U.S. patent application number 12/677167 was filed with the patent office on 2010-08-26 for lavatory treatment devices.
Invention is credited to Diane Joyce Burt, Jeanne Marie Weller.
Application Number | 20100212074 12/677167 |
Document ID | / |
Family ID | 38658961 |
Filed Date | 2010-08-26 |
United States Patent
Application |
20100212074 |
Kind Code |
A1 |
Burt; Diane Joyce ; et
al. |
August 26, 2010 |
Lavatory Treatment Devices
Abstract
An article or a device comprising a delivery means which
includes a non-liquid lavatory treatment material which includes a
first air treatment constituent in its composition, and wherein the
device also includes an air treatment means particularly where the
air treatment means is used to treat the ambient environment in the
near vicinity, or in the in the proximity of the lavatory appliance
with which the article or device is used. The article or device is
useful for providing both a treatment composition to the interior
of a lavatory appliance, and in particular to the interior of a
toilet bowl when such treatment composition is derived from the
non-liquid lavatory treatment material which can be for example: a
solid, a gel, or a paste which in addition to the first air
treatment constituent also contains one or more treatment
constituents from which may formed an aqueous treatment composition
when the non-liquid lavatory treatment material is contacted with
water, and in particular when contacted with water being flushed
through the lavatory appliance.
Inventors: |
Burt; Diane Joyce;
(Montvale, NJ) ; Weller; Jeanne Marie; (Rockledge,
FL) |
Correspondence
Address: |
PARFOMAK, ANDREW N.;NORRIS MCLAUGHLIN & MARCUS PA
875 THIRD AVE, 8TH FLOOR
NEW YORK
NY
10022
US
|
Family ID: |
38658961 |
Appl. No.: |
12/677167 |
Filed: |
September 8, 2008 |
PCT Filed: |
September 8, 2008 |
PCT NO: |
PCT/GB08/03038 |
371 Date: |
April 26, 2010 |
Current U.S.
Class: |
4/231 |
Current CPC
Class: |
E03D 9/032 20130101;
E03D 9/007 20130101; E03D 2009/024 20130101 |
Class at
Publication: |
4/231 |
International
Class: |
E03D 9/02 20060101
E03D009/02 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 14, 2007 |
GB |
0717951.8 |
Claims
1. A device adapted to be used with a toilet bowl for delivering a
treatment composition thereto comprising: a delivery means which
comprises a non-liquid lavatory treatment material which includes a
first air treatment constituent, which material forms an aqueous
treatment composition when the non-liquid lavatory treatment
material is contacted with water being flushed within a toilet
bowl; and, a further air treatment means containing a further air
treatment constituent which is separate from the non-liquid
lavatory treatment material which includes the first air treatment
constituent for providing a further air treatment constituent to
the ambient environment of the device.
2. The device according to claim 1 wherein: the delivery means is a
cage or container containing a quantity of a non-liquid lavatory
treatment material which in addition to the first air treatment
constituent also contains one or more surfactants, wherein an
aqueous treatment composition providing a cleaning and/or
sanitizing and/or disinfecting benefit to lavatory appliance is
formed by contacting the lavatory treatment material with
water.
3. The device according to claim 1 wherein: the non-liquid lavatory
treatment material is a solid, a gel, or a paste.
4. The device according to claim 1 wherein: the non-liquid lavatory
treatment material exhibits a viscosity of at least 1000 cps.
5. (canceled)
6. The device according to claim 1 wherein the first air treatment
constituent comprises one or more constituents selected from:
perfumes, fragrances, odor masking constituents, odor counteracting
constituents, odor neutralizing constituents, air
sanitizing/disinfecting constituents (such as one or more glycols,
and in particular triethylene glycol) insecticides, or
pesticides.
7. The device according to claim 1 wherein the further air
treatment constituent of the air treatment means comprises one or
more constituents selected from: perfumes, fragrances, odor masking
constituents, odor counteracting constituents, odor neutralizing
constituents, air sanitizing/disinfecting constituents (such as one
or more glycols, and in particular triethylene glycol)
insecticides, or pesticides.
8. (canceled)
9. A process for providing both a cleaning and/or sanitizing and/or
disinfecting treatment to a toilet bowl and to also provide a
treatment of the ambient environment in the proximity of the toilet
bowl being treated, which process includes the step of providing a
device according to claim 1, and mounting the device upon a rim of
a toilet bowl whereby the non-liquid lavatory treatment material
which includes a first air treatment which material forms an
aqueous treatment composition when the non-liquid lavatory
treatment material is contacted with water being flushed within a
toilet and, a further air treatment means containing a further air
treatment constituent which is separate from the non-liquid
lavatory treatment material which includes the first air treatment
constituent for providing a further air treatment constituent to
the ambient environment of the device.
Description
[0001] The present invention relates to improve the lavatory
treatment devices, and in particular is directed to articles and
devices used to provide a cleaning and/or sanitizing and/or
disinfecting treatment to a sanitary appliance, and in particular
to a toilet bowl.
[0002] In the developed world, toilets and toilet bowls are
ubiquitous. While they provide an important sanitary convenience to
persons using them, they also require maintenance. Apart from the
maintenance of the mechanical operation of the toilet bowl, toilets
also require periodic cleaning in order to ensure their
cleanliness, and hygienic condition. Frequently a cleaning
operation is performed by human action or human intervention. In
the most common cleaning operation a human periodically provides a
quantity of a treatment composition, such as from a bottle or other
dispenser, by manually dispensing said the treatment composition to
the interior and exterior surfaces of a toilet bowl. Usually, such
an operation is accompanied by manual agitation, e.g., scrubbing or
wiping, usually by the use of a toilet brush which can be used to
both spread in the treatment composition to surface it is including
inclined surfaces of the toilet bowl as well as to the portions of
the toilet bowl underneath the interior of the toilet bowl rim
wherein hard water stains are known to form. Such an operation
however is unpopular in fact it only provides for the periodic
cleaning of a toilet bowl or other lavatory appliance, and also
requires human intervention. Alternately, a cleaning operation can
be performed by providing a lavatory treatment device in the form
of a cleansing block which can be supplied either to the supply
tank or supply cistern of the toilet bowl within which treatment
chemicals provided as part of the cleaning block are dispersed in
order to form a liquid treatment composition which then comes into
contact with the inner surfaces of the toilet bowl during the flush
cycle. Such a cleaning operation utilizing a cleansing block is
particularly advantageous from a consumer standpoint to ask, with
each flush of the toilet bowl, a quantity of a treatment
composition is released to the toilet bowl which often functions to
minimize the buildup of stains, as well as assist in the removal of
lime scale which is frequently encountered on inner surfaces of
toilet bowls particularly where hard water is used as a supply
source. The primary consumer to do so where are the fact that the
use of such a cleansing block is convenient and requires no human
intervention other than that the act of installing a device or
article which includes cleansing block, optionally replenishing the
device or article with a new cleansing block, and ultimately
removing the device or article which includes the cleansing block.
Such articles or devices are themselves well known to the art and
are in widespread use.
[0003] Notwithstanding the benefits of the use of such articles or
devices which include cleansing blocks, their use is not without
shortcomings. One widely observed shortcoming is the fact that all
such articles or devices which include a cleansing block may
provide a generally satisfactory cleaning treatment, such requires
that the cleansing block be formulated in order to withstand
repeated flushings with water in order to import an appreciable and
satisfactory service life to the cleansing block. Such dictates
that the formulations useful in the formation of cleansing blocks
should be on the one hand, sufficiently resistant to the erosion
and or dissolution of the cleansing block when contacted with
water, yet on the other hand should be sufficiently dissolvable
search release effective amounts of cleaning constituents such as
one or more surfactants, and the like, into the flush water which
comes into contact with the cleansing block contained within the
article or device. Such are competing considerations, and typically
cleansing blocks are formulated to have a useful service life of at
least 14 days, and preferably a least 28 days which unfortunately
also limits the selection of constituents which may be used to
provide such cleansing blocks and, more significantly limits the
effective cleansing ability of the cleansing blocks. Further, the
formulation of such cleansing blocks typically dictates the use of
constituents which are either primarily provided to provide a
cleaning benefit, such as one or more surfactants (tensides), and
to control the rate of erosion of the cleansing block in order to
ensure that a satisfactory service life is provided. Such
limitations this would feed the incorporation of additives,
particularly one or more fragrances which may disrupt this delicate
balance between cleaning ability and service life, and few of these
factors fragrances are frequently omitted from cleansing block
compositions. In cleansing block compositions which do include a
fragrance constituent, frequently the consumer perception of any
fragrance included in the fragrance block is minimal as fragrance
constituents would be expected to form only a minor proportion of
the overall amount of the constituents use to provide the cleansing
block, and due to the limited dissolution or erosion of the
cleansing block during the use in a lavatory appliance, it would be
expected that very little of a fragrance composition would actually
be released with the flush water, and most likely would be
entrained in the flush water and flushed away, rather than
evaporating or emanating into the ambient environment of the
lavatory appliance, e.g., toilet bowl.
[0004] The present invention addresses this shortcoming in the art
and provides both improved devices and articles as well as
processes for the use of such improved devices and articles in
conjunction with a lavatory appliance, and particularly in
conjunction with a toilet.
[0005] In a broad sense the present invention provides an article
or a device comprising a delivery means which includes a non-liquid
lavatory treatment material which includes a first air treatment
constituent in its composition, and wherein the device also
includes an air treatment means particularly where the air
treatment means is used to treat the ambient environment in the
near vicinity, or in the in the proximity of the lavatory appliance
with which the article or device is used. The article or device is
useful for providing both a treatment composition to the interior
of a lavatory appliance, and in particular to the interior of a
toilet bowl when such treatment composition is derived from the
non-liquid lavatory treatment material which can be for example: a
solid, a gel, or a paste which in addition to the first air
treatment constituent also contains one or more treatment
constituents from which may formed an aqueous treatment composition
when the non-liquid lavatory treatment material is contacted with
water, and in particular when contacted with water being flushed
through the lavatory appliance.
[0006] In a further broad sense, the invention also provides an
improved process for providing both a cleaning and/or sanitizing
and/or disinfecting treatment to a sanitary appliance, and in
particular to a toilet bowl and to also treat the ambient
environment in the proximity of the sanitary appliance being
treated, which contemplates the use of any aspect of the device or
apparatus according to the inventive concept, and especially as
described herein.
[0007] According to first aspect of the invention there is provided
a device comprising a delivery means which delivery means includes
a non-liquid lavatory treatment material which includes a first air
treatment constituent, and which device also includes a further (at
least a second) air treatment means containing a further air
treatment constituent which is separate from the non-liquid
lavatory treatment material which includes the first air treatment
constituent for providing a further air treatment constituent to
the ambient environment of the device.
[0008] According to a second aspect of the invention, the delivery
means of the device according to the first aspect of the invention
is a cage or container containing a quantity of a non-liquid
lavatory treatment material which can be for example: a solid, a
gel, or a paste which in addition to the first air treatment
constituent also contains one or more treatment constituents, for
example, one a more surfactants, wherein an aqueous treatment
composition useful for providing a cleaning and/or sanitizing
and/or disinfecting benefit to lavatory appliance may be formed by
contacting the lavatory treatment material with water.
[0009] According to a third aspect of the invention, the delivery
means of the device according to the second aspect of the invention
is a cage or a container which includes one or more perforations or
passages which permit for the entry of, and for the egress of
water, and in particular flush water, to pass into the interior of
the delivery means and contact the non-liquid lavatory treatment
material.
[0010] According to a fourth aspect of the invention, the delivery
means of the device according to the invention excludes a cage or
container.
[0011] According to a fifth aspect of the invention there is
provided at least one hanger means which may be used to suspend the
device according to the invention upon a portion of a sanitary
appliance, and especially where the sanitary appliance is a toilet
bowl and said portion is a section of a toilet bowl rim.
[0012] According to the sixth aspect of the invention there is
provided a non-liquid lavatory treatment material according to the
first aspect of the invention which includes as a first air
treatment constituent and/or as part of the air treatment means one
or more constituents selected from: perfumes, fragrances, odor
masking constituents, odor counteracting constituents, odor
neutralizing constituents, air sanitizing/disinfecting constituents
(such as one or more glycols, and in particular triethylene glycol)
insecticides, or pesticides.
[0013] According to seventh aspect of the invention there is
provided a device according to the first aspect of the invention
wherein the air treatment means comprises a passive device for the
delivery of a second air treatment constituent to the ambient
environment.
[0014] According to an eighth aspect of the invention there is
provided a device according to the first aspect of the invention
wherein the air treatment means comprises an active device for the
delivery of a second air treatment constituent to the ambient
environment.
[0015] According to the ninth aspect of the invention there is
provided a device according to any prior aspect of the invention
described herein, wherein the delivery means positions the
non-liquid lavatory treatment material in the path of the flush
water provided by the lavatory appliance, and in particular a
toilet, and where the delivery means positions the air treatment
means outside of the path of the flush water provided by the
lavatory appliance.
