U.S. patent application number 12/969724 was filed with the patent office on 2011-06-23 for laundry detergent composition having a malodor control component and methods of laundering fabrics.
Invention is credited to Steven Anthony Horenziak, Rhonda Jean Jackson, Zaiyou Liu, Michael- Vincent Nario Malanyaon, Jason John Olchovy, Christine Marie Readnour, Ricky Ah-Man WOO.
Application Number | 20110146001 12/969724 |
Document ID | / |
Family ID | 43499978 |
Filed Date | 2011-06-23 |
United States Patent
Application |
20110146001 |
Kind Code |
A1 |
WOO; Ricky Ah-Man ; et
al. |
June 23, 2011 |
Laundry Detergent Composition Having A Malodor Control Component
And Methods Of Laundering Fabrics
Abstract
A detergent laundry composition comprising a malodor control
component having at least one volatile aldehyde and an acid
catalyst, and methods of laundry detergents are provided.
Inventors: |
WOO; Ricky Ah-Man;
(Hamilton, OH) ; Horenziak; Steven Anthony;
(Cincinnati, OH) ; Jackson; Rhonda Jean;
(Cincinnati, OH) ; Liu; Zaiyou; (West Chester,
OH) ; Malanyaon; Michael- Vincent Nario; (Indian
Springs, OH) ; Olchovy; Jason John; (West Chester,
OH) ; Readnour; Christine Marie; (Fort Mitchell,
KY) |
Family ID: |
43499978 |
Appl. No.: |
12/969724 |
Filed: |
December 16, 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: |
8/137 ; 510/355;
510/360 |
Current CPC
Class: |
C11D 3/50 20130101; A61L
9/01 20130101; C11D 3/3481 20130101; C11D 3/386 20130101; C11D 1/00
20130101; C11D 3/0068 20130101; C11D 3/2096 20130101; C11D 3/2075
20130101; C11D 3/2072 20130101; C11D 3/373 20130101; C11D 3/38663
20130101; C11D 1/83 20130101; C11D 3/2079 20130101; A47L 15/0005
20130101; C11D 3/33 20130101 |
Class at
Publication: |
8/137 ; 510/355;
510/360 |
International
Class: |
D06L 1/20 20060101
D06L001/20; C11D 3/60 20060101 C11D003/60; D06L 1/16 20060101
D06L001/16 |
Claims
1. A detergent laundry composition comprising: (a) a detersive
surfactant comprising anionic detersive surfactant and non-ionic
surfactant, wherein the weight ratio of anionic detersive
surfactant to non-ionic detersive surfactant is greater than 1:1;
and optionally wherein the anionic detersive surfactant has a
hydrophilic index (HI.sub.C) of from 8.0 to 9.1; (b) surfactancy
boosting polymer; (c) from 0 wt % to 5 wt % fatty acid; (d)
silicone suds suppressor; (e) structurant; (f) enzymes; and (g)
non-boron enzyme stabilizer; (h) a malodor control component
comprising an effective amount 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; wherein the
electrolytic strength of the composition at a concentration of 1
g/l in de-ionized water and at a temperature of 25.degree. C. in
mScm.sup.-1 is less than 200 mScm.sup.-1.
2. The composition 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.
3. The composition of claim 1 wherein said two or more volatile
aldehydes comprise flor super and o-anisaldehyde.
4. The composition of claim 1 wherein said two or more volatile
aldehydes have a VP from about 0.001 torr to about 0.100 torr.
5. The composition of claim 1 wherein said two or more volatile
aldehydes comprise about 25% of quad I volatile aldehydes, by
weight of said malodor control component.
6. The composition of claim 1 wherein said mixture of two or more
volatile aldehydes comprise about 10% of quad II volatile
aldehydes, by weight of said malodor control component.
7. The composition of claim 1 wherein said mixture of two or more
volatile aldehydes comprise from about 10% to about 30% of quad III
volatile aldehydes, by weight of said malodor control
component.
8. The composition of claim 1 wherein said mixture of two or more
volatile aldehydes comprise from about 35% to about 60% of quad IV
volatile aldehydes, by weight of said malodor control
component.
9. The composition of claim 1 wherein said two or more volatile
aldehydes is selected from the group consisting of: Accord A,
Accord B, Accord C, and mixtures thereof.
10. The composition of claim 1 wherein said two or more volatile
aldehydes comprise about 1% to about 10% of Accord A, by weight of
said malodor control component.
11. The composition of claim 1 wherein said composition has a pH of
above about 2.
12. The composition of claim 1 wherein said two or more volatile
aldehydes comprise three or more volatile aldehydes having a VP of
about 0.001 torr to about 0.100 torr.
13. The composition of claim 1 wherein said two or more volatile
aldehydes are present in an amount from about 0.015% to about 1%,
by weight of said detergent laundry composition.
14. The composition of claim 1 wherein said malodor control
component further comprises an acid catalyst having a vapor
pressure of about 0.01 to about 13 at 25.degree. C.
15. The composition of claim 1 wherein said composition further
comprises uncomplexed cyclodextrin.
16. The composition of claim 1 wherein said composition further
comprises a water-soluble metallic salt selected from the group
consisting of: zinc salts, copper salts, and mixtures thereof.
17. A detergent laundry composition comprising: (a) detersive
surfactant comprising anionic detersive surfactant and non-ionic
surfactant, wherein the weight ratio of anionic detersive
surfactant to non-ionic detersive surfactant is greater than 1:1;
(b) surfactancy boosting polymer; (c) from 0 wt % to 10 wt % fatty
acid; (d) silicone suds suppressor; (e) structurant; (f) enzyme;
and (g) nil-boron enzyme stabilizer; (h) a malodor control
component comprising: (i) at least one volatile aldehyde; and (ii)
an acid catalyst having a vapor pressure of about 0.01 to about 13
at 25.degree. C.; wherein the electrolytic strength of the
composition at a concentration of 1 g/l in de-ionized water and at
a temperature of 25.degree. C. in mScm.sup.-1 is less than 200
mScm.sup.-1.
18. The composition of claim 17 wherein said at least one volatile
aldehyde has a VP of about 0.001 to about 50 torr.
19. The composition of claim 17 wherein said at least one volatile
aldehyde has a VP of about 0.001 torr to about 15 torr.
20. The composition of claim 17 wherein said at least one volatile
aldehyde is 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.
21. The composition of claim 17 wherein said at least one volatile
aldehyde is selected from the group consisting of flor super,
o-anisaldehyde, and mixtures thereof.
22. The composition of claim 17 wherein said at least one volatile
aldehyde is present in an amount from about 1% to about 10%, by
weight of said malodor control component.
23. The composition of claim 17 wherein said at least one volatile
aldehyde is present in an amount from about 0.015% to about 1%, by
weight of said detergent laundry composition.
24. The composition of claim 17 wherein said at least one volatile
aldehyde comprises a mixture of volatile aldehydes selected from
the group consisting of Accord A, Accord B, Accord C, and mixtures
thereof.
25. The composition of claim 17 wherein said at least one volatile
aldehyde is present in an amount from about 1% to about 5%, by
weight of said malodor control component, and said acid catalyst is
present in an amount of about 0.4% to about 1.5%, by weight of said
malodor control component.
26. The composition of claim 17 wherein said acid catalyst is
present in an amount from about 0.1% to about 0.4%, by weight of
said malodor control composition.
27. The composition of claim 17 wherein said acid catalyst has a
vapor pressure of about 0.01 to about 2 torr at 25.degree. C.
28. The composition of claim 17 wherein said acid catalyst is a
carboxylic acid.
29. The composition of claim 17 wherein said acid catalyst is
5-methyl thiophene carboxylic acid.
30. A method of laundering a fabric, comprising the steps of: (a)
applying the detergent laundry composition according to claim 1
onto said fabric or said object; (b) leaving said composition on
said fabric to act; optionally wiping said fabric or object and/or
providing mechanical agitation, and then rinsing said fabric.
Description
CROSS REFERENCE 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 No. 61/287,383, filed Dec. 17, 2009.
FIELD OF THE INVENTION
[0002] The present invention relates to detergent laundry
compositions having a malodor control component, and methods of
laundering detergents.
BACKGROUND OF THE INVENTION
[0003] Consumers of laundry detergent products desire not only
clean clothes from their laundry products, but also fresh clothes
that do not have a malodor. They especially desire excellent
freshness the first time they wear or use a fabric after it has
been laundered. Typically, detergent manufactures have developed
sophisticated perfume technology to achieve this improved
freshness.
[0004] However, not all odors are effectively controlled by
products on the market because amine-based malodors such as fish
and urine malodors, and sulfur-based malodors such as garlic,
onion, foot, and fecal malodors are difficult to combat. Further,
the time required for a product to noticeably combat malodors may
create consumer doubt as to a product's efficacy on malodors. For
example, the consumer may finish laundering a fabric and leave the
area before the product begins to noticeably reduce the
malodor.
[0005] The difficulty in overcoming a broad range of malodors has
spawned a diverse assortment of products to neutralize, mask, or
contain the malodors. There remains a need for a detergent laundry
composition that quickly neutralizes and is effective on a broad
range of malodors, including amine-based and sulfur-based malodors,
while not overpowering malodors with an overwhelming perfume.
