Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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IMPROVEMENTS IN LAVATORY TREATMENT DEVICES
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.
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 undemeath 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
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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.
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
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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.
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.
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.
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.
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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.
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.
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.
According to a fourth aspect of the invention, the delivery means of the
device
according to the invention excludes a cage or container.
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.
According to the sixth aspect ofthe 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
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constituents (such as one or more glycols, and in particular triethylene
glycol)
insecticides, or pesticides.
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.
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.
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.
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.
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.
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.
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.
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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.
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
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.
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.
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
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those obtained by sulfating the higher alcohols (C8 -C18 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 RSO3 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 0-acetoxy- or 0-acetamido-alkanesulfonates where the alkane has from
8 to 22
carbon atoms.
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.
A further preferred class of anionic surfactants are alpha olefin sulfonates,
as well
as salts thereof, e.g., alkali metal salts. Preferred are C8 through C22 alpha
olefin
sulfonates, particularly Q2 through C18, and especially C14, and C16 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.
The detersive surfactant constituent of the solid block composition of the
invention may include one or more nonionic surfactants. Practically any
hydrophobic
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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.
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.
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 C6 -C1I 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.
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Examples include Alfonic 810-4.5, which is described in product literature
from Sasol
as a Cg-CI o 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 810-2, which is described in product literature as a Cg-Clo 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 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 10 oxo-alcohol ethoxylates available from BASF under
the
Lutensol ON tradename. They are available in grades containing from about 3
to about
11 moles of ethylene oxide (available under the names Lutensol ON 30;
Lutensol ON
50; Lutensol ON 60; Lutensol ON 65; Lutensol ON 66; Lutensol ON 70;
Lutensol ON 80; and Lutensol ON 110). Other examples of ethoxylated alcohols
include the Neodol 91 series non-ionic surfactants available from Shell
Chemical
Company which are described as C9-C>> ethoxylated alcohols. The Neodol 91
series
non-ionic surfactants of interest include Neodol 91-2.5, Neodol 91-6, and
Neodol
91-8. Neodol 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 Rhodasurm DA series non-
ionic
surfactants available from Rhodia which are described to be branched isodecyl
alcohol
ethoxylates. RhodasurM DA-530 has been described as having 4 moles of
ethoxylation
and an HLB of 10.5; Rhodasurffl DA-630 has been described as having 6 moles of
ethoxylation with an HLB of 12.5; and Rhodasurf DA-639 is a 90% solution of
DA-
630. Further examples of ethoxylated alcohols include those from Tomah
Products
(Milton, WI) under the Tomadol tradename with the formula RO(CH2CH2O)õH 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
C9/C lo/C 11 and n is 2.5, 6, or 8; 1-3; 1-5; 1-7; 1-73B; 1-9; where R is
linear C> > and n is 3,
5, 7 or 9; 23-1; 23-3; 23-5; 23-6.5 - where R is linear C12/Ci3 and n is 1, 3,
5, or 6.5; 25-3;
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25-7; 25-9; 25-12 - where R is linear C12/Ci3/C14/ C15 and n is 3, 7, 9, or
12; and 45-7; 45-
13 - where R is linear C 14/ C15 and n, is 7 or 13.
A further class of useful nonionic surfactants include primary and secondary
linear and branched alcohol ethoxylates, such as those based on C6-CI8
alcohols which
further include an average of from 2 to 80 moles of ethoxylation per mol of
alcohol.
These examples include the Genapol UD (ex. Clariant, Muttenz, Switzerland)
described
under the tradenames Genapol UD 030, C, i-oxo-alcohol polyglycol ether with 3
EO;
Genapol UD, 050 C1 i-oxo-alcohol polyglycol ether with 5 EO; Genapol UD 070,
C, 1-
oxo-alcohol polyglycol ether with 7 EO; Genapol UD 080, Cli-oxo-alcohol
polyglycol
ether with 8 EO; Genapol UD 088, C1 1-oxo-alcohol polyglycol ether with 8 EO;
and
Genapol UD 110, C1 i-oxo-alcohol polyglycol ether with 11 EO.
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 such as Tergitol 15-S-
12
which is described as being C>>- C15 secondary alkanol condensed with 9
ethylene oxide
units, or Tergitol 15-S-9 which is described as being C>> -C 15 secondary
alkanol
condensed with 12 ethylene oxide units per molecule.
A further class of useful nonionic surfactants include those surfactants
having a
formula:
RO(CH2CH2O)õH
wherein;
R is a mixture of linear, even carbon-number hydrocarbon chains ranging from
C12H25 to
C16H33 and n represents the number of ethoxy repeating units and is a number
of from
about 1 to about 12.
Surfactants of this formula are presently marketed under the Genapol
tradename
(ex. Clariant), which surfactants include the "26-L" series of the general
formula
RO(CH2CH2O)nH wherein R is a mixture of linear, even carbon-number hydrocarbon
chains ranging from C12H25 to C16H33 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-
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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% C12 and 45% C14
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 tradename.
