Note: Descriptions are shown in the official language in which they were submitted.
CA 02380328 2002-01-23
WO 01/10993 PCT/US00/21570
DETERGENT COMPOSITIONS COMPRISING HYDROTROPES
FIELD OF THE INVENTION
The present invention relates to detergent compositions, especially liquid,
granular and
tablet forms of laundry detergent compositions, that comprise improved
hydrotropes, wherein the
hydrotropes are organic molecules in which two polar groups are separated from
each other by at
least 5 aliphatic carbon atoms; liquid compositions that contain such
hydrotropes have a
viscosity, dilution profile and dissolution behavior that render the product
effective and
convenient for use as a liquid laundry detergent composition.
BACKGROUND OF THE INVENTION
In recent years, the popularity of detergent products is forms other than
granular/powder
has increased. These other forms include liquids and tablets.
Liquid laundry detergent products offer a number of advantages over dry,
powdered or
particulate laundry detergent products. Liquid laundry detergent products are
readily measurable,
speedily dissolved in wash water, non-dusting, are capable of being easily
applied in concentrated
solutions or dispersions to soiled areas on garments to be laundered and
usually occupy less
storage space than granular products. Additionally, liquid laundry detergents
may have
incorporated into their formulations materials which would deteriorate in the
drying operations
employed in the manufacture of particulate or granular laundry detergent
products. Because
liquid laundry detergents are usually considered to be more convenient to use
than granular
laundry detergents, they have found substantial favor with consumers.
Despite the advantages of liquid detergent compositions, granular products
retain
numerous advantages. These advantages include performance, formulation
capability, lower-cost
packaging and higher product stability. The advantages of product stability
and formulation
capability are derived in large part from the nature of granular admixtures
where components can
be individually stabilized and isolated into particles before being admixed
with other particles.
This physical separation in the final detergent composition allows the use of
materials that are
potentially unstable in a composition such as bleaches, enzymes, etc.
It is well-known to make detergent compositions in tablet form by compacting a
granular
detergent composition. Such tablets offer the convenience to consumers of a
pre-measured
detergent dosage without the inconvenience and untidiness of measuring a
sufficient amount of a
granular detergent composition for each wash. Such products also offer
considerable
convenience to those consumers who launder the clothes outside or away from
their residence
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(e.g. at a laundromat) because the consumer is required to transport only
precisely as much
laundry detergent as she or he needs for clothes laundering. Detergent
compositions may be
made in tablet form by compacting detergent particulates.
A disadvantage with conventional liquid detergent compositions has been
compatibility
of ingredients. Laundry detergent components which may be compatible with each
other in
granular and/or tablet products, may tend to interact or react with each other
in a liquid,
especially in an aqueous liquid environment.
A disadvantage with conventional granular/powder detergent compositions has
been
relatively poor dissolution, dispersion and solubility performance.
A disadvantage with conventional tablet detergent compositions has been the
conflict
between making the tablets sufficiently strong and durable to avoid breaking
apart during
manufacture, transportation and/or storage, while at the same time making the
tablets in a manner
such that the tablets rapidly disintegrate upon contact with wash water.
Given the foregoing, there is a continuing need to provide/formulate liquid
detergent
compositions which have not only excellent cleaning performance and
compositional and
physical stability but which also have a viscosity, dilution profile and
dissolution behavior that
render them useful and convenient for use as a liquid laundry detergent
composition; there is a
continuing need to provide/formulate granular/powder detergent compositions
which have
improved dissolution, dispersion and solubility performance while maintaining
the
granular/powder detergent's inherent formulation flexibility; and there is a
continuing need to
provide/formulate tablet detergent compositions which are both strong and
durable to resist
breakage during manufacture, transportation and/or storage, and which also
disintegrate rapidly
upon contact with wash water so that the components of the tablet can provide
detersive benefits
during the wash process.
SUMMARY OF THE INVENTION
It has now been discovered in the present invention that the addition of
certain
hydrotropes to the detergent compositions of the present invention, such as
aqueous or non-
aqueous liquid laundry detergent compositions, granular/powder laundry
detergent compositions
and/or tablet laundry detergent compositions, provides 1) a liquid detergent
product that has a
viscosity, dilution profile and dissolution behavior that render the product
useful and convenient
as a liquid laundry detergent composition, and/or 2) a granular/powder
detergent product having
improved dispersion, dissolution and/or solubility performance with the need
to reduce surfactant
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CA 02380328 2008-10-06
levels compared to granular/powder detergent products that lack such
hydrotropes, and/or 3) a tablet
detergent product, wherein the hydrotropes are useful as binding agents,
having improved strength
and durability properties with excellent disintegration and dissolution
properties compared to tablet
detergent products that lack such hydrotropes.
In one particular embodiment there is provided a non-aqueous liquid laundry
detergent
composition comprising: A) from 52% to 98.9% by weight of the composition of a
surfactant-containing non-aqueous liquid phase; and B) from 1% to 50% by
weight of the
composition of a particulate material which is substantially insoluble in said
liquid phase and which
is selected from the group consisting of peroxygen bleaching agents, bleach
activators, organic
detergent builders, inorganic alkalinity sources, enzymes, brighteners,
polymers and mixtures
thereof; and C) a hydrotrope wherein the hydrotrope comprises 1,4-cyclo hexane
dimethanol, and
wherein the composition comprises no quatemary compounds which are derivatives
of any of the
following: C16_1a unsaturated fatty acids, methyl diethanolamine or
methylchloride.
A. Liquid Products
The liquid detergent products containing these hydrotropes demonstrate
excellent cleaning
performance, -excellent compositional and physical stability and favorable
product rheological
behavior. These certain hydrotropes may be most generally classified as
organic molecules in which
two polar groups are separated from each other by at least 5 aliphatic carbon
atoms.
The liquid detergent products may be aqueous or non-aqueous. In a preferred
aspect of the
present invention a non-aqueous liquid detergent comprising a hydrotrope
having two polar groups
separated from each other by at least 5 aliphatic carbon atoms as well as from
about 49% to about
99.95% by weight of the composition of a surfactant-containing non-aqueous
liquid phase and from
about 1% to about 50% by weight of the composition of particulate material
which is substantially
insoluble in said liquid phase and which is selected from peroxygen bleaching
agents, bleach
activators, organic detergent builders, inorganic alkalinity sources and
combinations thereof, is
provided.
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B. Granular/Powder Products
The granular/powder detergent products containing these hydrotropes
demonstrate improved
dispersion, dissolution and/or solubility performance with the need to reduce
surfactant levels
compared to granular/powder detergent products that lack such hydrotropes.
These hydrotropes may
be most generally classified as an organic molecule which has a first polar
group and a second polar
group separated from each other by at least 5 aliphatic carbon atoms.
C. Tablet Products
The detergent tablets prepared according to the present invention comprise a
hydrotrope
("binding agent") characterized in that the binding agent may be most
generally classified as an
organic molecule which has a first polar group and a second polar group
separated from each other
by at least 5 aliphatic carbon atoms. The tablet detergent products exhibit
improved strength and
durability properties with excellent disintegration and dissolution properties
compared to tablet
detergent products that lack such hydrotropes.
3a
CA 02380328 2005-08-19
HO
HO H OH
HO g
All parts, percentages and ratios used herein are expressed as percent weight
unless
otherwise specified.
DETAILED DESCRIPTION OF THE Il\'VENTION
DEFINITIONS
"Hvdrotrope" - As used herein, "hydrotrope" generally means a compound with
the
ability to increase the solubilities, preferably aqueous solubilities, of
certain slightly soluble
organic compounds, more preferably "hydrotrope" is defined as follows (see
S.E. Friberg and M.
Chiu, J. Dispersion Science and Technology, 9(5&6), pages 443 to 457, (1988-
1989)):
1. A solution is prepared comprising 25% by weight of the specific compound
and 75% by
weight of water.
2. Octanoic Acid is thereafter added to the solution in a proportion of 1.6
times the weight
of the specific compound in solution, the solution being at a temperature of
20 Celsius. The
Tm
solution is mixed in a Sotax beaker with a stirrer with a marine propeller,
the propeller being
situated at about 5mm above the bottom of the beaker, the mixer being set at a
rotation speed of
200 rounds per minute.
3. The specific compound is hydrotrope if the the Octanoic Acid is completely
solubilised, i.e . if the solution comprises only one phase, the phase being a
liquid
phase.
"Non-Aqueous" or "Anhvdrous" - As used herein, "non-aqueous" or "anhydrous"
are
used synonymously and both describe a fluid in which the free water content is
less than about I
%.
"Polar Groups" - As used herein, "polar groups" refers to functional groups
which have a
permanent electric dipole moment that arises from the partial charges on atoms
linked by polar
bonds. The polar group itself may be anionic or uncharged.
"Dissolution" - As used herein, "dissolution" refers to the rate at which the
detergent
product mixes with water and releases the active ingredients in the wash
"Particles" - As used herein, the word "particles" means the entire size range
of a
detergent final product or component or the entire size range of discrete
particles, agglomerates,
or granules in a final detergent product or component admixture. It
specifically does not refer to
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WO 01/10993 PCTIUSOO/21570
a size fraction (i.e., representing less than 100% of the entire size range)
of any of these types of
particles unless the size fraction represents 100% of a discrete particle in
an admixture of
particles. For each type of particle component in an admixture, the entire
size range of discrete
particles of that type have the same or substantially similar composition
regardless of whether the
particles are in contact with other particles. For agglomerated components,
the agglomerates
themselves are considered as discrete particles and each discrete particle may
be comprised of a
composite of smaller primary particles and binder compositions.
"Geometric Mean Particle Diameter" - As used herein, the phrase "geometric
mean
particle diameter" means the geometric mass median diameter of a set of
discrete particles as
measured by any standard mass-based particle size measurement technique,
preferably by dry
sieving.
"Geometric Standard Deviation" or "Span" - As used herein, the phrase
"geometric
standard deviation" or "span" of a particle size distribution means the
geometric breadth of the
best-fitted log-normal function to the above-mentioned particle size data
which can be
accomplished by the ratio of the diameter of the 84.13 percentile divided by
the diameter of the
50th percentile of the cumulative distribution (D84.13/D50); See Gotoh et al,
Powder Technology
Handbook, pp. 6-11, Meral Dekker 1997.
HYDROTROPES
The hydrotropes described in this section are an essential component of the
present
detergent compositions.
It has been discovered in the present invention that the addition of a
hydrotrope in which
two polar groups are separated from each other by at least 5, preferably 6,
aliphatic carbon atoms.
Examples of suitable polar groups for inclusion in the hydrotrope include are
hydroxyl and
carboxyl ions. Particularly preferred hydrotropes are selected from the group
consisting of:
CA 02380328 2002-01-23
WO 01/10993 PCT/US00/21570
1,4 Cyclo Hexane Di Methanol:
HO H
1,6 Hexanediol:
HO
OH
1,7 Heptanediol:
HO H ~ and
mixtures thereof.
Mixtures of these organic molecules or any number of hydrotropes molecules
which
consist of two polar groups separated from each other by at least 5,
preferably 6, aliphatic carbon
atoms are also acceptable. 1,4 Cyclo Hexane Di Methanol may be present in
either its cis
configuration, its trans configuration or a mixture of both configurations.
A. LIQUID PRODUCTS
The present invention comprises liquid laundry detergent compositions which
are either
aqueous or non-aqueous and which are suitable for use in an automatic washing
machine or for
pretreating stains and spots on textile or fabric articles prior to washing.
The present liquid
laundry detergent compositions may comprise solely a surfactant-rich liquid-
phase or they may
contain both a surfactant-rich liquid-phase and solid particulate phase which
is suspended in the
liquid phase. Preferably, the surfactant-rich liquid-phase comprises the
hydrotropes, and
optionally organic diluents.
The hydrotropes of the present invention, when incorporated into liquid
products of the
present invention, provide the key ingredient to prevent gelling and/or
thickening of the liquid
detergent compositions taught herein.
Gelling has been previously observed in the liquid detergent products prepared
without
the hydrotropes as defined in the present invention, when the products are
first contacted and
diluted with water. Without being limited by theory, it is believed that this
gelling phenomenon
results from the surfactant system forming viscous surfactant phases
(typically lamellar,
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WO 01/10993 PCT/US00/21570
spherulitic or hexagonal phases) at certain concentrations of surfactants and
water. A correlation
has been found between the viscosity of the product: water mixture in the
critical dilution range
where gelling is observed, and the amount of viscous surfactant phase formed.
In a preferable embodiment, the detergent compositions are non-aqueous, having
a
surfactant-rich non-aqueous liquid phase and having a solid particulate phase
suspended in said
liquid phase. In this embodiment, the surfactant-containing, non-aqueous
liquid phase will
generally comprise from about 49% to 99.95% by weight of the detergent
compositions herein.
More preferably, this liquid phase is surfactant-structured and will comprise
from about 52% to
98.9% by weight of the compositions. Most preferably, this non-aqueous liquid
phase will
comprise from about 55% to 70% by weight of the compositions herein. Such a
surfactant-
containing liquid phase will frequently have a density of from about 0.6 to
1.4 g/cc, more
preferably from about 0.9 to 1.3 g/cc.
Without being bound by theory, it is believed that the hydrotropes described
above
prevent the formation of the viscous surfactant phases formed upon dilution,
because the
hydrotrope can effectively interact with the ordered, structured layers of
surfactant molecules,
disrupt them and promote the formation of isotropic low - viscosity surfactant
phases.
These hydrotropes also provide other benefits for improving the rheology of
liquid
detergent compositions. For example, it is often difficult to incorporate
ethoxylated quatemized
amine materials into detergent compositions containing anionic surfactant
because the
ethoxylated quatemized amine material causes the anionic surfactant to
precipitate out of the
liquid phase causing the liquid detergent composition to thicken considerably.
Nonetheless, it is
highly desirable to incorporate these clay soil removal/anti-redeposition
agents into a liquid
detergent product because they provide important performance benefits. It has
been discovered
in the present invention that by including the hydrotropes described above the
anionic surfactant
precipitation and the composition thickening usually observed is avoided and a
liquid detergent
composition of desirable rheological properties is produced.
Ethoxylated quaternized amine materials are described in greater detail below.
Surfactant-Containing Liquid-Phase
The liquid phase of the liquid detergent compositions herein is preferably
formed from
hydrotropes, nonionic and anionic surfactants, and one or more organic
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WO 01/10993 PCTIUSOO/21570
HO O~ HHO H
diluents.
HO H
Organic Diluents - The major component of the liquid phase of the detergent
compositions
herein comprises one or more aqueous or non-aqueous organic diluents. The
organic diluents
used in this invention may be either surface active liquids, i.e.,
surfactants, or non-surfactant
liquids referred to herein as solvents. The term "solvent" is used herein to
connote the non-
surfactant liquid portion of the compositions herein. While some of the
essential and/or optional
components of the compositions herein may actually dissolve in the "solvent"-
containing liquid
phase, other components will be present as particulate material dispersed
within the "solvent"-
containing liquid phase. Thus the term "solvent" is not meant to require that
the solvent material
be capable of actually dissolving all of the detergent composition components
added thereto.