[0016] According to tenth aspect of the invention there is provided
a device according to the ninth aspect of the invention wherein the
delivery means is within the interior of a toilet bowl, as
preferably situated proximate to the interior toilet bowl rim,
while the air treatment means is on the exterior of the toilet
bowl.
[0017] According to an eleventh aspect of the invention there is
provided a device according to the first aspect of the invention
wherein both the delivery means and the air treatment means are
positioned within the interior of a toilet bowl.
[0018] According to a twelfth aspect of the invention there is
provided a device according to the eleventh aspect of the invention
wherein the delivery means and the air treatment means present in a
device wherein both the delivery means and the air treatment means
are in the path of flushing water, or wherein the delivery means is
within the path of flushing water, while the air treatment means is
outside of the path of flushing water but within the interior of a
toilet bowl.
[0019] Further aspects of the invention, include processes for the
use of the devices according to the invention are described in
further detail hereinbelow, and in particular with reference to the
figures provided.
[0020] An essential element of the device according to the
invention is a non-liquid lavatory treatment material which
includes a first air treatment constituent, as well as further
constituents which are useful for providing a cleaning and/or
sanitizing and/or disinfecting benefit to lavatory appliance may be
formed by contacting the said lavatory treatment material with
water. The non-liquid lavatory treatment material may be a solid,
such as a block, tablet or cake, which can be formed by a number of
known techniques such as extrusion, or may be a compressed block,
tablet or cake or may be a gel, paste or pasty solid.
[0021] By the term "non-liquid lavatory treatment materials" are
materials which are distinguishable from "thin liquids", namely
those which have a viscosity of up to 50 cps as measured with a an
RVF Brookfield Viscometer, #2 spindle at 20 rpm and 21.degree. C.
Preferably the non-liquid lavatory treatment materials are
materials which have a viscosity of at least (in order of
increasing preference) 500 cps, 750 cps, 1000 cps, 1250 cps, 1500
cps, 1750 cps, 2000 cps as measured under these conditions. In many
preferred embodiments the non-liquid lavatory treatment materials
are in the form of a solid or compressed tablet, block or cake.
[0022] As chemical constituents the non-liquid lavatory treatment
materials 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 useful disinfecting agent.
[0023] Exemplary useful anionic surfactants which may be used in
the non-liquid lavatory treatment material 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.
[0024] 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.
[0025] 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.
[0026] 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.
[0027] 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.
[0028] 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.
[0029] 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.
[0030] 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.
[0031] 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.
[0032] 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.14
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.
[0033] 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.
[0034] 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.
[0035] 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.
[0036] 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.
[0037] 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-- (A)
where
[0038] EO represents ethylene oxide,
[0039] PO represents propylene oxide,
[0040] y equals at least 15,
[0041] (EO).sub.x+z equals 20 to 50% of the total weight of said
compounds, and,
[0042] the total molecular weight is preferably in the range of
about 2000 to 15,000.
[0043] 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.a(EO,PO).sub.b--H (B)
wherein R is an alkyl, aryl or aralkyl group, [0044] 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.
[0045] 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.
[0046] 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 R is an alkyl group containing 1 to 20 carbon atoms, [0047]
n is about 15 and x is about 15.
[0048] 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 [0049] n is about 15, [0050] x is about 15 and [0051] y is
about 15.
[0052] Still further useful nonionic block copolymer surfactants
include ethoxylated derivatives of propoxylated ethylene diamine,
which may be represented by the following formula:
##STR00001##
where
[0053] (EO) represents ethoxy,
[0054] (PO) represents propoxy,
[0055] 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.
Further useful nonionic surfactants include nonionic amine oxide
constituent. Exemplary amine oxides include:
[0056] 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;
[0057] 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;
[0058] 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
[0059] 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.
[0060] 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:
[0061] R.sub.1 is a straight chained C.sub.1-C.sub.4 alkyl group,
preferably both R.sub.1 are methyl groups; and,
[0062] 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.
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.12
alkyl groups and at least 25% wt. of C.sub.14 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.
[0063] Still further exemplary useful nonionic surfactants which
may be used include certain alkanolamides including
monoethanolamides and diethanolamides, particularly fatty
monoalkanolamides and fatty dialkanolamides.
[0064] 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 non-liquid lavatory treatment material. 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.
[0065] 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.
[0066] 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.
[0067] 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.
[0068] 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.
[0069] Preferred quaternary germicides used in the non-liquid
lavatory treatment materials are those which are supplied in a
solid or powdered form, as such greatly facilitates the manufacture
of the non-liquid lavatory treatment materials.
[0070] When present in a non-liquid lavatory treatment material, 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.
[0071] 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.
[0072] One or more detersive surfactant constituents may be present
in the non-liquid lavatory treatment material in any effective
amount and generally comprises up to about 60% wt. of the total
weight of the non-liquid lavatory treatment material. Preferably
detersive surfactant constituents comprise about 10-55% wt., more
preferably 20-50% wt. of the non-liquid lavatory treatment
material.
[0073] Further exemplary chemical constituents may be one or more
sanitizing agents or germicides which may be present in the
non-liquid lavatory treatment material.
[0074] 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.
[0075] By way of non-limiting example, the non-liquid lavatory
treatment material may include 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
non-liquid lavatory treatment material 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 non-liquid lavatory treatment material as
hypohalite-releasing bleaches are halohydantoins which may be used
include those which may be represented by the general
structure:
##STR00005##
[0076] X.sub.1 and X.sub.2 are independently hydrogen, chlorine or
bromine; and,
[0077] 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 non-liquid lavatory treatment materials.
[0078] 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.
[0079] 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 non-liquid lavatory treatment
material. More preferably, when present, the bleach constituent
comprises about 0.5-50% wt., more preferably at least 1-40% wt. of
the non-liquid lavatory treatment material.
[0080] 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.
[0081] 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.
[0082] As a further chemical constituent, the non-liquid lavatory
treatment materials of the invention may also comprise a coloring
agent which imparts either a color to the non-liquid lavatory
treatment material, or 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 the non-liquid lavatory treatment
materials 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
non-liquid lavatory treatment material, 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 non-liquid lavatory treatment material which includes a
bleach constituent do not comprise any colorants. Desirably the
colorants, when present, do not exceed 15% wt. of the non-liquid
lavatory treatment material, 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.
[0083] As an essential constituent, the non-liquid lavatory
treatment materials necessarily include a first air treatment
constituent which may be one or more constituents, which by way of
non-limiting example, include: perfumes, fragrances, odor masking
constituents, odor counteracting constituents, odor neutralizing
constituents, air sanitizing/disinfecting constituents (such as one
or more glycols, and in particular triethylene glycol,)
insecticides, or pesticides
[0084] 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, Anetlhole 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.
[0085] 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.
[0086] Additionally the first air treatment constituent may also be
any other material which is useful in providing treatment of
ambient air, such as a sanitizing agent. e.g., one or more glycols
or alcohols, particularly triethylene glycol, or one or more
materials which are intended to counteract, neutralize, or mask
odors in the absence of, or in conjunction with a fragrance or
perfume composition, as well as may be one or more materials which
provide an effective insecticide repelling or insecticidal benefit;
such would be particularly useful in climates or environments where
insects present a nuisance or health hazard.
[0087] As further chemical constituents, the non-liquid lavatory
treatment materials 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
4,578,207, 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.
[0088] The non-liquid lavatory treatment materials 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 non-liquid lavatory treatment
material.
[0089] The non-liquid lavatory treatment materials of the invention
may include one or more preservatives. Such preservatives are
primarily included to reduce the growth of undesired microorganisms
within the non-liquid lavatory treatment material 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.
[0090] The inventive non-liquid lavatory treatment materials 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.
[0091] 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.
[0092] 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.
[0093] The non-liquid lavatory treatment materials may optionally
include one or more dissolution control agents. Such dissolution
control agent are materials which provide a degree of
hydrophobicity to a treatment block formed from the non-liquid
lavatory treatment materials whose presence contributes to the slow
uniform dissolution of the treatment block when contacted with
water, and simultaneously the controlled release of the active
constituents such a solid block formed from the non-liquid lavatory
treatment materials. 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 non-liquid lavatory treatment
materials, although generally lesser amounts are usually effective.
Generally wherein the non-liquid lavatory treatment material is to
be used in an ITB ("in the bowl") article or device 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 non-liquid lavatory treatment material.
[0094] The non-liquid lavatory treatment material 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.
[0095] The non-liquid lavatory treatment material may optionally
include one or more solid water-soluble acids or acid-release
agents such as sulfamic acid, citric acid or sodium hydrogen
sulfate. 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.
[0096] The non-liquid lavatory treatment materials 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 non-liquid lavatory treatment material, although generally
lesser amounts are usually effective.
[0097] The non-liquid lavatory treatment materials, and
particularly lavatory 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
non-liquid lavatory treatment material, although generally lesser
amounts are usually effective.
[0098] Preferably when formed as a solid block the non-liquid
lavatory treatment materials formed into such a solid block
includes silica. Silica has been observed to aid in the controlling
the rate of dissolution of the non-liquid lavatory treatment
material when provided as compressed solid blocks.
[0099] The non-liquid lavatory treatment material 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.
[0100] 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.
[0101] 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.
[0102] Preferred diester constituents include those wherein Y is
--(CH.sub.2).sub.x-- 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.
[0103] 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.
[0104] When present such further processing aids are typically
included in amounts of up to about 30% by weight, preferably to 20%
wt. of a solid block composition formed from the non-liquid
treatment material although generally lesser amounts are usually
effective.
[0105] The non-liquid lavatory treatment materials may comprise
include a film forming constituent, viz., a film forming polymer in
an effective amount. Such are advantageously present when the
non-liquid lavatory treatment materials are in the form of a
tablet, cake or a block, although such may also be present when the
non-liquid lavatory treatment composition is in the form of a gel
or a paste. The use of film forming constituent is believed to
provide for a reduction in limescale deposition on the treated hard
surfaces, as the film forming constituent is provided with each
flush or wash of water passing around such treatment block. It is
believed that the long term buildup of limescale may be resisted or
retarded on hard surfaces, viz., lavatory surfaces and lavatory
appliances due to the presence of the film-forming constituent
thereon. While it is preferred that the film forming constituent
deposit a generally continuous film on a hard surface, it is to be
understood that while the film forming constituent need be present
in the present inventive compositions it is not required that any
layer or film formed therefrom which is formed on the surface of a
lavatory appliance, e.g., toilet bowl, be necessarily uniform
either in thickness or be a continuous film providing uninterrupted
surface coverage although such would be preferred. Rather it is
contemplated that film forming materials useful in the present
invention need not form a continuous or uniform coating, as it is
only required that the film forming materials provide some extent
of a surface coating to a hard surface upon which it is applied. It
is to be understood that the potential for forming the film layer
from a film forming composition is influenced by several factors,
inter alia, the nature of the hard surface being treated, the
geometry and configuration of the hard surface being treated, the
fluid dynamics of the water contacting the treatment block, the
quality of the water contacting the treatment block.
[0106] The film-forming constituent may be present in any amount
which is found effective in forming a film on a hard surface being
treated. It will be understood that this such a minimum amount will
vary widely, and is in part dependent upon the molecular weight of
the film forming polymer utilized in a formulation, but desirably
at least about 0.001% wt. should be present. More preferably the
film forming polymer comprises from 0.001% wt. to 10% wt. of the
non-liquid lavatory treatment material compositions of which it
forms a part. The identity of particularly preferred film-forming
polymers and preferred amounts are disclosed in one or more of the
following examples.
[0107] Exemplary materials useful in the film forming constituent
include film forming polymers such as:
[0108] a polymer having the formula
##STR00007##
in which n represents from 20 to 99 and preferably from 40 to 90
mol %, m represents from 1 to 80 and preferably from 5 to 40 mol %;
p represents 0 to 50 mol, (n+m+p=100); R.sub.1 represents H or
CH.sub.3; y represents 0 or 1; R.sub.2 represents
--CH.sub.2--CHOH--CH.sub.2-- or C.sub.xH.sub.2x in which x is 2 to
18; R.sub.3 represents CH.sub.3, C.sub.2H.sub.5 or t-butyl; R.sub.4
represents CH.sub.3, C.sub.2H.sub.5 or benzyl; X represents Cl, Br,
I, 1/2SO.sub.4, HSO.sub.4 and CH.sub.3SO.sub.3; and M is a vinyl or
vinylidene monomer copolymerisable with vinyl pyrrolidone other
than the monomer identified in [ ].sub.m;
[0109] quaternized copolymers of vinylpyrrolidone and
dimethylaminoethyl methacrylate;
[0110] polyvinylpyrrolidone;
[0111] vinylpyrrolidone/vinylacetate;
[0112] vinylpyrrolidone/vinyl caprolactam/ammonium derivative
terpolymer, especially where the ammonium derivative monomer has 6
to 12 carbon atoms and is selected from diallylamino alkyl
methacrylamides, dialkyl dialkenyl ammonium halides, and a
dialkylamino alkyl methacrylate or acrylate;
[0113] high molecular weight polyethylene glycol;
[0114] water soluble polyethylene oxide;
[0115] polyvinylcaprolactam;
[0116] polyvinylalcohol;
[0117] cationic cellulose polymer;
[0118] cationic fatty quaternary ammonium compounds;
[0119] organosilicone quaternary ammonium compounds;
[0120] 2-propenamide, N-[3-(dimethylamino)propyl]-2-methyl, polymer
with 1-ethenyl-2-pyrrolidone hydrochloride;
[0121] polynitrogen compounds, including amphoteric polyamide
polymers; and,
[0122] maleic acid/polyolefin copolymers;
one or more of which may be present in effective amounts.
