U.S. patent application number 12/885884 was filed with the patent office on 2011-06-23 for freshening compositions comprising malodor binding polymers and malodor control components.
Invention is credited to Carla Jean Colina, Cahit Eylem, Lon Montgomery Gray, Steven Anthony Horenziak, Rhonda Jean Jackson, Shih-Chuan Liou, Zaiyou Liu, Michael-Vincent Nario Malanyaon, Jason John Olchovy, Christine Marie Readnour, Kristin Rhedrick Williams, Ricky Ah-Man WOO.
Application Number | 20110150817 12/885884 |
Document ID | / |
Family ID | 43499978 |
Filed Date | 2011-06-23 |
United States Patent
Application |
20110150817 |
Kind Code |
A1 |
WOO; Ricky Ah-Man ; et
al. |
June 23, 2011 |
FRESHENING COMPOSITIONS COMPRISING MALODOR BINDING POLYMERS AND
MALODOR CONTROL COMPONENTS
Abstract
Freshening compositions comprising a malodor binding polymer,
malodor control components, and an aqueous carrier; and methods
thereof are provided. In some embodiments, the freshening
composition comprises a homopolymeric polyethylenimine having a
molecular weight of about 1,000 to about 2,000,000 and a mixture of
volatile aldehydes. Such freshening compositions may be used to
reduce malodor and/or microbes on inanimate surfaces or in the
air.
Inventors: |
WOO; Ricky Ah-Man;
(Hamilton, OH) ; Readnour; Christine Marie; (Fort
Mitchell, KY) ; Olchovy; Jason John; (West Chester,
OH) ; Malanyaon; Michael-Vincent Nario; (Indian
Springs, OH) ; Liu; Zaiyou; (West Chester, OH)
; Jackson; Rhonda Jean; (Cincinnati, OH) ;
Williams; Kristin Rhedrick; (West Chester, OH) ;
Colina; Carla Jean; (Cincinnati, OH) ; Eylem;
Cahit; (West Chester, OH) ; Gray; Lon Montgomery;
(Florence, KY) ; Liou; Shih-Chuan; (Cincinnati,
OH) ; Horenziak; Steven Anthony; (Fairfield,
OH) |
Family ID: |
43499978 |
Appl. No.: |
12/885884 |
Filed: |
September 20, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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61287348 |
Dec 17, 2009 |
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61287369 |
Dec 17, 2009 |
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61287383 |
Dec 17, 2009 |
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Current U.S.
Class: |
424/76.21 ;
424/76.1 |
Current CPC
Class: |
C11D 3/50 20130101; A61L
9/01 20130101; C11D 3/2079 20130101; C11D 1/00 20130101; C11D
3/0068 20130101; C11D 1/83 20130101; C11D 3/2096 20130101; A47L
15/0005 20130101; C11D 3/2075 20130101; C11D 3/33 20130101; C11D
3/373 20130101; C11D 3/38663 20130101; C11D 3/2072 20130101; C11D
3/386 20130101; C11D 3/3481 20130101 |
Class at
Publication: |
424/76.21 ;
424/76.1 |
International
Class: |
A61L 9/01 20060101
A61L009/01 |
Claims
1. A freshening composition for reducing malodor comprising: an
effective amount of a malodor binding polymer; a malodor control
component comprising an effective amount of a mixture of two or
more volatile aldehydes for neutralizing a malodor, wherein said
two or more volatile aldehydes are selected from the group
consisting of 2-ethoxy benzylaldehyde,
2-isopropyl-5-methyl-2-hexenal, 5-methyl furfural,
5-methyl-thiophene-carboxaldehyde, adoxal, p-anisaldehyde,
benzylaldehyde, bourgenal, cinnamic aldehyde, cymal, decyl
aldehyde, floral super, florhydral, helional, lauric aldehyde,
ligustral, lyral, melonal, o-anisaldehyde, pino acetaldehyde, P.T.
bucinal, thiophene carboxaldehyde, trans-4-decenal, trans trans
2,4-nonadienal, undecyl aldehyde, and mixtures thereof; and an
aqueous carrier.
2. The composition of claim 1 wherein said malodor binding polymer
is a polyamine having a molecular weight of at least 150 Daltons
and 15% to 80% primary amino groups
3. The composition of claim 1 wherein said malodor binding polymer
is a homopolymeric polyethyleneimine having a molecular weight of
about 1,000 to about 2,000,000 Daltons.
4. The composition of claim 1 wherein said malodor binding polymer
is present in an amount of about 0.01% to about 1% by weight of
said composition.
5. The composition of claim 3 wherein said homopolymeric
polyethyleneimine is present in an amount of about 0.01% to about
0.07% by weight of said composition.
6. The composition of claim 1 wherein said malodor binding polymer
is a homopolymeric polyethyleneimine having a molecular weight of
about 25,000 Daltons.
7. The malodor control component of claim 1 wherein said two or
more volatile aldehydes are selected from the group consisting of
2-ethoxy benzylaldehyde, 2-isopropyl-5-methyl-2-hexenal, 5-methyl
furfural, cinnamic aldehyde, floral super, florhydral,
o-anisaldehyde, pino acetaldehyde, trans-4-decenal, and mixtures
thereof.
8. The malodor control component of claim 1 wherein said two or
more volatile aldehydes comprise flor super and o-anisaldehyde.
9. The malodor control component of claim 1 wherein said two or
more volatile aldehydes have a VP from about 0.001 torr to about
0.100 torr.
10. The malodor control component of claim 1 wherein said two or
more volatile aldehydes comprise a mixture of volatile aldehydes
selected from the group consisting of: Accord A, Accord B, Accord
C, and mixtures thereof.
11. The malodor control component of claim 1 wherein said two or
more volatile aldehydes comprise a mixture of volatile aldehydes
comprising about 1% to about 10% of Accord A, by weight of said
malodor control component.
12. The composition of claim 1 wherein said malodor control
component further comprises about 0.001% to about 1% of an
aliphatic aldehyde by total weight of said composition.
13. The composition of claim 1 wherein said composition further
comprises a buffering agent selected from the group consisting of
carboxylic acid, dicarboxcylic acid,
N-(2-Acetamido)-2-aminoethanesulfonic acid, and mixtures
thereof.
14. The composition of claim 1 wherein said composition further
comprises maleic acid.
15. The composition of claim 1 wherein said composition comprises a
pH of about 5 to 8.
16. The composition of claim 1 wherein said composition is free of
anionic surfactants.
17. The composition of claim 1 wherein said composition comprises
no more than 3% surfactant by weight of said composition.
18. The composition of claim 1 wherein said aqueous carrier is
present in an amount of 90% to about 99.5%.
19. A freshening composition for reducing malodor comprising: an
effective amount of a malodor binding polymer; and a malodor
control component comprising: at least one volatile aldehyde; and
an acid catalyst having a vapor pressure of about 0.01 to about 13
at 25.degree. C.
20. The composition of claim 19 wherein said acid catalyst has a
vapor pressure of about 0.01 to about 2 torr at 25.degree. C.
21. The composition of claim 19 wherein said acid catalyst is a
carboxylic acid.
22. The composition of claim 19 wherein said acid catalyst is
5-methyl thiophene carboxylic acid.
23. The composition of claim 19 wherein said acid catalyst is
present in an amount from about 0.1% to about 0.4%, by weight of
said malodor control component.
24. The composition of claim 19 wherein said acid catalyst is
present in an amount of about 0.4%, by weight of said malodor
control component.
25. The composition of claim 19 wherein said at least one volatile
aldehyde is a mixture of two or more volatile aldehydes selected
from the group consisting of 2-ethoxy benzylaldehyde,
2-isopropyl-5-methyl-2-hexenal, 5-methyl furfural,
5-methyl-thiophene-carboxaldehyde, adoxal, p-anisaldehyde,
benzylaldehyde, bourgenal, cinnamic aldehyde, cymal, decyl
aldehyde, floral super, florhydral, helional, lauric aldehyde,
ligustral, lyral, melonal, o-anisaldehyde, pino acetaldehyde, P.T.
bucinal, thiophene carboxaldehyde, trans-4-decenal, trans trans
2,4-nonadienal, undecyl aldehyde, and mixtures thereof.
26. The composition of claim 19 wherein said a malodor binding
polymer is a homopolymeric polyethyleneimine present in an amount
of about 0.01% to about 0.07%, by weight of said composition.
27. The composition of claim 19 wherein said malodor binding
polymer is a homopolymeric polyethyleneimine having a molecular
weight of about 25,000 Daltons.
28. A method of reducing malodor comprising the steps of: a.
providing the freshening composition of claim 1; b. dispersing an
effective amount of said freshening composition on an inanimate
surface or in the air.
29. A method of neutralizing malodor comprising the step of: a.
providing the freshening composition of claim 19; b. dispersing an
effective amount of said freshening composition on an inanimate
surface of in the air.
Description
CROSS REFERENCES TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Application No. 61/287,348, filed, Dec. 17, 2009 and U.S.
Provisional Application No. 61/287,369, filed Dec. 17, 2009 and
U.S. Provisional Application No. 61/287,383, filed Dec. 17, 2009
and U.S. application Ser. No. 12/562,534, filed Sep. 18, 2009 and
U.S. application Ser. No. 12/562,553 filed Sep. 18, 2009.
FIELD OF THE INVENTION
[0002] The present invention relates to freshening compositions
comprising a malodor binding polymer, malodor control components,
and an aqueous carrier; and methods thereof.
BACKGROUND OF THE INVENTION
[0003] Freshening products for reducing or masking malodors on
fabrics and in air are currently available and are described in the
patent literature. The Procter & Gamble Company sells fabric
and air freshening products under the FEBREZE.RTM. brand name.
These products typically contain perfume, solubilizer,
cyclodextrin, and an aqueous carrier. S.C. Johnson sells products
such as Glade.RTM. Fabric and Air Odor Eliminator and Oust.RTM.
Surface Disinfectant and Air Sanitizer. Reckitt-Benckiser sells
products such as Lysol.RTM. Disinfectant Spray.
[0004] Certain freshening compositions do not effectively
neutralize a broad range of malodors on fabrics and in the air.
Further, the time required for a composition to noticeably combat
malodors may create consumer doubt as to a product's efficacy on
malodors. For example, the consumer may leave the treated space
before the product begins to noticeably reduce the malodor.
[0005] There remains a need for improved freshening compositions
that neutralize a broad range of malodors, including amine-base and
sulfur-based malodors and malodors caused by microbes, while not
overpowering malodors with overwhelming perfume.
SUMMARY OF THE INVENTION
[0006] The present invention relates to a freshening composition
for reducing malodor. In one embodiment, the freshening composition
for reducing malodor comprises an effective amount of a malodor
binding polymer; a malodor control component; an aqueous carrier.
In another embodiment, the freshening composition comprises a
homopolymeric polyethyleneimine having a molecular weight of 1,000
to 2,000,000; at least one aliphatic aldehyde; a glycol; a
dicarboxylic acid to provide a pH of about 3 to about 8; about 90%
to about 99.5% of an aqueous carrier; wherein said composition is
essentially free of any material that would soil or stain
fabric.
[0007] The present invention also relates to methods of reducing
malodor comprising the steps of: providing a freshening composition
comprising an effective amount of a malodor binding polymer, a
malodor counteractant comprising at least one aliphatic aldehyde,
an aqueous carrier, wherein said composition is essentially free of
any material that would soil or stain fabric; and dispersing an
effective amount of said freshening composition on an inanimate
surface or in the air.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 is a bar graph showing the reduction of aldehydic
malodors evaporating off fabrics treated with freshening
compositions according to the present invention containing a
malodor binding polymer in comparison to a freshening composition
lacking such malodor binding polymer.
[0009] FIG. 2 is a bar graph showing microbe reduction with a
freshening composition according to the present invention
containing a malodor binding polymer in comparison to a freshening
composition lacking such malodor binding polymer.