SUMMARY OF THE INVENTION
[0006] The present invention relates to a laundry detergent
composition as defined by claim 1.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 is a graph showing butanethiol reduction by thiophene
carboxaldehyde in combination with various acid catalysts.
DETAILED DESCRIPTION OF THE INVENTION
[0008] The present invention relates to a laundry detergent
composition for laundering fabrics and reducing malodors found
thereon. The present invention also relates to methods of
laundering fabrics.
I. Detergent Laundry Composition
[0009] The composition can be any form, for example a liquid, gel
form, solid, or any combination thereof. The composition may be in
any unit dose form, for example a pouch.
[0010] Typically, the composition is a fully formulated laundry
detergent composition, not a portion thereof such as a spray-dried
or agglomerated particle that only forms part of the laundry
detergent composition. However, it is within the scope of the
present invention for an additional rinse additive composition
(e.g. fabric conditioner or enhancer), or a main wash additive
composition (e.g. bleach additive) to also be used in combination
with the laundry detergent composition during the method of the
present invention. Although, it may be preferred for no bleach
additive composition is used in combination with the laundry
detergent composition during the method of the present
invention.
[0011] The composition typically comprises detergent ingredients.
Suitable detergent ingredients include: detersive surfactants
including anionic detersive surfactants, non-ionic detersive
surfactants, cationic detersive surfactants, zwitterionic detersive
surfactants, amphoteric detersive surfactants, and any combination
thereof; polymers including carboxylate polymers, polyethylene
glycol polymers, polyester soil release polymers such as
terephthalate polymers, amine polymers, cellulosic polymers, dye
transfer inhibition polymers, dye lock polymers such as a
condensation oligomer produced by condensation of imidazole and
epichlorhydrin, optionally in ratio of 1:4:1, hexamethylenediamine
derivative polymers, and any combination thereof; builders
including zeolites, phosphates, citrate, and any combination
thereof; buffers and alkalinity sources including carbonate salts
and/or silicate salts; fillers including sulphate salts and
bio-filler materials; bleach including bleach activators, sources
of available oxygen, pre-formed peracids, bleach catalysts,
reducing bleach, and any combination thereof; chelants;
photobleach; hueing agents; brighteners; enzymes including
proteases, amylases, cellulases, lipases, xylogucanases, pectate
lyases, mannanases, bleaching enzymes, cutinases, and any
combination thereof; fabric softeners including clay, silicones,
quaternary ammonium fabric-softening agents, and any combination
thereof; flocculants such as polyethylene oxide; perfume including
starch encapsulated perfume accords, perfume microcapsules, perfume
loaded zeolites, schif base reaction products of ketone perfume raw
materials and polyamines, blooming perfumes, and any combination
thereof; aesthetics including soap rings, lamellar aesthetic
particles, geltin beads, carbonate and/or sulphate salt speckles,
coloured clay, and any combination thereof: and any combination
thereof.
[0012] Solid particulate laundry detergent composition: In the case
of a solid laundry detergent composition, the composition may
comprises a plurality of chemically different particles, such as
spray-dried base detergent particles and/or agglomerated base
detergent particles and/or extruded base detergent particles, in
combination with one or more, typically two or more, or three or
more, or four or more, or five or more, or six or more, or even ten
or more particles selected from: surfactant particles, including
surfactant agglomerates, surfactant extrudates, surfactant needles,
surfactant noodles, surfactant flakes; polymer particles such as
cellulosic polymer particles, polyester particles, polyamine
particles, terephthalate polymer particles, polyethylene glycol
polymer particles; builder particles, such as sodium carbonate and
sodium silicate co-builder particles, phosphate particles, zeolite
particles, silicate salt particles, carbonate salt particles;
filler particles such as sulphate salt particles; dye transfer
inhibitor particles; dye fixative particles; bleach particles, such
as percarbonate particles, especially coated percarbonate
particles, such as percarbonate coated with carbonate salt,
sulphate salt, silicate salt, borosilicate salt, or any combination
thereof, perborate particles, bleach catalyst particles such as
transition metal bleach catalyst particles, or oxaziridinium-based
bleach catalyst particles, pre-formed peracid particles, especially
coated pre-formed peracid particles, and co-bleach particles of
bleach activator, source of hydrogen peroxide and optionally bleach
catalyst; bleach activator particles such as oxybenzene sulphonate
bleach activator particles and tetra acetyl ethylene diamine bleach
activator particles; chelant particles such as chelant
agglomerates; hueing dye particles; brightener particles; enzyme
particles such as protease prills, lipase prills, cellulase prills,
amylase prills, mannanase prills, pectate lyase prills,
xyloglucanase prills, bleaching enzyme prills, cutinase prills and
co-prills of any of these enzymes; clay particles such as
montmorillonite particles or particles of clay and silicone;
flocculant particles such as polyethylene oxide particles; wax
particles such as wax agglomerates; perfume particles such as
perfume microcapsules, especially melamine formaldehyde-based
perfume microcapsules, starch encapsulated perfume accord
particles, and pro-perfume particles such as Schiff base reaction
product particles; aesthetic particles such as coloured noodles or
needles or lamellae particles, and soap rings including coloured
soap rings; and any combination thereof.
[0013] Liquid laundry detergent composition: The composition may
also be in liquid form, for example a liquid or gel form, or any
combination thereof. The composition may be in any unit dose form,
for example a pouch.
[0014] In the case of a liquid laundry detergent composition, the
composition may include: (i) detersive surfactant comprising
anionic detersive surfactant and non-ionic surfactant, wherein the
weight ratio of anionic detersive surfactant to non-ionic detersive
surfactant is greater than 1:1; (ii) surfactancy boosting polymer;
(iii) from 0 wt % to 10 wt % fatty acid; (iv) silicone suds
suppressor; (v) structurant; (vi) enzymes; and (vii) nil-boron
enzyme stabilizer. The electrolytic strength of the composition at
a concentration of 1 g/l in de-ionized water and at a temperature
of 25.degree. C. in mScm.sup.-1 is preferably less than 200
mScm.sup.-1. It may be preferred to keep low levels of fatty acid
in the composition, and/or to use alkanolamines, preferably
tertiary alkanolamines having a pKa of less than 9.0, or even less
than 8.0, preferred are tri-isopropanolamine (TIPA), and/or
triethanolamine (TEA), especially preferred is TEA due to its low
molecular weight and low pKa, to provide some buffering capacity in
the formulation.
[0015] Preferably, a liquid laundry detergent composition
comprises: (i) detersive surfactant comprising anionic detersive
surfactant and non-ionic surfactant, wherein the weight ratio of
anionic detersive surfactant to non-ionic detersive surfactant is
greater than 1:1; and optionally wherein the anionic detersive
surfactant has a hydrophilic index (HI.sub.C) of from 8.0 to 9.1;
(ii) surfactancy boosting polymer; (iii) from 0 wt % to 5 wt %
fatty acid; (iv) silicone suds suppressor; (v) structurant; (vi)
enzymes; and (vii) non-boron enzyme stabilizer; and wherein the
electrolytic strength of the composition at a concentration of 1
g/l in de-ionized water and at a temperature of 25.degree. C. in
mScm.sup.-1 is preferably less than 200 mScm.sup.-1.
[0016] Detersive surfactant: The composition typically comprises
detersive surfactant. Suitable detersive surfactants include
anionic detersive surfactants, non-ionic detersive surfactant,
cationic detersive surfactants, zwitterionic detersive surfactants,
amphoteric detersive surfactants, and any combination thereof.
[0017] Anionic detersive surfactant: Suitable anionic detersive
surfactants include sulphate and sulphonate detersive
surfactants.
[0018] Suitable sulphonate detersive surfactants include alkyl
benzene sulphonate, such as C.sub.10-13 alkyl benzene sulphonate.
Suitable alkyl benzene sulphonate (LAS) is obtainable, or even
obtained, by sulphonating commercially available linear alkyl
benzene (LAB); suitable LAB includes low 2-phenyl LAB, such as
those supplied by Sasol under the tradename Isochem.RTM. or those
supplied by Petresa under the tradename Petrelab.RTM., other
suitable LAB include high 2-phenyl LAB, such as those supplied by
Sasol under the tradename Hyblene.RTM.. Another suitable anionic
detersive surfactant is alkyl benzene sulphonate that is obtained
by DETAL catalyzed process, although other synthesis routes, such
as HF, may also be suitable.
[0019] Suitable sulphate detersive surfactants include alkyl
sulphate, such as C.sub.8-18 alkyl sulphate, or predominantly
C.sub.12 alkyl sulphate. The alkyl sulphate may be derived from
natural sources, such as coco and/or tallow. Alternative, the alkyl
sulphate may be derived from synthetic sources such as C.sub.12-15
alkyl sulphate.
[0020] Another suitable sulphate detersive surfactant is alkyl
alkoxylated sulphate, such as alkyl ethoxylated sulphate, or a
C.sub.8-18 alkyl alkoxylated sulphate, or a C.sub.8-18 alkyl
ethoxylated sulphate. The alkyl alkoxylated sulphate may have an
average degree of alkoxylation of from 0.5 to 20, or from 0.5 to
10. The alkyl alkoxylated sulphate may be a C.sub.8-18 alkyl
ethoxylated sulphate, typically having an average degree of
ethoxylation of from 0.5 to 10, or from 0.5 to 7, or from 0.5 to 5
or from 0.5 to 3.
