Note: Descriptions are shown in the official language in which they were submitted.
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LIQUID LAUNDRY DETERGENT COMPOSITION
FIELD OF THE INVENTION
The present invention relates to liquid detergent compositions comprising only
biodegradable
and eco-friendly ingredients that exhibit exceptional performance compared to
traditional
detergent formulations that use less friendly surfactant and builder
ingredients. In particular, this
invention relates to ecologically responsible liquid laundry detergent
compositions that utilize
unique surfactant-builder-enzyme combinations in conjunction with performance
boosting
natural essences.
BACKGROUND OF THE INVENTION
Liquid laundry detergents have been known in the art for decades. Modem
detergents are often
comprised of blends of synthetic anionic, nonionic and cationic surfactants,
along with any
number of additional ingredients such as builders, water-conditioners,
dispersants, soil-release
polymers, detersive enzymes and bleaching agents to improve cleaning
performance and to
achieve performance/cost optimized compositions that are consumer acceptable.
Although major
strides over decades have moved laundry detergents away from environmentally
adverse
ingredients such as phosphates, much of the liquid detergents today
unfortunately continue to use
synthetic surfactants that although biodegradable are petroleum derived. There
is a continued
need to improve the environmental profile of these liquid laundry detergents.
Many of the
surfactants used today are of petroleum base rather than vegetable or animal
sourced.
Additionally, there is a need to improve the environmental profile of some
solvents, synthetic
polymers, chelants, and bleaching agents. The art is nearly void of
compositions that claim the
use of eco-friendly ingredients yet still have suitable performance.
Heretofore there have simply
been no suitable "across-the-board" substitutions of environmentally
challenging ingredients with
eco-friendly ingredients in a liquid laundry detergent composition that can
provide consumer
acceptable performance at reasonable cost to the manufacturer. It is simple
(as shown in the art)
to make small substitutions, for example, reduction of builder and/or
surfactant levels by
increasing enzyme levels, or elimination of phosphates by substitution with
other carbonate or
bicarbonate builders and biodegradable chelants, but no where is there
described the complete
replacement of all ingredients in a composition with eco-friendly ingredients
to produce an
environmentally responsible composition that still provides comparable
performance.
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One way to increase performance in a liquid laundry detergent and
concomitantly improve its
environmental profile is to replace high surfactant and builder levels with
high enzyme levels.
This strategy is well known in the art, for example US Patent Application
Publication
US2006/0205628 to Novozymes describes in general terms the "replacement of
surfactants,
builders, polymers, and bleaches in detergent compositions with enzymes".
However, it is
problematic to apply this strategy for the replacement of all environmentally
challenging
ingredients within a composition, as the required multiple types of enzymes
need to be combined
and stabilized in ways that heretofore have not been explored, and additional
ingredients beyond
the enzymes will be needed to make up for lost performance, (e.g. abnormally
high levels of
optical brightener, or synthetic polymers). For example, when common
surfactants are replaced
with eco-friendly surfactants, and the highly alkaline builder/chelant systems
are eliminated, then
simply increasing enzyme level is not enough, and the technology that is truly
missing from the
art is how to combine the right combinations of different enzymes at the right
levels, using the
right enzyme stabilizers with the right eco-friendly co-ingredients to boost
the performance back
to consumer acceptable levels.
One attempt to achieve a multiple-enzyme/surfactant based laundry detergent
system is described
in U.S. Pat. No. 6,060,441 to Hessel, et al.
Incorporating essential oils into detergent compositions is barely known in
the laundry detergent
context. However, solvent cleaners containing essential oils are well known in
institutional and
household hard surface cleaning. For example, the popular OrangeGlo®
cleaners, marketed
by Church & Dwight Co., Inc., are stable micro-emulsions of natural oils such
as orange oil in
water with surfactants and other ingredients. Patent examples include U.S.
Pat. No. 6,407,051 to
Smith, et al. that describes emulsifying oils or hydrocarbons such as mineral
oil, mineral spirits,
pine oil, fatty esters, carboxylic diester oils, motor oils, or triglycerides,
and the like into stable
water-in-oil micro-emulsions through a combination of alcohol ethoxylate and
alkyl
polyglycoside surfactant mixtures.
U.S. Pat. No. 6,136,778 to Kamiya describes the incorporation of essential
oils into dishwashing
detergents.
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Additionally, U.S. Pat. No. 6,333,301 also to Kamiya claims a particulate
detergent incorporating
as much as 10% by weight of terpenes.
Finally, U.S. Pat. No. 7,033,984 to Hafkamp, et al., and U.S. Pat. No.
7,030,077 to Beers, et al.,
claim herbal benefit in the laundry through the incorporation of herbal
extracts in laundry
detergents that deposit the benefit agent onto the clothing that then
transfers the benefit agent to
the person wearing that clothing.
SUMMARY OF THE INVENTION
The present invention provides a liquid laundry detergent composition as
defined in the claims.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a liquid composition for laundering fabrics
that exhibits good
performance such as stain removal and whiteness retention. In a preferred
embodiment, the
compositions are comprised entirely of ecologically responsible ingredients.