[0123] A first film-forming polymer contemplated to be useful in
the present compositions is one having the formula
##STR00008##
are more fully described in U.S. Pat. No. 4,445,521, U.S. Pat. No.
4,165,367, U.S. Pat. No. 4,223,009, U.S. Pat. No. 3,954,960, as
well as GB 1,331,819, the contents of which are hereby incorporated
by reference.
[0124] The monomer unit within [ ].sub.m is, for example, a
di-lower alkylamine alkyl acrylate or methacrylate or a vinyl ether
derivative. Examples of these monomers include dimethylaminomethyl
acrylate, dimethylaminomethyl methacrylate, diethylaminomethyl
acrylate, diethylaminomethyl methacrylate, dimethylaminoethyl
acrylate, dimethylaminoethyl methacrylate, dimethylaminobutyl
acrylate, dimethylaminobutyl methacrylate, dimethylaminoamyl
methacrylate, diethylaminoamyl methacrylate, dimethylaminohexyl
acrylate, diethylaminohexyl methacrylate, dimethylaminooctyl
acrylate, dimethylaminooctyl methacrylate, diethylaminooctyl
acrylate, diethylaminooctyl methacrylate, dimethylaminodecyl
methacrylate, dimethylaminododecyl methacrylate, diethylaminolauryl
acrylate, diethylaminolauryl methacrylate, dimethylaminostearyl
acrylate, dimethylaminostearyl methacrylate, diethylaminostearyl
acrylate, diethylaminostearyl methacrylate, di-t-butylaminoethyl
methacrylate, di-t-butylaminoethyl acrylate, and dimethylamino
vinyl ether.
[0125] Monomer M, which can be optional (p is up to 50) can
comprise any conventional vinyl monomer copolymerizable with
N-vinyl pyrrolidone. Thus, for example, suitable conventional vinyl
monomers include the alkyl vinyl ethers, e.g., methyl vinyl ether,
ethyl vinyl ether, octyl vinyl ether, etc.; acrylic and methacrylic
acid and esters thereof, e.g., methacrylate, methyl methacrylate,
etc.; vinyl aromatic monomers, e.g., styrene, a-methyl styrene,
etc; vinyl acetate; vinyl alcohol; vinylidene chloride;
acrylonitrile and substituted derivatives thereof;
methacrylonitrile and substituted derivatives thereof; acrylamide
and methacrylamide and N-substituted derivatives thereof; vinyl
chloride, crotonic acid and esters thereof; etc. Again, it is noted
that such optional copolymerizable vinyl monomer can comprise any
conventional vinyl monomer copolymerizable with N-vinyl
pyrrolidone. These film-forming polymers of the present invention
are generally provided as a technical grade mixture which includes
the polymer dispersed in an aqueous or aqueous/alcoholic carrier.
Such include materials which are presently commercially available
include quaternized copolymers of vinylpyrrolidone and
dimethylaminoethyl methacrylate sold as Gafquat.RTM. copolymers
(ex. ISP Corp., Wayne, N.J.) which are available in a variety of
molecular weights.
[0126] Further exemplary useful examples of the film-forming
polymers of the present invention include quaternized copolymers of
vinylpyrrolidone and dimethylaminoethyl methacrylate as described
in U.S. Pat. No. 4,080,310, to Ng, the contents of which are herein
incorporated by reference. Such quaternized copolymers include
those according to the general formula:
##STR00009##
wherein "x" is about 40 to 60. Further exemplary useful copolymers
include copolymers of vinylpyrrolidone and
dimethylaminoethylmethacrylate quaternized with diethyl sulphate
(available as Gafquat.RTM. 755 ex., ISP Corp., Wayne, N.J.).
[0127] Such a further useful film-forming polymer according to the
invention is a quaternized
polyvinylpyrrolidone/dimethylaminoethylmethacrylate copolymer which
is commercially available as Gafquat.RTM. 734, is disclosed by its
manufacturer to be:
##STR00010##
wherein x, y and z are at least 1 and have values selected such
that the total molecular weight of the quaternized
polyvinylpyrrolidone/dimethylamino ethylmethacrylate copolymer is
at least 10,000 more desirably has an average molecular weight of
50,000 and most desirably exhibits an average molecular weight of
100,000. A further useful, but less preferred quaternized
polyvinylpyrrolidone/dimethylamino ethylmethacrylate copolymer is
available as Gafquat.RTM. 755N which is similar to the Gafquat.RTM.
734 material describe above but has an average molecular weight of
about 1,000,000. These materials are sometimes referred to as
"Polyquaternium-11".
[0128] Exemplary polyvinylpyrrolidone polymers useful in the
present inventive compositions exhibit a molecular weight of at
least about 5,000, with a preferred molecular weight of from about
6,000-3,000,000.
[0129] Such polyvinylpyrrolidone polymers are generally provided as
a technical grade mixture of polyvinylpyrrolidone polymers within
approximate molecular weight ranges.
[0130] Exemplary useful polyvinylpyrrolidone polymers are available
in the PVP line materials (ex. ISP Corp.) which include PVP K 15
polyvinylpyrrolidone described as having molecular weight in the
range of from 6,000-15,000; PVP-K 30 polyvinylpyrrolidone with a
molecular weight in the range of 40,000-80,000; PVP-K 60
polyvinylpyrrolidone with a molecular weight in the range of
240,000-450,000; PVP-K 90 polyvinylpyrrolidone with a molecular
weight in the range of 900,000-1,500,000; PVP-K 120
polyvinylpyrrolidone with a molecular weight in the range of
2,000,000-3,000,000.
[0131] Other suppliers of polyvinylpyrrolidone include AllChem
Industries Inc, Gainesville, Fla., Kraft Chemical Co., Melrose
Park, Ill., Alfa Aesar, a Johnson Matthey Co., Ward Hill, Mass.,
and Monomer-Polymer & Dajac Labs Inc., Feasterville, Pa.
[0132] Exemplary vinylpyrrolidone/vinylacetate copolymers which
find use in the present inventive compositions as the film forming
constituent vinylpyrrolidone/vinylacetate copolymers comprised of
vinylpyrrolidone monomers which may be represented by the following
structural formula:
##STR00011##
and vinylacetate monomers which may be represented by the following
structural formula:
##STR00012##
which are usually formed by a free-radical polymerization reaction
to produce linear random vinylpyrrolidone/vinylacetate copolymers.
The resultant vinylpyrrolidone/vinylacetate copolymers may comprise
varying amounts of the individual vinylpyrrolidone monomers and
vinylacetate monomers, with ratios of vinylpyrrolidone monomer to
vinylacetate monomers from 30/70 to 70/30. The values of x and y in
the structural formula should have values such that x+y=100 to 500,
preferably x+y=150 to 300. Such values correspond to provide
vinylpyrrolidone/vinylacetate copolymers having a total molecular
weight in the range from about 10,000 to about 100,000, preferably
from about 12,000 to about 60,000. Alternately, desirably the ratio
of x:y is 0.1:4.0, preferably from 0.2:3.0. Such ratios of x:y
provide the preferred vinylpyrrolidone/vinylacetate copolymers
which have vinylpyrrolidone monomer to vinylacetate monomers from
0.3/2.5.
[0133] Exemplary useful vinylpyrrolidone/vinylcaprolactam/ammonium
derivative terpolymers useful as the film forming constituent are
comprised of vinylpyrrolidone monomers which may be represented by
the following structural formula:
##STR00013##
and vinylcaprolactam monomers which may be represented by the
following structural formula:
##STR00014##
and dimethylaminoethylmethacrylate monomers which may be
represented by the following structural formula:
##STR00015##
Exemplary vinylpyrrolidone/vinylcaprolactam/ammonium derivative
terpolymer wherein the ammonium derivative monomer has 6 to 12
carbon atoms and is selected from diallylamino alkyl
methacrylamides, dialkyl dialkenyl ammonium halides, and a
dialkylamino alkyl methacrylate or acrylate which find use in the
present inventive compositions include those marketed under the
tradename ADVANTAGE.RTM. (ex. ISP.) as well as GAFFIX.RTM. (ex. ISP
Corp). Such terpolymers are usually formed by a free-radical
polymerization reaction to produce linear random
vinylpyrrolidone/vinylcaprolactam/ammonium derivative terpolymers.
The vinylpyrrolidone/vinylcaprolactam/ammonium derivative
terpolymers useful in the present invention preferably comprise
17-32 weight % vinylpyrrolidone; 65-80 weight % vinylcaprolactam;
3-6 weight % ammonium derivative and 0-5 weight % stearyl
methacrylate monomers. The polymers can be in the form of random,
block or alternating structure having number average molecular
weights ranging between about 20,000 and about 700,000; preferably
between about 25,000 and about 500,000. The ammonium derivative
monomer preferably has from 6 to 12 carbon atoms and is selected
from the group consisting of dialkylaminoalkyl methacrylamide,
dialkyl dialkenyl ammonium halide and a dialkylamino alkyl
methacrylate or acrylate. Examples of the ammonium derivative
monomer include, for example, dimethylamino propyl methacrylamide,
dimethyl diallyl ammonium chloride, and dimethylamino ethyl
methacrylate (DMAEMA). These terpolymers are more fully described
in U.S. Pat. No. 4,521,404 to GAF Corporation, the contents of
which are hereby incorporated by reference.
[0134] High molecular weight polyethylene glycol polymers useful in
the present inventive compositions exhibit a molecular weight of at
least about 100, preferably exhibits a molecular weight in the
range of from about 100 to about 10,000 but most preferably a
molecular weight in the range of from about 2000 to about 10,000.
Particularly useful high molecular weight polyethylene glycols are
available under the tradename CARBOWAX.RTM. (ex. Union Carbide
Corp.). Other suppliers of high molecular weight polyethylene
glycols include Ashland Chemical Co., BASF Corp., Norman, Fox &
Co., and Shearwater Polymers, Inc.
[0135] Water soluble polyethylene oxides suitable for use as film
forming polymers in the compositions according to the invention may
be represented by the following structure:
(CH.sub.2CH.sub.2O).sub.x
where:
[0136] x has a value of from about 2000 to about 180,000.
[0137] Desirably, these polyethylene oxides may be further
characterized as water soluble or water dispersible resins, having
a molecular weight in the range of from about 100,000 to about
8,000,000. At room temperature (68.degree. F., 20.degree. C.) they
are solids. Particularly useful as the film-forming, water soluble
polyethylene oxide in the inventive compositions are POLYOX
water-soluble resins (ex. Union Carbide Corp., Danbury Conn.).
[0138] Further contemplated as useful in the place of, or in
combination with these polyethylene oxides are polypropylene
oxides, or mixed polyethylene oxides-polypropylene oxides having
molecular weights in excess of about 50,000 and if present,
desirably having molecular weights in the range of from about
100,000 to about 8,000,000. According to particularly desirable
embodiments of the invention, the film-forming constituent of the
present invention is solely a water soluble polyethylene oxide.
[0139] Exemplary film-forming polyvinylcaprolactams include
polyvinylcaprolactam compounds marketed under the tradename
LUVISKOL.RTM. (ex. BASF Corp.). Such polyvinylcaprolactams may be
represented by the following structural formula:
##STR00016##
Where n has a value of at least about 500, and preferably a value
in the range of from about 800 to about 1000.
[0140] Useful as the film forming constituent in the present
inventive compositions are polyvinylalcohols which include those
marketed under the tradename Airvol.RTM. (Air Products Inc.,
Allentown Pa.). These include: Airvol.RTM. 125, classified as a
"super hydrolyzed" polyvinylalcohol polymer having a degree of
hydrolysis of at least 99.3%, and a viscosity at a 4% solution in
20.degree. C. water of from 28-32 cps; Airvol.RTM. 165, and
Airvol.RTM. 165S, each being classified as "super hydrolyzed"
polyvinylalcohol polymer having a degree of hydrolysis of at least
99.3%, and a viscosity at a 4% solution in 20.degree. C. water of
from 62-72 cps; Airvol.RTM. 103, classified as a "fully hydrolyzed"
polyvinylalcohol polymer having a degree of hydrolysis of from
98.0-98.8%, and a viscosity at a 4% solution in 20.degree. C. water
of from 3.5-4.5 cps; Airvol.RTM. 305, classified as a "fully
hydrolyzed" polyvinylalcohol polymer having a degree of hydrolysis
of from 98.0-98.8%, and a viscosity at a 4% solution in 20.degree.
