U.S. patent application number 17/832523 was filed with the patent office on 2022-09-22 for long lasting disinfectant cleaning compositions and methods of use thereof.
The applicant listed for this patent is RHODIA OPERATIONS. Invention is credited to Celine Anna Simone BUREL, Tamara MAMISTVALOVA, Kamel RAMDANI, Amit SEHGAL, Amanda TORRES.
Application Number | 20220295789 17/832523 |
Document ID | / |
Family ID | 1000006381205 |
Filed Date | 2022-09-22 |
United States Patent
Application |
20220295789 |
Kind Code |
A1 |
SEHGAL; Amit ; et
al. |
September 22, 2022 |
LONG LASTING DISINFECTANT CLEANING COMPOSITIONS AND METHODS OF USE
THEREOF
Abstract
The present disclosure provides an antimicrobial composition
that includes: an antimicrobial component having at least one
quaternary ammonium compound; a synthetic polymer that includes: at
least one cationic monomer A.sub.b, optionally, at least one
anionic monomer B.sub.a, and optionally, at least one non-ionic
monomer C.sub.a; an organic acid; and a surfactant selected from
cationic surfactants, amphoteric surfactants and combinations
thereof; and at least one non-ionic surfactant selected from the
group consisting of low hydrophilic-lipophilic balance (HLB)
non-ionic surfactants with a delocalized electronic structure that
have moderate to poor water solubility. This composition when
applied to a surface demonstrates good cleaning ability and
provides robust long lasting disinfection.
Inventors: |
SEHGAL; Amit; (Potomac,
MD) ; MAMISTVALOVA; Tamara; (Huntingdon Valley,
PA) ; TORRES; Amanda; (Philadelphia, PA) ;
BUREL; Celine Anna Simone; (Philadelphia, PA) ;
RAMDANI; Kamel; (Princeton, NJ) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
RHODIA OPERATIONS |
Lyon Cedex 03 |
|
FR |
|
|
Family ID: |
1000006381205 |
Appl. No.: |
17/832523 |
Filed: |
June 3, 2022 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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16789940 |
Feb 13, 2020 |
11375715 |
|
|
17832523 |
|
|
|
|
62804923 |
Feb 13, 2019 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C11D 1/62 20130101; C11D
3/37 20130101; C11D 3/3773 20130101; A01N 33/12 20130101; C11D
3/0042 20130101; C11D 1/008 20130101; C11D 11/0023 20130101 |
International
Class: |
A01N 33/12 20060101
A01N033/12; C11D 3/37 20060101 C11D003/37; C11D 11/00 20060101
C11D011/00; C11D 1/62 20060101 C11D001/62; C11D 3/00 20060101
C11D003/00; C11D 1/00 20060101 C11D001/00 |
Claims
1. A hard surface treatment composition comprising: a. an
antimicrobial component comprising at least one quaternary ammonium
compound; b. a synthetic polymer comprising: i. at least one
cationic monomer A.sub.b, ii. optionally, at least one anionic
monomer B.sub.a, and iii. optionally, at least one non-ionic
monomer C.sub.a; c. an organic acid; d. a surfactant selected from
the group consisting of cationic surfactants, amphoteric
surfactants and combinations thereof; and e. and at least one
non-ionic surfactant selected from the group consisting of low
hydrophilic-lipophilic balance (HLB) non-ionic surfactants with a
delocalized electronic structure that have moderate to poor water
solubility.
2. The composition of claim 1, wherein a film formed from the
composition kills at least 95% of microorganisms for at least 3
abrasion cycles according to RSS-12h.
3. The composition of claim 1, wherein the antimicrobial component
is selected from the group consisting of monoalkyldimethylbenzyl
ammonium salts, dialkyldimethyl ammonium salts, and combinations
thereof.
4. The composition of claim 1, wherein the monomer A.sub.b is
selected from the group consisting of diallyldimethylammonium
halides.
5. The composition of claim 1, wherein the polymer comprises
monomer B.sub.a selected from the group consisting of acrylic acid,
methacrylic acid, and combinations thereof.
6. The composition of claim 1, wherein the polymer comprises
monomer C.sub.a selected from the group consisting of
2-(dimethylamino)ethyl methacrylate (DMAEMA); N-vinyl pyrrolidone
(NVP); N-vinylimidazole; acrylamide; methacrylamide; alkyl
acrylate; and combinations thereof.
7. The composition of claim 1, wherein the organic acid is selected
from the group consisting of citric, malic, maleic, lactic,
succinic, glutaric, adipic acids and combinations thereof.
8. The composition of claim 1, wherein the surfactant comprises a
cationic surfactant selected from the group consisting of cationic
amine oxides.
9. The composition of claim 1, wherein the surfactant comprises an
amphoteric surfactant selected from the group consisting of
sultaines, taurates, and combinations thereof.
10. The composition of claim 1 further comprising a polar
solvent.
11. A method of providing a surface with residual antimicrobial
action that comprises the step of applying the composition of claim
1 to the surface.
12. A substrate with residual antimicrobial action comprising a
substrate wherein at least a portion of the substrate is coated
with the composition of claim 1.
13. The use of a composition of claim 1 to substantially reduce or
control the formation of microbial colonies on or at a surface.
14. The use of claim 13, wherein a film formed from the composition
kills at least 95% of gram-positive bacteria and gram-negative
bacteria, or enveloped and non-enveloped viruses according to a
modified version of Environmental Protection Agency (EPA) Protocol
#01-1A residual self-sanitizing activity test.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application claims the benefit of priority under
35 U.S.C. .sctn. 119(e) of U.S. Provisional Application Ser. No.
62/804,923, filed on Feb. 13, 2019, the entire disclosure of which
is incorporated herein by reference.
BACKGROUND
[0002] Antimicrobial compositions commercially available as
disinfectants or as cleaners with disinfecting activity typically
achieve bacterial or viral kill at 99.9% or greater only at the
time of use. Re-contamination of the "clean" surface allows
microorganisms to survive and spread through contact until it is
treated again. The disinfection-cleaner market does not currently
address long lasting disinfection for high contact areas including
homes, public areas and healthcare environments. This has created
demand with modern, health-conscious consumers who care about a
clean home but do not have the time to clean and disinfect on a
regular basis.
[0003] The critical technical challenge for developing a long
lasting disinfectant cleaning composition is that while cleaning
requires the presence of effective surfactants for soil removal,
the presence of such surfactants reduces the durability or the long
lasting nature of the residual film. Deterioration of the residual
disinfectant film makes it extremely difficult to achieve 12 to 24
hour continuous disinfection.
[0004] Re-soiling or contamination of the surface requires
additional treatments with such compositions. A need, therefore,
exists for disinfectant cleaning formulations that provide high
microbial kill without the need for repeated applications. However,
designing compositions that meet the above requirements is a
difficult task in view of unpredictable and complicated
interactions between ingredients.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIG. 1 is flow chart depicting the RSS-12h analysis
conducted in the Examples;
[0006] FIG. 2 provides a frame of reference for reconciling the
cleaning application to desired performance;
[0007] FIG. 3 shows inadequate cleaning performance of a long
lasting disinfectant (Formulation A pH 4.5);
[0008] FIG. 4 shows the impact of varying amounts of TSP-8EO on
cleaning performance;
[0009] FIG. 5 shows the impact on cleaning of a formulation
containing a blend of TSP-4EO and TSP-8EO as compared to Benchmark
A;
[0010] FIG. 6 demonstrates an embodiment in which substrate wetting
was improved with removal of lactic acid; and
[0011] FIG. 7 shows the impact on cleaning of various non-ionic
surfactants.
SUMMARY
[0012] The present disclosure provides hard surface treatment
compositions that include an antimicrobial component including at
least one quaternary ammonium compound; a synthetic polymer
including: at least one cationic monomer A.sub.b, optionally, at
least one anionic monomer B.sub.a, and optionally, at least one
non-ionic monomer C.sub.a; an organic acid; a surfactant selected
from cationic surfactants, amphoteric surfactants and combinations
thereof; and at least one non-ionic surfactant selected from low
hydrophilic-lipophilic balance (HLB) non-ionic surfactants with a
delocalized electronic structure that have moderate to poor water
solubility. Also presented are methods of providing a surface with
residual antimicrobial action that include the step of applying a
composition of the present disclosure to the surface. The present
disclosure also provides a substrate with residual antimicrobial
action comprising a substrate wherein at least a portion of the
substrate is coated with a composition of the present
disclosure.