Further useful non-ionic surfactants which may be used in the inventive
compositions include those presently marketed under the trade name Plumnics
(ex.
BASF). The compounds are formed by condensing ethylene oxide with a
hydrophobic
base formed by the condensation ofpropylene 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 ofpolyoxyethylene 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 L62 and Pluronics
L64.
Further nonionic surfactants which may be included in the inventive
compositions
include alkoxylated alkanolamides, preferably C8-C24 alkyl di(C2-C3 alkanol
amides), as
represented by the following formula:
R5-CO-N H-R6-O H
wherein R5 is a branched or straight chain C8-C24 alkyl radical, preferably a
CIo-CI6 alkyl
radical and more preferably a Q2-Q4 alkyl radical, and R6 is a CI-C4 alkyl
radical,
preferably an ethyl radical.
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 C8 to C16, but
particularly a C9 to
C11 alkyl group, and having an average of between about 6 to about 8 moles of
ethoxylation.
One further useful class of nonionic surfactants include those in which the
major
portion of the molecule is made up of block polymeric C2-C4 alkylene oxides,
with
alkylene oxide blocks containing C3 to C4 alkylene oxides. Such nonionic
surfactants,
while preferably built up from an alkylene oxide chain starting group, can
have as a
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starting nucleus almost any active hydrogen containing group including,
without
limitation, amides, phenols, and secondary alcohols.
One group ofnonionic surfactants containing the characteristic alkylene oxide
blocks are those which may be generally represented by the formula (A):
HO-(EO)X(PO)y(EO)Z H ( A )
where EO represents ethylene oxide,
PO represents propylene oxide,
y equals at least 15,
(EO)X+Z equals 20 to 50% of the total weight of said compounds, and,
the total molecular weight is preferably in the range of about 2000 to 15,000.
Another group of nonionic surfactants appropriate for use in the new
compositions can be represented by the formula (B):
R-(EO,PO)a(EO,PO)b-H ( B )
wherein R is an alkyl, aryl or aralkyl group,
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.
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.
Still further useful nonionic surfactants containing polymeric butoxy (BO)
groups
can be represented by formula (C) as follows:
RO-(BO)n(EO)X-H ( C )
wherein R is an alkyl group containing 1 to 20 carbon atoms,
n is about 15 and x is about 15.
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):
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HO-(EO)X(BO)n(EO)y-H ( D )
wherein n is about 15,
x is about 15 and
y is about 15.
Still further useful nonionic block copolymer surfactants include ethoxylated
derivatives of propoxylated ethylene diamine, which may be represented by the
following
formula:
H(EO)y(PO k /(PO)X(EO)yH
N-CH2-CH2-N ( E )
H(EO)y(PO~ (PO)X(EO)yH
where (EO) represents ethoxy,
(PO) represents propoxy,
the amount of (PO), is such as to provide a molecular weight prior to
ethoxylation
of about 300 to 7500, and the amount of (EO)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:
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;
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;
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
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chain, saturated or unsaturated. Examples are cocoamidopropyl dimethyl amine
oxide
and tallowamidopropyl dimethyl amine oxide; and
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.
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:
R,
I
R2-i~O
R,
wherein each:
Ri is a straight chained CI-C4 alkyl group, preferably both Ri are methyl
groups;
and,
R2 is a straight chained C8-C18 alkyl group, preferably is CI o-Ci4 alkyl
group, most
preferably is a C12 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 R2 group are present. Preferably, the amine oxides used in the
present
invention include R2 groups which comprise at least 50%wt., preferably at
least 60%wt.
of C12 alkyl groups and at least 25%wt. of C14 alkyl groups, with not more
than 15%wt.
of C16, C18 or higher alkyl groups as the R2 group.
Still further exemplary useful nonionic surfactants which may be used include
certain alkanolamides including monoethanolamides and diethanolamides,
particularly
fatty monoalkanolamides and fatty dialkanolamides.
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 Fisnctional Materials,
Vol.2,
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1998; Kirk-Othmer, Encyclopedia of Chemical Technologv, 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.
Examples ofpreferred 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 quatemary ammonium compounds and
salts
thereof, which may be characterized by the general structural formula:
R,
I
R2-N R3 X-
R4
where at least one of Ri, R2, R3 and R4 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 RI, R2, R3 and R4 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 quatemary ammonium complex.
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 quatemary 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 quatemary ammonium compounds which are
useful as
germicides include those in which the hydrophobic radical is characterized by
a
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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.