C. water of from 4.5-5.5 cps; Airvol.RTM. 107, classified as a
"fully hydrolyzed" polyvinylalcohol polymer having a degree of
hydrolysis of from 98.0-98.8%, and a viscosity at a 4% solution in
20.degree. C. water of from 5.5-6.6 cps; Airvol.RTM. 321,
classified as a "fully hydrolyzed" polyvinylalcohol polymer having
a degree of hydrolysis of from 98.0-98.8%, and a viscosity at a 4%
solution in 20.degree. C. water of from 16.5-20.5 cps; Airvol.RTM.
325, classified as a "fully hydrolyzed" polyvinylalcohol polymer
having a degree of hydrolysis of from 98.0-98.8%, and a viscosity
at a 4% solution in 20.degree. C. water of from 28-32 cps; and
Airvol.RTM.350, classified as a "fully hydrolyzed" polyvinylalcohol
polymer having a degree of hydrolysis of from 98.0-98.8%, and a
viscosity at a 4% solution in 20.degree. C. water of from 62-72
cps; Airvol.RTM. 425, classified as being an "intermediate
hydrolyzed" polyvinylalcohol polymer classified having a degree of
hydrolysis of from 95.5-96.5%, and a viscosity at a 4% solution in
20.degree. C. water of from 27-31 cps; Airvol.RTM. 502, classified
as a "partially hydrolyzed" polyvinylalcohol polymer having a
degree of hydrolysis of from 87.0-89.0%, and a viscosity at a 4%
solution in 20.degree. C. water of from 3.0-3.7 cps; Airvol.RTM.
203 and Airvol.RTM. 203S, each classified as a "partially
hydrolyzed" polyvinylalcohol polymer having a degree of hydrolysis
of from 87.0-89.0%, and a viscosity at a 4% solution in 20.degree.
C. water of from 3.5-4.5 cps; Airvol.RTM. 205 and Airvol.RTM. 205S,
each classified as a "partially hydrolyzed" polyvinylalcohol
polymer having a degree of hydrolysis of from 87.0-89.0%, and a
viscosity at a 4% solution in 20.degree. C. water of from 5.2-6.2
cps; Airvol.RTM. 523, classified as a "partially hydrolyzed"
polyvinylalcohol polymer having a degree of hydrolysis of from
87.0-89.0%, and a viscosity at a 4% solution in 20.degree. C. water
of from 23-27 cps; and Airvol.RTM. 540, each classified as a
"partially hydrolyzed" polyvinylalcohol polymer having a degree of
hydrolysis of from 87.0-89.0%, and a viscosity at a 4% solution in
20.degree. C. water of from 45-55 cps. Of these, particularly
preferred are polyvinyl alcohol polymers which exhibit a degree of
hydrolysis in the range of from 87%-98% and which desirably also
exhibit a viscosity at a 4% solution in 20.degree. C. water of from
3.0-100.0 cps.
[0141] Exemplary cationic cellulose polymers which find use in the
present inventive compositions as the film forming constituent
include those described in U.S. Pat. No. 5,830,438 as being a
copolymer of cellulose or of a cellulose derivative grafted with a
water-soluble monomer in the form of quaternary ammonium salt, for
example, halide (e.g., chloride, bromide, iodide), sulfate and
sulfonate. Such polymers are described in U.S. Pat. No. 4,131,576
to National Starch & Chemical Company, the contents of which
are hereby hydroxyethyl- and hydroxypropylcelluloses grafted with a
salt of methacryloylethyltrimethyl ammonium,
methacrylamidopropyltrimethyl ammonium, or dialkyldiallyl ammonium,
wherein each alkyl has at least one carbon atom and wherein the
number of carbon atoms is such that the material is water soluble,
preferably from 1 to about 20 carbon atoms, more preferably from 1
to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl and
the like. The preferred materials can be purchased for example
under the trademarks "Celquat L 200" and "Celquat H 100" from
National Starch & Chemical Company.
[0142] Useful cationic cellulose polymers are, per se, generally
known. Exemplary cationic cellulose polymers useful in the present
inventive compositions exhibit generally a viscosity of at least
about 1,000 cps (as taken from a product specification of Celquat
H-100; measured as 2% solids in water using an RVF Brookfield
Viscometer, #2 spindle at 20 rpm and 21.degree. C.).
[0143] A further class of materials which find use in the film
forming constituent are film forming cationic polymers, an
especially film-forming fatty quaternary ammonium compounds which
generally conform to the following structure:
##STR00017##
wherein R is a fatty alkyl chain, e.g., C.sub.8-C.sub.32 alkyl
chain such as tallow, coco, stearyl, etc., R' is a lower
C.sub.1-C.sub.6 alkyl or alkylene group, the sum of both n is
between 12-48, and X is a salt-forming counterion which renders the
compound water soluble or water dispersible, e.g., an alkali,
alkaline earth metal, ammonium, methosulfate as well as
C.sub.1-C.sub.4 alkyl sulfates. Of these, a preferred film forming
film-forming fatty quaternary ammonium compound may be represented
by the following structure:
##STR00018##
wherein R is a fatty alkyl chain, e.g., C.sub.8-C.sub.32 alkyl
chain such as tallow, coco, stearyl, etc., the sum of both "n" is
between 12-48, and preferably the value of each n is the same as
the other, and X is a salt-forming counterion such as an alkali,
alkaline earth metal, ammonium, methosulfate but is preferably an
alkyl sulfate such as ethyl sulfate but especially diethyl sulfate.
An preferred example of a commercially available material which may
be advantageously used is CRODAQUAT TES (ex. Croda Inc.,
Parsippany, N.J.) described to be polyoxyethylene (16) tallow
ethylammonioum ethosfulfate. A further preferred commercially
available material is CRODAQUAT 1207 (ex. Croda Inc.)
[0144] A further class of particularly useful film forming
materials include film-forming, organosilicone quaternary ammonium
compounds. Such compounds may also exhibit antimicrobial activity,
especially on hard surfaces which may supplement the effect of the
quaternary ammonium surfactant compounds having germicidal
properties.
[0145] Specific examples of organosilicone quaternary ammonium
salts that may be used in the compositions of this invention
include organosilicone derivatives of the following ammonium salts:
di-isobutylcresoxyethoxyethyl dimethyl benzyl ammonium chloride,
di-isobutylphenoxyethoxyethyl dimethyl benzyl ammonium chloride,
myristyl dimethylbenzyl ammonium chloride, myristyl picolinium
chloride, N-ethyl morpholinium chloride, laurylisoquinolinium
bromide, alkyl imidazolinium chloride, benzalkonium chloride, cetyl
pyridinium chloride, coconut dimethyl benzyl ammonium chloride,
stearyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzyl
ammonium chloride, alkyl diethyl benzyl ammonium chloride, alkyl
dimethyl benzyl ammonium bromide, di-isobutyl phenoxyethoxyethyl
trimethyl ammonium chloride, di-isobutylphenoxyethoxyethyl dimethyl
alkyl ammonium chloride, methyl-dodecylbenzyl trimethyl ammonium
chloride, cetyl trimethyl ammonium bromide, octadecyl dimethyl
ethyl ammonium bromide, cetyl dimethyl ethyl ammonium bromide,
octadec-9-enyl dimethyl ethyl ammonium bromide, dioctyl dimethyl
ammonium chloride, dodecyl trimethyl ammonium chloride, octadecyl
trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide,
hexadecyl trimethyl ammonium iodide, octyl trimethyl ammonium
fluoride, and mixtures thereof. Other water dispersible salts, such
as the acetates, sulfates, nitrates, and phosphates, are effective
in place of the halides, but the chlorides and bromides are
preferred. The silicone group is preferably substituted with alkyl
ethers. Preferred alkyl ethers are short carbon chain ethers such
as methoxy and ethoxy substituents.
[0146] Still further examples of particularly preferred
film-forming, organosilicone quaternary ammonium compounds which
find use in the present inventive compositions include those which
may be represented by the following structural representation:
##STR00019##
wherein: [0147] R.sub.1 and R.sub.2 each independently represent
short chain alkyl or alkenyl groups, preferably C.sub.1-C.sub.8
alkyl or alkenyl groups; [0148] R.sub.3 represents a
C.sub.11-C.sub.22 alkyl group; and [0149] X represents a salt
forming counterion, especially a halogen.
[0150] Preferred short chain alkyl substituents for R.sub.1 are
methyl and ethyl, preferred short chain alkyl substituents for
R.sub.2 are straight chain links of methylene groups consisting of
from 1 to 4 members, preferred R.sub.3 substituents are straight
chain links of methylene groups consisting of from 11 to 22
members, and preferred halogens for X are chloride and bromide.
[0151] Exemplary and preferred film-forming, organosilicone
quaternary ammonium compounds useful in the inventive compositions
is AEM.RTM. 5772 or AEM.RTM. 5700 (from Aegis Environmental Co.,
Midland, Mich.). Both of these materials are described as being
3-(trimethoxysilyl)propyloctadecyldimethyl ammonium chloride,
AEM.RTM. 5700 and is sold as a 72% by weight active solution of the
compound in a water/methanol mixture, while AEM.RTM. 5772 is sold
as a 72% by weight active solution of the compound in a
water/methanol mixture. While the film-forming, organosilicone
quaternary ammonium compound may be present in any effective
amount, desirably it is present in amounts of from 0.01-5% wt.,
more desirably from 0.05-2.5% wt. based on the total weight of the
inventive compositions.
[0152] As further materials useful in as the film forming polymers
in the present invention includes materials currently being sold
under the VIVIPRINT tradename, e.g., VIVIPRINT 131, which is
described to be 2-propenamide,
N-[3-(dimethylamino)propyl]-2-methyl, polymer with
1-ethenyl-2-pyrrolidone hydrochloride.
[0153] One particularly preferred class of materials useful as the
film forming constituent of the present invention are polynitrogen
compounds, especially amphoteric polyamide polymers.
[0154] Organic polynitrogen compound in the sense of the present
invention means an organic compound comprising at least 3 nitrogen
atoms which are contained in the molecule in the form of an amine,
like a primary, a secondary or a teriary amine, and/or in the form
of an amide. By amphoteric is meant that the same compound may
function as acceptor as well as a donator for protons.
[0155] Exemplary suitable functional groups imparting proton
donator properties represent carboxy residues or derivatives
thereof, like amides, anhydrides or esters, as well as salts
thereof, like alkali salts, for example sodium or potassium salts,
or ammonium salts, which may be converted into the carboxy group.
Depending on the size of the polynitrogen moiety there may be one
or more proton donating functionalities in the molecule. It is
preferred that more than one proton donating functionalities are
present in the amphoteric polynitrogen compound.
[0156] Preferred amphoteric organic polynitrogen compounds are
polymeric amphoteric organic polynitrogen-compounds, having an
average molecular weight of at least about 200, preferably at least
about 300, 400, 500, 600, 700, 800, 900, 1000 or even greater.
[0157] The one or more amphoteric organic polynitrogen compounds
preferably are independently obtainable from reacting polyalkylene
polyamines, polyamidoamines, ethyleneimine-grafted
polyami-doamides, polyetheramines or mixtures thereof as component
A optionally with at least bi-functional cross-linking agents
having a functional group independently selected from a halohydrin,
a glycidyl, an aziridine or an isocyanate moiety or a halogen atom,
as component B, and with monoethylenically unsaturated carboxylic
acids; salts, esters, amides or nitriles of monoethylenically
unsaturated carboxylic acids; salts, esters, amides or nitriles of
monoethylenically unsaturated carboxylic acids, chlorocarboxylic
acids and/or glycidyl compounds such as glycidyl acid, glycidyl
amide or glycidyl esters. Such compounds are described for example
in WO 2005/073357 A2, the contents of which are herein incorporated
by reference.
[0158] The amphoteric organic polynitrogen compounds are obtainable
by reacting components A, optionally with B and with C. The
compound therefore can be present in cross-linked or uncross-linked
form, wherein component A in any case is modified with component C.
Components A, optionally B and C may be used in any possible ratio.
If component B is employed, preferably components A and B are used
in a molar ratio of from 100:1 to 1:1000, more preferred of from
20:1 to 1:20. The molar ratio of components A and C preferably is
chosen such that the molar ratio of the hydrogen atoms bonded to
the nitrogen in A and component C is from 1:0.2 to 1:0.95, more
preferred from 1:0.3 to 1:0.9, and even more preferred from 1:0.4
to 1:0.85.