DETAILED DESCRIPTION
[0013] The present disclosure relates to cleaning compositions that
provide continuous surface disinfection benefit for 12 to 24 hours
with only one application, obviating the need for repeated
decontamination. The cleaning efficacy of these compositions is
provided by inclusion of low hydrophilic-lipophilic balance (HLB)
non-ionic surfactants with delocalized electronic structure that
have moderate to poor water solubility. Such disinfectant cleaning
compositions provide a residual film that is abrasion resistant to
wet and dry wipes while providing long lasting disinfection.
[0014] The present compositions achieve microorganism (e.g.
bacterial, viral, or fungal) kill of at least 95% or greater, (e.g.
99.9% kill), for 12 to 24 hours obviating the need for repeated
treatment. In order to substantiate 24 hour long-term sanitization
claims with the United States Environmental Protection Agency
(EPA), compositions are evaluated with the residual
self-sanitization (RSS) method, EPA Protocol #01-1A
(https://www.epa.gov/sites/production/files/2015-09/documents/cloroxpcol_-
final.pdf). For validating longer term disinfection, all extant
test protocols emulate the maximum amount of recontamination and
abrasion by touching and wiping anticipated before reapplication,
typically a 24 hour period. An intermediate protocol with
approximately half the level abrasion and re-soiling challenge to a
surface is presented here as the "RSS-12h" test protocol.
[0015] In an embodiment, a film formed from the composition kills
at least 99.9% (e.g. log 3 reduction) of microorganisms according
to the residual self-sanitizing (RSS) activity test (EPA Protocol
#01-1A). In an embodiment, a film formed from the composition kills
at least 99.9% (e.g. log 3 reduction) of gram-positive bacteria and
gram-negative bacteria according to the residual self-sanitizing
(RSS) activity test (EPA Protocol #01-1A).
[0016] Long lasting disinfection claims are substantiated by the
RSS test, which challenges the applied composition by subjecting it
to recontamination (re-inoculation with microorganisms) and
abrasion (wear cycles). An intermediate test protocol, with
approximately half the number of re-inoculations and wear cycles
("RSS-12h") is used to predict disinfection that is durable up to
12 hours before reapplication of the test product. As outlined in
FIG. 1, this procedure requires preparation of the test bacterial
(microbial) culture over the first week (see EPA Protocol #01-1A)
followed by testing in week 2.
[0017] The testing involves inoculating the surface with bacteria,
followed by application of the product on the substrate and
allowing it to dry. The substrate may be glass, polycarbonate, or
steel. This substrate is then subjected to an
abrasion--re-inoculation regime of 3 "wear cycles". The abrasion is
conducted with a 1084 gwt. rectangular steel block covered with a
cloth with an underlying thin polyurethane-foam layer. Each wear
cycle is composed of a "dry" abrasion and a "wet" abrasion, the
latter with the cloth cover having been wet with a mist of water
using a Preval.RTM. sprayer. Each abrasion (dry/wet) is
characterized by a back and forth motion of the block across the
test substrate. Each abrasion cycle is followed by re-inoculation
the surface with a bacterial culture. The RSS-12h involves a
3-abrasion cycle/3-inoculations test as compared to the full RSS
test that outlines a 6-abrasion cycle/6-inoculation test regimen.
All other details of the test method are as outlined in the EPA
Protocol #01-1A.
[0018] The test substrate is allowed to dry overnight and then
finally inoculated again (sanitizer test) for 5 minutes, followed
by neutralization of the entire substrate. Surviving bacteria is
then harvested off the surface and cultured with serial dilutions
on agar plates, allowing colony formation over 24-48 hours.
Surviving bacteria are then counted as the number of colonies. The
difference in bacterial count inoculated and surviving bacteria
results in an efficacy evaluation in percent kill (e.g. 99.9% kill)
or log-reduction (e.g. 3-log reduction) on a logarithmic scale. The
bacteria in this test may be substituted for other microorganisms
such as fungi or viruses. In an embodiment, microorganisms are
selected from gram-positive bacteria (e.g Staphylococcus aureus),
gram-negative bacteria (e.g. Enterobacter aerogenes), fungi,
enveloped viruses, non-enveloped viruses, and combinations
thereof.
[0019] The composition of the present disclosure is a liquid
formulation. It is contemplated that one preferred method of making
use of the composition of the present disclosure is to apply a
layer of the composition to a substrate and dry the composition or
allow it to dry. The act of applying a layer of the composition to
a substrate and then drying it or allowing it to dry is known
herein as "treating" the substrate. It is contemplated that, as the
solvent evaporates, the composition will form a film on the
substrate. The dried layer of the composition is known herein as "a
film."
[0020] In an embodiment, the composition includes: an antimicrobial
component that includes at least one quaternary ammonium compound;
a synthetic polymer that includes: at least one cationic monomer
A.sub.b, optionally, at least one anionic monomer B.sub.a, and
optionally, at least one non-ionic monomer C.sub.a; an organic
acid; a surfactant selected from cationic surfactants, amphoteric
surfactants and combinations thereof; and at least one non-ionic
surfactant selected from the group consisting of low HLB non-ionic
surfactants with a delocalized electronic structure that have
moderate to poor water solubility. In an embodiment, the
composition includes two or more (e.g. three, four, five, etc.)
non-ionic surfactants selected from the group consisting of low HLB
non-ionic surfactants with a delocalized electronic structure that
have moderate to poor water solubility.
[0021] In an embodiment, the non-ionic surfactant(s) is/are
selected from the group consisting of non-ionic surfactants with a
delocalized electronic structure having an HLB value less than 9.
In an embodiment, the non-ionic surfactant(s) is/are selected from
the group consisting of non-ionic surfactants with a delocalized
electronic structure having an HLB value less than 8. In an
embodiment, the non-ionic surfactant(s) is/are selected from the
group consisting of non-ionic surfactants with a delocalized
electronic structure having an HLB value less than 7. In an
embodiment, the non-ionic surfactants possess a combination of
different HLB values. In an embodiment, the low HLB non-ionic
surfactant with a delocalized electronic structure that has
moderate to poor water solubility is selected from the group
consisting of tristyrylphenol ethoxylates, terpene alkoxylates,
alkanolamides, and combinations thereof. In an embodiment, the low
HLB non-ionic surfactant with a delocalized electronic structure
that has moderate to poor water solubility is selected from the
group consisting of amine surfactants. In an embodiment, the
non-ionic surfactant is a tristyrylphenol ethoxylate with a low
degree of ethoxylation (e.g. less than eight ethylene oxide (EO)
moieties).
[0022] In an embodiment, the pH of the composition ranges from
about 0 to about 5.5. In another embodiment, the pH of the
composition is less than 5.5. In another embodiment, the pH of the
composition ranges from 2 to 4.9. In yet another embodiment, the pH
of the composition ranges from 3 to 4.8. In an embodiment, the pH
of the composition ranges from 0.5 to 3.
[0023] The antimicrobial compositions of the present disclosure
include at least one quaternary ammonium compound. In an
embodiment, the quaternary ammonium compound is an antimicrobial
"quat." The term "quaternary ammonium compound" or "quat" generally
refers to any composition with the following formula:
##STR00001##
where R1-R4 are alkyl groups that may be alike or different,
substituted or unsubstituted, saturated or unsaturated, branched or
unbranched, and cyclic or acyclic and may contain ether, ester, or
amide linkages; they may be aromatic or substituted aromatic
groups. In an embodiment, groups R1, R2, R3, and R4 each have less
than a C20 chain length. X.sup.- is an anionic counterion. The term
"anionic counterion" includes any ion that can form a salt with
quaternary ammonium. Examples of suitable counterions include
halides such as chlorides, bromides, fluorides, and iodides,
sulphonates, propionates, methosulphates, saccharinates,
ethosulphates, hydroxides, acetates, phosphates, carbonates,
bicarbonates, and nitrates. In an embodiment, the anionic
counterion is chloride.
[0024] In some embodiments, quaternary ammoniums having carbon
chains of less than 20 or C2-C20 are included in compositions of
the present disclosure. In other embodiments, quaternary ammoniums
having carbon chains of C6-C18, C12-C18, C12-C16 and C6-C10 are
included in compositions of the present disclosure. Examples of
quaternary ammonium compounds useful in the present disclosure
include, but are not limited to, alkyl dimethyl benzyl ammonium
chloride, alkyl dimethyl ethylbenzyl ammonium chloride, octyl decyl
dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride, and
didecyl dimethyl ammonium chloride. A single quaternary ammonium or
a combination of more than one quaternary ammonium may be included
in compositions of the present disclosure. Further examples of
quaternary ammonium compounds useful in the present disclosure
include, but are not limited to, benzethonium chloride, ethylbenzyl
alkonium chloride, ethyl benzethonium chloride, myristyl trimethyl
ammonium chloride, methyl benzethonium chloride, cetalkonium
chloride, cetrimonium bromide (CTAB), carnitine, dofanium chloride,
tetraethyl ammonium bromide (TEAB), domiphen bromide,
benzododecinium bromide, benzoxonium chloride, choline, denatonium,
and mixtures thereof.