The liquid laundry
detergent compositions of the present invention may include anionic surfactant
components,
preferably alkyl ether sulfates, alkyl sulfate, alpha-sulfonated fatty acid
esters, and/or fatty acid
soaps, which together total from about lwt% to about 20wt%; optionally
nonionic surfactants,
most preferably the non-petroleum derived fatty alcohol ethoxylates and/or
alkyl polyglycoside
surfactants, totaling from about lwt% to about lOwt%; optionally, a "natural
essence" such as an
essential oil, natural tree, plant, fruit, nut or seed extract, or other
purified synthetic organic
material to boost performance and enzyme stability, and in many instances to
also provide
fragrance, totally from about O.lwt% to about 5wt%; optionally, a builder,
most preferably
carbonate, bicarbonate, and/or citrate, present from about O.lwt% to about
lOwt%; optionally a
soil dispersant/anti-redeposition or soil releasing polymer from about O.lwt%
to about 5wt%;
and, optionally one or more detersive enzymes at from about 0.0001wt% to about
5wt%.
It is highly preferred for the composition to be essentially free from Boron.
Preferably, no
deliberately added boron is incorporated into the composition.
Anionic Surfactant Component
The eco-friendly detergent compositions of the present invention preferably
include at least one
anionic surfactant. Preferred anionic surfactants for use in the present
invention include the alkyl
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ether sulfates, also known as alcohol ether sulfates. Alcohol ether sulfates
are the sulfuric
monoesters of the straight chain or branched alcohol ethoxylates and have the
general formula R-
-(OCH2CH2)x-O-SO3M, where R preferably comprises C7-C21 alcohol ethoxylated
with from
about 0.5 to about 9 mol of ethylene oxide (i.e., x=0.5 to 9 EO), such as C12-
C18 alcohols
containing from 0.5 to 9 EO, and where M is alkali metal or ammonium, alkyl
ammonium or
alkanol ammonium counterion. Preferred alkyl ether sulfates for use in one
embodiment of the
present invention are C8-C18 alcohol ether sulfates with a degree of
ethoxylation of from about
0.5 to about 9 ethylene oxide moieties and most preferred are the C12-C15
alcohol ether sulfates
with ethoxylation from about 4 to about 9 ethylene oxide moieties, with 7
ethylene oxide
moieties being most preferred. In another embodiment, the C12-C15 alcohol
ether sulfates with
ethoxylation from about 0.5 to about 3 ethylene oxide moieties are preferred.
In keeping with the
spirit of only using natural feedstock for ingredients for an eco-friendly
detergent of the present
invention, the fatty alcohol portion of the surfactant is preferably animal or
vegetable derived,
rather than petroleum derived. Therefore the fatty alcohol portion of the
surfactant will comprise
distributions of even number carbon chains, e.g. C12, C14, C16, C18, and so
forth. It is
understood that when referring to alkyl ether sulfates, these substances are
already salts (hence
"sulfate" nomenclature), and most preferred and most readily available are the
sodium alkyl ether
sulfates (also referred to as NaAES, or simply FAES). Commercially available
alkyl ether
sulfates include the CALFOAM® alcohol ether sulfates from Pilot Chemical,
the
EMAL®, LEVENOL® and LATEMAL® products from Kao Corporation, and
the
POLYSTEP® products from Stepan, most of these with fairly low EO content
(e.g., average
3 or 4-EO). Alternatively the alkyl ether sulfates for use in the present
invention may be prepared
by sulfonation of alcohol ethoxylates (i.e., nonionic surfactants) if the
commercial alkyl ether
sulfate with the desired chain lengths and EO content are not easily found,
but perhaps where the
nonionic alcohol ethoxylate starting material may be. For example, sodium
lauryl ether sulfate
("sodium laureth sulfate", having about 2-3 ethylene oxide moieties) is very
readily available
commercially and quite common in shampoos and detergents. Sodium lauryl ether
sulfate is
preferred for use in the detergents of the present invention. Depending on the
degree of
ethoxylation desired, it may be more practical to sulfonate a commercially
available nonionic
surfactant such as Neodol® 25-7 Primary Alcohol Ethoxylate (a C12-C15/7EO
nonionic
from Shell) to obtain for example the C12-C15/7EO alkyl ether sulfate that may
have been more
difficult to source commercially. However, the most preferred alkyl ether
sulfate for use in the
present invention is sodium lauryl sulfate-2EO, available as Calfoam® ES-
302 from Pilot
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Chemical. The preferred level of C12-C18/0.5-9EO alkyl ether sulfate for use
in the present
invention is from about lwt% to about 50wt%. More preferred is to incorporate
sodium lauryl
ether sulfate (e.g. Calfoam® ES-302) from about 3wt% to about 15wt%
actives weight
basis.
Other optionally anionic surfactants that may find use in the compositions of
the present
invention include the alpha-sulfonated alkyl esters of C12-C16 fatty acids.
The alpha-sulfonated
alkyl esters may be pure alkyl ester or a blend of (1) a mono-salt of an alpha-
sulfonated alkyl
ester of a fatty acid having from 8-20 carbon atoms where the alkyl portion
forming the ester is
straight or branched chain alkyl of 1-6 carbon atoms and (2) a di-salt of an
alpha-sulfonated fatty
acid, the ratio of mono-salt to di-salt being at least about 2:1. The alpha-
sulfonated alkyl esters
useful herein are typically prepared by sulfonating an alkyl ester of a fatty
acid with a sulfonating
agent such as S03. When prepared in this manner, the alpha-sulfonated alkyl
esters normally
contain a minor amount, (typically less than 33% by weight), of the di-salt of
the alpha-
sulfonated fatty acid which results from saponification of the ester.