[0021] The alkyl sulphate, alkyl alkoxylated sulphate and alkyl
benzene sulphonates may be linear or branched, substituted or
un-substituted.
[0022] The anionic detersive surfactant may be a mid-chain branched
anionic detersive surfactant, such as a mid-chain branched alkyl
sulphate and/or a mid-chain branched alkyl benzene sulphonate. The
mid-chain branches are typically C.sub.1-4 alkyl groups, such as
methyl and/or ethyl groups.
[0023] Another suitable anionic detersive surfactant is alkyl
ethoxy carboxylate.
[0024] The anionic detersive surfactants are typically present in
their salt form, typically being complexed with a suitable cation.
Suitable counter-ions include Na.sup.+ and K.sup.+, substituted
ammonium such as C.sub.1-C.sub.6 alkanolammonium such as
mono-ethanolamine (MEA) tri-ethanolamine (TEA), di-ethanolamine
(DEA), and any mixture thereof.
[0025] Non-ionic detersive surfactant: Suitable non-ionic detersive
surfactants are selected from the group consisting of:
C.sub.8-C.sub.18 alkyl ethoxylates, such as, NEODOL.RTM. non-ionic
surfactants from Shell; C.sub.6-C.sub.12 alkyl phenol alkoxylates
wherein optionally the alkoxylate units are ethyleneoxy units,
propyleneoxy units or a mixture thereof; C.sub.12-C.sub.18 alcohol
and C.sub.6-C.sub.12 alkyl phenol condensates with ethylene
oxide/propylene oxide block polymers such as Pluronic.RTM. from
BASF; C.sub.14-C.sub.22 mid-chain branched alcohols;
C.sub.14-C.sub.22 mid-chain branched alkyl alkoxylates, typically
having an average degree of alkoxylation of from 1 to 30;
alkylpolysaccharides, such as alkylpolyglycosides; polyhydroxy
fatty acid amides; ether capped poly(oxyalkylated) alcohol
surfactants; and mixtures thereof.
[0026] Suitable non-ionic detersive surfactants are alkyl
polyglucoside and/or an alkyl alkoxylated alcohol.
[0027] Suitable non-ionic detersive surfactants include alkyl
alkoxylated alcohols, such as C.sub.8-18 alkyl alkoxylated alcohol,
or a C.sub.8-18 alkyl ethoxylated alcohol. The alkyl alkoxylated
alcohol may have an average degree of alkoxylation of from 0.5 to
50, or from 1 to 30, or from 1 to 20, or from 1 to 10. The alkyl
alkoxylated alcohol may be a C.sub.8-18 alkyl ethoxylated alcohol,
typically having an average degree of ethoxylation of from 1 to 10,
or from 1 to 7, or from 1 to 5, or from 3 to 7. The alkyl
alkoxylated alcohol can be linear or branched, and substituted or
un-substituted.
[0028] Suitable nonionic detersive surfactants include secondary
alcohol-based detersive surfactants having the formula:
##STR00001##
[0029] wherein R.sup.1=linear or branched, substituted or
unsubstituted, saturated or unsaturated C.sub.2-8 alkyl;
[0030] wherein R.sup.2=linear or branched, substituted or
unsubstituted, saturated or unsaturated C.sub.2-8 alkyl,
[0031] wherein the total number of carbon atoms present in
R.sup.1+R.sup.2 moieties is in the range of from 7 to 13;
[0032] wherein EO/PO are alkoxy moieties selected from ethoxy,
propoxy, or mixtures thereof, optionally the EO/PO alkoxyl moieties
are in random or block configuration;
[0033] wherein n is the average degree of alkoxylation and is in
the range of from 4 to 10.
[0034] Other suitable non-ionic detersive surfactants include EO/PO
block co-polymer surfactants, such as the Plurafac.RTM. series of
surfactants available from BASF, and sugar-derived surfactants such
as alkyl N-methyl glucose amide.
[0035] Cationic detersive surfactant: Suitable cationic detersive
surfactants include alkyl pyridinium compounds, alkyl quaternary
ammonium compounds, alkyl quaternary phosphonium compounds, alkyl
ternary sulphonium compounds, and mixtures thereof.
[0036] Suitable cationic detersive surfactants are quaternary
ammonium compounds having the general formula:
(R)(R.sub.1)(R.sub.2)(R.sub.3)N.sup.+X.sup.-
[0037] wherein, R is a linear or branched, substituted or
unsubstituted C.sub.6-18 alkyl or alkenyl moiety, R.sub.1 and
R.sub.2 are independently selected from methyl or ethyl moieties,
R.sub.3 is a hydroxyl, hydroxymethyl or a hydroxyethyl moiety, X is
an anion which provides charge neutrality, suitable anions include:
halides, such as chloride; sulphate; and sulphonate. Suitable
cationic detersive surfactants are mono-C.sub.6-18 alkyl
mono-hydroxyethyl di-methyl quaternary ammonium chlorides. Suitable
cationic detersive surfactants are mono-C.sub.8-10 alkyl
mono-hydroxyethyl di-methyl quaternary ammonium chloride,
mono-C.sub.10-12 alkyl mono-hydroxyethyl di-methyl quaternary
ammonium chloride and mono-C.sub.10 alkyl mono-hydroxyethyl
di-methyl quaternary ammonium chloride.
[0038] Zwitterionic and/or amphoteric detersive surfactant:
Suitable zwitterionic and/or amphoteric detersive surfactants
include amine oxide such as dodecyldimethylamine N-oxide,
alkanolamine sulphobetaines, coco-amidopropyl betaines,
HN.sup.+--R--CO.sub.2.sup.- based surfactants, wherein R can be any
bridging group, such as alkyl, alkoxy, aryl or amino acids.
[0039] Polymer: Suitable polymers include carboxylate polymers,
polyethylene glycol polymers, polyester soil release polymers such
as terephthalate polymers, amine polymers, cellulosic polymers, dye
transfer inhibition polymers, dye lock polymers such as a
condensation oligomer produced by condensation of imidazole and
epichlorhydrin, optionally in ratio of 1:4:1, hexamethylenediamine
derivative polymers, and any combination thereof.
[0040] Carboxylate polymer: Suitable carboxylate polymers include
maleate/acrylate random copolymer or polyacrylate homopolymer. The
carboxylate polymer may be a polyacrylate homopolymer having a
molecular weight of from 4,000 Da to 9,000 Da, or from 6,000 Da to
9,000 Da. Other suitable carboxylate polymers are co-polymers of
maleic acid and acrylic acid, and may have a molecular weight in
the range of from 4,000 Da to 90,000 Da.
[0041] Polyethylene glycol polymer: Suitable polyethylene glycol
polymers include random graft co-polymers comprising: (i)
hydrophilic backbone comprising polyethylene glycol; and (ii)
hydrophobic side chain(s) selected from the group consisting of:
C.sub.4-C.sub.25 alkyl group, polypropylene, polybutylene, vinyl
ester of a saturated C.sub.1-C.sub.6 mono-carboxylic acid,
C.sub.1-C.sub.6 alkyl ester of acrylic or methacrylic acid, and
mixtures thereof. Suitable polyethylene glycol polymers have a
polyethylene glycol backbone with random grafted polyvinyl acetate
side chains. The average molecular weight of the polyethylene
glycol backbone can be in the range of from 2,000 Da to 20,000 Da,
or from 4,000 Da to 8,000 Da. The molecular weight ratio of the
polyethylene glycol backbone to the polyvinyl acetate side chains
can be in the range of from 1:1 to 1:5, or from 1:1.2 to 1:2. The
average number of graft sites per ethylene oxide units can be less
than 1, or less than 0.8, the average number of graft sites per
ethylene oxide units can be in the range of from 0.5 to 0.9, or the
average number of graft sites per ethylene oxide units can be in
the range of from 0.1 to 0.5, or from 0.2 to 0.4. A suitable
polyethylene glycol polymer is Sokalan HP22.
[0042] Polyester soil release polymers: Suitable polyester soil
release polymers have a structure as defined by one of the
following structures (I), (II) or (III):
--[(OCHR.sup.1--CHR.sup.2).sub.a--O--OC--Ar--CO--].sub.d (I)
--[(OCHR.sup.3--CHR.sup.4).sub.b--O--OC-sAr--CO--].sub.e (II)
--[(OCHR.sup.5--CHR.sup.6).sub.c--OR.sup.7].sub.f (III)
[0043] wherein:
[0044] a, b and c are from 1 to 200;
[0045] d, e and f are from 1 to 50;
[0046] Ar is a 1,4-substituted phenylene;
[0047] sAr is 1,3-substituted phenylene substituted in position 5
with SO.sub.3Me;
[0048] Me is Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri-,
or tetraalkylammonium wherein the alkyl groups are C.sub.1-C.sub.18
alkyl or C.sub.2-C.sub.10 hydroxyalkyl, or any mixture thereof;
[0049] R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are
independently selected from H or C.sub.1-C.sub.18 n- or iso-alkyl;
and
[0050] R.sup.7 is a linear or branched C.sub.1-C.sub.18 alkyl, or a
linear or branched C.sub.2-C.sub.30 alkenyl, or a cycloalkyl group
with 5 to 9 carbon atoms, or a C.sub.8-C.sub.30 aryl group, or a
C.sub.6-C.sub.30 arylalkyl group. Suitable polyester soil release
polymers are terephthalate polymers having the structure of formula
(I) or (II) above.