[0025] In some embodiments depending on the nature of the R group,
the anion, and the number of quaternary nitrogen atoms present, the
antimicrobial quaternary ammonium compounds may be classified into
one of the following categories: monoalkyltrimethyl ammonium salts;
monoalkyldimethylbenzyl ammonium salts; dialkyldimethyl ammonium
salts; heteroaromatic ammonium salts; polysubstituted quaternary
ammonium salts; bis-quaternary ammonium salts; and polymeric
quaternary ammonium salts. Each category will be discussed
herein.
[0026] Monoalkyltrimethyl ammonium salts contain one R group that
is a long-chain alkyl group, and the remaining R groups are
short-chain alkyl groups, such as methyl or ethyl groups. Some
non-limiting examples of monoalkyltrimethyl ammonium salts include
cetyltrimethylammonium bromide, commercial available under the
tradenames Rhodaquat.RTM. M242C/29 and Dehyquart.RTM. A;
alkyltrimethyl ammonium chloride, commercially available as
Arquad.RTM. 16; alkylaryltrimethyl ammonium chloride; and
cetyldimethyl ethylammonium bromide, commercially available as
Ammonyx.RTM. DME.
[0027] Monoalkyldimethylbenzyl ammonium salts contain one R group
that is a long-chain alkyl group, a second R group that is a benzyl
radical, and the two remaining R groups are short-chain alkyl
groups, such as methyl or ethyl groups. Some non-limiting examples
of monoalkyldimethylbenzyl ammonium salts include
alkyldimethylbenzyl ammonium chlorides, commercially available as
Barquat.RTM. from Lonza Inc.; and benzethonium chloride,
commercially available as Lonzagard.RTM., from Lonza Inc.
Additionally, the monoalkyldimethylbenzyl ammonium salts may be
substituted. Non-limiting examples of such salts include
dodecyldimethyl-3,4-dichlorobenzyl ammonium chloride. Finally,
there are mixtures of alkyldimethylbenzyl and alkyldimethyl
substituted benzyl (ethylbenzyl) ammonium chlorides commercially
available as BTC.RTM. 2125M from Stepan Company, and Barquat.RTM.
4250 from Lonza Inc. Other examples include
N,N-benzyldimethyloctylammonium chloride,
N,N-benzyldimethyldecylammonium chloride,
N-dodecyl-N-benzyl-N,N-dimethylammonium chloride,
N-tetradecyl-N-benzyl-N,N-dimethyl ammonium chloride,
N-hexadecyl-N,N-dimethyl-N-benzylammonium chloride, N,N-dimethyl
N-benzyl N-octadecyl ammonium chloride.
[0028] Dialkyldimethyl ammonium salts contain two R groups that are
long-chain alkyl groups, and the remaining R groups are short-chain
alkyl groups, such as methyl groups. Some non-limiting examples of
dialkyldimethyl ammonium salts include didecyldimethyl ammonium
halides, commercially available as Bardac.RTM. 22 from Lonza Inc.;
didecyl dimethyl ammonium chloride commercially available as
Bardac.RTM. 2250 from Lonza Inc.; dioctyl dimethyl ammonium
chloride, commercially available as Bardac.RTM. LF and Bardac.RTM.
LF-80 from Lonza Inc.; and octyl decyl dimethyl ammonium chloride
sold as a mixture with didecyl and dioctyl dimethyl ammonium
chlorides, commercially available as Bardac.RTM. 2050 and 2080 from
Lonza Inc.
[0029] Heteroaromatic ammonium salts contain one R group that is a
long-chain alkyl group, and the remaining R groups are provided by
some aromatic system. Accordingly, the quaternary nitrogen to which
the R groups are attached is part of an aromatic system such as
pyridine, quinoline, or isoquinoline. Some non-limiting examples of
heteroaromatic ammonium salts include cetylpyridinium halide,
commercially available as Sumquat.RTM. 6060/CPC from Zeeland
Chemical Inc.; 1-[3-chloroalkyl]-3,5,7-triaza-1-azoniaadamantane,
commercially available as Dowicil.RTM. 200 from The Dow Chemical
Company; and alkyl-isoquinolinium bromide.
[0030] Polysubstituted quaternary ammonium salts are a
monoalkyltrimethyl ammonium salt, monoalkyldimethylbenzyl ammonium
salt, dialkyldimethyl ammonium salt, or heteroaromatic ammonium
salt wherein the anion portion of the molecule is a large,
high-molecular weight (MW) organic ion. Some non-limiting examples
of polysubstituted quaternary ammonium salts include alkyldimethyl
benzyl ammonium saccharinate, and dimethylethylbenzyl ammonium
cyclohexyl sulfamate.
[0031] Bis-quatemary ammonium salts contain two symmetric
quaternary ammonium moieties having the general formula:
##STR00002##
where the R groups may be long or short chain alkyl, a benzyl
radical or provided by an aromatic system. Z is a carbon-hydrogen
chain attached to each quaternary nitrogen. Some non-limiting
examples of bis-quaternary ammonium salts include
1,10-bis(2-methyl-4-aminoquinolinium chloride)-decane; and
1,6-bis[1-methyl-3-(2,2,6-trimethyl
cyclohexyl)-propyldimethylammonium chloride] hexane or
triclobisonium chloride.
[0032] In an embodiment, the quaternary ammonium compound is a
medium to long chain alkyl R group, such as from 8 carbons to about
20 carbons, from 8 carbons to about 18 carbons, from about 10 to
about 18 carbons, and from about 12 to about 16 carbons, and
providing a soluble and good antimicrobial agent.
[0033] In an embodiment, the quaternary ammonium compound is a
short di-alkyl chain quaternary ammonium compound having an R
group, such as from 2 carbons to about 12 carbons, from 3 carbons
to about 12 carbons, or from 6 carbons to about 12 carbons.
[0034] The composition may include from about 100 to about 20,000
ppm of one or more quaternary ammonium compounds. In various
embodiments, the composition includes from about 500 to about
20,000 ppm; from about 500 to about 10,000 ppm; from about 100 to
about 500 ppm; or from about 500 to about 5000 ppm of one or more
quaternary ammonium compounds.
[0035] Polymers suitable for use in compositions of the present
disclosure include synthetic polymers having: at least one cationic
monomer A.sub.b, optionally, at least one anionic monomer B.sub.a,
and optionally, at least one non-ionic monomer C.sub.a. In one
embodiment, the synthetic polymer includes its homopolymer,
copolymer, terpolymer, block copolymer, random polymer, linear
polymer, comb polymer or branched polymer.
[0036] Any combination of these types of monomers may be used. For
example, suitable polymers include but are not limited to those
comprising, consisting of or consisting essentially of at least one
monomer of type A.sub.b and at least one monomer of type B.sub.a
and polymers comprising, consisting of or consisting essentially of
at least one monomer of type A.sub.b and at least one momoner of
type C.sub.a, and polymers comprising, consisting of or consisting
essentially of at least one of each of the three types of
monomer.
[0037] In an embodiment the cationic monomer A.sub.b includes an
ammonium group of formula --NR3+, wherein R, which is identical or
different, represents a hydrogen atom, an alkyl group comprising 1
to 10 carbon atoms, or a benzyl group, optionally carrying a
hydroxyl group, and comprise an anion (counter-ion). Examples of
anionic counter-ions are halides such as chloride and bromides,
sulphates, hydrosulphates, alkylsulphates (for example comprising 1
to 6 carbon atoms), sulfonates, phosphates, nitrates, citrates,
carbonates, bicarbonates, formates, and acetates.
[0038] Examples of cationic monomer A.sub.b include, but are not
limited to:
##STR00003##
[0039] Diallyldimethylammonium halides such as
diallyldimethylammonium chloride (DADMAC) or the corresponding
bromide. Alternatively, the counter ion may be sulphate, nitrate or
phosphate. Similar momomer units, such as those in which one or
more of the CH.sub.3 groups is replaced by a C.sub.2 to 12 for
example a C.sub.2 to 6 alkyl group or one or more of the CH.sub.2
groups is replaced by an alkyl group having from 2 to 12, for
example from 2 to 6 carbon atoms may be used. In other words, other
similar commercially available monomers or polymers containing such
monomers may be used.
##STR00004##
[0040]
N,N,N-trimethyl-3-((2-methyl-1-oxo-2-propenyl)amino)-1-propanaminiu-
m halides, such as the chloride (MAPTAC, also known as
methacryl-amido(propyl)-trimethyl ammonium chloride).
