cageless lavatory dispensing devices are useful in providing a
treatment composition to a sanitary appliance over repeated flushes
of water and/or repeated immersions in water wherein the compressed
blocks to not fall away from or break away from the hanger for a
reasonable duration of time. This result is unexpected as the prior
art dictates the use of a cage as previously described, and as is
also widely known in the art to support a lavatory block
composition over its useful lifespan, particularly wherein the
lavatory block comprises one or more surfactants. As is known to
the art, with repeated flushes of water, many such surfactant
containing lavatory blocks tend to swell and/or soften and very
frequently disintegrate or slump, thus requiring a cage to contain
the lavatory block. Alternately as is known in the art, with long
term immersion in water such as in a toilet cistern or toilet tank,
such surfactant containing lavatory blocks tend to swell and/or
soften and very frequently disintegrate or slump, thus requiring a
cage to contain the lavatory block.
[0025] The inventors have discovered that cageless lavatory
dispensing devices which comprise a hanger and a compressed solid
block composition depending from the hanger which solid block
compositions include one or more chemical constituents, preferably
at least a surfactant composition, may be formed by a process which
contemplates: (a) forming a mass comprising at least one or more
chemical constituents; (b) compressing a quantity of the mass to
encase a portion of the hanger. Optionally but preferably, the mass
comprising the at least one or more chemical constituents is mixed
and extruded into a preform shape, thereafter a portion of the
hanger is inserted into the preform shape or between a plurality of
preform shapes, and subsequently the perform shape(s) are
compressed in a die to provide the final form of the compressed
solid block composition of the cageless lavatory dispensing device.
The compressed solid blocks are retained on a part of the hanger
without the need of an enclosing cage, as well as without the need
of any separate adhesive material or composition which is placed
between the compressed solid block and the part of the hanger which
the compressed solid block contacts.
[0026] The inventors have also surprisingly discovered that the
surface appearance of the compressed solid block composition may be
significantly improved wherein there is included in the compressed
solid block composition an amount of titanium dioxide. The titanium
dioxide is necessarily present in the inventive compositions and
further is preferably included in amounts which are observed to be
effective in improving the visible surface appearance following
ageing or use of the block in a sanitary appliance, especially
following contact with and erosion by water such as flush water of
a sanitary appliance. The presence of the dioxide has been observed
to minimize or to eliminate the unattractive spotted, streaked, or
otherwise unattractive surface appearance of similar block which
include sodium sulfate as a constituent, but which exclude titanium
dioxide.
[0027] In its simplest form the hanger is merely an article which
comprises at one end, a hook end which is adapted to or configured
to suspend the hanger from a part of a sanitary appliance. The
hanger is preferably configured so to permit its use either as an
ITB device or as an ITC device. The hanger also includes a plate
which is adapted to be embedded within the compressed solid block
composition. While the hook end may be integrally formed and
approximate to the plate, quite frequently the hanger includes an
intermediate stalk connecting the hook end with the plate. The
hanger itself may be a single element of a unitary construction, or
alternately, may be formed from a plurality of elements which are
adapted to be linked or connected together. When the hanger is
formed from two or more such discrete elements, the individual
elements can be affixed, attached, or linked together to ultimately
form the hanger of the invention. The cageless lavatory dispensing
device of the invention may be provided as a multiple-use article,
wherein the consumer retains a part said device on the sanitary
appliance, but replaces a part of the said device periodically as
may be needed. In such a configuration, usually a part of the
hanger is retained and reused by a consumer, but upon consumption
of the compressed solid block, a new compressed solid block is
provided to the sanitary appliance where it may be removably
affixed to the retained part of the cageless lavatory dispensing
device. Most conveniently however the hanger is a single piece
article.
[0028] With regard to the hook end, it is to be understood that the
hook end of the hanger can be of any configuration which is
suitable to provide a hook-type support for suspending the plate
and the compressed solid block within the interior of a sanitary
appliance. Ideally, the hook is configured such that it is adapted
to be suspended over at least a part of the rim of sanitary
appliance. Such may be a rim of a urinal, a toilet bowl, or toilet
cistern or tank. The hook may be of any suitable dimension, and as
it is understood that as the configuration and geometry of sanitary
appliances vary, naturally the hook can be adapted to suit the
particular dimensional or geometric configurations of toilets.
Alternately and preferably the hook end is flexible and
configurable to adapt to various configurations and geometries so
that it may be used with different sanitary appliances. Typically
however, the hook end may be configured into a "U" shaped portion
of the hanger such that it may be used to suspend the hanger and
plate bearing the compressed solid block composition.
[0029] The hook may be provided in a rigid, preformed configuration
which is non-flexible or only sparingly flexible in order to
accommodate the dimensions of the hook to a particular sanitary
appliance. For example wherein the hook is provided as a rigid,
preformed configuration to be used in suspending the cageless
lavatory dispensing device in an ITC application the hook may be a
discrete element which is dimensioned to have a cross-section which
in adapted to accommodate a part of the upper rim or edge of a
toilet cistern or toilet tank. Such a hook may merely suspend the
device on the rim, or the hook may be configured so that when
applied to the part of the upper rim or edge of a toilet it
functions as a mechanical clip such that it is generally retained
at its point of installation and resists accidental misplacement or
movement. Additionally or alternately such a hook may further
include a connector element which may take any physical shape or
form and which is configured to cooperatively connect with a the
remaining element or elements of the cageless lavatory dispensing
device so that said remaining element or elements may be removably
affixed to such a hook. In such manner, the hook may be retained
although the remaining elements, viz., the plate bearing the
compressed block and/or the stalk may be replaced a number of times
once the compressed block is exhausted. Any suitable mechanical or
chemical fastener means may be used to provide such a function. By
way of non-limiting example may be used any of a number of
cooperating mechanical elements such as clips, hook-and-loop
fasteners, pins, springs, elastic bands, loops, eyelets as well as
chemical means including adhesives such as light or medium duty
adhesives may be used as the fastener means. Other fastener means
not elucidated herein but known to the art may also be used. In one
preferred embodiment the hook includes a part which includes a
mortise shaped element, which cooperates with the stalk or plate
which is configured as a cooperating tenon which is removably
insertable into the mortise shaped element. In another preferred
embodiment the hook includes a peg or hook, and the stalk or plate
includes a cooperating loop or eye from which the stalk and/or
plate bearing the compressed block may be suspended. The use of
such two-part embodiments of the inventive cageless lavatory block
is in certain embodiments of the invention preferred as such
provide a great deal of flexibility and also permits for the reuse
of at least one element of the cageless lavatory dispensing device
multiple times without requiring replacement of the complete
cageless lavatory dispensing device when a compressed lavatory
block is exhausted. Thus is certain embodiments, certain elements
of the cageless lavatory dispensing device may be reused, while
others are intended to be single-use elements.
[0030] Conveniently however, the hook end is provided as one or
more articulated elements which can be flexed or bent from a first
or a "folded" configuration to a second or "open hook"
configuration. It is to be understood that according to preferred
embodiments, in order to minimize the volume of the hanger and in
particular the hook end thereof, the hanger may be provided in a
collapsed or folded configuration when placed into a package. Upon
opening of the package, the consumer is then expected to easily
unfold, extend, or otherwise stretch a portion of the hanger in
order to form the hook end. A further important advantage is that
the degree of flexibility provided into the hanger in order to
provide for such a foldable and unfoldable hook end also introduces
a degree of tension when the hook end is configured to be hung upon
a sanitary appliance, and in particular the rim of a urinal, a
toilet tank or cistern, or the rim of a toilet bowl. In such a
configuration, the tension actually aids in the gripping of the
hook upon the portion of the sanitary appliance upon which it is
originally positioned by the consumer. Such tension reduces the
likelihood of lateral movement or translation from its initial
placement by a consumer unless desired by the consumer. Thus,
specific placement of the cageless lavatory dispensing device, and
a reasonable expectation that it will be retained at or near the
position in which it was originally installed by a consumer
relative upon a sanitary appliance is provided. Furthermore, the
tension provided also provides for a degree of resiliency and also
aids in the positioning of the compressed solid block at, or near,
a specific part of the sloping interior wall of a sanitary
appliance, e.g., a toilet bowl. Such can be beneficially
particularly due to the fact that flush water from the toilet bowl
typically exits from beneath the rim. Utilizing the tensile
property of the hanger, the continuous positioning of the
compressed solid block within the path of the flowing flush water
is assured under most circumstances.
[0031] As has been noted above, in certain preferred embodiments
and indeed, according to most preferred embodiments a stalk exists
to connect the plate with the hook end of the hanger. The stalk
itself may be of any dimension or length, however when used in an
embodiment of the invention wherein the device is an ITC type
device, desirably the stalk is of sufficient length to ensure that
the compressed block will be at least partially immersed, but
preferably wholly immersed, in the water present in the toilet tank
or cistern between flushes. When the stalk is used in an ITB type
device, advantageously once the hook end is suspended upon a
sanitary appliance, particularly the rim of a toilet bowl, the
stalk extends a sufficient length to the plate such that
ultimately, the positioning of the hook and the length of the stalk
as such that the compressed solid block enrobing the plate is
positioned in the path of the flush water. Again, the dimensions
and in particular the length of the stalk can be varied in order to
meet the specific requirements of a specific configuration of a
sanitary appliance, particularly in the case of a toilet bowl, the
distance from the top of the rim downwardly into the interior of
the toilet bowl, or in the case of a cistern or tank, the distance
from the top of the rim of the tank or cistern downwardly such that
the plate intersects or is beneath the waterline of the water
present in the tank or cistern between flushes. For example, when
used as an ITB device, in toilets typically found in use in North
America, the interior sloping walls of the toilet bowl are
typically of a smaller and a more circular radius, thereby
providing a "shallower" distance between the top of the rim of the
toilet bowl, and the sump or water outlet at the bottom of the
toilet bowl. In such a circumstance, a shorter stalk length is
typically adequate in order to ensure that the compressed solid
block is placed within the path of the flush water. In European
toilets, typically, the configuration of the toilet bowl and its
sloping walls are usually in the form of a more frusto-conical
configuration, thus providing a "deeper" toilet bowl as measured
from the rim to the top level of the water in the sump. In such
configuration, frequently, a longer stalk length then would be
required for a North American toilet is typically preferred. Of
course, different configurations of other toilet bowls are
contemplated as well.
[0032] The hanger of the invention also requires a plate which is
adapted to be embedded and/or enrobed within the compressed solid
block composition. The plate itself is at the end distal to the
hook end of the hanger and typically is integrally formed with the
stalk, or where a stalk is not provided, with the hook end of the
hanger. The plate itself may be essentially of any useful
configuration, but desirably, the plate is dimensioned such that it
is completely encased by the compressed solid block composition.
Conveniently, the plate has a geometry which is symmetrical about
the longitudinal center line or axis of the stalk and/or hook and
depends directly from the stalk where present, or from the end of
the hook end of the hanger. Conveniently, the plate is generally of
a flat, planar configuration, and has a uniform thickness across
its surface. However, it is also contemplated that the plate may
include regions of diminishing thickness i.e. such as tapered
sections or margins at or near the boundaries of the plate.
[0033] The plate itself need not necessarily be limited to a
generally planar, and generally two-dimensional configuration, but
may include elements or sections which extend outwardly from the
top and/or bottom surfaces of the plate, such as in the form of one
or more pegs, studs, pins, fins, rods, loops or the like which
might be useful in providing further physical support between the
plate, and the compressed solid block composition enrobing it.
Alternately, the plate may include one or more perforations passing
therethrough whereby, upon compression adjacent portions of the
solid block composition meet and pass through one or more
perforations which may be provided within the plate.
[0034] The plate itself may be of any configuration and when in a
planar form can be square, rectangular, triangular, polygonal,
ellipsoid, circular, oblate, or for that matter any configuration
which may be embedded within the interior of the compressed solid
block. Alternately, the plate can may be one or more elements such
as rods or tubes, which depend from and extend outwardly from the
stalk. While the thickness of the plate may vary, preferably it is
between 0.05-3 mm thick, preferably between 0.1 and 2 mm thick, and
most preferably between 0.25 and 1.5 mm thick. The thickness of the
plate may vary across its surface, and in certain embodiments the
thickness of the plate decreases across its dimensions with the
thickest portion of the plate being near its geometric center, and
the thinnest parts of the plate being one or more of the margins or
peripheral sections of the plate. Such may be used to form a plate
of tapering dimensions. Preferably however the plate is of
generally uniform in thickness with at least 90%, preferably at
least 95% of its surface being of a constant thickness with a
variance of not more than +/-5%.
[0035] Alternately the plate can be of a configuration other than a
planar configuration, e.g., the plate can may be one or more
elements such as rods or tubes, which depend from and extend
outwardly from the stalk.
[0036] The inventors have also unexpectedly observed that the
preferred configuration of the plate is a generally planar plate
which has sloping top edges which are angled downwardly and form an
obtuse angle with the center line (or center-axis) of the stalk or
hook of the hanger, as measured from the points from which the
edges of plate intersect the stalk or hook end. The downwardly
sloping edges may be linear or straight-edged, or arcuate. The
inventors have found that downwardly sloping edges are advantageous
in resisting pooling of water, and permit for the runoff of water
during the service life of the cageless lavatory dispensing devices
when the compressed solid blocks may have sufficiently eroded to
expose part of the plate from within the interior of the said
blocks.
[0037] Surprisingly, the inventors have found that the best
configuration for the plate is indeed a generally planar plate
having a generally uniform thickness across its surface. The
dimensions of the plate should be such that when considering the
cross-sectional area of the plate with that of the cross-sectional
laminar layer of the block within which it is positioned, the
percent coverage of the plate area to the laminar compressed solid
block area should be not more than about 90%, more preferably the
ratio is between about 10% and 90%, more preferably between about
20% and 80% of the surface area of the laminar layer or plane of
the compressed solid block composition within which the plate
lies.
[0038] The inventors have also surprisingly found that while many
plate configurations are possible, the longest service life of the
cageless lavatory dispensing devices were observed with generally
planar plates which were substantially embedded and enrobed within
the interior of the compressed solid block composition. The
compressed solid blocks do not require the use of an adhesive
substance or material intermediate the plate and the compressed
solid block in order to retain the compressed solid block on the
faces of the plate. While not wishing to be bound by the following,
it was theorized that when used as an ITB type device, during
repeated flushes of water coming into contact with the upper
surface of the compressed solid block, viz, the region from which
the stalk or hook end extends, minimal cracking or delamination of
the regions of the block which had been joined together by the
compression of the solid block was observed. This reduction of
delamination or otherwise observed as splitting of the block in
this region ensured the longer term retention of the compressed
solid block composition upon the plate, and thereby the improved
duration of the service life of the cageless lavatory dispensing
device used in conjunction with the sanitary appliance.
Surprisingly, it was observed that when perforations, including
large diameter circles or other discontinuities were present
passing through the plate, the compressed solid blocks mounted upon
the plates were observed to often prematurely fail. Again, and
while I am not wishing to be bound by the following, it is believed
that the formation of miniscule channels in the region of the
compressed solid block which had been laminated may have formed
during repeated flush cycles, and these channels passing into the
interior of the block formed cavities and/or otherwise soften the
interior of the compressed solid block in the region of such
discontinuities in the plate, thereby mechanically softening the
block and weakening its hold upon the plate. Similarly, it is also
observed that when the plate had a more three-dimensional shape,
that is to say included elements such as studs, or pins extending
outwardly from one or more faces of the plate, that again,
premature failure of the compressed solid block compositions was
observed. Again, it is believed that a similar phenomenon also
occurred, namely in the formation of microchannels in the region of
the lamination of portions of the block were formed, and provided
for the flow of flush water into the interior of the block and to
the region of the plate and particularly to the regions surrounding
the extended studs or pins. Again, this was believed to be
responsible for premature softening of the interior of the
compressed solid block, and its premature failure.
[0039] Thus, in particularly preferred embodiments, the plate
configuration is absent any perforations, as well as being absent
of any elements or protrusions extending outwardly from one or more
faces of the plate.
[0040] The hanger, whether a single unitary piece or assembled from
a composite of discrete pieces or elements may be formed from any
of a variety of materials which can be used for the purpose
described herein. Exemplary and preferred materials include metals
including wires or rods which are bendable and are preferably
coated with flexible non-metallic material such as a flexible
polymer, a paint or a sheath, as well as one or more synthetic
polymers which are preferred. Preferably the hanger may be formed
of any of a number of thermosettable or thermoformable synthetic
polymers such as are widely used in casting or injection molding.