[0010] FIG. 3 is a graph showing the performance of one embodiment
of a malodor control component, in accordance with the present
invention, on a sulfur-based malodor.
[0011] FIG. 4 is a graph showing the performance of one embodiment
of a malodor control component, in accordance with the present
invention, on an amine-based malodor.
[0012] FIG. 5 is a graph showing butanethiol reduction by thiophene
carboxaldehyde in combination with various acid catalysts.
DETAILED DESCRIPTION OF THE INVENTION
[0013] The freshening composition of the present invention is
designed to deliver genuine malodor reduction and not function
merely by using perfume to cover up or mask odors. The freshening
composition reduces malodor in the air or on inanimate surfaces,
for example, fabrics that are contaminated with environmental odors
such as food and tobacco odors, or wetted with perspiration. The
freshening composition may also reduce microbes on inanimate
surfaces or in air. The freshening composition may also act as a
barrier to prevent malodors from adhering to or penetrating an
inanimate surface.
[0014] A genuine malodor reduction provides a sensory and
analytically measurable (e.g. gas chromatograph) malodor reduction.
Thus, if the freshening composition delivers a genuine malodor
reduction, the freshening composition will neutralize malodors in
the air and/or on fabrics. "Neutralize" or "neutralization" as used
herein means chemically reacting with malodor components (e.g. the
reaction of primary amines with aldehydes to form imines, reductive
alkylation of amines, protonation and deprotonation of amines,
polymerization or de-polymerization); or suppressing the volatility
of malodorous components such that other parts of the composition
may react (e.g. acid-base neutralization); or physically entrapping
odorous molecules such that they are not re-released into the air
(e.g. cyclodextrin inclusion complexes as described herein). Odor
neutralization may be distinguished from odor masking or odor
blocking by a change in the malodorous compound, as opposed to a
change in the ability to perceive the malodor without any
corresponding change in the condition of the malodorous
compound.
I. Freshening Composition
[0015] The freshening composition for reducing malodor comprises a
malodor binding polymer, a malodor counteractant comprising at
least one aliphatic aldehyde, and an aqueous carrier, wherein said
composition is essentially free of materials that soil or stain
fabric. The total amount of surfactants (e.g. solubilizer, wetting
agent) in the freshening composition is from 0% to 3% or no more
than 3%, alternatively from 0% to 1% or no more than 1%,
alternatively from 0% to 0.9% or no more than 0.9%, alternatively
from 0% to 0.7 or no more than 0.7%, alternatively from 0% to 0.5%
or no more than 0.5%, alternatively from 0% to 0.3% or no more than
0.3%, by weight of the composition. Compositions with higher
concentrations can make fabrics susceptible to soiling and/or leave
unacceptable visible stains on fabrics as the solution
evaporates.
[0016] A. Malodor Binding Polymer
[0017] The freshening composition of the present invention includes
a malodor binding polymer. A malodor binding polymer is polymer
having an available functional group (e.g. amine) that has the
affinity to neutralize malodor components. Monomers having an
available function group with an affinity to neutralize malodor
components are also contemplated. In the case of amine based
compounds, the amine will have an affinity for aldehyde malodors.
The amine may react with aldehyde malodors and form a new compound,
such as an aminol, imine, or enamine which is not odorous.
[0018] A malodor binding polymer may include amine based compounds,
such as monoamines, amino acids, polyethyleneimine polymers (PEIs),
modified PEIs, substituted PEIs; acrylic acid polymers, such as
polyacrylate co-polymer (e.g. Acumer.TM. 9000 from Rohm &
Haas), polyacrylic acid polymers (e.g. Acusol.TM. from Rohm &
Haas), and modified acrylate copolymers (e.g. Aculyn.TM. from Rohm
& Haas); and modified methacrylate copolymers (e.g.
HydroSal.TM. from Salvona Technologies); or mixtures thereof.
[0019] 1. Amine Based Compounds
[0020] In some embodiments, the malodor binding polymer is an amine
based compound with a molecular weight greater than 100 Daltons and
at least 10% of its amine groups are primary amines. In one
embodiment, the amine-based compound will be a polyamine with a
molecular weight greater than 150 Daltons and 15% to 80% of its
amine groups are primary amines. In another embodiment, the malodor
binding polymer is an amine-based compound with a molecular weight
greater than 1000 Daltons and from 0% to about 10% or less than 10%
of its amine groups are primary amines.
[0021] A general structure for a primary amine compound useful in
this invention is as follows:
B--(NH.sub.2).sub.n;
wherein B is a carrier material, and n is an index of value of at
least 1. Suitable B carriers include both inorganic and organic
carrier moieties. By "inorganic carrier", it is meant a carrier
which is comprised of non- or substantially non-carbon based
backbones.
[0022] Compounds containing a secondary amine group have a
structure similar to the above with the exception that the compound
comprises one or more --NH-- groups as well as --NH.sub.2 groups.
The amine compounds of this general type may be relatively viscous
materials.
[0023] Exemplary amine based compounds are those selected from
monoamines, aminoaryl derivatives, polyamines and derivatives
thereof, polyamino acids and copolymers thereof, glucamines,
dendrimers, PEIs, substituted amines and amides monoamines, or
mixtures thereof.
[0024] a. Monoamines
[0025] Monoamines may be utilized in the present invention.
Nonlimiting examples of suitable monoamines for use in the present
invention include, but are not limited to, primary amines that also
contain hydroxy and/or alkoxy functional groups, such as the
2-hydroxyamines and/or 3-hydroxyamines; primary or secondary amines
that also contain a functional group that enhances deposition of
the monoamine compared to monoamines that lack that functional
group, especially when the monoamine is interacting with the
benefit agent. Primary monoamines may also be used herein in
combination with secondary monoamines. However, sufficient levels
of the primary monoamine must be used to provide at least 10% of
the total amine groups within such combinations as primary amine
groups.
[0026] b. Aminoaryl Derivatives
[0027] Exemplary aminoaryl derivatives are the amino-benzene
derivatives including the alkyl esters of 4-amino benzoate
compounds, ethyl-4-amino benzoate, phenylethyl-4-aminobenzoate,
phenyl-4-aminobenzoate, 4-amino-N'-(3-aminopropyl)-benzamide, or
mixtures thereof.
[0028] c. Polyamines
[0029] Examples of suitable amino functional polymers containing at
least one primary amine group for the purposes of the present
invention are:
[0030] Polyvinylamine with a MW of 300-2.10E6 Daltons (e.g Lupamine
series 1500, 4500, 5000, 9000 available from BASF);
[0031] Polyvinylamine alkoxylated with a MW of .gtoreq.600 Daltons
and a degree of ethoxylation of at least 0.5;
[0032] Polyvinylamine vinylalcohol--molar ratio 2:1,
polyvinylaminevinylformamide--molar ratio 1:2 and polyvinylamine
vinylformamide-molar ratio 2:1;
[0033] Triethylenetetramine, diethylenetriamine,
tetraethylenepentamine;
[0034] Bis-aminopropylpiperazine;
[0035] amino substituted polyvinylalcohol with a MW ranging from
400-300,000 Daltons;
[0036] polyoxyethylene bis[amine] available from e.g. Sigma;
[0037] polyoxyethylene bis[6-aminohexyl] available from e.g.
Sigma;
[0038] N,N'-bis-(3-aminopropyl)-1,3-propanediamine linear or
branched (TPTA);
[0039] N,N'-bis-(3-aminopropyl)ethylenediamine;
[0040] bis(amino alkyl)alkyl diamine, linear or branched; and
[0041] 1,4-bis-(3-aminopropyl)piperazine (BNPP).
[0042] d. Polyamino Acids
[0043] Suitable amine based compounds include polyamino acids.
Polyamino acids are made up of amino acids or chemically modified
amino acids. The amino acids may be selected from cysteine,
histidine, isoleucine, tyrosine, tryptophane, leucine, lysine,
glutamic acid, glutamine, glycine, alanine, aspartic acid,
arginine, asparagine, phenylalanine, proline, serine, histidine,
threonine, methionine, valine, and mixtures thereof. Amino acid
derivatives may be tyrosine ethylate, glycine methylate,
tryptophane ethylate, or mixtures thereof; homopolymers of amino
acids; hydroxyamines; polyamino acids; or mixtures thereof.
[0044] In chemically modified amino acids, the amine or acidic
function of the amino acid has reacted with a chemical reagent.
This is often done to protect these chemical amine and acid
functions of the amino acid in a subsequent reaction or to give
special properties to the amino acids, like improved solubility.
Examples of such chemical modifications are benzyloxycarbonyl,
aminobutyric acid, butyl ester, and pyroglutamic acid. More
examples of common modifications of amino acids and small amino
acid fragments can be found in the Bachem, 1996, Peptides and
Biochemicals Catalog.
[0045] One polyamino acid is polylysine, alternatively polylysines
or polyamino acids where more than 50% of the amino acids are
lysine, since the primary amine function in the side chain of the
lysine is the most reactive amine of all amino acids. One polyamino
acid has a molecular weight of 500 to 10,000,000, alternatively
between 2000 and 25,000.
[0046] The polyamino acid can be cross linked. The cross linking
can be obtained for example by condensation of the amine group in
the side chain of the amino acid like lysine with the carboxyl
function on the amino acid or with protein cross linkers like PEG
derivatives. The cross linked polyamino acids still need to have
free primary and/or secondary amino groups left for neutralization.
Cross linked polyamino acid has a molecular weight of 20,000 to
10,000,000; alternatively between 200,000 and 2,000,000.
[0047] The polyamino acid or the amino acid can be co-polymerized
with other reagents like for instance with acids, amides, acyl
chlorides, aminocaproic acid, adipic acid, ethylhexanoic acid,
caprolactam, or mixtures thereof. The molar ratio used in these
copolymers ranges from 1:1 (reagent/amino acid (lysine)) to 1:20,
alternatively from 1:1 to 1:10. The polyamino acid like polylysine
can be unethoxylated or partially ethoxylated so long as the
requisite amount of primary amine remains in the polymer.
[0048] e. Dendrimers
[0049] Also useful amine based compounds are polypropylenimine
dendrimers and the commercially available Starburst.RTM..sup.
polyamidoamines (PAMAM) dendrimers, generation G0-G10 from
Dendritech and the dendrimers Astromols.RTM., generation 1-5 from
DSM being DiAminoButane PolyAmine DAB (PA)x dendrimers with
x=2.sup.n.times.4 and n being generally comprised between 0 and
4.
[0050] f. PEIs
[0051] In one embodiment, the malodor binding polymer is a PEI. It
has been surprisingly discovered that amine based polymers at a pH
of about 4 to about 8, alternatively above 5 to about 8,
alternatively 7 can neutralize amine based odors. PEIs have the
following general formula:
--(CH2-CH2-NH)n-; n=10-105
[0052] Homopolymeric PEIs are branched, spherical polyamines with a
well defined ratio of primary, secondary and tertiary amine
functions. They are best described in the following partial
structural formula:
##STR00001##
The chemical structure of homopolymeric PEIs follows a simple
principle: one amine function-two carbons.
[0053] The freshening composition may comprise a homopolymeric
polyethylenimine having a molecular weight of about 800 to about
2,000,000, alternatively about 1,000 to about 2,000,000,
alternatively about 1,200 to about 25,000, alternatively about
1,300 to about 25,000, alternatively about 2,000 to about 25,000,
alternatively about 10,000 to about 2,000,000, alternatively about
25,000 to about 2,000,000, alternatively about 25,000. Exemplary
homopolymeric PEIs include those that are commercially available
under the tradename Lupasol.RTM. from BASF. Lupasol products are
usually obtained through polymerization of the ethylenimine
monomer. The ethylenimine monomer has totally reacted in the
polymer matrix. Suitable Lupasol products include Lupasol FG (MW
800), G20 wfv (MW 1300), PR8515 (MW 2000), WF (MW 25,000), FC (MW
800), G20 (MW 1300), G35 (MW 1200), G100 (MW 2000), HF (MW 25,000),
P (MW 750,000), PS (MW 750,000), SK (MW 2,000,000), SNA (MW
1,000,000).