[0159] Exemplary suitable compounds useful as component A include
polyalkylene polyamines, which are to be understood as referring to
compounds comprising at least 3 nitrogen atoms, including but not
limited to: diethylenetriamine, triethylenetetraamine,
tetraethylenepentaamine, pentaethylenehexamine,
diaminopropylenediamine, trisaminopropylamine and polyethyleneimine
Polyethyleneimines preferably have an average molecular weight (Mw)
of at least 300. It is particularly preferred that the average
molecular weight of the poyethyleneimines ranges from about 600 to
about 2,000,000, more preferred from 20,000 to 1,000,000, and even
more preferred from 20,000 to 750,000, as may be determined by
means of light scattering. The polyethyleneimines may be partially
amidated, and such may be obtained by reacting polyalkylene
polyamines with carboxylic acids, carboxylic acid esters,
carboxylic acid anhydrides or acylhalides. The polyalkylene
polyamines as suitable in the present invention preferably are
amidated to an extent of 1 to 30, more preferred of up to 20% for
the subsequent reactions. The amidated polyalkylene polyamines are
required to contain free NH-groups in order to let them react with
compounds B and C. Suitable carboxylic acids which may be used to
amidate the polyalkylene polyamines are exemplified by
C.sub.1-C.sub.28 carboxylic acids, including but not limited to
formic acid, acetic acid, propionic acid, benzoic acid, lauric
acid, palmitic acid, stearic acid, oleic acid, linoleic acid and
behenic acid. Alternately the polyethyleneimines may be partially
amidated by reacting the polyalkylene polyamine with
alkyldiketene.
[0160] The polyalkylene polyamines may be used partly in
quaternized form as component A. Suitable quaternization agents
include, for example, alkyl halides, such as methyl chloride, ethyl
chloride, butyl chloride, epichlorohydrin, hexyl chloride, dimethyl
sulfate, diethyl sulfate and benzyl chloride. If quaternized
polyalkyleneamines are used as component A, the degree of
quaternization preferably is 1 to 30.
[0161] Further compounds which may also be used as component A
included polyamidoamines. Polyamidoamines are obtainable, for
example, by reacting C.sub.4-C.sub.10 dicarboxylic acids with
polyalkylene polyamines containing preferably 3 to 10 alkaline
nitrogen atoms. Suitable dicarboxylic acids can be exemplified by
succinic acid, maleic acid, adipic acid, glutaric acid, suberic
acid, sebacic acid and terephthalic acid. It is also possible to
use mixtures of carboxylic acids, like a mixture of adipic acid and
glutaric acid, or maleic acid and adipic acid. Preferably adipic
acid is used to produce the polyamidoamines. Suitable polyalkylene
polyamines which may be condensed with the dicarboxylic acids are
similar to the ones mentioned above, and can be exemplified by
diethylenetriamine, triethylenetetraamine, dipropylenetriamine,
tripropylenetetraamine, dihexamethylenetriamine, aminopropyl
ethylenediamine as well as bis-aminopropyl ethylenediamine.
Mixtures of polyalkylene polyamines may also be used to prepare
polyamidoamines. Preferably the preparation of the polyamidoamines
takes place in substance, however optionally the preparation can be
carried out in inert solvents. The condensation reaction of the
dicarboxylic acids with the polyalkylene polyamines is carried out
at elevated temperatures such as in the range of from about
120.degree. C. to about 220.degree. C. The water formed during the
reaction is distilled off the reaction mixture. Lactones or lactams
derivable from carboxylic acids having 4 to 8 carbon atoms also may
be present during the condensation reaction. Generally, 0.8 to 1.4
mole of polyalkyleneamines are used with each mole of dicarboxylic
acid. The thus obtained polyamidoamines have primary and secondary
NH-groups and are soluble in water.
[0162] A further compound which is suitable as component A includes
ethyleneimine grafted polyamidoamines. Such products are obtainable
by reacting ethyleneimine with the above described polyamidoamines
in the presence of Bronnstedt-acids or Lewis-acids, such as
sulfuric acid, phosphoric acid or boron trifluoride etherate. Such
reaction conditions result in a graft of ethyleneimine to the
polyamidoamine. For example, each alkaline nitrogen group of the
polyamidoamine may be grafted with 1 to 10 ethyleneimine units,
i.e. 10 to 500 parts by weight of ethyleneimine are used with 100
parts by weight of a polyamidoamine
[0163] Still further compounds useful as component A include
polyetheramines. Such compounds are known to the art and are
described, for example, in DE-A 2916356. Polyetheramines are
obtainable from condensing diamines and polyamines with
chlorohydrin ethers at elevated temperatures. The polyamines may
comprise up to 10 nitrogen atoms. The chlorohydrin ethers
themselves can be prepared by reacting a dihydric alcohol having 2
to 5 carbon atoms, the alkoxylation products thereof having up to
60 alkyleneoxide units, glycerol or polyglycerol comprising up to
15 glycerol units, erythritol or pentaerythritol with
epichlorohydrin. At least 2 to 8 moles of epichlorohydrin are
reacted with each mole of said alcohol. The reaction of the
diamines and the polyamines on one hand and the chlorohydrin ethers
on the other hand generally takes place at temperatures of from
about 1.degree. C. to about 200.degree. C., preferably of from
110.degree. C. to 200.degree. C. Moreover, polyetherpolyamines may
be prepared by condensing diethanolamine or triethanolamine
according to the methods known in the art, such as the methods
disclosed in U.S. Pat. No. 4,404,362, U.S. Pat. No. 4,459,220 and
U.S. Pat. No. 2,407,895.
[0164] Particularly preferred as component A are polyalkylene
polyamines, which may be optionally are amidated up to 20%. Further
preferred compounds include polyalkylene polyamines, especially
polyethyleneimines, which have an average molecular weight of from
about 800 to 2,000,000, more preferably from 200,000 to 1,000,000,
and most preferably from 20,000 to 750,000.
[0165] Compounds suitable as component B include bifunctional
cross-linking agents comprising halohydrin units, glycidyl units,
aziridine units or isocyanate units or a halogen atom as functional
groups.
[0166] By way of non-limiting example, suitable cross-linking
agents include epihalohydrin, preferably epichlorohydrin, as well
as .alpha.,.omega.-bis-(chlorohydrin)-polyalkylene glycol ether and
the .alpha., .omega.-bis-(epoxides) of polyalkylene glycol ethers
which are obtainable therefrom by treatment with bases. The
chlorohydrinethers may be prepared, for example, by reacting
polyalkylene glycols with epichlorohydrin in a molar ratio of 1 to
at least 2 to 5. Appropriate polyalkylene glycols include, for
example, polyethylene glycol, polypropylene glycol and polybutylene
glycol as well as block copolymers of C.sub.2 to C.sub.4
alkyleneoxides. The average molecular weight (Mw) of the
polyalkylene glycols generally ranges from about 100 about to 6000,
preferably from 300 to 2000 g/mol. .alpha.,
.omega.-bis-(chlorohydrin) polyalkylene glycol ether are, per se,
known to the art and for example are described in U.S. Pat. No.
4,144,123. Further, .alpha.,.omega.-dichloropolyalkylene glycols
are also suitable as cross-linking agents, such as those disclosed
in EP-A 0 025 515. Such .alpha., .omega.-dichloropolyalkylene
glycols are obtainable by reacting dihydric to tetrahydric
alcohols, preferably alkoxylated dihydric to tetrahydric alcohols
either with thionyl chloride resulting in a cleavage of HCI
followed by catalytic decomposition of the chlorosulfonated
compound while eliminating sulfur dioxide, or with phosgene
resulting in the corresponding bis-chlorocarbonic acid ester while
eliminating HCI, which bischlorocarbonic acid esters are
catalytically decomposed eliminating carbondioxid to result in
.alpha.,.omega.-dichloro ether. Preferably the dihydric to
tetrahydric alcohols are ethoxylated and/or propoxylated glycols
wherein each mole of glycol is reacted with 1 to 100, in particular
with 4 to 40 moles of ethylene oxide.
[0167] Further appropriate crosslinking agent include .alpha.,
.omega.- or vicinal dichloroalkanes, including but not limited to
1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane,
1,4-dichlorobutane and 1,6-dichlorohexane. It is further to be
understood that crosslinking agents which are obtainable from
reacting at least trihydric alcohols with epichlorohydrin,
resulting in reaction products having at least two chlorohydrin
moieties may also be used. Examples for polyhydric alcohols are
glycerol, ethoxylated or propoxylated glycerol, polyglycerol having
2 to 15 glycerol units within the molecule and optionally
ethoxylated and/or propoxylated polyglycerol. Cross-linking agents
of this kind are per se, known to the art and include those
described in DE-A 2916356. Still further exemplary useful
crosslinking agents include crosslinking agents containing blocked
isocyanate groups such as trimethylhexamethylene diisocyanate
blocked with 2,2,3,6-tetramethylpiperidone-4. Such cross-linking
agents are also per se, know to the art and are described in DE-A
4028285. Moreover, crosslinking agents based on polyethers or
substituted hydrocarbons containing aziridine moieties like
1,6-bis-N-aziridinohexane represent further suitable as
cross-linking agents.
[0168] According to the present invention the cross-linking agents
may be employed individually or as a mixture of two or more
cross-linking agents. Particularly preferred are epihalohydrins,
especially epichlorohydrin, .alpha.,
.omega.-bis-(chlorohydrin)polyalkylene glycol ether, .alpha.,
.omega.-bis-(epoxides) of polyalkylene glycol ethers and/or
bisglycidylethers of polyalkylene glycols as component B.
[0169] Exemplary compounds suitable as component C include
monoethylenically unsaturated carboxylic acids having preferably 3
to 18 carbon atoms in their alkenyl residue. Appropriate
monoethylenically unsaturated carboxylic acids include by acrylic
acid, methacrylic acid, diemethacrylic acid, ethyl acrylic acid,
allyl acetic acid, vinyl acetic acid, maleic acid, fumaric acid,
itaconic acid, methylene malonic acid, oleic acid and linoleic
acid. Monoethylenically unsaturated carboxylic acids selected from
the group comprising acrylic acid, methacrylic acid and maleic acid
are especially preferred. It is also possible to use the salts of
the aforementioned monoethylenically unsaturated carboxylic acids
as component C. Suitable salts generally represent alkali metal,
alkaline earth metal and ammonium salts of the aforementioned
acids. Particularly preferred are sodium, potassium and ammonium
salts. Ammonium salts can be derived from ammonia as well as from
amines or amine derivatives like ethanolamine, diethanolamine and
triethanolamine. Examples for alkaline earth metal salts generally
represent magnesium and calcium salts of the aforementioned
monoethylenically unsaturated carboxylic acids.
[0170] Exemplary suitable esters of the aforementioned
monoethylenically unsaturated carboxylic acids are derivable from
monohydric C.sub.1-C.sub.20 alcohols or from dihydric
C.sub.2-C.sub.6 alcohols. Esters which may be used herein can be
exemplified by methyl acrylate, ethyl acrylate, n-propyl acrylate,
isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl
methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl
methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate,
palmityl acrylate, lauryl acrylate, diaryl acrylate, lauryl
methacrylate, palmityl methacrylate, stearyl methacrylate, dimethyl
maleate, diethyl maleate, isopropyl maleate, 2-hydroxyethyl
acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
3-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate,
3-hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl
methacrylate and hydroxyhexyl acrylate and hydroxy-hexyl
methacrylate.
[0171] Representative appropriate amides of monoethylenically
unsaturated carboxylic acids include acrylamide, methacrylamide and
oleic amide. Suitable nitriles of the mono-ethylenically
unsaturated carboxylic acids are acrylonitrile and
methacrylonitrile. Further contemplated as useful amides include
amides which are derivable by reacting monoethylenically
unsaturated carboxylic acids, in particular (meth)acrylic acid,
with amidoalkane sulfonic acids. Those amides are especially
advantageous which are obtainable from reacting monoethylenically
unsaturated carboxylic acids, especially (meth)acrylic acid, with
amidoalkane sulfonic acids, as represented by the following
formulae I or II:
H.sub.2C.dbd.CH--X--SO.sub.3H (I)
H.sub.2C.dbd.C(CH.sub.3)--X--SO.sub.3H (II)
wherein X either is not present or when present is a spacing group
according to one or more of the formulae:
--C(O)--NH--CH.sub.2-n(CH.sub.3).sub.n(CH.sub.2).sub.m--,
--C(O)NH--, --C(O)--NH--(CH(CH.sub.3)CH.sub.2)-- or
--C(O)--NH--CH(CH.sub.2CH.sub.3)--, with n being 0 to 2 and m being
0 to 3. Particularly preferred are 1-acrylamido-1-propanesulfonic
acid (X--C(O)--NH--CH(CH2CH3)-- in formula I),
2-acrylamido-1-propanesulfonic acid (X.dbd.(O)--NH--(CH(CH3)CH2)--
in formula I), 2-acrylamido-2-methyl-1-propanesulfonic acid
(--C(O)--NH--C(CH3)2(CH2)-- in formula I),
2-methacrylamido-2-methyl-1-propanesulfonic acid
(X.ident.--C(O)--NH--C(CH3)2(CH2)-- in formula II) and
vinylsulfonic acid (X not present in formula I).
[0172] Chlorocarboxylic acids are also appropriate as component C.