Exemplary synthetic polymers such as polyamides, polyolefins (e.g.,
polypropylene, polyethylene) as well as polyalkyleneterephalates
(i.e., polyethylene terephthalate, polybutylene terephthalate),
polystyrenes, polysulfones, polycarbonates as well as copolymers
formed from monomers of one or more of the foregoing being several
nonlimiting examples of useful synthetic polymers. Preferably the
material of construction is at least somewhat flexible. As to the
material of construction of the hanger, the only criteria being
that the selected materials used to fabricate the hanger is not
deleteriously affected by the chemical constituents of the
compressed solid block composition with which part of the hanger,
viz., the plate and possibly part of the stalk. contacts.
[0041] The cageless lavatory dispensing devices according to the
invention necessarily also comprise a compressed solid block
comprising at least one or more chemical constituents such that
when the block is immersed, rinsed or washed with water, said
chemical constituents are eluted or dissolved into said water and
forms a treatment composition which is useful in treating a
sanitary appliance, and particularly a toilet tank or cistern or a
toilet bowl.
[0042] As chemical constituents the compressed solid block may
include any known art cleaning agents or cleaning constituents
known to those of ordinary skill in the relevant art, and without
limitation include one or more detersive surfactants selected from
anionic, cationic, nonionic as well as amphoteric or zwitterionic
surfactants. Certain detersive surfactants may also provide a dual
role in providing detergency as well as a disinfecting effect, viz,
certain cationic surfactants, which are described hereinafter as a
disinfecting agent. These one or more cleaning agents or cleaning
constituents may be used with or without other constituents being
present in the compressed solid blocks of the invention.
[0043] The solid block composition of the invention desirably
comprises a surfactant constituent which may be one or more
detersive surfactants. Exemplary useful surfactants include
anionic, nonionic, cationic, amphoteric, and zwitterionic
surfactants, particularly those whose melting points are
sufficiently high, above about 110.degree. F., preferably above
125.degree. F., to permit processing according to known art
techniques. However, small amounts of low melting point surfactants
and even liquid surfactants may be used in providing the surfactant
constituent.
[0044] Exemplary useful anionic surfactants which may be used in
the compressed solid block composition of the invention can be
broadly described as the water-soluble salts, particularly the
alkali metal salts, of organic sulfuric acid reaction products
having in their molecular structure an alkyl or alkaryl radical
containing from about 8 to about 22 carbon atoms and a radical
selected from the group consisting of sulfonic acid and sulfuric
acid ester radicals. (Included in the term alkyl is the alkyl
portion of higher acyl radicals.) Important examples of the anionic
surfactants which can be employed in practicing the present
invention are the sodium or potassium alkyl sulfates, especially
those obtained by sulfating the higher alcohols (C.sub.8-C.sub.18
carbon atoms) produced by reducing the glycerides of tallow or
coconut oil; sodium or potassium alkyl benzene sulfonates, in which
the alkyl group contains from about 9 to about 15 carbon atoms,
(the alkyl radical can be a straight or branched aliphatic chain);
paraffin sulfonate surfactants having the general formula RSO.sub.3
M, wherein R is a primary or secondary alkyl group containing from
about 8 to about 22 carbon atoms (preferably 10 to 18 carbon atoms)
and M is an alkali metal, e.g., sodium, lithium or potassium;
sodium alkyl glyceryl ether sulfonates, especially those ethers of
the higher alcohols derived from tallow and coconut oil; sodium
coconut oil fatty acid monoglyceride sulfates and sulfonates;
sodium or potassium salts of sulfuric acid esters of the reaction
product of one mole of a higher fatty alcohol (e.g., tallow or
coconut oil alcohols) and about 1 to 10 moles of ethylene oxide;
sodium or potassium salts of alkyl phenol ethylene oxide ether
sulfates with about 1 to about 10 units of ethylene oxide per
molecule and in which the alkyl radicals contain from about 8 to
about 12 carbon atoms; the reaction products of fatty acids
esterified with isethionic acid and neutralized with sodium
hydroxide where, for example, the fatty acids are derived from
coconut oil; sodium or potassium salts of fatty acid amides of a
methyl tauride in which the fatty acids, for example, are derived
from coconut oil and sodium or potassium .beta.-acetoxy- or
.beta.-acetamido-alkanesulfonates where the alkane has from 8 to 22
carbon atoms.
[0045] A preferred class of anionic surfactants are linear alkyl
benzene sulfonate surfactant wherein the alkyl portion contains 8
to 16 carbon atoms, and most preferably about 11 to 13 carbon
atoms. According to particularly preferred embodiments of the
invention, the solid block compositions necessarily include an
anionic surfactant.
[0046] A further preferred class of anionic surfactants are alpha
olefin sulfonates, as well as salts thereof, e.g., alkali metal
salts. Preferred are C.sub.8 through C.sub.22 alpha olefin
sulfonates, particularly C.sub.12 through C.sub.18, and especially
C.sub.14, and C.sub.16 alpha olefin sulfonates as well as blends of
two or more thereof. According to particularly preferred
embodiments of the invention, the solid block compositions
necessarily include an alpha olefin sulfonate anionic
surfactant.
[0047] The detersive surfactant constituent of the solid block
composition of the invention may include one or more nonionic
surfactants. Practically any hydrophobic compound having a carboxy,
hydroxy, amido, or amino group with a free hydrogen attached to the
nitrogen can be condensed with an alkylene oxide, especially
ethylene oxide or with the polyhydration product thereof, a
polyalkylene glycol, especially polyethylene glycol, to form a
water soluble or water dispersible nonionic surfactant compound.
Further, the length of the polyethenoxy hydrophobic and hydrophilic
elements may various. Exemplary nonionic compounds include the
polyoxyethylene ethers of alkyl aromatic hydroxy compounds, e.g.,
alkylated polyoxyethylene phenols, polyoxyethylene ethers of long
chain aliphatic alcohols, the polyoxyethylene ethers of hydrophobic
propylene oxide polymers, and the higher alkyl amine oxides.
[0048] One class of useful nonionic surfactants include
polyalkylene oxide condensates of alkyl phenols. These compounds
include the condensation products of alkyl phenols having an alkyl
group containing from about 6 to 12 carbon atoms in either a
straight chain or branched chain configuration with an alkylene
oxide, especially an ethylene oxide, the ethylene oxide being
present in an amount equal to 5 to 25 moles of ethylene oxide per
mole of alkyl phenol. The alkyl substituent in such compounds can
be derived, for example, from polymerized propylene, diisobutylene
and the like. Examples of compounds of this type include nonyl
phenol condensed with about 9.5 moles of ethylene oxide per mole of
nonyl phenol; dodecylphenol condensed with about 12 moles of
ethylene oxide per mole of phenol; dinonyl phenol condensed with
about 15 moles of ethylene oxide per mole of phenol and diisooctyl
phenol condensed with about 15 moles of ethylene oxide per mole of
phenol.
[0049] A further class of useful nonionic surfactants include the
condensation products of aliphatic alcohols with from about 1 to
about 60 moles of an alkylene oxide, especially an ethylene oxide.
The alkyl chain of the aliphatic alcohol can either be straight or
branched, primary or secondary, and generally contains from about 8
to about 22 carbon atoms. Examples of such ethoxylated alcohols
include the condensation product of myristyl alcohol condensed with
about 10 moles of ethylene oxide per mole of alcohol and the
condensation product of about 9 moles of ethylene oxide with
coconut alcohol (a mixture of fatty alcohols with alkyl chains
varying in length from about 10 to 14 carbon atoms). Other examples
are those C.sub.6-C.sub.11 straight-chain alcohols which are
ethoxylated with from about 3 to about 6 moles of ethylene oxide.
Their derivation is well known in the art. Examples include
Alfonic.RTM. 810-4.5, which is described in product literature from
Sasol as a C.sub.8-C.sub.10 straight-chain alcohol having an
average molecular weight of 356, an ethylene oxide content of about
4.85 moles (about 60 wt. %), and an HLB of about 12; Alfonic.RTM.
810-2, which is described in product literature as a
C.sub.8-C.sub.10 straight-chain alcohols having an average
molecular weight of 242, an ethylene oxide content of about 2.1
moles (about 40 wt. %), and an HLB of about 12; and Alfonic.RTM.
610-3.5, which is described in product literature as having an
average molecular weight of 276, an ethylene oxide content of about
3.1 moles (about 50 wt. %), and an HLB of 10. Other examples of
alcohol ethoxylates are C.sub.10 oxo-alcohol ethoxylates available
from BASF under the Lutensol.RTM. ON tradename. They are available
in grades containing from about 3 to about 11 moles of ethylene
oxide (available under the names Lutensol.RTM. ON 30; Lutensol.RTM.
ON 50; Lutensol.RTM. ON 60; Lutensol.RTM. ON 65; Lutensol.RTM. ON
66; Lutensol.RTM. ON 70; Lutensol.RTM. ON 80; and Lutensol.RTM.ON
110). Other examples of ethoxylated alcohols include the
Neodol.RTM. 91 series non-ionic surfactants available from Shell
Chemical Company which are described as C.sub.9-C.sub.11
ethoxylated alcohols. The Neodol.RTM. 91 series non-ionic
surfactants of interest include Neodol.RTM. 91-2.5, Neodol.RTM.
91-6, and Neodol.RTM. 91-8. Neodol.RTM. 91-2.5 has been described
as having about 2.5 ethoxy groups per molecule; Neodol 91-6 has
been described as having about 6 ethoxy groups per molecule; and
Neodol 91-8 has been described as having about 8 ethoxy groups per
molecule. Further examples of ethoxylated alcohols include the
Rhodasurf.RTM. DA series non-ionic surfactants available from
Rhodia which are described to be branched isodecyl alcohol
ethoxylates. Rhodasurf.RTM. DA-530 has been described as having 4
moles of ethoxylation and an HLB of 10.5; Rhodasurf.RTM. DA-630 has
been described as having 6 moles of ethoxylation with an HLB of
12.5; and Rhodasurf.RTM. DA-639 is a 90% solution of DA-630.
Further examples of ethoxylated alcohols include those from Tomah
Products (Milton, Wis.) under the Tomadol.RTM. tradename with the
formula RO(CH.sub.2CH.sub.2O).sub.nH where R is the primary linear
alcohol and n is the total number of moles of ethylene oxide. The
ethoxylated alcohol series from Tomah include 91-2.5; 91-6; 91-8-
where R is linear C.sub.9/C.sub.10/C.sub.11 and n is 2.5, 6, or 8;
1-3; 1-5; 1-7; 1-73B; 1-9; where R is linear C.sub.11 and n is 3,
5, 7 or 9; 23-1; 23-3; 23-5; 23-6,5- where R is linear
C.sub.12/C.sub.13 and n is 1, 3, 5, or 6.5; 25-3; 25-7; 25-9;
25-12- where R is linear C.sub.12/C.sub.13/C.sub.14/C.sub.15 and n
is 3, 7, 9, or 12; and 45-7; 45-13- where R is linear
C.sub.14/C.sub.15 and n is 7 or 13.
[0050] A further class of useful nonionic surfactants include
primary and secondary linear and branched alcohol ethoxylates, such
as those based on C.sub.6-C.sub.18 alcohols which further include
an average of from 2 to 80 moles of ethoxylation per mol of
alcohol. These examples include the Genapol.RTM. UD (ex. Clariant,
Muttenz, Switzerland) described under the tradenames Genapol.RTM.
UD 030, C.sub.11-oxo-alcohol polyglycol ether with 3 EO;
Genapol.RTM. UD, 050 C.sub.11-oxo-alcohol polyglycol ether with 5
EO; Genapol.RTM. UD 070, C.sub.11-oxo-alcohol polyglycol ether with
7 EO; Genapol.RTM. UD 080, C.sub.11-oxo-alcohol polyglycol ether
with 8 EO; Genapol.RTM. UD 088, C.sub.11-oxo-alcohol polyglycol
ether with 8 EO; and Genapol.RTM. UD 110, C.sub.11-oxo-alcohol
polyglycol ether with 11 EO.
[0051] Exemplary useful nonionic surfactants include the
condensation products of a secondary aliphatic alcohols containing
8 to 18 carbon atoms in a straight or branched chain configuration
condensed with 5 to 30 moles of ethylene oxide. Examples of
commercially available nonionic detergents of the foregoing type
are those presently commercially available under the trade name of
Tergitol.RTM. such as Tergitol 15-S-12 which is described as being
C.sub.11-C.sub.15 secondary alkanol condensed with 9 ethylene oxide
units, or Tergitol 15-S-9 which is described as being
C.sub.11-C.sub.15 secondary alkanol condensed with 12 ethylene
oxide units per molecule.
[0052] A further class of useful nonionic surfactants include those
surfactants having a formula:
RO(CH.sub.2CH.sub.2O).sub.nH
wherein; R is a mixture of linear, even carbon-number hydrocarbon
chains ranging from C.sub.12H.sub.25 to C.sub.16H.sub.33 and n
represents the number of ethoxy repeating units and is a number of
from about 1 to about 12.
[0053] Surfactants of this formula are presently marketed under the
Genapol.RTM. tradename (ex. Clariant), which surfactants include
the "26-L" series of the general formula
RO(CH.sub.2CH.sub.2O).sub.nH wherein R is a mixture of linear, even
carbon-number hydrocarbon chains ranging from C.sub.12H.sub.25 to
C.sub.16H.sub.33 and n represents the number of repeating units and
is a number of from 1 to about 12, such as
26-L-1,26-L-1,6,26-L-2,26-L-3,26-L-5,26-L-45, 26-L-50, 26-L-60,
26-L-60N, 26-L-75, 26-L-80, 26-L-98N, and the 24-L series, derived
from synthetic sources and typically contain about 55% C.sub.12 and
45% C.sub.1-4 alcohols, such as 24-L-3,24-L-45, 24-L-50, 24-L-60,
24-L-60N, 24-L-75, 24-L-92, and 24-L-98N, all sold under the
Genapol.RTM. tradename.
[0054] Further useful non-ionic surfactants which may be used in
the inventive compositions include those presently marketed under
the trade name Pluronics.RTM. (ex. BASF). The compounds are formed
by condensing ethylene oxide with a hydrophobic base formed by the
condensation of propylene oxide with propylene glycol. The
molecular weight of the hydrophobic portion of the molecule is of
the order of 950 to 4,000 and preferably 200 to 2,500. The addition
of polyoxyethylene radicals of the hydrophobic portion tends to
increase the solubility of the molecule as a whole so as to make
the surfactant water-soluble. The molecular weight of the block
polymers varies from 1,000 to 15,000 and the polyethylene oxide
content may comprise 20% to 80% by weight. Preferably, these
surfactants are in liquid form and particularly satisfactory
surfactants are available as those marketed as Pluronics.RTM. L62
and Pluronics.RTM. L64.
[0055] Further nonionic surfactants which may be included in the
inventive compositions include alkoxylated alkanolamides,
preferably C.sub.8-C.sub.24 alkyl di(C.sub.2-C.sub.3 alkanol
amides), as represented by the following formula:
R.sub.5--CO--NH--R.sub.6--OH
wherein R.sub.5 is a branched or straight chain C.sub.8-C.sub.24
alkyl radical, preferably a C.sub.10-C.sub.16 alkyl radical and
more preferably a C.sub.12-C.sub.14 alkyl radical, and R.sub.6 is a
C.sub.1-C.sub.4 alkyl radical, preferably an ethyl radical.
[0056] According to certain particularly preferred embodiments the
detersive surfactant constituent necessarily comprises a nonionic
surfactant based on a linear primary alcohol ethoxylate
particularly wherein the alkyl portion is a C.sub.8 to C.sub.16,
but particularly a C.sub.9 to C.sub.11 alkyl group, and having an
average of between about 6 to about 8 moles of ethoxylation.
[0057] One further useful class of nonionic surfactants include
those in which the major portion of the molecule is made up of
block polymeric C.sub.2-C.sub.4 alkylene oxides, with alkylene
oxide blocks containing C.sub.3 to C.sub.4 alkylene oxides. Such
nonionic surfactants, while preferably built up from an alkylene
oxide chain starting group, can have as a starting nucleus almost
any active hydrogen containing group including, without limitation,
amides, phenols, and secondary alcohols.
[0058] One group of nonionic surfactants containing the
characteristic alkylene oxide blocks are those which may be
generally represented by the formula (A):
HO-(EO).sub.x(PO).sub.y(EO).sub.z--H (A)
where [0059] EO represents ethylene oxide, [0060] PO represents
propylene oxide, [0061] y equals at least 15, [0062] (EO).sub.x+z
equals 20 to 50% of the total weight of said compounds, and, [0063]
the total molecular weight is preferably in the range of about 2000
to 15,000.
