Note: Descriptions are shown in the official language in which they were submitted.
CA 02228966 2001-O1-02
I
DETERGENT COMPOSITIONS CONTAINING AMINE
AND SPECIALLY SELECTED PERFUMES
TECHNICAL FIELD
This invention relates to laundry detergent compositions containing amine
detersive surfactants and specially selected perfume components which reduce
the
malodor of the amine.
BACKGROUND OF THE INVENTION
It has long been known that certain amines are effective detergent
surfactants. However, a problem associated with many amines is an unattractive
odor resembling fish which remains present in detergent compositions
containing
the amine and even in fabrics which have been washed with the amine-containing
detergent.
It has now been found that including a certain amount of specially selected
perfume components in the laundry detergent can markedly reduce or eliminate
this malodor.
SUMMARY OF THE INVENTION
In one embodiment there is provided a laundry detergent composition in
liquid form comprising: (a) from about 0.05% to about 10%, by weight of
detergent composition of an amine detersive surfactant of the formula:
Rl-X-(CHZ)"N(R3)(R4)
wherein RI is a C6-C1z alkyl group; n is from about 2 to about 4, X is a
bridging
group which is selected from NH, CONH, COO, or O or X can be absent; and
R3 and R-0 are individually selected from H, C~-C4 alkyl, or (CHZ-CHZ-O(RS))
wherein RS is H or methyl; (b) FROM ABOUT 0.00001% to about 5%, by
weight of the composition, of a perfume component selected from the group
consisting of dodecahydro-3a,6,6,9A-tetramethylnaphtho (2,1-B) furan, 3,3-
dimethyl-5-(2,2,3 trimethyl-3 cyclopenten-1-yl)-4 pentenol, methyl lonone, cis
3
hexenyl iso butyrate, undecalactone, phenyl ethyl phenyl acetate, hexyl-ortho-
hydroxybenzoate, and mixtures thereof; and (c) from about 1 to about 95%, by
CA 02228966 2001-O1-02
la
weight of the composition, of other non-amine detersive surfactants selected
from anionic, nonionic, ampholytic, cationic, zwitterionic, and mixtures
thereof.
These perfume components act to reduce the malodor associated with
amine surfactants. Preferably the perfume components is selected from the
group
consisting of dodecahydro-3a,6,6,9A-tetramethylnaphtho (2,1-B) furan, 3,3-
dimethyl-5-(2,2,3 trimethyl-3 cyclopenten-1-yl)-4 pentenol, methyl lonone, cis
3
hexenyl iso butyrate, undecalactone, phenyl ethyl phenyl acetate, hexyl-ortho-
CA 02228966 2001-O1-02
2
hydroxybenzoate, and mixtures thereof; and
The compositions of this invention preferably further comprise a performance
enhancing amount of a detergent-compatible enzyme selected 6rom the group
consisting of proteax, lipase, amylase, ceUulase, peroxidase, and mixtures
thereof.
All parts, percentages and ratios used herein are expressed as percent ,weight
unless otherwix specified.
DESCRIPTION OF THE INVEN~~
The laundry detergent compositions herein comprix an effective amount of a
perfume component which acts to reduce the malodor associtated with the amine
surfactant. By "effective amount" means an amount sufficient to reduce the
amino-
type odor of the detergent compositions. Preferably, the detergent
compositions
herein will comprise from about 0.00001 % to about 5, more preferably about
0.00001% to about 2%, most preferably about 0.0001% to about 0.5%, by weight,
of speasUy selected perfume components. The perfume components which have
been found to reduce the amine malodor are thox with a low solubility in
water, i.e.,
they have a partition coeffcient value, (clogP), egos! to or higher than 2.0,
at
standard conditions of 25oC and 760 mm Hg in a water/octanol system.
Additionally
the perfume components of this invention should have a boiling point greater
than
200oF. The perfume components also have a unique properly of having a low odor
detection threshold (ODT) lower than about 300 PPB, preferably equal to or
Iowa
than shout 0.1 PP8. Than parameters ue fully explained in 'Compilation of Odor
and Taste T'tueshold Value Dsts. (ASTM DS 48 A)'. Edited by F. A Fauatari,
Inta~nationa! Businaa Machines, HopweU Juntion , NY.
Examples of preferred perfume components are thox selected from the group
coos;sting of dodxahydro-3a,6,6,9A-tetmrnr<hytnaphtho (2,1-g) furan, 3,3-
dimahyl-5-(Z,2,3 tlimathyt-3 cyclopenten-1-yl)-4 p~u~o~ lono
ne, cis 3
hexaryi iso butyrate, undecalactone, Phenyl ethyl Phenyl acetate, hexyl-ortho-
hydruxybenzoate, and mixtures thereof.
It is preferred that the speaally selected perfume components herein be mixed
together prior to addition to the laundry detergent composition. Those perfume
components may be combined with other perfume ingredients before addition to
the
composition.
The perfume containing these specially selected perfume components is
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WO 97/06235 PCT/US96/12611
3
preferably sprayed onto the final granular detergent composition or mixed into
the
final liquid laundry detergent in a manner which does not adversely affect the
perfume.
The amine - Although certain amines are effective surfactants, when present in
sufficient amounts, many posses an unattractive amine-type malodor which makes
them undesirable for laundry applications. Amines suitable for use in the
detergent
compositions herein include those according to the formula:
Rl-X-(CH2)n-N~3)~4)
wherein Rl is a C6-C12 alkyl group; n is from about 2 to about 4, X is a
bridging
group which is selected from NH, CONH, COO, or O or X can be absent; and R3
and R4 are individually selected from H, C 1-C4 alkyl, or (CH2-CH2-O(RS))
wherein
RS is H or methyl.