Such chloro carboxylic acids include chloroacetic acid,
2-chloropropionic acid, 2-chlorobutanoic acid, dichloroacetic acid
and 2,2'-dichloro propionic acid. Further compounds suitable as
component C are glycidyl compounds which are represented by the
following formula (III):
##STR00020##
wherein:
[0173] X represents NH.sub.2, OMe, OR
[0174] Me represents H, Na, K, ammonium, and
[0175] R represents C.sub.1-C.sub.4 alkyl or C.sub.2-C.sub.4
hydroxyalkyl.
[0176] Preferred compounds of formula III include but are not
limited to: glycidyl acid, sodium, potassium, ammonium, magnesium
or calcium salts thereof, glycidyl amide and glycidyl ester like
glycidyl methyl ester, glycidyl ethyl ester, glycidyl n-propyl
ester, glycidyl n-butyl ester, glycidyl iso-butyl ester,
glycidyl-2-ethylhexyl ester, glycidyl-2-hydroxypropyl ester and
glycidyl-4-hydroxybutyl ester. Glycidyl acid and sodium, potassium
or ammonium salts thereof, or glycidyl amide are particularly
preferred.
[0177] Preferably, a monoethylenically unsaturated carboxylic acid
is used as component C, particularly wherein the monoethylenically
unsaturated carboxylic acid is one or more of acrylic acid,
methacrylic acid or maleic acid, and especially preferably wherein
the monoethylenically unsaturated carboxylic acid is acrylic
acid.
[0178] The above described preferred amphoteric organic
polynitrogen compounds can be produced according to methods known
in the art. Exemplary methods of production are disclosed for
example in DE-A 4244194, in which component A at first reacts with
component C and afterwards component B is added. According to the
disclosure of DE-A 4244194 it is also possible to have components C
and B reacted simultaneously with component A. In a preferred
embodiment the amphoteric organic polynitrogen compounds comprising
components A, B and C are prepared using a process comprising the
following steps:
[0179] AA) cross-linking of polyalkylene polyamines,
polyamidoamines, ethyleneimine-grafted polyaminoamides,
polyetheramines or mixtures thereof as component A with at least
bifunctional cross-linking agents having a functional group
independently selected from a halohydrin, a glycidyl, an aziridine
or an isocyanate moiety or a halogen atom, as component B, and
[0180] BB) reacting the product obtained in step i) with
monoethylenically unsaturated carboxylic acids; salts, esters,
amides or nitriles of monoethylenically unsaturated carboxylic
acids, chlorocarboxylic acids and/or glycidyl compounds like
glycidyl acid, glycidyl amide or glycidyl esters as component
C.
[0181] In step AA), the cross-linking of the compounds exemplified
for component A with the cross-linking agents C proceeds according
to methods known to the skilled person. Generally, the
cross-linking is carried out at a temperature of from about
10.degree. C. to about 200.degree. C., preferably of from
30.degree. C. to 100.degree. C. and typically at standard pressure.
The reaction times depend on the components A and B used, and in
most cases range from 0, 5 to 20 hours, preferably from 1 to 10
hours. In general, curing component B is added in the form of an
aqueous solution such that the reaction take place in aqueous
medium as well. The product obtained can be isolated or directly
used in step BBj) without further isolation which is preferred.
[0182] In step BB), the reaction product obtained in step AA) is
reacted with the compound according to group C. If the compound of
group C comprises a monoethylenically unsaturated compound having a
double bonding system the primary or secondary amine groups of the
cross-linked product obtained in step AA) are added to the free end
of the double bond similar to a Michael-addition. If the compound
of group C is a chlorocarboxylic acid or a glycidyl compound of
formula I the reaction of the amine moieties proceeds at the chloro
group or the epoxy group. The reaction typically is carried out at
a temperature of from about 10.degree. C. to about 200.degree. C.,
preferably of from 30.degree. C. to 100.degree. C. and usually at
standard pressure. The reaction time depends on the components used
and generally lies within the range of from 0, 5 to 100 hours,
preferably from 1 to 50 hours. It is contemplated that the
foregoing reaction may take place in an aqueous solution wherein
the reaction product obtained in step AA) already is present in an
aqueous solution.
[0183] Specific, albeit nonlimiting examples for the preparation of
such compounds are also described in WO 2005/073357 A2.
[0184] One particularly preferred compound of the amphoteric
organic polynitrogen compounds as specified above, which may be
used as the film forming constituent in the compositions of the
present invention is presently commercially available under the
trade name SOKALAN HP70 (ex. BASF AG).
[0185] Further exemplary film forming constituent useful in the
compositions of the present invention include maleic acid/olefin
copolymers useful as the film forming constituent of the present
invention include maleic acid/olefin copolymers which may be
represented by the following formula (IV):
##STR00021##
[0186] Especially preferred are maleic acid/olefin copolymers of
formula IV wherein A is selected frown the group of hydrogen,
ammonium or an alkali metal; and R.sub.1, R.sub.2, R.sub.3 and
R.sub.4 are each independently selected from the group of hydrogen
or an alkyl group, which alkyl group may be straight or branched,
saturated or unsaturated, containing from 1 to about 8 carbon
atoms, preferably from 1 to about 5 carbon atoms. The monomer ratio
of x to y is from about 1:5 to about 5:1, preferably from about 1:3
to about 3:1, and most preferably from 1.5:1 to about 1:1.5. The
average molecular weight of the maleic acid/olefin copolymer will
typically be less than about 20,000, more typically between about
4,000 and about 12,000.
[0187] A preferred maleic acid-olefin copolymer is a maleic
acid-di-isobutylene copolymer having an average molecular weight of
about 12,000 and a monomer ratio (x to y) of about 1:1. Such a
copolymer is presently commercially available as SOKALAN CP-9, and
is believed to be represented by formula IV wherein A is hydrogen
or sodium, R.sub.1 and R.sub.3 are hydrogen, R.sub.2 is methyl, and
R.sub.4 is neopentyl. Another preferred product is a maleic
acid-trimethyl isobutylene ethylene copolymer according to formula
IV wherein A is hydrogen or sodium, R.sub.1 and R.sub.3 are each
methyl, R.sub.2 is hydrogen and R.sub.4 is tertiary butyl.
[0188] It is of course contemplated that a mixture or blend of two
or more distinct compounds or materials may be used to provide the
film forming constituent of the inventive compositions.
[0189] In addition to the film forming materials described
immediately above, other film forming materials which are
compatible with the balance of the constituents present in the
non-liquid lavatory treatment material are also contemplated as
being useful and within the scope of the present invention.
[0190] 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 non-liquid lavatory treatment
material and that they are retained with minimal degradation in the
non-liquid lavatory treatment material 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 non-liquid
lavatory treatment material is contacted with water supplied either
in the cistern or in the toilet bowl.
[0191] Ideally when the non-liquid lavatory treatment material is
provided in such a form, 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 treatment blocks formed from the
non-liquid lavatory treatment material 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.
[0192] When formed into compressed solid blocks, the non-liquid
lavatory treatment materials 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 non-liquid lavatory treatment material compositions.
[0193] It will be appreciated by those of ordinary skill in the art
that several of the components which are directed to provide a
non-liquid lavatory treatment material 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.
[0194] The non-liquid lavatory treatment material 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.
[0195] The non-liquid lavatory treatment material may also include
two or more parts, or may include two or more regions, but only one
such part or region necessarily includes the first air treatment
constituent in its composition. For example a non-liquid lavatory
treatment material may be formed by combining a non-liquid lavatory
treatment material which includes a first air treatment constituent
in its composition with a further non-liquid lavatory treatment
material which may exclude a further air treatment constituent in
its composition, such as by pressing, coextrusion or lamination,
particularly wherein the non-liquid lavatory treatment material are
blocks or tablets. Alternately the two or more parts of the
non-liquid lavatory treatment material may be discrete bodies of
non-liquid lavatory treatment material which may merely be placed
near each other without necessarily requiring physical contact with
each other.
[0196] The non-liquid lavatory treatment material may also include
two or more parts, or may include two or more regions, wherein a
plurality of parts or regions necessarily each includes an air
treatment constituent in its composition. The air treatment
composition present may be the same in each of the parts or
regions, or may be different air treatment compositions in
different parts or regions. For example a non-liquid lavatory
treatment material may be formed by combining a non-liquid lavatory
treatment material which includes a first air treatment constituent
in its composition with a further non-liquid lavatory treatment
material which includes a further air treatment constituent (which
may be the same or different) in its composition, such as by
pressing, coextrusion or lamination, particularly wherein the
non-liquid lavatory treatment material are blocks or tablets.
Alternately the two or more parts of the non-liquid lavatory
treatment material may be discrete bodies of non-liquid lavatory
treatment material which may merely be placed near each other
without necessarily requiring physical contact with each other.
Such non-liquid lavatory treatment material may also include two or
more parts, or may include two or more regions may permit for the
provision of chemically incompatible air treatment constituents in
a single device according to the invention. Alternately such
non-liquid lavatory treatment material may also include two or more
parts, or may include two or more regions may permit for the
provision of devices which provide mutually exclusive air treatment
benefits provided by different air treatment constituents, e.g., at
least two of: perfumes, fragrances, odor masking constituents, odor
counteracting constituents, odor neutralizing constituents, air
sanitizing/disinfecting constituents (such as one or more glycols,
and in particular triethylene glycol,) insecticides, or
pesticides.
[0197] Any form of the non-liquid lavatory treatment material 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 non-liquid lavatory treatment material 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
thereon.
[0198] Exemplary materials which may be used to provide such a
coating on some or all of the surfaces of the non-liquid lavatory
treatment materials 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 non-liquid lavatory treatment
material 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 non-liquid lavatory treatment materials may be
affixed to the plate of a hanger are then conveniently dipped into
the said bath, thereby providing a coating layer to the non-liquid
lavatory treatment material. Alternately, the coating materials may
be sprayed, brushed on or padded onto at least part of the surfaces
of a body formed from the non-liquid lavatory treatment
material.
[0199] 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 non-liquid lavatory
treatment material during packaging and storage prior to use of the
devices of the invention. 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.
[0200] A first exemplary non-liquid lavatory treatment material
which includes a first air treatment constituent in its
composition, and which is adapted to be formed into a block or
tablet is described as follows:
TABLE-US-00001 % wt/wt. sodium dodecyl benzene sulfonate (85%
20-45% wt. actives) C.sub.14/C.sub.16 olefin sulfonate, sodium salt
(80%) 18-30% wt. sodium lauryl ether sulfate (80%) 0-10% wt.
anhydrous sodium sulfate 15-50% wt. lauryl monoenthanolamide 0-20%
wt. anhydrous silica 0-2% wt. fragrance 0.001-7% wt. colorant 0-5%
wt. mineral oil 0-5% wt.
[0201] A second representative non-liquid lavatory treatment
material which includes a first air treatment constituent in its
composition, and which is adapted to be formed into a block or
tablet is described as follows:
TABLE-US-00002 % wt/wt. alpha olefin sulfonate, sodium salt,
95-100% wt. 12-35% wt. actives lauramide monoethanolamide, 98% wt.
actives 3-33% wt. anionic surfactant, dodecylbenzene sulfonate,
12-38% wt. 80% wt. actives sodium sulfate, 100% wt. actives 12-35%
wt. anionic surfactant, sodium lauryl ether sulfate, 0-10% wt. 70%
wt. actives anhydrous silica, 100% wt. actives 0-10% wt. fragrance
or odor masking agent 0.001-5% wt. colorant 0-5% wt.
[0202] Further representative non-liquid lavatory treatment
materials which include a first air treatment constituent, and
which is adapted to be formed into a block or tablet are described
as follows:
TABLE-US-00003 A B C D E (% wt/wt) (% wt/wt) (% wt/wt) (% wt/wt) (%
wt/wt) dodecyl benzene sulfonate, sodium 25 10 40 35 35 salt
(80-90% active) alpha olefin sulfonate, sodium salt 25 10 5 32 32
lauryl monoethanolamide3 10 8 5 2 5 lauryl ether sulfate, sodium
salt 10 -- -- 4.5 5 polyoxyethylene (160) 10 -- -- 3 --
polyoxypropylene (30) glycol sodium sulfate 20 -- -- 21.5 21
Pluronic 87 or Pluronic88.sup.1 -- 70 50 -- -- C.sub.9-C.sub.11
alcohol ethoxylate, 6EO -- 2 -- -- -- fragrance or odor masking
agent 0.01-3 0.01-3 0.01-3 0.01-3 0.01-3 colorant .sup. 0-1.2 .sup.