[0064] Another group of nonionic surfactants appropriate for use in
the new compositions can be represented by the formula (B):
R-(EO,PO).sub.a(EO,PO).sub.b--H (B)
wherein [0065] R is an alkyl, aryl or aralkyl group, [0066] the
alkoxy group contains 1 to 20 carbon atoms, the weight percent of
EO is within the range of 0 to 45% in one of the blocks a, b, and
within the range of 60 to 100% in the other of the blocks a, b, and
the total number of moles of combined EO and PO is in the range of
6 to 125 moles, with 1 to 50 moles in the PO rich block and 5 to
100 moles in the EO rich block.
[0067] Further nonionic surfactants which in general are
encompassed by Formula B include butoxy derivatives of propylene
oxide/ethylene oxide block polymers having molecular weights within
the range of about 2000-5000.
[0068] Still further useful nonionic surfactants containing
polymeric butoxy (BO) groups can be represented by formula (C) as
follows:
RO--(BO).sub.n(EO).sub.x--H (C)
wherein [0069] R is an alkyl group containing 1 to 20 carbon atoms,
[0070] n is about 15 and x is about 15.
[0071] Also useful as the nonionic block copolymer surfactants
which also include polymeric butoxy groups are those which may be
represented by the following formula (D):
HO-(EO).sub.x(BO).sub.n(EO).sub.y--H (D)
wherein [0072] n is about 15, [0073] x is about 15 and [0074] y is
about 15.
[0075] Still further useful nonionic block copolymer surfactants
include ethoxylated derivatives of propoxylated ethylene diamine,
which may be represented by the following formula:
##STR00001##
where [0076] (EO) represents ethoxy, [0077] (PO) represents
propoxy,
[0078] the amount of (PO).sub.x is such as to provide a molecular
weight prior to ethoxylation of about 300 to 7500, and the amount
of (EO).sub.y is such as to provide about 20% to 90% of the total
weight of said compound.
[0079] Further useful nonionic surfactants include nonionic amine
oxide constituent. Exemplary amine oxides include:
[0080] A) Alkyl di (lower alkyl) amine oxides in which the alkyl
group has about 10-20, and preferably 12-16 carbon atoms, and can
be straight or branched chain, saturated or unsaturated. The lower
alkyl groups include between 1 and 7 carbon atoms. Examples include
lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, and
those in which the alkyl group is a mixture of different amine
oxide, dimethyl cocoamine oxide, dimethyl (hydrogenated tallow)
amine oxide, and myristyl/palmityl dimethyl amine oxide; [0081] B)
Alkyl di (hydroxy lower alkyl) amine oxides in which the alkyl
group has about 10-20, and preferably 12-16 carbon atoms, and can
be straight or branched chain, saturated or unsaturated. Examples
are bis(2-hydroxyethyl)cocoamine oxide,
bis(2-hydroxyethyl)tallowamine oxide; and
bis(2-hydroxyethyl)stearylamine oxide;
[0082] C) Alkylamidopropyl di(lower alkyl)amine oxides in which the
alkyl group has about 10-20, and preferably 12-16 carbon atoms, and
can be straight or branched chain, saturated or unsaturated.
Examples are cocoamidopropyl dimethyl amine oxide and
tallowamidopropyl dimethyl amine oxide; and
[0083] D) Alkylmorpholine oxides in which the alkyl group has about
10-20, and preferably 12-16 carbon atoms, and can be straight or
branched chain, saturated or unsaturated.
[0084] Preferably the amine oxide constituent is an alkyl di(lower
alkyl)amine oxide as denoted above and which may be represented by
the following structure:
##STR00002##
wherein each:
[0085] R.sub.1 is a straight chained C.sub.1-C.sub.4 alkyl group,
preferably both R.sub.1 are methyl groups; and,
[0086] R.sub.2 is a straight chained C.sub.8-C.sub.18 alkyl group,
preferably is C.sub.10-C.sub.14 alkyl group, most preferably is a
C.sub.12 alkyl group.
[0087] Each of the alkyl groups may be linear or branched, but most
preferably are linear. Most preferably the amine oxide constituent
is lauryl dimethyl amine oxide. Technical grade mixtures of two or
more amine oxides may be used, wherein amine oxides of varying
chains of the R.sub.2 group are present. Preferably, the amine
oxides used in the present invention include R.sub.2 groups which
comprise at least 50% wt., preferably at least 60% wt. of C.sub.1-2
alkyl groups and at least 25% wt. of C.sub.1-4 alkyl groups, with
not more than 15% wt. of C.sub.16, C.sub.18 or higher alkyl groups
as the R.sub.2 group.
[0088] Still further exemplary useful nonionic surfactants which
may be used include certain alkanolamides including
monoethanolamides and diethanolamides, particularly fatty
monoalkanolamides and fatty dialkanolamides.
[0089] A cationic surfactant may be incorporated as a germicide or
as a detersive surfactant in the solid block composition of the
present invention, particularly wherein a bleach constituent is
absent from the solid block composition. Cationic surfactants are
per se, well known, and exemplary useful cationic surfactants may
be one or more of those described for example in McCutcheon's
Functional Materials, Vol. 2, 1998; Kirk-Othmer, Encyclopedia of
Chemical Technology, 4th Ed., Vol. 23, pp. 481-541 (1997), the
contents of which are herein incorporated by reference. These are
also described in the respective product specifications and
literature available from the suppliers of these cationic
surfactants.
[0090] Examples of preferred cationic surfactant compositions
useful in the practice of the instant invention are those which
provide a germicidal effect to the concentrate compositions, and
especially preferred are quaternary ammonium compounds and salts
thereof, which may be characterized by the general structural
formula:
##STR00003##
where at least one of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 is a
alkyl, aryl or alkylaryl substituent of from 6 to 26 carbon atoms,
and the entire cation portion of the molecule has a molecular
weight of at least 165. The alkyl substituents may be long-chain
alkyl, long-chain alkoxyaryl, long-chain alkylaryl,
halogen-substituted long-chain alkylaryl, long-chain
alkylphenoxyalkyl, arylalkyl, etc. The remaining substituents on
the nitrogen atoms other than the abovementioned alkyl substituents
are hydrocarbons usually containing no more than 12 carbon atoms.
The substituents R.sub.1, R.sub.2, R.sub.3 and R.sub.4 may be
straight-chained or may be branched, but are preferably
straight-chained, and may include one or more amide, ether or ester
linkages. The counterion X may be any salt-forming anion which
permits water solubility of the quaternary ammonium complex.
[0091] Exemplary quaternary ammonium salts within the above
description include the alkyl ammonium halides such as cetyl
trimethyl ammonium bromide, alkyl aryl ammonium halides such as
octadecyl dimethyl benzyl ammonium bromide, N-alkyl pyridinium
halides such as N-cetyl pyridinium bromide, and the like. Other
suitable types of quaternary ammonium salts include those in which
the molecule contains either amide, ether or ester linkages such as
octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride,
N-(laurylcocoaminoformylmethyl)-pyridinium chloride, and the like.
Other very effective types of quaternary ammonium compounds which
are useful as germicides include those in which the hydrophobic
radical is characterized by a substituted aromatic nucleus as in
the case of lauryloxyphenyltrimethyl ammonium chloride,
cetylaminophenyltrimethyl ammonium methosulfate,
dodecylphenyltrimethyl ammonium methosulfate,
dodecylbenzyltrimethyl ammonium chloride, chlorinated
dodecylbenzyltrimethyl ammonium chloride, and the like.
[0092] Preferred quaternary ammonium compounds which act as
germicides and which are be found useful in the practice of the
present invention include those which have the structural
formula:
##STR00004##
wherein R.sub.2 and R.sub.3 are the same or different
C.sub.8-C.sub.12alkyl, or R.sub.2 is C.sub.12-16alkyl,
C.sub.8-18alkylethoxy, C.sub.8-18alkylphenolethoxy and R.sub.3 is
benzyl, and X is a halide, for example chloride, bromide or iodide,
or is a methosulfate anion. The alkyl groups recited in R.sub.2 and
R.sub.3 may be straight-chained or branched, but are preferably
substantially linear.
[0093] Particularly useful quaternary germicides include
compositions which include a single quaternary compound, as well as
mixtures of two or more different quaternary compounds. Such useful
quaternary compounds are available under the BARDAC.RTM.,
BARQUAT.RTM., HYAMINE.RTM., LONZABAC.RTM., and ONYXIDE.RTM.
trademarks, which are more fully described in, for example,
McCutcheon's Functional Materials (Vol. 2), North American Edition,
1998, as well as the respective product literature from the
suppliers identified below. For example, BARDAC.RTM. 205M is
described to be a liquid containing alkyl dimethyl benzyl ammonium
chloride, octyl decyl dimethyl ammonium chloride; didecyl dimethyl
ammonium chloride, and dioctyl dimethyl ammonium chloride (50%
active) (also available as 80% active (BARDAC.RTM. 208M));
described generally in McCutcheon's as a combination of alkyl
dimethyl benzyl ammonium chloride and dialkyl dimethyl ammonium
chloride); BARDAC.RTM. 2050 is described to be a combination of
octyl decyl dimethyl ammonium chloride/didecyl dimethyl ammonium
chloride, and dioctyl dimethyl ammonium chloride (50% active) (also
available as 80% active (BARDAC.RTM. 2080)); BARDAC.RTM. 2250 is
described to be didecyl dimethyl ammonium chloride (50% active);
BARDAC.RTM. LF (or BARDAC.RTM. LF-80), described as being based on
dioctyl dimethyl ammonium chloride (BARQUAT.RTM. MB-50, MX-50,
OJ-50 (each 50% liquid) and MB-80 or MX-80 (each 80% liquid) are
each described as an alkyl dimethyl benzyl ammonium chloride;
BARDAC.RTM. 4250 and BARQUAT.RTM. 4250Z (each 50% active) or
BARQUAT.RTM. 4280 and BARQUAT 4280Z (each 80% active) are each
described as alkyl dimethyl benzyl ammonium chloride/alkyl dimethyl
ethyl benzyl ammonium chloride. Also, HYAMINE.RTM. 1622, described
as diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium
chloride (50% solution); HYAMINE.RTM. 3500 (50% actives), described
as alkyl dimethyl benzyl ammonium chloride (also available as 80%
active (HYAMINE.RTM. 3500-80)); and HYMAINE.RTM. 2389 described as
being based on methyldodecylbenzyl ammonium chloride and/or
methyldodecylxylene-bis-trimethyl ammonium chloride. (BARDAC.RTM.,
BARQUAT.RTM. and HYAMINE.RTM. are presently commercially available
from Lonza, Inc., Fairlawn, N.J.). BTC.RTM. 50 NF (or BTC.RTM. 65
NF) is described to be alkyl dimethyl benzyl ammonium chloride (50%
active); BTC.RTM. 99 is described as didecyl dimethyl ammonium
chloride (50% active); BTC.RTM. 776 is described to be
myrisalkonium chloride (50% active); BTC.RTM. 818 is described as
being octyl decyl dimethyl ammonium chloride, didecyl dimethyl
ammonium chloride, and dioctyl dimethyl ammonium chloride (50%
active) (available also as 80% active (BTC.RTM. 818-80%)); BTC.RTM.
824 and BTC.RTM. 835 are each described as being of alkyl dimethyl
benzyl ammonium chloride (each 50% active); BTC.RTM. 885 is
described as a combination of BTC.RTM. 835 and BTC.RTM. 818 (50%
active) (available also as 80% active (BTC.RTM. 888)); BTC.RTM.
1010 is described as didecyl dimethyl ammonium chloride (50%
active) (also available as 80% active (BTC.RTM. 1010-80)); BTC.RTM.
2125 (or BTC.RTM. 2125 M) is described as alkyl dimethyl benzyl
ammonium chloride and alkyl dimethyl ethylbenzyl ammonium chloride
(each 50% active) (also available as 80% active (BTC.RTM. 2125 80
or BTC.RTM. 2125 M)); BTC.RTM. 2565 is described as alkyl dimethyl
benzyl ammonium chlorides (50% active) (also available as 80%
active (BTC.RTM. 2568)); BTC.RTM. 8248 (or BTC.RTM. 8358) is
described as alkyl dimethyl benzyl ammonium chloride (80% active)
(also available as 90% active (BTC.RTM. 8249)); ONYXIDE.RTM. 3300
is described as n-alkyl dimethyl benzyl ammonium saccharinate (95%
active). (BTC.RTM. and ONYXIDE.RTM. are presently commercially
available from Stepan Company, Northfield, Ill.) Polymeric
quaternary ammonium salts based on these monomeric structures are
also considered desirable for the present invention. One example is
POLYQUAT.RTM., described as being a 2-butenyldimethyl ammonium
chloride polymer.
[0094] Preferred quaternary germicides used in the compressed solid
block compositions are those which are supplied in a solid or
powdered form, as such greatly facilitates the manufacture of the
compressed solid block compositions.
[0095] When present in a compressed solid block composition, it is
preferred that the germicidal cationic surfactant(s) are present in
amounts so to dispense at least about 200 parts per million (ppm)
in the water flushed into the sanitary appliance, e.g., toilet
bowl, or into the water retained in the sanitary appliance at the
conclusion of the flush cycle.
[0096] Further detersive surfactants which may be included are
amphoteric and zwitterionic surfactants which provide a detersive
effect. Exemplary useful amphoteric surfactants include
alkylbetaines, particularly those which may be represented by the
following structural formula:
RN.sup.+(CH.sub.3).sub.2CH.sub.2COO.sup.-
wherein R is a straight or branched hydrocarbon chain which may
include an aryl moiety, but is preferably a straight hydrocarbon
chain containing from about 6 to 30 carbon atoms. Further exemplary
useful amphoteric surfactants include amidoalkylbetaines, such as
amidopropylbetaines which may be represented by the following
structural formula:
RCONHCH.sub.2CH.sub.2CH.sub.2N.sup.+(CH.sub.3).sub.2CH.sub.2COO.sup.-
wherein R is a straight or branched hydrocarbon chain which may
include an aryl moiety, but is preferably a straight hydrocarbon
chain containing from about 6 to 30 carbon atoms.
[0097] As noted above, preferred detersive surfactants are those
which exhibit a melting points above about 110.degree. F.,
preferably above 125.degree. F., in order to permit convenient
processing according to known art techniques. Nonetheless small
amounts of low melting point surfactants, i.e., those exhibiting
melting points below about 110.degree. F. and even liquid
surfactants may be used in providing the surfactant constituent of
the solid block composition.
[0098] As the performance requirements of the compressed solid
blocks may differ according to their use as either an ITB or as an
ITC block, the amounts of the constituents present in the block may
vary as well depending upon the final intended use of the treatment
block.
[0099] When intended for use as an ITB block, the detersive
surfactant constituent may be present in any effective amount and
generally comprises up to about 90% wt. of the total weight of the
solid block composition, and the resultant treatment block formed
therefrom. Preferably the detersive surfactant constituent
comprises about 20-90% wt., more preferably 35-80% wt. of the solid
block composition, and when used as an ITB block the detersive
surfactant constituent most preferably comprises about 50-75% wt.
of the solid block composition, and the resultant treatment block
formed therefrom. When intended for use as an ITC block, the
detersive surfactant constituent may be present in any effective
amount and generally comprises up to about 60% wt. of the total
weight of the solid block composition, and the resultant treatment
block formed therefrom. Preferably the detersive surfactant
constituent comprises about 10-55% wt., more preferably 20-50% wt.
of the solid block composition, and the resultant treatment block
formed therefrom.
[0100] In particularly preferred embodiments the compressed solid
blocks of the invention necessarily comprise at least one
surfactant, preferably at least one anionic surfactant.
[0101] As noted previously, the inventors have also surprisingly
discovered that the surface appearance of the compressed solid
block composition may be significantly improved wherein there is
included in the compressed solid block composition an amount of
titanium dioxide. According to the present invention titanium
dioxide is necessarily present in the compressed solid block
compositions described herein. The present inventors have observed
that the inclusion of titanium dioxide beneficially improves the
visual surface appearance of the compressed solid block
compositions particularly following contact with and erosion by
water such as flush water of a sanitary appliance. This surprising
and unexpected effect has been observed with various compressed
solid block compositions and particularly pronounced reduction or
elimination of an unattractive spotted, streaked or speckled
surface appearance due to the inclusion of the titanium dioxide.