Preferred amines include the following:
Rl-(CH2)2-NH2
Rl-O-(CHa)3-NH2
Rl-C(O)-NH-(CH2)3 N(CFi3)2
Rl-N(CHZ-CH(OITj-RS)2
wherein Rl is a C6-C 12 alkyl group and RS is H or CH3.
In a highly preferred embodiment, the amine is described by the formula:
Ri-C(O)-NH-(CH2)3-N(CH3)2
wherein Rl is Cg-C12 alkyl.
Particularly preferred amines include those selected from the group consisting
of octyl amine, hexyl amine, decyl amine, dodecyl amine, Cg-C 12
bis(hydroxyethyl~mine, Cg-C12 bis(hydroxyisopropyl)amine, and Cg-C12 amido-
propyl dimethyl amine, and mixtures.
The laundry detergent compositions of the present invention typically comprise
from about 0.5% to about 10%, preferably from about 1% to about 5%, by weight
of
amine surfactants.
Non-Amine n~P~Pnt Surfactants - A wide range of non-amine, secondary
surfactants can be used in the detergent composition of the present invention.
By
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4
"non-amine" is meant herein any detersive surfactant which does not have the
unattractive "amine" malodor associated with its use in a detergent
composition.
Included in this definition of non-amine, therefor, is amine oxides.which do
not have
an amine-type odor.
A typical listing of anionic, nonionic, ampholytic and zwitterionic classes,
and
species of these w~ is given in US Patent 3,664,961 issued to Norris on May
23, 1972. The laundry detergent compositions of the present invention
typically
comprise from about 1°/. to about 95%, preferably from about 3% to
about 40%,
more preferably from about 5% to about 25%, by weight of such secondary, non-
amine surfactants.
One class of preferred anionic surfactants to be used in this invention are
the
alkyl alkoxylated sulfate surfactants which are water soluble salts or acids
of the
formula RO(A)mSO,M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl
group having a C 10-C24 ~ ~omPonent, prefasbly a C 12-C 18 ~Y1 or
hydroxyalkyl, more preferably C 12-C 15 ~ or hydroxyalkyi, A is an ethoxy or
propoxy unit, m is ,greater than zero, typically betyv~ 0.5 and about 6, more
preferably between about 0.5 and about 3, and M is H or a canon which can be,
for
example, a metal canon (e.g., sodium, potassium, lithium, calaum, ntagnaium,
ecc )
ammonium or sub~nium canon. Alkyl ethoxylued sulfates as well as
~ ProPoxY~~d are contemplated herein. Specific examples of substituted
atnrnonium canons ittchrde ethanol-, triahanol-, rr~yl_ ~~yl, yl-
ammomium rations and quaternary ammonium rations such as tetrameth
yl-ammonium
~ PiP~~m rations and those derived from alkylarnines such as
~~ ~~Y~~ylamine. mixtures thereof and the like. Exemplary
surfactants aro a 12-C 1 s ~ Poke ( 1.o) sulfate (e I2-c 1 sE( 1.oj~, c 12-
C 15 alkyl poiyethoxylate (2.25) sulfate (C 12-C 1 SE(2.25~, C 12-C 15 FYI
poiyethoxylste (3.0) sulfate (C 12'C 1 SF(3.0~, and C 12-C 15 ~ poiyethoxytate
(4.0) site (C 12~ 1 SE(4.0~, wherein M is conveniently selected from sodium
and potassium.
Another useful and preferred class of anionic s<ufiaants are the alkyl sulfate
p~ ~ a!~ sulfates which era wale soluble salts
or acids of the formula ROS03M wherein R preferably is a C8-C 18 hydrocubyl,
preferably an alkyl or hydroxyalkyl having a C 10-C 18 FYI component, more
preferably a C 12-C 15 a~ or hydroxyalkyl, and M is H or a ration, e.g., an
alkali
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WO 97/06235 PCT/US96/12611
metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted
ammonium (e.g. methyl-, dimethyl-, and trimethyl ammonium cations and
quaternary
ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium
cations
and quaternary ammonium cations derived from alkylamines such as ethylamine,
diethylamine, triethylamine, and mixtures thereof, and the like).
Other suitable anionic surfactants that can be used are alkyl ester sulfonate
surfactants including linear esters of Cg-C20 carboxylic acids (i.e., fatty
acids) which
are sulfonated with gaseous S03 according to "The Journal of the American Oil
Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials would
include
natural fatty substances as derived from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially for laundry
applications, comprise alkyl ester sulfonate surfactants of the structural
formula
R3-CH(S03 M)-C(O)-OR4
wherein R3 is a Cg-C20 hydrocarbyl, preferably an alkyl, or combination
thereof; R4
is a C 1-C6 hydrocacbyl, preferably an alkyl, or combination thereof, and M is
a cation
which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-
forming
cations include metals such as sodium, potassium, and lithium, and substituted
or
unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and
triethanolamine. Preferably, R3 is C 10-C 16 alkyl, and R4 is methyl, ethyl or
isopropyl. Especially preferred are the methyl ester sulfonates wherein R3 is
C 10-
016 ~Yl.