[0051] Suitable polyester soil release polymers include the
Repel-o-tex series of polymers such as Repel-o-tex SF2 (Rhodia)
and/or the Texcare series of polymers such as Texcare SRA300
(Clariant).
[0052] Amine polymer: Suitable amine polymers include polyethylene
imine polymers, such as alkoxylated polyalkyleneimines, optionally
comprising a polyethylene and/or polypropylene oxide block.
[0053] Cellulosic polymer: The composition can comprise cellulosic
polymers, such as polymers selected from alkyl cellulose, alkyl
alkoxyalkyl cellulose, carboxyalkyl cellulose, alkyl carboxyalkyl,
and any combination thereof. Suitable cellulosic polymers are
selected from carboxymethyl cellulose, methyl cellulose, methyl
hydroxyethyl cellulose, methyl carboxymethyl cellulose, and
mixtures thereof. The carboxymethyl cellulose can have a degree of
carboxymethyl substitution from 0.5 to 0.9 and a molecular weight
from 100,000 Da to 300,000 Da. Another suitable cellulosic polymer
is hydrophobically modified carboxymethyl cellulose, such as
Finnfix SH-1 (CP Kelco).
[0054] Other suitable cellulosic polymers may have a degree of
substitution (DS) of from 0.01 to 0.99 and a degree of blockiness
(DB) such that either DS+DB is of at least 1.00 or DB+2DS-DS.sup.2
is at least 1.20. The substituted cellulosic polymer can have a
degree of substitution (DS) of at least 0.55. The substituted
cellulosic polymer can have a degree of blockiness (DB) of at least
0.35. The substituted cellulosic polymer can have a DS+DB, of from
1.05 to 2.00. A suitable substituted cellulosic polymer is
carboxymethylcellulose.
[0055] Another suitable cellulosic polymer is cationically modified
hydroxyethyl cellulose.
[0056] Dye transfer inhibitor polymer: Suitable dye transfer
inhibitor (DTI) polymers include polyvinyl pyrrolidone (PVP), vinyl
co-polymers of pyrrolidone and imidazoline (PVPVI), polyvinyl
N-oxide (PVNO), and any mixture thereof.
[0057] Hexamethylenediamine derivative polymers: Suitable polymers
include hexamethylenediamine derivative polymers, typically having
the formula:
R.sub.2(CH.sub.3)N.sup.+(CH.sub.2)6N.sup.+(CH.sub.3)R.sub.2.2X.sup.-
wherein X.sup.- is a suitable counter-ion, for example chloride,
and R is a poly(ethylene glycol) chain having an average degree of
ethoxylation of from 20 to 30. Optionally, the poly(ethylene
glycol) chains may be independently capped with sulphate and/or
sulphonate groups, typically with the charge being balanced by
reducing the number of X.sup.- counter-ions, or (in cases where the
average degree of sulphation per molecule is greater than two),
introduction of Y.sup.+ counter-ions, for example sodium
cations.
[0058] Builder: Suitable builders include zeolites, phosphates,
citrates, and any combination thereof.
[0059] Zeolite builder: The composition typically comprises from 0
wt % to 10 wt %, zeolite builder, or to 8 wt %, or to 6 wt %, or to
4 wt %, or to 3 wt %, or to 2 wt %, or even to 1 wt % zeolite
builder. The composition may even be substantially free of zeolite
builder; substantially free means "no deliberately added". Typical
zeolite builders include zeolite A, zeolite P, zeolite MAP, zeolite
X and zeolite Y.
[0060] Phosphate builder: The composition typically comprises from
0 wt % to 10 wt % phosphate builder, or to 8 wt %, or to 6 wt %, or
to 4 wt %, or to 3 wt %, or to 2 wt %, or even to 1 wt % phosphate
builder. The composition may even be substantially free of
phosphate builder; substantially free means "no deliberately
added". A typical phosphate builder is sodium tri-polyphosphate
(STPP).
[0061] Citrate: A suitable citrate is sodium citrate. However,
citric acid may also be incorporated into the composition, which
can form citrate in the wash liquor.
[0062] Buffer and alkalinity source: Suitable buffers and
alkalinity sources include carbonate salts and/or silicate salts
and/or double salts such as burkeitte.
[0063] Carbonate salt: A suitable carbonate salt is sodium
carbonate and/or sodium bicarbonate. The composition may comprise
bicarbonate salt. It may be suitable for the composition to
comprise low levels of carbonate salt, for example, it may be
suitable for the composition to comprise from 0 wt % to 10 wt %
carbonate salt, or to 8 wt %, or to 6 wt %, or to 4 wt %, or to 3
wt %, or to 2 wt %, or even to 1 wt % carbonate salt. The
composition may even be substantially free of carbonate salt;
substantially free means "no deliberately added".
[0064] The carbonate salt may have a weight average mean particle
size of from 100 to 500 micrometers. Alternatively, the carbonate
salt may have a weight average mean particle size of from 10 to 25
micrometers.
[0065] Silicate salt: The composition may comprise from 0 wt % to
20 wt % silicate salt, or to 15 wt %, or to 10 wt %, or to 5 wt %,
or to 4 wt %, or even to 2 wt %, and may comprise from above 0 wt
%, or from 0.5 wt %, or even from 1 wt % silicate salt. The
silicate can be crystalline or amorphous. Suitable crystalline
silicates include crystalline layered silicate, such as SKS-6.
Other suitable silicates include 1.6R silicate and/or 2.0R
silicate. A suitable silicate salt is sodium silicate. Another
suitable silicate salt is sodium metasilicate.
[0066] Filler: The composition may comprise from 0 wt % to 70%
filler. Suitable fillers include sulphate salts and/or bio-filler
materials.
[0067] Sulphate salt: A suitable sulphate salt is sodium sulphate.
The sulphate salt may have a weight average mean particle size of
from 100 to 500 micrometers, alternatively, the sulphate salt may
have a weight average mean particle size of from 10 to 45
micrometers.
[0068] Bio-filler material: A suitable bio-filler material is
alkali and/or bleach treated agricultural waste.
[0069] Bleach: The composition may comprise bleach. Alternatively,
the composition may be substantially free of bleach; substantially
free means "no deliberately added". Suitable bleach includes bleach
activators, sources of available oxygen, pre-formed peracids,
bleach catalysts, reducing bleach, and any combination thereof. If
present, the bleach, or any component thereof, for example the
pre-formed peracid, may be coated, such as encapsulated, or
clathrated, such as with urea or cyclodextrin.
[0070] Bleach activator: Suitable bleach activators include:
tetraacetylethylenediamine (TAED); oxybenzene sulphonates such as
nonanoyl oxybenzene sulphonate (NOBS), caprylamidononanoyl
oxybenzene sulphonate (NACA-OBS), 3,5,5-trimethyl
hexanoyloxybenzene sulphonate (Iso-NOBS), dodecyl oxybenzene
sulphonate (LOBS), and any mixture thereof; caprolactams;
pentaacetate glucose (PAG); nitrile quaternary ammonium; imide
bleach activators, such as N-nonanoyl-N-methyl acetamide; and any
mixture thereof.
[0071] Source of available oxygen: A suitable source of available
oxygen (AvOx) is a source of hydrogen peroxide, such as
percarbonate salts and/or perborate salts, such as sodium
percarbonate. The source of peroxygen may be at least partially
coated, or even completely coated, by a coating ingredient such as
a carbonate salt, a sulphate salt, a silicate salt, borosilicate,
or any mixture thereof, including mixed salts thereof. Suitable
percarbonate salts can be prepared by a fluid bed process or by a
crystallization process. Suitable perborate salts include sodium
perborate mono-hydrate (PB1), sodium perborate tetra-hydrate (PB4),
and anhydrous sodium perborate which is also known as fizzing
sodium perborate. Other suitable sources of AvOx include
persulphate, such as oxone. Another suitable source of AvOx is
hydrogen peroxide.
[0072] Pre-formed peracid: A suitable pre-formed peracid is
N,N-pthaloylamino peroxycaproic acid (PAP).
[0073] Bleach catalyst: Suitable bleach catalysts include
oxaziridinium-based bleach catalysts, transition metal bleach
catalysts and bleaching enzymes.
[0074] Oxaziridinium-based bleach catalyst: A suitable
oxaziridinium-based bleach catalyst has the formula:
##STR00002##
[0075] wherein: R.sup.1 is selected from the group consisting of:
H, a branched alkyl group containing from 3 to 24 carbons, and a
linear alkyl group containing from 1 to 24 carbons; R.sup.1 can be
a branched alkyl group comprising from 6 to 18 carbons, or a linear
alkyl group comprising from 5 to 18 carbons, R.sup.1 can be
selected from the group consisting of: 2-propylheptyl,
2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-hexyl, n-octyl,
n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl,
iso-nonyl, iso-decyl, iso-tridecyl and iso-pentadecyl; R.sup.2 is
independently selected from the group consisting of: H, a branched
alkyl group comprising from 3 to 12 carbons, and a linear alkyl
group comprising from 1 to 12 carbons; optionally R.sup.2 is
independently selected from H and methyl groups; and n is an
integer from 0 to 1.