The liquid diluent component will generally comprise from about 50% to 90%,
more
preferably from about 50% to 80%, most preferably from about 55% to 75%, of a
structured,
surfactant-containing liquid phase. Preferably the liquid phase of the
compositions herein, will
comprise both liquid surfactants and non-surfactant solvents.
i) Surfactant Liquids - Suitable types of surfactant liquids which can be used
to form
the liquid phase of the compositions herein include the alkoxylated alcohols,
ethylene oxide
(EO)-propylene oxide (PO) block polymers, polyhydroxy fatty acid amides,
alkylpolysaccharides,
and the like. Such normally liquid surfactants are those having an HLB ranging
from 10 to 16.
Most preferred of the surfactant liquids are the alcohol alkoxylate nonionic
surfactants.
Alcohol alkoxylates are materials which correspond to the general formula:
R1(CmH2mO)nOH
wherein R1 is a C8 - C16 alkyl group, m is from 2 to 4, and n ranges from
about 2 to 12.
Preferably Rl is an alkyl group, which may be primary or secondary, that
contains from about 9
to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms.
Preferably also the
alkoxylated fatty alcohols will be ethoxylated materials that contain from
about 2 to 12 ethylene
oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide
moieties per
molecule.
The alkoxylated fatty alcohol materials useful in the liquid phase will
frequently have a
hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17. More
preferably, the
HLB of this material will range from about 6 to 15, most preferably from about
8 to 15.
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CA 02380328 2005-08-19
Examples of fatty alcohol alkoxylates useful in or as the liquid phase of the
compositions herein will include those which are made from alcohols of 12 to
15 carbon atoms
and which contain about 7 moles of ethylene oxide. Such materials have been
commercially
marketed under the trade marks Neodo125-7 and Neodo123-6.5 by Shell Chemical
Company.
Other useful Neodols include Neodol 1-5, an ethoxylated fatty alcohol
averaging 11 carbon atoms
in its alkyl chain with about 5 moles of ethylene oxide; Neodo123-9, an
ethoxylated primary C12
- C13 alcohol having about 9 moles of ethylene oxide and Neodol 91-10, an
ethoxylated C9-C1 l
primary alcohol having about 10 moles of ethylene oxide. Alcohol ethoxylates
of this type have
also been marketed by Shell Chemical Company under the Dobanol trademark.
Dobanol 91-5 is
an ethoxylated C9-CI I fatty alcohol with an average of 5 moles ethylene oxide
and Dobanol 25-7
is an ethoxylated C12-C15 fatty alcohol with an average of 7 moles of ethylene
oxide per mole of
fatty alcohol.
Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7 and
Tergitol
Tm
15-S-9 both of which are linear secondary alcohol ethoxylates that have been
commercially
marketed by Union Carbide Corporation. The former is a mixed ethoxylation
product of CI I to
C15 linear secondary alkanol with 7 moles of ethylene oxide and the latter is
a similar product
but with 9 moles of ethylene oxide being reacted.
Other types of alcohol ethoxylates useful in the present compositions are
higher
molecular weight nonionics, such as Neodol 45-11, which are similar ethylene
oxide
condensation products of higher fatty alcohols, with the higher fatty alcohol
being of 14-15
carbon atoms and the number of ethylene oxide groups per mole being about 11.
Such products
have also been commercially marketed by Shell Chemical Company.
If alcohol alkoxylate nonionic surfactant is utilized as part of the liquid
phase in the
detergent compositions herein, it will preferably be present to the extent of
from about 1% to
60% of the composition structured liquid phase. More preferably, the alcohol
alkoxylate
component will comprise about 5% to 40% of the structured liquid phase. Most
preferably, an
alcohol alkoxylate component will comprise from about 5% to 35% of the
detergent composition
structured liquid phase. Utilization of alcohol alkoxylate in these
concentrations in the liquid
phase corresponds to an alcohol alkoxylate concentration in the total
composition of from about
1% to 60% by weight, more preferably from about 2% to 40% by weight, and most
preferably
from about 5% to 25% by weight, of the composition.
Another type of surfactant liquid which may be utilized in this invention are
the ethylene
oxide (EO) - propylene oxide (PO) block polymers. Materials of this type are
well known
9
CA 02380328 2005-08-19
nonionic surfactants which have been marketed under the tradename Pluronic.
These materials
are formed by adding blocks of ethylene oxide moieties to the ends of
polypropylene glycol
chains to adjust the surface active properties of the resulting block
polymers. EO-PO block
polymer nonionics of this type are described in greater detail in Davidsohn
and Milwidsky;
Svnthetic DeterQents. 7th Ed.; Longman Scientific and Technical (1987) at pp.
34-36 and pp.
189-191 and in U.S. Patents 2,674,619 and 2,677,700. These PluronicTM type
nonionic surfactants
are also believed to function as effective suspending agents for the
particulate material which is
dispersed in the liquid phase of the detergent compositions herein.
Another possible type of surfactant liquid useful in the compositions herein
comprises
polyhydroxy fatty acid amide surfactants. Materials of this type of nonionic
surfactant are those
which conform to the formula:
O i pH2p+1
R-C-N-Z
wherein R is a C9-17 alkyl or alkenyl, p is from I to 6, and Z is glycityl
derived from a reduced
sugar or alkoxylated derivative thereof. Such materials include the C12-Cl8 N-
methyl
glucamides. Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methyl N-1-
deoxyglucityl oleamide. Processes for making polyhydroxy fatty acid, amides
are know and can
be found, for example, in Wilson, U.S. Patent 2,965,576 and Schwartz, U.S.
Patent 2,703,798.
The materials themselves and their preparation are also described in greater
detail in Honsa, U.S.
Patent 5,174,937, issued December 26, 1992.
The detergent compositions of the present invention may also contain anionic,
cationic,
and/or amphoteric types. In a preferred embodiment, where the liquid phase is
non-aqueous, the
liquid phase is prepared by combining the non-aqueous organic liquid diluents
described in the
present invention with a surfactant which is generally, but not necessarily,
selected to add
structure to the non-aqueous liquid phase of the detergent compositions
herein. Structuring
surfactants can be of the anionic, nonionic, cationic, and/or amphoteric
types. Thus the
surfactants described below may be added for solely their surface-active
attributes or for those
attributes as well as their structuring ability.
Preferred surfactants are the anionic surfactants such as the alkyl sulfates,
the alkyl
polyalkxylate sulfates and the linear alkyl benzene sulfonates. Another common
type of anionic
CA 02380328 2005-08-19
surfactant material which may be optionally added to the detergent
compositions herein as
structurant comprises carboxylate-type anionics. Carboxylate-type anionics
include the C10-C18
alkyl alkoxy carboxylates (especially the EO 1 to 5 ethoxycarboxylates) and
the C10-C18
sarcosinates, especially oleoyl sarcosinate. Yet another common type of
anionic surfactant
material which may be employed as a structurant comprises other sulfonated
anionic surfactants
such as the Cg-CIg paraffin sulfonates and the Cg-Clg olefin sulfonates.
Structuring anionic
surfactants will generally comprise from about 1% to 30% by weight of the
compositions herein.
As indicated, one preferred type of structuring anionic surfactant comprises
primary or
secondary alkyl sulfate anionic surfactants. Such surfactants are those
produced by the sulfation
of higher Cg-C20 fatty alcohols.
Conventional primary alkyl sulfate surfactants have the general formula
ROSO3-Mt
wherein R is typically a linear Cg - C20 hydrocarbyl group, which may be
straight chain or
branched chain, and M is a water-solubilizing cation. Preferably R is a C10-14
alkyl, and M is
alkali metal. Most preferably R is about C12 and M is sodium.
Conventional secondary alkyl sulfates, as described above, may also be
utilized as a
structuring anionic surfactant for the liquid phase of the compositions
herein.
If utilized, alkyl sulfates will generally comprise from about 1% to 30% by
weight of the
composition, more preferably from about 5% to 25% by weight of the
composition. Non-aqueous
liquid detergent compositions containing alkyl sulfates, peroxygen bleaching
agents, and bleach
activators are described in greater detail in Kong-Chan et al.; WO 96/10073;
Published April 4,
1996.
Another preferred type of anionic surfactant material which may be optionally
added to the
non-aqueous cleaning compositions herein as a structurant comprises the alkyl
polyalkoxylate
sulfates. Alkyl polyalkoxylate sulfates are also known as alkoxylated alkyl
sulfates or alkyl ether
sulfates. Such materials are those which correspond to the formula
R2-O-(CmH2mO)n-SO3M
wherein R2 is a CI O-C22 alkyl group, m is from 2 to 4, n is from about 1 to
15, and M is a salt-
forming cation. Preferably, R2 is a C12-Cl8 alkyl, m is 2, n is from about 1
to 10, and M is
sodium, potassium, ammonium, alkylammonium or alkanolammonium. Most
preferably, R2 is a
C12-C16, m is 2, n is from about I to 6, and M is sodium. Ammonium,
alkylammonium and
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alkanolamtnonium counterions are preferably avoided when used in the
compositions herein
because of incompatibility with peroxygen bleaching agents.
If utilized, alkyl polyalkoxylate sulfates can also generally comprise from
about 1% to 30%
by weight of the composition, more preferably from about 5% to 25% by weight
of the
composition. Non-aqueous liquid detergent compositions containing alkyl
polyalkoxylate
sulfates, in combination with polyhydroxy fatty acid amides, are described in
greater detail in
CA 2,216,937.
The most preferred type of anionic surfactant for use as a structurant in the
compositions
herein comprises the linear alkyl benzene sulfonate (LAS) surfactants. In
particular, such LAS
surfactants can be formulated into a specific type of anionic surfactant-
containing powder which
is especially useful for incorporation into the non-aqueous liquid detergent
compositions of the
present invention. Such a powder comprises two distinct phases. One of these
phases is insoluble
in the non-aqueous organic liquid diluents used in the compositions herein;
the other phase is
soluble in the non-aqueous organic liquids. It is the insoluble phase of this
preferred anionic
surfactant-containing powder which can be dispersed in the non-aqueous liquid
phase of the
preferred compositions herein and which forms a network of aggregated small
particles that
allows the final product to stablely suspend other additional solid
particulate materials in the
composition.
Further descriptions of suitable surfactants, and methods for preparing such
surfactants
can be found in the patent of Jay I. Kahn et al., entitled "Preparation of
Nonaqueous, Particulate-Containing Liquid Detergent Compositions with
Surfactant-Structured
Liquid Phase", U. S. Patent No. 6,277,804.
Generally, the liquid surfactant can comprise from about 25% to 70% of the
liquid phase
of the compositions herein. More preferably, the liquid surfactant will
comprise from about 30%
to 65% of a structured liquid phase. This corresponds to a liquid surfactant
concentration in the
total composition of from about 10% to 70% by weight, more preferably from
about 20% to 50%
by weight, of the composition. The amount of total liquid surfactant in the
preferred surfactant-
structured, non-aqueous liquid phase herein is as described above and will be
further determined
by the type and amounts of other composition components and by the desired
composition
properties.
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ii) Non-surfactant Organic Solvents - The liquid phase of the detergent
compositions
herein may also comprise one or more non-surfactant organic solvents. Such non-
surfactant
liquids are preferably those of low polarity. For purposes of this invention,
"low-polarity" liquids
are those which have little, if any, tendency to dissolve one of the preferred
types of particulate
material used in the compositions herein, i.e., the peroxygen bleaching
agents, sodium perborate
or sodium percarbonate. Thus relatively polar solvents such as ethanol are
preferably not
utilized. Suitable types of low-polarity solvents useful in the liquid
detergent compositions herein
do include alkylene glycol mono lower alkyl ethers, lower molecular weight
polyethylene glycols,
lower molecular weight methyl esters and amides, and the like.
A preferred type of low-polarity solvent for use in the compositions herein
comprises the
C4-Cg branched or straight chain alkylene glycols. Materials of this type
include hexylene glycol
(4-methyl-2,4-pentanediol), 1,3-butylene glycol and 1,4-butylene glycol.
Another preferred type of low-polarity solvent for use herein comprises the
mono-, di-, tri-,
or tetra- C2-C3 alkylene glycol mono C2-C6 alkyl ethers. The specific examples
of such
compounds include diethylene glycol monobutyl ether, tetraethylene glycol
monobutyl ether,
dipropolyene glycol monoethyl ether, and dipropylene glycol monobutyl ether.
Diethylene glycol
monobutyl ether, dipropylene glycol monobutyl ether and butoxy-propoxy-
propanol (BPP) are
especially preferred. Compounds of the type have been connnercially marketed
under the
trademarks Dowanol, Carbitol, and Cellosolve.
Another preferred type of low-polarity organic solvent useful herein comprises
the lower
molecular weight polyethylene glycols (PEGs). Such materials are those having
molecular
weights of at least about 150. PEGs of molecular weight ranging from about 200
to 600 are most
preferred.
Yet another preferred type of non-polar solvent comprises lower molecular
weight methyl
esters. Such materials are those of the gcneral formula: Rl-C(O)-OCH3 wherein
R1 ranges from
1 to about 18. Examples of suitable lower molecular weight methyl esters
include methyl acetate,
methyl propionate, methyl octanoate, and methyl dodecanoate.
The generally low-polarity, non-surfactant organic solvent(s) employed should,
of course, be
compatible and non-reactive with other composition components, e.g., bleach
and/or activators,
used in the liquid detergent compositions herein. Such a solvent component is
preferably utilized
in an amount of from about 1% to 70% by weight of the liquid phase. More
preferably, a low-
polarity, non-surfactant solvent will comprise from about 10% to 60% by weight
of a structured
liquid phase, most preferably from about 20% to 50% by weight, of a structured
liquid phase of
13
CA 02380328 2005-08-19
the composition. Utilization of non-surfactant solvent in these concentrations
in the liquid phase
corresponds to a non-surfactant solvent concentration in the total composition
of from about 1% to
50% by weight, more preferably from about 5% to 40% by weight, and most
preferably from about
10% to 30% by weight, of the composition.
iii) Blends of Surfactant and Non-surfactant Solvents - In the preferred
embodiments which
employ both non-aqueous surfactant liquids, and non-aqueous non-surfactant
solvents, the ratio of
surfactant to non-surfactant liquids, e.g., the ratio of alcohol alkoxylate to
low polarity solvent,
within a structured, surfactant-containing liquid phase can be used to vary
the rheological properties
of the detergent compositions eventually formed. Generally, the weight ratio
of surfactant liquid to
non-surfactant organic solvent will range about 50:1 to 1:50. More preferably,
this ratio will range
from about 3:1 to 1:3, most preferably from about 2:1 to 1:2.
O ~
(RI)x-N-(Rz.)y, =N--(Rt)x
I
(R3)Z
Solid Particulate Materials
In addition to the surfactant-containing liquid phase, the liquid detergent
compositions
herein also preferably comprise from about 1% to 50% by weight, more
preferably from about 29%
to 44% by weight, of additional solid phase particulate material which is
dispersed and suspended
within the liquid phase. Generally such particulate material will range in
size from about 0.1 to
1500 microns, more preferably from about 0.1 to 900 microns. Most preferably,
such material will
range in size from about 5 to 200 microns.
The additional particulate material utilized herein can comprise one or more
types of
detergent composition components which in particulate form are substantially
insoluble in the liquid
phase of the composition. Such materials include peroxygen bleaching agents,
bleach activators,
organic detergent builders, inorganic alkalinity sources, enzymes,
brighteners, polymers and
combinations thereof. The types of particulate materials which can be utilized
are described in detail,
below, as follows, however, some materials can either be included in the
particulate component or in
the surfactant-containing liquid phase.