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:
CH3
Rz-N R3 X-
CH3
wherein R2 and R3 are the same or different C8-C12alkyl, or R2 is C12_16alkyl,
C8_
18alkylethoxy, C8_18alkylphenolethoxy and R3 is benzyl, and X is a halide, for
example
chloride, bmmide or iodide, or is a methosulfate anion. The alkyl groups
recited in R2
and R3 may be straight-chained or branched, but are preferably substantially
linear.
Particularly useful quatemary germicides include compositions which include a
single quaternary compound, as well as mixtures of two or more different
quatemary
compounds. Such useful quaternary compounds are available under the BARDACO,
BARQUATO, HYAMINEO, LONZABACO, and ONYXIDEO 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, BARDACO 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 (BARDACO 208M)); described generally in
McCutcheon's as a combination of alkyl dimethyl benzyl ammonium chloride and
dialkyl
dimethyl ammonium chloride); BARDACO 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
(BARDACO 2080)); BARDAC O 2250 is described to be didecyl dimethyl ammonium
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chloride (50% active); BARDACO LF (or BARDACO LF-80), described as being based
on dioctyl dimethyl ammonium chloride (BARQUATO 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; BARDACO 4250 and BARQUATO 4250Z (each
50% active) or BARQUATO 4280 and BARQUAT 4280Z (each 80% active) are each
described as alkyl dimethyl benzyl ammonium chloride/alkyl dimethyl ethyl
benzyl
ammonium chloride. Also, HYAMINEO 1622, described as diisobutyl phenoxy ethoxy
ethyl dimethyl benzyl ammonium chloride (50% solution); HYAMINEO 3500 (50%
actives), described as alkyl dimethyl benzyl ammonium chloride (also available
as 80%
active (HYAMINEO 3500-80)); and HYMAINEO 2389 described as being based on
methyldodecylbenzyl ammonium chloride and/or methyldodecylxylene-bis-trimethyl
ammonium chloride. (BARDACO, BARQUATO and HYAMINEO are presently
commercially available from Lonza, Inc., Fairlawn, New Jersey). BTCO 50 NF (or
BTCO 65 NF) is described to be alkyl dimethyl benzyl ammonium chloride (50%
active); BTCO 99 is described as didecyl dimethyl ammonium chloride (50%
acive);
BTCO 776 is described to be myrisalkonium chloride (50% active); BTCO 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 (BTCO 818-80%)); BTCO 824 and BTCO 835 are each described
as
being of alkyl dimethyl benzyl ammonium chloride (each 50% active); BTCO 885
is
described as a combination of BTCO 835 and BTCO 818 (50% active) (available
also as
80% active (BTCO 888)); BTCO 1010 is described as didecyl dimethyl ammonium
chloride (50% active) (also available as 80% active (BTCO 1010-80)); BTCO 2125
(or
BTCO 2125 M) is described as alkyl dimethyl benzyl ammonium chloride and alkyl
dimethyl ethylbenzyl ammonium chloride (each 50% active) (also available as
80%
active (BTCO 2125 80 or BTCO 2125 M)); BTCO 2565 is described as alkyl
dimethyl
benzyl ammonium chlorides (50% active) (also available as 80% active (BTCO
2568));
BTCO 8248 (or BTCO 8358) is described as alkyl dimethyl benzyl ammonium
chloride
(80% active) (also available as 90% active (BTCO 8249)); ONYXIDEO 3300 is
described as n-alkyl dimethyl benzyl ammonium saccharinate (95% active). (BTCO
and
ONYXIDEO are presently commercially available from Stepan Company, Northfield,
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Illinois.) Polymeric quatemary ammonium salts based on these monomeric
structures are
also considered desirable for the present invention. One example is POLYQUAT ,
described as being a 2-butenyldimethyl ammonium chloride polymer.
Preferred quatemary 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.
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.
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+(CH3)2CH2COO-
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:
RC ONHCHZCHzCHZN+(CH3)2CH2COO-
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.
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.
Further exemplary chemical constituents may be one or more sanitizing agents
or
germicides which may be present in the non-liquid lavatory treatment material.
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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-quatemary ammonium based
germicidal
compounds as well as quatemary ammonium germicidal compounds.
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 monopelphosphate 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:
R2
R
X11/NyX2
0
X, and X2 are independently hydrogen, chlorine or bromine; and,
R, and R2 are independently alkyl groups having from 1 to 6 carbon atoms.
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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.
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.
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
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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.
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-pmpyl-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-
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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, dichlom meta xylenol, chlorothymol,
and 5-
chloro-2-hydroxydiphenylmethane.
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.
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 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. Exemplarly 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
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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.
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
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 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, Isobomyl
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,
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Sassafras oil, Spearmint oil, Spike lavender, Tagetes, Tea tree oil, Vanilin,
Vetyver oil
(Java), and Wintergreen oil.
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 ofthe fragrance agent desirably emanates a pleasing fragrance, but
the
nature of the fragrance agent is not critical to the success of the invention.
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 ot
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.