[0076] Transition metal bleach catalyst: The composition may
include transition metal bleach catalyst, typically comprising
copper, iron, titanium, ruthenium, tungsten, molybdenum, and/or
manganese cations. Suitable transition metal bleach catalysts are
manganese-based transition metal bleach catalysts.
[0077] Reducing bleach: The composition may comprise a reducing
bleach. However, the composition may be substantially free of
reducing bleach; substantially free means "no deliberately added".
Suitable reducing bleach include sodium sulphite and/or thiourea
dioxide (TDO).
[0078] Co-bleach particle: The composition may comprise a co-bleach
particle. Typically, the co-bleach particle comprises a bleach
activator and a source of peroxide. It may be highly suitable for a
large amount of bleach activator relative to the source of hydrogen
peroxide to be present in the co-bleach particle. The weight ratio
of bleach activator to source of hydrogen peroxide present in the
co-bleach particle can be at least 0.3:1, or at least 0.6:1, or at
least 0.7:1, or at least 0.8:1, or at least 0.9:1, or at least
1.0:1.0, or even at least 1.2:1 or higher.
[0079] The co-bleach particle can comprise: (i) bleach activator,
such as TAED; and (ii) a source of hydrogen peroxide, such as
sodium percarbonate. The bleach activator may at least partially,
or even completely, enclose the source of hydrogen peroxide.
[0080] The co-bleach particle may comprise a binder. Suitable
binders are carboxylate polymers such as polyacrylate polymers,
and/or surfactants including non-ionic detersive surfactants and/or
anionic detersive surfactants such as linear C.sub.11-C.sub.13
alkyl benzene sulphonate.
[0081] The co-bleach particle may comprise bleach catalyst, such as
an oxaziridium-based bleach catalyst.
[0082] Chelant: Suitable chelants are selected from: diethylene
triamine pentaacetate, diethylene triamine penta(methyl phosphonic
acid), ethylene diamine-N'N'-disuccinic acid, ethylene diamine
tetraacetate, ethylene diamine tetra(methylene phosphonic acid),
hydroxyethane di(methylene phosphonic acid), and any combination
thereof. A suitable chelant is ethylene diamine-N'N'-disuccinic
acid (EDDS) and/or hydroxyethane diphosphonic acid (HEDP). The
laundry detergent composition may comprise ethylene
diamine-N'N'-disuccinic acid or salt thereof. The ethylene
diamine-N'N'-disuccinic acid may be in S,S enantiomeric form. The
composition may comprise 4,5-dihydroxy-m-benzenedisulfonic acid
disodium salt. Suitable chelants may also be calcium crystal growth
inhibitors.
[0083] Calcium carbonate crystal growth inhibitor: The composition
may comprise a calcium carbonate crystal growth inhibitor, such as
one selected from the group consisting of:
1-hydroxyethanediphosphonic acid (HEDP) and salts thereof;
N,N-dicarboxymethyl-2-aminopentane-1,5-dioic acid and salts
thereof; 2-phosphonobutane-1,2,4-tricarboxylic acid and salts
thereof; and any combination thereof.
[0084] Photobleach: Suitable photobleaches are zinc and/or
aluminium sulphonated phthalocyanines.
[0085] Hueing agent: The hueing agent (also defined herein as
hueing dye) is typically formulated to deposit onto fabrics from
the wash liquor so as to improve fabric whiteness perception. The
hueing agent is typically blue or violet. It may be suitable that
the hueing dye(s) have a peak absorption wavelength of from 550 nm
to 650 nm, or from 570 nm to 630 nm. The hueing agent may be a
combination of dyes which together have the visual effect on the
human eye as a single dye having a peak absorption wavelength on
polyester of from 550 nm to 650 nm, or from 570 nm to 630 nm. This
may be provided for example by mixing a red and green-blue dye to
yield a blue or violet shade.
[0086] Dyes are typically coloured organic molecules which are
soluble in aqueous media that contain surfactants. Dyes maybe
selected from the classes of basic, acid, hydrophobic, direct and
polymeric dyes, and dye-conjugates. Suitable polymeric hueing dyes
are commercially available, for example from Milliken, Spartanburg,
S.C., USA.
[0087] Examples of suitable dyes are violet DD, direct violet 7,
direct violet 9, direct violet 11, direct violet 26, direct violet
31, direct violet 35, direct violet 40, direct violet 41, direct
violet 51, direct violet 66, direct violet 99, acid violet 50, acid
blue 9, acid violet 17, acid black 1, acid red 17, acid blue 29,
solvent violet 13, disperse violet 27 disperse violet 26, disperse
violet 28, disperse violet 63 and disperse violet 77, basic blue
16, basic blue 65, basic blue 66, basic blue 67, basic blue 71,
basic blue 159, basic violet 19, basic violet 35, basic violet 38,
basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic
blue 122, basic blue 124, basic blue 141, thiazolium dyes, reactive
blue 19, reactive blue 163, reactive blue 182, reactive blue 96,
Liquitint.RTM. Violet CT (Milliken, Spartanburg, USA) and
Azo-CM-Cellulose (Megazyme, Bray, Republic of Ireland). Other
suitable hueing agents are hueing dye-photobleach conjugates, such
as the conjugate of sulphonated zinc phthalocyanine with direct
violet 99. A particularly suitable hueing agent is a combination of
acid red 52 and acid blue 80, or the combination of direct violet 9
and solvent violet 13.
[0088] Brightener: Suitable brighteners are stilbenes, such as
brightener 15. Other suitable brighteners are hydrophobic
brighteners, and brightener 49. The brightener may be in micronized
particulate form, having a weight average particle size in the
range of from 3 to 30 micrometers, or from 3 micrometers to 20
micrometers, or from 3 to 10 micrometers. The brightener can be
alpha or beta crystalline form.
[0089] Enzyme: Suitable enzymes include proteases, amylases,
cellulases, lipases, xylogucanases, pectate lyases, mannanases,
bleaching enzymes, cutinases, and mixtures thereof.
[0090] For the enzymes, accession numbers and IDs shown in
parentheses refer to the entry numbers in the databases Genbank,
EMBL and/or Swiss-Prot. For any mutations, standard 1-letter amino
acid codes are used with a * representing a deletion. Accession
numbers prefixed with DSM refer to micro-organisms deposited at
Deutsche Sammlung von Mikroorganismen and Zellkulturen GmbH,
Mascheroder Weg 1b, 38124 Brunswick (DSMZ).
[0091] Protease. The composition may comprise a protease. Suitable
proteases include metalloproteases and/or serine proteases,
including neutral or alkaline microbial serine proteases, such as
subtilisins (EC 3.4.21.62). Suitable proteases include those of
animal, vegetable or microbial origin. In one aspect, such suitable
protease may be of microbial origin. The suitable proteases include
chemically or genetically modified mutants of the aforementioned
suitable proteases. In one aspect, the suitable protease may be a
serine protease, such as an alkaline microbial protease or/and a
trypsin-type protease. Examples of suitable neutral or alkaline
proteases include:
[0092] (a) subtilisins (EC 3.4.21.62), including those derived from
Bacillus, such as Bacillus lentus, Bacillus alkalophilus (P27963,
ELYA_BACAO), Bacillus subtilis, Bacillus amyloliquefaciens (P00782,
SUBT_BACAM), Bacillus pumilus (P07518) and Bacillus gibsonii
(DSM14391).
[0093] (b) trypsin-type or chymotrypsin-type proteases, such as
trypsin (e.g. of porcine or bovine origin), including the Fusarium
protease and the chymotrypsin proteases derived from Cellumonas
(A2RQE2).
[0094] (c) metalloproteases, including those derived from Bacillus
amyloliquefaciens (P06832, NPRE_BACAM).
[0095] Suitable proteases include those derived from Bacillus
gibsonii or Bacillus Lentus such as subtilisin 309 (P29600) and/or
DSM 5483 (P29599).
[0096] Suitable commercially available protease enzymes include:
those sold under the trade names Alcalase.RTM., Savinase.RTM.,
Primase.RTM., Durazym.RTM., Polarzyme.RTM., Kannase.RTM.,
Liquanase.RTM., Liquanase Ultra.RTM., Savinase Ultra.RTM.,
Ovozyme.RTM., Neutrase.RTM., Everlase.RTM. and Esperase.RTM. by
Novozymes A/S (Denmark); those sold under the tradename
Maxatase.RTM., Maxacal.RTM., Maxapem.RTM., Properase.RTM.,
Purafect.RTM., Purafect Prime.RTM., Purafect Ox.RTM., FN3.RTM.,
FN4.RTM., Excellase.RTM. and Purafect OXP.RTM. by Genencor
International; those sold under the tradename Opticlean.RTM. and
Optimase.RTM. by Solvay Enzymes; those available from
Henkel/Kemira, namely BLAP (P29599 having the following mutations
S99D+S101 R+S103A+V104I+G159S), and variants thereof including BLAP
R (BLAP with S3T+V4I+V199M+V205I+L217D), BLAP X (BLAP with
S3T+V4I+V205I) and BLAP F49 (BLAP with
S3T+V4I+A194P+V199M+V205I+L217D) all from Henkel/Kemira; and KAP
(Bacillus alkalophilus subtilisin with mutations A230V+S256G+S259N)
from Kao.