In a preferred embodiment the particulate material comprises the dye transfer
inhibitor
PVNO (see above for detailed description), an aluminosilicate detergent
builder
as well as other particulate minor components.
(a) BleachingAgcent With Optional Bleach Activators - The most preferred type
of
14
CA 02380328 2005-08-19
particulate material useful in the detergent compositions herein comprises
particles of a
peroxygen bleaching agent. Such peroxygen bleaching agents may be organic or
inorganic in
nature. Inorganic peroxygen bleaching agents are frequently utilized in
combination with a
bleach activator.
Useful organic peroxygen bleaching agents include percarboxylic acid bleaching
agents and
salts thereof. Suitable examples of this class of agents include magnesium
monoperoxyphthalate
hexahydrate, the magnesium salt of inetachloro perbenzoic acid, 4-nonylamino-4-
oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents
are disclosed in
U.S. Patent 4,483,781, I=lartman, Issued November 20, 1984; European Patent
Application EP-A-
133,354, Banks et al., Published February 20, 1985; and U.S. Patent 4,412,934,
Chung et al.,
Issued November 1, 1983. Highly preferred bleaching agents also include 6-
nonylamino-6-
oxoperoxycaproic acid (NAPAA) as described in U.S. Patent 4,634,551, Issued
January 6, 1987
to Burns et al.
Inorganic peroxygen bleaching agents may also be used in particulate form in
the detergent
compositions herein. Inorganic bleaching agents are in fact preferred. Such
inorganic peroxygen
compounds include alkali metal perborate and percarbonate materials, most
preferably the
percarbonates. For example, sodium perborate (e.g. mono- or tetra-hydrate) can
be used.
Suitable inorganic bleaching agents can also include sodium or potassium
carbonate
peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate
peroxyhydrate,
TM
urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE,
manufactured
commercially by DuPont) can also be used. Frequently inorganic peroxygen
bleaches will be
coated with silicate, borate, sulfate or water-soluble surfactants. For
example, coated
percarbonate particles are available from various commercial sources such as
FMC, Solvay
Interox, Tokai Denka and Degussa.
Inorganic peroxygen bleaching agents, e.g., the perborates, the percarbonates,
etc., are
preferably combined with bleach activators, which lead to the in situ
production in aqueous
solution (i.e., during use of the compositions herein for fabric
laundering/bleaching) of the peroxy
acid corresponding to the bleach activator. Various non-limiting examples of
activators are
disclosed in U.S. Patent 4,915,854, Issued April 10, 1990 to Mao et al.; and
U.S. Patent 4,412,934
Issued November 1, 1983 to Chung et al. The nonanoyloxybenzene sulfonate
(NOBS) and
tetraacetyl ethylene diamine (TAED) activators are typical. Mixtures thereof
can also be used.
See also the hereinbefore referenced U.S. 4,634,551 for other typical bleaches
and activators
useful herein.
CA 02380328 2005-08-19
Other useful amido-derived bleach activators are described in U.S. Pat. No.
5,891,838,
issued April 6, 1999 to Angell et al.
If peroxygen bleaching agents are used as all or part of the additional
particulate material,
they will generally comprise from about 1% to 30% by weight of the
composition. More
preferably, peroxygen bleaching agent will comprise from about 1% to 20% by
weight of the
composition. Most preferably, peroxygen bleaching agent will be present to the
extent of from
about 5% to 20% by weight of the composition. If utilized, bleach activators
can comprise from
about 0.5% to 20%, more preferably from about 3% to 10%, by weight of the
composition.
Frequently, activators are employed such that the molar ratio of bleaching
agent to activator
ranges from about 1:1 to 10:1, more preferably from about 1.5:1 to 5:1.
(b) Transition Metal Bleach Catalysts - Another possible type of additional
particulate
material which can be suspended in the liquid detergent compositions herein
comprises transition
metal bleach catalysts which encourage the catalytic oxidation of soils and
stains on fabrie
surfaces. Such compounds are present in a catalytically effective amount,
preferably from about 1
ppb to about 99.9%, more typically from about 0.001 ppm to about 49%,
preferably from about
0.05 ppm to about 500 ppm (wherein "ppb" denotes parts per billion by weight
and "ppm"
denotes parts per million by weight), of a laundry detergent composition. The
transition-metal
bleach catalyst comprises a complex of a transition metal selected from the
group consisting of
Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II),
Co(III), Ni(I), Ni(II),
Ni(III), Cu(I), Cu(II), Cu(11I), Cr(II), Cr(III), Cr(N), Cr(V), Cr(VI),
V(III), V(N), V(V), Mo(IV),
Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(11I), and Ru(IV)
coordinated with a
macropolycyclic rigid ligand, preferably a cross-bridged macropolycyclic
ligand, having at least 4
donor atoms, at least two of which are bridgehead donor atoms. These catalysts
are discussed
with greater specificity in the published application of Daryle H. Busch et
al., entitled "Catalysts
and Methods for Catalytic Oxidation", CA 2,282,406.
(c) Organic Builder Material - Another possible type of additional particulate
material
which can be suspended in the liquid detergent compositions herein comprises
an organic
detergent builder material which serves to counteract the effects of calcium,
or other ion, water
16
CA 02380328 2005-08-19
hardness encountered during laundering/bleaching use of the compositions
herein. Examples of
such materials include the alkali metal, citrates, succinates, malonates,
fatty acids, carboxymethyl
succinates, carboxylates, polycarboxylates and polyacetyl carboxylates.
Specific examples
include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic
acid, benzene
polycarboxylic acids and citric acid. Other examples of organic phosphonate
type sequestering
agents such as those which have been sold by Monsanto under the Dequest
trademark and
alkanehydroxy phosphonates. Citrate salts are highly preferred.
Other suitable organic builders include the higher molecular weight polymers
and
copolymers known to have builder properties. For example, such materials
include appropriate
polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers
and their salts,
such as those sold by BASF under the Sokalan trademark which have molecular
weight ranging
from about 5,000 to 100,000.
Another suitable type of organic builder comprises the water-soluble salts of
higher fatty
acids, i.e., "soaps". These include alkali metal soaps such as the sodium,
potassium, ammonium,
and alkylolammonium salts of higher fatty acids containing from about 8 to
about 24 carbon
atoms, and preferably from about 12 to about 18 carbon atoms. Soaps can be
made by direct
saponification of fats and oils or by the neutralization of free fatty acids.
Particularly useful are
the sodium and potassium salts of the mixtures of fatty acids derived from
coconut oil and tallow,
i.e., sodium or potassium tallow and coconut soap.
If utilized as all or part of the additional particulate material, insoluble
organic detergent
builders can generally comprise from about 2% to 20% by weight of the
compositions herein.
More preferably, such builder material can comprise from about 4% to 10% by
weight of the
composition.
(d) Inorganic Alkalinity Sources - Another possible type of additional
particulate
material which can be suspended in the liquid detergent compositions herein
can comprise a
material which serves to render aqueous washing solutions formed from such
compositions
generally alkaline in nature. Such materials may or may not also act as
detergent builders, i.e., as
materials which counteract the adverse effect of water hardness on detergency
performance.
Examples of suitable alkalinity sources include water-soluble alkali metal
carbonates,
bicarbonates, borates, silicates and metasilicates. Although not preferred for
ecological reasons,
water-soluble phosphate salts may also be utilized as alkalinity sources.
These include alkali
metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Of all
of these
alkalinity sources, alkali metal carbonates such as sodium carbonate are the
most preferred.
17
CA 02380328 2005-08-19
The alkalinity source, if in the form of a hydratable salt, may also serve as
a desiccant in
the liquid detergent compositions herein. The presence of an alkalinity source
which is also a
desiccant may provide benefits in terms of chemically stabilizing those
composition components
such as the peroxygen bleaching agent which may be susceptible to deactivation
by water.
If utilized as all or part of the additional particulate material component,
the alkalinity
source will generally comprise from about 1% to 25% by weight of the
compositions herein.
More preferably, the alkalinity source can comprise from about 2% to 15% by
weight of the
composition. Such materials, while water-soluble, will generally be insoluble
in the non-aqueous
detergent compositions described herein.
As indicated hereinafter, the aqueous and non-aqueous liquid detergent
compositions
herein may be in the form of bleaching agent and/or other materials in
particulate form as a solid
phase suspended in and dispersed throughout a surfactant-containing,
preferably structured,
preferably non-aqueous liquid phase. Generally, the structured non-aqueous
liquid phase will
comprise from about 49% to 99.95%, more preferably from about 52% to 98.5%, by
weight of
the composition with the dispersed additional solid materials comprising from
about 1% to 50%,
more preferably from about 29% to 44%, by weight of the composition.
Very small amounts of water may be incorporated into the particulate-
containing non-
aqueous embodiments of the present liquid detergent composition. However, in
such
embodiments, the amount of free water should in no event exceed about 1% by
weight of the
compositions herein. More preferably, the water content of the non-aqueous
detergent
compositions herein will comprise less than about 1% by weight.
As disclosed herein, the compositions of this invention can also be used to
form aqueous
laundry detergent compositions. Additional components suitable for use in an
aqueous liquid
laundry detergent composition can be found in U. S. Pat. No. 5,783,548, to
Fredj et al. and U. S.
Pat. No. 5,648,327, to Smerznak et al.
The particulate-containing non-aqueous liquid detergent compositions herein
will be
relatively viscous and phase stable under conditions of commercial marketing
and use of such
compositions. Frequently the viscosity of the compositions herein will range
from about 300 to
8,000 cps, more preferably from about 1000 to 4,000 cps. For purposes of this
invention,
Tm
viscosity is measured with a Carrimed CSL2 Rheometer at a shear rate of 20 s-
1.
The preparation of non-aqueous liquid detergent compositions is discussed in
detail in
the patent of Jay I. Kahn et al., entitled "Preparation of Nonaqueous,
Particulate-
Containing Liquid Detergent Compositions with Surfactant-Structured Liquid
Phase",
18
CA 02380328 2005-08-19
U.S. Patent No. 6,277,804.
An effective amount of the liquid detergent compositions herein added to water
to form
aqueous laundering/bleaching solutions can comprise amounts sufficient to form
from about 500
to 10,000 ppm of composition in aqueous solution. More preferably, from about
800 to 8,000
ppm of the detergent compositions herein will be provided in aqueous
washing/bleaching
solution.
B. GRA]VULAR/POWDER PRODUCTS
The granular/powder detergent products of the present invention comprise in
addition to
one or more of the hydrotropes, preferably one or more preferred ingredients
hereinbelow and
optionally, one or more conventional detergent adjunct materials. Such
conventional adjunct
materials can include one or more of the solid particulate materials described
under the Liquid
Products section hereinabove or under the Conventional Detergent Adjunct
Materials section
hereinafter.
While the use of hydrotropes is to provide desirable phase formation and
product
viscosity is well-known, the use of these organic molecules as hydrotropes to
prevent gelling
and/or thickening of the detergent compositions taught herein and thus improve
the dissolution
and dispersion performance of a granular detergent product has not been
previously disclosed.
Gelling has been previously observed in detergent products prepared without
the hydrotropes as
defined in the present invention, when the products are first contacted and
diluted with water.
Without being limited by theory, it is believed that this gelling phenomenon
results from
the surfactant-containing particles forming either viscous surfactant phases
(typically lamellar,
spherulitic or hexagonal phases) or inner-connected "lump-gels" the upon
contact with water in
the wash-liquor or wash-water at certain concentrations of surfactant. A
correlation has been
found between the viscosity of the product-water mixture in the critical
dilution range where
gelling is observed, and the amount of viscous surfactant phase formed in this
range.
The problem is particularly pronounced in those areas in which fabric
laundering in
automatic clothes washer occurs in relatively cold wash water or under mild
agitation (such as in
Japan). The typical surfactant-water phase diagram shows regions of stability
for high-viscosity
neat or gel surfactant phases at the relatively cold wash-water temperatures.
And under
conditions of mild agitation, there is insufficient mechanical energy imparted
by the agitator to
disrupt the formation of these high-viscosity phases.
19
CA 02380328 2005-08-19
The granular detergent compositions taught herein can be either in the form of
a single
particle or may be in the form of multiple particles each with its own
composition. In the case
where the detergent is composed of multiple detergent particles, it is
preferred that the organic
hydrotrope disclosed above be contained in or coat the surface of those
particles which are
surfactant rich.
Preferred Ingredients
Detersive Surfactants - The anionic surfactants useful in the present
invention are split
into the alkyl sulfate surfactants which according to the present invention
are separated from the
electrolytes in the detergent composition and the remaining anionic
surfactants which may be
formulated in either particle. For the purposes of the present invention, the
alkyl sulfates are
defined as alkyl sulfates, alkyl alkoxy sulfate, alkyl sulfonates, alkyl
alkoxy carboxylate, alkyl
alkoxylated sulfates with the remaining anionic surfactant being selected from
the group
consisting of alkylbenzene sulfonate, alpha olefin sulfonate, paraffin
sulfonates, alkyl ester
sulfonates, sarcosinates, taurinates, and mixtures thereof.
When present, anionic surfactant will be present typically in an effective
amount in the
overall detergent composition. More preferably, the composition may contain at
least about
0.5%, more preferably at least about 5%, even more preferably still, at least
about 10% by weight
of said composition of anionic surfactant. The composition will also
preferably contain no more
than about 90%, more preferably no more than about 50%, even more preferably,
no more than
about 30% by weight of said composition of anionic surfactant.
Alkyl sulfate surfactants providing excellent overall cleaning ability alone
and particularly
when used in combination with polyhydroxy fatty acid amides (see below),
including good
grease/oil cleaning over a wide range of temperatures, wash concentrations,
and wash times,
dissolution of alkyl sulfates can be obtained, as well as improved
formulability in liquid detergent
formulations are water soluble salts or acids of the formula ROSO3M wherein R
preferably is a
C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20
alkyl component,
more preferably a Cl2-C18 alkyl or hydroxyalkyl, and M is H or a cation, e.g.,
an alkali (Group
IA) metal cation (e.g., sodium, potassium, lithium), substituted or
unsubstituted amrnonium
cations such as methyl-, dimethyl-, and trimethyl anunonium and quatemary
annnonium cations,
e.g., tetramethyl-ammonium and dimethyl piperdinium, and cations derived from
alkanolamines
such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof,
and the like.
Typically, alkyl chains of C12-16 are preferred for lower wash temperatures
(e.g., below about
CA 02380328 2005-08-19
50 C) and C16-18 alkyl chains are preferred for higher wash temperatures
(e.g., above about
50 C).
Another suitable type of alkyl sulfate surfactant according to the present
invention are
the secondary (2,3) alkyl sulfates. These surfactants preferably are of the
formula:
O SO3 M* OS03 NI'
CH3(Uk12)x(UH)CH3 Ur CH3(CH2)y(CH)CI12L;H3
wherein x and (y + 1) are integers of at least about 7, preferably at least
about 9. Preferably these
surfactants contain from 10 to 18 carbon atoms. Suitable examples of these
anionic surfactants
are disclosed in U.S. 3,234,258 Morris, issued February 8, 1966; U.S.
5,075,041 Lutz, issued
December 24, 1991; U.S. 5,349,101 Lutz et al., issued September 20, 1994; and
U.S. 5,389,277
Prieto, issued February 14, 1995.