[0054] In some embodiments, the freshening composition comprises
Lupasol HF or WF (MW 25,000), P (MW 750,000), PS (MW 750,000), SK
(MW 2,000,000), 620 wfv (MW 1300) or PR 1815 (MW 2000), or Epomin
SP-103, Epomin SP-110, Epomin SP-003, Epomin SP-006, Epomin SP-012,
Epomin SP-018, Epomin SP-200, or partially alkoxylated
polyethyleneimine, like polyethyleneimine 80% ethoxylated from
Aldrich. In one embodiment, the freshening composition contains
Lupasol WF (MW 25,000).
[0055] Also suitable amine based compounds for use in the
freshening composition are modified PEIs, partially alkylated
polyethylene polymers, PEIs with hydroxyl groups,
1,5-pentanediamine, 1,6-hexanediamine, 1,3 pentanediamine,
3-dimethylpropanediamine, 1,2-cyclohexanediamine,
1,3-bis(aminomethyl)cyclohexane, tripropylenetetraamine,
bis(3-aminopropyl)piperazine, dipropylenetriamine,
tris(2-aminoethylamine), tetraethylenepentamine,
bishexamethylenetriamine, bis(3-aminopropyl)
1,6-hexamethylenediamine, 3,3'-diamino-N-methyldipropylamine,
2-methyl-1,5-pentanediamine,
N,N,N',N'-tetra(2-aminoethyl)ethylenediamine,
N,N,N',N'-tetra(3-aminopropyl)-1,4-butanediamine,
pentaethylhexamine, 1,3-diamino-2-propyl-tert-butylether,
isophorondiamine, 4,4'-diaminodicyclohylmethane,
N-methyl-N-(3-aminopropyl)ethanolamine, spermine, spermidine,
1-piperazineethaneamine, 2-(bis(2-aminoethyl)amino)ethanol,
ethoxylated N-(tallowalkyl)trimethylene diamines,
poly[oxy(methyl-1,2-ethanediyl)],
.alpha.-(2-aminomethyl-ethoxy)-(=C.A.S No. 9046-10-0);
poly[oxy(methyl-1,2-ethanediyl)],
.alpha.-hydro-)-.omega.-(2-aminomethylethoxy)-, ether with
2-ethyl-2-(hydroxymethyl)-1,3-propanediol (=C.A.S, No. 39423-51-3);
commercially available under the tradename Jeffamines T-403, D-230,
D-400, D-2000; 2,2',2''-triaminotriethylamine;
2,2'-diamino-diethylamine; 3,3'-diamino-dipropylamine, 1,3 bis
aminoethyl-cyclohexane commercially available from Mitsubishi, and
the C12 Sternamines commercially available from Clariant like the
C12 Sternamin(propylenamine).sub.n with n=3/4.
[0056] In one embodiment, the malodor binding polymer may be used
in an effective amount to provide a reduction of microbes on fabric
and/or in the air. When using a malodor binding polymer, an
effective amount reduces microbes by at least 1 log difference as
compared to a composition lacking the malodor binding polymer. This
difference is then attributed to the use of the malodor binding
polymer and not the inherent variability in the microbial
species.
[0057] Suitable levels of malodor binding polymer are from about
0.01% to about 2%, alternatively from about 0.01% to about 1%,
alternatively about 0.01% to about 0.8%, alternatively about 0.01%
to about 0.6%, alternatively about 0.01% to about 0.1%,
alternatively about 0.01% to about 0.07%, alternatively about
0.07%, by weight of the freshening composition. Compositions with
higher amount of malodor binding polymer may make fabrics
susceptible to soiling and/or leave unacceptable visible stains on
fabrics as the solution evaporates off of the fabric.
[0058] B. Malodor Control Components
[0059] The freshening composition may include malodor control
components. The malodor control component includes a mixture of
volatile aldehydes and is designed to deliver genuine malodor
neutralization and not function merely by covering up or masking
odors. A genuine malodor neutralization provides a sensory and
analytically measurable (e.g. gas chromatograph) malodor reduction.
Thus, if the malodor control component delivers a genuine malodor
neutralization, the composition will reduce malodors in the vapor
and/or liquid phase. When used in combination with the malodor
binding polymer, the freshening composition may neutralize a
broader range of malodor causing materials which, in turn, further
reduces malodors in the air or on inanimate surfaces.
[0060] 1. Volatile Aldehydes
[0061] The malodor control component includes a mixture of volatile
aldehydes that neutralize malodors in vapor and/or liquid phase via
chemical reactions. Aldehydes that are partially volatile may be
considered a volatile aldehyde as used herein. Volatile aldehydes
may react with amine-based odors, following the path of Schiff-base
formation. Volatiles aldehydes may also react with sulfur-based
odors, forming thiol acetals, hemi thiolacetals, and thiol esters
in vapor and/or liquid phase. It may be desirable for these vapor
and/or liquid phase volatile aldehydes to have virtually no
negative impact on the desired perfume character of a product.
[0062] Suitable volatile aldehydes may have a vapor pressure (VP)
in the range of about 0.0001 torr to 100 torr, alternatively about
0.0001 torr to about 10 torr, alternatively about 0.001 torr to
about 50 torr, alternatively about 0.001 torr to about 20 torr,
alternatively about 0.001 torr to about 0.100 torr, alternatively
about 0.001 torr to 0.06 torr, alternatively about 0.001 torr to
0.03 torr, alternatively about 0.005 torr to about 20 torr,
alternatively about 0.01 torr to about 20 torr, alternatively about
0.01 torr to about 15 torr, alternatively about 0.01 torr to about
10 torr, alternatively about 0.05 torr to about 10 torr, measured
at 25.degree. C.
[0063] The volatile aldehydes may also have a certain boiling point
(B.P.) and octanol/water partition coefficient (P). The boiling
point referred to herein is measured under normal standard pressure
of 760 mmHg. The boiling points of many volatile aldehydes, at
standard 760 mm Hg are given in, for example, "Perfume and Flavor
Chemicals (Aroma Chemicals)," written and published by Steffen
Arctander, 1969.
[0064] The octanol/water partition coefficient of a volatile
aldehyde is the ratio between its equilibrium concentrations in
octanol and in water. The partition coefficients of the volatile
aldehydes used in the malodor control component may be more
conveniently given in the form of their logarithm to the base 10,
logP. The logP values of many volatile aldehydes have been
reported. See, e.g., the Pomona92 database, available from Daylight
Chemical Information Systems, Inc. (Daylight CIS), Irvine, Calif.
However, the logP values are most conveniently calculated by the
"CLOGP" program, also available from Daylight CIS. This program
also lists experimental logP values when they are available in the
Pomona92 database. The "calculated logP" (ClogP) is determined by
the fragment approach of Hansch and Leo (cf., A. Leo, in
Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G.
Sammens, J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon
Press, 1990). The fragment approach is based on the chemical
structure of each volatile aldehyde, and takes into account the
numbers and types of atoms, the atom connectivity, and chemical
bonding. The ClogP values, which are the most reliable and widely
used estimates for this physicochemical property, are preferably
used instead of the experimental logP values in the selection of
volatile aldehydes for the malodor control component.
[0065] The ClogP values may be defined by four groups and the
volatile aldehydes may be selected from one or more of these
groups. The first group comprises volatile aldehydes that have a
B.P. of about 250.degree. C. or less and ClogP of about 3 or less.
The second group comprises volatile aldehydes that have a B.P. of
250.degree. C. or less and ClogP of 3.0 or more. The third group
comprises volatile aldehydes that have a B.P. of 250.degree. C. or
more and ClogP of 3.0 or less. The fourth group comprises volatile
aldehydes that have a B.P. of 250.degree. C. or more and ClogP of
3.0 or more. The malodor control component may comprise any
combination of volatile aldehydes from one or more of the ClogP
groups.
[0066] In some embodiments, the malodor control component of the
present invention may comprise, by total weight of the malodor
control component, from about 0% to about 30% of volatile aldehydes
from group 1, alternatively about 25%; and/or about 0% to about 10%
of volatile aldehydes from group 2, alternatively about 10%; and/or
from about 10% to about 30% of volatile aldehydes from group 3,
alternatively about 30%; and/or from about 35% to about 60% of
volatile aldehydes from group 4, alternatively about 35%.
[0067] Exemplary volatile aldehydes which may be used in a malodor
control component include, but are not limited to, Adoxal
(2,6,10-Trimethyl-9-undecenal), Bourgeonal
(4-t-butylbenzenepropionaldehyde), Lilestralis 33
(2-methyl-4-t-butylphenyl)propanal), Cinnamic aldehyde,
cinnamaldehyde (phenyl propenal, 3-phenyl-2-propenal), Citral,
Geranial, Neral (dimethyloctadienal,
3,7-dimethyl-2,6-octadien-1-al), Cyclal C
(2,4-dimethyl-3-cyclohexen-1-carbaldehyde), Florhydral
(3-(3-Isopropyl-phenyl)-butyraldehyde), Citronellal (3,7-dimethyl
6-octenal), Cymal, cyclamen aldehyde, Cyclosal, Lime aldehyde
(Alpha-methyl-p-isopropyl phenyl propyl aldehyde), Methyl Nonyl
Acetaldehyde, aldehyde C12 MNA (2-methyl-1-undecanal),
Hydroxycitronellal, citronellal hydrate (7-hydroxy-3,7-dimethyl
octan-1-al), Helional
(alpha-methyl-3,4-(methylenedioxy)-hydrocinnamaldehyde,
hydrocinnamaldehyde (3-phenylpropanal, 3-phenylpropionaldehyde),
Intreleven aldehyde (undec-10-en-1-al), Ligustral, Trivertal
(2,4-dimethyl-3-cyclohexene-1-carboxaldehyde), Jasmorange,
satinaldehyde (2-methyl-3-tolylproionaldehyde,
4-dimethylbenzenepropanal), Lyral (4-(4-hydroxy-4-methyl
pentyl)-3-cyclohexene-1-carboxaldehyde), Melonal
(2,6-Dimethyl-5-Heptenal), Methoxy Melonal
(6-methoxy-2,6-dimethylheptanal), methoxycinnamaldehyde
(trans-4-methoxycinnamaldehyde), Myrac aldehyde isohexenyl
cyclohexenyl-carboxaldehyde, trifernal ((3-methyl-4-phenyl
propanal, 3-phenyl butanal), lilial, P.T. Bucinal, lysmeral,
benzenepropanal (4-tert-butyl-alpha-methyl-hydrocinnamaldehyde),
Dupical, tricyclodecylidenebutanal
(4-Tricyclo5210-2,6decylidene-8butanal), Melafleur
(1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde), Methyl
Octyl Acetaldehyde, aldehyde C-11 MOA (2-methyl deca-1-al),
Onicidal (2,6,10-trimethyl-5,9-undecadien-1-al), Citronellyl
oxyacetaldehyde, Muguet aldehyde 50
(3,7-dimethyl-6-octenyl)oxyacetaldehyde), phenylacetaldehyde,
Mefranal (3-methyl-5-phenyl pentanal), Triplal, Vertocitral
dimethyl tetrahydrobenzene aldehyde
(2,4-dimethyl-3-cyclohexene-1-carboxaldehyde),
2-phenylproprionaldehyde, Hydrotropaldehyde, Canthoxal,
anisylpropanal 4-methoxy-alpha-methyl benzenepropanal
(2-anisylidene propanal), Cylcemone A
(1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde), and
Precylcemone B (1-cyclohexene-1-carboxaldehyde).