[0097] Amylase: Suitable amylases are alpha-amylases, including
those of bacterial or fungal origin. Chemically or genetically
modified mutants (variants) are included. A suitable alkaline
alpha-amylase is derived from a strain of Bacillus, such as
Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus
stearothermophilus, Bacillus subtilis, or other Bacillus sp., such
as Bacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, sp 707, DSM
9375, DSM 12368, DSMZ no. 12649, KSM AP1378, KSM K36 or KSM K38.
Suitable amylases include:
[0098] (a) alpha-amylase derived from Bacillus licheniformis
(P06278, AMY_BACLI), and variants thereof, especially the variants
with substitutions in one or more of the following positions: 15,
23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202,
208, 209, 243, 264, 304, 305, 391, 408, and 444.
[0099] (b) AA560 amylase (CBU30457, HD066534) and variants thereof,
especially the variants with one or more substitutions in the
following positions: 26, 30, 33, 82, 37, 106, 118, 128, 133, 149,
150, 160, 178, 182, 186, 193, 203, 214, 231, 256, 257, 258, 269,
270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315,
318, 319, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445,
446, 447, 450, 461, 471, 482, 484, optionally that also contain the
deletions of D183* and G184*.
[0100] (c) variants exhibiting at least 90% identity with the
wild-type enzyme from Bacillus SP722 (CBU30453, HD066526),
especially variants with deletions in the 183 and 184
positions.
[0101] Suitable commercially available alpha-amylases are
Duramyl.RTM., Liquezyme.RTM. Termamyl.RTM., Termamyl Ultra.RTM.,
Natalase.RTM., Supramyl.RTM., Stainzyme.RTM., Stainzyme Plus.RTM.,
Fungamyl.RTM. and BAN.RTM. (Novozymes A/S), Bioamylase.RTM. and
variants thereof (Biocon India Ltd.), Kemzym.RTM. AT 9000 (Biozym
Ges. m.b.H, Austria), Rapidase.RTM., Purastar.RTM., Optisize HT
Plus.RTM., Enzysize.RTM., Powerase.RTM. and Purastar Oxam.RTM.,
Maxamyl.RTM. (Genencor International Inc.) and KAM.RTM. (KAO,
Japan). Suitable amylases are Natalase.RTM., Stainzyme.RTM. and
Stainzyme Plus.RTM..
[0102] Cellulase: The composition may comprise a cellulase.
Suitable cellulases include those of bacterial or fungal origin.
Chemically modified or protein engineered mutants are included.
Suitable cellulases include cellulases from the genera Bacillus,
Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g., the
fungal cellulases produced from Humicola insolens, Myceliophthora
thermophila and Fusarium oxysporum.
[0103] Commercially available cellulases include Celluzyme.RTM.,
and Carezyme.RTM. (Novozymes A/S), Clazinase.RTM., and Puradax
HA.RTM. (Genencor International Inc.), and KAC-500(B).RTM. (Kao
Corporation).
[0104] The cellulase can include microbial-derived endoglucanases
exhibiting endo-beta-1,4-glucanase activity (E.C. 3.2.1.4),
including a bacterial polypeptide endogenous to a member of the
genus Bacillus sp. AA349 and mixtures thereof. Suitable
endoglucanases are sold under the tradenames Celluclean.RTM. and
Whitezyme.RTM. (Novozymes A/S, Bagsvaerd, Denmark).
[0105] The composition may comprise a cleaning cellulase belonging
to Glycosyl Hydrolase family 45 having a molecular weight of from
17 kDa to 30 kDa, for example the endoglucanases sold under the
tradename Biotouch.RTM. NCD, DCC and DCL (AB Enzymes, Darmstadt,
Germany).
[0106] Suitable cellulases may also exhibit xyloglucanase activity,
such as Whitezyme.RTM..
[0107] Lipase. The composition may comprise a lipase. Suitable
lipases include those of bacterial or fungal origin. Chemically
modified or protein engineered mutants are included. Examples of
useful lipases include lipases from Humicola (synonym Thermomyces),
e.g., from H. lanuginosa (T. lanuginosus), or from H. insolens, a
Pseudomonas lipase, e.g., from P. alcaligenes or P.
pseudoalcaligenes, P. cepacia, P. stutzeri, P. fluorescens,
Pseudomonas sp. strain SD 705, P. wisconsinensis, a Bacillus
lipase, e.g., from B. subtilis, B. stearothermophilus or B.
pumilus.
[0108] The lipase may be a "first cycle lipase", optionally a
variant of the wild-type lipase from Thermomyces lanuginosus
comprising T231R and N233R mutations. The wild-type sequence is the
269 amino acids (amino acids 23-291) of the Swissprot accession
number Swiss-Prot O59952 (derived from Thermomyces lanuginosus
(Humicola lanuginosa)). Suitable lipases would include those sold
under the tradenames Lipex.RTM., Lipolex.RTM. and Lipoclean.RTM. by
Novozymes, Bagsvaerd, Denmark.
[0109] The composition may comprise a variant of Thermomyces
lanuginosa (O59952) lipase having >90% identity with the wild
type amino acid and comprising substitution(s) at T231 and/or N233,
optionally T231R and/or N233R.
[0110] Xyloglucanase: Suitable xyloglucanase enzymes may have
enzymatic activity towards both xyloglucan and amorphous cellulose
substrates. The enzyme may be a glycosyl hydrolase (GH) selected
from GH families 5, 12, 44 or 74. The glycosyl hydrolase selected
from GH family 44 is particularly suitable. Suitable glycosyl
hydrolases from GH family 44 are the XYG1006 glycosyl hydrolase
from Paenibacillus polyxyma (ATCC 832) and variants thereof.
[0111] Pectate lyase: Suitable pectate lyases are either wild-types
or variants of Bacillus-derived pectate lyases (CAF05441, AAU25568)
sold under the tradenames Pectawash.RTM., Pectaway.RTM. and
X-Pect.RTM. (from Novozymes A/S, Bagsvaerd, Denmark).
[0112] Mannanase: Suitable mannanases are sold under the tradenames
Mannaway.RTM. (from Novozymes A/S, Bagsvaerd, Denmark), and
Purabrite.RTM. (Genencor International Inc., Palo Alto,
Calif.).
[0113] Bleaching enzyme: Suitable bleach enzymes include
oxidoreductases, for example oxidases such as glucose, choline or
carbohydrate oxidases, oxygenases, catalases, peroxidases, like
halo-, chloro-, bromo-, lignin-, glucose- or manganese-peroxidases,
dioxygenases or laccases (phenoloxidases, polyphenoloxidases).
Suitable commercial products are sold under the Guardzyme.RTM. and
Denilite.RTM. ranges from Novozymes. It may be advantageous for
additional organic compounds, especially aromatic compounds, to be
incorporated with the bleaching enzyme; these compounds interact
with the bleaching enzyme to enhance the activity of the
oxidoreductase (enhancer) or to facilitate the electron flow
(mediator) between the oxidizing enzyme and the stain typically
over strongly different redox potentials.
[0114] Other suitable bleaching enzymes include perhydrolases,
which catalyse the formation of peracids from an ester substrate
and peroxygen source. Suitable perhydrolases include variants of
the Mycobacterium smegmatis perhydrolase, variants of so-called
CE-7 perhydrolases, and variants of wild-type subtilisin Carlsberg
possessing perhydrolase activity.
[0115] Cutinase: Suitable cutinases are defined by E.C. Class
3.1.1.73, optionally displaying at least 90%, or 95%, or most
optionally at least 98% identity with a wild-type derived from one
of Fusarium solani, Pseudomonas Mendocina or Humicola Insolens.
[0116] Identity. The relativity between two amino acid sequences is
described by the parameter "identity". For purposes of the present
invention, the alignment of two amino acid sequences is determined
by using the Needle program from the EMBOSS package
(http://emboss.org) version 2.8.0. The Needle program implements
the global alignment algorithm described in Needleman, S. B. and
Wunsch, C. D. (1970) J. Mol. Biol. 48, 443-453. The substitution
matrix used is BLOSUM62, gap opening penalty is 10, and gap
extension penalty is 0.5.
[0117] Enzyme stabilizer. The composition may comprise an enzyme
stabilizer. Suitable enzyme stabilizers include polyols such as
propylene glycol or glycerol, sugar or sugar alcohol, lactic acid,
reversible protease inhibitor, boric acid, or a boric acid
derivative, e.g., an aromatic borate ester, or a phenyl boronic
acid derivative such as 4-formylphenyl boronic acid. It may be
preferred for the composition to comprise a nil-boron enzyme
stabilizer, preferably selected from polyols such as propylene
glycol or glycerol, sugar or sugar alcohol. It may even be
preferred for the composition to be substantially free of boron. By
substantially free it is typically meant: "comprises no
deliberately added". Free of boron also typically includes being
free of sources of boron such as borax.
[0118] Fabric-softener: Suitable fabric-softening agents include
clay, silicone and/or quaternary ammonium compounds. Suitable clays
include montmorillonite clay, hectorite clay and/or laponite clay.
A suitable clay is montmorillonite clay. Suitable silicones include
amino-silicones and/or polydimethylsiloxane (PDMS). A suitable
fabric softener is a particle comprising clay and silicone, such as
a particle comprising montmorillonite clay and PDMS.
[0119] Flocculant: Suitable flocculants include polyethylene oxide;
for example having an average molecular weight of from 300,000 Da
to 900,000 Da.
[0120] Suds suppressor: Suitable suds suppressors include silicone
and/or fatty acid such as stearic acid.