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
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can be found in, for example, United States Patent Nos. 5,759,974; 4460490;
and
4578207, the contents of which are herein incorporated by reference. Further
examples of
anti-limescale agents include organic acids (for example, citric acid, lactic
acid, adipic
acid, oxalic acid and the like), organic phosphoric salts, alkali metal
polyphosphates,
sulfonic, and sulfamic acids and their salts, bisulfate salts, EDTA,
phosphonates, and the
like.
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.
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
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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-chlom-2-methyl-4-isothiazolin-3-one and
2-
methyl-4-isothiazolin-3 -one marketed under the trademark KATHON CG/ICP as a
preservative composition presently commercially available from Rohm and Haas
(Philadelphia, PA). Further useful preservative compositions include KATHON
CG/ICP II, a further preservative composition presently commercially available
from
Rohm and Haas (Philadelphia, PA), PROXEL which is presently commercially
available from Zeneca Biocides (Wilmington, DE), SUTTOCIDE A which is
presently
commercially available from Sutton Laboratories (Chatam, NJ) as well as
TEXTAMER
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.
The inventive non-liquid lavatory treatment materials may include a binder
constituent. The binder may function in part contmlling 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 tenn "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
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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.
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.
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.
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 C8-C16 fatty acids, especially C12-CI4 fatty acids having
a C2-C6
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
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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.
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
nitrilotri acetic 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.
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.
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.
The non-liquid lavatory treatment materials, and particularly lavatory
treatment
blocks formed therefrom may include one or more fillers. Such fillers are
typically
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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.
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.
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 pmcess.
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.
One advantageously utilized processing aid is a diester constituent which may
be
represented by the following structure:
0 0
RI-O II Y II O R2
wherein:
Ri and R2 can independently be CI-C6 alkyl which may optionally substituted,
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Y is (CHZ)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.
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-C12_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.
Preferred diester constituents include those wherein Y is -(CH2),7 wherein x
has
a value of from 0- 6, preferably a value of 0- 5, more preferably a value of
from 1-4,
while Rl and R2 are CI-C6 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.
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
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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 isoparaffmic organic solvents include
ISOPAR C described to be primarily a mixture of C7-C8 isoparaffins, ISOPAR E
described to be primarily a mixture of Cg-C9 isoparaffins, ISOPAR G described
to be
primarily a mixture of Clo-C>> isoparaffins, ISOPAR H described to be
primarily a
mixture of C>>-C1z isoparaffins, ISOPAR J, ISOPAR K described to be primarily
a
mixture of C11-C12 isoparaffins, ISOPAR L described to be primarily a mixture
of C>>-C13
isoparaffms, ISOPAR M described to be primarily a mixture of C13-C14
isoparaffins,
ISOPAR P and ISOPAR V described to be primarily a mixture of QZ-C20
isoparaffins.
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.
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
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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.
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 ofthe 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. ofthe 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.
Exemplary materials useful in the film forming constituent include film
forming
polymers such as:
a polymer having the formula
rc0i
R,
I I
CH2-CH CH2-C M~
n I m p
(C
=O~
I
O- R2- N(R3)2R4 XO
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, represents H or CH3; y represents 0 or 1; R2 represents --CH2--CHOH--CH2--
or CXH2,
in which x is 2 to 18; R3 represents CH3, C2H5 or t-butyl; R4 represents CH3,
C2H5 or
benzyl; X represents Cl, Br, I, 1/2SO4, HSO4 and CH3SO3; and M is a vinyl or
vinylidene
monomer copolymerisable with vinyl pyrrolidone other than the monomer
identified
ln [ ]m;
quaternized copolymers of vinylpyrrolidone and dimethylaminoethyl
methacrylate;
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polyvinylpyrrolidone;
vinylpyrrolidone/vinylacetate;
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;
high molecular weight polyethylene glycol;
water soluble polyethylene oxide;
p o lyvinylc apro l ac tam;
polyvinylalcohol;
cationic cellulose polymer;
cationic fatty quaternary ammonium compounds;
organosilicone quaternary ammonium compounds;
2-propenamide, N-[3-(dimethylamino)propyl]-2-methyl, polymer with 1-ethenyl-
2-pyrrolidone hydrochloride;
polynitrogen compounds, including amphoteric polyamide polymers; and,
maleic acid/polyolefin copolymers;
one or more of which may be present in effective amounts.
A first film-forming polymer contemplated to be useful in the present
compositions is one having the formula
~O
N R,
I I
LCH2H [CH2C JM~
n I m p
(C=O~
O- R2- N(R3)2R4 XO
are more fully described in United States Patent No. 4,445,521, United States
Patent No.
4,165,367, United States Patent No. 4,223,009, United States Patent No.
3,954,960, as
well as GB 1,331,819, the contents of which are hereby incorporated by
reference.