[0041] Additional examples of cationic monomer A.sub.b include, but
are not limited to:
[0042] 1. aminoalkyl (meth)acrylates, aminoalkyl
(meth)acrylamides,
[0043] 2. monomers, including particularly (meth)acrylates, and
(meth)acrylamides derivatives, comprising at least one secondary,
tertiary or quaternary amine function, or a heterocyclic group
containing a nitrogen atom, vinylamine or ethylenimine;
[0044] 3. diallyldialkyl ammonium salts;
[0045] 4. their mixtures, their salts, and macromonomers deriving
from therefrom;
[0046] 5. dimethylaminoethyl (meth)acrylate, dimethylaminopropyl
(meth)acrylate, ditertiobutylaminoethyl (meth)acrylate,
dimethylaminomethyl (meth)acrylamide, dimethylaminopropyl
(meth)acrylamide;
[0047] 6. ethylenimine, vinylamine, 2-vinylpyridine,
4-vinylpyridine;
[0048] 7. trimethylammoniumethyl (meth)acrylate chloride,
trimethylammonium ethyl (meth)acrylate methyl sulphate,
dimethylammonium ethyl (meth)acrylate benzyl chloride,
4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethyl
ammonium ethyl (meth)acrylamido (also called
2-(acryloxy)ethyltrimethylammonium, TMAEAMS) chloride,
trimethylammoniumethyl (meth)acrylate (also called
2-(acryloxy)ethyltrimethylammonium, TMAEAMS) methyl sulphate,
trimethyl ammonium propyl (meth)acrylamido chloride, vinylbenzyl
trimethyl ammonium chloride,
[0049] 8. diallyldimethyl ammonium chloride,
[0050] 9. monomers having the following formula A(II):
##STR00005##
wherein R.sub.1 is a hydrogen atom or a methyl or ethyl group;
R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6, which are identical
or different, are linear or branched C.sub.1-C.sub.6, preferably
C.sub.1-C.sub.4, alkyl, hydroxyalkyl or aminoalkyl groups; m is an
integer from 0 to 10, for example 1; n is an integer from 1 to 6,
preferably 2 to 4; Z represents a --C(O)O-- or --C(O)NH-- group or
an oxygen atom; A represents a (CH.sub.2).sub.p group, p being an
integer from 1 to 6, preferably from 2 to 4; B represents a linear
or branched C.sub.2-C.sub.12, typically C.sub.3-C.sub.6,
polymethylene chain optionally interrupted by one or more
heteroatoms or heterogroups, in particular O or NH, and optionally
substituted by one or more hydroxyl or amino groups, preferably
hydroxyl groups; X, which are identical or different, represent
counterions, and their mixtures, and macromonomers deriving
therefrom.
[0051] Other cationic monomers include compounds of general formula
A(I):
##STR00006##
in which: R.sub.1 and R.sub.4, independently of each other,
represent a hydrogen atom or a linear or branched C.sub.1-C.sub.6
alkyl group; R.sub.2 and R.sub.3, independently of each other,
represent an alkyl, hydroxyalkyl or aminoalkyl group in which the
alkyl group is a linear or branched C.sub.1-C.sub.6 chain,
preferably a methyl group; n and m are integers between 1 and 3; X,
which may be identical or different, represent counterions which
are compatible with the water-soluble or water-dispersible nature
of the polymer. In one embodiment, X is selected from the group of
halide anions, sulfate anions, hydrogen sulfate anions, phosphate
anions, nitrate anions, citrate anions, formate anions, or acetate
anions.
[0052] The polymers used in the present invention may have a
polyampholyte structure such that the charge and surface adsorption
are determined by pH. In an embodiment, the polymer is an acrylic
acid amine-functional polymer. Examples of suitable hydrophilic
polymers are described in U.S. Pat. Nos. 6,569,261, 6,593,288,
6,703,358 and 6,767,410, the disclosure of these documents is
incorporated herein by reference. These documents describe
water-soluble or water-dispersible copolymers including, in the
form of polymerized units, (1) at least one amine-functional
monomer, (2) at least one hydrophilic monomer with an acidic nature
and (3) optionally at least one neutral hydrophilic monomer having
an ethylenic unsaturation. The copolymers include quaternized
ammonium acrylamide acid copolymers.
[0053] Examples of the anionic monomer B.sub.a include, but are not
limited to, acrylic acid, methacrylic acid, .alpha.-ethacrylic
acid, .beta.,.beta.-dimethacrylic acid, methylenemalonic acid,
vinylacetic acid, allylacetic acid, ethylideneacetic acid,
propylideneacetic acid, crotonic acid, maleic acid, fumaric acid,
itaconic acid, citraconic acid, mesaconic acid,
N-methacryloylalanine, N-acryloylhydroxyglycine, sulfopropyl
acrylate, sulfoethyl acrylate, sulfoethyl methacrylate, sulfoethyl
methacrylate, styrenesulfonic acid, vinylsulfonic acid,
vinylphosphonic acid, phosphoethyl acrylate, phosphonoethyl
acrylate, phosphopropyl acrylate, phosphonopropyl acrylate,
phosphoethyl methacrylate, phosphonoethyl methacrylate,
phosphopropyl methacrylate and phosphonopropyl methacrylate, and
the ammonium and alkali metal salts of these acids.
[0054] Examples of the non-ionic monomer C.sub.a include, but are
not limited to, alkyl acrylate; 2-(Dimethylamino)ethyl methacrylate
(DMAEMA),
##STR00007##
N-vinyl pyrrolidone (NVP), N-vinylimidazole, acrylamide, and
##STR00008##
methacrylamide.
[0055] An example of a polymer suitable for use in the composition
of the present disclosure is a polymer comprising, consisting of or
consisting essentially of DMAEMA, MAPTAC and methylacrylic
acid.
[0056] Suitable polymers include those sold under the trade name
Mirapol.RTM., for example as Mirapol.RTM. Surf-SHO, Mirapol.RTM.
Surf-S110, Mirapol.RTM. HSC-310, Mirapol.RTM. CP-412, Mirapol.RTM.
Surf-5200 or Mirapol.RTM. Surf-5500 available from Solvay,
Novecare.
[0057] Other suitable polymers include polymers comprising,
consisting of or consisting essentially of DADMAC and acrylamide,
such as those sold under the trade name Polyquat.RTM. 7 or PQ7 from
Surfacare or under the trade name Merquat.RTM. S from Lubrizol.
Other suitable polymers include polymers comprising, consisting of
or consisting essentially of DADMAC and methacrylamide and/or,
acrylic acid or methacrylic acid.
[0058] Polymers comprising, consisting of or consisting essentially
of MAPTAC and acrylamide or methacrylamide are also suitable for
use in the composition of the present disclosure. Also suitable are
polymers comprising, consisting of or consisting essentially of
MAPTAC and vinyl pyrrolidone, such as Polyquat.RTM. 28. Suitable
polymers include those sold under the trade names Polyquart.RTM.
Pro. (which is polyquat 28 plus silicone) and Polyquart.RTM. Ampo
140 from BASF.
[0059] Other suitable polymers include polymers comprising,
consisting of or consisting essentially of MAPTAC and acrylic acid
or methacrylic acid, such as those sold under the trade name
Polyquat.RTM. Ampho, eg Polyquat.RTM. Ampho 149.
[0060] Polymers comprising, consisting of or consisting essentially
of DMAEMA and vinylpyrrolidone are suitable for use in the
composition of the present disclosure. An example of such a polymer
is sold under the name PQ11 by BRB International.
[0061] Other suitable polymers include polymers comprising,
consisting of or consisting essentially of DMAEMA and acrylamide,
such as the polymer sold under the trade name Polyquat.RTM. 5.
[0062] In an embodiment, the molecular weight of the polymer ranges
from about 130,000 g/mol to about 2 million g/mol.
[0063] In an embodiment, the amount of polymer in the composition
ranges from about 200 ppm to about 4,000 ppm.
[0064] Compositions of the present disclosure further include one
or more organic acids. In an embodiment, the organic acid is
selected from citric, malic, maleic, oxalic, glutaric, succinic,
lactic, glycolic, fumaric, acetic, benzoic, propionic, sorbic,
tartaric, formic and mixtures of one or more such organic acids. In
another embodiment, the counterion acid may be polymeric acid, such
as, for example, poly(acrylic acid) or other polycarboxylic acids
(e.g. maleic anhydride, methacrylic acid, etc.) or homopolymers or
copolymers (e.g. methyl methacrylate, butyl acrylate, etc.)
thereof, such as those in the Rhodoline.RTM. series available from
Solvay. The composition may include from 500 to 7,000 ppm of one or
more organic acids.