[0068] Still other exemplary aldehydes include, but are not limited
to, acetaldehyde (ethanal), pentanal, valeraldehyde, amylaldehyde,
Scentenal
(octahydro-5-methoxy-4,7-Methano-1H-indene-2-carboxaldehyde),
propionaldehyde (propanal), Cyclocitral, beta-cyclocitral,
(2,6,6-trimethyl-1-cyclohexene-1-acetaldehyde), Iso Cyclocitral
(2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde), isobutyraldehyde,
butyraldehyde, isovaleraldehyde (3-methyl butyraldehyde),
methylbutyraldehyde (2-methyl butyraldehyde, 2-methyl butanal),
Dihydrocitronellal (3,7-dimethyl octan-1-al), 2-Ethylbutyraldehyde,
3-Methyl-2-butenal, 2-Methylpentanal, 2-Methyl Valeraldehyde,
Hexenal (2-hexenal, trans-2-hexenal), Heptanal, Octanal, Nonanal,
Decanal, Lauric aldehyde, Tridecanal, 2-Dodecanal,
Methylthiobutanal, Glutaraldehyde, Pentanedial, Glutaric aldehyde,
Heptenal, cis or trans-Heptenal, Undecenal (2-, 10-),
2,4-octadienal, Nonenal (2-, 6-), Decenal (2-, 4-), 2,4-hexadienal,
2,4-Decadienal, 2,6-Nonadienal, Octenal, 2,6-dimethyl 5-heptenal,
2-isopropyl-5-methyl-2-hexenal, Trifemal, beta methyl
Benzenepropanal, 2,6,6-Trimethyl-1-cyclohexene-1-acetaldehyde,
phenyl Butenal (2-phenyl 2-butenal),
2.Methyl-3(p-isopropylphenyl)-propionaldehyde,
3-(p-isopropylphenyl)-propionaldehyde, p-Tolylacetaldehyde
(4-methylphenylacetaldehyde), Anisaldehyde (p-methoxybenzene
aldehyde), Benzaldehyde, Vernaldehyde
(1-Methyl-4-(4-methylpentyl)-3-cyclohexenecarbaldehyde),
Heliotropin (piperonal) 3,4-Methylene dioxy benzaldehyde,
alpha-Amylcinnamic aldehyde, 2-pentyl-3-phenylpropenoic aldehyde,
Vanillin (4-methoxy 3-hydroxy benzaldehyde), Ethyl vanillin
(3-ethoxy 4-hydroxybenzaldehyde), Hexyl Cinnamic aldehyde, Jasmonal
H (alpha-n-hexyl-cinnamaldehyde), Floralozone,
(para-ethyl-alpha,alpha-dimethyl Hydrocinnamaldehyde), Acalea
(p-methyl-alpha-pentylcinnamaldehyde), methylcinnamaldehyde,
alpha-Methylcinnamaldehyde (2-methyl 3-pheny propenal),
alpha-hexylcinnamaldehyde (2-hexyl 3-phenyl propenal),
Salicylaldehyde (2-hydroxy benzaldehyde), 4-ethyl benzaldehyde,
Cuminaldehyde (4-isopropyl benzaldehyde), Ethoxybenzaldehyde,
2,4-dimethylbenzaldehyde, Veratraldehyde
(3,4-dimethoxybenzaldehyde), Syringaldehyde (3,5-dimethoxy
4-hydroxybenzaldehyde), Catechaldehyde (3,4-dihydroxybenzaldehyde),
Safranal (2,6,6-trimethyl-1,3-diene methanal), Myrtenal
(pin-2-ene-1-carbaldehyde), Perillaldehyde
L-4(1-methylethenyl)-1-cyclohexene-1-carboxaldehyde),
2,4-Dimethyl-3-cyclohexene carboxaldehyde, 2-Methyl-2-pentenal,
2-methylpentenal, pyruvaldehyde, formyl Tricyclodecan, Mandarin
aldehyde, Cyclemax, Pino acetaldehyde, Corps Iris, Maceal, and
Corps 4322.
[0069] In one embodiment, the malodor control component includes a
mixture of two or more volatile aldehydes selected from the group
consisting of 2-ethoxy Benzylaldehyde,
2-isopropyl-5-methyl-2-hexenal, 5-methyl Furfural,
5-methyl-thiophene-carboxaldehyde, Adoxal, p-anisaldehyde,
Benzylaldehyde, Bourgenal, Cinnamic aldehyde, Cymal, Decyl
aldehyde, Floral super, Florhydral, Helional, Lauric aldehyde,
Ligustral, Lyral, Melonal, o-anisaldehyde, Pino acetaldehyde, P.T.
Bucinal, Thiophene carboxaldehyde, trans-4-Decenal, trans trans
2,4-Nonadienal, Undecyl aldehyde, and mixtures thereof.
[0070] In some embodiments, the malodor control component includes
fast reacting volatile aldehydes. "Fast reacting volatile
aldehydes" refers to volatile aldehydes that either (1) reduce
amine odors by 20% or more in less than 40 seconds; or (2) reduce
thiol odors by 20% or more in less than 30 minutes.
[0071] In one embodiment, the malodor control component includes a
mixture of the volatile aldehydes listed in Table 1 and referred to
herein as Accord A.
TABLE-US-00001 TABLE 1 ClogP VP (torr) Material Wt. % CAS Number
Group @25.degree. C. Intreleven Aldehyde 5.000 112-45-8 3 0.060
Florhydral 10.000 125109-85-5 4 0.008 Floral Super 25.000
71077-31-1 3 0.030 Scentenal 10.000 86803-90-9 2 0.010 Cymal 25.000
103-95-7 4 0.007 o-anisaldehyde 25.000 135-02-4 1 0.032
[0072] In another embodiment, the malodor control component
includes a mixture of the volatile aldehydes listed in Table 2 and
referred to herein as Accord B.
TABLE-US-00002 TABLE 2 ClogP VP (torr) Material Wt. % CAS Number
Group @25.degree. C. Intreleven Aldehyde 2.000 112-45-8 3 0.060
Florhydral 20.000 125109-85-5 4 0.008 Floral Super 10.000
71077-31-1 3 0.030 Scentenal 5.000 86803-90-9 2 0.010 Cymal 25.000
103-95-7 4 0.007 Floralozone 10.000 67634-14-4 4 0.005 Adoxal 1.000
141-13-9 4 0.007 Methyl Nonyl 1.000 110-41-8 3 0.030 Acetaldehyde
Melonal 1.000 106-72-9 3 0.670 o-anisaldehyde 25.000 135-02-4 1
0.032
[0073] In another embodiment, the malodor control component
includes a mixture of about 71.2% volatile aldehydes, the remainder
being other an ester and an alcohol perfume raw material. This
mixture is listed in Table 3 and referred to herein as Accord
C.
TABLE-US-00003 TABLE 3 ClogP VP (torr) Material Wt. % CAS Number
Group @25.degree. C. Intreleven Aldehyde 2.000 112-45-8 3 0.060
Florhydral 10.000 125109-85-5 4 0.008 Floral Super 5.000 71077-31-1
3 0.030 Scentenal 2.000 86803-90-9 2 0.010 Cymal 15.000 103-95-7 4
0.007 Floralozone 12.000 67634-14-4 4 0.005 Adoxal 1.000 141-13-9 4
0.007 Methyl Nonyl 1.000 110-41-8 3 0.030 Acetaldehyde Melonal
1.000 106-72-9 3 0.670 Flor Acetate 11.800 5413-60-5 1 0.060
Frutene 7.000 17511-60-3 4 0.020 Helional 5.000 1205-17-0 2 0.0005
Bourgeonal 2.000 18127-01-0 4 0.004 Linalool 10.000 78-70-6 3 0.050
Benzaldehyde 0.200 100-52-7 1 1.110 o-anisaldehyde 15.000 135-02-4
1 0.320
[0074] Accords A, B, or C can be formulated in with other perfume
raw materials in an amount, for example, of about 10% by weight of
the malodor control component. Additionally, the individual
volatile aldehydes or a various combination of the volatile
aldehydes can be formulated into a malodor control component. In
certain embodiments, the volatile aldehydes may be present in an
amount up to 100%, by weight of the malodor control component,
alternatively from 1% to about 100%, alternatively from about 2% to
about 100%, alternatively from about 3% to about 100%,
alternatively about 50% to about 100%, alternatively about 70% to
about 100%, alternatively about 80% to about 100%, alternatively
from about 1% to about 20%, alternatively from about 1% to about
10%, alternatively from about 2% to about 20%, alternatively from
about 3% to about 20%, alternatively from about 4% to about 20%,
alternatively from about 5% to about 20%.
[0075] In some embodiments where volatility is not important for
neutralizing a malodor, the present invention may include
poly-aldehydes, for example, di-, tri-, tetra-aldehydes. Such
embodiments may include laundry detergents, additive, and the like
for leave-on, through the wash, and rinse-off type of
applications.
[0076] 2. Aliphatic Aldehydes
[0077] In one embodiment, the freshening composition comprises a
perfume mixture having one or more fabric-safe, non-yellowing
aliphatic aldehydes. Certain types of aldehydes that predominately
comprise a straight chain aliphatic backbone will not discolor
fabrics, unlike products that utilize types of aldehydes that
contain multiple double bonds and benzene rings. The following
table illustrates the selection of aldehydes to avoid fabric
yellowing.
TABLE-US-00004 Fadometer Test on treated Fabric (0.75 grams of
product are pipetted onto a 4 inch .times. 4 inch (10 cm .times. 10
cm) swatch which is then subjected to 5 hours of exposure to
simulated sunlight using a SUNTEST CPS+ model Fadometer supplied by
Aldehyde Solution Tested Atlas, Chicago, Illinois, USA. Control-
untreated fabric swatch No yellowing 1000 ppm amylic cinnamic
aldehyde Yellowish brown (aromatic) 1000 ppm citronellal (aromatic)
Yellowish brown 1000 ppm citral aldehyde (aliphatic) No yellowing
1000 ppm lauric aldehyde (aliphatic) No yellowing
[0078] Examples of suitable aliphatic aldehydes are R--COH where R
is saturated C.sub.7 to C.sub.22 linear and/or branched with no
more than two double bonds. Examples of suitable aliphatic
aldehydes are bourgeonal, citral, citronellyl oxyacetaldehyde,
cymal, decyl aldehyde, helional, hexyl cinnamic aldehyde, lauric
aldehyde, ligustral, lyral, melonal, methyl dihydro jasmonate,
methyl nonyl acetaldehyde, methyl phenyl carbinyl acetate, nonyl
aldehyde, octyl aldehyde, oxane, P. T. bucinal, polysantol,
rhubafuran, tripal, or mixtures thereof.
[0079] In one embodiment, the freshening composition includes at
least one aliphatic aldehyde selected from the group consisting of:
bourgeonal, citral, citronellyl oxyacetaldehyde, cymal, decyl
aldehyde, helional, hexyl cinnamic aldehyde, lauric aldehyde,
ligustral, lyral, melonal, methyl dihydro jasmonate, methyl nonyl
acetaldehyde, methyl phenyl carbinyl acetate, nonyl aldehyde,
2,6-nonadien-1-al, octyl aldehyde, oxane, P.T. bucinal, polysantol,
rhubafuran, tripal, and mixtures thereof.
[0080] In another embodiment, the freshening composition includes
at least one aliphatic aldehyde selected from the group consisting
of: burgeonal, cymal, hexyl cinnamic aldehyde, methyl dihydro
jasmonate, methyl nonyl acetaldehyde, P.T. bucinal, and mixtures
thereof.
[0081] The aliphatic aldehydes may be present in an amount from
about 0.001% to about 10%, alternatively from about 0.001% to about
5%, alternatively from about 0.01% to about 1%, alternatively from
about 0.02% to about 1%, alternatively from about 0.02% to about
0.5%, alternatively from about 0.02% to about 0.06%, alternatively
about 0.06%, by weight of the freshening composition.
[0082] In addition to aliphatic aldehydes, the freshening
composition may also include perfume materials for their scent
experience including enones, ketones, ionones including ionone
alpha, ionone beta, ionone gamma methyl, or mixtures thereof.
Suitable perfume materials are discussed in U.S. Pat. No.