Other anionic surfactants useful for detersive purposes can also be included
in
the laundry detergent compositions of the present invention. These can include
salts
(including, for example, sodium, potassium, ammonium, and substituted ammonium
salts such as mono-, di- and triethanolamine salts) of soap, Cg-022 primary of
secondary alkanesulfonates, Cg-024 olefinsulfonates, sulfonated polycarboxylic
acids
prepared by sulfonation of the pyrolyzed product of alkaline earth metal
citrates, e.g.,
as described in British patent specification No. 1,082,179, Cg-024
alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide);
alkyl
glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol
sulfates, alkyl
~ phenol ethylene oxide ether sulfates, parai~n sulfonates, alkyl phosphates,
isethionates such as the aryl isethionates, N-aryl taurates, alkyl
succinamates and
' sulfosuccinates, monoesters of sulfosuccinates (especially saturated and
unsaturated
CA 02228966 2001-O1-02
6
C 12-C 1 g monoesters) and diesters of sulfosuccinates (especially saturated
and
unsaturated C6-C 12 diesters), sulfates of alkylpolysaccharides such as the
sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds being described below),
and
alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2p)k_
CH2C00-M+ ~,,~h~ R is a C8-C22 alkyl, k is an integer from 0 to 10, and M is a
soluble salt-forming cation. Resin acids and hydrogenated resin acids are also
suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated
resin
acids present in or derived from tall oil. Further examples are described in
"Surface
Active Agents and Detergents" (Vol. I and II by Schwarez, Perry and Berth). A
variety of such ~t$ ~e d~ g~erally disclosed in U.S. Patent 3,929,678,
iced December 30, 1975 to Laughlin, tt al. at Column 23, line 58 through
Column
29, line 23 .
One class of nonionic s~rrfactants useful in the present invention are
condensates
of ethylene oxide with s hydrophobic moiety to provide a surfactant having an
average hydrophilic-Gpophilic balance (HI.8) in the range from 8 to 17,
preferably
from 9.5 to 14, more preferably from 12 to 14. The hydrophobic (lipophilic)
moiety
may be aliphatic or aromatic in nature and the length of the polyoxyethylene
group
wtuch rs condensed with any particular hydrophobic group can be readily
adjusted to
yidd a water-soluble compound having the desired degree of balance between
hydrophilic and hydrophobic dements.
Espaialty preferred nonionic surfactants of this type are the C9-C I 5 PAY
doo~l ~Oxylatas containing 3-12 moles of ethylene oxide per mole of alcohol,
p~~ C12'C15 P~nnu'Y alcohols containing 5-8 moles of ethylene oxide per
mole of alcohol.
Another dasa of nonionic s<rrfactants comprises alkyl polyglucoside compounds
of general fonau4
R~CnH2n0)t~c
whadn Z is a moiety derived from glucox; R is a saturated hydrophobic alkyl
group
that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x
is from
1.3 to 4, thn compounds including less than I0~/. unrfatty d~hol and less than
50'/~ short chain alkyl polyglucosides. Compounds of this type and their use
in
d~aBeM are disclosed in F.P-8 0 070 077, 0 075 996 and 0 094 118.
Very suitable as nonionic surfactants are poly hydroxy fatty acid amide
sirr&aaras of the formula
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7
R2_C(O)-N(R 1 )-Z.
wherein R 1 is H, or R 1 is C 1 ~ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl or a
mixture thereof, R2 is CS_31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl
having
a Linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the
chain, or
as alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight
CI1-15
alkyl or alkenyl chain such as coconut alkyl or mixtures thereo>~ and Z is
derived from
a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive
amination
reaction.
krghly preferted nonionics are amine oxide surfactants. The compositions of
the present invention may comprise amine oxide in acxordance with the general
formula I:
RI~O~c(PO~O)zN(OXCH2R'~.qH20 (n
In general, it can be seen that the structure (I) provides one long-chain
moiety
R1(EO~(POh,(BO~ and two short chain moieties, CH2R'. R' is preferably selected
from hydrogen, methyl and -CH20H. In general R1 is a primary or branched
hydroca:byl moiety which can be saturated or unsat<usted, preferably, R 1 is a
Primacy alkyl moiety. When x+y+z = 0, Rl is a hydrocarbyl moiety having
chainlength of from about 8 to about 18. When x+y+z is different from 0, R1
may be
somewhat longer, having a chainlength in the range C 12-C24. The general
formula
also encompasxs amine oxides wherein x+y+z = 0, R 1 = Cg-C l g, R' = H and q =
0-
2, Pr~IY 2. These amine oxides are illustrated by C 12.14 ~~~Yi amine
oxide,hexsdecyl dimahylamine oxide, octadecylamine oxide and their hydrates,
~peaally the dihydrsta as dixlosed in U.S. Patents 5,075,501 and 5,071,594.
The invardon also encompasses amine oxides wherein x+y+z is dif~'erent from
zero, speeiseally x+y+z is from about 1 to about 10, Rl is a primary alkyl
group
containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon
atoms; in thex embodiments y + z is preferably 0 and x is preferably from
about 1 to
about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy;
PO
repraa~ts propyleneoxy; and BO represents butyleneoxy. Such amine oxides can
be
prepared by conventional synthetic methods, e.g., by the reaction of
alkylethoxysulfates with dimethylamine followed by oxidation of the
ethoxylated
CA 02228966 2001-O1-02
8
amine with hydrogen peroxide.
Highly preferred amine oxides herein are solids at ambient temperature, more
preferably they have melting-points in the range 30°C to 9Q°C,
pm;ne oxides
suitable for use herein are made commercially by a number of suppliers,
including
Akzo Chemie, Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation
and Kirk-Othmer review article for alternate amine oxide manufacturers.
Preferred
commercially available amine oxides are the solid, dehydrate ADMOXM 16 and
ADMOX 18, ADMOX 12 and especially A,DMOX 14 from Ethyl Corp.
Preferred embodiments include hexadecyldimethylamine oxide dehydrate,
octadecyldimethylamine oxide dehydrate, hexadecyltris(ethyleneoxy)dimethyl-
amine
oxide, and tetradecytdimethylamine oxide dehydrate.