The inclusion of titanium dioxide, particularly in the preferred
amounts indicated herein exhibit a reduction in the amount of
visible white spots at the surface of the block as it erodes. It is
believed that these white spots or streaked may be crystallized
and/or agglomerated silica which are visibly discernible and
provide a mottled surface appearance when ordinarily observed. Such
is highly undesirable from a consumer standpoint and is most
desirably avoided. Surprisingly the he inclusion of titanium
dioxide in the block composition appears to minimize and/or inhibit
the formation of such visible white spots or surface regions to a
significant degree. This surprising benefit has been specifically
observed with compressed solid blocks which also comprise a sulfate
salt, especially sodium sulfate as a further constituent. The
distinctions between similar compressed solid block compositions,
one containing titanium dioxide and sodium sulfate, the other
containing sodium sulfate but excluding titanium dioxide are
strikingly apparent particularly after such blocks are eroded by
flush water and thereafter allowed to dry. Such an effect is more
apparent with increased amounts of erosion due to increased flush
cycles. Thus, the inclusion of titanium dioxide as an essential
constituent of the compressed solid block composition provides such
blocks which have a much more attractive appearance to the unaided
eye of an observer, particularly following repeated use of the
compressed solid block composition and cageless lavatory dispensing
devices which include such titanium dioxide comprising lavatory
block compositions.
[0102] While the precise mechanism for such improvements in the
surface of the compressed lavatory blocks is unknown, and while not
wishing to be bound by the following hypothesis, it is suspected by
the inventors that the presence of the titanium dioxide in
effective amounts may interfered with the crystallization process
of the sulfate salt, particularly sodium sulfate as the compressed
solid block composition is washed with, and eroded by water. The
reduction in the rate of, or prevalence of the crystallization of
the sulfate salt per an interaction with the titanium dioxide may
reduce the size of the crystals formed, or the distribution of the
crystals form, or both, which limits their size to one which is
imperceptible or only poorly perceptible to the unaided eye of an
ordinary human observer. Of course, other mechanisms as yet not
clearly understood may be responsible for the minimization and/or
inhibition of such visible white spots in the lavatory block
compositions of the invention.
[0103] Thus, the compressed solid block compositions necessarily
comprise between about 0.001% wt. to about 10% wt, preferably
between about 0.01% wt. and about 5% wt., yet more preferably
comprise between about 0.05% wt. and about 1.5% wt., but most
preferably comprise between about 0.05% wt. and about 0.5% wt. of
the lavatory block compositions of which they form a part.
[0104] Further exemplary chemical constituents may be one or more
sanitizing agents or germicides which may be present with our
without other constituents being present in the compressed solid
blocks of the cageless lavatory dispensing devices.
[0105] The sanitizing agent can be any sanitizing composition known
to those of ordinary skill in the relevant art, and without
limitation exemplary sanitizing compositions include materials
containing alkyl halohydantoins, alkali metal haloisocyanurates,
bleach, essential oils, non-quaternary ammonium based germicidal
compounds as well as quaternary ammonium germicidal compounds.
[0106] By way of non-limiting example, exemplary a bleach
constituent. The bleach constituent is relatively inert in the dry
state but, which on contact with water, releases oxygen, hypohalite
or a halogen especially chlorine. Representative examples of
typical oxygen-release bleaching agents, suitable for incorporation
in the solid block composition include the alkali metal perborates,
e.g., sodium perborate, and alkali metal monopersulfates, e.g.,
sodium monopersulfates, potassium monopersulfate, alkali metal
monoperphosphates, e.g., disodium monoperphosphate and dipotassium
monoperphosphate, as well as other conventional bleaching agents
capable of liberating hypohalite, e.g., hypochlorite and/or
hypobromite, include heterocyclic N-bromo- and N-chloro-cyanurates
such as trichloroisocyanuric and tribromoiscyanuric acid,
dibromocyanuric acid, dichlorocyanuric acid,
N-monobromo-N-mono-chlorocyanuric acid and
N-monobromo-N,N-dichlorocyanuric acid, as well as the salts thereof
with water solubilizing cations such as potassium and sodium, e.g.,
sodium N-monobromo-N-monochlorocyanurate, potassium
dichlorocyanurate, sodium dichlorocyanurate, as well as other
N-bromo and N-chloro-imides, such as N-brominated and N-chlorinated
succinimide, malonimide, phthalimide and naphthalimide. Also useful
in the solid block composition as hypohalite-releasing bleaches are
halohydantoins which may be used include those which may be
represented by the general structure:
##STR00005##
wherein:
[0107] X.sub.1 and X.sub.2 are independently hydrogen, chlorine or
bromine; and,
[0108] R.sub.1 and R.sub.2 are independently alkyl groups having
from 1 to 6 carbon atoms. Examples of halohydantoins include, for
example, N,N'-dichloro-dimethyl-hydantoin,
N-bromo-N-chloro-dimethyl-hydantoin,
N,N'-dibromo-dimethyl-hydantoin, 1,4-dichloro, 5,5-dialkyl
substituted hydantoin, wherein each alkyl group independently has 1
to 6 carbon atoms, N-monohalogenated hydantoins such as
chlorodimethylhydantoin (MCDMH) and N-bromo-dimethylhydantoin
(MBDMH); dihalogenated hydantoins such as dichlorodimethylhydantoin
(DCDMH), dibromodimethylhydantoin (DBDMH), and
1-bromo-3-chloro-5,5,-dimethylhydantoin (BCDMH); and halogenated
methylethylhydantoins such as chloromethylethylhydantion (MCMEH),
dichloromethylethylhydantoin (DCMEH), bromomethylethylhydantoin
(MBMEH), dibromomethylethylhydantoin (DBMEH), and
bromochloromethylethylhydantoin (BCMEH), and mixtures thereof.
Other suitable organic hypohalite liberating bleaching agents
include halogenated melamines such as tribromomelamine and
trichloromelamine. Suitable inorganic hypohalite-releasing
bleaching agents include lithium and calcium hypochlorites and
hypobromites. The various chlorine, bromine or hypohalite
liberating agents may, if desired, be provided in the form of
stable, solid complexes or hydrates, such as sodium p-toluene
sulfobromamine trihydrate; sodium benzene sulfochloramine
dihydrate; calcium hypobromite tetrahydrate; and calcium
hypochlorite tetrahydrate. Brominated and chlorinated trisodium
phosphates formed by the reaction of the corresponding sodium
hypohalite solution with trisodium orthophosphate (and water, as
necessary) likewise comprise useful inorganic bleaching agents for
incorporation into the inventive solid block composition and the
treatment blocks formed therefrom.
[0109] When present, preferably the bleach constituent is a
hypohalite liberating compound and more preferably is a hypohalite
liberating compound in the form of a solid complex or hydrate
thereof. Particularly preferred are chloroisocynanuric acids and
alkali metal salts thereof, preferably potassium, and especially
sodium salts thereof. Examples of such compounds include
trichloroisocyananuric acid, dichloroisocyanuric acid, sodium
dichloroisocyanurate, potassium dichloroisocyanurate, and
trichloro-potassium dichloroisocynanurate complex. The most
preferred chlorine bleach material is sodium dichloroisocyanurate;
the dihydrate of this material being particularly preferred.
[0110] When present, the bleach constituent may be present in any
effective amount and may comprise up to about 90% wt., preferably
at least about 0.1-60% wt of the compressed solid block
composition. More preferably, when present, the bleach constituent
comprises about 0.5-50% wt., more preferably at least 1-40% wt. of
the compressed solid block composition.
[0111] Other germicidally effective agents useful as sanitizing
agents include sodium dichloroisocyanurate (DCCNa) and sodium
dibromoisocyanurate. Further examples of non-quaternary ammonium
based sanitizing agents include pyrithiones, dimethyldimethylol
hydantoin, methylchloroisothiazolinone/methylisothiazolinone sodium
sulfite, sodium bisulfite, imidazolidinyl urea, diazolidinyl urea,
benzyl alcohol, 2-bromo-2-nitropropane-1,3-diol, formalin
(formaldehyde), iodopropenyl butylcarbamate, chloroacetamide,
methanamine, methyldibromonitrile glutaronitrile, glutaraldehyde,
5-bromo-5-nitro-1,3-dioxane, phenethyl alcohol,
o-phenylphenol/sodium o-phenylphenol, sodium
hydroxymethylglycinate, polymethoxy bicyclic oxazolidine,
dimethoxane, thimersal dichlorobenzyl alcohol, captan,
chlorphenenesin, dichlorophene, chlorbutanol, glyceryl laurate,
halogenated diphenyl ethers, phenolic compounds, mono- and
poly-alkyl and aromatic halophenols, resorcinol and its
derivatives, bisphenolic compounds, benzoic esters (parabens),
halogenated carbanilides,
3-trifluoromethyl-4,4'-dichlorocarbanilide, and
3,3',4-trichlorocarbanilide. More preferably, the non-cationic
antimicrobial agent is a mono- and poly-alkyl and aromatic
halophenol selected from the group p-chlorophenol, methyl
p-chlorophenol, ethyl p-chlorophenol, n-propyl p-chlorophenol,
n-butyl p-chlorophenol, n-amyl p-chlorophenol, sec-amyl
p-chlorophenol, n-hexyl p-chlorophenol, cyclohexyl p-chlorophenol,
n-heptyl p-chlorophenol, n-octyl p-chlorophenol, o-chlorophenol,
methyl o-chlorophenol, ethyl o-chlorophenol, n-propyl
o-chlorophenol, n-butyl o-chlorophenol, n-amyl o-chlorophenol,
tert-amyl o-chlorophenol, n-hexyl o-chlorophenol, n-heptyl
o-chlorophenol, o-benzyl p-chlorophenol, o-benzyl-m-methyl
p-chlorophenol, o-benzyl-m, m-dimethyl p-chlorophenol,
o-phenylethyl p-chlorophenol, o-phenylethyl-m-methyl
p-chlorophenol, 3-methyl p-chlorophenol, 3,5-dimethyl
p-chlorophenol, 6-ethyl-3-methyl p-chlorophenol,
6-n-propyl-3-methyl p-chlorophenol, 6-iso-propyl-3-methyl
p-chlorophenol, 2-ethyl-3,5-dimethyl p-chlorophenol,
6-sec-butyl-3-methyl p-chlorophenol, 2-iso-propyl-3,5-dimethyl
p-chlorophenol, 6-diethylmethyl-3-methyl p-chlorophenol,
6-iso-propyl-2-ethyl-3-methyl p-chlorophenol,
2-sec-amyl-3,5-dimethyl p-chlorophenol 2-diethylmethyl-3,5-dimethyl
p-chlorophenol, 6-sec-octyl-3-methyl p-chlorophenol,
p-chloro-m-cresol, p-bromophenol, methyl p-bromophenol, ethyl
p-bromophenol, n-propyl p-bromophenol, n-butyl p-bromophenol,
n-amyl p-bromophenol, sec-amyl p-bromophenol, n-hexyl
p-bromophenol, cyclohexyl p-bromophenol, o-bromophenol, tert-amyl
o-bromophenol, n-hexyl o-bromophenol, n-propyl-m,m-dimethyl
o-bromophenol, 2-phenyl phenol, 4-chloro-2-methyl phenol,
4-chloro-3-methyl phenol, 4-chloro-3,5-dimethyl phenol,
2,4-dichloro-3,5-dimethylphenol, 3,4,5,6-terabromo-2-methylphenol,
5-methyl-2-pentylphenol, 4-isopropyl-3-methylphenol,
para-chloro-meta-xylenol, dichloro meta xylenol, chlorothymol, and
5-chloro-2-hydroxydiphenylmethane.
[0112] Quaternary ammonium based sanitizing agents include any
cationic surfactant which is known or may be found to provide a
broad antibacterial or sanitizing function; these have been
described above with reference to detersive surfactants.
[0113] As a further chemical constituent, the compressed solid
block compositions of the invention may also comprise a coloring
agent which imparts either a color to the compressed solid blocks,
to the water in which it comes into contact, but especially which
imparts color to the water contained within the sanitary appliance.
Where the sanitary appliance is a toilet, desirably the coloring
agent imparts a color to the water contained within the cistern, or
within the toilet bowl particularly following the flush cycle of a
toilet, or may impart a color in both locations. Such coloring
agents have great consumer appeal, and indeed any known art
coloring agent may be provided in any effective amount in order to
impart a coloring effect. Colorants, especially dyes, are preferred
when formulated as dry powders to enable direct incorporation into
compressed solid blocks of the invention, however, liquid colorants
may be employed in conjunction with suitable carriers. Useful
colorants include any materials which may provide a desired
coloring effect. Exemplary useful coloring agents include dyes,
e.g., Alizarine Light Blue B (C.I. 63010), Carta Blue VP (C.I.
24401), Acid Green 2G (C.I. 42085), Astragon Green D (C.I. 42040)
Supranol Cyanine 7B (C.I. 42675), Maxilon Blue 3RL (C.I. Basic Blue
80), acid yellow 23, acid violet 17, a direct violet dye (Direct
violet 51), Drimarine Blue Z-RL (C.I. Reactive Blue 18), Alizarine
Light Blue H-RL (C.I. Acid Blue 182), FD&C Blue No. 1, FD&C
Green No. 3 and Acid Blue No. 9. When a bleach constituent is
included in the compressed solid block composition, the colorant,
e.g., dye, should be selected so to ensure the compatibility of the
colorant with the bleach constituent, or so that its color persists
despite the presence in the toilet bowl of a concentration of
hypochlorite which is effective to maintain sanitary conditions.
Frequently however, a compressed solid block composition which
includes a bleach constituent do not comprise any colorants.
Desirably the colorants, when present, do not exceed 15% wt. of the
compressed solid block composition, although generally lesser
amounts are usually effective. When present, colorants are
desirably present in an amount from about 0.1 to 15 percent of the
total weight of the chemical composition.
[0114] The compressed solid block compositions may include a
fragrance or other air treatment constituent. The fragrance may be
any composition which is known to the art to provide a perceptible
fragrancing benefit, any may be based on naturally occurring
materials such as one or more essential oils, or may be based on
synthetically produced compounds as well. Examples of essential
oils include pine oil, Anethole 20/21 natural, Aniseed oil china
star, Aniseed oil globe brand, Balsam (Perui), Basil oil (India),
Black pepper oil, Black pepper oleoresin 40/20, Bois de Rose
(Brazil) FOB, Bomneol Flakes (China), Camphor oil, White, Camphor
powder synthetic technical, Canaga oil (Java), Cardamom oil, Cassia
oil (China), Cedarwood oil (China) BP, Cinnamon bark oil, Cinnamon
leaf oil, Citronella oil, Clove bud oil, Clove leaf, Coriander
(Russia), Counmarin 69.degree. C. (China), Cyclamen Aldehyde,
Diphenyl oxide, Ethyl vanilin, Eucalyptol, Eucalyptus oil,
Eucalyptus citriodora, Fennel oil, Geranium oil, Ginger oil, Ginger
oleoresin (India), White grapefruit oil, Guaiacwood oil, Gurjun
balsam, Heliotropin, Isobornyl acetate, Isolongifolene, Juniper
berry oil, L-methyl acetate, Lavender oil, Lemon oil, Lemongrass
oil, Lime oil distilled, Litsea Cubeba oil, Longifolene, Menthol
crystals, Methyl cedryl ketone, Methyl chavicol, Methyl salicylate,
Musk ambrette, Musk ketone, Musk xylol, Nutmeg oil, Orange oil,
Patchouli oil, Peppermint oil, Phenyl ethyl alcohol, Pimento berry
oil, Pimento leaf oil, Rosalin, Sandalwood oil, Sandenol, Sage oil,
Clary sage, Sassafras oil, Spearmint oil, Spike lavender, Tagetes,
Tea tree oil, Vanilin, Vetyver oil (Java), and Wintergreen oil.
[0115] Many of these essential function as a fragrance agent, which
fragrance agent which may be a substance or mixture of various
substances including those which are naturally derived (i.e.,
obtained by extraction of flower, herb, blossom or plant), those
which are artificially derived or produced (i.e., mixture of
natural oils and/or oil constituents), and those which are
synthetically produced substances (odiferous substances). Generally
fragrance agents are complex mixtures or blends various organic
compounds including, but not limited to, certain alcohols,
aldehydes, ethers, alamatic compounds and varying amounts of
essential oils such as from about 0 to about 25% by weight, usually
from about 0.05 to about 12% by weight, the essential oils
themselves being volatile odiferous compounds and also functioning
to aid in the dissolution of the other components of the fragrance
agent. In the present invention, the precise composition of the
fragrance agent desirably emanates a pleasing fragrance, but the
nature of the fragrance agent is not critical to the success of the
invention.