5,714,137. The freshening composition may contain an effective
amount of perfume to provide the freshening fragrance when first
sprayed, some lingering fragrance, and some extra fragrance to be
released upon fabric rewetting. It may be desirable for the
aliphatic aldehydes to have virtually no negative impact on the
desired perfume character.
[0083] Certain malodor counteractants may be odoriferous and
negatively impact the overall character of the fragrance. In this
case, a perfume/malodor counteractant premix is formed such that
the perfume raw materials used are selected to neutralize any odor
of the malodor counteractants. This odor neutralized premix can
then be added to a parent perfume mixture without affecting the
character of the parent fragrance. This permits the malodor
counteractants to be used broadly with a large variety of fragrance
types.
[0084] The following are non-limiting examples of perfume
formulations that include fabric-safe malodor counteractants.
(1) Pine
TABLE-US-00005 [0085] Material Name Amount Rosemary 10.00 Spike
Lavender 10.00 Lavandin Grosso 5.00 Spruce (conf.-manh) 5.00
Camphor Gum 5.00 Melonal 0.30 Eucalyptol 15.00 Iso Menthone 15.00
Iso Bornyl Acetate 21.70 Ionone Beta 8.00 Iso E Super 5.00
100.00
(2) Ozonic
TABLE-US-00006 [0086] Material Name Amount Xi Aldehyde 8.00 2' 6
Nonadienol 10% In Dpg 5.00 Helional 13.00 Hydroxycitronellal 11.50
Calone 1951 0.50 2' 6-Nonadien-1-al/10% In Dpg 5.00 Lyral 20.00
Melonal 1.00 Iso Menthone 10.00 Floralozone 10.00 Bourgeonal 10.00
Delta Muscenone 962191 1.00 Habanolide 100% 5.00 100.00
(3) Fruity
TABLE-US-00007 [0087] Material Name Amount Fruitate 5.00 Orange
Terpenes 13.00 Ethyl Acetoacetate 3.00 2' 6 Nonadienol 10% In Dpg
1.00 Ethyl Acetate 3.00 Benzaldehyde 2.00 Prenyl Acetate 8.00
Benzyl Acetate 15.00 2' 6-Nonadien-1-al/10% In Dpg 1.00
Ethyl-2-methyl Butyrate 8.00 Amyl Acetate 3.00 Cis 3 Hexenyl
Acetate 3.00 Methyl Dihydro Jasmonate 10.00 Ligustral 5.00 Melonal
1.00 Ethyl 2 Methyl Pentanoate 8.00 Hexyl Acetate 8.00 Habanolide
100% 3.00 100.00
(4) Citrus
TABLE-US-00008 [0088] Material Name Amount Orange Terpenes 20.00
Lemon Terpenes X5 Fold 20.00 Lime Oil Cf-8-1285-1 (conf.- 10.00
berje) Grapefruit Phase C-Ref. N*12245 20.00 Italian Orange Phase
Oil 22.90 Delta Muscenone 962191 0.50 Oxane 0.30 Iso Menthone 1.00
Rhubafuran 0.30 Habanolide 100% 5.00 100.00
(5) Floral
TABLE-US-00009 [0089] Material Name Amount Spike Lavender 5.00
Rosemary 5.00 Helional 10.00 Hydroxycitronellal 10.00 Benzyl
Acetate 9.30 Lyral 20.00 Ligustral 2.00 Melonal 0.20 Eucalyptol
2.00 Iso Menthone 8.00 Bourgeonal 20.00 Undecavertol 3.00 Delta
Muscenone 962191 0.50 Habanolide 100% 5.00 100.00
[0090] In certain cases, fabrics that are laundered will have
residual brighteners deposited from detergents with which they are
washed. Therefore, it may be desirable for the aliphatic aldehydes
to be compatible with brighteners so that the freshening
composition will not discolor any fabrics with which it comes into
contact. A number of the examples above are compatible with
brighteners.
[0091] 3. Low Molecular Weight Polyols
[0092] Low molecular weight polyols with relatively high boiling
points, as compared to water, such as ethylene glycol, diethylene
glycol, triethylene glycol, propylene glycol, dipropylene glycol,
and/or glycerine may be utilized as a malodor counteractant for
improving odor neutralization of the freshening composition of the
present invention. Some polyols, e.g., dipropylene glycol, are also
useful to facilitate the solubilization of some perfume ingredients
in the composition of the present invention.
[0093] The glycol used in the freshening composition of the present
invention may be glycerine, ethylene glycol, propylene glycol,
dipropylene glycol, polyethylene glycol, propylene glycol methyl
ether, propylene glycol phenyl ether, propylene glycol methyl ether
acetate, propylene glycol n-butyl ether, dipropylene glycol n-butyl
ether, dipropylene glycol n-propyl ether, ethylene glycole phenyl
ether, diethylene glycol n-butyl ether, dipropylene glycol n-butyl
ether, diethylene glycol mono butyl ether, dipropylene glycol
methyl ether, tripropylene glycol methyl ether, tripropylene glycol
n-butyl ether, other glycol ethers, or mixtures thereof. In one
embodiment, the glycol used is ethylene glycol, propylene glycol,
or mixtures thereof. In another embodiment, the glycol used is
diethylene glycol.
[0094] Typically, the low molecular weight polyol is added to the
composition of the present invention at a level of from about 0.01%
to about 5%, by weight of the composition, alternatively from about
0.05% to about 1%, alternatively from about 0.1% to about 0.5%, by
weight of the composition. Compositions with higher concentrations
may make fabrics susceptible to soiling and/or leave unacceptable
visible stains on fabrics as the solution evaporates off of the
fabric. The weight ratio of low molecular weight polyol to the
malodor binding polymer is from about 500:1 to about 4:1,
alternatively from about 1:100 to about 25:1, alternatively from
about 1:50 to about 4:1, alternatively about 4:1.
[0095] 4. Cyclodextrin
[0096] In some embodiments, the freshening composition may include
solubilized, water-soluble, uncomplexed cyclodextrin. As used
herein, the term "cyclodextrin" includes any of the known
cyclodextrins such as unsubstituted cyclodextrins containing from
six to twelve glucose units, especially, alpha-cyclodextrin,
beta-cyclodextrin, gamma-cyclodextrin and/or their derivatives
and/or mixtures thereof. The alpha-cyclodextrin consists of six
glucose units, the beta-cyclodextrin consists of seven glucose
units, and the gamma-cyclodextrin consists of eight glucose units
arranged in a donut-shaped ring. The specific coupling and
conformation of the glucose units give the cyclodextrins a rigid,
conical molecular structure with a hollow interior of a specific
volume. The "lining" of the internal cavity is formed by hydrogen
atoms and glycosidic bridging oxygen atoms, therefore this surface
is fairly hydrophobic. The unique shape and physical-chemical
property of the cavity enable the cyclodextrin molecules to absorb
(form inclusion complexes with) organic molecules or parts of
organic molecules which can fit into the cavity. Many perfume
molecules can fit into the cavity.
[0097] Cyclodextrin molecules are described in U.S. Pat. No.
5,714,137, and U.S. Pat. No. 5,942,217. Suitable levels of
cyclodextrin are from about 0.1% to about 5%, alternatively from
about 0.2% to about 4%, alternatively from about 0.3% to about 3%,
alternatively from about 0.4% to about 2%, by weight of the
freshening composition. Freshening compositions with higher
concentrations can make fabrics susceptible to soiling and/or leave
unacceptable visible stains on fabrics as the solution evaporates
off of the fabric. The latter is especially a problem on thin,
colored, synthetic fabrics. In order to avoid or minimize the
occurrence of fabric staining, the fabric may be treated at a level
of less than about 5 mg of cyclodextrin per mg of fabric,
alternatively less than about 2 mg of cyclodextrin per mg of
fabric.
[0098] 5. Acid Catalyst
[0099] The malodor control component of the present invention may
include an effective amount of an acid catalyst to neutralize
sulfur-based malodors. It has been found that certain mild acids
have an impact on aldehyde reactivity with thiols in the liquid and
vapor phase. It has been found that the reaction between thiol and
aldehyde is a catalytic reaction that follows the mechanism of
hemiacetal and acetal formation path. When the present malodor
control component contains an acid catalyst and contacts a
sulfur-based malodor, the volatile aldehyde reacts with thiol. This
reaction may form a thiol acetal compound, thus, neutralizing the
sulfur-based odor. Without an acid catalyst, only hemi-thiol acetal
is formed.
[0100] Suitable acid catalysts have a VP, as reported by Scifinder,
in the range of about 0.001 torr to about 38 torr, measured at
25.degree. C., alternatively about 0.001 torr to about 14 torr,
alternatively from about 0.001 to about 1, alternatively from about
0.001 to about 0.020, alternatively about 0.005 to about 0.020,
alternatively about 0.010 to about 0.020.
[0101] The acid catalyst may be a weak acid. A weak acid is
characterized by an acid dissociation constant, K.sub.a, which is
an equilibrium constant for the dissociation of a weak acid; the
pKa being equal to minus the decimal logarithm of K.sub.a. The acid
catalyst may have a pKa from about 4.0 to about 6.0, alternatively
from about 4.3 and 5.7, alternatively from about 4.5 to about 5,
alternatively from about 4.7 to about 4.9. Suitable acid catalyst
include those listed in Table 4.
TABLE-US-00010 TABLE 4 VP (torr) @ Material 25.degree. C. Formic
Acid 36.5 Acetic Acid 13.9 Trimethyl Acetic Acid 0.907 Phenol
(alkaline in liquid apps yet 0.610 acidic in vapor phase) Tiglic
acid 0.152 Caprylic acid 0.0222 5-Methyl thiophene carboxylic acid
0.019 Succinic acid 0.0165 Benzoic acid 0.014 Mesitylenic acid
0.00211
[0102] Depending on the desired use of the malodor control
component, one may consider the scent character or the affect on
the scent of the malodor control component when selecting an acid
catalyst. In some embodiments of the malodor control component, it
may be desirable to select an acid catalyst that provides a neutral
to pleasant scent. Such acid catalysts may have a VP of about 0.001
torr to about 0.020 torr, measured at 25.degree. C., alternatively
about 0.005 torr to about 0.020 torr, alternatively about 0.010
torr to about 0.020 torr. Non-limiting examples of such acid
catalyst include 5-methyl thiophene carboxaldehyde with carboxylic
acid impurity, succinic acid, or benzoic acid.
[0103] The malodor control component may include about 0.05% to
about 5%, alternatively about 0.1% to about 1.0%, alternatively
about 0.1% to about 0.5%, alternatively about 0.1% to about 0.4%,
alternatively about 0.4% of an acid catalyst by weight of the
malodor control component.
[0104] In an acetic acid system, the present malodor control
component may include about 0.4% of acetic acid (50:50 TC:DPM, 0.4%
acetic acid).
TABLE-US-00011 TABLE 5 % Butanethiol Actual % acetic reduction @
Sample Formulated acid in DPM 30 min. 50:50 TC:DPM 0% Acetic Acid
0.00 12.00 50:50 TC:DPM 0.05% Acetic Acid 0.04 14.65 50:50 TC:DPM
0.1% Acetic Acid 0.10 25.66 50:50 TC:DPM 0.2% Acetic Acid 0.42
34.68 50:50 TC:DPM 0.5% Acetic Acid 1.00 24.79 50:50 TC:DPM 1.0%
Acetic Acid 2.00 7.26
[0105] The malodor control component may have a pH from about 3 to
about 8, alternatively from about 4 to about 7, alternatively from
about, alternatively from about 4 to about 6.
[0106] 6. Optional Ingredients
[0107] The malodor control component may, optionally, include odor
masking agents, and/or odor blocking agents. "Odor blocking" refers
to the ability of a compound to dull the human sense of smell.
"Odor-masking" refers to the ability of a compound to mask or hide
a malodorous compound. Odor-masking may include a compound with a
non-offensive or pleasant smell that is dosed such that it limits
the ability to sense a malodorous compound. Odor-masking may
involve the selection of compounds which coordinate with an
anticipated malodor to change the perception of the overall scent
provided by the combination of odorous compounds.