Whueas in certain of the preferred embodiments R' = H, there is some latitude
with respect to having R' slightly larger than H. Specifically, the invention
further
encompasses embodiments wherein R' = CH20H, such as hexadecylbis(2-
hY~xY~thYl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-
hY~xYethyl~ne oxide and oleylbis(2- hydroxyethyl~n~ine oxide.
Cationic detaaive ~rr~ccan~ ~i~le for use in the laundry detergent
compositions of the present invention are those having one long-chain
hydrocarbyl
B~P~ ~ples of such cationic surfactants include tha ammonium surfactants such
as aUcyldimethylammonium halogenides, and those surfactants having the formula
[R2(OR3h,J(R4(OR3 )y12R5~-
wherein R2 is as alkyl or alkyl benryl group having from about 8 to about 18
carbon
atoms in the alkyl chtin, each R3 is selected from the group consisting of -
CH2CH2-,
-~2~~3~'. -CH2CH(CHZOH)-, -CH2CH2CH2-, and mixtures thereof each
R4 is sdaxed from the group consisting of CI-C4 alkyl, C -C h
ring struc~ura formed by joining the ~ R41 4 Y~oxY~cyt, benzyl
gr~Ps. -CH2CHOH
CHOHCOR6CHOHCH20H wherein R6 is any hexose or hexose polymer having a
molecular wdght less than about 1000, and hydrogen when y is not 0; R5 is the
same
as R4 or is an alkyl chain wherein the total number of carbon stoma of R2 plus
RS is
not moro than about 18; each y is from 0 to about 10 and the sun, of the y
values is
from 0 to about 15; and X is any compatible anion.
Frefa~red cuionic surfactants are the water-soluble quaternary ammonium
compounds useful in tix present composition having the formula
CA 02228966 2001-O1-02
9
R1R2R3R4N+X- (i)
wherein R 1 is Cg-C l 6 alkyl, each of R2, R3 and R4 is independently C 1-C4
alkyl,
CI-C4 hydroxy alkyl, benzyl, and -(C2H40}xH where x has a value from 1 to 5,
and
X is an anion. Not more than one of R2, R3 or R,4 should be benryl.
The preferred alkyl chain length for R 1 is C 12-C 15 P~~1~'lY where the alkyl
group is a mixture of chain lengths derived from coconut or palm kernel fat or
is
derived synthetically by olefin build up or OXO alcohols synthesis. Preferred
groups
for R2Rg and Rd are methyl and hydroxyethy) groups and the anion X may be
selected from halide, methosulphate, acetate and phosphate ions.
>:xamples'of suitable quaternary ammonium compounds of formulae (i) for use
herein are:
coconut trimethyl ammonium chloride or bromide;
coconut methyl dihydroxyethyl ammonium chloride or bromide;
decyl methyl ammonium chloride;
decyl dimethyl hydroxyethyl ammonium chloride or bromide;
C12-15 Yl l~Ydroxyethyi ammonium chloride or bromide;
coconut dimethyl hydroxyethyl ammonium chloride or bromide;
myristyl ttirntthyl ammonium methyl sulphate;
lauryl dimethyl benryl ammonium chloride or bromide;
lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide;
choline esters (compounds of formula (i) wherein Rl is -CH2-O.C(p).C12-14 ~Yl
and R2R3R4 are methyl).
Other cationic surfactants useful herein are also described in U. S. Patent
4,228,044, Carrrbre , issued October 14, 1980.
$y~,g - T to compositions according to tha pr~aar< invention ~ may further
comprise a builds systan. Any conventional builder system is suitable for use
herein
indudmg auurrinosiliate nutaials, silicsta, Polycarboxylates and fatty acids,
mstaials such as ethylenediamine tetraacetate, metal ion sequestrants such as
amnopotyphosphonstes, particulatfy ethylenediamine trtramrthylene phosphoric
acid
sad diethylene triamine pentamethylenephosphonic sad. Though less preferred
for
obvious environmental reasons, phosphate builders can also be used herein.
Suitable polycarboxylata builders for use herein include atric acid,
preferably
in the foam of a water-soluble salt, derivatives of succinic acid of the
formula R-
CH(COOH)CH~,~COOH) wherein R is C 10.20 alkyl or alkenyl, preferably C 12-16~
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WO 97/06235 PCT/US96/12611
or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone
substituents.
Specific examples include lauryl succinate , myristyl succinate, palmityl
succinate 2-
dodecenylsuccinate, Z-tetradecenyl succinate. Succinate builders are
preferably used .
in the form of their water-soluble salts, including sodium, potassium,
ammonium and
alkanolammonium salts.
Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate
monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
Especially for the liquid execution herein, suitable fatty acid builders for
use
herein are saturated or unsaturated C 10.18 fatty acids, as well as the
corresponding
soaps. Preferred saturated species have from 12 to 16 carbon atoms in the
alkyl
chain. The preferred unsaturated fatty acid is oleic acid. Other preferred
builder
system for liquid compositions is based on dodecenyl succinic acid and citric
acid.
Detergency builder salts are normally included in amounts of from 3% to 50%
by weight of the composition preferably from 5% to 30% and most usually from
5%
to 25% by weight.
Optional Deter~rrent Ingredients: - Preferred detergent compositions of the
present invention may further comprise one or more enzymes which provide
cleaning
performance and/or fabric care benefits. Said enzymes include enzymes selected
from
cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases,
lipases,
cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases,
lipoxygenases,
ligninases, pullulanases, tannases, pentosanases, malanases, . 13-glucanases,
arabinosidases or mixtures thereof.