0-1.2 .sup. 0-1.2 .sup. 0-1.5 .sup. 0-1.5 silica -- -- -- 2 2
.sup.1Pluronic 87 E.sub.61 P.sub.41.5 E.sub.61 -- Molecular Weight
7700 -- HLB 24 -- non-ionic surfactant Pluronic 88 E.sub.98
P.sub.41.5 E.sub.98 -- Molecular Weight 10800 -- HLB 28-- non-ionic
surfactant
[0203] Yet further representative non-liquid lavatory treatment
materials which include a first air treatment constituent, and
which is adapted to be formed into a block or tablet are described
as follows:
TABLE-US-00004 % w/w alpha olefin sulfonate 0-35 sodium lauryl
ether sulfate 3.0-6.0 bleaching agent (e.g., DCCNa or
halohydantoin) 0.5-25 lauryl monoethanolamide 2.0-5.0 dodecyl
benzene sulfonate, sodium salt 50-70 Anhydrous sodium sulfate 15-25
fragrance, odor masking agent or insecticide 0.001-5 colorant 0-3.5
silica 1.0-2.0
[0204] Still further representative non-liquid lavatory treatment
materials which include a first air treatment constituent as well
as a film forming constituent, and which are adapted to be formed
into a block or tablet are described in the following tables:
TABLE-US-00005 % w/w C.sub.10-C.sub.14benzene sulfonate, sodium
salt (80% 30-38 wt. active); supplied as NANSA HS 80/PF lauryl
monoethanol amide (98% wt. active) 0-7 alkene sulfonate, sodium
salt; supplied as 25-40 supplied as NANSA LSS 480/H
C.sub.12-C.sub.16 ethoxy (2-3 EO) sulfate, sodium salt 0-4 (70% wt.
active); supplied as EMPICOL ESB 70 silica 0-5 sodium sulfate 15-25
3-(trimethoxysilyl)propyloctadecyldimethyl 0.05-0.4 ammonium
chloride (72% wt active); supplied as AEM 5772, 72% wt. actives
(ex. Aegis Environmental Co.,) citric acid 0-5 sodium bicarbonate
0-1 fragrance, odor masking agent or insecticide 0.001-5 colorant
0-3.5 deionized water .sup. 0-q.s.
TABLE-US-00006 % w/w C.sub.10-C.sub.14benzene sulfonate, sodium
salt (80% wt. 25-40 actives); supplied as NANSA HS 80/PF lauryl
monoethanol amide (98% wt. actives) 0-5 alkene sulfonate, sodium
salt; supplied as supplied as 25-40 NANSA LSS 480/H
C.sub.12-C.sub.16 ethoxy (2-3 EO) sulfate, sodium salt (70% wt. 0-4
actives); supplied as EMPICOL ESB 70 silica 0-5 sodium sulfate
15-25 sulfamic acid 0-15 citric acid 0-15 polyoxyethylene (16)
tallow ethylammonioum 0-4 ethosfulfate (100% wt. actives); supplied
as CRODAQAT TES, 100% wt. actives fragrance, odor masking agent or
insecticide 0.001-5 colorant 0-3.5 d.i. water .sup. 0-q.s.
TABLE-US-00007 % wt/wt C.sub.10-C.sub.14benzene sulfonate, sodium
salt (80% wt. 22-32 actives); supplied as NANSA HS 80/PF
C.sub.14/C.sub.16 olefin sulfonate, sodium salt 30-42 (80% wt.
actives); supplied as supplied as NANSA LSS 480/H sodium sulfate
20-30 lauryl monoethanol amide (98% wt. actives) 0.1-3 silica 0-2
citric acid 0.5-7 sodium lauryl ether sulfate (70% wt. actives)
0.5-4 amphoteric organic polynitrogen compound, 0.5-6 35%-35% wt.
actives, supplied as SOKOLAN HP70 (ex. BASF) fragrance, odor
masking agent or insecticide 0.001-5 colorant 0-3.5 d.i. water
.sup. 0-q.s.
TABLE-US-00008 % wt/wt C.sub.10-C.sub.14benzene sulfonate, sodium
salt (80% wt. 22-32 actives); supplied as NANSA HS 80/PF
C.sub.14/C.sub.16 olefin sulfonate, sodium salt 30-42 (80% wt.
actives); supplied as supplied as NANSA LSS 480/H sodium sulfate
20-30 lauryl monoethanol amide (98% wt. actives) 0.1-3 silica 0-2
citric acid 0.5-7 sodium lauryl ether sulfate (70% wt. actives)
0.5-4 maleic acid-di-isobutylene copolymer, 25% wt. 0.5-6 actives,
supplied as SOKOLAN CP-9 (ex. BASF) fragrance, odor masking agent
or insecticide 0.001-5 colorant 0-3.5 d.i. water .sup. 0-q.s.
[0205] As a further essential element the devices of the invention
also necessarily include an air treatment means, which is
distinguishable from and separate from the non-liquid lavatory
treatment material. The air treatment means can be an article,
composition or device which can be used to deliver a quantity of an
air treatment constituent into the ambient environment of the
laboratory appliance, and preferably wherein the laboratory
appliance is a toilet bowl. The air treatment means is used to
deliver a second air treatment constituent to the ambient
environment which may be one or more: perfumes, fragrances, odor
masking constituents, odor counteracting constituents, odor
neutralizing constituents, air sanitizing/disinfecting constituents
(such as one or more glycols, and in particular triethylene
glycol,) insecticides, or pesticides. The second air treatment
constituent may be immaterial which is the same as, or which is
different than the first-year treatment constituents. Additionally,
the air treatment means may be a "passive" type or "active"
type.
[0206] Various examples of useful air treatment means are discussed
with reference to the following figures.
[0207] Turning now to FIG. 1, there is disclosed in a perspective
you a first embodiment of a device 10 according to the invention.
The device is configured to be a in-the-bowl type device which is
intended to be suspended from the rim of a toilet bowl,
[0208] wherein the delivery means is a cage 20 which contains
within its interior 22 a non-liquid lavatory treatment material
which includes a first air treatment constituent, herein the form
of a longitudinal block 40 which is visible through a series of
passages 24 which extend through the sidewall 26 of the cage 20.
These passages 24 permit for the entry of water into the interior
22 of the cage 20, wherein it may contact block 40 in order to form
a liquid treatment composition, which liquid treatment composition
made an exit via the cage 20 via one or more of the series of
passages 24 and be delivered to the lavatory appliance, especially
a toilet bowl. Such an operation may also release a quantity of the
first air treatment composition from the block 40 wherein it may be
supplied to the ambient environment such as by evaporation, or
entrainment in the ambient air. The device 10 further includes as
air treatment means a housing 50 adapted to retain an article from
which the second air treatment composition may be dispensed to the
ambient environment. The housing 50 may be openable and resealable
such as depicted in FIG. 1 said it would permit for the insertion
of the article from which the second air treatment composition may
be dispensed within its interior. Interconnecting the cage 20 and
the housing 50 is a hanger 30, here in the form of a generally
planar but flexible strip which is adapted to suspended the device
10 from a part of the laboratory appliance, and in particular a
section of the rim of a toilet bowl such that the cage 20 is
positioned within the interior of the toilet bowl and desirably
wherein in the cages exposed to the path of flushing water, while
the housing 50 is suspended on the exterior of the toilet bowl. In
this position, the housing 50 is not expected to come into the path
of flushing water, but rather is exposed to the ambient environment
of the laboratory appliance. This condition persists even when the
lid of the toilet seat is in a closed position, thereby permitting
the continued release of the second air treatment composition to
the ambient environments of the toilet bowl.
[0209] FIG. 2 depicted in a cross-sectional view the device 10 of
FIG. 1, showing certain interior details. As is visible therefrom,
the block 40 occupies part of the interior 22 of the cage 20. In
this embodiment of the air treatment means, the housing 50 includes
a top part 50a, which it is openably connected to a bottom part
50b. Generic representation of an article 60 from which the second
air treatment composition may be dispensed is depicted as being
within the interior of the housing 50.
[0210] FIGS. 3A and 3B depict in two further views the device 10 of
FIGS. 1 and 2, as mounted on the rim 82 of a toilet bowl 80. In
FIG. 3A, the cage 20 is seen to be suspended from and positioned by
the hanger 30 such that it is positioned within the path of the
flushing water represented by the arrows labeled "f". As is visible
from the figure, part of the flush water passes around the exterior
of the cage 20, while part of the flush water enters into the
interior of the cage 20, and subsequently exits after it has come
into contact with the block 40. The quantity of the flush water
which had contacted the block 40 during its transit, and dissolves
at least a portion of the block 40 forms the liquid treatment
composition which is useful in the treatment of the laboratory
appliance. Now looking to the reverse view, which is depicted on
FIG. 3B, there is visible in the housing 50 which is also suspended
by the hanger 30 from the rim 82 of the toilet bowl in the city.
However, the housing 50 is positioned on the exterior of the toilet
bowl 80. The housing is shown to include a plurality of passages 52
which extend through the front sidewall 53 of the housing. These
passages 52 provide for the inflow of, and outflow of air from the
ambient environment surrounding or in the near proximity of the
device 10, with the interior of the housing 50. These passages 52
also provide a flow path for the delivery of the second air
treatment composition from the interior of the housing 50 to the
ambient environment.
[0211] FIG. 4 depicts a further alternative embodiment of the
device 10 according to the invention which includes at one end of a
hanger 30 a cage 20 which includes a plurality of passages 24
passing into its interior, wherein the cage 20 is understood to
contain within its interior a non-liquid lavatory treatment
material although it is not visible from the figure, and at the
other end of the hanger 30 a housing 50 which contains article (60,
not visible) from which the second air treatment composition may be
dispensed. The housing 50 also includes a plurality of passages 52
which extends through the front sidewall 53 of the housing 50,
which provide a flow path for the delivery of the second air
treatment composition from the interior of the housing 50 to the
ambient environment.
[0212] FIGS. 5A through 5G represent various embodiments of an
article 60 from which the second air treatment composition may be
dispensed from the device 10. It is to be understood that any of
these embodiments may be used in conjunction with anti-device 10
according to the invention and for ease of convenient reference,
have been illustrated as alternative embodiments of the article 60
which may be used with the device 10 according to FIG. 4.
[0213] FIG. 5A illustrates an interior view of the housing 50
containing as the article 60 from which the second air treatment
composition may be dispensed from the device 10 a container 70,
having a neck 72 through which extends a porous wick 74. They
container 70 includes a quantity of the second air treatment
composition which may be delivered to the ambient environment by
being transported outwardly from the container 70 via the porous
wick 74, from whence it may be transferred such as by evaporation
into the ambient air and exit the housing 50 through one or more of
the passages 52.
[0214] FIG. 5B illustrates an interior view of the housing 50
containing as the article 60 from which the second air treatment
composition may be dispensed, here, an electrically operated device
80 which includes a reservoir 82 containing a quantity of the
second air treatment composition, a power source 84 such as one or
more batteries, and a vibrating perforated elements, such as an
electrically operable piezoelectric spraying device 86 which when
energized causes the element oscillate, and provide a spray or
missed out at the second air treatment composition into the ambient
air within the housing which may then and exit the housing 50
through one or more of the passages 52.
[0215] FIG. 5C illustrates an interior view of the housing 50
containing as the article 60 from which the second air treatment
composition may be dispensed, namely an aerosol or pressurized
canister 90 which includes an actuator 92 which, upon operation of
the actuator 92 dispenses a quantity of the second air treatment
composition into the ambient air within the housing which may then
and exit the housing 50 through one or more of the passages 52.
[0216] FIG. 5D illustrates an interior view of the housing 50
containing as the article 60 from which the second air treatment
composition may be dispensed, here a pair of trays 100 each of
which contains a quantity of a material containing the second air
treatment composition which may be for example, a gel, a paste, a
solid, or a fluid or liquid which may be covered with a
semipermeable membrane so to ensure that the said fluid or liquid
does not prematurely leak from the tray 100. The second air
treatment composition emanates from the tray 100 into the ambient
air within the housing which may then and exit the housing 50
through one or more of the passages 52.
[0217] FIG. 5E illustrates an interior view of the housing 50
containing as the article 60 from which the second air treatment
composition may be dispensed, namely a porous article 100 such as a
sheet, plate, web, pad or the like within which, or upon which, a
quantity of a material containing the second air treatment
composition which may be provided. The second air treatment
composition emanates from the tray 100 into the ambient air within
the housing which may then exit the housing 50 through one or more
of the passages 52.
[0218] FIG. 5F illustrates an interior view of the housing 50
containing as the article 60 from which the second air treatment
composition may be dispensed, here an electrically operated device
which includes a fan 120, a power supply means here one or more
batteries 122, and the downstream from the fan a perforated base
124 which has extending perpendicularly therefrom a number of
elements 126 upon which, or within which is contained the second
air treatment composition. The fan 120 be operated in order to
provide airflow between in the number of elements 126 and thereby
ensuring the second air treatment composition or induce the
volatilization of the air treatment composition from the number of
elements 126, from whence the second air treatment composition may
then exit the housing 50 through one or more of the passages
52.