[0116] As noted above, in conjunction with or in the absence of a
fragrance constituent, the compressed solid block compositions may
comprise an air treatment constituent. Such may be any other
material which is useful in providing treatment of ambient air,
such as a sanitizing agents. e.g., one or more glycols or alcohols,
or materials which are intended to counteract, neutralize, or mask
odors in the absence of, or in conjunction with, the fragrance
composition of the present invention. Alternatively, the air
treatment constituent may be one or more materials which provide
and effective insecticide repelling or insecticidal benefit; such
would be particularly useful in climates or environments where
insects present a nuisance or health hazard.
[0117] As further chemical constituents, the compressed solid block
compositions of the invention may comprise an anti-limescale agent,
which can be generally classified as a cleaning agent in that it
provides a cleaning effect to treated lavatory device surfaces. The
anti-limescale agent can virtually any known anti-limescale agent
compositions known to those of ordinary skill in the relevant art.
For example, compositions containing anionic and/or nonionic
surfactants together with typical anti-limescale agents, for
example, amidosulfonic acid, bisulfate salts, organic acids,
organic phosphoric salts, alkali metal polyphosphates, and the
like. Examples of anti-limescale agent compositions can be found
in, for example, U.S. Pat. Nos. 5,759,974; 4,460,490; and 4578207,
the contents of which are herein incorporated by reference. Further
examples of anti-limescale agents include organic acids (for
example, citric acid, lactic acid, adipic acid, oxalic acid and the
like), organic phosphoric salts, alkali metal polyphosphates,
sulfonic, and sulfamic acids and their salts, bisulfate salts,
EDTA, phosphonates, and the like.
[0118] The compressed solid block compositions may comprise stain
inhibiting materials. The solid block composition of the invention
may, for example, include an effective amount of a manganese stain
inhibiting agent which is advantageously included wherein the
sanitary appliance is supplied by a water source having an
appreciable or high amount of manganese. Such water containing a
high manganese content are known to frequently deposit unsightly
stains on surfaces of sanitary appliances, especially when the
solid block composition also contains a bleach source which
provides a hypochlorite. To counteract such an effect the solid
block composition of the present invention may comprise a manganese
stain inhibiting agent, such as a partially hydrolyzed
polyacrylamide having a molecular weight of about 2000 to about
10,000, a polyacrylate with a molecular weight of about 2000 to
about 10,000, and/or copolymers of ethylene and maleic acid
anhydride with a molecular weight of from about 20,000 to about
100,000. When present the satin inhibiting materials may comprise
to about 10% wt. of the weight of the compressed solid block
composition.
[0119] The compressed solid block compositions of the invention may
include one or more preservatives. Such preservatives are primarily
included to reduce the growth of undesired microorganisms within
the treatment blocks formed from the solid block composition during
storage prior to use or while used, although it is expected that
the such a preservative may impart a beneficial antimicrobial
effect to the water in the sanitary appliance to which the
treatment block is provided. Exemplary useful preservatives include
compositions which include parabens, including methyl parabens and
ethyl parabens, glutaraldehyde, formaldehyde,
2-bromo-2-nitropropoane-1,3-diol,
5-chloro-2-methyl-4-isothiazolin-3-one,
2-methyl-4-isothiazoline-3-one, and mixtures thereof. One exemplary
composition is a combination 5-chloro-2-methyl-4-isothiazolin-3-one
and 2-methyl-4-isothiazolin-3-one where the amount of either
component may be present in the mixture anywhere from 0.001 to
99.99 weight percent, based on the total amount of the
preservative. For reasons of availability, the most preferred
preservative are those commercially available preservative
comprising a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and
2-methyl-4-isothiazolin-3-one marketed under the trademark
KATHON.RTM. CG/ICP as a preservative composition presently
commercially available from Rohm and Haas (Philadelphia, Pa.).
Further useful preservative compositions include KATHON.RTM. CG/ICP
II, a further preservative composition presently commercially
available from Rohm and Haas (Philadelphia, Pa.), PROXEL.RTM. which
is presently commercially available from Zeneca Biocides
(Wilmington, Del.), SUTTOCIDE.RTM. A which is presently
commercially available from Sutton Laboratories (Chatam, N.J.) as
well as TEXTAMER.RTM. 38AD which is presently commercially
available from Calgon Corp. (Pittsburgh, Pa.). When present, the
optional preservative constituent should not exceed about 5% wt. of
the solid block composition, although generally lesser amounts are
usually effective.
[0120] The inventive compressed solid block compositions may
include a binder constituent. The binder may function in part
controlling the rate of dissolution of the tablet. The binder
constituent may be a clay, but preferably is a water-soluble or
water-dispersible gel-forming organic polymer. The term
"gel-forming" as applied to this polymer is intended to indicate
that on dissolution or dispersion in water it first forms a gel
which, upon dilution with further water, is dissolved or dispersed
to form a free-flowing liquid. The organic polymer serves
essentially as binder for the tablets produced in accordance with
the invention although, as will be appreciated, certain of the
polymers envisaged for use in accordance with the invention also
have surface active properties and thereby serve not only as
binders but also enhance the cleansing ability of the tablets of
the invention. Further certain organic polymers, such as
substituted celluloses, also serve as soil antiredeposition agents.
A wide variety of water-soluble organic polymers are suitable for
use in the solid block composition of the present invention. Such
polymers may be wholly synthetic or may be semi-synthetic organic
polymers derived from natural materials. Thus, for example, on
class of organic polymers for use in accordance with the invention
are chemically modified celluloses such as ethyl cellulose, methyl
cellulose, sodium carboxymethyl cellulose, hydroxypropyl cellulose,
hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose,
carboxymethyl hydroxyethyl cellulose, and hydroxyethyl cellulose.
Another class of organic polymers which may be used include
naturally derived or manufactured (fermented) polymeric materials
such as alginates and carageenan. Also, water-soluble starches and
gelatin may be used as the optional binder constituent. The
cellulose based binders are a preferred class of binders for use in
the solid block composition and may possess the property of inverse
solubility that is their solubility decreases with increasing
temperature, thereby rendering the tablets of the invention
suitable for use in locations having a relatively high ambient
temperature.
[0121] The optional binder constituent may also be one or more
synthetic polymers e.g., polyvinyl alcohols; water-soluble
partially hydrolyzed polyvinyl acetates; polyacrylonitriles;
polyvinyl pyrrolidones; water-soluble polymers of ethylenically
unsaturated carboxylic acids, such as acrylic acid and methacrylic
acid, and salts thereof; base-hydrolysed starch-polyacrylonitrile
copolymers; polyacrylamides; ethylene oxide polymers and
copolymers; as well as carboxypolymethylenes.
[0122] In the case of the organic polymeric binders it may be noted
that, in general, the higher the molecular weight of the polymer
the greater the in-use life of the treatment block of the
invention. When present, the total binder content may comprise up
to 75% wt. of the solid block composition, but preferably is from
0.5 to 70% by weight, preferably from 1 to 65% by weight, more
preferably from 5 to 60% by weight.
[0123] The solid block composition may optionally include one or
more dissolution control agents. Such dissolution control agent are
materials which provide a degree of hydrophobicity to the treatment
block formed from the solid block composition whose presence in the
treatment block contributes to the slow uniform dissolution of the
treatment block when contacted with water, and simultaneously the
controlled release of the active constituents of the solid block
composition. Preferred for use as the dissolution control agents
are mono- or di-alkanol amides derived from C.sub.8-C.sub.16 fatty
acids, especially C.sub.12-C.sub.14 fatty acids having a
C.sub.2-C.sub.6 monoamine or diamine moiety. When included the
dissolution control agent may be included in any effective amount,
but desirably the dissolution control agent is present in an amount
not to exceed about 600% wt. of the solid block composition,
although generally lesser amounts are usually effective. Generally
wherein the treatment block is to be used in an ITB application the
dissolution control agent is present to about 12% wt., more
preferably is present from 0.1-10% wt. and most preferably is
present from about 3-8% wt. of the solid block compositions, as
well as in the treatment blocks formed therefrom. Generally wherein
the treatment block is to be used in an ITC application the
dissolution control agent is present to about 50% wt., more
preferably is present from 1-50% wt. and most preferably is present
from about 10-40% wt. of the solid block compositions, as well as
in the treatment blocks formed therefrom.
[0124] The compressed solid block compositions may optionally
include one or more water-softening agents or one or more chelating
agents, for example inorganic water-softening agents such as sodium
hexametaphosphate or other alkali metal polyphosphates or organic
water-softening agents such as ethylenediaminetetraacetic acid and
nitrilotriacetic acid and alkali metal salts thereof. When present,
such water-softening agents or chelating agents should not exceed
about 20% wt. of the solid block composition, although generally
lesser amounts are usually effective.
[0125] The compressed solid block composition may optionally
include one or more solid water-soluble acids or acid-release
agents such as sulphamic acid, citric acid or sodium hydrogen
sulphate. When present, such solid water-soluble acids or
acid-release agents should not exceed about 20% wt. of the solid
block composition, although generally lesser amounts are usually
effective.
[0126] The compressed solid block compositions may include diluent
materials may be included to provide additional bulk of the product
solid block composition and may enhance leaching out of the
surfactant constituent when the solid block composition is placed
in water. Exemplary diluent materials include any soluble inorganic
alkali, alkaline earth metal salt or hydrate thereof, for example,
chlorides such as sodium chloride, magnesium chloride and the like,
carbonates and bicarbonates such as sodium carbonate, sodium
bicarbonate and the like, sulfates such as magnesium sulfate,
copper sulfate, sodium sulfate, zinc sulfate and the like, borax,
borates such as sodium borate and the like, as well as others known
to the art but not particularly recited herein. Exemplary organic
diluents include, inter alia, urea, as well as water soluble high
molecular weight polyethylene glycol and polypropylene glycol. When
present, such diluent materials should not exceed about 80% wt. of
the compressed solid block composition, although generally lesser
amounts are usually effective. Preferably a sulfate salt, e.g.,
magnesium sulfate, copper sulfate, sodium sulfate, zinc sulfate and
the like, and particularly sodium sulfate is necessarily present in
the compressed solid block composition and treatment blocks formed
therefrom.
[0127] The compressed solid block composition and treatment blocks
formed therefrom may include one or more fillers. Such fillers are
typically particulate solid water-insoluble materials which may be
based on inorganic materials such as talc or silica, particulate
organic polymeric materials such as finely comminuted water
insoluble synthetic polymers. When present, such fillers should not
exceed about 30% wt. of the compressed solid block composition,
although generally lesser amounts are usually effective.
[0128] Preferably the compressed solid block of the invention
includes silica. Silica has been observed to aid in the controlling
the rate of dissolution of the compressed solid blocks of the
invention.
[0129] The compressed solid block composition and treatment blocks
formed therefrom may include one or more further processing aids.
For example, the solid block composition may also include other
binding and/or plasticizing ingredients serving to assist in the
manufacture thereof, for example, polypropylene glycol having a
molecular weight from about 300 to about 10,000 in an amount up to
about 20% by weight, preferably about 4% to about 15% by weight of
the mixture may be used. The polypropylene glycol reduces the melt
viscosity, acts as a demolding agent and also acts to plasticize
the block when the composition is prepared by a casting process.
Other suitable plasticizers such as pine oil fractions, d-limonene,
dipentene and the ethylene oxide-propylene oxide block copolymers
may be utilized. Other useful processing aids include tabletting
lubricants such as metallic stearates, stearic acid, paraffin oils
or waxes or sodium borate which facilitate in the formation of the
treatment blocks in a tabletting press or die.
[0130] One advantageously utilized processing aid is a diester
constituent which may be represented by the following
structure:
##STR00006##
wherein: R.sup.1 and R.sup.2 can independently be C.sub.1-C.sub.6
alkyl which may optionally substituted, Y is (CH.sub.2).sub.x,
wherein x is 0-10, but is preferably 1-8, and while Y may be a
linear alkyl or phenyl moiety, desirably Y includes one or more
oxygen atoms and/or is a branched moiety.
[0131] Exemplary diester constituents include the following diester
compounds according to the foregoing structure: dimethyl oxalate,
diethyl oxalate, diethyl oxalate, dipropyl oxalate, dibutyl
oxalate, diisobutyl oxalate, dimethyl succinate, diethyl succinate,
diethylhexyl succinate, dimethyl glutarate, diisostearyl glutarate,
dimethyl adipate, diethyl adipate, diisopropyl adipate, dipropyl
adipate, dibutyl adipate, diisobutyl adipate, dihexyladipate,
di-C.sub.12-15-alkyl adipate, dicapryl adipate, dicetyl adipate,
diisodecyl adipate, diisocetyl adipate, diisononyl adipate,
diheptylundecyl adipate, ditridecyl adipate, diisostearyl adipate,
diethyl sebacate, diisopropyl sebacate, dibutyl sebacate,
diethylhexylsebacate, diisocetyl dodecanedioate, dimethyl
brassylate, dimethyl phthalate, diethyl phthalate, dibutyl
phthalate.
[0132] Preferred diester constituents include those wherein Y is
--(CH.sub.2).sub.n-- wherein x has a value of from 0-6, preferably
a value of 0-5, more preferably a value of from 1-4, while R.sup.1
and R.sup.2 are C.sub.1-C.sub.6 alkyl groups which may be straight
chained alkyl but preferably are branched, e.g., iso- and
tert-moieties. Particularly preferred diester compounds are those
in which the compounds terminate in ester groups.
[0133] A further advantageously utilized processing aid is a
hydrocarbon solvent constituent. The hydrocarbon solvents are
immiscible in water, may be linear or branched, saturated or
unsaturated hydrocarbons having from about 6 to about 24 carbon
atoms, preferably comprising from about 12 to about 16 carbon
atoms. Saturated hydrocarbons are preferred, as are branched
hydrocarbons. Such hydrocarbon solvents are typically available as
technical grade mixtures of two or more specific solvent compounds,
and are often petroleum distillates. Nonlimiting examples of some
suitable linear hydrocarbons include decane, dodecane, decene,
tridecene, and combinations thereof. Mineral oil is one
particularly preferred form of a useful hydrocarbon solvent.
Further preferred hydrocarbon solvents include paraffinic
hydrocarbons including both linear and branched paraffinic
hydrocarbons. The former are commercially available as NORPAR
solvents (ex. ExxonMobil Corp.) while the latter are available as
ISOPAR solvents (ex. ExxonMobil Corp.) Mixtures of branched
hydrocarbons especially as isoparaffins form a further particularly
preferred form of a useful hydrocarbon solvent of the invention.
Particularly useful technical grade mixtures of isoparaffins
include mixtures of isoparaffinic organic solvents having a
relatively narrow boiling range. Examples of these commercially
available isoparaffinic organic solvents include ISOPAR C described
to be primarily a mixture of C.sub.7-C.sub.8 isoparaffins, ISOPAR E
described to be primarily a mixture of C.sub.8-C.sub.9
isoparaffins, ISOPAR G described to be primarily a mixture of
C.sub.10-C.sub.11 isoparaffins, ISOPAR H described to be primarily
a mixture of C.sub.11-C.sub.12 isoparaffins, ISOPAR J, ISOPAR K
described to be primarily a mixture of C.sub.11-C.sub.12
isoparaffins, ISOPAR L described to be primarily a mixture of
C.sub.11-C.sub.13 isoparaffins, ISOPAR M described to be primarily
a mixture of C.sub.13-C.sub.14 isoparaffins, ISOPAR P and ISOPAR V
described to be primarily a mixture of C.sub.12-C.sub.20
isoparaffins.
[0134] When present such further processing aids are typically
included in amounts of up to about 30% by weight, preferably to 20%
wt. of the solid block composition, although generally lesser
amounts are usually effective.
[0135] Optionally but in some cases, preferably one or more of the
foregoing constituents may be provided as an encapsulated,
particularly a microencapsulated material. That is to say,
quantities of one or more constituents are provided covered or
encapsulated in an encapsulating material. Methods suitable for
such an encapsulation include the customary methods and also the
encapsulation of the granules by a melt consisting e.g. of a
water-soluble wax, coacervation, complex coacervation and surface
polymerization. Non-limiting examples of useful encapsulating
materials include e.g. water-soluble, water-dispersible or
water-emulsifiable polymers and waxes. Advantageously, reactive
chemical constituents, particularly the fragrance composition when
present, may be provided in an encapsulated form so to ensure that
they do not prematurely degrade during processing of the
constituents used to form the compressed solid block composition
and that they are retained with minimal degradation in the
compressed solid block composition prior to their use. The use of
water soluble encapsulating material is preferred as such will
release the one or more chemical constituents when the compressed
solid block composition is contacted with water supplied either in
the cistern or in the toilet bowl.
[0136] Ideally the compressed solid blocks exhibit a density
greater than that of water which ensures that they will sink when
suspended in a body of water, e.g., the water present within a
cistern. Preferably the treatment blocks formed from the solid
block composition exhibit a density in excess of about 1 g/cc of
water, preferably a density in excess of about 1.5 g/cc of water
and most preferably a density of at least about 2 g/cc of
water.