Preferred alpha-sulfonated
alkyl esters contain less than about 10% by weight of the di-salt of the
corresponding alpha-
sulfonated fatty acid.
The alpha-sulfonated alkyl esters, i.e., alkyl ester sulfonate surfactants,
include linear esters of
C8-C20 carboxylic acids that are sulfonated with gaseous S03 as described in
the The Journal
of American Oil Chemists Society," 52 (1975), pp. 323-329. Suitable starting
materials
preferably include natural fatty substances as derived from tallow, palm oil,
etc., rather than
petroleum derived materials. The preferred alkyl ester sulfonate surfactants,
especially for
laundry detergent compositions of the present invention, comprise alkyl ester
sulfonate
surfactants of the structural formula R3-CH(SO3M)-CO2R4, wherein R3 is a C8-
C20
hydrocarbon chain preferably naturally derived, R4 is a straight or branched
chain Cl-C6 alkyl
group and M is a cation which forms a water soluble salt with the alkyl ester
sulfonate, including
sodium, potassium, magnesium, and ammonium cations. Preferably, R3 is C10-C16
fatty alkyl,
and R4 is methyl or ethyl. Most preferred are alpha-sulfonated methyl or ethyl
esters of a
distribution of fatty acids having an average of from 12 to 16 carbon atoms.
For example, the
alpha-sulfonated esters; Alpha-Step® BBS-45, Alpha-Step® MC-48, and
Alpha-
Step® PC-48, all available from the Stepan Co. of Northfield, Ill., may
find use in the
present invention. However, the methyl esters are derived from methanol
sources. Thus, the ethyl
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esters, which are currently not commercially available, would be the most
preferred alpha-
sulfonated fatty acid esters. When used in the present invention, the alpha-
sulfonated alkyl ester
is preferably incorporated at from about 3% to about 15% by weight actives.
The compositions of the present invention may also include fatty acid soaps as
an anionic
surfactant ingredient. The fatty acids that may find use in the present
invention may be
represented by the general formula R-COOH, wherein R represents a linear or
branched alkyl or
alkenyl group having between about 8 and 24 carbons. It is understood that
within the
compositions of the present invention, the free fatty acid form (the
carboxylic acid) will be
converted to the carboxylate salt in-situ (that is, to the fatty acid soap),
by the excess alkalinity
present in the composition from added alkaline builder. As used herein, "soap"
means salts of
fatty acids. Thus, after mixing and obtaining the compositions of the present
invention, the fatty
acids will be present in the composition as R--COOM, wherein R represents a
linear or branched
alkyl or alkenyl group having between about 8 and 24 carbons and M represents
an alkali metal
such as sodium or potassium. The fatty acid soap, which is often a desirable
component having
suds reducing effect in the washer, (and especially advantageous for side
loading or horizontal
tub laundry machines), is preferably comprised of higher fatty acid soaps. The
fatty acids that are
added directly into the compositions of the present invention may be derived
from natural fats
and oils, such as those from animal fats and greases and/or from vegetable and
seed oils, for
example, tallow, hydrogenated tallow, whale oil, fish oil, grease, lard,
coconut oil, palm oil, palm
kernel oil, olive oil, peanut oil, corn oil, sesame oil, rice bran oil,
cottonseed oil, babassu oil,
soybean oil, castor oil, and mixtures thereof. Although fatty acids can be
synthetically prepared,
for example, by the oxidation of petroleum, or by hydrogenation of carbon
monoxide by the
Fischer-Tropsch process, the naturally obtainable fats and oils are preferred.
The fatty acids of
particular use in the present invention are linear or branched and containing
from about 8 to
about 24 carbon atoms, preferably from about 10 to about 20 carbon atoms and
most preferably
from about 14 to about 18 carbon atoms. Preferred fatty acids for use in the
present invention
include coconut, tallow or hydrogenated tallow fatty acids, and most preferred
is to use entirely
coconut fatty acid. Preferred salts of the fatty acids are alkali metal salts,
such as sodium and
potassium or mixtures thereof and, as mentioned above, preferably the soaps
generated in-situ by
neutralization of the fatty acids with excess alkali from the silicate. Other
useful soaps are
ammonium and alkanol ammonium salts of fatty acids, with the understanding
that these soaps
would necessarily be added to the compositions as the preformed ammonium or
alkanol
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ammonium salts and not neutralized in-situ within the added alkaline builders
of the present
invention. The fatty acids that may be included in the present compositions
will preferably be
chosen to have desirable detergency and suds reducing effect. Fatty acid soaps
may be
incorporated in the compositions of the present invention at from about 1 % to
about 10%.
The compositions of the present invention may also include alkyl sulfate as
the sole anionic
surfactant component, or in combination with one of more other anionic
surfactants mentioned
above. Fatty alkyl sulfates have the general formula R--SO3M, where R
preferably comprises a
C7-C21 fatty alkyl chain, and where M is alkali metal or ammonium, alkyl
ammonium or alkanol
ammonium counterion. Preferred alkyl sulfates for use in the present invention
are C8-C18 fatty
alkyl sulfate. Most preferred is to incorporate sodium lauryl sulfate, such as
Standapol®
WAQ-LC marketed by Cognis, and to have from about 1% to about 10% by actives
weight basis
in the composition.