[0108] The malodor control component may also, optionally, include
perfume raw materials that solely provide a hedonic benefit (i.e.
that do not neutralize malodors yet provide a pleasant fragrance).
Suitable perfumes are disclosed in U.S. Pat. No. 6,248,135, which
is incorporated in its entirety by reference.
[0109] For example, the malodor control component may include a
mixture of volatile aldehydes for neutralizing a malodor, perfume
ionones, and a diluent. Alternatively, the malodor control
component may include 100% volatile aldehydes.
[0110] C. Buffering Agent
[0111] The freshening composition of the present invention includes
a buffering agent which may be a dibasic acid, carboxylic acid, or
a dicarboxylic acid like maleic acid. The acid may be sterically
stable, and used in this composition solely for maintaining the
desired pH. The freshening composition may have a pH from about 3
to about 8, alternatively from about 4 to about 7, alternatively
from about 5 to about 8, alternatively from about 6 to about 8,
alternatively about 6 to about 7, alternatively about 7,
alternatively about 6.5.
[0112] Carboxylic acids such as citric acid may act as metal ion
chelants and can form metallic salts with low water solubility. As
such, in some embodiments, the freshening composition is
essentially free of citric acids. The buffer can be alkaline,
acidic or neutral.
[0113] Other suitable buffering agents for freshening compositions
of this invention include biological buffering agents. Some
examples are nitrogen-containing materials, sulfonic acid buffers
like 3-(N-morpholino)propanesulfonic acid (MOPS) or
N-(2-Acetamido)-2-aminoethanesulfonic acid (ACES), which have a
near neutral 6.2 to 7.5 pKa and provide adequate buffering capacity
at a neutral pH. Other examples are amino acids such as lysine or
lower alcohol amines like mono-, di-, and tri-ethanolamine. Other
nitrogen-containing buffering agents are tri(hydroxymethyl)amino
methane (HOCH2)3CNH3 (TRIS),2-amino-2-ethyl-1,3-propanediol,
2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanol, disodium
glutamate, N-methyl diethanolamide,
2-dimethylamino-2-methylpropanol (DMAMP),
1,3-bis(methylamine)-cyclohexane, 1,3-diamino-propanol
N,N'-tetra-methyl-1,3-diamino-2-propanol,
N,N-bis(2-hydroxyethyl)glycine (bicine) and
N-tris(hydroxymethyl)methyl glycine (tricine). Mixtures of any of
the above are also acceptable.
[0114] The freshening compositions may contain at least about 0%,
alternatively at least about 0.001%, alternatively at least about
0.01%, by weight of the composition, of a buffering agent. The
composition may also contain no more than about 1%, alternatively
no more than about 0.75%, alternatively no more than about 0.5%, by
weight of the composition, of a buffering agent.
[0115] D. Solubilizer
[0116] The freshening composition of the present invention may
contain a diluent or solubilizing aid to solubilize any excess
hydrophobic organic materials, particularly any perfume materials,
and also optional ingredients (e.g., insect repelling agent,
antioxidant, etc.) which can be added to the composition, that are
not readily soluble in the composition, to form a clear solution.
Exemplary solubilizing aids include such as a no-foaming or
low-foaming surfactants, nonionic surfactants, cationic
surfactants, amphoteric surfactants, zwitterionic surfactants, and
mixtures thereof. Exemplary solubilizing aids also include
dipropylene glycol methyl ether, 3-methoxy-3-methyl-1-butanol, and
mixtures thereof.
[0117] In some embodiments, the freshening composition contains
nonionic surfactants, cationic surfactants, and mixtures thereof.
In one embodiment, the freshening composition contains hydrogenated
castor oil. One suitable hydrogenated castor oil that may be used
in the present composition is Basophor.TM., available from
BASF.
[0118] Compositions containing anionic surfactants and/or detergent
surfactants may make fabrics susceptible to soiling and/or leave
unacceptable visible stains on fabrics as the solution evaporates
off of the fabric. In some embodiments, the freshening composition
is free of anionic surfactants and/or detergent surfactants.
[0119] When the solubilizing agent is present, it is typically
present at a level of from about 0.01% to about 3%, alternatively
from about 0.05% to about 1%, alternatively from about 0.01% to
about 0.05%, by weight of the freshening composition. Freshening
compositions with higher concentrations may make fabrics
susceptible to soiling and/or leave unacceptable visible stains on
fabrics as the solution evaporates off of the fabric.
[0120] E. Antimicrobial Compounds
[0121] The freshening composition of the present invention may
include an effective amount of a compound for reducing microbes in
the air or on inanimate surfaces. Antimicrobial compounds are
effective on gram negative and gram positive bacteria and fungi
typically found on indoor surfaces that have contacted human skin
or pets such as couches, pillows, pet bedding, and carpets. Such
microbial species include Klebsiella pneumoniae, Staphylococcus
aureus, Aspergillus niger, Klebsiella pneumoniae, Steptococcus
pyogenes, Salmonella choleraesuis, Escherichia coli, Trichophyton
mentagrophytes, and Pseudomonoas aeruginosa. In some embodiments,
the antimicrobial compounds are also effective on viruses such
H1-N1, Rhinovirus, Respiratory Syncytial, Poliovirus Type 1,
Rotavirus, Influenza A, Herpes simplex types 1 & 2, Hepatitis
A, and Human Coronavirus.
[0122] Antimicrobial compounds suitable in the freshening
composition of the present invention can be any organic material
which will not cause damage to fabric appearance (e.g.,
discoloration, coloration such as yellowing, bleaching).
Water-soluble antimicrobial compounds include organic sulfur
compounds, halogenated compounds, cyclic organic nitrogen
compounds, low molecular weight aldehydes, quaternary compounds,
dehydroacetic acid, phenyl and phenoxy compounds, or mixtures
thereof.
[0123] In one embodiment, a quaternary compound is used. Examples
of commercially available quaternary compounds suitable for use in
the freshening composition is Barquat available from Lonza
Corporation; and didecyl dimethyl ammonium chloride quat under the
trade name Bardac.RTM. 2250 from Lonza Corporation.
[0124] The antimicrobial compound may be present in an amount from
about 500 ppm to about 7000 ppm, alternatively about 1000 ppm to
about 5000 ppm, alternatively about 1000 ppm to about 3000 ppm,
alternatively about 1400 ppm to about 2500 ppm, by weight of the
freshening composition.
[0125] F. Preservatives
[0126] The freshening composition of the present invention may
include a preservative. The preservative is included in the present
invention in an amount sufficient to prevent spoilage or prevent
growth of inadvertently added microorganisms for a specific period
of time, but not sufficient enough to contribute to the odor
neutralizing performance of the freshening composition. In other
words, the preservative is not being used as the antimicrobial
compound to kill microorganisms on the surface onto which the
composition is deposited in order to eliminate odors produced by
microorganisms. Instead, it is being used to prevent spoilage of
the freshening composition in order to increase the shelf-life of
the composition.
[0127] The preservative can be any organic preservative material
which will not cause damage to fabric appearance, e.g.,
discoloration, coloration, bleaching. Suitable water-soluble
preservatives include organic sulfur compounds, halogenated
compounds, cyclic organic nitrogen compounds, low molecular weight
aldehydes, parabens, propane diaol materials, isothiazolinones,
quaternary compounds, benzoates, low molecular weight alcohols,
dehydroacetic acid, phenyl and phenoxy compounds, or mixtures
thereof.
[0128] Non-limiting examples of commercially available
water-soluble preservatives for use in the present invention
include a mixture of about 77%
5-chloro-2-methyl-4-isothiazolin-3-one and about 23%
2-methyl-4-isothiazolin-3-one, a broad spectrum preservative
available as a 1.5% aqueous solution under the trade name
Kathon.RTM. CG by Rohm and Haas Co.; 5-bromo-5-nitro-1,3-dioxane,
available under the tradename Bronidox L.RTM. from Henkel;
2-bromo-2-nitropropane-1,3-diol, available under the trade name
Bronopol.RTM. from Inolex; 1,1'-hexamethylene
bis(5-(p-chlorophenyl)biguanide), commonly known as chlorhexidine,
and its salts, e.g., with acetic and digluconic acids; a 95:5
mixture of
1,3-bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione and
3-butyl-2-iodopropynyl carbamate, available under the trade name
Glydant Plus.RTM. from Lonza;
N-[1,3-bis(hydroxymethyl)2,5-dioxo-4-imidazolidinyl]-N,N'-bis(hydroxy-met-
hyl)urea, commonly known as diazolidinyl urea, available under the
trade name Germall.RTM. II from Sutton Laboratories, Inc.;
N,N''-methylenebis{N'-[1-(hydroxymethyl)-2,5-dioxo-4-imidazolidinyl]urea}-
, commonly known as imidazolidinyl urea, available, e.g., under the
trade name Abiol.RTM. from 3V-Sigma, Unicide U-13.RTM. from
Induchem, Germall 115.RTM. from Sutton Laboratories, Inc.;
polymethoxy bicyclic oxazolidine, available under the trade name
Nuosept.RTM. C from Huls America; formaldehyde; glutaraldehyde;
polyaminopropyl biguanide, available under the trade name Cosmocil
CQ.RTM. from ICI Americas, Inc., or under the trade name
Mikrokill.RTM. from Brooks, Inc; dehydroacetic acid; and
benzsiothiazolinone available under the trade name Koralone.TM.
B-119 from Rohm and Hass Corporation.
[0129] Suitable levels of preservative are from about 0.0001% to
about 0.5%, alternatively from about 0.0002% to about 0.2%,
alternatively from about 0.0003% to about 0.1%, by weight of the
freshening composition.
[0130] G. Wetting Agent
[0131] The freshening composition may include a wetting agent that
provides a low surface tension that permits the composition to
spread readily and more uniformly on hydrophobic surfaces like
polyester and nylon. It has been found that the aqueous solution,
without such a wetting agent will not spread satisfactorily. The
spreading of the composition also allows it to dry faster, so that
the treated material is ready to use sooner. Furthermore, a
composition containing a wetting agent may penetrate hydrophobic,
oily soil better for improved malodor neutralization. A composition
containing a wetting agent may also provide improved "in-wear"
electrostatic control. For concentrated compositions, the wetting
agent facilitates the dispersion of many actives such as
antimicrobial actives and perfumes in the concentrated aqueous
compositions.
[0132] Nonlimiting examples of wetting agents include block
copolymers of ethylene oxide and propylene oxide. Suitable block
polyoxyethylene-polyoxypropylene polymeric surfactants include
those based on ethylene glycol, propylene glycol, glycerol,
trimethylolpropane and ethylenediamine as the initial reactive
hydrogen compound. Polymeric compounds made from a sequential
ethoxylation and propoxylation of initial compounds with a single
reactive hydrogen atom, such as C.sub.12-18 aliphatic alcohols, are
not generally compatible with the cyclodextrin. Certain of the
block polymer surfactant compounds designated Pluronic.RTM. and
Tetronic.RTM. by the BASF-Wyandotte Corp., Wyandotte, Mich., are
readily available.
[0133] Nonlimiting examples of cyclodextrin-compatible wetting
agents of this type are described in U.S. Pat. No. 5,714,137 and
include the Silwet.RTM. surfactants available from Momentive
Performance Chemical, Albany, N.Y. Exemplary Silwet surfactants are
as follows:
TABLE-US-00012 Name Average MW L-7608 600 L-7607 1,000 L-77 600
L-7605 6,000 L-7604 4,000 L-7600 4,000 L-7657 5,000 L-7602
3,000;
and mixtures thereof.