[0065] In compositions of the present disclosure, the surfactant is
selected from cationic surfactants, amphoteric surfactants and
combinations thereof. Cationic surfactants are surfactants that
dissolve in water to result in a net cationic charge. In an
embodiment, when present, the cationic surfactant is selected from
cationic amine oxides, cationic betaines, propionates,
amphoacetates and combinations thereof. Amine oxides, propionates,
amphoacetates and betaines are cationic in the acidic pH conditions
of the present disclosure. In an embodiment, the propionate is
selected from cationic C8-C22 propionates and salts thereof. In
another embodiment, the cationic C8-C22 propionate is selected from
alkyl ampho(di)propionate, alkyl aminopropionates, alkyl
amphopropionates, salts thereof, and combinations thereof. In an
embodiment the cationic amphoacetate is selected from amphoacetates
according to the following formula:
##STR00009##
and diamphoacetates according to the following formula:
##STR00010##
where R is an aliphatic group of 8 to 18 carbon atoms, and M is a
cation such as sodium, potassium, ammonium, or substituted
ammonium. Sodium lauroamphoacetate, sodium cocoamphoacetate,
disodium lauroamphoacetate, and disodium cocoamphodiacetate are
preferred in some embodiments.
[0066] In an embodiment, the betaine is selected from cationic
C8-C22 betaines and salts thereof. In a further embodiment, the
cationic C8-C22 betaine is selected from alkyl dimethylbetaines,
alkylamidopropyl betaines, alkylampho(di)acetates, salts thereof,
and combinations thereof. Where reference is made herein to "salts
thereof" for cationic surfactants, these may be any suitable salts.
In one embodiment the salt is a salt based on a monovalent cation,
such as Na, K, or NH.sub.4. In one embodiment, the salt is a salt
based on an alkali metal, e.g. Na or K. The use of alternative
salts, e.g. alkali earth metal salts such as Ca and Mg could also
be contemplated; however the solubility of the product would need
to be borne in mind when using such salts.
[0067] Amphoteric surfactants contain both a basic and an acidic
hydrophilic group and an organic hydrophobic group. In an
embodiment, when present, the amphoteric surfactant is selected
from sultaines, taurates, and combinations thereof. In an
embodiment, the composition includes a combination of one or more
cationic and amphoteric surfactants.
[0068] In addition to the components described herein, the
composition may also include a polar carrier solvent (e.g. water),
chelating agent, fragrance, preservative, dye, corrosion inhibitor,
builder, cleansing solvent and other components known to be useful
in antimicrobial compositions.
[0069] The compositions according to the present disclosure include
both disinfectant cleaning compositions and concentrates which only
differ in the relative proportion of water to that of the other
constituents. The concentrate can be used without dilution
(concentrate:water 1:0) to extremely dilute dilutions (e.g.,
1:10,000). In an embodiment, a range of dilution is from about 1:1
to about 1:1,000. In another embodiment, a range of dilution is
from about 1:1 to about 1:500. In yet another embodiment, a range
of dilution is from about 1:10 to about 1:128.
[0070] Also disclosed are methods of providing a surface with
residual antimicrobial action that includes the step of applying a
composition of the present disclosure to the surface.
[0071] The composition may be applied to a surface by any method,
including methods conducted by hand and methods conducted by
machine and combinations thereof. For example, composition may be
applied by spraying (pump, aerosol, pressure, etc.), pouring,
spreading, metering (for example, with a rod or bar), mopping,
wiping, brushing, dipping, mechanical application, other
application methods, or combination thereof.
[0072] In an embodiment, compositions of the present disclosure are
suited for use in a "spray and wipe" application. In such an
application, the user generally applies an effective amount of the
cleaning composition using the pump and within a few moments
thereafter, wipes off the treated area with a rag, towel, or
sponge, usually a disposable paper towel or sponge.
[0073] Compositions of the present disclosure, whether as described
herein or in a concentrate or super concentrate form, can also be
applied to a hard surface by using a wet wipe. The wipe can be of a
woven or non-woven nature. Fabric substrates can include non-woven
or woven pouches, sponges, in the form of abrasive or non-abrasive
cleaning pads. Such fabrics are known commercially in this field
and are often referred to as wipes. Such substrates can be resin
bonded, hydroentangled, thermally bonded, meltblown, needlepunched,
or any combination of the former.
[0074] The non-woven fabrics may be a combination of wood pulp
fibers and textile length synthetic fibers formed by well-known
dry-form or wet-lay processes. Synthetic fibers such as rayon,
nylon, orlon and polyester as well as blends thereof can be
employed. The wood pulp fibers should comprise about 30 to about 60
percent by weight of the non-woven fabric, preferably about 55 to
about 60 percent by weight, the remainder being synthetic fibers.
The wood pulp fibers provide for absorbency, abrasion and soil
retention whereas the synthetic fibers provide for substrate
strength and resiliency.
[0075] The compositions of the present disclosure are absorbed onto
the wipe to form a saturated wipe. The wipe can then be sealed
individually in a pouch which can then be opened when needed or a
multitude of wipes can be placed in a container for use on an as
needed basis. The container, when closed, sufficiently sealed to
prevent evaporation of any components from the compositions.
[0076] Also provided are substrates with residual antimicrobial
action that include a substrate wherein at least a portion of the
substrate is coated with a composition of the present disclosure.
The formulation of the present disclosure may be put to use by
application any substrate. Some suitable substrates include, for
example, countertops, mirrors, sinks, toilets, light switches,
doorknobs, walls, floors, ceilings, partitions, railings, computer
screens, keyboards, instruments, etc. Suitable substrates may be
found in various settings including, for example, food preparation
areas, households, industrial settings, architectural settings,
medical settings, sinks, toilets, etc. Substrates may be made of
any material; some suitable substrate compositions include, for
example, plastic (including, for example, laminates and wall
coverings), Formica, metal, glass, ceramic tile, paper (such as,
for example, wallpaper), fabric, finished or unfinished wood,
etc.
[0077] Also provided is the use of a composition of the present
disclosure to substantially reduce or control the formation of
microbial colonies on or at a surface. In an embodiment, a film
formed from the composition kills at least 95% of microorganisms
for at least 3 abrasion cycles according to RSS-12h. In another
embodiment, a film formed from the composition kills at least 95%
of microorganisms according to Environmental Protection Agency
(EPA) Protocol #01-1A residual self-sanitizing activity test (e.g.
6 abrasion cycles for a 24 hour claim). In another embodiment, a
film formed from the composition kills at least 99.9% of
microorganisms for at least 3 abrasion cycles according to RSS-12h.
In yet another embodiment, a film formed from the composition kills
at least 99.9% of microorganisms according to Environmental
Protection Agency (EPA) Protocol #01-1A residual self-sanitizing
activity test (e.g. 6 abrasion cycles for a 24 hour claim).
[0078] In an embodiment, a film formed from the composition kills
at least 95% of gram-positive bacteria and gram-negative bacteria,
fungi, or enveloped and non-enveloped viruses for at least 3
abrasion cycles according to RSS-12h. In another embodiment, a film
formed from the composition kills at least 95% of gram-positive
bacteria and gram-negative bacteria, fungi, or enveloped and
non-enveloped viruses according to Environmental Protection Agency
(EPA) Protocol #01-1A residual self-sanitizing activity test (e.g.
6 abrasion cycles for a 24 hour claim). In another embodiment, a
film formed from the composition kills at least 99.9% of
gram-positive bacteria and gram-negative bacteria, fungi, or
enveloped and non-enveloped viruses for at least 3 abrasion cycles
according to RSS-12h. In yet another embodiment, a film formed from
the composition kills at least 99.9% of gram-positive bacteria and
gram-negative bacteria, fungi, or enveloped and non-enveloped
viruses according to Environmental Protection Agency (EPA) Protocol
#01-1A residual self-sanitizing activity test (e.g. 6 abrasion
cycles for a 24 hour claim).
[0079] While specific embodiments are discussed, the specification
is illustrative only and not restrictive. Many variations of this
disclosure will become apparent to those skilled in the art upon
review of this specification.
[0080] Unless defined otherwise, all technical and scientific terms
used herein have the same meaning as is commonly understood by one
of skill in the art to which this specification pertains.
[0081] As used in the specification and claims, the singular form
"a", "an" and "the" includes plural references unless the context
clearly dictates otherwise.
[0082] As used herein, and unless otherwise indicated, the term
"about" or "approximately" means an acceptable error for a
particular value as determined by one of ordinary skill in the art,
which depends in part on how the value is measured or determined.
In certain embodiments, the term "about" or "approximately" means
within 1, 2, 3, or 4 standard deviations. In certain embodiments,
the term "about" or "approximately" means within 50%, 20%, 15%,
10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, or 0.05% of a given
value or range.