The Nonionic Surfactant Component
The compositions of the present invention may also include at least one
nonionic surfactant since
these materials are particularly good at removing oily soils from fabrics and
may be naturally
derived and have good biodegradability. For example, the liquid compositions
herein may
contain ethoxylated primary alcohols represented by the general formula R--
(OCH2CH2)x--OH,
where R is C10 to C18 carbon atoms preferably from natural, non-petroleum
sources, and x is on
average from 4 to 12 mol of ethylene oxide (EO). Further examples are alcohol
ethoxylates
containing linear radicals from alcohols of natural origin having 12 to 18
carbon atoms, e.g.,
from coconut, palm, tallow fatty or oleyl alcohol and on average from 4 to
about 12 EO per mole
of alcohol. Most useful as a nonionic surfactant in the present invention is
the C12-C14 alcohol
ethoxylate-7EO, and the C12-C14 alcohol ethoxylate-12EO incorporated in the
composition at
from about lwt% to about lOwt%. Preferred nonionic surfactants for use in this
invention include
for example, Neodol® 45-7, Neodol® 25-9, or Neodol® 25-12 from
Shell
Chemical Company and most preferred are Surfonic® L24-7, which is a C12-
C14 alcohol
ethoxylate-7EO, and Surfonic® L24-12, which is a C12-C14 alcohol
ethoxylate-12EO, both
available from Huntsman. Combinations of more than one alcohol ethoxylate
surfactant may also
be desired in the detergent composition in order to maximize cleaning
performance in the
washing machine.
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Nonionic surfactants useful in the present invention may also include the
alkyl polyglycoside
surfactants. The alkyl polyglycosides (APGs), also called alkyl polyglucosides
if the saccharide
moiety is glucose, are naturally derived, nonionic surfactants. The alkyl
polyglycosides that may
be used in the present invention are fatty ester derivatives of saccharides or
polysaccharides that
are formed when a carbohydrate is reacted under acidic condition with a fatty
alcohol through
condensation polymerization. The APGs are typically derived from corn-based
carbohydrates
and fatty alcohols from natural oils in animals, coconuts and palm kernels.
Such methods for
preparing APGs are well known in the art. For example, U.S. Pat. No. 5,003,057
to McCurry, et
al., incorporated herein, describes methods for making APGs, along with their
chemical
properties. The alkyl polyglycosides that are preferred for use in the present
invention contain a
hydrophilic group derived from carbohydrates and is composed of one or more
anhydroglucose
units. Each of the glucose units can have two ether oxygen atoms and three
hydroxyl groups,
along with a terminal hydroxyl group, which together impart water solubility
to the glycoside.
The presence of the alkyl carbon chain leads to the hydrophobic tail to the
molecule. When
carbohydrate molecules react with fatty alcohol compounds, alkyl polyglycoside
molecules are
formed having single or multiple anhydroglucose units, which are termed
monoglycosides and
polyglycosides, respectively. The final alkyl polyglycoside product typically
has a distribution of
varying concentration of glucose units (or degree of polymerization).
The APGs that may be used in the detergent composition of the invention
preferably comprise
saccharide or polysaccharide groups (i.e., mono-, di-, tri-, etc. saccharides)
of hexose or pentose,
and a fatty aliphatic group having 6 to 20 carbon atoms. Preferred alkyl
polyglycosides that can
be used according to the present invention are represented by the general
formula, Gx-O--R1,
wherein G is a moiety derived from reducing saccharide containing 5 or 6
carbon atoms, e.g.,
pentose or hexose; R1 is fatty alkyl group containing 6 to 20 carbon atoms;
and x is the degree of
polymerization of the polyglycoside, representing the number of monosaccharide
repeating units
in the polyglycoside. Generally, x is an integer on the basis of individual
molecules, but because
there are statistical variations in the manufacturing process for APGs, x may
be a noninteger on
an average basis when referred to APG used as an ingredient for the detergent
composition of the
present invention. For the APGs of use in the compositions of the present
invention, x preferably
has a value of less than 2.5, and more preferably is between 1 and 2.
Exemplary saccharides from
which G can be derived are glucose, fructose, mannose, galactose, talose,
gulose, allose, altrose,
idose, arabinose, xylose, lyxose and ribose. Because of the ready availability
of glucose, glucose
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is preferred in polyglycosides. The fatty alkyl group is preferably saturated,
although unsaturated
fatty chains may be used. Generally, the commercially available polyglycosides
have C8 to C16
alkyl chains and an average degree of polymerization of from 1.4 to 1.6.
Commercially available alkyl polyglycoside can be obtained as concentrated
aqueous solutions
ranging from 50 to 70wt% actives and are available from Cognis. Most preferred
for use in the
present compositions are APGs with an average degree of polymerization of from
1.4 to 1.7 and
the chain lengths of the aliphatic groups are between C8 and C16. For example,
one preferred
APG for use herein has chain length of C8 and C10 (ratio of 45:55) and a
degree of
polymerization of 1.7. The detergent compositions of the present invention
have the advantage of
having less adverse impact on the environment than conventional detergent
compositions. Alkyl
polyglycosides used in the present invention exhibit low oral and dermal
toxicity and irritation on
mammalian tissues. These alkyl polyglycosides are also biodegradable in both
anaerobic and
aerobic conditions and they exhibit low toxicity to plants, thus improving the
environmental
compatibility of the rinse aid of the present invention. Because of the
carbohydrate property and
the excellent water solubility characteristics, alkyl polyglycosides are
compatible in high caustic
and builder formulations. The detergent compositions may include a sufficient
amount of alkyl
polyglycoside surfactant in an amount that provides a desired level of
cleaning on fabrics, that
being from about 0.01% and about 10% by weight alkyl polyglycoside surfactant.