[0134] H. Aqueous Carrier
[0135] The freshening composition of the present invention may
include an aqueous carrier. The aqueous carrier which is used may
be distilled, deionized, or tap water. Water may be present in any
amount for the composition to be an aqueous solution. In some
embodiments, water may be present in an amount of about 85% to
99.5%, alternatively about 90% to about 99.5%, alternatively about
92% to about 99.5%, alternatively about 95%, by weight of said
freshening composition. Water containing a small amount of low
molecular weight monohydric alcohols, e.g., ethanol, methanol, and
isopropanol, or polyols, such as ethylene glycol and propylene
glycol, can also be useful. However, the volatile low molecular
weight monohydric alcohols such as ethanol and/or isopropanol
should be limited since these volatile organic compounds will
contribute both to flammability problems and environmental
pollution problems. If small amounts of low molecular weight
monohydric alcohols are present in the composition of the present
invention due to the addition of these alcohols to such things as
perfumes and as stabilizers for some preservatives, the level of
monohydric alcohol may be less than about 6%, alternatively less
than about 3%, alternatively less than about 1%, by weight of the
freshening composition.
[0136] I. Other Optional Ingredients
[0137] Adjuvants can be optionally added to the freshening
composition herein for their known purposes. Such adjuvants
include, but are not limited to, water soluble metallic salts,
antistatic agents, insect and moth repelling agents, colorants,
antioxidants, and mixtures thereof.
[0138] II. Method of Making
[0139] The freshening composition can be made in any suitable
manner known in the art. All of the ingredients can simply be mixed
together. In certain embodiments, it may be desirable to make a
concentrated mixture of ingredients and dilute by adding the same
to an aqueous carrier before dispersing the composition into the
air or on an inanimate surface. In another embodiment, the malodor
binding polymer may be dispersed in one vessel containing deionized
water and ethanol, and low molecular polyols. To this vessel, then,
the buffer is added until fully dispersed and visually dissolved.
In a separate vessel, the solubilizer and perfume are mixed until
homogenous. The solution of solubilizer and perfume are then added
to the first mixing vessel, and mixed until homogenous.
[0140] III. Methods of Use
[0141] The freshening composition of the present invention can be
used by dispersing, e.g., by placing the aqueous solution into a
dispensing means, such as a spray dispenser and spraying an
effective amount into the air or onto the desired surface or
article. An effective amount as defined herein means an amount
sufficient to neutralize malodor to the point that it is not
discernible by the human sense of smell yet not so much as to
saturate or create a pool of liquid on an article or surface and so
that, when dry, there is no visual deposit readily discernible.
Dispersing can be achieved by using a spray device, a roller, a
pad, etc.
[0142] The present invention encompasses the method of dispersing
an effective amount of the composition for reducing malodor onto
household surfaces. The household surfaces are selected from the
group consisting of countertops, cabinets, walls, floors, bathroom
surfaces, and kitchen surfaces.
[0143] The present invention encompasses the method of dispersing a
mist of an effective amount of the composition for reducing malodor
onto fabric and/or fabric articles. The fabric and/or fabric
articles include, but are not limited to, clothes, curtains,
drapes, upholstered furniture, carpeting, bed linens, bath linens,
tablecloths, sleeping bags, tents, car interior, e.g., car carpet,
fabric car seats, etc.
[0144] The present invention encompasses the method of dispersing a
mist of an effective amount of the composition for reducing malodor
impression onto and into shoes wherein the shoes are not sprayed to
saturation.
[0145] The present invention encompasses the method of dispersing a
mist of an effective amount of the composition for reducing malodor
impression onto shower curtains.
[0146] The present invention relates to the method of dispersing a
mist of an effective amount of the composition for reducing malodor
impression onto and/or into garbage cans and/or recycling bins.
[0147] The present invention relates to the method of dispersing a
mist of an effective amount of the composition for reducing malodor
impression into the air to neutralize malodor.
[0148] The present invention relates to the method of dispersing a
mist of an effective amount of the composition for reducing malodor
impression into and/or onto major household appliances including,
but not limited to, refrigerators, freezers, washing machines,
automatic dryers, ovens, microwave ovens, dishwashers, etc., to
neutralize malodor.
[0149] The present invention relates to the method of dispersing a
mist of an effective amount of the composition for reducing malodor
impression onto cat litter, pet bedding and pet houses to
neutralize malodor.
[0150] The present invention relates to the method of dispersing a
mist of an effective amount of the composition for reducing malodor
impression onto household pets to neutralize malodor.
EXAMPLES
Malodor Reduction
[0151] Table 6 show non-limiting examples of freshening
compositions according to the present invention.
TABLE-US-00013 TABLE 6 V I II III IV (Control) VI VII VIII Lupasol
WF 0.070 0.070 0.015 0.035 0 0.035 0.0525 0.07 CAS 9002-98-6
Diethylene 0.175 0.175 0.070 0.175 0.175 0.175 0.170 0.175 Glycol
Perfume mixture 0.2102 0.4880 0.020 0.236 0.655 0.655 0.655 0.655
comprising (0% (0.012 (0.012 (0.012 (0.012 aliphatic aldehydes)
aldehydes) aldehydes) aldehydes) aldehydes) aldehydes Hydroxypropyl
0.630 0.630 0.630 0 0.630 0.630 0.630 0.630 Beta CD Basophor ELH 0
0.050 0.050 0.050 0.050 0.050 0.050 0.050 60 Uniquat 2250 0 0.060 0
0.060 0.060 0.060 0.060 0.060 Bardac 2250J 0.139 0.100 0 0 0 0 0
Silwet L-7600 0.100 0.100 0.175 0.100 0.100 0.100 0.100 0.100
Citric Acid 0.045 0.015 0.015 0.015 0.015 0.015 0.15 0.015 Maleic
Acid 0 0.050 0.060 0.050 0.050 0.050 0.050 0.050 CAS 110-16-7 ACES
0.100 0 0 0 0 0 0 0 Sodium 0 0 0 0.020 0.020 0.020 0.020 0.020
Hydroxide Koralone B-119 0 0.0150 0 0.015 0.015 0.015 0.015 0.015
Ethanol 3.000 3.000 3.000 3.000 3.000 3.000 3.000 3.000 Deionized
95.571 95.347 95.865 96.264 95.318 95.180 95.095 95.148 Water Total
100 100 100 100 100
[0152] Formulations VI, VII, and VIII in Table 6 are prepared and
compared to Control Formulation V, a composition containing no
malodor binding polymer, for their effect on malodor. FIG. 1 shows
that when including a malodor binding polymer in a freshening
composition in accordance with the present invention, aldehydic
malodor evaporating off the treated fabric decreases.
[0153] Fabric samples are infused with the malodor of interest. For
grease infusion, place 8 ounces of grease in a Presto.TM. electric
skillet and cover with the skillet lid. Place the skillet in a 30
gallon metal garbage can. Run the electric cord from the skillet
through a 1.5 inch hole in the garbage can. Heat the skillet to
121.degree. C. and allow it to equilibrate for 15 minutes. Remove
the lid. Suspend 8 inch by 8 inch fabric swatches from the metal
clips on a carousel in the garbage can lid. Measured from the
bottom of the swatches, the distance to the top of the skillet is 8
inches. Place lid on garbage can and manually turn the carousel 15
rotations per minute for a period of 40 minutes. After infusion,
spray the swatches with the respective freshening compositions that
are to be tested. The spray for each swatch consists of two full
strokes of the trigger sprayer bottle. The bottle is held 6 inches
away from the fabric and the spray is centered on the fabric.
[0154] Immediately after treatment, cut each swatch in half, roll,
and place each into a 125 mL headspace vial. Seal the vials. Allow
the vials to equilibrate for at least 2 hours at 100.degree. C. and
then analyze by sampling each vial using a PDMS SPME fiber and
analyze by GC/MS. Malodor components, previously identified, are
then tracked through all the samples. Data is compiled of total
area count of the cumulative area counts of the individual
peaks.
Microbe Reduction
[0155] Table 7 show non-limiting examples of freshening
compositions according to the present invention.
TABLE-US-00014 TABLE 7 IX (Control) X Lupasol WF 0 0.07 CAS
9002-98-6 Diethylene Glycol 0.25 0.25 Perfume mixture 0.02 0.02
comprising aliphatic (0.002 aldehydes) (0.002 aldehydes) aldehydes
Hydroxypropyl Beta CD 0.63 0.63 Basophor ELH 60 0.15 0.15 Uniquat
2250 0 0 Bardac 2250J 0.5 0.5 Silwet L-7600 0.1 0.1 Citric Acid 0 0
Maleic Acid 0 0 CAS 110-16-7 ACES 0.1 0.1 Sodium Hydroxide 0.006
0.006 Koralone B-119 0 0 Ethanol 3.000 3.000 Deionized Water 95.244
95.174 Total 100 100
[0156] Formulation IX, the control formulation containing no
malodor binding polymer, and Formulation X are compared for their
effect on microbe reduction. FIG. 2 shows the results of
formulations with and without PEIs when tested for non-residual
fabric sanitizer efficacy against Staphylococcus aureus (ATCC
6538), Aspergillus niger (ATCC 6275), Proteus mirabilis (ATCC 7002)
and Pseudomonas aeruginosa (ATCC 15442).
[0157] Formulation efficacy was assessed by employing a North
American Bactericidal Fabric Spray Test Method that is a
quantitative modification of the AOAC Germicidal Spray Products
Test method (961.02). This method is a recognized test standard in
accordance to U.S. EPA Pesticide Assessment Guidelines Subdivision
G, Series 91-52(b)(1). The referenced AOAC method was applied to
fabric surfaces. Fabric swatches (1.5 inch, 100% blue oxford
cotton) as can be obtained from Testfabrics Inc. were treated with
2 fully depressed sprays of trigger sprayer bottle containing the
respective formulation. A contact time between 10 to 30 minutes at
ambient temperature was chosen as a conservative time estimate for
sprayed fabric surfaces, as provided in Subdivision G, Series 91-1
(b) (4) (i). Any excess liquid is drained off and then transferred
to a jar containing 20 ml neutralizer and/or growth promoting
broth. The jar is mixed by vortexing, followed by sonication in a
Branson Bransonic Ultrasonic Sonicator for 5 minutes. Within 30
minutes of neutralization, the jar is mixed for 2-3 seconds on a
vortex type mixer and serially diluted. All the samples were
incubated (48.+-.4 hours) under the appropriate conditions and
monitored for growth or no growth. Samples are plated and counted
to determine mean log 10 reduction.
Effect of Volatile Aldehydes on Amine-Based and Sulfur-Based
Malodors
[0158] Malodor standards are prepared by pipeting 1 mL of
butylamine (amine-based malodor) and butanethiol (sulfur-based
malodor) into a 1.2 liter gas sampling bag. The bag is then filled
to volume with nitrogen and allowed to sit for at least 12 hours to
equilibrate.
[0159] A 1 .mu.L sample of each volatile aldehyde listed in Table 6
and each Accord (A, B, and C) listed in Tables 1 to 3 is pipeted
into individual 10 mL silanized headspace vials. The vials are
sealed and allowed to equilibrate for at least 12 hours. Repeat 4
times for each sample (2 for butylamine analysis and 2 for
butanethiol analysis).
[0160] After the equilibration period, 1.5 mL of the target malodor
standard is injected into each vial containing a volatile aldehyde
or Accord sample. For thiol analysis, the samples are held at room
temperature for 30 minutes prior to injection into the system. A 1
mL headspace syringe is used to inject 250 .mu.L of each sample
into the system for the thiol samples. For amine analysis, the
samples are injected immediately into the system after the malodor
is introduced. A 1 mL headspace syringe is used to inject 500 .mu.L
of each sample into the system for the amine samples. A GC pillow
is used for the amine analysis to shorten the run times. Samples
are then analyzed using a GC/MS with a DB-5, 20 m, 1 .mu.m film
thickness column with an MPS-2 autosampler equipment with static
headspace function. Data is analyzed by ion extraction on each
total ion current current (56 for thiol-30 for amine) and the area
is used to calculate the percent reduction from the malodor
standard for each sample.
[0161] Table 8 shows the effect of certain volatile aldehydes on
neutralizing amine-based and sulfur based malodors at 40 seconds
and 30 minutes, respectively.