Another suitable type of alkyl sulfate surfactant according to the present
invention are the
alkyl alkoxylated sulfate. These surfactants are water soluble salts or acids
typically of the
formula RO(A)mSO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl
group
having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl,
more preferably
C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater
than zero, typically
between about 0.5 and about 6, more preferably between about 0.5 and about 3,
and M is H or a
cation which can be, for example, a metal cation (e.g., sodium, potassium,
lithium, etc.),
ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well as
alkyl
propoxylated sulfates are contemplated herein. Specific examples of
substituted ammonium
cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary
anunonium cations, such
as tetramethyl-anunonium, dimethyl piperidinium and cations derived from
alkanolamines, e.g.
monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof.
Exemplary
surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate, C12-C18 alkyl
polyethoxylate (2.25)
sulfate, C12-C18 alkyl polyethoxylate (3.0) sulfate, and C12-C18 alkyl
polyethoxylate (4.0)
sulfate wherein M is conveniently selected from sodium and potassium.
Surfactants for use
herein can be made from natural or synthetic alcohol feedstocks. Chain lengths
represent average
hydrocarbon distributions, including branching. The anionic surfactant
component may comprise
alkyl sulfates and alkyl ether sulfates derived from conventional alcohol
sources, e.g., natural
alcohols, synthetic alcohols such as those sold under the trade marks of
NEODOLTM', ALFOLT",
LIALT", LUTENSOLT" and the like. Alkyl ether sulfates are also known as alkyl
polyethoxylate
sulfates.
21
CA 02380328 2002-01-23
WO 01/10993 PCTIUSOO/21570
Another type of alkyl sulfate surfactant according to the present invention
are one or
more (preferably a mixture of two or more) mid-chain branched surfactants,
preferably mid-chain
branched alkyl alkoxy alcohols having the formula:
R R' R2
I I I
CH3CH2(CH2) ,CH(CH2).CH(CH2)yCH(CH2)z,(EO/P O)IõOH
mid-chain branched alkyl sulfates having the formula:
R R' R2
CH3CH2(CH2)N,CH(CH2)XCH(CH2)yCH(CH2)ZOSO3M
and mid-chain branched alkyl alkoxy sulfates having the formula:
R R1 RZ
I I I
CH3CH2(CH2),CH(CH2),CH(CH2)yCH(CH2)z,(EO/P O)71OSO3M
wherein the total number of carbon atoms in the branched primary alkyl moiety
of these formulae
(including the R, Rl, and R2 branching, but not including the carbon atoms
which comprise any
EO/PO alkoxy moiety) is from 14 to 20, and wherein further for this surfactant
mixture the
average total number of carbon atoms in the branched primary alkyl moieties
having the above
formula is within the range of greater than 14.5 to about 17.5 (preferably
from about 15 to about
17); R, R1, and R2 are each independently selected from hydrogen, CI-C3 alkyl,
and mixtures
thereof, preferably methyl; provided R, R1, and R2 are not all hydrogen and,
when z is 1, at least
R or RI is not hydrogen. M is a water soluble cation and may comprises more
than one type of
cation, for example, a mixture of sodium and potassium. The index w is an
integer from 0 to 13;
x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer of
at least 1; provided w +
x+ y + z is from 8 to 14. EO and PO represent ethyleneoxy units and
propyleneoxy units having
the formula:
C
IH3 IC H3
-CHCH2O- or -CH2CHO-
respectively, however, other alkoxy units inter alia 1,3-propyleneoxy, butoxy,
and mixtures
thereof are suitable as alkoxy units appended to the mid-chain branched alkyl
moieties.
The mid-chain branched surfactants are preferably mixtures which comprise a
surfactant
system. Therefore, when the surfactant system comprises an alkoxylated
surfactant, the index m
indicates the average degree of alkoxylation within the mixture of
surfactants. As such, the index
m is at least about 0.01, preferably within the range of from about 0.1, more
preferably from
about 0.5, most preferably from about 1 to about 30, preferably to about 10,
more preferably to
22
CA 02380328 2005-08-19
about 5. When considering a mid-chain branched surfactant system which
comprises only
alkoxylated surfactants, the value of the index m represents a distribution of
the average degree
of alkoxylation corresponding to m, or it may be a single specific chain with
alkoxylation (e.g.,
ethoxylation and/or propoxylation) of exactly the number of units
corresponding to m.
The preferred mid-chain branched surfactants of the present invention which
are suitable
for use in the surfactant systems of the present invention have the formula:
CH3
CH3(CH2)aCH(CH2)bCH2(EO/P O)mOSO3M
or the formula:
CH3 i H3
CH3(CH2)dCH(CH2)eCHCH2(EO/P O)mOSO3M
wherein a, b, d, and e are integers such that a + b is from 10 to 16 and d + e
is from 8 to 14; M is
selected from sodium, potassium, magnesium, amrnonium and substituted
ammonium, and
mixtures thereof.
The surfactant systems of the present invention which comprise mid-chain
branched
surfactants are preferably formulated in two embodiments. A first preferred
embodiment
comprises mid-chain branched surfactants which are formed from a feedstock
which comprises
25% or less of mid-chain branched alkyl units. Therefore, prior to admixture
with any other
conventional surfactants, the mid-chain branched surfactant component will
comprise 25% or
less of surfactant molecules which are non-linear surfactants.
A second preferred embodiment comprises mid-chain branched surfactants which
are
formed from a feedstock which comprises from about 25% to about 70% of mid-
chain branched
alkyl units. Therefore, prior to admixture with any other conventional
surfactants, the mid-chain
branched surfactant component will comprise from about 25% to about 70%
surfactant molecules
which are non-linear surfactants.
These surfactants are further described in W099/19434; W099/18929; W099/19435;
W099/18928; W099/19448; and W099/19449. Other suitable mid-chain branched
surfactants
can be found in W097/39087; W097/39088; W097/39091; W098/23712; W097/38972;
W097/39089; and W097/39090.
23
CA 02380328 2005-08-19
Mixtures of these branched surfactants with conventional linear surfactants
are also suitable for
use in the present compositions.
Of the anionic surfactants according to the present invention which are not
included in the
alkyl sulfates according to the present invention one type of anionic
surfactant which can be
utilized encompasses alkyl ester sulfonates. These are desirable because they
can be made with
renewable, non-petroleum resources. Preparation of the alkyl ester sulfonate
surfactant
component can be effected according to known methods disclosed in the
technical literature. For
instance, linear esters of C8-C20 carboxylic acids can be 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,
and coconut oils,
etc.
The preferred alkyl ester sulfonate surfactant, especially for laundry
applications,
comprises alkyl ester sulfonate surfactants of the structural formula:
0
R3CHCOR4
I
SO3M
wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination
thereof, R4 is a C1-C6
hydrocarbyl, preferably an alkyl, or combination thereof, and M is a soluble
salt-forming cation.
Suitable salts include metal salts such as sodium, potassium, and lithium
salts, and substituted or
unsubstituted ammonium salts, such as methyl-, dimethyl, -trimethyl, and
quaternary anunonium
cations, e.g. tetramethyl-ammonium and dimethyl piperdinium, and cations
derived from
alkanolamines, e.g. monoethanol-amine, diethanolamine, and triethanolamine.
Preferably, R3 is
Cl0-C16 alkyl, and R4 is methyl, ethyl or isopropyl. Especially preferred are
the methyl ester
sulfonates wherein R3 is C14-C16 alkyl.
Another type of anionic surfactant which can be utilized encompasses
alkylbenzenesulphonates. These include the hard (ABS, TPBS), linear types,
also known as
LAS, and made by known process such as various HF or solid HF e.g., DETAL
(UOP) process,
or made by using other Lewis Acid catalysts e.g., AIC33i or made using acidic
silica/alumina or
made from chlorinated hydrocarbons, such as C9-C20 linear alkylbenzene
sulfonates, particularly
sodium linear alkyl C10-C15 benzene sulfonate. These surfactants are water
soluble salts or
acids typically of the formula RASO3M wherein R is a branched or linear C10-
C24 alkyl group,
preferably a C10-C20 alkyl, more preferably C10-C18 alkyl, A is an aryl group
, preferably
benzene, or toluene, more preferably benzene unit, and M is H or a cation
which can be, for
24
CA 02380328 2005-08-19
example, a metal cation (e.g., sodium, potassium, lithium, etc.), ammonium or
substituted-
ammonium cation.
The surfactant systems of the laundry detergent compositions of the present
invention
can also comprise from about 0.001%, preferably from about 1%, more preferably
from about
5%, most preferably from about 10% to about 100%, preferably to about 60%,
more preferably to
about 30% by weight, of the surfactant system, of one or more (preferably a
mixture of two or
more) modified alkyl arylsulfonate surfactants, or MLAS preferably surfactants
wherein the aryl
unit is a benzene ring having the formula:
RtR2L R3
[M 9fl b
S03
a
wherein L is an acyclic hydrocarbyl moiety comprising from 6 to 18 carbon
atoms; R', RZ, and R3
are cach independently hydrogen or CI-C3 alkyl, provided R' and R 2 are not
attached at the
terminus of the L unit; M is a water soluble cation having charge q wherein a
and b are taken
together to satisfy charge neutrality.
These and other suitable MLAS surfactants are further described in W099/05243;
W099/05242; WO99/05244; W099/05082; W099/05084; W099/05241; W000/23549; and
W000/23548. Mixtures of these modified surfactants with conventional
surfactants and/or
branched surfactants, such as those described herein, are also suitable for
use in the present
compositions.
Examples of suitable anionic surfactants are given in "Surface Active Agents
and
Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such
surfactants are also
generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to
Laughlin, et al. at
Column 23, line 58 through Column 29, line 23.
Other anionic surfactants useful for detersive purposes can also be included
in the
compositions hereof. These can include salts (including, for example, sodium,
potassium,
CA 02380328 2005-08-19
ammonium, and substituted anunonium salts such as mono-, di- and
triethanolamine salts) of
soap, C8-C22 primary or secondary alkanesulphonates, C8-C24 olefinsulphonates,
sulphonated
polycarboxylic acids prepared by sulphonation of the pyrolyzed product of
alkaline earth metal
citrates, e.g., as described in British patent specification No. 1,082,179,
alkyl glycerol sulfonates,
fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol
ethylene oxide ether
sulfates, paraffin sulfonates, alkyl phosphates, isothionates such as the acyl
isothionates, N-acyl
taurates, fatty acid amides of inethyl tauride, alkyl succinamates and
sulfosuccinates, monoesters
of sulfosuccinate (especially saturated and unsaturated C12-C18 monoesters)
diesters of
sulfosuccinate (especially saturated and unsaturated C6-C14 diesters), N-acyl
sarcosinates,
sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside
(the nonionic
nonsulfated compounds being described below), branched primary alkyl sulfates,
alkyl
polyethoxy carboxylates such as those of the formula RO(CH2CH2O)kCH2COO-W
wherein R
is a C8-C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-
forming cation, and fatty
acids esterified with isethionic acid and neutralized with sodium hydroxide.
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 given in
"Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and
Berch). A variety
of such surfactants are also generally disclosed in U.S. Patent 3,929,678,
issued December 30,
1975 to Laughlin, et al. at Column 23, line 58 through Colurnn 29, line 23.
Another type of useful anionic surfactant are the so-called dianionics. These
are
surfactants which have at least two anionic groups present on the surfactant
molecule. Some
suitable dianionic surfactants are further described in W098/00498;
W098/00503; U.S.
5,958,858; W098/05742; and W098/05749.
C. TABLET PRODUCTS
The tablet detergent products of the present invention comprise in addition to
one or
more of the hydrotropes ("binding agents" because they have a cohesive effect
on the tablets),
preferably one or more preferred ingredients hereinbelow and optionally, one
or more
conventional detergent adjunct materials. Such conventional adjunct materials
can include one or
more of the solid particulate materials described under the Liquid Products
section and/or
26
CA 02380328 2002-01-23
WO 01/10993 PCT/US00/21570
Granular/Powder Products section hereinabove or under the Conventional
Detergent Adjunct
Materials section hereinafter.
Detergent tablet formulations generally contain at least a small amount of
binding agent
in the composition in order to provide a cohesive effect and promote the
integrity of the tablets.
For the purpose of this invention, the Cohesive Effect on the particulate
material of a detergent
matrix is characterised by the force required to break a tablet based on the
examined detergent
matrix pressed under controlled compression conditions. Means to assess tablet
strength (also
refer to diametrical fracture stress) are given in Pharmaceutical dosage forms
: tablets volume 1
Ed. H.A. Lieberman et al, published in 1989.
It has been found that the addition of these hydrotrope compounds to a
particulate
material prepared according to the present invention has a cohesive effect
while also providing
excellent disintegration performance in wash-water when it is formed into a
tablet by
compressing the particulate material. Detergent tablets containing this
hydrotrope have a higher
tensile strength at constant compacting force or an equal tensile strength at
lower compacting
force when compared to traditional tablets.
In addition to the cohesive effect that they provide, these hydrotropes also
provide the
key ingredient to prevent gelling and/or thickening of the detergent
compositions taught herein.
Gelling has been previously observed in detergent products prepared without
the hydrotropes as
defined in the present invention, when the products are first contacted and
diluted with water.
Without being limited by theory, it is believed that this gelling phenomenon
results from the
surfactant-containing particles forming viscous surfactant phases (typically
lamellar, spherulitic
or hexagonal phases) upon contact with water in the wash-liquor or wash-water
at certain
concentrations of surfactant. A correlation has been found between the
viscosity of the product-
water mixture in the critical dilution range where gelling is observed, and
the amount of viscous
surfactant phase formed in this range.
Without being bound by theory, it is believed that the hydrotropes described
above prevent the
formation of the viscous surfactant phases formed upon dilution, because the
hydrotrope can
effectively interact with the ordered, structured layers of surfactant
molecules, disrupt them and
promote the formation of isotropic low - viscosity surfactant phases.
In the present invention, there is also an additional benefit that the
inclusion of these
special hydrotropes expands the "operating window" of the detergent tablets.
The operating
window relates to the range in the bulk density of the detergent tablets, when
the detergent tablets
are manufactured on an industrial scale. Because of several variables, during
the industrial-scale
27
CA 02380328 2002-01-23
WO 01/10993 PCT/US00/21570
manufacture of detergent tablets the density of the detergent tablets varies
somewhat from the
ideal or preferred density. The operating window is the range of densities
surrounding the
preferred density where the tablet is not at the preferred density but is
still acceptable. Below the
operating window, the density is too low as a result of insufficient packing
and cohesion during
the compression step and thus the tablet is very friable and likely to be
broken during handling
and storage. Above the operating window, the tablet is packed too tightly and
is likely to be
insufficiently dissolved and dispersed in a wash liquor during a wash process.
In addition to these hydrotropes discussed above, the present detergent
tablets may also
include additional non-gelling binders. Non-gelling binders not only provide
cohesive benefits,
but also facilitate dissolution.
If non gelling binders are used, suitable non-gelling binders include
synthetic organic
polymers such as polyethylene glycols, polyvinylpyrrolidones, polyacrylates
and water-soluble
acrylate copolymers. The handbook of Pharmaceutical Excipients second edition,
has the
following binders classification: Acacia, Alginic Acid, Carbomer,
Carboxymethylcellulose
sodium, Dextrin, Ethylcellulose, Gelatin, Guar gum, Hydrogenated vegetable oil
type I,
Hydroxyethyl cellulose, Hydroxypropyl methylcellulose, Liquid glucose,
Magnesium aluminum
silicate, Maltodextrin, Methylcellulose, polymethacrylates, povidone, sodium
alginate, starch and
zein. Most preferable binders also have an active cleaning function in the
laundry wash such as
cationic polymers, i.e. ethoxylated hexamethylene diamine quaternary
compounds,
bishexamethylene triamines, or others such as pentaamines, ethoxylated
polyethylene amines,
maleic acrylic polymers.