The monomer unit within [],,, is, for example, a di-lower alkylamine alkyl
acrylate or methacrylate or a vinyl ether derivative. Examples of these
monomers include
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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.
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 copolymers (ex. ISP
Corp.,
Wayne, NJ) which are available in a variety of molecular weights.
Further exemplary useful examples of the film-forming polymers of the present
invention include quatemized copolymers of vinylpyrrolidone and
dimethylaminoethyl
methacrylate as described in U.S. Patent No. 4,080,310, to Ng, the contents of
which are
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herein incorporated by reference. Such quatemized copolymers include those
according
to the general formula:
O O CI-
NH-C-(CH2)4-C-NH-CH2-CH2- W,-CH2-CH2
H2C~ /CH2
CH
I
OH
x
wherein "x" is about 40 to 60. Further exemplary useful copolymers include
copolymers
of vinylpyrrolidone and dimethylaminoethylmethacrylate quatemized with diethyl
sulphate (available as Gafquat0 755 ex., ISP Corp., Wayne, NJ).
Such a further useful film-forming polymer according to the invention is a
quaternized polyvinylpyrrolidone/dimethylaminoethylmethacrylate copolymer
which is
commercially available as Gafquat0 734, is disclosed by its manufacturer to
be:
CH3
I
CH2- CH CH2- C
I I
N O C=0
H2 ~ O
H2C- CH2 I
x iH2
iH2
H3C- I+-CH3
C2H5
y
z
wherein x, y and z are at least 1 and have values selected such that the total
molecular
weight of the quatemized 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 quatemized polyvinylpyrrolidone/dimethylamino
ethylmethacrylate
copolymer is available as Gafquat0 755N which is similar to the Gafquat0 734
material
describe above but has an average molecular weight of about 1,000,000. These
materials
are sometimes referred to as "Polyquatemium - 11".
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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.
Such polyvinylpyrrolidone polymers are generally provided as a technical grade
mixture of polyvinylpyrrolidone polymers within approximate molecular weight
ranges.
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.
Other suppliers ofpolyvinylpyrrolidone include AllChem Industries Inc,
Gainesville, FL, Kraft Chemical Co., Melrose Park, IL, Alfa Aesar, a Johnson
Matthey
Co., Ward Hill, MA, and Monomer-Polymer & Dajac Labs Inc., Feasterville, PA.
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:
+CH2?H
L ]
x
and vinylacetate monomers which may be represented by the following structural
formula:
CI i2-C
O
I
c-CF13
0
v
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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 0.2:3Ø
Such ratios of
x:y provide the preferred vinylpyrrolidone/vinylacetate copolymers which have
vinylpyrrolidone monomer to vinylacetate monomers from 0.3/2.5.
Exemplary useful vinylpyrrolidone/vinylcaprolactatn/ammonium derivative
terpolymers useful as the film forming constituent are comprised
ofvinylpyrrolidone
monomers which may be represented by the following structural formula:
+(2_?
O
x
and vinylcaprolactam monomers which may be represented by the following
structural
formula:
CH2- i
T i
CD7 20
and dimethylaminoethylmethacrylate monomers which may be represented by the
following structural formula:
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CFi3
CF~ C
C=0 CH3
OCF~CFi2N
CFi3
z
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 fmd use in the present
inventive
compositions include those marketed under the tradename ADVANTAGE (ex. ISP.)
as
well as GAFFIX (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 United States Patent
No.
4,521,404 to GAF Corporation, the contents of which are hereby incorporated by
reference.
High molecular weight polyethylene glycol polymers useful in the present
inventive compositions exhibit a molecular weight of at least about 100,
preferably
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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 (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.
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:
(CH2CH2O)x
where:
x has a value of from about 2000 to about 180,000.
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 F, 20 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
CT).
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.
Exemplary film-forming polyvinylcaprolactams include polyvinylcaprolactam
compounds marketed under the tradename LUVISKOL (ex. BASF Corp.). Such
polyvinylcaprolactams may be represented by the following structural formula:
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I 1--CHz
C
[oJ
n
Where n has a value of at least about 500, and preferably a value in the range
of from
about 800 to about 1000.
Useful as the film forming constituent in the present inventive compositions
are
polyvinylalcohols which include those marketed under the tradename Airvol
(Air
Products Inc., Allentown PA). These include: Airvol 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 C water of from 28-32 cps ; Airvol
165, and
Airvol 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 C
water of from 62-72 cps; Airvol 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 C water of from 3.5 - 4.5 cps; Airvol 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 C water of from 4.5 - 5.5
cps;
Airvol 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 C
water of from 5.5 - 6.6 cps; Airvol 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 C water of from 16.5-20.5 cps; Airvol 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 C water of from 28 - 32
cps; and
Airvol 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 C
water of
from 62 - 72 cps; Airvol 425, classified as being an "intermediate
hydrolyzed"
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polyvinylalcohol polymer classified having a degree of hydrolysis of from 95.5
- 96.5%,
and a viscosity at a 4% solution in 20 C water of from 27 - 31 cps; Airvol
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 C
water of from
3.0 - 3.7 cps; Airvol 203 and Airvol 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 C water of from 3.5 - 4.5 cps; Airvol 205
and Airvol
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 C
water of from 5.2 - 6.2 cps; Airvol 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 C water of from 23 - 27 cps; and Airvol 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 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 C water of from 3.0 - 100.0 cps.