[0083] Also, it should be understood that any numerical range
recited herein is intended to include all sub-ranges subsumed
therein. For example, a range of "1 to 10" is intended to include
all sub-ranges between and including the recited minimum value of 1
and the recited maximum value of 10; that is, having a minimum
value equal to or greater than 1 and a maximum value of equal to or
less than 10. Because the disclosed numerical ranges are
continuous, they include every value between the minimum and
maximum values. Unless expressly indicated otherwise, the various
numerical ranges specified in this application are
approximations.
[0084] The present disclosure will further be described by
reference to the following examples. The following examples are
merely illustrative and are not intended to be limiting.
EXAMPLES
[0085] ASTM Procedure for Cleaning
[0086] The ASTM Method for Cleaning D4488 is intended for testing
the performance of products used on resilient flooring and washable
walls. This method includes preparation of soil, set-up for
cleaning and evaluation of performance under hard surface cleaning
conditions. A straight-line wash ability apparatus is used to clean
surface. This method is designed to be analogous to that of a
surface that is soiled and then cleaned by a consumer. This test is
used to test the cleaning efficacy of all types of multipurpose
household cleaners.
[0087] Preparation of the Substrate: This test protocol calls for
preparation of a double coated Masonite tiles with latex paint
using a paint roller. This paint must be an interior acrylic flat
white. The paint brand has been predetermined by the customer to be
highly porous to allow absorption of the soil. The ASTM method
traditionally calls for California Paints Brand that has since been
discontinued. The tiles are then set to dry for 24 hours at
45.degree. C. prior to any soil application. The next day the
center test area is marked off with a pencil at about 3.5'' length
to show boundaries of where the soil needs to be applied with a
cheesecloth.
[0088] Preparation of Cheesecloth: A cheesecloth is used to apply
the soil onto the substrate. The cheesecloth should be cut to
18''.times.36''dimensions and then folded in half several times to
finally provide with a 2.5''.times.2'' piece that is locked into a
large 2'' binder clip.
[0089] Sponge Preparation: A cellulose sponge is used for the
cleaning of the soil on the surface. The sponge is cut into 4
pieces to fit snug into the sponge box of the wear tester and as
described below. The sponges are then thoroughly washed and
squeezed to semi-dry prior to any application of product.
[0090] Preparation of Soil: A blend of 33% vegetable shortening is
combined with 33% lard, 33% vegetable oil and 1% carbon black. Soil
is made fresh by warming the mixture for 30 minutes at 75.degree.
C. and applied 24 hours prior to testing.
[0091] Application of Soil to Substrate: Once the blend of oils and
carbon black is heated and homogenous, it can be applied to the
substrate with the cheesecloth while maintaining constant heat and
mixing. The cheesecloth is soaked in the heated mixture for a few
minutes to allow the absorption into the cheesecloth and then
applied at moderate speed for a total of six strokes in a downward
motion. The application of the soil onto the substrate is applied
perpendicular to the cleaning direction of the scrubbing apparatus.
The cheesecloth is dipped into the heated mixture between each
stroke.
[0092] Cleaning Test: 15 g of the cleaner is pipetted evenly
throughout the surface of the cellulose sponge. It is then placed
into a sponge box (Total weight .about.350 g) and placed onto the
board that is clamped into the straight-line washability apparatus.
A predetermined number of cycles and speed are established to allow
the sponge to go over the surface in a consistent manner usually a
total of 5 cycles.
[0093] Soil Blend Ratios: Initially when the wallboard cleaning
method was implemented, the soil ratios of lard, oil, shortening
and carbon black differed from that of the ASTM method. The altered
ratio (30% vegetable shortening; 30% lard; 30% vegetable oil; and
10% carbon black) was initially conducted due to test protocols
with a greater amount of carbon black. Additional carbon black was
used to visualize the difference between various products tested.
This could be due to multiple factors such as particle size of the
carbon black as well as its aggregation behavior with polymers in
formulations.
[0094] Substrate Paint: As per ASTM Method the type of paint was
specified to be an acrylic flat white interior paint by California
Paints (Item 53300). An alternative flat white paint was used since
the supplier no longer produces that exact version that was
outlined in the test method due to the lack of scrub resistance. It
was determined that a Behr Pro Dead Flat Paint would be used going
forward in testing.
[0095] Supplier of Carbon Black: The ASTM method calls for use of
Acros Carbonlamp, but since this exact grade has been discontinued,
we experimented with different types of carbon black. We identified
a grade of carbon black (Panther 405) which shows better variation
of cleaning between different cleaning products.
[0096] Application of Soil: In the development stages of the
cleaning protocol we were using a 50 mil (1 mil=1/1000 inch)
drawdown bar. The soil was pipetted parallel to the board on the
top edge and was then flow coated down with 1 stroke from the
drawdown bar. We have since switched away from this form of
application to be more compliant to the ASTM protocol.
Comparative Example 1--Evaluation of Current Disinfectant Cleaning
Benchmarks
[0097] Ready-to-use trigger spray benchmarks readily available on
the market as disinfectant cleaners were tested for their cleaning
performance with ASTM D4488 wallboard cleaning test. All these
products claim >99.9% kill for bacteria and viruses and are
efficient disinfectants. However, it is clearly apparent that
Benchmark A ("quat" based all-purpose cleaner--APC) is highly
effective at removing the carbonaceous greasy soil, compared to
Benchmark B (bleach based APC), Benchmark C (citric acid based
bathroom cleaner--BC) and "Harsh Free" Benchmark D (peroxide based
APC). None of these cleaner disinfectants provide long lasting
cleaning-disinfection which would require passing the RSS-12h or
RSS-24h protocol. The disinfectant cleaners provide a frame of
reference for reconciling the cleaning application to desired
performance. (FIG. 2).
Comparative Example 2--Cleaning Efficacy of Long Lasting
Disinfectant
[0098] The composition of long lasting disinfectant Formulation A
is shown in Table 1. Films prepared from Formulation A were
evaluated using RSS-12h protocol with E. aerogenes as described
above, a modified version the residual self-sanitization (RSS)
method, EPA Protocol #01-1A. All the films were prepared by
pipetting 150 microliters of the formulation on a (1.times.1) inch
steel substrate and allowed to air dry. Formulation A provides a
robust formulation which passes RSS-12h with 4.82 LR (log
reduction--greater than 3); it is a long lasting disinfectant.
Formulation A has pH 4.5 with the additional lactic acid for pH
control as detailed below, at which the added amine oxide is
cationic giving a clear and stable solution. Formulation A is free
of non-ionic surfactants.
TABLE-US-00001 TABLE 1 Components A (actives) (ppm)
Alkyldimethylbenzylammonium chloride 1960 (ADBAC) (CAS 68424-85-1)
Dimethyldidecylammonium chloride 7840 (DDAC) (CAS 7173-51-5)
Mirapol .RTM. Surf-S110 4000 Lactic acid 810 Glutamic acid diacetic
acid, tetrasodium 760 salt (GLDA) Decylamine oxide (e.g. Mackamine
.RTM. 2700 C10) Water Balance Test Microorganism Enterobacter
aerogenes Test Substrate Steel Log Reduction 4.82
[0099] Formulation A was further evaluated for cleaning performance
by ASTM D4488 as described above and compared to the best
performing cleaner, Benchmark A. As can be seen in FIG. 3,
Formulation A performs poorly compared to the cleaning efficacy of
Benchmark A. Benchmark A removed roughly around 70% of the soil,
whereas the Formulation A removed roughly 30%.
Example 3--Addition of Low HLB Tristyrylphenol Ethoxylate
(TSP-xEO)
[0100] The addition of tristyrylphenol ethoxylate surfactants in
Formulation A showed instant improvement in the dispersion of
carbon black. The effect on cleaning performance of adding
different levels of TSP-8EO to Formulation A (Table 2) while
maintaining the composition at pH 4.5 was studied.
TABLE-US-00002 TABLE 2 Components A (Actives) (ppm)
Alkyldimethylbenzylammonium 1960 chloride (ADBAC) (CAS 68424-85-1)
Dimethyldidecylammonium chloride 7840 (DDAC) (CAS 7173-51-5)
Mirapol .RTM. Surf-S110 4000 Lactic acid 810 Glutamic acid diacetic
acid, 760 tetrasodium salt (GLDA) Decylamine oxide (e.g. Mackamine
.RTM. 2700 C10) Tristyrylphenol ethoxylate - 8EO 2500-10000
[0101] The cleaning performance at different levels of added
TSP-8EO is shown in FIG. 4. The addition of TSP-8EO drastically
improves cleaning at levels above 0.5%.