Most preferred
is to include an amount between about 0.5% and about 5% by weight actives.
The Natural Essences Component
In addition to anionic and nonionic surfactant components, the liquid laundry
detergents
compositions of the present invention may include a "natural essence". As
referred to for
purposes of this invention, "natural essence" is intended to include a broader
class of natural
products comprising natural oils extracted from plants and trees and their
fruits, nuts and seeds,
(for example by steam or liquid extraction of ground-up plant/tree material),
natural products that
may be purified by distillation, (i.e., purified single organic molecules or
close boiling point
"cuts" of organic materials such as terpenes and the like), and synthetic
organic materials that are
the synthetic versions of naturally occurring materials (e.g., either
identical to the natural
material, or the optical isomer, or the racemic mixture). An example of the
latter is D,L-limonene
that is synthetically prepared and is a good and eco-friendly substitute for
natural orange oil
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(mostly D-limonene) when crop yields are expensive due to citrus crop freezes.
Thus, it should
be understood that "natural essence" incorporates a wide range of pure organic
materials either
natural or synthetic versions thereof, mixtures of these previously purified
individual materials or
distillate cuts of materials, and complex natural mixtures directly extracted
from plant/tree
materials through infusion, steam extraction, etc. Also, it should be
understood that these natural
essence ingredients may double as fragrance materials for the detergent
composition, and in fact
many natural extracts, oils, essences, infusions and such are very fragrant
materials. However, for
use in the present compositions, these materials are used at higher levels
than would be typical
for fragrance purposes, and it should be also understood that depending on
optical isomers used,
there may be no smell or a reduced smell, or even a masking effect to the
human sensory
perception. Thus by judicious choice of natural essence mixtures, performance
boosting may be
effected without making the compositions overwhelmingly scented. Also, actual
fragrance
masking materials (such as used for household cleaners and available from the
fragrance supply
houses such as International Flavors & Fragrances, Symrise, Givaudan,
Firmenich, and others)
may be added to mask the smells of the natural essences.
Some of the naturally derived essences for use in the present compositions
include, but are not
limited to, musk, civet, ambergis, castoreum and similar animal derived oils;
abies oil, ajowan
oil, almond oil, ambrette seed absolute, angelic root oil, anise oil, basil
oil, bay oil, benzoin
resinoid, bergamot oil, birch oil, bois de rose oil, broom abs., cajeput oil,
cananga oil, capsicum
oil, caraway oil, cardamon oil, carrot seed oil, cassia oil, cedar leaf oil,
cedar wood oil, celery
seed oil, cinnamon bark oil, citronella oil, clary sage oil, clove oil, cognac
oil, coriander oil,
cubeb oil, cumin oil, camphor oil, dill oil, elemi gum, estragon oil,
eucalyptol nat., eucalyptus oil,
fennel sweet oil, galbanum res., garlic oil, geranium oil, ginger oil,
grapefruit oil, hop oil,
hyacinth abs., jasmin abs., juniper berry oil, labdanum res., lavender oil,
laurel leaf oil, lavender
oil, lemon oil, lemongrass oil, lime oil, lovage oil, mace oil, mandarin oil,
mimosa abs., myrrh
abs., mustard oil, narcissus abs., neroli bigarade oil, nutmeg oil, oakmoss
abs., olibanum res.,
onion oil, opoponax res., orange oil, orange flower oil, origanum, orris
concrete, pepper oil,
peppermint oil, peru balsam, petitgrain oil, pine needle oil, rose abs., rose
oil, rosemary oil, safe
officinalis oil, sandalwood oil, sage oil, spearmint oil, styrax oil, thyme
oil, tolu balsam, tonka
beans abs., tuberose abs., turpentine oil, vanilla beans abs., vetiver oil,
violet leaf abs., ylang
ylang oil and similar vegetable oils, etc.