Exemplary cationic cellulose polymers which find use in the present inventive
compositions as the film forming constituent include those described in U.S.
Patent 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 quatemary ammonium salt, for example,
halide
(e.g., chloride, bromide, iodide), sulfate and sulfonate. Such polymers are
described in
U.S. Patent 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.
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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 C).
A further class of materials which find use in the film forming constituent
are film
forming cationic polymers, an especially film-forming fatty quatemary ammonium
compounds which generally conform to the following structure:
(CH2CH2O)nH
R-N R' X
(CH2CH2O)õH
wherein R is a fatty alkyl chain, e.g., Cg - C32 alkyl chain such as tallow,
coco,
stearyl, etc., R' is a lower CI-C6 alkyl or alkylene groiup, 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
C1-C4 alkyl sulfates. Of these, a preferred film forming film-forming fatty
quaternary
ammonium compound may be represented by the following structure:
(CH2CH2O)nH
CH2CH3 XO
(CH2CH2O)nH
wherein R is a fatty alkyl chain, e.g., C8 - C32 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,
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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,
NJ) described to be polyoxyethylene (16) tallow ethylammonioum ethosfulfate. A
further preferred commercially available material is CRODAQUAT 1207 (ex. Croda
Inc.)
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.
Specific examples of organosilicone quatemary 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.
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Still further examples of particularly preferred film-forming, organosilicone
quatemary ammonium compounds which find use in the present inventive
compositions
include those which may be represented by the following structural
representation:
R +
I'
(CH3O)3Si-R2-I~R3 X-
Rl
wherein:
R, and R2 each independently represent short chain alkyl or alkenyl groups,
preferably CI-C8 alkyl or alkenyl groups;
R3 represents a C>>-C22 alkyl group; and
X represents a salt forming counterion, especially a halogen.
Preferred short chain alkyl substituents for R, are methyl and ethyl,
preferred
short chain alkyl substituents for R2 are straight chain links ofinethylene
groups
consisting of from 1 to 4 members, preferred R3 substituents are straight
chain links of
methylene groups consisting of from 11 to 22 members, and preferred halogens
for X are
chloride and bromide.
Exemplary and preferred film-forming, organosilicone quatemary ammonium
compounds useful in the inventive compositions is AEM 5772 or AEM 5700 (from
Aegis Environmental Co., Midland, MI). Both of these materials are described
as being
3-(trimethoxysilyl)propyloctadecyldimethyl ammonium chloride, AEM 5700 and is
sold as a 72% by weight active solution of the compound in a water/methanol
mixture,
while AEM 5772 is sold as a 72% by weight active solution of the compound in
a
water/methanol mixture. While the film-forming, organosilicone quatemary
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.
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-pmpenamide, N-[3-
(dimethylamino)propyl]-
2-methyl, polymer with 1-ethenyl-2-pyrrolidone hydrochloride.
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One particularly preferred class of materials useful as the film forming
constituent
of the present invention are polynitrogen compounds, especially amphoteric
polyamide
polymers.
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.
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.
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.
The one or more amphoteric organic polynitmgen compounds preferably are inde-
pendently obtainable from reacting polyalkylene polyamines, polyamidoamines,
ethyleneimine-gra$ed 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.
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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.
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 CI -C28 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.
The polyalkylene polyamines may be used partly in quatemized form as
component A. Suitable quatemization agents include, for example, alkyl
halides, such as
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methyl chloride, ethyl chloride, butyl chloride, epichlorohydrin, hexyl
chloride, dimethyl
sulfate, diethyl sulfate and benzyl chloride. If quatemized polyalkyleneamines
are used as
component A, the degree of quaternization preferably is 1 to 30.
Further compounds which may also be used as component A included
polyamidoamines. Polyamidoamines are obtainable, for example, by reacting C4-
CIo
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 C
to about
220 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.
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
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ethyleneimine units, i.e. 10 to 500 parts by weight of ethyleneimine are used
with 100
parts by weight of a polyamidoamine.
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 condesing 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 C to about 200 C, preferably of
from 110 C
to 200 C. Moreover, polyetherpolyamines may be prepared by condesing
diethanolamine
or triethanolamine according to the methods known in the art, such as the
methods
disclosed in US 4,404,362, US 4,459,220 and US 2,407,895.
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.
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.