Example 4--Impact on RSS-12h of Varying Quat Levels
[0102] Formulation B (Table 3) was prepared using Mirapol.RTM.
HSC-310, adjusting the level of citric acid, and reducing the
TSP-8EO. Formulation B showed very similar cleaning to Benchmark A
(FIG. 5), which is one of the most effective disinfectant cleaners
on the market.
TABLE-US-00003 TABLE 3 Components B C (Actives) (ppm) (ppm)
Alkyldimethylbenzylammonium 1960 1960 chloride (ADBAC) (CAS
68424-85-1) Dimethyldidecylammonium chloride 7840 7840 (DDAC) (CAS
7173-51-5) Mirapol .RTM. HSC-310 400 400 Citric acid 6720 6720
Lactic acid 810 -- Glutamic acid diacetic acid, 760 760 tetrasodium
salt (GLDA) Decylamine oxide (e.g. Mackamine .RTM. 2700 2700 C10)
Tristyrylphenol ethoxylate - 4EO 1000 1000 Tristyrylphenol
ethoxylate - 8EO 3500 3500 Water Balance Balance Test Microorganism
Enterobacter aerogenes Test Substrate Steel Steel Log Reduction
TNTC 4.55
[0103] The effect of minimizing acids on abrasion and RSS-12h was
studied. Formulation B was further adapted to remove the lactic
acid in the composition (Formulation C-- Table 3) while maintaining
the additional multivalent citric acid and GLDA. The removal of
lactic acid from the formulation led to an interesting wetting
pattern on steel tiles used for RSS-12h. Product dewetting to the
corner was not observed, in contrast to what as was seen with
Formulations A and B. In the absence of lactic acid, the product
was more wetting on the surface (FIG. 6). This improved wetting
effect is desirable when testing for abrasion resistance and
RSS-12h.
[0104] Samples of the above formulations were submitted for
RSS-12h. These samples included Formulations B and C with and
without lactic acid. Formulation C (without lactic acid) showed
4.55 log reduction and passed RSS-12h. The achievement of greater
than 3 log reduction provides a disinfectant-cleaner with a 12 hour
claim for 99.9% residual kill following 3 wet and 3 dry abrasions.
The cleaning efficacy was not impacted due to the removal of lactic
acid (Formulation C) where even at pH 4.0 the performance was
equivalent to the market leading Benchmark A while providing long
lasting disinfection.
[0105] In another embodiment, reduction of quat content was
studied. It is desirable to have the least amount of quats feasible
to get acceptable residue feel while achieving long lasting
disinfection. Formulation D is a clear stable composition at half
(5000 ppm) quat as shown in Table 4.
TABLE-US-00004 TABLE 4 Components D (actives) (ppm)
Alkyldimethylbenzylammonium 1000 chloride (ADBAC) (CAS 68424-85-1)
Dimethyldidecylammonium chloride 4000 (DDAC) (CAS 7173-51-5)
Mirapol .RTM. HSC-310 1200 Citric acid 3300 Glutamic acid diacetic
acid, 760 tetrasodium salt (GLDA) Decylamine oxide (e.g. Mackamine
.RTM. 2700 C10) Tristyrylphenol ethoxylate - 4EO 1000
Tristyrylphenol ethoxylate - 8EO 2000 Water Balance Test
Microorganism Enterobacter aerogenes Test Substrate Steel Log
Reduction 3.99
[0106] Formulation D, showed 3.99 log reduction with the RSS-12h
test. The achievement of greater than 3 log reduction provides a
cleaner-disinfectant with a 12 hour claim for 99.9% residual kill
following 3 wet and 3 dry abrasions. The cleaning efficacy was
slightly reduced due to the reduced quat. However, even at pH 4.0
the performance of Formulation D was equivalent to most benchmarks
(other than Benchmark A) while providing long lasting
disinfection.
Example 5--RSS-24h for Disinfectant Cleaners at Varying Quat
Levels
[0107] RSS-24h performance was studied using Formulations E and F
(Table 5).
TABLE-US-00005 TABLE 5 Components E F (actives) (ppm) (ppm)
Alkyldimethylbenzylammonium chloride 7840 1000 (ADBAC) (CAS
68424-85-1) Dimethyldidecylammonium chloride 1960 4000 (DDAC) (CAS
7173-51-5) Mirapol .RTM. HSC-310 3200 1600 Citric acid 4803 3300
Glutamic acid diacetic acid, tetrasodium 760 760 salt (GLDA)
Dodecylamine oxide (e.g. Mackamine .RTM. 2700 2700 LA)
Tristyrylphenol ethoxylate - 4EO 1000 1000 Tristyrylphenol
ethoxylate - 8EO 3500 2000 Water Balance Balance Test Microorganism
Enterobacter Enterobacter aerogenes aerogenes Test Substrate Steel
Steel Log Reduction 2.76 3.76
[0108] Formulation E is close to passing RSS-24h with 2.76 LR.
Formulation F does succeed in passing RSS-24h with 3.76 LR. The HLB
of the mixed non-ionic surfactant (TSP-4EO+TSP-8EO) for Formulation
F is less than for Formulation E. The formulations also provide
excellent cleaning performance.
[0109] Further improvements in RSS-24h performance can be achieved
using a lower HLB non-ionic surfactant such as Tristyrylphenol
ethoxylate--6.5 EO instead of a mixture of 8EO even when mixed with
4EO, as shown in Table 5.1. Both Formulation G and Formulation H
pass RSS-24h with 3.95 LR and 4.18 LR, respectively, against E.
aerogenes on stainless steel. Both formulations are at pH 4.5.
TABLE-US-00006 TABLE 5.1 Components G H (actives) (ppm) (ppm)
Alkyldimethylbenzylammonium chloride 4000 2500 (ADBAC) (CAS
68424-85-1) Dimethyldidecylammonium 1000 2500 chloride (DDAC) (CAS
7173-51-5) Mirapol .RTM. HSC-310 1200 1200 Citric acid 2200 2200
Ethylenediamine tetaracetic 1500 1500 acid, Disodium salt
(EDTA-Na2) Dodecylamine oxide (e.g. Mackamine .RTM. 1350 1350 LA)
Decylamine oxide (e.g. Mackamine .RTM. 1350 1350 C10)
Tristyrylphenol ethoxylate - 6.5EO 4500 4500 Water Balance Balance
Test Microorganism Enterobacter Enterobacter aerogenes aerogenes
Test Substrate Steel Steel Log Reduction 3.95 4.18
[0110] To further evaluate the efficacy of the formulation with
respect to antimicrobial performance [ready to use (RTU)
application], Formulation H liquid was tested for Virucidal
Efficacy against Human Coronavirus (ATCC VR-740, Strain 229E). For
Viral Efficacy test, EPA recommends the AOAC Use-Dilution Test
modified for viruses or the ASTM E1053. The formulation was tested
for 10 minute exposure time with an organic soil load of 5% fetal
bovine serum. The recoveries were tested with WI-38 (human lung)
cell line. Complete inactivation of the test virus was
demonstrated. A 23.00 log 10 reduction in viral titer was
demonstrated per volume inoculated per well and per carrier
(PASSED). All test control results met acceptance criteria for a
valid test.
[0111] The robust use of lower HLB non-ionic Tristyrylphenol
ethoxylate was further explored by reducing the "quat"
concentration to less than 3000 ppm while improving cleaning
performance (Table 5.2). Reduction in "quat" concentration is
desirable for improving the hazard profile of the formulation.
Further improved cleaning performance is achieved by an overall
increase in concentration of surfactant, while increased polymer
concentration. Formulations I, J, K as outlined in Table 5.2, all
pass RSS-24H and provide excellent cleaning performance.
TABLE-US-00007 TABLE 5.2 Components I J K (actives) (ppm) (ppm)
(ppm) Alkyldimethylbenzylam- 1450 600 2300 monium chloride (ADBAC)
(CAS 68424-85-1) Dimethyldidecylammonium 1450 2300 600 chloride
(DDAC) (CAS 7173- 51-5) Mirapol .RTM. HSC-310 2400 2400 2400 Citric
acid 4000 4000 4000 Ethylenediamine tetaracetic 2200 2200 2200
acid, Disodium salt (EDTA- Na2) Dodecylamine oxide 4050 4050 4050
(e.g. Mackamine .RTM. LA) Decylamine oxide 4050 4050 4050 (e.g.