[0137] While the mass of the compressed solid blocks may vary, and
amount of up to an including 500 grams may be practiced, generally
the mass of the compressed solid block compositions do not exceed
about 150 grams. Advantageously the mass of the compressed solid
blocks is between about 20 and 100 grams. It is appreciated that
compressed solid blocks having great mass should provide a longer
useful service life of the cageless lavatory dispensing devices,
with the converse being equally true.
[0138] The compressed solid blocks according to the present
invention may also be provided with a coating of a water-soluble
film, such as polyvinyl acetate following the formation of the
treatment blocks from the recited solid block composition. Such may
be desired for improved handling, however such is often unnecessary
as preferred embodiments of the compressed blocks exhibit a lower
likelihood of sticking to one another following manufacture than
many prior art treatment block compositions.
[0139] It will be appreciated by those of ordinary skill in the art
that several of the components which are directed to provide a
chemical composition can be blended into one chemical composition
with the additional appreciation that potential blending of
incompatible components will be avoided. For example, those of
ordinary skill in the art will appreciate that certain anionic
surfactants may have to be avoided as some may be incompatible with
certain sanitizing agents and/or certain anti-lime scale agents
mentioned herein. Those of ordinary skill in the art will
appreciate that the compatibility of the anionic surfactant and the
various sanitizing and anti-limescale agents can be easily
determined and thus incompatibility can be avoided in the
situations.
[0140] The compressed solid blocks may be formed of a single
chemical composition, or may formed of two (or more) different
chemical compositions which may be provided as separate regions of
a solid block, such as a first layer of a solid block consisting of
a first chemical composition, alongside a second layer of a the
solid block consisting of a second chemical composition which is
different than the first chemical composition. The block may also
be formed of two or more separate blocks which are simply layered
or otherwise assembled, without or without the use of an adhesive.
Further layers of still further different chemical compositions may
also be present. Such solid blocks formed having two or more
discrete layers or regions of, respectively, two or more different
chemical compositions may be referred to as composite blocks.
[0141] Any form of the compressed solid blocks may also be provided
with a coating film or coating layer, such as a water soluble film
which is used to overwrap the chemical composition provided in the
device which film provides a vapor barrier when dry, but which
dissolves when contacted with water. Alternately the compressed
solid blocks may be oversprayed or dipped into a bath of a water
soluble film forming constituent, and thereafter removed and thus
allowing the water soluble film forming constituent to dry and form
a coating layer on the compressed solid block.
[0142] Exemplary materials which may be used to provide such a
coating on some or all of the surfaces of the compressed solid
block compositions include one or more of the following: Rhodasurf
TB-970 described by its supplier to be a tridecyl alcohol having a
degree of ethoxylation of approximately 100 having an HLB of 19,
and exhibiting a melting point in the range of 52-55.degree. C.;
Antarox F-108 which is described to be an EO-PO block copolymer
having a degree of ethoxylation of approximately 80% and having a
melting point in the range of 54-60.degree. C.; further materials
including those identified as Pluriol Z8000, and Pluriol E8000
which are believed to be optionally substituted, high molecular
weight polyethylene glycols ("PEG") having a sufficiently high
molecular weight such that they have a melting point of at least
25.degree. C., preferably a melting point of at least about
30.degree. C. may also be used. Other water soluble materials,
desirably those which have a melting point in the range of about
30-70.degree. C., and which may be used to provide a water soluble
or water dispersible coating on the compressed solid blocks are
also contemplated to be useful, especially synthetic or naturally
occurring waxy materials, and high molecular weight polyalkylene
glycols, especially polyethylene glycols. Certain of these coating
materials may be surfactants. Generally such materials may be
provided as a dispersion in water, an organic solvent or in an
aqueous/organic solvent, but preferably are used as supplied from
their respective supplier and are heated to at least their melting
points in order to form a liquid bath. Conveniently, the compressed
solid blocks affixed to the plate of a hanger are then conveniently
dipped into the said bath, thereby providing a coating layer to the
compressed solid blocks. Alternately, the coating materials may be
sprayed, brushed on or padded onto at least part of the surfaces of
the previously formed compressed solid blocks.
[0143] The application of a water soluble film or coating is
preferred in certain embodiments of the invention as the surface
film may facilitate the handling of the blocks during packaging and
storage prior to use of the cageless lavatory dispensing devices.
Further, the application of a water soluble film or coating is
preferred as certain water soluble film former compositions may
impart a desirable surface gloss to the compressed lavatory
blocks.
[0144] Preferably the compressed solid block compositions useful in
the cageless lavatory dispensing devices include those which
comprise at least one surfactant, preferably at least one anionic
or nonionic surfactant.
[0145] Exemplary compositions which can be used to form the
compressed solid blocks of the present invention are shown in the
following table below; the amounts indicates are in % wt. of the
"as supplied" constituent used to form an example block
compositions, labeled A through F.
TABLE-US-00001 Component A B C E F Dodecyl Benzene Sulfonate
Na.sup.1 25 10 40 35 35 Alfa Olefine Sulfonate Na.sup.2 25 10 5 32
32 Lauryl monoethanolamide.sup.3 10 8 5 2 5 Sodium Lauryl Ether
Sulfate.sup.4 10 -- -- 4.5 5 Pluronic 68.sup.5 10 -- -- 3 -- Na
Sulfate 20 -- -- 21.5 21 Pluronic 87 or 88.sup.6 -- 70 50 -- --
Alcohol ethoxylate C.sub.9-C.sub.11 6EO.sup.7 -- 2 -- -- -- Silica
-- -- -- 2 2 Titanium dioxide 0.0001-10 0.0001-10 0.0001-10
0.0001-10 0.0001-10 .sup.1Dodecyl Benzene Sulfonate Sodium (80-90%
active) -- anionic .sup.2Alpha Olefin Sulfonate Sodium -- anionic
.sup.3Lauryl Monoethanolamide -- non-ionic .sup.4Sodium Lauryl
Ether Sulfate (70% active) -- anionic .sup.5Polyoxyethylene (160)
polyoxypropylene (30) glycol -- non-ionic .sup.6Pluronic 87
E.sub.61 P.sub.41.5 E.sub.61 -- Molecular Weight 7700 -- HLB 24 --
non-ionic Pluronic 88 E.sub.98 P.sub.41.5 E.sub.98 -- Molecular
Weight 10800 -- HLB 28-- non-ionic .sup.7Alcohol ethoxylate
C.sub.9-C.sub.11 6EO -- non-ionic
[0146] Further exemplary bleach containing compositions which can
be used to form the compressed solid blocks of the present
invention include compositions indicated on the next table having
the general ranges as follows:
TABLE-US-00002 % w/% w alpha olefin sulfonate 0-35 Sodium lauryl
ether sulfate 3.0-6.0 Bleaching agent (e.g., DCCNa or Hydantoin)
0.5-25 Lauryl monoethanolamide 2.0-5.0 Dodecyl benzene sulfonate Na
50-70 Na sulfate anhydrous 15-25 Silica 1.0-2.0 Titanium dioxide
0.0001-10
[0147] Further exemplary preferred embodiments of blocks which are
useful as compressed solid blocks of the present invention include
those which comprise:
[0148] 10-35% wt., preferably 15-30% wt. of an alpha olefin
sulfonate anionic surfactant;
[0149] 10-35% wt., preferably 15-30% wt. of a linear
monoethanolamide;
[0150] 5-50% wt., preferably 15-35% wt. of a linear dodecylbenzene
sulfonate anionic surfactant;
[0151] 5-50% wt., preferably 20-35% wt. of sodium sulfate
[0152] 0.1-15% wt., preferably 0.5-5% wt. of silica
[0153] 0.1-25% wt., preferably 1-10% wt. sodium lauryl ether
sulfate
[0154] 0.0001-10, preferably 0.01-0.5% wt. titanium dioxide
[0155] optionally to 40% wt. further additive constituents,
including but not limited to further surfactants, fillers, binders,
fragrances, processing aids such as lubricants and tabletting aids,
bleaches, sanitizing compositions and the like.
[0156] Yet further exemplary compositions which include a bleach
constituent which find use as compressed solid blocks of the
present invention include those recited on the following tables,
and labeled as G through N:
TABLE-US-00003 G H I J K L dodecylbenzene sulfonate, 27.0 22.0 32.0
35.00 37.8 32.0 sodium salt (80%) sodium C14/C16 olefin 15.0 20.0
15.0 22.0 23.62 20.0 sulfonates (80%) silica 2.0 2.0 2.0 2.0 1.89
2.0 lauramide monoethanol 30.0 30.0 25.0 15.00 12.28 20.0 amide
(98%) sodium sulfate 20.5 20.5 20.5 20.50 18.90 20.5
dichlorocyanurate 2.5 2.5 2.5 2.4 2.41 2.5 dihydrate, sodium salt
(56% bleach) paraffinic hydrocarbons 3.0 3.0 3.0 3.1 3.09 3.0 M N O
dodecylbenzene sulfonate, 35.0 37.0 32.0 sodium salt (80%) sodium
C14/C16 olefin 22.0 25.0 20.0 sulfonates (80%) silica 2.0 2.0 2.0
lauramide monoethanol 15.0 10.0 20.0 amide (98%) sodium sulfate
20.5 20.5 18.5 dichlorocyanurate 2.5 2.5 2.5 dihydrate, sodium salt
(56% bleach) paraffinic hydrocarbons 3 3 5 titanium dioxide
0.0001-10 0.0001-10 0.0001-10
[0157] The identity of the constituents used to form the foregoing
compressed solid blocks G-O are identified more specifically on the
following table.
TABLE-US-00004 dodecylbenzene sulfonate, anionic surfactant,
dodecylbenzene sodium salt (80%) sulfonate, 80% wt. actives sodium
C14/C16 olefin anionic surfactant, sodium C14/C16 sulfonates (80%)
olefin sulfonates, 80% wt. actives silica filler anhydrous silica,
100% wt. actives. lauramide monoethanol solubility control agent,
lauramide amide (98%) monoethanol amide, 98% wt. actives sodium
sulfate diluent, sodium sulfate, 100% wt. actives dichlorocyanurate
dihydrate, bleach constituent, dichlorocyanurate sodium salt (56%)
dihydrate, sodium salt, 56% wt. bleach actives Isopar M hydrocarbon
solvent, isoparaffinic organic solvents, 100% wt. actives mineral
oil Hydrocarbon solvent, mineral oil, 100% wt. actives paraffinic
hydrocarbons Hydrocarbon solvent, white paraffin oil, 100% wt.
actives Titanium dioxide Titanium dioxide
[0158] Still further exemplary compositions which include
diisopropyl adipates which find use as compressed solid blocks of
the present invention include those recited on the following
tables, and labeled as P through W:
TABLE-US-00005 P Q R S dodecylbenzene 55.85 58.85 62.51 62.51
sulfonate, sodium salt (80%) silica 2.41 2.41 2.56 2.56 lauramide
6.01 6.01 6.38 6.38 monoethanolamide (98%) sodium sulfate 12 12
12.75 12.75 dichlorocyanurate 14.63 14.63 9.32 9.32 dihydrate,
sodium salt (56%) diisopropyl adipate 6.1 6.1 6.48 6.48 T U V W
dodecylbenzene 58.61 67.27 69.25 70.83 sulfonate, sodium salt (80%)
silica 2.40 1.91 1.96 2.01 lauramide 5.98 4.74 4.88 4.99
monoethanolamide (98%) sodium sulfate 11.95 17.37 17.88 18.29
dichlorocyanurate 14.6 4.98 2.41 0.55 dihydrate, sodium salt (56%)
diisopropyl adipate 6.46 3.73 3.61 3.33 Titanium dioxide 0.0001-10
0.0001-10 0.0001-10 0.0001-10
[0159] The identity of the constituents used to form the foregoing
compressed solid blocks labeled P through W are identified more
specifically on the following table:
TABLE-US-00006 dodecylbenzene sulfonate, anionic surfactant,
dodecylbenzene sodium salt (80%) sulfonate, 80% wt. actives silica
anhydrous silica, 100% wt. actives. lauramide monoethanolamide
solubility control agent, lauramide (98%) monoethanolamide, 98% wt.
actives sodium sulfate diluent, sodium sulfate, 100% wt. actives
dichlorocyanurate dihydrate, bleach constituent, dichlorocyanurate
sodium salt (56%) dihydrate, sodium salt, 56% wt. bleach actives
diisopropyl adipate diester constituent, diisopropyl adipate, 100%
wt. actives Titanium dioxide Titanium dioxide, 100% wt. actives
[0160] Yet further exemplary compositions which include paraffinic
hydrocarbon solvents or mineral oil which find use as compressed
solid blocks of the present invention include those recited on the
following tables, and labeled as AA through AK:
TABLE-US-00007 AA AB AC AD AE dodecylbenzene sulfonate, sodium salt
(80%) 65.8 65.8 65 64.17 69.25 silica 2.69 2.69 2.66 2.63 1.96
lauramide monoethanolamine (98%) 6.72 6.72 6.64 6.55 4.88 sodium
sulfate 13.42 13.42 13.26 13.09 17.88 dichlorocyanurate dihydrate,
sodium salt (56% 8.89 8.89 8.78 9.57 2.41 bleach) Isopar M 2.47
2.47 -- -- -- mineral oil -- -- 3.66 3.99 3.61 Titanium dioxide
0.0001-10 0.0001-10 0.0001-10 0.0001-10 0.0001-10 AF AG AH AI AJ AK
dodecylbenzene sulfonate, sodium salt (80%) 70.83 69.25 69.25 69.25
70.83 68.31 silica 2.01 1.96 1.96 1.96 2.01 2.90 lauramide
monoethanolamine (98%) 4.99 4.88 4.88 4.88 4.99 4.88 sodium sulfate
18.29 17.88 17.88 17.88 18.29 17.88 dichlorocyanurate dihydrate,
sodium salt (56% 0.55 2.41 2.41 2.41 0.55 2.41 bleach) Isopar M
3.33 3.61 3.61 -- -- 3.61 mineral oil -- -- -- 3.61 3.33 --
Titanium dioxide 0.0001-10 0.0001-10 0.0001-10 0.0001-10 0.0001-10
0.0001-10
[0161] The identity of the constituents used to form the foregoing
blocks AA through AK are identified more specifically on the
following table:
TABLE-US-00008 dodecylbenzene sulfonate, anionic surfactant,
dodecylbenzene sodium salt (80%) sulfonate, 80% wt. actives silica
filler anhydrous silica, 100% wt. actives. lauramide
monoethanolamide solubility control agent, lauramide (98%)
monoethanolamide, 98% wt. actives sodium sulfate diluent, sodium
sulfate, 100% wt. actives dichlorocyanurate dihydrate, bleach
constituent, dichlorocyanurate sodium salt (56%) dihydrate, sodium
salt, 56% wt. bleach actives Isopar M hydrocarbon solvent,
isoparaffinic organic solvents, 100% wt. actives Mineral oil
Hydrocarbon solvent, mineral oil, 100% wt. actives Titanium dioxide
Titanium dioxide, anhydrous (100% wt. actives)
[0162] Yet further and particularly preferred embodiments of
compressed solid blocks and their compositions include those which
are recited on Table 1.
[0163] The manufacture of the cageless lavatory dispensing device
first contemplates mixing the constituents of the block composition
into a generally homogenous mass such as by noodling, as well as by
plodding, but preferably by extruding, and thereafter forming a
"preform" from a measured quantity of the homogenous mass. Usually
all of the solid ingredients are mixed in any suitable blending
equipment followed by the addition of liquid ingredients under
blending conditions. In an extrusion process a mixture of the
chemical constituents used to ultimately form the compressed solid
block composition is made, followed by extrusion of this mixture
into a rod or bar form which is then cut into appropriately sized
pieces or blocks which are to be used in the subsequent, separate
compression process. These pieces or blocks of extrudate are the
preforms. When the compressed solid block is formed from a single
perform it is required to provide a cavity, channel or recess
within the preform of suitable dimensions to accept at least the
plate of a hanger. Conveniently a channel may be provided by
cutting a slot in the preform of sufficient depth and width such
that the plate may be fully inserted into the interior of the
preform prior to the subsequent compression process. The channel
may be cut, or carved such as by the use of a saw, or other cutting
device which will either split or shape the preform adequately to
provide such a suitable sized channel or recess. Alternately a
channel may be providing by extruding through a die which includes
a blade or other cutter means which extends into the open
cross-section of the die such that as the extrudate exits the die,
it is provided with such a channel which partially splits the
extrudate into the legs of a "V", which remain attached however at
the base of each leg. Such a channel may extend across the length
of the preform and through the ends thereof. Alternately,
subsequent to extrusion a tool such as a plunging blade may be used
to partially split a portion of a preform in order to provide a
cavity or slot which is of sufficient width and depth to
accommodate at least the plate of the hanger. Such a cavity formed
by such blade typically does not extend across the length of the
preform nor through the ends thereof.