[0121] Structurant/thickener. Structured liquids can either be
internally structured, whereby the structure is formed by primary
ingredients (e.g. surfactant material) and/or externally structured
by providing a three dimensional matrix structure using secondary
ingredients (e.g. polymers, clay and/or silicate material).
[0122] The composition may comprise a structurant, preferably from
0.01 wt % to 5 wt %, from 0.1 wt % to 2.0 wt % structurant. The
structurant is typically selected from the group consisting of
diglycerides and triglycerides, ethylene glycol distearate,
microcrystalline cellulose, cellulose-based materials, microfiber
cellulose, biopolymers, xanthan gum, gellan gum, and mixtures
thereof. A suitable structurant includes hydrogenated castor oil,
and non-ethoxylated derivatives thereof. It may be preferred for
the composition to substantially free of lipase, by substantially
free it is typically meant: "comprises no deliberately added". This
is especially preferred when the composition comprises hydrogenated
castor oil, and non-ethoxylated derivatives thereof. A suitable
structurant is U.S. Pat. No. 6,855,680, such structurants have a
thread-like structuring system having a range of aspect ratios.
Other suitable structurants and the processes for making them are
described in WO2010/034736.
[0123] Perfume: Suitable perfumes include perfume microcapsules,
polymer assisted perfume delivery systems including Schiff base
perfume/polymer complexes, starch-encapsulated perfume accords,
perfume-loaded zeolites, blooming perfume accords, and any
combination thereof. A suitable perfume microcapsule is melamine
formaldehyde based, typically comprising perfume that is
encapsulated by a shell comprising melamine formaldehyde. It may be
highly suitable for such perfume microcapsules to comprise cationic
and/or cationic precursor material in the shell, such as polyvinyl
formamide (PVF) and/or cationically modified hydroxyethyl cellulose
(catHEC).
[0124] Aesthetic: Suitable aesthetic particles include soap rings,
lamellar aesthetic particles, geltin beads, carbonate and/or
sulphate salt speckles, coloured clay particles, and any
combination thereof.
[0125] Solvent: The composition may comprise a solvent. Preferred
solvents include alcohols and/or glycols, preferably methanol,
ethanol and/or propylene glycol. Preferably, the composition
comprises no or minimal amounts of methanol and ethanol and instead
comprises relatively high amounts of propylene glycol, for improved
enzyme stability. Preferably, the composition comprises propylene
glycol.
[0126] Suitable solvents include C.sub.4-C.sub.14 ethers and
diethers, glycols, alkoxylated glycols, C.sub.6-C.sub.16 glycol
ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic
branched alcohols, alkoxylated aliphatic branched alcohols,
alkoxylated linear C.sub.1-C.sub.5 alcohols, linear C.sub.1-C.sub.5
alcohols, amines, C.sub.8-C.sub.14 alkyl and cycloalkyl
hydrocarbons and halohydrocarbons, and mixtures thereof.
[0127] Preferred solvents are selected from methoxy octadecanol,
2-(2-ethoxyethoxy)ethanol, benzyl alcohol, 2-ethylbutanol and/or
2-methylbutanol, 1-methylpropoxyethanol and/or
2-methylbutoxyethanol, linear C.sub.1-C.sub.5 alcohols such as
methanol, ethanol, propanol, butyl diglycol ether (BDGE),
butyltriglycol ether, tert-amyl alcohol, glycerol, isopropanol and
mixtures thereof. Particularly preferred solvents which can be used
herein are butoxy propoxy propanol, butyl diglycol ether, benzyl
alcohol, butoxypropanol, propylene glycol, glycerol, ethanol,
methanol, isopropanol and mixtures thereof. Other suitable solvents
include propylene glycol and diethylene glycol and mixtures
thereof.
[0128] Free Water: The composition may comprise less than 10 wt %,
or less than 5 wt %, or less than 4 wt % or less than 3 wt % free
water, or less than 2 wt % free water, or less than 1 wt % free
water, and may even be anhydrous, typically comprising no
deliberately added free water. Free water is typically measured
using Karl Fischer titration. 2 g of the laundry detergent
composition is extracted into 50 ml dry methanol at room
temperature for 20 minutes and analyse 1 ml of the methanol by Karl
Fischer titration.
Malodor Control Component
[0129] The detergent laundry composition comprises a malodor
control component. The malodor control component may include at
least one volatile aldehyde and an acid catalyst. The malodor
control component 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.
[0130] 1. Volatile Aldehydes
[0131] The malodor control component includes a mixture of volatile
aldehydes that neutralize malodors in vapor and/or liquid phase via
chemical reactions. Such volatile aldehydes are also called
reactive aldehydes (RA). 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. Aldehydes that are
partially volatile may be considered a volatile aldehyde as used
herein.
[0132] 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.
[0133] 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.
[0134] 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 alternatively
used instead of the experimental logP values in the selection of
volatile aldehydes for the malodor control component.
[0135] 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.
[0136] 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%.
[0137] 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),
Dupic al, 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).
[0138] 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, Trifernal, 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.
[0139] 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.
[0140] 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.
[0141] 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 Accord A 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
[0142] 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 Accord B 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
[0143] 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 Accord C 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
[0144] 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 1% to about 5%, alternatively from
about 1% to about 3%, 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%, by
weight of the composition.
[0145] 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.
[0146] 2. Acid Catalyst
[0147] 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.
[0148] 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.
[0149] 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-00004 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
[0150] 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.
[0151] 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% to about 1.5%, alternatively about 0.4% of
an acid catalyst by weight of the malodor control component.
[0152] 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-00005 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
[0153] When an acid catalyst is present with a volatile aldehyde
(or RA), the acid catalyst may increase the efficacy of the
volatile aldehyde on malodors in comparison to the malodor efficacy
of the volatile aldehyde on its own. For example, 1% volatile
aldehyde and 1.5% benzoic acid provides malodor removal benefit
equal to or better than 5% volatile aldehyde alone.
[0154] 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.
[0155] 3. Optional Ingredients
[0156] The malodor control component may, optionally, include odor
masking agents, odor blocking agents, and/or diluents. 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.
[0157] "Odor-masking agents" refer to known compounds (e.g. perfume
raw materials) that mask or hide a malodorous compound.
Odor-masking may include a compound with a non-offensive or
pleasant smell that is dosed such 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.
[0158] "Odor blocking agents" refer to known compounds that dull
the human sense of smell.
[0159] Exemplary diluents include dipropylene glycol methyl ether,
and 3-methoxy-3-methyl-1-butanol, and mixtures thereof.
[0160] 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.
II. Method of Laundering a Fabric
[0161] The method of laundering fabric typically comprises the step
of contacting the composition to water to form a wash liquor, and
laundering fabric in said wash liquor, wherein typically the wash
liquor has a temperature of above 0.degree. C. to 90.degree. C., or
to 60.degree. C., or to 40.degree. C., or to 30.degree. C., or to
20.degree. C., or to 10.degree. C., or even to 8.degree. C. The
fabric may be contacted to the water prior to, or after, or
simultaneous with, contacting the laundry detergent composition
with water. The composition can be used in pre-treatment
applications.
[0162] Typically, the wash liquor is formed by contacting the
laundry detergent to water in such an amount so that the
concentration of laundry detergent composition in the wash liquor
is from above 0 g/l to 5 g/l, or from 1 g/l, and to 4.5 g/l, or to
4.0 g/l, or to 3.5 g/l, or to 3.0 g/l, or to 2.5 g/l, or even to
2.0 g/l, or even to 1.5 g/l.
[0163] The method of laundering fabric may be carried out in a
top-loading or front-loading automatic washing machine, or can be
used in a hand-wash laundry application. In these applications, the
wash liquor formed and concentration of laundry detergent
composition in the wash liquor is that of the main wash cycle. Any
input of water during any optional rinsing step(s) is not included
when determining the volume of the wash liquor.
[0164] The wash liquor may comprise 40 litres or less of water, or
30 litres or less, or 20 litres or less, or 10 litres or less, or 8
litres or less, or even 6 litres or less of water. The wash liquor
may comprise from above 0 to 15 litres, or from 2 litres, and to 12
litres, or even to 8 litres of water.
[0165] Typically from 0.01 kg to 2 kg of fabric per litre of wash
liquor is dosed into said wash liquor. Typically from 0.01 kg, or
from 0.05 kg, or from 0.07 kg, or from 0.10 kg, or from 0.15 kg, or
from 0.20 kg, or from 0.25 kg fabric per litre of wash liquor is
dosed into said wash liquor.
[0166] Optionally, 50 g or less, or 45 g or less, or 40 g or less,
or 35 g or less, or 30 g or less, or 25 g or less, or 20 g or less,
or even 15 g or less, or even 10 g or less of the composition is
contacted to water to form the wash liquor.
[0167] The compositions herein may be packaged in any suitable
container, such as bottles, alternatively plastic bottles,
optionally equipped with an electrical or manual trigger
spray-head.
EXAMPLES
[0168] The examples herein are meant to exemplify the present
invention but are not necessarily used to limit or otherwise define
the scope of the present invention. All numerical values in the
below examples are weight %, by total weight of the composition
unless otherwise stated.