Non-gelling binder materials are preferably sprayed on and hence have an
appropriate
melting point temperature below 90 C, preferably below 70 C and even more
preferably below
50 C so as not to damage or degrade the other active ingredients in the
matrix. Most preferred
are non-aqueous liquid binders (i.e. not in aqueous solution) which may be
sprayed in molten
form. However, they may also be solid binders incorporated into the matrix by
dry addition but
which have binding properties within the tablet.
The detergent tablets prepared according to the present invention will
comprise from
about 0.05% to about 5%, preferably from about 0.1% to about 3%, most
preferably from about
0.1% to about 1% of the essential hydrotrope in which two polar groups are
separated from each
other by at least 5, preferably 6, aliphatic carbon atoms. When the optional
non-gelling binder
materials are used, they will be present in the detergent tablets, they will
be used in levels of from
about 0.1% to about 7%, pref. from about 0.5% to about 5%, more pref. from
about 1% to about
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CA 02380328 2002-01-23
WO 01/10993 PCT/US00/21570
3% of the detergent tablet. When the optional non-gelling binders are used
they will be present
in the detergent tablets in a ratio of non-gelling binder to special
hydrotrope binder of from about
2:1 to about 60:1, preferably from about 3:1 to about 30:1, more preferably
from about 3:1 to
about 15:1.
Disintegrants - Although it is necessary that the tablets should have good
integrity before
use, it is necessary also that they should disintegrate rapidly during use,
when contacted with
wash-water. Thus it is also known to include a disintegrant which will promote
disintegration of
the tablet. Various classes of disintegrant are known, including the class in
which disintegration
is caused by swelling of the disintegrant. Various swelling disintegrants have
been proposed in
the literature, with the preference being directed predominantly towards
starches, celluloses and
water soluble organic polymers. Inorganic swelling disintegrants such as
bentonite clay have also
been mentioned, for instance in EP-A-466,484.
Some materials acts as binder and disintegrant. It is also mentioned therein
that the
disintegrant may give supplementary building, anti-redeposition or fabric
softening properties.
The amount of disintegrant is preferably 1 to 5%. It is proposed in EP-A-
466,484 that the tablet
may have a heterogeneous structure comprising a plurality of discrete regions,
for example
layers, inserts or coatings.
Tablet Manufacture - Detergent tablets of the present invention can be
prepared simply
by mixing the solid ingredients together and compressing the mixture in a
conventional tablet
press as used, for example, in the pharmaceutical industry. Preferably the
principal ingredients, in
particular gelling surfactants, are used in particulate form. Any liquid
ingredients, for example
surfactant or suds suppressor, can be incorporated in a conventional manner
into the solid
particulate ingredients.
The ingredients such as builder and surfactant can be spray-dried in a
conventional
manner and then compacted at a suitable pressure. Preferably, the tablets
according to the
invention are compressed using a force of less than 100000N, more preferably
of less than
50000N, even more preferably of less than 5000N and most preferably of less
than 3000 N.
Indeed, the most preferred embodiment is a tablet compressed using a force of
less than 2500N.
The particulate material used for making the tablet of this invention can be
made by any
particulation or granulation process. An example of such a process is spray
drying (in a co-
current or counter current spray drying tower) which typically gives low bulk
densities 600g/1 or
lower. Particulate materials of higher density can be prepared by granulation
and densification in
a high shear batch mixer/granulator or by a continuous granulation and
densification process (e.g.
29
CA 02380328 2005-08-19
using LodigeTM CB and/or Lodige KM mixers). Other suitable processes include
fluid bed
processes, compaction processes (e.g. roll compaction), extrusion, as well as
any particulate
material made by any chemical process like flocculation, crystallisation
sentering, etc. Individual
particles can also be any other particle, granule, sphere or grain.
The components of the particulate material may be mixed together by any
conventional
means. Batch is suitable in, for example, a concrete mixer, Nauta mixer,
ribbon mixer or any
other. Alternatively the mixing process may be carried out continuously by
metering each
component by weight on to a moving belt, and blending them in one or more
drum(s) or mixer(s).
Non-gelling binder can be sprayed on to the mix of some, or all of, the
components of the
particulate material. Other liquid ingredients may also be sprayed on to the
mix of components
either separately or premixed. For example perfume and slurries of optical
brighteners may be
sprayed. A finely divided flow aid (dusting agent such as zeolites,
carbonates, silicas) can be
added to the particulate material after spraying the binder, preferably
towards the end of the
process, to make the mix less sticky.
The tablets may be manufactured by using any compacting process, such as
tabletting,
briquetting, or extrusion, preferably tabletting. Suitable equipment includes
a standard single
stroke or a rotary press (such as Courtoy , Korch , Manesty , or Bonals~
Tm Tm Tm
). The tablets
prepared according to this invention preferably have a diameter of between
20mm and 60nun,
preferably of at least 35 and up to 55 mm, and a weight between 15 g and 100
g. The ratio of
height to diameter (or width) of the tablets is preferably greater than 1:3,
more preferably greater
than 1:2. The compaction pressure used for preparing these tablets need not
exceed 100000
kN/m2, preferably not exceed 30000 kN/m2, more preferably not exceed 5000
kN/m2, even more
preferably not exceed 3000kN/rn2 and most preferably not exceed l000kN/m2. In
a preferred
embodiment according to the invention, the tablet has a density of at least
0.9 g/cc, more
preferably of at least 1.0 g/cc, and preferably of less than 2.0 g/cc, more
preferably of less than
1.5 g/cc, even more preferably of less than 1.25 g/cc and most preferably of
less than 1.1 g/cc.
Multi-layer tablets can be made by known techniques.
Coatine - Solidity of the tablet according to the invention may be further
improved by
making a coated tablet, the coating covering a non-coated tablet according to
the invention,
thereby further improving the mechanical characteristics of the tablet while
maintaining or
further improving dispersion.
In one embodiment of the present invention, the tablets may then be coated so
that the
tablet does not absorb moisture, or absorbs moisture at only a very slow rate.
The coating is also
CA 02380328 2002-01-23
WO 01/10993 PCT/US00/21570
strong so that moderate mechanical shocks to which the tablets are subjected
during handling,
packing and shipping result in no more than very low levels of breakage or
attrition. Finally the
coating is preferably brittle so that the tablet breaks up when subjected to
stronger mechanical
shock. Furthermore it is advantageous if the coating material is dispersed
under alkaline
conditions, or is readily emulsified by surfactants. This contributes to
avoiding the problem of
visible residue in the window of a front-loading washing machine during the
wash cycle, and also
avoids deposition of particles or lumps of coating material on the laundry
load.
Water solubility is measured following the test protocol of ASTM E1148-87
entitled,
"Standard Test Method for Measurements of Aqueous Solubility".
Suitable coating materials are dicarboxylic acids. Particularly suitable
dicarboxylic acids
are selected from the group consisting of oxalic acid, malonic acid, succinic
acid, glutaric acid,
adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid,
undecanedioic acid,
dodecanedioic acid, tridecanedioic acid and mixtures thereof. The coating
material has a melting
point preferably of from 40 C to 200 C.
The coating can be applied in a number of ways. Two preferred coating methods
are a)
coating with a molten material and b) coating with a solution of the material.
In a), the coating material is applied at a temperature above its melting
point, and
solidifies on the tablet. In b), the coating is applied as a solution, the
solvent being dried to leave
a coherent coating. The substantially insoluble material can be applied to the
tablet by, for
example, spraying or dipping. Normally when the molten material is sprayed on
to the tablet, it
will rapidly solidify to form a coherent coating. When tablets are dipped into
the molten material
and then removed, the rapid cooling again causes rapid solidification of the
coating material.
Clearly substantially insoluble materials having a melting point below 40 C
are not sufficiently
solid at ambient temperatures and it has been found that materials having a
melting point above
about 200 C are not practicable to use. Preferably, the materials melt in the
range from 60 C to
160 C, more preferably from 70 C to 120 C.
By "melting point" is meant the temperature at which the material when heated
slowly in,
for example, a capillary tube becomes a clear liquid.
A coating of any desired thickness can be applied according to the present
invention. For
most purposes, the coating forms from 1% to 10%, preferably from 1.5% to 5%,
of the tablet
weight.
The tablet coatings are preferably very hard and provide extra strength to the
tablet.
In a preferred embodiment of the present invention the fracture of the coating
in the wash
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WO 01/10993 PCT/US00/21570
is improved by adding a disintegrant in the coating. This disintegrant will
swell once in contact
with water and break the coating in small pieces. This will improve the
dispersion of the coating
in the wash solution. The disintegrant is suspended in the coating melt at a
level of up to 30%,
preferably between 5% and 20%, most preferably between 5 and 10% by weight.
Possible
disintegrants are described in Handbook of Pharmaceutical Excipients (1986).
Examples of
suitable disintegrants include starch: natural, modified or pregelatinized
starch, sodium starch
gluconate; gum: agar gum, guar gum, locust bean gum, karaya gum, pectin gum,
tragacanth gum;
croscarmylose Sodium, crospovidone, cellulose, carboxymethyl cellulose,
algenic acid and its
salts including sodium alginate, silicone dioxide, clay, polyvinylpyrrolidone,
soy polysacharides,
ion exchange resins and mixtures thereof.
Tensile StrenQth - Depending on the composition of the starting material, and
the shape of the
tablets, the used compacting force may be adjusted to not affect the tensile
strength, and the
disintegration time in the washing machine. This process may be used to
prepare homogenous or
layered tablets of any size or shape.
For a cylindrical tablet, the tensile strength corresponds to the diametrical
fracture stress
(DFS) which is a way to express the strength of a tablet, and is determined by
the following
equation :
= 2F
71 Dt
Where F is the maximum force (Newton) to cause tensile failure (fracture)
measured by a
VK 200 tablet hardness tester supplied by Van Kell industries, Inc. D is the
diameter of the
tablet, and t the thickness of the tablet.
(Method Pharmaceutical Dosage Forms : Tablets Volume 2 Page 213 to 217). A
diametral fracture stress of at least 25 kPa is preferred.
This applies similarly to non cylindrical tablets, to define the tensile
strength, whereby
the cross section normal to the height of the tablet is non round, and whereby
the force is applied
along a direction perpendicular to the direction of the height of the tablet
and normal to the side
of the tablet, the side being perpendicular to the non round cross section.
OPTIONAL CONVENTIONAL DETERGENT ADJUNCT INGREDIENTS
In addition to the components of the compositions of the present invention
hereinabove
described, the detergent compositions herein can, and preferably will, contain
various other
optional components.
32
CA 02380328 2005-08-19
(a) Inorganic Detergent Builders - The detergent compositions herein may also
optionally
contain one or more types of inorganic detergent builders beyond those listed
hereinbefore that
also function as alkalinity sources. Such optional inorganic builders can
include, for example,
aluminosilicates such as zeolites. Aluminosilicate zeolites, and their use as
detergent builders are
more fully discussed in Corkill et al., U.S. Patent No. 4,605,509; Issued
August 12, 1986.
Also crystalline layered silicates, such as those discussed in this `509 U.S.
patent, are also
suitable for use in the detergent compositions herein. If utilized, optional
inorganic detergent
builders can comprise from about 2% to 15% by weight of the compositions
herein.
(b) En , es - Enzymes can be included in the formulations herein for a wide
variety of fabric
laundering purposes, including removal of protein-based, carbohydrate-based,
or triglyceride-
based stains; for the prevention of refugee dye transfer; and for fabric
restoration. It is believed
that the addition of the special hydrotropes described above will enhance the
performance of
enzymes in a detergent composition. This is because as the hydrotropes
increase the rate of
dissolution of the detergent composition, the rate at which enzymes come into
contact with water
and are activated will also increase and the corresponding detersive benefits
provided by
activated enzymes will also increase. This behavior is seen in both aqueous
and non-aqueous
detergent compositions.
The enzymes to be incorporated include proteases, amylases, lipases,
mannanase, cellulases,
and peroxidases, as well as mixtures thereof. Other types of enzymes may also
be included. They
may be of any suitable origin, such as vegetable, animal, bacterial, fungal
and yeast origin. However,
their choice is governed by several factors such as pH-activity and/or
stability optima, thermostability,
stability versus active detergents, builders and so on. In this respect
bacterial or fungal enzymes are
preferred, such as bacterial amylases and proteases, and fungal cellulases.
Enzymes are normally incorporated at levels sufficient to provide up to about
5 mg by weight,
more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the
composition. Stated
otherwise, the compositions herein will typically comprise from about 0.001%
to about 5%,
preferably 0.01%-1.0% by 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.
Suitable examples of proteases are the subtilisins which are obtained from
particular strains
of Bacillus subtilis and Bacillus licheni. forms. Another suitable protease is
obtained from a strain of
Bacillus, having maximum activity throughout the pH range of 8-12, developed
and sold by Novo
33
CA 02380328 2005-08-19
Industries A/S under the registered trade mark ESPERASE . The preparation of
this enzyme and
analogous enzymes is described in British Patent Specification No. 1,243,784
of Novo Industries A/S.
Proteolytic enzymes suitable for removing protein-based stains that are
commercially available
include those sold under the trademarks ALCALASE and SAVINASE by Novo
Industries A/S
(Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The
Netherlands). Other
proteases include Protease A (see European Patent Application 130,756,
published January 9, 1985)
and Protease B (see European Patent Application 251446 published January 7,
1988, and
European Patent Application 130,756, Bott et al, published January 9, 1985).
Amylases include, for example, amylases described in British Patent
Specification No.
1,296,839 (Novo Industries A/S), RA.PIDASE , International Bio-Synthetics,
Inc. and
TERMAMYL , Novo Industries A/S.
Mannanases include the following three mannans-degrading enzymes : EC 3.2.1.25
mannosidase, EC 3.2.1.78 : Endo-1,4-p-mannosidase, referred therein after as
"mannanase" and EC
3.2.1.100: 1,4-(3-mannobiosidase (IUPAC Classification- Enzyme nomenclature,
1992 ISBN 0-12-
227165-3 Academic Press).
More preferably, the detergent compositions of the present invention comprise
a(3-1,4-
Mannosidase (E.C. 3.2.1.78) referred to as Mannanase. The terrn "mannanase" or
"galactomannanase"
denotes a mannanase enzyme defined according to the art as officially being
named mannan endo-l,4-
beta-mannosidase and having the alternative names beta-mannanase and endo-1,4-
mannanase and
catalysing the reaction: random hydrolysis of 1,4-beta-D- mannosidic linkages
in mannans,
galactomannans, glucomannans, and galactoglucomannans. In particular,
Mannanases (EC 3.2.1.78)
constitute a group of polysaccharases which degrade mannans and denote enzymes
which are capable
of cleaving polyose chains containing mannose units, i.e. are capable of
cleaving glycosidic bonds in
mannans, glucomannans, galactomannans and galactogluco-mannans. Mannans are
polysaccharides
having a backbone composed of (3-1,4- linked mannose; glucomannans are
polysaccharides having a
backbone or more or less regularly alternating (3-1,4 linked mannose and
glucose; galactomannans
and galactoglucomannans are mannans and glucomannans with a-1,6 linked
galactose sidebranches.