Mackamine .RTM. C10) Tristyryl phenol 4500 4500 4500 ethoxylate -
6.5EO Water Balance Balance Balance Test Microorganism Enterobacter
Enterobacter Enterobacter aerogenes aerogenes aerogenes Test
Substrate Steel Steel Steel Log Reduction 3.85 4.73 4.73
[0112] Performance in RSS-24h performance were also explored with
variations in polymer type. The polymer Mirapol.RTM.HSC-310 above
is an acrylic acid/DADMAC co-polymer (anion-cation). Table 5.3
outlines use of 3 other polymers HSC-500 (polysulfobetaine),
HSC-500 VPA (polysulfobetaine vinylphosphonic acid co-polymer)
& HSC-2 (ethyl ester of acrylic acid/DADMAC co-polymer). The
HSC-500 (sulfobetaine) has a concurrence of a cationic and anionic
moiety, while the HSC-500 VPA has additional phosphonic acid
anions, and the HSC-2 has more hydrophobic non-ionic/cationic
character. Another commercially available form of the HSC-500 with
added citric acid is outlined in the specification as
Mirapol.RTM.Surf 5500. At the use levels outlined in Table 5.3,
when RSS-24h was conducted with Enterobacter aerogenes on stainless
steel, Formulation L shows 1.81 LR (98.45% kill), improving for
Formulation M to 3.15 LR (99.93% kill), and for Formulation N to
4.66 LR (99.998% kill). Formulation L, M, and N have pH 5.5, 5.5,
& 4.2 respectively. The "quat" (ADBAC+DDAC) level was further
reduced from Formulation N (5000 ppm), to Formulation 0 (2900 ppm)
and further to Formulation P (1000 ppm). All the Formulations N, O
& P are at pH 4.2. Even at 1000 ppm "quat" (ADBAC+DDAC) level,
Formulation P shows "full kill" and >4.66 LR or 99.99% kill with
RSS-24h.
TABLE-US-00008 TABLE 5.3 Components L M N O P (actives) (ppm) (ppm)
(ppm) (ppm) (ppm) Alkyldimethylbenzylam- 2500 2500 2500 2300 200
monium chloride (ADBAC) (CAS 68424- 85-1) Dimethyldidecylam- 2500
2500 2500 600 800 monium chloride (DDAC) (CAS 7173-51-5) Mirapol
.RTM. HSC-500 2500 -- -- -- -- Mirapol .RTM. HSC-500 -- 1300 -- --
-- VPA Mirapol .RTM. HSC-2 1600 2400 2400 Citric acid 200 200 2500
4000 3200 Ethylenediamine 1500 1500 1500 2200 1100 tetaracetic
acid, Disodium salt (EDTA-Na2) Dodecylamine oxide 1400 1400 1400
4050 4050 (e.g. Mackamine .RTM. LA) Decylamine oxide 3100 3100 3100
4050 4050 (e.g. Mackamine .RTM. C10) Tristyrylphenol 6300 9400 5000
5000 3900 ethoxylate - 6.5EO Water Balance Balance Balance Balance
Balance Test Microorganism E. aero E. aero E. aero E. aero E. aero
Test Substrate Steel Steel Steel Steel Steel Log Reduction 1.81
3.15 4.66 4.66 4.66
Example 6--Long Lasting Dilutable Concentrates
[0113] Formulations Q and R (Table 6) were diluted and tested for
cleaning performance and RSS-12h with E. aerogenes on steel.
[0114] The cleaning performance was comparable to other dilutable
concentrate benchmarks at similar dilution factors. Table 6 shows
30.times. dilution of Q and R (Q-30.times. and R-30.times.,
respectively) and further 60.times. dilution of R (R-60.times.).
100 microliters of the diluted compositions were applied on steel
substrates for RSS-12h. While Formulation Q is higher in total
actives compared with Formulation R (16% w/w), the RSS-12h results
show >3 LR for 30.times. dilutions and even for the 60.times.
dilution of Formulation R.
TABLE-US-00009 TABLE 6 Components Q R Q-30X R-30X R-60X (actives)
(ppm) (ppm) (ppm) (ppm) (ppm) Alkyldimethylbenzylammonium 21800
18000 727 599 300 chloride (ADBAC) (CAS 68424-85-1)
Dimethyldidecylammonium chloride 5400 4500 180 148 74.0 (DDAC) (CAS
7173-51-5) Mirapol .RTM. CP-412 22300 18400 743 613 306.0 Citric
acid 28600 23600 953 786 393.0 Glutamic acid diacetic acid, 6900
5700 230 190 95.0 tetrasodium salt (GLDA) Decylamine oxide (e.g.
Mackamine .RTM. 40900 33700 1363 1124 562.0 C10) Dodecylamine oxide
(e.g. Mackamine .RTM. 40900 33700 1363 1124 562.0 C12)
Tristyrylphenol ethoxylate - 6EO 27300 22500 910 750 375.0
(TSP-6EO) Water Balance Balance Balance Balance Balance Total
Actives (% w/w) 19.41 16.01 0.65 0.53 0.2667 100 microliters Test
Microorganism Enterobacter aerogenes Test Substrate Steel Steel
Steel Steel Steel Log Reduction -- -- 4.58 4.28 4.06
Example 7--Improved Environmental Profile
[0115] In another embodiment, to further improve the environmental
profile of the concentrates, formulations were adapted to reduce
the hazardous components. These compositions are shown in Table 7
as Formulations S and T. DDAC was removed (more chronic
environmental hazard) and ADBAC was used in a reduced amount (15900
ppm vs. 18000 ppm). These compositions were then further diluted
30.times. (S-30.times. and T-30.times.) and applied (100
microliters) on steel substrates and tested by RSS-12h protocol
with E. aerogenes. These environmentally improved compositions pass
RSS-12h with >3 LR.
TABLE-US-00010 TABLE 7 Components S T S-30X T-30X (actives) (ppm)
(ppm) (ppm) (ppm) Alkyldimethylbenzylam- 15900 15900 530 530 monium
chloride (ADBAC) (CAS 68424- 85-1) Dimethyldidecylam- 0 0 0 0
monium chloride (DDAC) (CAS 7173- 51-5) Mirapol .RTM. CP-412 22484
22484 749 749 Citric acid 19155 19155 638 638 Glutamic acid
diacetic 2900 0 97 0 acid, tetrasodium salt (GLDA) Decylamine oxide
33700 33700 1123 1123 (e.g. Mackamine .RTM. C10) Dodecylamine oxide
33700 33700 1123 1123 (e.g. Mackamine .RTM. C12) Tristyrylphenol
22500 22500 750 750 ethoxylate -6EO (TSP-6EO) Water Balance Balance
Balance Balance Total Actives (% w/w) 15.0339 14.7439 0.50 0.49 100
microliters Test Microorganism Enterobacter aerogenes Test
Substrate Steel Steel Steel Steel Log Reduction -- -- 4.09 3.26
Example 8--Non-Ionic Surfactants
[0116] Three nonionic surfactants were added to Formulation A at
0.5% actives to alter cleaning performance. The addition of alcohol
ethoxylates (Rhodasurf.RTM. BC-630 and Rhodasurf.RTM. 91-6) to
Formulation A did not improve cleaning performance. In contrast,
tristyrylphenol exthoxylate 8-EO showed a dramatic improvement in
cleaning performance at the same use level (FIG. 7).
[0117] The disclosed subject matter has been described with
reference to specific details of particular embodiments thereof. It
is not intended that such details be regarded as limitations upon
the scope of the disclosed subject matter except insofar as and to
the extent that they are included in the accompanying claims.
[0118] Therefore, the exemplary embodiments described herein are
well adapted to attain the ends and advantages mentioned as well as
those that are inherent therein. The particular embodiments
disclosed above are illustrative only, as the exemplary embodiments
described herein may be modified and practiced in different but
equivalent manners apparent to those skilled in the art having the
benefit of the teachings herein. Furthermore, no limitations are
intended to the details of construction or design herein shown,
other than as described in the claims below. It is therefore
evident that the particular illustrative embodiments disclosed
above may be altered, combined, or modified and all such variations
are considered within the scope and spirit of the exemplary
embodiments described herein. The exemplary embodiments described
herein illustratively disclosed herein suitably may be practiced in
the absence of any element that is not specifically disclosed
herein and/or any optional element disclosed herein. While
compositions and methods are described in terms of "comprising,"
"containing," or "including" various components or steps, the
compositions and methods can also "consist essentially of" or
"consist of" the various components, substances and steps. As used
herein the term "consisting essentially of" shall be construed to
mean including the listed components, substances or steps and such
additional components, substances or steps which do not materially
affect the basic and novel properties of the composition or method.
In some embodiments, a composition in accordance with embodiments
of the present disclosure that "consists essentially of" the
recited components or substances does not include any additional
components or substances that alter the basic and novel properties
of the composition. If there is any conflict in the usages of a
word or term in this specification and one or more patent or other
documents that may be incorporated herein by reference, the
definitions that are consistent with this specification should be
adopted.
* * * * *
References