[0164] In a next process step, the plate of a hanger is inserted
within the interior of the channel or cavity such that the plate is
preferably wholly encased within the interior of the preform.
Preferably also the hanger extends outwardly from the preform at an
angle which is approximately perpendicular to, more specifically
90.degree..+-./-10.degree., preferably 90.degree..+-./-5.degree.
with respect to tangent of the surface from which point the hanger
extends outwardly therefrom. Such ensures that consistent loading
and proper weight distribution of the hook, and proper placement of
the cageless device in the sanitary appliance, especially a toilet
is maintained.
[0165] Advantageously the cavity, channel or recess is essentially
planar in configuration and is situated within the compressed solid
block such that the plate is not placed within the symmetrical
center or the mid-plane of the said block but rather is positioned
to be parallel to a face or surface of the block such that the
plate is positioned within a plane which is at a distance between
10%-80%, preferably 30%-70% of the distance between the face of
surface of the said block, and the symmetrical center or the
mid-plane of the said block. Further preferably, the hanger and the
compressed solid block is so positioned with respect to one another
that the face of the said block nearest to the embedded plate is on
the side opposite of the hook end of the hanger.
[0166] Alternately the extrudate may be of an alternate
configuration, e.g., a rectangular, square or oblate
cross-sectional configuration, which is formed into preforms. A
cavity, channel or recess within the preform is not required as in
an alternative process to the above, two or more discrete preforms
are used together with then plate of the hanger positioned
intermediate two adjacent preforms which are subsequently
compressed.
[0167] The preform comprising the hanger is then compressed in a
die which imparts the final shape to the compressed solid block.
This compression step may be practiced as a single compression
operation or as a series of compression steps, i.e., with two or
more stamping or compression operations. Advantageously the
preform(s) are positioned in a die such that the plane of the plate
of the hanger is parallel to the opposing major faces of the
compression dies which are brought together. Optionally a mold
release agent, such as a waxy material or an oil, such as a
paraffin oil or mineral oil may be applied to one or more surfaces
of the die. Such may improve the ease of release of the compressed
solid block, and/or aid in the formation of a smooth external
surface to the compressed solid block. Following compression the
compressed solid block are affixed onto the hanger, and may be
removed from or ejected from the die. The cageless delivery device
thus formed is ready for use.
[0168] As noted previously the preform used to form the compressed
solid blocks may be formed from a plurality of preforms which are
conveniently layered in register, with the hanger inserted between
two preforms in the orientation as described above. For example,
two or more physically separate preforms may be layered in register
to form a laminated compressed solid block. Such may be desired
when it is intended that the compressed solid block be formed from
two or more masses having different chemical compositions. For
example, it is contemplated that the compressed solid mass may be
formed from a first preform having a first chemical composition,
compressed to a second preform having a second chemical composition
which is different than the first chemical composition. By way of
non-limiting example, the first preform may be of a first color,
while the second preform may be of different, second color so that
when compressed the preforms are compressed to form a single
compressed solid block having two different colored layers. Of
course, three or more preforms may be compressed to form a single
compressed block. Again the chemical compositions of the first,
second and third preforms may be of the same, similar or of
different compositions.
[0169] During the compression step, several simultaneous technical
effects occur. The block compositions are densified due to the
compression, and concurrently the embedded hanger is sealed and
mechanically anchored within the interior of the block. Preferably
the of the compressed solid block as at least 1.5% greater than the
density of the density of the extrudate. Preferably the density of
the compressed solid block is at least 2%, more preferably at least
3% greater than the density of the preform or extrudate from which
it is formed. Additionally during the compression step, the
channel, slot or recess which had been formed to accept the hanger
is sealed to form a smooth surface. Still further the exterior
surface of the block composition takes on the volume configuration
and the surface shape of the die. Such is particularly advantageous
when the interior surface of the die is smooth walled which will,
in preferred embodiments, impart a smooth exterior surface to the
compressed solid block.
[0170] In certain particularly preferred embodiments the compressed
solid blocks of the present invention weigh from 15 to 150 grams,
preferably from about 20 to about 75 grams. The blocks are
typically oblate in shape, having a length of from about 1 to about
4 inches and having a thickness of from about 0.5-1.5 inches.
[0171] The service life of the compressed solid blocks should be
from about 10 to about 90 days, based on 12 flushes per day.
Preferably the service life of the compressed solid blocks is at
least about 14 days when installed on the rim of a toilet bowl such
that the said block is positioned adjacent to the sloping interior
sidewall of the toilet bowl and is subjected to between 6-12
flushes per day. Preferably the temperature of the water which is
flushed is in the range of 16-24.degree. C. The length of life of
the compressed solid blocks will of course depend on a variety of
factors including product formulation, water temperature, tank
size, the number of flushes over the period of use and the volume
of the water which contacts the compressed solid blocks.
[0172] Various configurations of the cageless lavatory dispensing
device, including certain particularly preferred embodiments, are
depicted on the following figures. In the accompanying figures,
like elements are indicated using the same numerals throughout the
figures.
[0173] FIG. 1 depicts a hanger 10 comprising a hook end 20
comprising an end member 12 flexibly attached to a top member 14 as
well as part of the stalk 16. Depending from the end of the stalk
16 distally from the hook end 20 is a plate 30. As can be seen from
the perspective view provided by FIG. 1, the plate itself is
generally rectangular in configuration, and it is coplanar with the
ribbon-type or strip-type configuration and construction of both
the stalk 16 and hook end 20. The plate 30 has a width dimension
"W1" as well as a height dimension "H1" and as depicted, desirably
the width is greater than the height. As is visible from the
figure, the hanger 10 is generally symmetrical about a center line
"CL" which is drawn with respect to the midline of the stalk 16.
The center line does not exist as an actual element of the device
but is illustrated for the sake of convenient reference. While not
illustrated with sufficient particularity in the figure, it is of
course understood that the plate, stalk 16 and the hook end 20 all
have a thickness which may be consistent throughout, or which can
vary.
[0174] FIG. 2 depicts a side view of a further embodiment of the
hanger 10 of FIG. 1. As is more clearly seen in this figure, the
hook end 20 is formed from first and second elements 12, 14 and
part of the stalk 16. Depending from the stalk 16 is the plate 30.
In this embodiment the plate 30 has a thickness "T1" which is
greater than the thickness "T2" of the stalk 16 and the hook end
20. Of course, it will be understood that each of the hook end,
stalk, and plate can have different thicknesses or can all share
the same thickness as illustrated in FIG. 1.
[0175] FIG. 3 depicts a further embodiment of a hanger 10 according
to the invention, in which the hook end 20 is a flexible element.
As can be seen from the figure, the hook end is comprised of a
first element 12 flexibly connected to a top element 14 which in
turn is flexibly connected to the stalk 16. At the end opposite the
hook end, depends the plate 30. With regard to the hook end, as can
be seen, at the terminal end of the first element 12 is seen a
broadened region which is referred to as a "pad" 15. The pad region
is of the same thickness as the first element 12, but is slightly
broader. The width of the pad end 15 is greater than the width of
the first element 12. This increased width is sometimes useful to
stabilize the hook end of the cageless lavatory dispensing device
when suspended upon part of a sanitary appliance. As is further
visible from FIG. 3, the plate 30 is substantially planar in
configuration has a width W1 as well as height H1 and is symmetric
around the center line CL of the stalk 16. The plate has a
generally linear bottom edge 39 at opposite ends thereof to
generally straight end walls 36, 38 which end walls proceed and
extend to the stalk 16 via sloping top walls 32, 34.
[0176] FIG. 4 depicts the hanger 10 of FIG. 3 in both a "folded" as
well as in an "unfolded" configuration.
[0177] As seen from the solid line elements depicted on FIG. 4, the
hanger 10 on the folded configuration illustrates, that when the
hook end and the stalk are untensioned, the hook end 20 is retained
in a closed configuration. In the unfolded configuration, as
depicted by the elements depicted in a broken line format, the
first element 12 and the pad 15 are extended away from the stalk 16
and are more distantly positioned with respect to the stalk than in
the prior, folded configuration. Typically, this also causes a
degree of translation of the top element 14 which may extend down
to, include a portion of the stalk 16 as well. When made of a
flexible material, in the unfolded configuration as depicted in
FIG. 4, the elastic bias of the material of construction, such as a
polymer, tends to cause the hook end to seek to return to the
folded configuration. However, when placed about the rim of a
portion of a sanitary device, i.e. a toilet bowl, this action
causes the hook end to impart a degree of gripping to that portion
of the rim upon which it is mounted. This is turn helps retain the
relative position of the hook end, as well as that of the cageless
lavatory dispensing device until repositioned, or removed by a
consumer.
[0178] FIG. 5 depicts a still further embodiment of a hanger 10. In
this embodiment, the hanger includes a coiled hook end 20 comprised
of the first element 12, the second element 13 and a top element 14
which is in a compressed, coiled arrangement thus making it
particularly convenient to include in a consumer package. The top
end of the top element 14 extends to a stalk 16 having at its
opposite end a depending plate 30. In this configuration, the plate
30 is oblate in shape and is generally symmetrical about a center
line (CL). The plate has a width dimension (W1) as well as a height
dimension (H1). Further, the plate illustrates that it can be
produced with perforations passing there through. Here, two
similarly shaped, generally triangular passages 33, 33 are
provided. As has been discussed previously in the specification,
while it is contemplated that the plate of the hanger may include
one or more perforations passing there through, for reasons
observed although not yet fully understood by the applicants, it is
believed that the use of plates having such perforations passing
there through are to be preferably avoided as such may undesirably
reduce the service life of the cageless lavatory dispensing
device.
[0179] FIG. 6 depicts a still further embodiment of a hanger 10
according to the invention. As is shown, the hanger includes a hook
end which is comprised of the first element 12, flexibly connected
to a second element 13, which is in turn flexibly connected to a
top element 14, which in turn is flexibly connected to a part of
the stalk 16. The opposite end of the stalk terminates in a
generally oblate shaped plate 30 having a width dimension (W1), a
height dimension (H1) wherein the plate is generally symmetrically
about the center line (CL) as depicted in the dotted line drawn on
FIG. 6. Whereas the hanger is depicted in a folded or otherwise
coiled configuration, it is to be understood that the hook end can
be extended by a user of the hanger and the cageless lavatory
dispensing device to reconfigure said hook end 20 to form a hook
end which can be used to suspend the hanger and the cageless
lavatory dispensing device upon a part of a sanitary device
particularly a toilet bowl rim. The embodiment according to FIG. 6
also illustrates that, according to preferred embodiments, the
plate 30 is substantially planar and as is shown in FIG. 6, it is
of generally uniform thickness. The embodiment depicted in FIG. 6
is preferred in that the hook end is particularly well coiled when
in its folded configuration, but when uncoiled or in its unfolded
configuration, provides a significant degree of tension which is
useful in retaining the respective position of the cageless
lavatory dispensing device when installed upon a sanitary
appliance, particularly when the hook is affixed on a part of a
toilet bowl rim. Furthermore, FIG. 6 depicts that that embodiment
also includes a slanting neck 17 formed as part of the stalk 16 and
immediately adjacent to the region of the plate 30 which is
connected to the stalk 16. As depicted, the neck positions the
plate at a position which is beneath the major portion of the stalk
16 but is parallel thereto. This positioning beneath the major part
of the stalk 16 is beneficial and ultimately, it acts to also
thereby position the compressed solid block enrobing the plate 30
such that when mounted upon a toilet bowl, the compressed solid
block is in contact with, or is in very proximity to the interior
sloping side wall of a toilet bowl. Such positioning is
advantageous in that it ensures that the compressed solid block
remains in the flow path of the flush water throughout the useful
service life of the cageless lavatory dispensing device.
[0180] FIGS. 7A through 7D depict various alternate configurations
which may also be used for the plate 30 for the hanger as described
herein. FIG. 7A depicts a diamond-shaped plate 30 depending at one
vertex from the stalk 16. FIG. 7B depicts a substantially circular
plate 30 depending from one part of its circumference from the
stalk 16. FIG. 7C depicts an equilateral-triangular shaped plate 30
depending at one vertex from the stalk 16. FIG. 7D depicts a
further plate 30 which is generally rectangular but having two
opposite semi-circular ends depending from the stalk 16. In each of
the foregoing, it is seen that the configuration of the plates is
generally symmetrical about the center line, CL.
[0181] FIG. 8 depicts an embodiment of a portion of the hanger
wherein the plate 30 includes a series of perforations 33 passing
there through. As is depicted, the perforations are not symmetrical
with respect to either the center line CL or the configuration of
the semi-circular shaped plate 30. As noted above, plates 30 having
perforations passing there through are less preferred embodiments
of the hangers and useful with the cageless lavatory dispensing
devices taught herein.
[0182] FIGS. 9A and 9B depict in two views an embodiment of a plate
30 depending from a stalk 16 wherein the plate comprises at least
one, here a plurality of projections 35 extending outwardly from
the generally planar and opposite faces 37, 37 of the plate. As is
seen in particular in FIG. 9B, the projections 35 are in the form
of generally cylindrical studs having a base coincident with the
respective face 37, 37 of the plate 30. The studs terminate at flat
ends. The studs have a height which is approximately equal to, or
slightly greater than thickness of the plate 30. Again, while these
figures depict the utility of outwardly extending elements
extending outward from the plate, again, as noted above embodiments
of the hanger having such outwardly extending elements from the
plate are less preferred.
[0183] FIGS. 10A and 10B depict two views of an embodiment of a
two-part cageless lavatory dispensing device 10 of the invention.
FIG. 10A depicts a perspective view of a hook end 20 comprising a
first element 12, a top element 14 and a front element 14' having
extending from a part thereof a hanger peg 40. The hook end 20 is
configured to be suspended upon the rim of a toilet bowl "WC" and
may be used a single time but desirably is used several times by a
consumer. The second part of the cageless lavatory dispensing
device of the invention 10 includes a stalk 16 having at a proximal
end an eyelet or loop 44 which is sufficiently sized so that the
stalk 16 may be removably affixed to and suspended from the hanger
peg 40. The stalk 16 extends downwardly from the proximal end to
the distal end and includes a slanting neck 17, which terminates in
plate 30 which is encased in a compressed solid block 50. This
second part may be installed by a user, and when the compressed
solid block 50 is consumed, this second part may be removed by the
consumer and replaced with a further second part with a new
compressed solid block 50 and utilized.
[0184] As is more clearly depicted on FIG. 10B, the hook end 20 is
mounted upon a part of a rim "R" of a toilet bowl "WC". The second
part is suspended by eyelet 44 such that the compressed solid block
50 is positioned adjacent to or upon the inner sidewall "SW" of the
toilet bowl WC. In this manner, flush water released from the rim
downwardly into the toilet bowl WC contacts the compressed solid
block 50 to form a treatment composition which is used to treat the
toilet bowl.
[0185] While a cooperating hanger peg 40 and eyelet 44 exemplified
one embodiment of a useful fastener means which may be used to
assemble a cageless lavatory dispensing device 10 within the
meaning of the invention, it is contemplated that any other
effective means, particularly mechanical means and/or chemical
means may be used as well and is considered to be within the scope
of the invention, although not specifically depicted in the
figures.
[0186] FIGS. 11A and 11B depict two views of an embodiment of a
two-part cageless lavatory dispensing device 10 of the invention
configured for use as an ITC device.
[0187] FIG. 11A depicts a perspective view of a two-part cageless
lavatory dispensing device 10 comprising a first part, a rigid hook
end 20 adapted to be suspended upon the rim "R" of a toilet cistern
"C", and a second part, a stalk 16 having a sloped, tenon-shaped
proximal end 46 inserted in a suitably shaped mortise 19 present in
the hook end 20, and at its distal end a plate 30 encased by a
compressed solid block 50. The stalk 16 is of sufficient length
that between flushes of the toilet to which it is attached, the
block 50 is submerged beneath the water line "WL" so that the water
contacts the block 50 to form a treatment composition within the
cistern C.