These compounds may be acetylated.
The cellulase enzymes used in the instant detergent composition are preferably
incorporated at
levels sufficient to provide up to about 5 mg by weight, more preferably about
0.01 mg to about 3 mg, of
active enzyme per gram of the composition. Stated otherwise, the compositions
herein preferably
comprise from about 0.001% to about 5%, preferably 0.01%-1.0% by weight of a
commercial enzyme
34
CA 02380328 2005-08-19
preparation. The cellulase usable in the present invention includes 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 No. 4,435,307, Barbesgoard et a], issued March 6, 1984, which discloses
fungal cellulase produced
from Humicola insolens and Humicola strain DSM 1800 or a cellulase 212-
producing microorganism
belonging to the genus Aeromonas, and cellulase extracted from the
hepatopancreas of a marine mollusk
(Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-
2.075.028; GB-A-
2.095.275 and DE-OS-2.247.832. In addition, cellulase especially suitable for
use herein are disclosed in
WO 92-13057 (The Procter & Gamble Company). Most preferably, the cellulases
used in the instant
detergent compositions are purchased connnercially from NOVO Industries A/S
under the product names
CAREZYME and CELLUZYME .
Suitable lipase enzymes for detergent usage include those produced by
microorganisms
of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as
disclosed in British
Patent 1,372,034. See also lipases in Japanese Patent Application 53,20487,
laid open to public
inspection on February 24, 1978. This lipase is available from Amano
Pharmaceutical Co. Ltd.,
Nagoya, Japan, under the trade mark Lipase P AMANO , hereinafter referred to
as "Amano-P."
Other conunercial lipases include AMANO-CES , lipases from Chromobacter
viscosum, e.g.
Chromobacter viscosum var. lipolyticuin NRRLB 3673, convnercially available
from Toyo Jozo
Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S.
Biochemical Corp.,
U.S.A. and Disoynth Co., The Netherlands, and lipases from Pseudomonas
gladioli. The
LIPOLASE enzyme derived from Humicola lanuginosa and commercially available
from Novo
Industries A/S(see also EPO 341,947) is a preferred lipase for use herein.
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. Peroxidase-containing detergent compositions are disclosed, for
example, in PCT
International Application WO 89/099813, published October 19, 1989, by O.
Kirk, assigned to
Novo Industries A/S.
A wide range of enzyme materials and means for their incorporation into
synthetic
detergent compositions are also disclosed in U.S. Patent No. 3,553,139, issued
January 5, 1971 to
McCarty et al. Enzymes are further disclosed in U.S. Patent No. 4,101,457,
Place et al, issued
July 18, 1978, and in U.S. Patent No. 4,507,219, Hughes, issued March 26,
1985. Enzyme
CA 02380328 2005-08-19
materials useful for liquid detergent formulations, and their incorporation
into such formulations,
are disclosed in U.S. Patent No. 4,261,868, Hora et al, issued April 14, 1981.
Enzymes for use in
detergents can be stabilized by various techniques. Enzyme stabilization
techniques are disclosed
and exemplified in U.S. Patent No. 3,600,319, issued August 17, 1971 to Gedge,
et al, and
European Patent Application Publication No. 0 199 405, published
October 29, 1986, Venegas. Enzyme stabilization systems are also described,
for example, in
U.S. Patent No. 3,519,570. Enzymes added to the compositions herein in the
form of
conventional enzyme prills are especially preferred for use herein. Such
prills will generally
range in size from about 100 to 1,000 microns, more preferably from about 200
to 800 microns
and will be suspended throughout the liquid phase of the composition. Prills
in the compositions
of the present invention have been found, in comparison with other enzyme
forms, to exhibit
especially desirable enzyme stability in tenns of retention of enzymatic
activity over time. Thus,
compositions which utilize enzyme prills need not contain conventional enzyme
stabilizing such
as must frequently be used when enzymes are incorporated into aqueous liquid
detergents.
(c) ChelatingAeents - The detergent compositions herein may also optionally
contain a
chelating agent which serves to chelate metal ions, e.g., iron and/or
manganese, within the
detergent compositions herein. Such chelating agents thus serve to form
complexes with metal
impurities in the composition which would otherwise tend to deactivate
composition components
such as the peroxygen bleaching agent. Useful chelating agents can include
amino carboxylates,
phosphonates, amino phosphonates, polyfunctionally-substituted aromatic
chelating agents and
mixtures thereof.
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetraacetates, N-hydroxyethyl-ethylenediaminetriacetates,
nitrilotriacetates,
ethylene-diamine tetrapropionates, triethylenetetraaminehexacetates,
diethylenetriaminepentaacetates, ethylenediaminedisuccinates and ethanol
diglycines. The alkali
metal salts of these materials are preferred.
Amino phosphonates are also suitable for use as chelating agents in the
compositions of
this invention when at least low levels of total phosphorus are permitted in
detergent
TM
compositions, and include ethylenediaminetetrakis (methylene-phosphonates) as
DEQUEST.
Preferably, these amino phosphonates do not contain alkyl or alkenyl groups
with more than
about 6 carbon atoms.
Preferred chelating agents include hydroxy-ethyldiphosphonic acid (HEDP),
diethylene
triamine penta acetic acid (DTPA), ethylenediamine disuccinic acid (EDDS) and
dipicolinic acid
36
CA 02380328 2005-08-19
(DPA) and salts thereof. The chelating agent may, of course, also act as a
detergent builder during
use of the compositions herein for fabric laundering/bleaching. The chelating
agent, if employed,
can comprise from about 0.1% to 4% by weight of the compositions herein. More
preferably, the
chelating agent will comprise from about 0.2% to 2% by weight of the detergent
compositions
herein.
(d) Suds Suppressors - Suds suppression can be of particular importance in the
present
invention because of the high concentration of the detergent composition. The
use of suds
suppressors in "high concentration cleaning process" is described in greater
detail U.S. 4,489,455
and 4,489,574.
A wide variety of materials may be used as suds suppressors, and suds
suppressors are well
known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia
of Chemical
Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc.,
1979). One
category of suds suppressor of particular interest encompasses monocarboxylic
fatty acid and
soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to
Wayne St. John.
The monocarboxylic fatty acids and salts thereof used as suds suppressor
typically have
hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon
atoms. Suitable
salts include the alkali metal salts such as sodium, potassium, and lithium
salts, and ammonium
and alkanolammonium salts.
The detergent compositions herein may also contain non-surfactant suds
suppressors.
These include, for example: high molecular weight hydrocarbons, N-alkylated
amino triazines,
monostearyl phosphates, silicone suds suppressors, secondary alcohols (e.g., 2-
alkyl alkanols)
and mixtures of such alcohols with silicone oils. Hydrocarbon suds suppressors
are described, for
example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al.
Silicone suds
suppressors are well known in the art and are, for example, disclosed in U.S.
Patent 4,265,779,
issued May 5, 1981 to Gandolfo et al and European Patent Application 354016,
published February 7, 1990, by Starch, M. S. Mixtures of alcohols and silicone
oils are
described in U.S. 4,798,679, 4,075,118 and EP 150,872
Additional examples of all of the aforementioned suds suppressors may be found
in the
published patent application of Pramod K. Reddy, entitled "Hydrophilic Index
for Aqueous,
Liquid Laundry Detergent Compositions containing LAS", CA 2,347,695.
37
CA 02380328 2005-08-19
The preferred particulate foam control agent used herein contains a silicone
antifoam
compound, an organic material and a carrier material onto which the silicone
antifoam compound
and the organic material are deposited. The carrier material is preferably a
native starch or
zeolite. The silicone antifoam compound is selected from the group consisting
of
polydiorganosiloxane, solid silica and mixtures thereof. Preferably, the
organic material is
selected from:
(a) at least one fatty acid having a carbon chain containing from 12 to 20
carbon atoms,
said organic material having a melting point in the range 45 C to 80 C and
being
insoluble in water;
(b) at least one fatty alcohol, having a carbon chain containing from 12 to 20
carbon
atoms, said organic material having a melting point in the range 45 C to 80 C
and
being insoluble in water;
(c) a mixture of at least one fatty acid and one fatty alcohol, each having a
carbon chain
containing from 12 to 20 carbon atoms, said organic material having a melting
point
in the range 45 C to 80 C and being insoluble in water;
(d) an organic material having a melting point in the range 50 C to 85 C and
comprising
a monoester of glycerol and a fatty acid having a carbon chain containing from
12 to
20 carbon atoms; and
(e) a dispersing polymer; and mixtures thereof.
Preferably, the dispersing polymer is selected from the group consisting of
copolymers of acrylic
acid and maleic acid, polyacrylates and mixtures thereof.
Silicone suds suppressors known in the art which can be used are, for example,
disclosed
in U.S. Pat. No. 4,265,779, issued May 5, 1981 to Gandolfo et al and European
Patent
Application 354016, published Feb. 7, 1990, by Starch, M. S. Silicone
defoamers and
suds controlling agents in granular detergent compositions are disclosed in
U.S. Pat. No.
3,933,672, Bartolotta et al, and in U.S. Pat. No. 4,652,392, Baginski et al,
issued Mar. 24, 1987.
An exemplary silicone based suds suppressor for use herein is a suds
suppressing amount of a
particulate foam control agent consisting essentially of:
(a) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to
about 1,500 cs. at
25 C.;
(b) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane
resin
composed of (CH3)3 Si01/2 units of Si02 units in a ratio of from (CH3)3 SiOjn
units of
from about 0.6:1 to about 1.2:1; and
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CA 02380328 2002-01-23
WO 01/10993 PCT/US00/21570
(c) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid
silica gel.
Additional suds suppressor suitable for use in the present invention are
described in
greater detail in U.S. Pat. No. 5,762,647, issued June 9, 1998, to Brown et
al.
(e) Dye Transfer Inhibiting Agents and Other Fabric Care Components - The
compositions of
the present invention may also include one or more materials effective for
inhibiting the transfer
of dyes from one fabric to another during the cleaning process. These agents
may be included
either in the nonaqueous surfactant-containing liquid phase or in the solid
particulate material.
Generally, such dye transfer inhibiting agents include polyvinyl pyrrolidone
polymers,
polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-
vinylimidazole,
manganese phthalocyanine, peroxidases, and mixtures thereof. These agents
typically comprise
from about 0.01% to about 10% by weight of the composition, preferably from
about 0.01% to
about 5%, and more preferably from about 0.05% to about 2%.
More specifically, the polyamine N-oxide polymers preferred for use herein
contain units
having the following structural formula: R-Ax-P; wherein P is a polymerizable
unit to which an
N-O group can be attached or the N-O group can form part of the polymerizable
unit or the N-O
group can be attached to both units; A is one of the following structures: -
NC(O)-, -C(O)O-, -S-, -
0-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics,
heterocyclic or alicyclic
groups or any combination thereof to which the nitrogen of the N-O group can
be attached or the
N-O group is part of these groups. Preferred polyamine N-oxides are those
wherein R is a
heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine,
piperidine and derivatives
thereof.
The N-O group can be represented by the following general structures:
0 0
1 1
(R,)x- i -~2)y; =N-(Rj)x
(R3)Z
wherein Rl, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups
or combinations
thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be
attached or form part of
any of the aforementioned groups. The amine oxide unit of the polyamine N-
oxides has a pKa
<10, preferably pKa <7, more preferred pKa <6.
Any polymer backbone can be used as long as the amine oxide polymer formed is
water-
soluble and has dye transfer inhibiting properties. Examples of suitable
polymeric backbones are
polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides,
polyacrylates and
39
CA 02380328 2005-08-19
mixtures thereof. These polymers include random or block copolymers where one
monomer type is
an amine N-oxide and the other monomer type is an N-oxide. The aniine N-oxide
polymers typically
have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However,
the number of amine
oxide groups present in the polyamine oxide polymer can be varied by
appropriate copolymerization
or by an appropriate degree of N-oxidation. The polyamine oxides can be
obtained in almost any
degree of polymerization. Typically, the average molecular weight is within
the range of 500
to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to
100,000.
The most preferred polyamine N-oxide useful in the detergent compositions
herein is
poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about
50,000 and an amine
"PVNO".
to amine N-oxide ratio of about 1:4. This preferred class of materials can be
referred to as
Further suitable dye transfer inhibitors can be found in U.S. Patent No.
5,466,802, issued
November 14, 1995 to Panandiker et al.
In addition to the dye transfer inhibitors, the present invention further
comprises additional
agents to provide fabric care benefits. As described above, these additional
agents may be necessary
because the high concentrations of detergent concentration in the aqueous
laundering solutions used
in the present invention may damage the garments and fabrics contacted by the
aqueous laundering
solutions.
Thus the present invention may also include materials which could be added to
laundry
products that would associate themselves with the fibers of the fabrics and
textiles laundered using
such products and thereby reduce or minimize the tendency of the laundered
fabric/textiles to
deteriorate in appearance. Any such detergent product additive material or
fabric care agent should,
of course, be able to benefit fabric appearance and integrity without unduly
interfering with the
ability of the laundry product to perform its intended function. Such fabric
appearance benefits can
include, for example, improved overall appearance of the laundered fabrics,
reduction of the
formation of pills and fuzz, protection against color fading, improved
abrasion resistance, etc. Such
fabric care agents are generally included in the detergent composition in an
amount of from 0.01%
to 10% by weight of the composition.
One such fabric care agent which specifically acts to prevent dyes from
migrating from the
surface of a garment and into the aqueous laundering solution but also
provides other fabric care
benefits is 30 polyethyleneimine, PEI 600 E20, having the general formula:
CA 02380328 2005-08-19
E B
I 1
[EZNCHZCH2]W [NCH2CH2]x [NCH2CH2)y NE2
wherein B is a continuation by branching of the polyethyleneimine backbone. E
is an
ethyleneoxy unit having the formula: ~I
-(CH2CH2O)mH
wherein m has an average value of about 20. What is meant herein by an average
value of 20 is
that sufficient ethylene oxide or other suitable reagent is reacted with the
polyethyleneiniine
starting material to fully ethoxylate each N-H unit to a degree of 20
ethoxylations. However,
those skilled in the art will realize that some N-H unit hydrogen atoms will
be replaced by less
than 20 ethoxy units and some will be replaced by more than 20 ethoxy units,
therefore, the
average of the number of ethoxylations is 20.
The units which make up the polyalkyleneimine backbones are primary amine
units
having the formula:
HaN-CH2CH2]- and -NH2
which terminate the main backbone and any branching chains, secondary amine
units having the
formula:
H
I
-[N-CH2CH2]-
and which, after modification, have their hydrogen atom substituted by an
average of 20
ethyleneoxy units, and tertiary amine units having the formula:
B
1
-[N- CH2CH2]-
which are the branching points of the main and secondary backbone chains, B
representing a
continuation of the chain structure by branching. The tertiary units have no
replaceable hydrogen
atom and are therefore not modified by substitution with ethyleneoxy units.
During the formation
of the polyamine backbones cyclization may occur, therefore, an amount of
cyclic polyamine can
be present in the parent polyalkyleneimine backbone mixture. Each primary and
secondary amine
unit of the cyclic alkyleneimines undergoes modification by the addition of
alkyleneoxy units in
the same manner as linear and branched polyalkyleneimines.