A preferred combination is a detergent composition having a cocktail of
conventional applicable enzymes like protease, amylase, lipase, cutinase
and/or
cellulase in conjunction with the lipolytic enzyme variant D96L at a level of
from 50
LU to 8500 LU per liter wash solution.
The cellulases usable in the present invention include both bacterial or
fungal
cellulase. Preferably, they will have a pH optimum of between 5 and 9.5.
Suitable
cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which
discloses
fungal cellulase produced from Humicola insolens. Suitable cellulases are also
disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
Examples of such cellulases are cellulases produced by a strain of Humicola
insolens (Humicola grisea var. thermoidea), particularly the Humicola strain
DSM
1800. Other suitable cellulases are cellulases originated from Humicola
insolens
CA 02228966 2001-O1-02
11
having a molecular weight of about SOKDa, an isoelectric point of 5.5 and
containing
415 amino acids. Especially suitable cellulases are the cellulases having
color care
benefits. Examples of such cellulases are cellulases described in United
States
Patent No. 5,520,838 issued May 28,1996 (Novo).
Peroxidase enzymes are used in combination with oxygen sources, e.g.
percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for
"solution bleaching", i.e. to prevent transfer of dyes or pigments removed
from
substrates during wash operations to other substrates in the wash solution.
Peroxidase enzymes are known in the art, and include, for example, horseradish
peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-
peroxidase.
Peroxidssc-containing detergent compositions are disclosed, for example, in
PCT
International Application WO 89/099813 and in Canadian Patent application EP
No. 2,122,987 filed October 28, 1992.
Said cellulases andlor ptroxidases.are normally incorporated in the detergent
composition at levels from 0.0001% to 2% of active enzyme by weight of the
detergent composition.
Preferred commercially available protease enzymes include those sold under
the trademarks Alcalase, Savinase, Primase, Durazym,, and Esperase by Novo
Nordisk A/S (Denmark), those sold under the trademarks Maxatase, Maxacal and
Maxapem by Grist-Brocades,- those sold by Gmencor International, and those
sold
undo the trademarks Opticlean and Optima~e by Solvay Fnzymea. Also professes
described in our co-pending appUcation CA 2173105 can be included in the
detergent composition of the imrention. Protease enzyme may be incorporated
into
the compositions in u;cordance with the invention at a lend of from 0.0001'/.
to 2°/.
active a~zyme by weight of the composition.
A prefaced protease herein referred to as "Proteax D' is a carbonyl
hydrolsse variant having an amirro acid sequence not found in nature, which is
derived from a precursor carbonyl hydrolase by substituting a different amino
aad for
the amino acid residue at a position in said carbonyl hydrolase equivalent to
position
+76, preferably also in comb'u~ation with one or more amino acid residue
positions
equivalent to those selected from the group consisting of +99, +101, +103,
+104,
+107, +123, +27, +105, +109, +126, +I28, +135, +156, +166, +195, +197, +204,
+206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the
rurrnbering of Bacillus ~nyloliquefaciercs subtilisin, as described in the
concurrently
CA 02228966 2001-O1-02
12
filed patent application of A. Baeck et al. entitled "Protease-Containing
Cleaning
Compositions" having U.S. Patent No. 5679630 issued October 21, 1997.
F~ghly preferred enzymes that can be included in the detergent compositions
of the present invention include Gpases. It has been found that the cleaning
performance on greasy soils is synergistically improved by using Gpases.
Suitable
lipase enzymes include those produced by microorganisms of the Pseudomonas
group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British
Patent
1,372,034. Suitable lipases include those which show a positive immunological
aoss-reaction with the antibody of the lipase, produced by the microorganism
Pseudonrwas Jluorescens 1AM 1057. This lipase is available from Amano
Pharmacartical Co. Ltd., Nagoya, Japan, under the trade mark Lipase P
»Arnano,"
hereinafter referred to as "A~rnano.P». Further suitable lipases are fipases
such as M1
LipsseR and LipomaxR (Gist-Brocades). I~ghlY preferred .Lipase are the D96L
4Po~o variant of the native lipase derived from Humicola lanuginosa as
described in US Patent No. 5837010. Preferably the Humicola lanuginosa strain
DSM 4106 is used. This enzyme is incorporated into the composition in
accordance
with the invention at a levd of from 50 LU to 8500 LU per liter wash solution.
DIY ~ v~ant D96L is present at s levd of from 100 LU to 7500 LU pa liter
of wash solution. More preferably at a level of from 150 LU to 5000 LU per
liter of
wash solution.
By D96L lipolytic enzyme variant is meant the lipase variant as described in
patent application WO 92/05249 viz. wherein the naive lipase ex Humicola
lanuginosa aspartic acid (D) residue at position 96 is changed to Leucine (L).
According to this noma~clature said substitution of aspartic acid to Leucine
in
position 96 is shown as : D96L.
Also ~ritable are autinases [EC 3.1.1.50] which can be considered as a specdal
kind of lipase, sandy lipases which do not require interfaaal uxivation.
Addition of
cutinsaes to detergent compositions have been described in e.g. WO-A 88/09367
(Gara~cor).
The lipases and/or cutinaxs are norntally incorporated in the detergent
composition st levels from 0.0001 % to 2% of active enzyme by weight of the
detergent composition.
CA 02228966 2001-O1-02
13
Amylases (& and/or Q) can be included for removal of carbohydrate-based
stains. Suitable amylases are Termamyl~ (Novo Nordisk), FungamylR and BANK
(Novo Nordisk).
The above-mentioned enzymes may be of any suitable origin, such as
vegetable, animal, bacterial, fungal and yeast origin.
Said enzymes are normally incorporated in the detergent composition at levels
from 0.0001 % to 2% of active enzyme by weight of the detergent composition.