[0219] FIG. 5G illustrates an interior view of the housing 50
containing as the article 60 from which the second air treatment
composition may be dispersed a particulate material, preferably a
particulate material 130 such as a plurality of spheres, or beads
which function as a reservoir for the second air treatment
composition, and from whence they may be delivered to the ambient
environment. Advantageously, such particulate materials,
particularly beads may be based on a polymer or alternately, on an
inner gimmick material which has absorbed therein, and/or adsorbed
thereon a quantity of the second air treatment composition.
Non-limiting examples of such materials include those currently
marketed under the tradename Auracell.RTM. (ex. Rotuba Extruders)
which are based on fragranced cellulosic polymers, as well as
Polyiff.RTM. (ex. International Flavors and Fragrances Inc.), as
well as Tenite.RTM. (ex. Eastman Chemical Co.).
[0220] FIGS. 6A and 6B illustrates an alternative embodiment of the
air treatment means which is provided by a housing 130 mounted upon
or otherwise affixable to a part of the device 10, and preferably
to a part of the hanger 30, which housing 130 includes a quantity
of a gel 132 in a cavity 133 which incorporates a second air
treatment composition as a constituent thereof. Optionally, but in
certain instances desirably, extending upwardly from the base 136
of the cavity 133 are one or more anchor elements 134 which are
embedded into the gel 132. Providing such one or more anchor
elements 134 provides a useful and effective means for retaining
the gel 132 within that the interior of the cavity 133 so that it
is not prematurely fall out from the cavity 133.
[0221] FIG. 7 is a still further embodiment of the device 10
according to the invention. As opposed to the embodiments depicted
on the earlier figures, which included a specific elements or
article for providing the second air treatment composition, and the
embodiment according to the present figure satisfies this
requirement as a part of the device 10 is molded from a so-called
"fragranced polymer" which includes a quantity of an air treatment
composition, preferably a fragment or a perfume. Such materials are
per se, known to the art and include by way of moldable polymer
compositions which include 5% or more by weight of one or more
fragrancing, perfuming, odor treatment or other air treatment
constituents, as well as materials previously or presently
commercially available as Polyiff.RTM. (ex. International Flavors
and Fragrances Inc.) and Tenite.RTM. (ex. Eastman Chemical Co.)
polymers. The formation of one more elements or parts of the
devices 10 according to the invention utilizing such a material may
provide a continuous, and durable air treatment benefit.
[0222] FIG. 8 depicts a further embodiment of the device 10
according to the invention, here in the form of a cage-type
lavatory dispensing device which includes a hanger 30 from one end
of which depends a cage 20, which contains in its interior a
rearward cavity 140 containing a non-liquid lavatory treatment
material which includes a first air treatment constituent in its
composition in the form of a compressed block, which rearward
cavity includes a series of passages 24. The device 10 in intended
to be installed with respect to a toilet bowl such that the
rearward cavity 140 is positioned beneath or proximate to the
interior toilet bowl rim and within the path of the flushing water
such that, part of the flush water passes around the exterior of
the cage 20, while part of the flush water enters into the rearward
cavity 140 in the interior of the cage 20, and subsequently exits
after it has come into contact with the block (not visible). The
quantity of the flush water which had contacted the block during
its transit through the rearward cavity 140 and dissolves at least
a portion of the block forms the liquid treatment composition which
is useful in the treatment of the laboratory appliance. The cage 20
also includes, opposite to the rearward cavity 140 a fragranced gel
132 in a cavity 133 which incorporates a second air treatment
composition as a constituent thereof. Visible in this figure as
extending upwardly from the base 136 of the cavity 133 are one or
more anchor elements 134 which are embedded into the gel 132.
Providing such one or more anchor elements 134 provides a useful
and effective means for retaining the gel 132 within that the
interior of the cavity 133 so that it is not prematurely fall out
from the cavity 133. When the device 10 is installed in the manner
described within the interior of a toilet bowl, it is to be
understood that the cavity 133 as well as the gel 132 contained
therein, viz, the air treatment means, is usually not in the path
of the flushing water released from the rim of the toilet bowl as
the dimensions of the device 10 are desirably established such that
the thickness or the height of the cage 20 extends the cavity 133
and its contents beyond the normal path of flushing water. In such
a manner the air treatment means may dispense the at least second
air treatment composition to the ambient environment, here the
interior of a toilet bowl.
[0223] FIGS. 9A and 9B depicts to alternate views of a further
device 10 according to the present invention, which are in many
respects similar to the device discussed with reference to FIG. 8.
First with reference to FIG. 9A, depicted in a front perspective
view of is a device 10 includes a cage 20, from which extends a
hanger 30. Integrally formed from the front part of the cage is a
cavity 133 containing a quantity of an air treatment means, here a
fragranced polymer or a fragranced gel 132. Now with reference to
FIG. 9B, there is illustrated a rear elevational view of the device
10 depicting in better detail the rearward cavity 140 which is
spanned by a plate 142 having passing therethrough a plurality of
passages 22 which permits for the entry and egress of water into
the interior 24 of the rearward cavity 140 of the cage 20. Further
visible within the interior 24 non-liquid lavatory treatment
material which includes a first air treatment constituent in its
composition in the form of a compressed block 40. The device 10 in
intended to be installed with respect to a toilet bowl such that
the rearward cavity 140 is positioned beneath or proximate to the
interior toilet bowl rim and within the path of the flushing water
such that, part of the flush water passes around the exterior of
the cage 20, while part of the flush water enters into the rearward
cavity 140 in the interior of the cage 20, and subsequently exits
after it has come into contact with the block 40. Concurrently, it
is to be understood that the cavity 133 as well as the gel 132
contained therein, viz, the air treatment means, is usually not in
the path of the flushing water released from the rim of the toilet
bowl as the dimensions of the device 10 are desirably established
such that the thickness or the height of the cage 20 extends the
cavity 133 and its contents beyond the normal path of flushing
water. In such a manner the air treatment means may dispense the at
least second air treatment composition to the ambient environment,
here the interior of a toilet bowl.
[0224] FIGS. 10A and 10B depicts to alternate views of a further
device 10 according to the present invention, wherein the device 10
is configured to be suspended from the upper rim of a toilet tank
(toilet cistern) 150. The device 10 includes a hanger 30 from one
end of which depends a cage 20, which contains containing a
non-liquid lavatory treatment material which includes a first air
treatment constituent in its composition in the form of a
compressed block, which cage 20 includes a series of passages 24.
The cage 24 containing the non-liquid lavatory treatment material
is adapted to be suspended within the water contained in a toilet
tank 150. The device 10 also includes an air treatment means
comprising a housing 50 which includes a fragranced gel 132 in a
cavity 133 which incorporates a second air treatment composition as
a constituent thereof. Visible in this figure as extending upwardly
from the base 136 of the cavity 133 are one or more anchor elements
134 which are embedded into the gel 132. Providing such one or more
anchor elements 134 provides a useful and effective means for
retaining the gel 132 within that the interior of the cavity 133 so
that it is not prematurely fall out from the cavity 133. When
installed on a toilet tank 150, as is depicted on FIG. 10B the
housing 50 is positioned on the exterior of the toilet tank 150
which exposes the cavity 133 and the gel 132 to the ambient
environment, allowing the second air treatment composition to be
delivered to the ambient environment on the exterior of the toilet
tank 150. At the same time, the cage 20 is it immersed within the
water contains within the toilet tank, particularly between flush
cycles thereof, causing said water to come into contact with the
compressed block form of the non-liquid lavatory treatment material
which is at least partially diluted or dispersed into the water,
and thereby forming a lavatory treatment composition which will be
released in the flush water on the next flush cycle of the
toilet.
[0225] FIG. 11 depicts a "cageless" type of a device 10 according
to the invention, which includes a hanger 30 having mounted on
parts thereof, respectively an air treatment means in the form of a
housing 50 which includes a fragranced gel 132 in a cavity 133
which incorporates a second air treatment composition as a
constituent thereof, and a non-liquid lavatory treatment material
which includes a first air treatment constituent in its composition
in the form of a compressed block 40 which is attached directly to
the hanger 30 great visibly absent from the depicted device 10 is a
cage, or other container surrounding the block 40. It is to be
understood that the composition of the block 40 is such that it may
be directly affixed to a portion of the anger 30 without requiring
an enclosing, or encasing element or body. The device 10 in
intended to be installed with respect to a toilet bowl such that
the end of the hanger 30 is extended to grasp at least part of a
toilet bowl rim such that the block 40 is positioned beneath or
proximate to the interior toilet bowl rim and within the path of
the flushing water such that, part of the flush water passes around
the block 40. Further, concurrently the air treatment means may
dispense the at least second air treatment composition to the
ambient environment, here the interior of the toilet bowl as it is
to be understood that the cavity 133 as well as the gel 132
contained therein, viz, the air treatment means, is usually not in
the path of the flushing water released from the rim of the toilet
bowl and its position on the hanger 30 normally places it in a
location beyond the normal path of flushing water. Advantageously,
the housing 50 comprising the cavity 133 as well as the gel 132
contained therein is positioned to be adjacent to or abutting the
inner side wall of the toilet bowl rim, and above the normal path
of water being flushed from the underside of the rim.
[0226] FIGS. 12A, 12B and 12C all depict in a frontal perspective
views three similar embodiments of a further device 10 according to
the present invention.
[0227] First with respect to FIG. 12A, the device 10 includes a
hanger 30 (shown in phantom for sake of clarity) having suspended
thereon a housing 50 which includes as air treatment means a
fragranced gel 132 in a cavity 133 which incorporates a second air
treatment composition as a constituent thereof, and the device 10
further includes a cage 20 which contains within its interior 22 a
non-liquid lavatory treatment material which includes a first air
treatment constituent, herein the form of a longitudinal block 40
which is visible through a series of passages 24 which extend
through the sidewall 26 of the cage 20. These passages 24 permit
for the entry of water into the interior 22 of the cage 20, wherein
it may contact block 40 in order to form a liquid treatment
composition, which liquid treatment composition made an exit via
the cage 20 via one or more of the series of passages 24 and be
delivered to the lavatory appliance, especially a toilet bowl. Such
an operation may also release a quantity of the first air treatment
composition from the block 40 wherein it may be supplied to the
ambient environment such as by evaporation, or entrainment in the
ambient air. Concurrently with the release of the first air
treatment composition, the second air treatment composition may be
dispensed to the ambient environment from the housing 50. The
device 10 further includes at ends 21, 23 thereof further housings
50a, 50b which include in their interior is yet further air
treatment composition which can be the same as, or different than
the first air treatment composition or the second air treatment
composition. Indeed, the air treatment composition separately
contained in the further housings 50a, 50b maybe this the same as
or different from one another. The further housings 50a, 50b
include respective passages 52 which extend through the front
sidewall 53 of the housing. These passages 52 provide for the
inflow of, and outflow of air from the ambient environment
surrounding or in the near proximity of the device 10, with the
interior of the further housings 50a, 50b. These passages 52 also
provide a flow path for the delivery of the second air treatment
composition from the interior of the further housings 50a, 50b to
the ambient environment. The device 10 in intended to be installed
with respect to a toilet bowl such that the cage 20 containing the
block 40 is positioned beneath or proximate to the interior toilet
bowl rim and within the path of the flushing water such that, part
of the flush water passes contacts the block 40, thus forming a
treatment composition which can then be dispensed to the interior
of the toilet bowl. Concurrently, the housing 50 is usually not in
the path of flush water, and thus may dispense the second air
treatment composition to the ambient environment, here the interior
of the toilet bowl. Further concurrently, the further air treatment
composition's present within the further housings 50a, 50b may also
release and deliver their air treatment materials to the ambient
environment as well, even though they are in the path of flushing
water.
[0228] With respect now to FIG. 12B, the device 10 includes in
further housings 50a, 50b at the ends of the cage 20 as air
treatment means a fragranced gel 132 in respective cavities 133a,
133b which incorporates a second (and optionally further) air
treatment composition as a constituent thereof. Within the interior
22 of the cage 20 the device 10 further includes a non-liquid
lavatory treatment material which includes a first air treatment
constituent, herein the form of a longitudinal block 40 which is
visible through a series of passages 24 which extend through the
sidewall 26 of the cage 20. These passages 24 permit for the entry
of water into the interior 22 of the cage 20, wherein it may
contact block 40 in order to form a liquid treatment composition,
which liquid treatment composition may exit via the cage 20 via one
or more of the series of passages 24 and be delivered to the
lavatory appliance, especially a toilet bowl. Simultaneously the
second (and optionally further) air treatment composition may
emanate from the cavities 133a, 133b into the ambient environment.
Optionally, but preferably a hanger is also included as part of the
device 10, in a manner similar to that discussed with reference to
the following FIG. 12C although such has been omitted in the
depiction of the present embodiment.
[0229] FIG. 12C illustrates an embodiment of the device 10 which
closely corresponds to that discussed with reference to FIG. 12A,
but differs only in the omission of the housing which includes as
air treatment means a fragranced gel in a cavity which incorporates
a second air treatment composition as a constituent thereof, but
which for all other purposes includes the same elements, and
functions in the same manner as discussed with reference to FIG.
12A.
[0230] 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.
* * * * *