41
CA 02380328 2005-08-19
The indices w, x, and y have values such that the average molecular weight of
the
polyethyleneimine backbone prior to modification is about 600 daltons. In
addition, those skilled
in the art will recognize that each branch chain must terminate in a primary
amine unit, therefore
the value of the index w is y + I in the case where no cyclic amine backbones
are present. The
average molecular weight for each ethylene backbone unit, -NCH2CH2-, is
approximately 43
daltons.
The polyamines of the present invention can be prepared, for example, by
polymerizing
ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium
bisulfite, sulfuric acid,
hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for
preparing these
polyamine backbones are disclosed in U.S. Patent 2,182,306, Ulrich et al.,
issued December 5,
1939; U.S. Patent 3,033,746, Mayle et al., issued May 8,1962; U.S. Patent
2,208,095, Esselmann
et al., issued July 16,1940; U.S. Patent 2,806,839, Crowther, issued September
17,1957; and U.S.
Patent 2,553,696, Wilson, issued May 21,1951.
Other suitable fabric care agents for use in the present detergent
compositions include
dye maintenance polymers. One example of such a polymer is the Adduct of
Imidazole-
epichlorohydrin:
NOH
(Idealized Structure)
This has a ratio of imidazole:epichlorohydrin of 1.36:1. Further dye
maintenance polymers as
well as the Dye Maintenance Parameter Test are described in the published
application of Rajan K. Panandiker et al., entitled "Laundry Detergent
Compositions with a
Cationically Charged Dye Maintenance Polymer," CA 2,346,347. As described
above,
these dye maintenance polymers provide overall fabric care benefits in
addition to color care
protection.
(f) Thickening, Viscosity Control and/or Dispersine Agents - The detergent
compositions herein
may also optionally contain a polymeric material which serves to enhance the
ability of the
composition to maintain its solid particulate components in suspension. Such
materials may thus
act as thickeners, viscosity control agents and/or dispersing agents. Such
materials are frequently
polymeric polycarboxylates but can include other polymeric materials such as
polyvinylpyrrolidone (PVP) or polyamide resins.
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CA 02380328 2002-01-23
WO 01/10993 PCT/US00/21570
Polymeric polycarboxylate materials can be prepared by polymerizing or
copolymerizing
suitable unsaturated monomers, preferably in their acid form. Unsaturated
monomeric acids that
can be polymerized to form suitable polymeric polycarboxylates include acrylic
acid, maleic acid
(or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic
acid, citraconic acid
and methylenemalonic acid. The presence in the polymeric polycarboxylates
herein of
monomeric segments, containing no carboxylate radicals such as vinylmethyl
ether, styrene,
ethylene, etc. is suitable provided that such segments do not constitute more
than about 40% by
weight of the polymer.
Particularly suitable polymeric polycarboxylates can be derived from acrylic
acid. Such
acrylic acid-based polymers which are useful herein are the water-soluble
salts of polymerized
acrylic acid. The average molecular weight of such polymers in the acid form
preferably ranges
from about 2,000 to 100,000, more preferably from about 2,000 to 10,000, even
more preferably
from about 4,000 to 7,000, and most preferably from about 4,000 to 5,000.
Water-soluble salts of
such acrylic acid polymers can include, for example, the alkali metal, salts.
Soluble polymers of
this type are known materials. Use of polyacrylates of this type in detergent
compositions has
been disclosed, for example, Diehl, U.S. Patent 3,308,067, issued March 7,
1967. Such materials
may also perform a builder function.
Other suitable polymeric materials suitable for use as thickening, viscosity
control and/or
dispersing agents include polymers of: castor oil derivatives; polyurethane
derivatives, and
polyethylene glycol.
If utilized, the optional thickening, viscosity control and/or dispersing
agents should be
present in the compositions herein to the extent of from about 0.1 % to 4% by
weight. More
preferably, such materials can comprise from about 0.1% to 2% by weight of the
detergents
compositions herein.
(g) Clay Soil Removal/Anti-redeposition Agents - The compositions of the
present invention
can also optionally contain water-soluble ethoxylated amines having clay soil
removal and anti-
redeposition properties. If used, soil materials can contain from about 0.01%
to about 5% by
weight of the compositions herein.
The most preferred soil release and anti-redeposition agent is ethoxylated
tetraethylenepentamine. Exemplary ethoxylated amines are further described in
U.S. Patent
4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay
soil removal-anti-
redeposition agents are the cationic compounds disclosed in European Patent
Application
111,965, Oh and Gosselink, published June 27, 1984. Other clay soil
removal/anti-redeposition
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WO 01/10993 PCTIUSOO/21570
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. Preferred
clay-removing
compounds include ethoxylated quaternized amines. Preferred ethoxylated
quatemized amine
materials are selected from the group consisting of compounds having the
general formula:
iH3
CH3
EOx-N+ I +
I N - EOx
EOx I
EOx
wherein each x is independently less than about 16, preferably from about 6 to
about 13, more
preferably from about 6 to about 8, or wherein each x is independently greater
than about 35.
Materials suitable for use in the present invention, such as those defined
above, can be purchased
from the BASF Corporation in Germany, and the Witco Chemical Company.
It has been determined that the degree of ethoxylation is important to the
viscosity of the
final detergent compositions described herein. Specifically, for the general
structure:
iH3
CH3
EOx-N+ I +
I N - EOx
EOx I
EOx
when x is less than about 13 the ethoxylated quaternized amine clay materials
can be added to the
present liquid heavy duty detergent compositions as liquids without causing
undesired
thickening at low temperatures. Likewise, when the degree of ethoxylation for
the same structure
is greater than about 35, that is when x is greater than about 35, these
higher ethoxalated
materials can be added to the formulations as stable solid without melting at
high temperatures
and without causing low temperature product thickening.
Of course, it will be appreciated that other, conventional optical brightener
types of
compounds can optionally be used in the present compositions to provide
conventional fabric
"brightness" benefits, rather than a true dye transfer inhibiting effect. Such
usage is conventional
and well-known to detergent formulations.
Other clay soil removal andlor anti-redeposition agents known in the art can
also be utilized
in the compositions herein. Another type of preferred anti-redeposition agent
includes the
carboxy methyl cellulose (CMC) materials. These materials are well known in
the art.
44
CA 02380328 2005-08-19
(h) Liquid Bleach Activators - The detergent compositions herein may also
optionally contain
bleach activators which are liquid in form at room temperature and which can
be added as liquids to
the liquid phase of the detergent compositions herein. One such liquid bleach
activator is glycerol
triacetate, which serves as a solvent in the composition during storage but
when released into the
wash water solution is peroxidized and functions as a bleach activator. Other
examples of bleach
activators include acetyl triethyl citrate (ATC) and nonanoyl valerolactam.
Liquid bleach activators
can be dissolved in the liquid phase of the compositions herein.
(i) Briteners, Dyes and/or Perfumes - The detergent compositions herein may
also optionally
contain conventional brighteners, bleach catalysts, dyes and/or perfume
materials. Such brighteners,
silicone oils, bleach catalysts, dyes and perfumes must, of course, be
compatible and non-reactive
with the other composition components in the aqueous or non-aqueous liquid
environment. If
present, brighteners, dyes and/or perfumes will typically comprise from about
0.0001% to 2% by
weight of the compositions herein.
(j) Structure Elasticizing Agents - The liquid detergent compositions herein
can also contain
from about 0.1 % to 5%, preferably from about 0.1 % to 2% by weight of a
finely divided, solid
particulate material which can include silica, e.g., fumed silica, titanium
dioxide, insoluble
carbonates, finely divided carbon, SD-3 bentone, clays, or combinations of
these materials. Clays are
well known to those skilled in the art and are commercially available from
companies such as
Rheox. Fine particulate material of this type functions as a structure
elasticizing agent in the
products of this invention. Such material has an average particle size ranging
from about 7 to
40 nanometers, more preferably from about 7 to 15 nanometers. Such material
also has a specific
surface area which ranges from about 40 to 400m2/g.
The finely divided elasticizing agent material can improve the shipping
stability of the liquid
detergent products herein by increasing the elasticity of the surfactant-
structured liquid phase
without increasing product viscosity. This penmits such products to withstand
high frequency
vibration which may be encountered during shipping without undergoing
undesirable structure
breakdown which could lead to sedimentation in the product.
In the case of titanium dioxide, the use of this material also imparts
whiteness to the
suspension of particulate material within the detergent compositions herein.
This effect improves the
overall appearance of the product.
CA 02380328 2005-08-19
(k) Microspheres - Microspheres may be used in the present invention. Suitable
microspheres may
be made of one or more water-insoluble materials selected from the group
consisting of: polymers;
silicaceous materials; ceramics and mixtures thereof. The microspheres
generally have a median particle
size of from 10 microns to 150 microns and an average density of from 0.1g/ml
to 1.8g/ml. For further
discussion of microspheres, see "Microencapsulation" in Kirk-Othmer
Encyclopedia of Chemical
Technology, Third Edition, Volume 16, pages 628-651 (John Wiley & Sons, Inc.,
1979).
Polymer microspheres of the present invention are preferably made of a water-
insoluble material
selected from the group consisting of: thermoplastics; acylonitrile;
methacrylonitrile; polyacrylonitrile;
polymethacrylonitrile and mixtures thereof. Silicaceous microspheres of the
present invention are
preferably made of one or more silicaceous materials selected from the group
consisting of glass.
Borosilicate glass is particularly preferred.
Commercially available microspheres are available from Akzo-Nobel of Sweden
under the
trademark EXPANCEL ; PQ Corp. under the trade marks PM 6545, PM 6550, PM 7220,
PM 7228,
EXTENDOSPHERES , LUXSIL , Q-CEL , SPHERICEL ; and Malinckrodt under the
trademark
ALBUMEX .
Suitable examples of microspheres and further disclosure on microsphere-
containing liquid
detergents may be found in U.S. Patent No. 6,503,876 of Broeckx et al.,
entitled "Stable Non-aqueous
Liquid Laundry Detergents Comprising Low Density Particles".
In addition to the types of microspheres discussed above, suitable
microspheres for use in the
present invention may also be made from wash-water soluble biomaterials (such
as starches and proteins).
In addition, the microspheres used in the present invention may be used as the
core of a particle
which is formed by substantially encapsulating the core with detergent
components. A non-exclusive list
of such components includes organic and inorganic builder material, alkalinity
source material and other
coating components.
(1) Effervescent - In another preferred embodiment of the present invention
the tablets
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WO 01/10993 PCT/US00/21570
further comprises an effervescent.
Effervescency as defined herein means the evolution of bubbles of gas from a
liquid, as
the result of a chemical reaction between a soluble acid source and an alkali
metal carbonate, to
produce carbon dioxide gas,
i.e. C6H807 + 3NaHCO3 Na3C6H5O7 + 3CO2 + 3H20
Further examples of acid and carbonate sources and other effervescent systems
may be
found in :(Pharmaceutical Dosage Forms : Tablets Volume 1 Page 287 to 291).
An effervescent may be added to the tablet mix in addition to the detergent
ingredients.
The addition of this effervescent to the detergent tablet improves the
disintegration time of the
tablet. The amount will preferably be between 5 and 20 % and most preferably
between 10 and
20% by weight of the tablet. Preferably the effervescent should be added as an
agglomerate of
the different particles or as a compact, and not as separated particles.
Due to the gas created by the effervescency in the tablet, the tablet can have
a higher
D.F.S. and still have the same disintegration time as a tablet without
effervescency. When the
D.F.S. of the tablet with effervescency is kept the same as a tablet without,
the disintegration of
the tablet with effervescency will be faster.
Further dispersion aid could be provided by using compounds such as sodium
acetate or
urea. A list of suitable dispersion aid may also be found in Pharmaceutical
Dosage Forms:
Tablets, Volume 1, Second edition, Edited by H.A. Lieberman et all, ISBN 0-
8247-8044-2.
The effervescent system may comprise and acid and a base, such as citric acid
and
sodium bicarbonate, and/or the effervescent system may comprise an enzyme,
such as catalase
and/or peroxidase and a source of peroxide, such as hydrogen peroxide.
(m) Binders - Non gelling binders can be integrated to the particles forming
the tablet in order
to further facilitate dispersion.
If non gelling binders are used, suitable non-gelling binders include
synthetic organic
polymers such as polyethylene glycols, polyvinylpyrrolidones, polyacrylates
and water-soluble
acrylate copolymers. The handbook of Pharmaceutical Excipients second edition,
has the
following binders classification: Acacia, Alginic Acid, Carbomer,
Carboxymethylcellulose
sodium, Dextrin, Ethylcellulose, Gelatin, Guar gum, Hydrogenated vegetable oil
type I,
Hydroxyethyl cellulose, Hydroxypropyl methylcellulose, Liquid glucose,
Magnesium aluminum
silicate, Maltodextrin, Methylcellulose, polymethacrylates, povidone, sodium
alginate, starch and
zein. Most preferable binders also have an active cleaning function in the
laundry wash such as
cationic polymers, i.e. ethoxylated hexamethylene diamine quaternary
compounds,
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WO 01/10993 PCT/US00/21570
bishexamethylene triamines, or others such as pentaamines, ethoxylated
polyethylene amines,
maleic acrylic polymers.
Non-gelling binder materials are preferably sprayed on and hence have an
appropriate
melting point temperature below 90 C, preferably below 70 C and even more
preferably below
50 C so as not to damage or degrade the other active ingredients in the
matrix. Most preferred
are non-aqueous liquid binders (i.e. not in aqueous solution) which may be
sprayed in molten
form. However, they may also be solid binders incorporated into the matrix by
dry addition but
which have binding properties within the tablet.
Non-gelling binder materials are preferably used in an amount within the range
from 0.1
to 15% of the composition, more preferably below 5% and especially if it is a
non laundry active
material below 2% by weight of the tablet.
It is preferred that gelling binders, such as nonionic surfactants are avoided
in their liquid
or molten form. Nonionic surfactants and other gelling binders are not
excluded from the
compositions, but it is preferred that they be processed into the detergent
tablets as components
of particulate materials, and not as liquids.
(n) Clays - The clay minerals used to provide the softening properties of the
instant
compositions can be described as expandable, three-layer clays, i.e., alumino-
silicates and
magnesium silicates, having an ion exchange capacity of at least 50 meq/100g.
of clay. The term
"expandable" as used to describe clays relates to the ability of the layered
clay structure to be
swollen, or expanded, on contact with water. The three-layer expandable clays
used herein are
those materials classified geologically as smectites.
There are two distinct classes of smectite-type clays; in the first, aluminum
oxide is
present in the silicate crystal lattice; in the second class of smectites,
magnesium oxide is present
in the silicate crystal lattice. The general formulas of these smectites are
AlZ(SiZ05)Z(OH)z and
Mg3(SiZO5) (OH)2 for the aluminum and magnesium oxide type clay, respectively.
It is to be
recognised that the range of the water of hydration in the above formulas can
vary with the
processing to which the clay has been subjected. This is immaterial to the use
of the smectite
clays in the present invention in that the expandable characteristics of the
hydrated clays are
dictated by the silicate lattice structure. Furthermore, atom substitution by
iron and magnesium
can occur within the crystal lattice of the smectites, while metal cations
such as Na+, Ca++, as
well as H+, can be co-present in the water of hydration to provide electrical
neutrality. Except as
noted hereinafter, such cation substitutions are immaterial to the use of the
clays herein since the
desirable physical properties of the clays are not substantially altered
thereby.