Other suitable detergent ingredients that can be added are enzyme oxidation
scavengers which are described in European Patent Publication 553607 published
August 4, 1993. Examples of such enzyme oxidation scavengers are ethoxylated
tetraethylene polyamines.
Other components used in detergent compositions may be employed, such as
soil-suspending agents, soil-release polymers, abrasives, bactericides,
tarnish
inhibitors, coloring agents, foam control agents, corrosion inhibitors and
other
perfumer.
Soil Release Anent - Arry soil release agents known to thox skilled in the art
can be employed in the practice of this invention. Prefaced polymeric soil
releaser
agents are characterized by having both hydrophilic xgments, to hydrophilize
the
surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic
xgments, to deposit upon hydrophobic fibers and remain adhered thereto through
completion of washing and rinsing cycles and, thus, save as an anchor for the
hydrophilic segments. This can enable stains occurring subsequent to treatment
with
the soil releax agent to be more easily cleaned in later washing procedures.
Useful soil rdease polymers are described in U.S. Pata~t 4,000,093, issued
Decanter 28, 1976 to Ncol et al., European Patent Application 0 219 048,
published April 22, 1987 by Kud et al. U.S. Patent 3,959,230 to Flays, issued
May
25; 1976, U.S. Patent 3,893,929 to Basadur issued July 8, 1975, U.S. Patent
4,702,857, issued October 27, 1987 to Gosselink, U.S. Patent 4,711,730, issued
December 8, 1987 to Gosselink et al., U.S. Patent 4,721,580, issued January
26,
1988 to Cossdidc, U.S. Patent 4,702,857, issuod October 27, 1987 to Gosse4nk,
U.S. Patent 4,877,896, issued October 31, 1989 to Maldonsdo et al.
If utilized, soil rdease agents will generally comprise from about 0.01 % to
about 10.0%, by weight, of the detergent compositions herein, typically from
about
CA 02228966 2001-O1-02
14
0.1% to about 5%, preferably from about 0.2% to about 3.0%.
~~- The detergent compositions herein may also optionally
contain one or more iron and manganese chelating agents as a builder adjunct
material. Such chelating agents can be selected from the group consisting of
am;no
carboxylates, amino phosphonates, polyfunctionally -substituted aromatic
chelating
agents and mixtures thereo>; all as hereinafter defined. Without intending to
be
bound by theory, it is believed that the b~~t of these materials is due in
part to their
exceptional ability to remove iron and manganese ions from washing solutions
by
formation of soluble chelates.
If utilized, these chelating agents will generally comprise from about 0.1 %
to
about 10% by weight of the detergent compositions herein. More preferably
chelating agents will comprise from about 0.1% to about 3.0~/° by
weight of such
compositions.
Cl_av .~ ~I -1'he compositions of the present
invention can also optionally contain water-soluble ethoxylated amines having
clay
soil removal and anti-redeposidon properties. Liquid detergent compositions
which
contain these compou~s typically contain from about 0.01 % to 5%.
The most preferred soil rdease and anti-redeposit;on agent is ethoxylated
tYl~apentamine. Exemplary ethoxylated amines are firrtha descr,'b~ in U. S.
Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred
clay soil removaUanti-redeposition agents are the cationic compounds disclosed
in
European Patent Application 111,965, Oh and Gosselink, published June 27,
1984.
Other clay soil removaUanti-redeposition agents which can be used include the
ethoxylated amine polymers disclosed in European Patent Application 111,984,
Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in
European Patent Application 112,592, Gosselink, published July 4, 1984; and
the
amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22,
1985.
Other clay soil removal and/or anti redeposition agents known in the art can
also be utilized in the compositions hereof. Another type of preferred anti-
redeposition agent includes the carboxymethylcellulose (CMC) materials.
~~.~~.AQI~ - Polymeric dispersing agents can advantageously
be utilized in the compositions hereof. These materials can aid in calcium and
CA 02228966 2001-O1-02
15
magnesium hardness control. Suitable polymeric dispersing agents include
polymeric
polycarboxylates and polyethylene glycols, although others known in the art
can also
be used. The compositions hereof will generally comprise from 0% to about 5%
of
polymeric dispersing agent.
Suitable polymeric dispersing agents for ux herein are described in U.S.
Patent
3,308,067, Diehl, issued March 7, 1967, and European Patent App4eation No.
66915, published December 15, 1982,
Brig - Any suitable optical brightenen or other brightening or whitening
agents known in the art can be incorporated into the detergent compositions
hereof.
The compositions hereof will generally comprise atom 0% to about 5% of
brightener
Commercial optical brighteners which may be useful in the present invention
can be classified into subgroups which include, but are not necessarily
limited to,
derivatives of stilbene, pyrazoline, coumarin, carboxylic acid,
mtthinecyanines,
dibenzothiphene-5,5-dioxide, azoles, 5~ and 6-membered-ring heterocycles, and
other
misceUacteous agents. Examples of such brighteners are discloxd in "The
Production
and Application of Fluarescertt Brightening Agents", M. Zahradnik, Published
by
John Whey & Sons, New York (1982
Suds Supi~messur. -Compounds known, or which become known, for reducing
or suppressing the formation of suds can be incorporated into the compositions
of the
prexnt imemion. Suitable suds supprcssors are described in. ICirk Othmer
Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447
(John Whey 8t Sons, Inc., 1979), U.S. Patent 2,954,347, issued September 27,
1960
to St. John, U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo a at., U.S.
Patent 4,265,779, issued Msy 5, 1981 to Gandolfo et al. and European Patent
Publication 354016, published February 7, 1990, U.S. Pstent 3,455,839,
German Patent Application DOS 2,124,526, U.S. Pata~t 3,933,672, Bartolotta et
al.,
and U.S. Patent 4,652,392, Baginski et al., issued March 24, 1987.