By way of non-limiting example, suitable cross-linking agents include
epihalohydrin, preferably epichlorohydrin, as well as a,c)-bis-(chlorohydrin)-
polyalkylene glycol ether and the a,cw -bis-(epoxides) ofpolyalkylene 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
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copolymers of C2 to C4 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. a,co -bis- (chlorohydrin) polyalkylene glycol ether are, per
se, known to
the art and for example are described in US 4,144,123. Further, a,w -
dichloropolyalkylene glycols are also suitable as cross-linking agents, such
as those
disclosed in EP-A 0 025 515. Such ap -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 ap-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.
Further appropriate crosslinking agent include a,co - 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 glyceml
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.
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
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are epihalohydrins, especially epichlorohydrin, a,cw - bis-
(chlorohydrin)polyalkylene
glycol ether, a,w -bis-(epoxides) of polyalkylene glycol ethers and/or
bisglycidylethers of
polyalkylene glycols as component B.
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 unsaturaed 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.
Exemplary suitable esters of the aforementioned monoethylenically unsatureated
carboxylic acids are derivable from monohydric Ci-CZO alcohols or from
dihydric C2-C6
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.
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
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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:
H2C=CH-X-SO3H (I)
H2C=C(CH3)-X-SO3H (II)
wherein X either is not present or when present is a spacing group according
to one or
more ofthe formulae: -C(O)-NH-CH2_ õ(CH3)n(CH2)m-, -C(O)NH-, -C(O)-NH-
(CH(CH3)CH2)- or -C(O)-NH-CH(CH2CH3)-, with n being 0 to 2 and m being 0 to 3.
Particularly preferred are 1-acrylamido-l- propanesulfonic acid (X-C(O)-NH-
CH(CH2CH3)- in formula 1), 2-acrylamido-l- propanesulfonic acid (X=(O)-NH-
(CH(CH3)CH2)- in formula I), 2-acrylamido-2- methyl-l-propanesulfonic acid (-
C(O)-
NH-C(CH3)2(CH2)- in formula 1), 2- methacrylamido-2-methyl-1 -propanesulfonic
acid
(X=-C(O)-NH-C(CH3)2(CH2)- in formula II) and vinylsulfonic acid (X not present
in
formula I).
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 glycidylcompounds which are represented by the following
formula
(III):
H
I
H2C-C-C-X (III)
0 O
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wherein:
X represents NHZ, OMe, OR
Me represents H, Na, K, ammonium, and
R represents Ci-C4 alkyl or C2-C4 hydroxyalkyl.
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 thereot or glycidyl amide are particularly
preferred.
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.
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:
AA) cross-linking ofpolyalkylene 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
BB) reacting the product obtained in step i) with monoethylenically
unsaturated
carboxylic acids; salts, esters, amides or nitriles of monoethylenically
unsaturated
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carboxylic acids, chlorocarboxylic acids and/or glycidyl compounds like
glycidyl acid,
glycidyl amide or glycidyl esters as component C.
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 C to
about 200 C, preferably of from 30 C to 100 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.
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 C to about 200 C, preferably of
from 30 C
to 100 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.
Specific, albeit nonlimiting examples for the preparation of such compounds
are
also described in WO 2005/073357 A2.
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).
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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 (N):
R, R2 CO2A C02A
C-C C C (N)
R3 R4 H H
Lx
y
Especially preferred are maleic acid/olefin copolymers of formula N wherein A
is selected frown the group of hydrogen, ammonium or an alkali metal; and Ri,
R2, R3
and R4 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.
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 N wherein A is hydrogen or
sodium,
R, and R3 are hydrogen, R2 is methyl, and R4 is neopentyl. Another preferred
product is a
maleic acid-trimethyl isobutylene ethylene copolymer according to formula IV
wherein A
is hydrogen or sodium, R1 and R3 are each methyl, R2 is hydrogen and R4 is
tertiary butyl.
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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.
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.
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.
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
cistem. 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.
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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.
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.
The non-liquid lavatory treatment material may be formed of a single chemical
composition, or may fornied 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.
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
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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.
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.
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 the non-
liquid
lavatory treatment material may be oversprayed or dipped into a bath of a
water soluble
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film forming constituent, and thereafter removed and thus allowing the water
soluble film
forming constituent to dry and form a coating layer thereon.
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 appmximately 100 having an HLB ofl9, and exhibiting
a
melting point in the range of 52-55 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 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 C, preferably a
melting point of
at least about 30 C may also be used. Other water soluble materials, desirably
those
which have a melting point in the range of about 30 - 70 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.
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
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preferred as certain water soluble film former compositions may impart a
desirable
surface gloss to the compressed lavatory blocks.