TABLE-US-00015 TABLE 8 At least 20% At least 20% butylamine
butanethiol reduction at 40 reduction at 30 Perfume Raw Material
(R--CHO) seconds? minutes? 2,4,5 Trimethoxy Benzaldehyde No No
2,4,6-Trimethoxy-benzylaldehyde No No 2-ethoxy benzylaldehyde Yes
Yes 2-isopropyl-5-methyl-2-hexenal Yes Yes
2-methyl-3-(2-furyl)-propenal No No 3,4,5 Trimethoxy Benzaldehyde
No No 3,4-Trimethoxy-benzylaldehyde No No 4-tertbutyl
benzylaldehyde Yes No 5-methyl furfural Yes Yes
5-methyl-thiophene-carboxaldehyde No Yes Adoxal Yes No Amyl
cinnamic aldehyde No No Benzylaldehyde Yes No Bourgenal No Yes
Cinnamic aldehyde Yes Yes Citronelyl Oxyacetaldehyde No No Cymal
Yes No Decyl aldehyde Yes No Floral Super Yes Yes Florhydral Yes
Yes Floralozone No No Helional Yes No Hydroxycitronellal No No
Lauric aldehyde Yes No Ligustral Yes No Lyral Yes No Melonal Yes No
Methyl nonyl acetaldehyde No No o-anisaldehyde Yes Yes
p-anisaldehyde Yes No Pino acetaldehyde Yes Yes P.T. Bucinal Yes No
Thiophene Carboxaldehyde Yes No Trans-4-decenal Yes Yes Trans Trans
2,4-Nonadienal Yes No Undecyl aldehyde Yes No
[0162] Table 9 shows the percent reduction of butylamine and
butaniethiol at 40 seconds and 30 minutes, respectively, for
Accords A, B, and C.
TABLE-US-00016 TABLE 9 % reduction % reduction of butylamine of
butanethiol Accord at 40 sec. at 30 min. Accord A 76.58 25.22
Accord B 51.54 35.38 Accord C 65.34 24.98
Sensory Test--Effect of Volatile Aldehydes on a Sulfur-Based
Malodor
[0163] Place Presto.TM. skillet into fume hood and turn on to
250.degree. F. Place 80 grams of Crisco.RTM. oil into skillet and
cover with skillet lid. Allow 10 minutes for equilibration. Remove
skillet lid and check oil temperature with thermometer. Place 50
grams of chopped, commercially prepared garlic in water into
skillet. Cover skillet with lid. Cook for 2.5 minutes or until
garlic is translucent, with a portion staring to turn brown but not
burn. Remove garlic from the skillet. Place 5 grams of garlic in
each of 4 Petri dishes. Place covers on each Petri dish.
[0164] Place each covered Petri dish into individual test chambers.
Each test chamber is 39.25 inches wide, by 25 inches deep, by 21.5
inches high with a volume of 12.2 cubic feet (0.34 cubic meters).
The test chamber can be purchased from Electro-Tech Systems,
Glenside, Pa. Each test chamber is equipped with a fan (Newark
catalog #701(9932, 115 VAC, 90CFM) purchased from Newark
Electronics, Chicago, Ill.
[0165] Remove the lids of the Petri dishes to expose the malodor
for a dwell time sufficient to provide an initial odor intensity
grade of 70-80 (about 1 minute). Once the initial odor intensity
grade has been reached in a test chamber, remove the Petri dish
from the test chamber.
[0166] Next, 3 Noticeables.RTM. air freshening devices, marketed by
P&G, are each filled with the Control composition shown in
Table 10.
TABLE-US-00017 TABLE 10 Material Name Wt % Benzaldehyde 0.150
Floralozone 0.097 Helional 1.455 Hydroxycitronellal 3.880 Ligustral
Or Triplal 1.028 Esters 12.950 Ethers 50.190 Ketones 3.010 Lactones
0.490 Alcohols 21.610 Terpenes 5.140
The devices are set to the low intensity position and plugged into
3 of the 4 test chambers. All doors on chamber are closed.
[0167] At 5, 15, 20, 30, 45, and 60 minutes, trained evaluators
open each chamber, smell the chamber for malodor intensity, and
assign a malodor score, based on the scale in Table 11. The chamber
door is closed but not locked between sequential evaluators. The
scores are tabulated and the average score for each time interval
is recorded.
TABLE-US-00018 TABLE 11 Expert Sensory Grader Malodor Evaluation
Scale Score Description corresponding to Score 0 No malodor present
10 Very slight malodor - "I think there is a malodor present" 20
Slight malodor - "I detect something but cannot identify specific
malodor 25 Slight malodor 50 Moderate 75 Strong Malodor 100
Extremely Strong Malodor
[0168] The above protocol is repeated using Prototype I shown in
Table 12 (instead of Control composition) in the 3 Noticeables air
freshening devices.
TABLE-US-00019 TABLE 12 Material Name Wt. % Benzaldehyde 0.135
Floralozone 0.087 Helional 1.310 Hydroxycitronellal 3.492 Ligustral
Or Triplal 0.925 o-anisaldehyde 2.500 Intreleven Aldehyde 0.500
Florhydral 1.000 Floral Super 2.500 Scentenal 1.000 Cymal 2.500
Esters 11.662 Ethers 45.171 ketones 2.705 lactones 0.437 Alcohols
19.446 Terpenes 4.632
[0169] The above protocol is repeated using Prototype 2 shown in
Table 13 in the 3 Noticeables.RTM. air freshening devices.
TABLE-US-00020 TABLE 13 Material Name Wt. % Benzaldehyde 0.135
Floralozone 0.087 Helional 1.310 Hydroxycitronellal 3.492 Ligustral
Or Triplal 0.925 o-anisaldehyde 2.250 Intreleven Aldehyde 0.450
Florhydral 0.900 Floral Super 2.250 Scentenal 0.900 Cymal 2.250
5-Methyl Thiophene Carboxaldehyde 1.000 Esters 11.662 Ethers 45.171
Ketones 2.705 Lactones 0.437 Alcohols 19.446 Terpenes 4.632
[0170] FIG. 3 shows that the formulation having 10% of the malodor
control composition of the present invention reduces the garlic
malodor more than the Control composition that lacks such malodor
control composition.
Sensory Test--Effect of Volatile Aldehydes on an Amine-Based
Malodor
[0171] Separate fresh ocean perch fillets from skin and add to a
Magic Bullet.TM. food chopper. Fish meat is chopped for 35-40
seconds. 25 grams of chopped fish is weighed and fashioned into a
patty suitable to fit into a 60.times.15 mm Petri dish. Repeat 3
more times so there is one fish patty in each of 4 Petri dishes.
Add 40 g of Crisco.RTM. oil to Presto.TM. skillet. Place lid on
skillet and turn on to 350.degree. F. Allow 10 minutes for
equilibration. Remove lid. Cut a slit in the middle of each patty,
place 1 patty into skillet, and begin frying. Replace lid. After
2.5 minutes, flip fish patty and fry an additional 2.5 minutes.
Remove fish patty from skillet and blot briefly onto a paper towel
for 10 seconds. Fry the remaining 3 patties in the same manner.
Place each fish patty into a 60.times.15 mm Petri dish and cover
with a lid.
[0172] Introduce each Petri dish containing a fish patty into
individual test chambers. The specifications of the test chamber
are the same as those in the above sulfur-based (i.e. garlic)
malodor test. Remove the lids to expose the malodor for a dwell
time sufficient for providing an initial odor intensity grade of
70-80 (about 1 minute). Once the initial odor intensity grade has
been reached in a test chamber, remove the Petri dish from the test
chamber.
[0173] Next, 3 Noticeables.RTM. air freshening devices, marketed by
P&G, are each filled with the Control composition outlined in
Table 10. The devices are set to the low intensity position and
plugged into 3 of the 4 test chambers. All doors on chamber are
closed.
[0174] At 5, 15, 20, 30, 45, and 60 minutes, trained evaluators
open each chamber, smell the chamber for malodor intensity, and
assign a malodor score, based on the scale in Table 9. The chamber
door is closed but not locked between sequential evaluators. The
scores are tabulated and the average score for each time interval
is recorded.
[0175] The above protocol is repeated using Prototype I shown in
Table 10 (instead of Control composition) in the 3 Noticeables.RTM.
air freshening devices. The above protocol is also repeated using
Prototype 2 shown in Table 11 in the 3 Noticeables.RTM. air
freshening devices.
[0176] FIG. 4 shows that the formulation having 10% of the malodor
control composition of the present invention reduces the fish
malodor more than the Control that lacks such malodor control
composition.
Effect of Acid Catalysts on Sulfur-Based Malodors
[0177] Malodor standards are prepared by pipeting 1 mL of
butanethiol (sulfur-based malodor) into a 1.2 liter gas sampling
bag. The bag is then filled to volume with nitrogen and allowed to
sit for at least 12 hours to equilibrate.
[0178] A 1 .mu.L aliquot of each of the following samples are
pipeted into individual 10 mL silanized headspace vials in
duplicate. The following samples were analyzed: Thiophene
carboxyaldehyde as a control, and a 50/50 mixture of Thiophene
Carboxaldehyde and each of the following acid catalysts, at 0.04%,
at 0.10%, at 0.43% in DPM, at 1.02% in DPM, and at 2.04% in DPM, is
pipeted into individual 10 mL silanized headspace vials: phenol,
mesitylenic acid, caprylic acid, succinic acid, pivalic acid,
tiglic acid, and benzoic acid. The vials are sealed and allowed to
equilibrate for at least 12 hours.
[0179] After the equilibration period, 1.5 mL of the target malodor
standard is injected into each vial containing a sample. The
samples are held at room temperature for 30 minutes prior to
injection. Samples are then analyzed using a GC/MS with a DB-5, 20
m, 1 .mu.m film thickness column with an MPS-2 autosampler
utilizing static headspace function. A 1 mL headspace syringe is
used to inject 250 .mu.L of each sample into the system. As with
the samples, a repetition of at least 2 of the malodor standard is
run according to the respective method. Data is analyzed by ion
extraction on each total ion current current (56 for thiol), and
the area is used to calculate the % reduction from the malodor
standard for each acid catalyst sample.
[0180] FIG. 5 demonstrates that low vapor pressure acid catalysts
provide up to 3 times better reduction of sulfur-based malodors in
comparison to the control.
[0181] All percentages stated herein are by weight unless otherwise
specified. It should be understood that every maximum numerical
limitation given throughout this specification will include every
lower numerical limitation, as if such lower numerical limitations
were expressly written herein. Every minimum numerical limitation
given throughout this specification will include every higher
numerical limitation, as if such higher numerical limitations were
expressly written herein. Every numerical range given throughout
this specification will include every narrower numerical range that
falls within such broader numerical range, as if such narrower
numerical ranges were all expressly written herein.
[0182] The dimensions and values disclosed herein are not to be
understood as being strictly limited to the exact numerical values
recited. Instead, unless otherwise specified, each such dimension
is intended to mean both the recited value and a functionally
equivalent range surrounding that value. For example, a dimension
disclosed as "40 mm" is intended to mean "about 40 mm."
[0183] Every document cited herein, including any cross referenced
or related patent or application, is hereby incorporated herein by
reference in its entirety unless expressly excluded or otherwise
limited. The citation of any document is not an admission that it
is prior art with respect to any invention disclosed or claimed
herein or that it alone, or in any combination with any other
reference or references, teaches, suggests or discloses any such
invention. Further, to the extent that any meaning or definition of
a term in this document conflicts with any meaning or definition of
the same term in a document incorporated by reference, the meaning
or definition assigned to that term in this document shall
govern.
[0184] While particular embodiments of the present invention have
been illustrated and described, it would be obvious to those
skilled in the art that various other changes and modifications can
be made without departing from the spirit and scope of the
invention. It is therefore intended to cover in the appended claims
all such changes and modifications that are within the scope of
this invention.
* * * * *