The vompositions hareof will generally comprix from 0°/. to about 5%
of suds
suppressor.
Other ~ ~ The compositions herein may also contain other perfume
ingredients such as aldehydes, ketones, alcohols and esters. They have been
described by Parry in Parry's Cycloyedia of Perfumarv (1925) Vol. I and II
published
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WO 97/06235 PCT/US96/12611
16
by P. Blakiston's Son & Co.; and also by Bedoukian in Perfumarv and Flavoring
Synthet~ (1967), published by Elsevier Publishing Company.
A wide variety of other ingredients useful in detergent compositions can be
included in the compositions hereof, including other active ingredients,
carriers,
hydrotropes, processing aids, dyes or pigments, solvents for liquid
formulations,
bleaches, bleach activators, enzyme stabilizing systems, etc.
Lei uid Comnositions - The laundry detergent compositions herein preferably
have a pH in a 10% solution in water at 20oC of between about 5 and about 12,
more preferably between about 8 and about 12 for granular compositions.
Liquid detergent compositions can contain water and other solvents as
carriers.
Low molecular weight primary or secondary alcohols exemplified by methanol,
ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are
preferred
for solubilizing surfactant, but polyols such as those containing from 2 to
about 6
carbon atoms and from 2 to about 6 hydroxy groups (e.g., propylene glycol,
ethylene
glycol, glycerine, and 1,2-propanediol) can also be used.
Preferred liquid laundry detergent compositions hereof will preferably be
formulated such that during use in aqueous cleaning operations, the wash water
will
have a pH of between about 6.5 and 11.0, preferably between about 7.0 and 8.5,
The
liquid detergent compositions herein preferably have a pH in a 10% solution in
water
at 20oC of between about 6.5 and 11.0, preferably 7.0 to 8.5. Techniques for
controlling pH at recommended usage levels include the use of buffers,
alkalis, acids,
etc., and are well known to those skilled in the art.
Preferably, the liquid compositions according to the present invention are in
"concentrated form"; in such case, the liquid detergent compositions according
to the
present invention will contain a lower amount of water, compared to
conventional
liquid detergents. The level of water is less than 50%, preferably less than
30% by
weight of the detergent compositons.
Said concentrated products provide advantages to the consumer, who has a
product which can be used in lower amounts and to the producer, who has lower
shipping costs.
The liquid compositions are especially effective when applied directly to
soils
and stains in a pretreatment step.
The detergent compositions of the present invention can also be used as
detergent additive products. Such additive products are intended to supplement
or
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WO 97/06235 PCT/US96/12611
17
boost the performance of conventional detergent compositions.
The detergent compositions according to the present invention include
compositions which are to be used for cleaning of substrates,
such as fabrics, fibers,
hard surfaces, skin etc., for example hard surface cleaning
compositions (with or
without abrasives), laundry detergent compositions, automaticand non-automatic
dishwashing compositions.
The following examples illustrate the compositions of the
present invention.
All parts, percentages and ratios used herein are by weightotherwise
specified.
unless
EXAIyIPLE I
A "fresh~citrus" perfume is prepared using the following
components:
PERFUM1E A % BY
WEIGFIZ'
Alpha terpineol 1.80
Citronellol 1.50
Citronellyl acetate 1.08
Geraniot 1.26
Isobornyl acetate 1.08
Linaloot 1.44
Linalyl acetate 2.10 ,
Campl~ne 0.78
Fenchyl acetate 0.12
Alpha pinene 1.50
Beta pinene 1.08
Citral 2.40
Citrathal 0.74
Citronella) nitrite 0.84
Dihydromyrcenol 0.60
Dipenteae 3.00
Geranyl nitrite 0.60
Lemon oil 0.30
Orange oil 2x rectified 2.40
p~y 1.26
Pseudo linalyl acetate 1.20
dodecahydro-3a,6,6,9Axerramethylnaphtho (2,1-B) furan 5.00
Other perfume components 72.74
100.00
This perfume is then useful in detergent compositions, particularly
when amine
surfactants are present. The perfume can be used at a level
of from about 0.01% to
about 1%, by weight of the detergent composition.
The dodecahydro-3a,6,6,9A-tetramethylnaphtho (2,1-B) furan is
substituted
with an equal amount of one or more of the following perfume
components: 3,3-
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18
dimethyl-5-(2,2,3 trimethyl-3 cyclopenten-1-yl)-4 pentenol, methyl lonone, cis
3
hexenyl iso butyrate, undecalactone, phenyl ethyl phenyl acetate, hexyl-ortho-
hydroxybenzoate, and mixtures thereof. ,
EXAMPLE II
A "fresh" perfume is prepared using the following components:
~E1~FLJME B % BY
~V_EIGHT'
IFF-917* 92.00
Dodecahydro-3a,6,6,9A-tetramethylnaphtho (2,1-B) furan 0.30
3,3-dimethyl-5-X2,2,3 trimethyl-3 cyclopenten-1-yl)-4 pentenol 0.15
Methyl lonone 1.55
Cis 3 hexenyl iso butyrate 0.25
IJndecalactone 0.30
Phenyl ethyl phenyl acetate 1.15
Hexyl-ortho-hydroxybenzoate 4.30
100.00
*Supptied by International Flavor and Fragrance Company of New Jersey
This perfume is then useful in detergent compositions, particularly when amine
surfactants are present. The perfume can be used at a level of from about
0.01% to
about 1%, by weight ofthe detergent composition.