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:
%wt/wt.
sodium dodecyl benzene sulfonate (85% 20-45%wt.
actives
C14/C16 olefin sulfonate, sodium salt (80%) 18 - 30%wt.
sodium lauryl ether sulfate (80%) 0-10%wt.
anh drous sodium sulfate 15 - 50%wt.
lau I monoenthanolamide 0 - 20%wt.
anhydrous silica 0 - 2%wt.
fragrance 0.001 - 7%wt.
colorant 0 - 5%wt.
mineral oil 0 - 5%wt.
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:
%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
anh drous silica, 100%wt. actives 0-10%wt.
fragrance or odor masking agent 0.001 - 5%wt.
colorant 0 - 5%wt.
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:
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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 -
ol ox ro lene (30) glycol
sodium sulfate 20 - - 21.5 21
Pluronic 87 or Pluronic88' - 70 50 - -
C9-Cl1 alcohol ethoxylate, 6E0 - 2 - - -
fragrance or odor masking agent 0.01 - 0.01 - 0.01 - 0.01 - 0.01 -
3 3 3 3 3
colorant 0- 0- 0- 0- 0-
1.2 1.2 1.2 1.5 1.5
silica - - - 2 2
~ Pluronic 87 E61 P41.5 E61 -- Molecular Weight 7700 -- HLB 24 -- non-ionic
surfactant
Pluronic 88 E98 P41.5 E98 -- Molecular Weight 10800 -- HLB 28-- non-ionic
surfactant
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:
%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
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:
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%w/w
C10-C,4benzene sulfonate, sodium salt (80%
wt. active ; supplied as NANSA HS 80/PF 30 - 38
lauryl monoethanol amide (98% wt. active) 0-7
alkene sulfonate, sodium salt; supplied as
supplied as NANSA LSS 480/H 25 - 40
C12-C16 ethoxy (2-3 EO) sulfate, sodium salt
(70% wt. active); supplied as EMPICOL ESB
70 0-4
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 0 - g.s.
%w/w
C1o-C,4benzene sulfonate, sodium salt (80%wt.
actives ; supplied as NANSA HS 80/PF 25 - 40
lauryl monoethanol amide (98%wt. actives) 0-5
alkene sulfonate, sodium salt; supplied as supplied as
NANSA LSS 480/H 25 - 40
C12-C16 ethoxy (2-3 EO) sulfate, sodium salt (70% wt.
actives ; supplied as EMPICOL ESB 70 0-4
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 0 - g.s.
%wt/wt
C10-C,4benzene sulfonate, sodium salt (80%wt.
actives ; supplied as NANSA HS 80/PF 22 - 32
C14/C16 olefin sulfonate, sodium salt
(80%wt.actives); supplied as supplied as NANSA 30 - 42
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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,
35%-35%wt. actives, supplied as SOKOLAN
HP70 ex. BASF) 0.5 - 6
fragrance, odor masking agent or insecticide 0.001 - 5
colorant 0 - 3.5
d.i. water 0 - g.s.
%Wt/Wt
C1o-Cl4benzene sulfonate, sodium salt (80%wt.
actives ; supplied as NANSA HS 80/PF 22 - 32
C14/C16 olefin sulfonate, sodium salt
(80%wt.actives); supplied as supplied as NANSA
LSS 480/H 30 - 42
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.
actives, supplied as SOKOLAN CP-9 (ex. BASF) 0.5 - 6
fragrance, odor masking agent or insecticide 0.001 - 5
colorant 0 - 3.5
d.i. water 0 - g.s.
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
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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.
Various examples of useful air treatment means are discussed with reference to
the following figures.
Tuming now to Figure 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,
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
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continued release of the second air treatment composition to the ambient
environments of
the toilet bowl.
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 ofthe
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.
Figures 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 bow180. 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 ofthe 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
ofthe 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.
Figure 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 ofpassages 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
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article (60, not visible) from which the second air treatment composition may
be
dispensed. The housing 50 also includes a plurality ofpassages 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.
Figures 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.
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.
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.
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
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air within the housing which may then and exit the housing 50 thmugh one or
more of the
passages 52.
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.
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.
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.
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
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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 (ex. Rotuba Extruders) which
are
based on fragranced cellulosic polymers, as well as Polyiffg (ex.
International Flavors
and Fragrances Inc.), as well as Tenite (ex. Eastman Chemical Co.).
Figures 6A and 6B illustrates an alteinative 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 thereo 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.
Figure 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 (ex. International Flavors and Fragrances Inc.) and
Tenite (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.
Figure 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
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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 pmvides 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.
Figures 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
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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 ofpassages 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.
Figures l0A and l OB 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 ofpassages 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
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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. lOB
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.
Figure 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
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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.
Figures 12A, 12B and 12C all depict in a frontal perspective views three
similar
embodiments of a further device 10 according to the present invention.
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 ofpassages 24 which extend thmugh the sidewal126
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
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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.
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.
Figure 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
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other purposes includes the same elements, and functions in the same manner as
discussed with reference to Fig. 12A.
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.
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