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Synthetic essences include but are not limited to pinene, limonene and like
hydrocarbons; 3,3,5-
trimethylcyclohexanol, linalool, geraniol, nerol, citronellol, menthol,
borneol, borneyl methoxy
cyclohexanol, benzyl alcohol, anise alcohol, cinnamyl alcohol, .beta.-phenyl
ethyl alcohol, cis-3-
hexenol, terpineol and like alcohols; anethole, musk xylol, isoeugenol, methyl
eugenol and like
phenols; .alpha.-amylcinnamic aldehyde, anisaldehyde, n-butyl aldehyde, cumin
aldehyde,
cyclamen aldehyde, decanal, isobutyl aldehyde, hexyl aldehyde, heptyl
aldehyde, n-nonyl
aldehyde, nonadienol, citral, citronellal, hydroxycitronellal, benzaldehyde,
methyl nonyl
acetaldehyde, cinnamic aldehyde, dodecanol, .alpha.-hyxylcinnamic aldehyde,
undecenal,
heliotropin, vanillin, ethyl vanillin and like aldehydes; methyl amyl ketone,
methyl .beta.-
naphthyl ketone, methyl nonyl ketone, musk ketone, diacetyl, acetyl propionyl,
acetyl butyryl,
carvone, menthone, camphor, acetophenone, p-methyl acetophenone, ionone,
methyl ionone and
like ketones; amyl butyrolactone, diphenyl oxide, methyl phenyl glycidate,
gamma.-nonyl
lactone, coumarin, cineole, ethyl methyl phenyl glicydate and like lactones or
oxides; methyl
formate, isopropyl formate, linalyl formate, ethyl acetate, octyl acetate,
methyl acetate, benzyl
acetate, cinnamyl acetate, butyl propionate, isoamyl acetate, isopropyl
isobutyrate, geranyl
isovalerate, allyl capronate, butyl heptylate, octyl caprylate octyl, methyl
heptynecarboxylate,
methine octynecarboxylate, isoacyl caprylate, methyl laurate, ethyl myristate,
methyl myristate,
ethyl benzoate, benzyl benzoate, methylcarbinylphenyl acetate, isobutyl
phenylacetate, methyl
cinnamate, cinnamyl cinnamate, methyl salicylate, ethyl anisate, methyl
anthranilate, ethyl
pyruvate, ethyl .alpha.-butyl butylate, benzyl propionate, butyl acetate,
butyl butyrate, p-tert-
butylcyclohexyl acetate, cedryl acetate, citronellyl acetate, citronellyl
formate, p-cresyl acetate,
ethyl butyrate, ethyl caproate, ethyl cinnamate, ethyl phenylacetate, ethylene
brassylate, geranyl
acetate, geranyl formate, isoamyl salicylate, isoamyl isovalerate, isobornyl
acetate, linalyl
acetate, methyl anthranilate, methyl dihydrojasmonate, nopyl acetate, .beta.-
phenylethyl acetate,
trichloromethylphenyl carbinyl acetate, terpinyl acetate, vetiveryl acetate
and the like.
Suitable essence mixtures may produce synergistic performance attributes for
the detergent
composition and may help to impart an overall fragrance perception as well to
the composition
including but not limited to, fruity, musk, floral, herbaceous (including
mint), and woody, or
perceptions that are in-between (fruity-floral for example). Typically these
essence or essential
oil mixtures may be compounded by mixing a variety of these active extract or
synthetic
materials along with various solvents to adjust cost, viscosity, flammability,
ease of handling, etc.
Since many natural extract ingredients are compounded into fragrances, the
essential oils,
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infusions, distillates, etc. that are considered "natural essences" within
this invention are also
available from the fragrance companies such as International Flavors &
Fragrances, Givaudan,
Symrise, Firmenich, Robertet, and many others. The natural essences for use in
the present
invention are preferably incorporated at a level of from about O.lwt% to about
5wt% as the
100wt% neat substance or mixture of substances. It is important to note that
these levels tend to
be greater than those levels used for scenting a product with a perfume.
The Builder Component
The liquid laundry detergent compositions of the present invention may also
include at least one
builder. Builders are well known in the laundry detergent art and include such
species as
hydroxides, carbonates, sesquicarbonates, bicarbonates, borates, citrates,
silicates, zeolites, and
such. Preferred builders for use in the present invention include but are not
limited to sodium
hydroxide (NaOH), potassium hydroxide (KOH), magnesium hydroxide (Mg(OH)2),
sodium
carbonate (Na2CO3), potassium carbonate (K2CO3), sodium bicarbonate (NaHCO3),
potassium
bicarbonate (KHCO3), sodium sesquicarbonate (Na2CO3.NaHCO3.2H20), sodium
silicate
(Si02/Na2O), sodium borate (Na2B4O7--(H20)10 or "borax"), citric acid
(C6H807),
monosodium citrate (NaC6H7O7), disodium citrate (Na2C6H6O7), and trisodium
citrate
(Na3C6H5O7), and mixtures thereof. It should be understood that combinations
of free acid
materials (like citric acid) when combined with alkali such as sodium
hydroxide can generate the
mono-, di-, or trisodium salts of citric acid in situ. The preferred level of
builder for use in these
laundry detergents is from about 0.lwt% to about 5wt% by weight.
Preferably, the composition comprises from Owt% to 5wt% zeolite builder. The
composition
preferably comprises from Owt% to 3wt%, or from Owt% to 2wt%, or from Owt% to
lwt%
zeolite builder. It may even be preferred for the composition to be
essentially free from zeolite
builder. By essentially free from zeolite builder it is typically meant that
the composition
comprises no deliberately added zeolite builder. This is especially preferred
if it is desirable for
the composition to be very highly soluble, to minimise the amount of water-
insoluble residues
(for example, which may deposit on fabric surfaces), and also when it is
highly desirable to have
transparent wash liquor. Zeolite builders include zeolite A, zeolite X,
zeolite P and zeolite MAP.
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Preferably, the composition comprises from Owt% to 4wt% phosphate builder. The
composition
preferably comprises from Owt% to 3wt%, or from Owt% to 2wt%, or from Owt% to
lwt%
phosphate builder. . It may even be preferred for the composition to be
essentially free from
phosphate builder. By essentially free from phosphate builder it is typically
meant that the
composition comprises no deliberately added phosphate builder. This is
especially preferred if it
is desirable for the composition to have a very good environmental profile.