E~~AMPLE III-VIII
The following liquid detergent compositions are made
In edient Exam le III Exam le IV
Wt % Wt
Sodium C12-l5alkyl polyethoxylate13.50 13.70
(2.5)
sulfate
Sodium 12-15 1 sulfate 4.50 4.00
Ethanol 3.50 2.64
Monoethanolamine 1.00 0.75
C 10 amido ro ldameth i amine 1.75 1.3
Pro andiol 7.50 7.50
C12-13A1 1 0l etho late 9 2.00 0.63
C12-14 1 ucose amide 4.50 3.35
C12-14 fa acid 2.00 3.50
Sodium toluene sulfonate 2.50 2.25
Citric acid 3.00 2.65
PERFRJMfC A 0.01 1.00 ,
Enzymes ~ 0.05 0.05
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WO 97/06235 PCT/US96/12611
19
Borax _ 3.50 3.50
Sodium h droxide to H 8.0 2.95 to H =8.02.10 to H =
7.6
Tetraeth lene entamine etho fated1.18 1.18
15-18
Water to 100% to 100%
Perfume A may be substituted with an equal amount of Perfume B.
The Clp amidopropyldimethyl amine is substituted with an equal amount of the
following amines: octyl amine, hexyl amine, decyl amine, dodecyl amine, Cg-C
12
bis(hydroxyethyl)amine, Cg-C 12 bis(hydroxyisopropyl)amine, and Cg, C~, C 11
or
C 12 amido-propyl dimethyl amine, and mixtures.
The follovtring enzymes are used: protease, lipase, amylase, cellulase,
peroxidase, and mixtures thereof.
In edient Exam le V
Wt%
Sodium C12-15 1 0l etho late 2.5 sulfate 9.40
Sodium 12-15 1 sulfate 3.10
Ethanol 2.18
Monoethanolamine 1.00
C10 amido ro Idimeth 1 amine surfactant 4.30
Pro andiol 3.20
C12-13A1 1 0l etho late 9 1.00
C12-14 1 ucose amide 2.00
C 12-14 fa acid 1.00
Sodium toluene sulfonate 2.25
Citric acid 1.80
P~ A 0.5
E es 0.05
Borax -
Sodium h droxide to H 8.0 2.07 to H
= 8.0
Tetraeth lene entamine etho fated 15-18 1.00
Water to 100%
The C 1 p amidopropyldimethyl amine is substituted with an equal amount of the
following amines: octyl amine, hexyl amine, decyl amine, dodecyl amine, Cg-C12
bis(hydroxyethyl)amine, Cg-C 12 bis(hydroxyisopropyl)amine, and Cg, Cg, C 11
or
C 12 amido-propyl dimethyl amine, and mixtures.
' The following enzymes are used: protease, lipase, amylase, cellulase,
peroxidase, and mixtures thereof.
Perfume A may be substituted with an equal amount of Perfume B.
CA 02228966 1998-02-06
WO 97/06235 PCT/US96/1261 I
ZO
In edient Exam le VI Exam le VII
Wt% Wt%
Sodium C12-15 1 0l etho late 3 13.70 13.70
sulfate
Sodium 12-15 1 sulfate 4.00 4.00
Ethanol 2.64 2.64
Monoethanolamine 0.75 0.75
O 1 amine 3,0
C 12 amido ro Idimeth 1 amine -- 0.5
Pro andiol 7.50 7.50
C12-13AI I of etho late 9 0.63 0.63
C12-14 I ucose amide 3.35 3.35
C 12-16 fa acid 3.50 3.50
Sodium toluene sulfonate 2.25 2.25
Citric acid 2.65 2.65
PERFUME A 0.25 0.05
E a 0.1 0.075
Borax 3.50 3.50
Sodium h droxide 2.1 to H 2.1 to H
= 7.6 = 7.6
Tetraeth lene entamine etho fated 1.18 1.18
15-18
Water, & other o tional in edientsto 100% to 100%
Perfume A may be substituted with an equal amount of Perfume B.
The amines are substituted with an equal amount of the following amines:
hexyl amine, decyl amine, dodecyl amine, Cg-C 12 bis(hydroxyethyl)amine, Cg-C
12
bis(hydroxyisopropyl)amine, and Cg_11 amido-propyl dimethyl amine, and
mixtures.
The following enzymes are used: protease, lipase, amylase, cellulase,
peroxidase, and mixtures thereof.
In edient Exam le VIII
Wt%
Sodium C12-15 I of etho late 3 sulfate 13.70
Sodium 12-15 1 sulfate 4,00
Ethanol 2.64
Monoethanolamine 0.75
O I amine
C12 bis h dro eth 1 amine 2.0
Pro andiol 7.50
C12-13AI 1 0l etho late 9 0.63 '
C12-14 1 ucose amide 3.35
C12-16 fa acid 3.50
Sodium toluene sulfonate 2.25
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WO 97/06235 PCT/US96/12611
21
Citric acid 2.65
PERFLTME B 0.75
E a 0.25
Borax 3.50
Sodium h droxide 2.1 to H =
7.6
Tetraeth lene entamine etho fated 15-18 1.18
Water, & other o tional in edients to 100%
Perfume B may be substituted with an equal amount of Perfume A.
The C 12 bis (hydroxyethyl) amine is substituted with an equal amount of the
following amines: octyl amine, hexyl amine, decyl amine, dodecyl amine, Cg-C
11
bis(hydroxyethyl)amine, Cg-C12 bis(hydroxyisopropyl)amine, and Cg-12 amido-
propyl dimethyl amine, and mixtures.
The following enzymes are used: protease, lipase, amylase, cellulase,
peroxidase, and mixtures thereof.
All detergent compositions in the above examples have a significantly reduced
amine malodor as compared to equal formulations which do not contain the
perfume
components included above.
A