TABLE-US-00006 Ingredient Amount (in wt %) Anionic detersive
surfactant (such as alkyl benzene from 8 wt % to 15 wt %
sulphonate, alkyl ethoxylated sulphate and mixtures thereof)
Non-ionic detersive surfactant (such as alkyl ethoxylated from 0.5
wt % to 4 wt % alcohol) Cationic detersive surfactant (such as
quaternary ammonium from 0 to 4 wt % compounds) Other detersive
surfactant (such as zwiterionic detersive from 0 wt % to 4 wt %
surfactants, amphoteric surfactants and mixtures thereof)
Carboxylate polymer (such as co-polymers of maleic acid and from 1
wt % to 4 wt % acrylic acid) Polyethylene glycol polymer (such as a
polyethylene glycol from 0.5 wt % to 4 wt % polymer comprising poly
vinyl acetate side chains) Polyester soil release polymer (such as
Repel-o-tex and/or from 0.1 to 2 wt % Texcare polymers) Cellulosic
polymer (such as carboxymethyl cellulose, methyl from 0.5 wt % to 2
wt % cellulose and combinations thereof) Other polymer (such as
amine polymers, dye transfer from 0 wt % to 4 wt % inhibitor
polymers, hexamethylenediamine derivative polymers, and mixtures
thereof) Zeolite builder and phosphate builder (such as zeolite 4A
from 0 wt % to 4 wt % and/or sodium tripolyphosphate) Other builder
(such as sodium citrate and/or citric acid) from 0 wt % to 3 wt %
Carbonate salt (such as sodium carbonate and/or sodium from 15 wt %
to 30 wt % bicarbonate) Silicate salt (such as sodium silicate)
from 0 wt % to 10 wt % Filler (such as sodium sulphate and/or
bio-fillers) from 10 wt % to 40 wt % Source of available oxygen
(such as sodium percarbonate) from 10 wt % to 20 wt % Bleach
activator (such as tetraacetylethylene diamine (TAED) from 2 wt %
to 8 wt % and/or nonanoyloxybenzenesulphonate (NOBS) Bleach
catalyst (such as oxaziridinium-based bleach catalyst from 0 wt %
to 0.1 wt % and/or transition metal bleach catalyst) Other bleach
(such as reducing bleach and/or pre-formed from 0 wt % to 10 wt %
peracid) Chelant (such as ethylenediamine-N'N'-disuccinic acid from
0.2 wt % to 1 wt % (EDDS) and/or hydroxyethane diphosphonic acid
(HEDP) Photobleach (such as zinc and/or aluminium sulphonated from
0 wt % to 0.1 wt % phthalocyanine) Hueing agent (such as direct
violet 99, acid red 52, acid blue from 0 wt % to 1 wt % 80, direct
violet 9, solvent violet 13 and any combination thereof) Brightener
(such as brightener 15 and/or brightener 49) from 0.1 wt % to 0.4
wt % Protease (such as Savinase, Savinase Ultra, Purafect, FN3,
from 0.1 wt % to 0.4 wt % FN4 and any combination thereof) Amylase
(such as Termamyl, Termamyl ultra, Natalase, from 0.05 wt % to 0.2
wt % Optisize, Stainzyme, Stainzyme Plus and any combination
thereof) Cellulase (such as Carezyme and/or Celluclean) from 0.05
wt % to 0.2 wt % Lipase (such as Lipex, Lipolex, Lipoclean and any
from 0.2 to 1 wt % combination thereof) Other enzyme (such as
xyloglucanase, cutinase, pectate lyase, from 0 wt % to 2 wt %
mannanase, bleaching enzyme) Fabric softener (such as
montmorillonite clay and/or from 0 wt % to 4 wt %
polydimethylsiloxane (PDMS) Flocculant (such as polyethylene oxide)
from 0 wt % to 1 wt % Suds suppressor (such as silicone and/or
fatty acid) from 0 wt % to 0.1 wt % Perfume (such as perfume
microcapsule, spray-on perfume, from 0.1 wt % to 1 wt % starch
encapsulated perfume accords, perfume loaded zeolite, and any
combination thereof) Aesthetics (such as coloured soap rings and/or
coloured from 0 wt % to 1 wt % speckles/noodles) Miscellaneous
balance
TABLE-US-00007 Ingredient wt % Linear alkyl benzene sulphonic acid
(HLAS) 11 C1214 alkyl ethoxylated alcohol having an average degree
of 2 ethoxylation of 9 (AE9) C1214 alkyl ethoxylated sulphonic acid
having an average 23 degree of ethoxylation of 3 (HAES) C1617alkyl
mid chain branched alkyl sulphate 4 Amine oxide 1 C1218 fatty acid
2 Protease 2 Natalase 0.9 PE20 polymer 3 Polyethylene imine polymer
3 Chelant 1.4 FWA 15 Brightener 0.4 p-glycol 8 DEG 0.5 Ethanol 3
Monoethanolamine 6 Water 26 NaOH 0.3 Perfume 1 Silicone suds
suppressor 0.06 Violet DD dye 0.01 Other dyes 0.03 Hydrogenated
castor oil 0.1 Mica 0.2 Calcium formate 0.1 Sodium formate 0.2
Miscellaneous to 100
Analytical Test--Effect of Volatile Aldehydes on Amine-Based and
Sulfur-Based Malodors
[0169] 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.
[0170] A 1 .mu.L sample of each volatile aldehyde listed in Table 6
and of 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).
[0171] After the equilibration period, 1.5 mL of the target malodor
standard is injected into each 10 mL vial. For thiol analysis, the
vials containing a sample+malodor standard are held at room
temperature for 30 minutes. Then, a 1 mL headspace syringe is then
used to inject 250 .mu.L of each sample/malodor into a GC/MS
split/splitless inlet. For amine analysis, a 1 mL headspace syringe
is used to inject 500 .mu.L of each sample/malodor immediately into
the GC/MS split/splitless inlet. A GC pillow is used for the amine
analysis to shorten the run times.
[0172] 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 (56 for thiol and 30 for amine) and the
area is used to calculate the percent reduction from the malodor
standard for each sample.
[0173] Table 6 shows the effect of certain volatile aldehydes on
neutralizing amine-based and sulfur based malodors at 40 seconds
and 30 minutes, respectively.
TABLE-US-00008 TABLE 6 At least 20% At least 20% butylamine
butanethiol reduction at reduction at Perfume Raw Material (R--CHO)
40 secs.? 30 mins.? 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
[0174] Table 7 shows the percent reduction of butylamine and
butaniethiol at 40 seconds and 30 minutes, respectively, for
Accords A, B, and C.
TABLE-US-00009 TABLE 7 % reduction of % reduction of butylamine at
butanethiol at Accord 40 secs. 30 mins. Accord A 76.58 25.22 Accord
B 51.54 35.38 Accord C 65.34 24.98
Analytical Test--Effect of Acid Catalysts on Sulfur-Based
Malodors
[0175] The above analytical test is repeated using samples
containing an acid catalyst to test their effect on sulfur-based
malodors. Specifically, a 1 .mu.L aliquot of each of the following
controls and acid catalyst samples are pipeted into individual 10
mL silanized headspace vials in duplicate: thiophene
carboxyaldehyde as a control; a 50/50 mixture of thiophene
carboxaldehyde and each of the following acid catalysts at 0.04%,
0.10%, 0.43% in DPM, 1.02% in DPM, and 2.04% in DPM: phenol,
mesitylenic acid, caprylic acid, succinic acid, pivalic acid,
tiglic acid, and benzoic acid.
[0176] FIG. 1 demonstrates that low vapor pressure acid catalysts
provide up to 3 times better reduction of sulfur-based malodors in
comparison to the control.
Analytical Test--Effect of Volatile Aldehydes and Acid Catalyst on
Amine-Based and Sulfur-Based Malodors
[0177] The above analytical test is repeated using sample
formulations containing volatile aldehydes (or RA) and an acid
catalyst, as outlined in Tables 8 and 9.
[0178] Tables 8 and 9 show that a perfume mixture having as little
as 1% volatile aldehyde along with 1.5% acid catalyst performs
better at reducing butylamine and butanethiol than the same perfume
mixture having 5% volatile aldehyde.
TABLE-US-00010 TABLE 8 % butylamine % butanethiol reduction at
reduction at Formulation 40 secs. 30 mins. Perfume Mixture w/ 5% RA
34.21 -- 2.40 -- (Control) Perfume Mixture w/ 1% RA and 41.63 +7.42
11.95 +9.55 w/ 1.5% Benzoic Acid Perfume Mixture w/ 3% RA and 36.19
+1.98 13.56 +11.16 w/ 1.5% Benzoic Acid Perfume A Mixture w/ 5% RA
and 41.26 +7.05 9.56 +5.02 w/ 1.5% Benzoic Acid
TABLE-US-00011 TABLE 9 % butylamine % butanethiol Reduction at
reduction at Formulation 40 secs. 30 mins Perfume mixture w/ 5% RA
4.94 -- 10.52 -- (Control) Perfume mixture w/ 1% RA and 11.61 +6.67
18.82 +8.30 w/ 1.5% Benzoic Acid Perfume mixture w/ 3% RA and 26.89
+21.95 14.85 +4.33 w/ 1.5% Benzoic Acid Perfume mixture w/ 5% RA
and 20.27 +15.33 16.84 +6.32 w/ 1.5% Benzoic Acid
[0179] 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."
[0180] 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.
[0181] 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.
* * * * *
References