Phosphate builders
include sodium tripolyphosphate.Preferably, the composition comprises from
Polymer Components
The compositions of the present invention may also include at least one soil
dispersing and/or
anti-redeposition or water conditioning polymers such as sodium polyacrylate
or
carboxymethylcellulose (CMC). Particularly suitable polymeric polycarboxylates
are derived
from acrylic acid, and this polymer and the corresponding neutralized forms
include and are
commonly referred to as polyacrylic acid, 2-propenoic acid homopolymer or
acrylic acid
polymer, and sodium polyacrylate, 2-propenoic acid homopolymer sodium salt,
acrylic acid
polymer sodium salt, poly sodium acrylate, or polyacrylic acid sodium salt.
Preferred in the
compositions of the present invention is sodium polyacrylate with average
molecular weight
from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most
preferably from
about 4,000 to 5,000. Soluble polymers of this type are known materials, for
example the sodium
polyacrylates and polyacrylic acids from Rohm and Haas marketed under the
trade name
Acusol®. Of particular use in the present invention is the average 4500
molecular weight
sodium polyacrylate, (for example, Acusol® 425, Acusol® 430,
Acusol® 445 and
Acusol® 445ND, and mixtures of these), and carboxymethylcellulose, either
or a
combination of the two at a preferred level of from about O.lwt% to about
3wt%. Polyacrylates
are "biodegradable", however, the cellulosic materials such as CMC may show a
faster
biodegradation profile and may be more preferred in keeping with the spirit of
the eco-friendly
character of the present invention.
Electrolytes
The detergent compositions of the present invention may also include one or
more electrolytes.
For example, preferred electrolytes include but are not limited to sodium
chloride, sodium
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sulfate, calcium chloride, and borax (sodium tetraborate-decahydrate), and
combinations thereof.
Of course, some of these have dual purposes such as alkalinity builders or
enzyme stabilizers.
Enzyme Component
The compositions of the present invention may optionally include one or more
detersive
enzymes, either singly or in any combination of two or more. Enzymes may be
included in the
present detergent compositions for a variety of purposes, including removal of
protein-based,
carbohydrate-based, or triglyceride-based stains from substrates. Generally,
suitable enzymes
include cellulases, hemicellulases, proteases, gluco-amylases, amylases,
lipases, cutinases,
pectinases, xylanases, keratinases, reductases, oxidases, phenoloxidases,
lipoxygenases,
ligninases, pullulanases, tannases, chondriotinases, thermitases,
pentosanases, malanases, .beta.-
glucanases, arabinosidases or mixtures thereof of any suitable origin, such as
vegetable, animal,
bacterial, fungal and yeast origin. Preferred enzymes for use in the present
invention are dictated
by factors such as formula pH, thermostability, and stability to surfactants,
builders and the like.
In this respect bacterial or fungal enzymes are preferred, such as bacterial
amylases and
proteases, and fungal cellulases. A preferred combination is a detergent
composition having a
mixture of conventional detergent enzymes like protease, amylase, lipase,
cutinase and/or
cellulase. Suitable enzymes are also described in U.S. Pat. Nos. 5,677,272,
5,679,630, 5,703,027,
5,703,034, 5,705,464, 5,707,950, 5,707,951, 5,710,115, 5,710,116, 5,710,118,
5,710,119 and
5,721,202.
"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain
removing or
otherwise beneficial effect in a detergent compositions. Preferred detersive
enzymes are
hydrolases such as proteases, amylases and lipases. Highly preferred are
amylases and/or
proteases, including both current commercially available types and improved
types. Enzymes are
normally incorporated into detergent compositions at levels sufficient to
provide a "cleaning-
effective amount". The term "cleaning effective amount" refers to any amount
capable of
producing a cleaning, stain removal, soil removal, whitening, deodorizing, or
freshness
improving effect on substrates such as fabrics, dishware and the like. In
practical terms for
current commercial preparations, typical amounts are up to about 5 mg by
weight, more typically
0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. In
other words, the
compositions herein will typically comprise from 0.001% to 5%, preferably
0.001%-l% by
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weight of a commercial enzyme preparation. Protease enzymes are usually
present in such
commercial preparations at levels sufficient to provide from 0.005 to 0.1
Anson units (AU) of
activity per gram of composition. For certain detergents it may be desirable
to increase the active
enzyme content of the commercial preparation in order to minimize the total
amount of non-
catalytically active materials and thereby improve spotting/filming or other
end-results. Higher
active levels may also be desirable in highly concentrated detergent
formulations. Proteolytic
enzymes can be of animal, vegetable or microorganism (preferred) origin. The
proteases for use
in the detergent compositions herein include (but are not limited to) trypsin,
subtilisin,
chymotrypsin and elastase-type proteases. Preferred for use herein are
subtilisin-type proteolytic
enzymes. Particularly preferred is bacterial serine proteolytic enzyme
obtained from Bacillus
subtilis and/or Bacillus licheniformis. Suitable proteolytic enzymes include
Novo Industri A/S
Alcalase® (preferred), Esperase®, Savinase® (Copenhagen, Denmark),
Gist-
brocades' Maxatase®, Maxacal® and Maxapem 15® (protein engineered
Maxacal®) (Delft, Netherlands), and subtilisin BPN and BPN' (preferred),
which are
commercially available. Preferred proteolytic enzymes are also modified
bacterial serine
proteases, such as those made by Genencor International, Inc. (San Francisco,
Calif.), which are
described in U.S. Pat. Nos. 5,972,682, 5,763,257 and 6,465,235 and which are
also called herein
"Protease B". U.S. Pat. No. 5,030,378, Venegas, issued Jul. 9, 1991, refers to
a modified bacterial
serine proteolytic enzyme (Genencor International), which is called "Protease
A" herein (same as
BPN'). In particular, see columns 2 and 3 of U.S. Pat. No. 5,030,378 for a
complete description,
(including the amino sequence), of Protease A and its variants. Other
proteases are sold under the
tradenames: Primase®, Durazym®, Opticlean® and Optimase®.