[0188] FIG. 11B depicts a top view of the two-part cageless
lavatory dispensing device 10 of FIG. 11A. As is more clearly
visible the mortise 19 includes two sloped mortise sidewalls 19'
which abut correspondingly shaped tenon sidewalls 46' of the
proximal end 46 of the stalk 16. Further, as is more apparent from
FIG. 11A the tenon sidewalls 46' of the proximal end 46 of the
stalk 16 are seen to taper inwardly toward one another as well, as
well as the two sloped mortise sidewalls 19' which are configured
to correspondingly conform.
[0189] FIG. 12A and FIG. 12B depict respectively a front sectional
view of a compressed solid block 50 encasing/enrobing a plate 30
which depends from a stalk 16, while FIG. 12B depicts the side view
of the foregoing. As is depicted on FIG. 12B, there is depicted a
compressed solid block 50 encasing the plate 30 as well as the
stalk 16 extending outwardly from the compressed solid block. The
compressed solid block has a thickness "TB" as well as a height
"HB". FIG. 12B illustrates a preferred embodiment of the invention,
namely wherein the plate 30 is positioned on the interior of the
block 50 and is in a plane parallel to the mid-plane "MP" which
bisects the block 50 and is between the mid-plane MP and the front
face 53 of the block 50. The front face 53 of the block 50 is the
face which faces the interior of a sanitary appliance, here the
interior of a toilet bowl WC, while the back face 55 is intended to
be positioned adjacent to or abutting the interior sidewall SW of
the toilet bowl WC.
[0190] Further depicted on FIG. 12B is a sectional line "ZZ" which
is intended to indicate a cross section of the block 50 coincident
with a face of the plate 30. Returning to FIG. 10A, this sectional
view referred to is depicted. As can be understood with reference
to the figure, the cross sectional area of the base has dimension
30A, which is less than about half of the surface area AB of the
section of the compressed solid block 50 which is coincident with
the face of the plate 30. More accurately, it should be understood
that the calculation of respective ratios of the plate area, 30A to
the cross sectional area of the block, AB, is made with the plate
30 being removed from the compressed solid block so that the area
AB is unobscured.
[0191] FIG. 13 illustrates a sectional view of a cageless lavatory
dispensing device according to the invention installed within the
interior of a toilet bowl WC. The embodiment illustrated on the
following FIGS. 14A, 14B and 14C. As is visible from the FIG. 13,
the block is positioned adjacent to the interior sidewall SW of the
toilet bowl WC. During the flush cycle, the flow of flush water
(indicated by arrows "F") flows about the block 50 wherein the
water dissolves at least part of the compressed solid block 50
composition to form a treatment composition which is used to treat
the toilet bowl WC.
[0192] FIGS. 14A, 14B and 14C illustrate further views of a
cageless lavatory dispensing device 10 in various views. With
reference to FIG. 14A, therein is depicted a cageless lavatory
dispensing device 10 which includes a hanger 16, having at its
proximal end a hook end 20, and at its distal end a depending plate
30 embedded within a compressed solid block composition 50. For the
sake of clarity in these figures, the compressed solid block is
illustrated in phantom. With reference now to FIG. 14B therein is
illustrated the cageless lavatory dispensing device 10 in a rear
plan view. As is illustrated in the figure, the respective areas of
the plate 30A and the area AB of the block 50 at the transverse
plane coincident with a face of the plate 30A, further illustrating
a preferred ratio of these two surface areas. FIG. 14C illustrates
a side view of the cageless lavatory dispensing device 10
illustrating the relationship of the placement of the plate 30
within the block 50. More specifically the plane of the plate 30 is
between the mid-plane MP and the front face 53 of the block 50.
[0193] FIGS. 15A, 15B illustrate views of a hanger useful with a
still further cageless lavatory dispensing device in both a
perspective view and in a side view.
[0194] FIGS. 15C and 15C illustrate an embodiment of a cageless
lavatory dispensing device 10 which utilizes the hanger depicted in
prior FIGS. 15A, and 15B.
[0195] It is to be understood that cageless the lavatory device
according to the invention may also have a different geometry,
configuration or and appearance than the embodiments described in
the Figures and still be considered to fall within the scope of the
invention.
[0196] In order to further illustrate the present invention,
various examples of preferred embodiments of the invention are
described, following. In these examples, as well as throughout the
balance of this specification and claims, all parts and percentages
are by weight unless otherwise indicated.
EXAMPLES
[0197] Compressed solid blocks according to the invention were
produced from the described on the following tables; examples
according to the invention are indicated by a letter "E" preceding
one or more digits. Several comparative compositions were also
produced and are indicated by a letter "E" preceding one or more
digits; these do not include titanium dioxide. The compressed solid
blocks were produced in the manner described above and where
affixed to a hook generally in accordance with FIG. 3.
[0198] The compositions recited on Table 1 demonstrate non-bleach
containing lavatory block compositions according to the
invention.
TABLE-US-00009 TABLE 1 E1 E2 E3 E4 E5 E6 E7 E8 sodium dodecyl
benzene 23 23 23 23 23 23 23 23 sulfonate (85%) C.sub.14/C.sub.16
olefin sulfonate, 26.4 26.4 26.4 26.4 26.4 26.4 26.4 26.4 sodium
salt (80%) anhydrous sodium sulfate 41.9 42 41.946 41.940 41.947
41.949 41.997 41.993 anhydrous silica 2 2 2 2 2 2 2 2 fragrance 4 4
4 4 4 4 4 4 colorant (pigment) -- 0.04 0.0035 0.01 0.0025 0.0008
0.0025 0.0065 mineral oil 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 titanium
dioxide 0.2 0.06 0.15 0.15 0.15 0.15 0.10 0.10 E9 E10 E11 E12 E13
E14 E15 E16 sodium dodecyl benzene 23 23 23 24.03 23 21.7 23 23
sulfonate (85%) C.sub.14/C.sub.16 olefin sulfonate, 26.4 26.4 26.4
27.59 26.4 24.91 26.4 26.4 sodium salt (80%) anhydrous sodium
sulfate 41.998 41.998 41.998 39.06 37.31 35.21 42.297 42.297
anhydrous silica 2 2 2 2.09 2 1.89 2 2 fragrance 4 4 4 4 4 4 4 4
colorant (pigment) 0.0018 0.0012 0.0018 0.018 0.09 0.09 0.0022
0.003 mineral oil 2.5 2.5 2.5 2.2 2.2 2.2 2.2 2.2 titanium dioxide
0.10 0.10 0.10 1.0 5 10.0 0.10 0.10
TABLE-US-00010 TABLE 1A C1 C2 C3 C4 sodium dodecyl benzene 23 23 23
23 sulfonate (85%) C.sub.14/C.sub.16 olefin sulfonate, 26.4 26.4
26.4 26.4 sodium salt (80%) anhydrous sodium sulfate 42.099 42.098
42.097 42.097 anhydrous silica 2 2 2 2 fragrance 4 4 4 4 colorant
(pigment) 0.0005 0.0018 0.0025 0.0023 mineral oil 2.5 2.5 2.5 2.5
titanium dioxide -- -- -- --
[0199] The identity of the constituents used to form the forgoing
compressed solid blocks are identified more specifically on the
following Table 2. The individual constituents were used "as
supplied" from their respective suppliers and may constitute less
than 100% wt, or 100% wt. of the named compound, as indicated on
Table 1. If less than 100%, the amount of actives present in the
"as supplied" material are indicated in Table 1 and 2.
TABLE-US-00011 TABLE 2 sodium dodecyl benzene sodium dodecyl
benzene sulfonate sulfonate (85%) (85% wt. actives), supplied as
UFARYL DL85, or other source C.sub.14/C.sub.16 olefin sulfonate,
C.sub.14/C.sub.16 olefin sulfonate, sodium salt sodium salt (80%)
(80% wt. actives), supplied as LSS 480/H, or other source anhydrous
sodium sulfate anhydrous sodium sulfate anhydrous silica supplied
as MICROSIL ED, or other source fragrance proprietary composition
of its respective supplier colorant (pigment) proprietary pigment
composition of its respective supplier mineral oil technical grade
mineral oil; technical grade paraffin oil
[0200] Certain of the foregoing example compositions were subjected
to service life testing to evaluate compressed solid block
compositions used as ITB cageless lavatory dispensing devices. In
accordance with the tests, ITB cageless lavatory dispensing device
were produced in accordance with the foregoing discussion in the
specification wherein a mass of the compressed solid block
compositions were extruded into a preform, a slot was provided in
the preform, and a hanger generally in accordance with that
illustrated in FIG. 3 was provided such that the plate of the
hanger was fully inserted into the slot of the preform. The preform
was then subjected to a single compression operation in a suitable
die to compress and form the compressed solid block composition
into a block having a configuration also generally as depicted on
FIG. 14A. The initial mass of the compressed solid block
composition varied slightly from sample to sample, but initial mass
is indicated on the following table.
[0201] In accordance with the test sample ITB cageless lavatory
dispensing devices were supplied to a toilet, a "Remo" model toilet
bowl, (ex. Shires Co., Ireland) or a "Jacob Delafon" toilet bowl
(ex. Delafon, France). The test samples were subjected to an
"accelerated" testing protocol wherein the toilets were flushed 40
times per each day of the test. The placement of the ITB device
varied but once positioned prior to the test was not moved until
the test was concluded. The test was performed over a number of
successive days, and all testing was performed at approximately
room temperature (19-22.degree. C.). Each of the toilets were
periodically and automatically flushed by a machine-controlled
device which operated the toilets to flush 40 times daily at
intervals of approximately 30 minutes between flushes. The
appearance of the compressed solid blocks during the duration of
the test were observed, and prior to testing and the initial flush
each of the ITB cageless lavatory dispensing devices were weighed,
and then placed suspended from the rim of a toilet bowl. At the
conclusion of 315 flush cycles, the test sample ITB cageless
lavatory dispensing devices were removed and allowed to dry for at
least 60 minutes, and thereafter weighed. In this manner, the loss
of the mass of generally dry compressed solid blocks were
evaluated. In the following test, sample devices including a
compressed solid block composition according to several of the
example compositions according to Table 1, as well as the example
compositions according to Table 1A were tested. The results of the
test are indicated on the following Table 3.
TABLE-US-00012 TABLE 3 Final mass of compressed solid % mass loss
of Initial mass of block (grams) compressed solid Sample #/
compressed solid following block following composition block
(grams) 315 flushes 315 flushes 1/E8 44.30 9.50 78.55 1/E9 44.30
16.73 62.23 2/E9 44.30 8.77 80.20 3/E9 44.30 7.44 83.20 4/E9 44.30
8.22 81.44 5/E9 44.30 7.38 83.34 1/E7 44.30 15.49 65.03 2/E8 44.30
7.22 83.70 3/E8 44.30 4.24 90.42 6/E9 44.30 11.66 73.67 1/E10 44.30
17.97 59.43 2/E7 44.30 3.45 92.21 1/C1 44.30 3.94 91.10 1/C2 44.30
5.08 88.53 1/C3 44.30 4.79 89.18
During the test and following the conclusion of the test, no
breaking off of the compressed solid block compositions were
observed, demonstrating surprisingly effective adhesion of the
compositions to the plate notwithstanding multiple flush cycles
wherein flowing water delivered from the rim of the toilet
impinging directly on the plate and the respective compositions.
The compositions also delivered an effective amount of the
surfactants present in the blocks as evidenced by the formation of
bubbles or foam at the waterline of the toilet bowl following a
flush cycle.
[0202] The disparities in the rate of dissolution of the tested
sample devices at like numbers of flushes may often attributed to
the placement of the sample with respect to specific positions on
the rim of the toilet bowl, as in some positions greater volumes of
water were released with each flush and tended to erode or dissolve
the compressed block composition more quickly than at other
positions. Such is not considered to be a detriment, but rather
permits the consumer to selectively place the ITB cageless lavatory
dispensing devices to provide a degree of control over the useful
life of the block, and upon the degree of foaming which is desired
following individual flushes of the toilet bowl.
[0203] On visual observation the surface appearance of the blocks,
as formed and prior to the above test were substantially smooth
with a generally uniform color. Such was observed for the blocks
according to the invention as disclosed in Table 1 as well as the
comparative block compositions according to Table 1A which excluded
the titanium dioxide. However, following the test and after the
blocks had been allowed to dry, the sample blocks according to
Table 1A had a pronounced and unattractive spotted or speckled
surface appearance with significant amounts of sodium sulfate
crystals (or agglomerates) very plainly visible to the unaided eye.
In contrast, the similarly tested and dried sample blocks of the
invention according to Table 1 were generally smooth and uniform in
surface appearance with little surface speckling or spotting
visible to the unaided eye.
[0204] FIG. 1-P is a photograph of two blocks which omit titanium
dioxide which have been suspended beneath the rim of a toilet bowl
which has been flushed 96 times, at a frequency of 12 times per
day, the photograph the photograph being taken prior to the next
successive flush with the block having been allowed to dry in this
position between 30 and 120 minutes. The block "B1-C4" is a block
having a composition according to formula "C4" of Table 1A, and the
block "B2-C3" having a composition according to formula "C3"
according to Table 1A. As is particularly evident from the darker
colored block B1-C4, the surface thereof has very visible and
distinct mottled whitish regions "MS".
[0205] FIG. 2-P is a photograph of two further blocks which omit
titanium dioxide which have been suspended beneath the rim of a
toilet bowl which has been flushed 167 times, at a frequency of 12
times per day, the photograph the photograph being taken prior to
the next successive flush with the block having been allowed to dry
in this position between 30 and 120 minutes. The block "B3-C3" is a
block having a composition according to formula "C3" of Table 1A,
and the block "B4-C3" having a composition according to formula
"C3" according to Table 1A, albeit with a different colorant and
fragrance than that of block B3-C3. As is particularly evident from
the figure, both the darker pigmented block B3-C3, as well as the
lighter pigmented block B4-C4 include on their surfaces thereof
very visible and distinct mottled, streaked whitish regions MS.
[0206] FIG. 3-P is a photograph of several further blocks all of
which have been subjected to at least 70 flush cycles after which,
flushing was terminated and the blocks allowed to dry as suspended
from the rim of the toilet bowl as illustrated at 56 hours
following contact with flush water, but in contact with ambient air
humidity. The darker pigmented blocks, B5-C4, B7-C4, B8-C4, B9-C4
all had compositions in accordance with composition C4 of Table 1A.
The lighter pigmented blocks B6-C3 and B10-C3 all had compositions
in accordance with compositions C3 of Table 1A. As is very evident
from the photograph, all of the block surfaces included mottled,
streaked or spotted whitish regions MS.
[0207] FIG. 4-P is a photograph of the same blocks as in FIG. 3-P,
however the blocks had been further permitted to dry without
contact with flush water but in contact with ambient air humidity
for 72 hours. As is very evident from the photograph, all of the
block surfaces included mottled, streaked or spotted whitish
regions MS, most of which increased in relative size or surface
area in relation to the total surface of the block.
[0208] FIG. 5-P is a photograph of two blocks B11-E7, B12-E7 having
block compositions which comprise titanium dioxide having
compositions according to E7 of Table 1. The blocks have been
suspended beneath the rim of a toilet bowl which has been flushed
82 times, at a frequency of 12 times per day, the photograph being
taken prior to the next successive flush with the block having been
allowed to dry in this position between 30 and 120 minutes. As is
seen from the photograph, little or no surface mottling or spotting
FIG. 6-P is a photograph of two blocks B13-E8, B14-E8 having block
compositions which comprise titanium dioxide having compositions
according to E8 of Table 1. The blocks have been suspended beneath
the rim of a toilet bowl which has been flushed 147 times, at a
frequency of 12 times per day, the photograph being taken prior to
the next successive flush with the block having been allowed to dry
in this position between 30 and 120 minutes. As is seen from the
photograph, little or no surface mottling or spotting FIG. 7-P is a
photograph of two blocks B15-E10, B16-E10 having block compositions
which comprise titanium dioxide having compositions according to
E10 of Table 1. The blocks have been suspended beneath the rim of a
toilet bowl which has been flushed 147 times, at a frequency of 12
times per day, the photograph being taken prior to the next
successive flush with the block having been allowed to dry in this
position between 30 and 120 minutes. As is seen from the
photograph, little or no surface mottling or spotting
[0209] It is to be specifically noted that each of the foregoing
tested sample ITB cageless lavatory dispensing devices exhibited a
satisfactory service life and none of the tested samples exhibited
breakage or delamination of the compressed solid block composition
from the plate of the hanger.
[0210] While the invention is susceptible of various modifications
and alternative forms, it is to be understood that specific
embodiments thereof have been shown by way of example in the
drawings which are not intended to limit the invention to the
particular forms disclosed; on the contrary the intention is to
cover all modifications, equivalents and alternatives falling
within the scope and spirit of the invention as expressed in the
appended claims.
* * * * *