Preferred
proteolytic enzymes, then, are selected from the group consisting of
Alcalase® (Novo
Industri A/S), BPN', Protease A and Protease B (Genencor), and mixtures
thereof. Protease B is
most preferred. The compositions of the present invention will preferably
contain at least about
0.0001%, more preferably at least about 0.0005%, and most preferably at least
about 0.001% by
weight of the composition of enzyme. The detergent composition will also
preferably contain no
more than about 5%, more preferably no more than about 2%, and most
preferably, no more than
about 1% by weight of the composition of enzyme. Although proteases may be
used alone, it is
preferable to have a combination of protease and amylase, or a combination of
protease, lipase
and amylase in the compositions of the present invention.
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Enzyme stabilization system
Preferably, the enzyme stabilization system selected from the group consisting
of: formate salt
selected from calcium formate and/or sodium formate; polyol selected from
propane 1,2 diol,
glycerol and/or sorbitol; and any combination thereof. Preferred are calcium
formate and/or
propane 1,2 diol.
Preferably, the composition comprises from O.Olwt% to 0.5wt% calcium cation,
preferably from
0.03wt% to 0.5wt% calcium cation.
Preferably, the composition comprises from O.lwt% to 5wt% formate anion,
preferably from
0.3wt% to 2wt% formate anion.
Preferably, the composition comprises propane 1,2 diol, preferably from 0.5wt%
to 20wt%, or
from lwt% to 3wt% propane 1,2 diol.
Preferably, the composition comprises calcium formate.
This preferred enzyme stabilization system enables good enzyme stability, and
allows good
surfactant stability. In a further preferred embodiment, these preferred
enzyme stabilization
systems also enable the removal of boron from the compositions.
Adjuvant
Optional ingredients for use in the present detergent compositions may also
include peroxide and
active oxygen ("peroxygen") organic and inorganic compounds for non-chlorine
bleaching of
bleachable stains. Such bleaching materials may include, but are not limited
to hydrogen
peroxide, sodium percarbonate and sodium perborate, or mixtures thereof.
Additional optional materials for use in the present detergents may include
chelants such as
tetrasodium ethylenediamine tetraacetate-EDTA, Trilon® chelants from BASF,
phosphates,
zeolite, nitrilotriacetate (NTA) and its corresponding salts, optical
brighteners, dye fixatives or
transfer inhibitors, perfumes, additional fragrance and fragrance masking
agents to coordinate
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with the natural essences, odor neutralizers, dyes, pigments and colorants,
solvents, cationic
surfactants, other softening or antistatic agents, thickeners, emulsifiers,
bleach catalysts, enzyme
stabilizers, clays, surface modifying polymers, pH-buffering agents,
abrasives, preservatives and
sanitizers or disinfectants, anti-redeposition agents, opacifiers, anti-
foaming agents, cyclodextrin,
rheology-control agents, vitamins and other skin benefit agents, nano-
particles and encapsulated
particles, visible plastic particles, visible beads, etc., and the like, and
any combination of
adjuvant.
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.
EXAMPLES
Example Number 1 2
Ingredient Weight Percentage % %
Lauryl ether sulphate 12 11
Palm AE3 sulphate 9 8.5
Palm alkyl 7-ethoxylate 8 7.5
Natural essences 2 2
Palm Fatty acid 10 9.5
Citric acid 3 3
Coupling polymer: Ethoxysulfated Hexamethylene 2.2 2.2
Diamine Dimethyl Quat *
Non-coupling cleaning polymer: PEG-PVAc Polymer 0.9 0.8
Chelant: Hydroxyethane diphosphonic acid 0 1.6
Fluorescent Whitening Agent 49 0.2 0.2
Non-aminofunctional solvent: 1,2 Propanediol 8.5 6.0
Non-aminofunctional solvent: Diethylene Glycol - 4.0
Calcium formate 0.1 0.1
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Calcium chloride 0.06 0.06
Potassium bisulfite 0.3 -
Perfume 1.7 1.7
Protease enzyme FNA (40.6 mg/g) 1.5 1.5
Amylase enzyme Termamyl Ultra 0.1 0.1
(25.1 mg /g)
Mannanase enzyme (25 mg/g) 0.1 0.1
Cellulase enzyme (25 mg / g) 0.1 0.1
Xyloglucanase enzyme (20 mg /g) 0.1 0.1
Pectate lyase enzyme (20 mg/ g) 0.1 0.1
Water & minors, e.g. antifoam, dyes To To
lOOwt% lOOwt%
t 24
24 N+
N
(SOA
H' 24
3 PEG-PVA graft copolymer is a polyvinyl acetate grafted polyethylene oxide
copolymer having
a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The
molecular weight
of the polyethylene oxide backbone is about 6000 and the weight ratio of the
polyethylene oxide
to polyvinyl acetate is about 40 to 60 and no more than 1 grafting point per
50 ethylene oxide
units.
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".