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WO 01/10993 PCT/US00/21570
The three-layer, expandable alumino-silicates useful herein are further
characterised by a
dioctahedral crystal lattice, while the expandable three-layer magnesium
silicates have a
trioctahedral crystal lattice.
As noted herein above, the clays employed in the compositions of the instant
invention
contain cationic counterions such as protons, sodium ions, potassium ions,
calcium ion,
magnesium ion, and the like. It is customary to distinguish between clays on
the basis of one
cation predominantly or exclusively absorbed. For example, a sodium clay is
one in which the
absorbed cation is predominantly sodium. Such absorbed cations can become
involved in
exchange reactions with cations present in aqueous solutions. A typical
exchange reaction
involving a smectite-type clay is expressed by the following equation:
smectite clay (Na) + NH40H - smectite clay (NH4) + NaOH.
Since in the foregoing equilibrium reaction, one equivalent weight of ammonium
ion
replaces an equivalent weight of sodium, it is customary to measure cation
exchange capacity
(sometimes termed "base exchange capacity") in terms of milliequivalents per
100 g. of clay
(meq./100 g.). The cation exchange capacity of clays can be measured in
several ways, including
by electrodialysis, by exchange with ammonium ion followed by titration or by
a methylene blue
procedure, all as fully set forth in Grimshaw, "The Chemistry and Physics of
Clays", pp. 264-
265, Interscience (1971). The cation exchange capacity of a clay mineral
relates to such factors
as the expandable properties of the clay, the charge of the clay, which, in
turn, is determined at
least in part by the lattice structure, and the like. The ion exchange
capacity of clays varies
widely in the range from about 2 meq/100 g. for kaolinites to about 150
meq/100 g., and greater,
for certain clays of the montmorillonite variety. Illite clays have an ion
exchange capacity
somewhere in the lower portion of the range, i.e., around 26 meq/100 g. for an
average illite clay.
Illite and kaolinite clays, with their relatively low ion exchange capacities,
are preferably
not used as the clay in the instant compositions. Indeed, such illite and
kaolinite clays constitute
a major component of clay soils and, as noted above, are removed from fabric
surfaces by means
of the instant compositions. However, smectites, such as nontonite, having an
ion exchange
capacity of around 70 meq/100 g., and montmorillonite, which has an ion
exchange capacity
greater than 70 meq/100 g., have been found to be useful in the instant
compositions in that they
are deposited on the fabrics to provide the desired softening benefits.
Accordingly, clay minerals
useful herein can be characterised as expandable, three-layer smectite-type
clays having an ion
exchange capacity of at least about 50 meq/100 g.
While not intending to be limited by theory, it appears that advantageous
softening (and
49
CA 02380328 2005-08-19
potentially dye scavenging, etc.) benefits of the instant compositions are
obtainable and are
ascribable to the physical characteristics and ion exchange properties of the
clays used therein.
That is to say, experiments have shown that non-expandable clays such as the
kaolinites and the
illites, which are both classes of clays having an ion exchange capacities
below 50 meq/100 g., do
not provide the beneficial aspects of the clays employed in the instant
compositions.
The smectite clays used in the compositions herein are all commercially
available. Such
clays include, for example, montmorillonite, volchonskoite, nontronite,
hectorite, saponite,
sauconite, and vermiculite. The clays herein are available under various
trademarks, for
TM TM
example, Thixogel #1 and Gelwhite GP from Georgia Kaolin Co., Elizabeth, New
Jersey;
Volclay BC and Volclay #325, from American Colloid Co., Skokie, Illinois;
Black Hills
Tm
Tm
Bentonite BH450, from International Minerals and Chemicals; and Veegum Pro and
Veegum F,
from R.T. Vanderbilt. It is to be recognised that such smectite-type minerals
obtained under the
foregoing tradenames can comprise mixtures of the various discrete mineral
entities. Such
mixtures of the smectite minerals are suitable for use herein.
While any of the smectite-type clays having a cation exchange capacity of at
least about
50 meq/100 g. are useful herein, certain clays are preferred. For example,
Gelwhite GP is an
extremely white form of smectite clay and is therefore preferred when
formulating white granular
detergent compositions. Volclay BC, which is a smectite-type clay mineral
containing at least
3% of iron (expressed as Fe203) in the crystal lattice, and which has a very
high ion exchange
capacity, is one of the most efficient and effective clays for use in laundry
compositions and is
preferred from the standpoint of product perfonnance.
Appropriate clay minerals for use herein can be selected by virtue of the fact
that
smectites exhibit a true 14A x-ray diffraction pattern. This characteristic
pattern, taken in
combination with exchange capacity measurements performed in the manner noted
above,
provides a basis for selecting particular smectite-type minerals for use in
the granular detergent
compositions disclosed herein.
The clay is preferably mainly in the form of granules, with at least 50% (and
preferably
at least 75% or at least 90%) being in the form of granules having a size of
at least 100mm up to
1800nun, preferably up to 1180mm, preferably 150-850mm. Preferably the amount
of clay in the
granules is at least 50%, usually at least 70% or 90%, of the weight of the
granules.
(o) Flocculants - Most clay flocculating polymers are fairly long chained
polyrners and co-
polymers derived from such monomers as ethylene oxide, acrylamide, acrylic
acid,
dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrrolidone and
ethylene imine. Gums,
CA 02380328 2002-01-23
WO 01/10993 PCT/US00/21570
like guar gum, are suitable as well.
Preferred are polymers of ethylene oxide, acrylamide or acrylic acid. These
polymers
dramatically enhance the deposition of a fabric softening clay if their
molecular weights are in
the range of from 100 000 to 10 million. Preferred are such polymers having a
weight average
molecular weight of from 150000 to 5 million.
The most preferred polymer is poly (ethylene oxide). Molecular weight
distributions can
be readily determined using gel permeation chromatography, against standards
of poly (ethylene
oxide) of narrow molecular weight distributions.
The amount of flocculant is preferably 0.5-10% by weight of the tablet, most
preferably
about 2 to 6%.
The flocculant is preferably mainly in the form of granules, with at least 50%
by weighty
(and preferably at least 75% and most preferably at least 90%) being in the
form of granules
having a size of at least 100mm up to 1800mm, preferably up to 1180mm and most
preferably
150-850mm Preferably the amount of flocculant in the granules is at least 50%,
generally at least
70% or 90%, of the weight of the granules.
Other components which are commonly used in detergent compositions and which
may
be incorporated into the detergent tablets of the present invention include
chelating agents, soil
release agents, soil antiredeposition agents, dispersing agents, brighteners,
suds suppressors,
fabric softeners, dye transfer inhibition agents and perfumes.
It should be noted that when a clay material is compressed prior to
incorporation into a
tablet or in a cleaning composition, improved disintegration or dispensing is
achieved. For
example, tablets comprising clay which is compressed prior to incorporation
into a tablet,
disintegrate more rapidly than tablets comprising the same clay material which
has not been
compressed prior to incorporation into a tablet. In particular the amount of
pressure used for the
compression of the clay is of importance to obtain clay particles which aid
disintegration or
dispensing.
Further, when softening clays are compressed and then incorporated in cleaning
compositions or tablets, not only improved disintegration or dispensing is
obtained, but also good
softening of the fabrics. Preferably, the clay component is obtained by
compression of a clay
material.
A preferred process comprises the steps of submitting the clay material to a
pressure of
at least 10MPa, or even at least 20MPa or even 40MPa. This can for example be
done by
tabletting or roller compaction of a clay material, optionally together with
one or more other
51
CA 02380328 2005-08-19
ingredients, to form a clay tablet or sheet, preferably followed by size
reduction, such as grinding,
of the compressed clay sheet or tablet, to form compressed clay particles. The
particles can then
be incorporated in a tablet or cleaning composition.
Tabletting methods and roller compaction methods are known in the art. For
example, the
TM TM
compression of the clay can be done in a Lloyd 50K tablet press or with a
Chilsonator roller
compaction equipment, available form Fitzpatrick Company.
In order to make the present invention more readily understood, reference is
made to the
following example, which is intended to be illustrative only and not intended
to be limiting in
scope.
The following examples are presented for illustrative purposes only and are
not to be
construed as limiting the scope of the appended claims in any way.
Abbreviations used in Examples
In the detergent compositions, the abbreviated component identifications have
the following
meanings:
LAS . Sodium linear C11-13 alkyl benzene sulfonate
TAS . Sodium tallow alkyl sulfate
C45AS . Sodium C14 - C15 alkyl sulfate
C45E3S . Sodium C14-C15 alkyl sulfate condensed with 3 moles of ethylene oxide
QAS . RZ.N+(CH3)2(C2H4OH) with R2 = C12 - C14
Soap . Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow
and coconut fatty acids
Zeolite A . Hydrated sodium aluminosilicate of formula
Na12(A1O2SiO2)1Z.27H20 having a primary particle size in the range
from 0.1 to 10 micrometers (weight expressed on an anhydrous basis)
NaSKS-6 . Crystalline layered silicate of formula d- NaZSiZO5
Citric acid . Anhydrous citric acid
Carbonate . Anydrous sodium carbonate with a particle size between 200 m and
900 m
Bicarbonate . Anhydrous sodium bicarbonate with a particle size distribution
between
400 m and 1200 m
Silicate . Amorphous sodium silicate (SiO2:NaZO = 2.0:1)
Sulfate . Anhydrous sodium sulfate
52
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Mg sulfate . Anhydrous magnesium sulfate
Citrate . Tri-sodium citrate dihydrate of activity 86.4% with a particle size
distribution between 425 m and 850 m
MA/AA . Copolymer of 1:4 maleic/acrylic acid, average molecular weight about
70,000
AA . Sodium polyacrylate polymer of average molecular weight 4,500
CMC . Sodium carboxymethyl cellulose
Protease . Proteolytic enzyme, having 4% by weight of active enzyme, as
described
in WO 95/10591, sold by Genencor lnt. Inc.
Cellulase . Cellulytic enzyme, having 0.23% by weight of active enzyme, sold
by
NOVO Industries A/S under the trademark Carezyme
Amylase . Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by
NOVO Industries A/S under the trademark Termamyl 120T
Lipase . Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by
NOVO Industries A/S under the trademark Lipolase
Perborate . Sodium perborate
Percarbonate . Sodium percarbonate
NOBS . Nonanoyloxybenzene sulfonate in the form of the sodium salt
NAC-OBS . (6-nonamidocaproyl) oxybenzene sulfonate
TAED . Tetraacetylethylenediamine
DTPA . Diethylene triamine pentaacetic acid
EDDS . Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of its
sodium salt.
Photoactivated : Sulfonated zinc phthlocyanine encapsulated in bleach (1)
dextrin soluble
polymer
CHDM . 1,4 CycloHexaneDiMethanol
Brightener . Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-
yl)amino)
stilbene-2:2'-disulfonate
HEDP . 1,1-hydroxyethane diphosphonic acid
PEGx . Polyethylene glycol, with a molecular weight of x (typically 4,000)
QEA . bis((C2H5O)(C2H4O)õ)(CH3)1V+-C6Hl2-N+-(CH3) bis((C2H50)
-(CZH4O)),,, wherein n = from 20 to 30
SRP . Diethoxylated poly (1, 2 propylene terephtalate) short block polymer
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WO 01/10993 PCT/US00/21570
Silicone . Polydimethylsiloxane foam controller with siloxane-oxyalkylene
antifoam copolymer as dispersing agent with a ratio of said foam controller to
said
dispersing agent of 10:1 to 100:1
In the following examples all levels are quoted as % by weight of the
composition:
LIQUID PRODUCT FORMULATION EXAMPLES
Example I
Nonaqueous liquid detergent compositions comprising a surfactant-rich liquid
phase and
a solid phase were prepared as follows:
%, By weight
Composition A Composition B
Nonionic Surfactant 21.27 20.14
BPP Solvent 18.30 17.33
LAS Surfactant 15.83 14.99
Ethoxylated quaternized 1.29 1.22
amine clay material
Hydrotrope 4.80 0.00
Na-Citrate dihydrate 6.73 6.37
Na-Carbonate 9.89 9.37
Bleach Activator 5.94 5.62
Sodium Perborate 11.87 11.24
EDDS 1.17 1.11
Duramyl Enzyme 0.79 0.87
Carezyme Enzyme 0.03 0.03
Protease Enzyme 0.79 0.75
Antifoaming Agents 0.61 0.85
Plastic Microspheres 0.51 0.49
Titanium dioxide 0.50 0.47
Brightener 0.20 0.19
PEG 8000 0.40 0.38
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Perfume 1.72 1.63
Miscellaneous 2.16 2.15
Liquid detergent composition A is prepared according to the present invention
and thus
contains the preferred hydrotrope 1,4 Cyclo Hexane Di Methanol. As can be seen
above, liquid
detergent composition B is nearly identical to composition A, except that
composition B contains
none of the hydrotrope and its other components have been slightly rebalanced.
The benefits of the hydrotropes discussed herein can be readily seen through
an
experimental test which measures the rate of dissolution of a liquid detergent
composition in
water.
Rate of Liquid Detergent Product Dissolution in Water Test
1. Fill a glass beaker with 3 liters of deionised water at approximately 25 C.
2. Insert a 5 cm magnetic stirbar and a conductivity electrode into the water.
Begin
mixing the water rate at a rate of 400 rpm and maintain this constant rate
throughout the
experiment.
3. Place an 85 ml-capacity screen cup with a 60 mesh screen on the surface of
the
water and in the center of the beaker in such a way so that the top of the cup
is just above the
water and no water can come in from the top side, only through the screen.
4. Very slowly add 1 ml of the liquid detergent product (via a syringe) into
the
middle of the screen cup. This is To. Measure the conductivity at To.
5. Repeat the measurement of the electrical conductivity of the detergent
product-
water mixture at regular intervals, such as after 0.5, 1, 2, 4, 6 and 10
minutes.
6. After a suitable amount of time (e.g. 10 minutes) the liquid detergent
product that
remains inside the screen cap is added to the product-water mixture by
immersing the cap into the
mixture and increasing the rate of stirring.
7. When all of the product has been dissolved and the conductivity has reached
a
steady-state value, said value is recorded.
Both of these compositions were tested using the "Rate of Liquid Detergent
Product
Dissolution in Water Test" described in great detail above. The conductivity
was measured by
electrode immersed in the water at the beginning of the test-detergent
composition solution and
the % of dissolution by and converted into The following results were
obtained:
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WO 01/10993 PCT/US00/21570
Composition A Composition B
Time Conductivity % Dissolution Conductivity % Dissolution
0 s(To) 0 0 0 0
30s 28 19 12 7
60s 40 27 17 10
120s 54 37 23 14
180s 62 42 31 18
240s 68 47 39 23
360s 78 53 44 26
600s 81 55 49 29
660s 91 62 51 30
After 11 minutes, full dissolution of the detergent composition was forced by
high
agitation and the conductivity measured:
Full 100 100 146 100
Dissolution
The dissolution values were obtained by dividing the measured conductivity at
each
individual time by the measured conductivity at full dissolution and
multiplying by 100.
Example II
An aqueous liquid detergent composition according to the present invention is
prepared
as follows:
Composition C
Component Wt. %
C12-15 alkyl ether (2.5) sulfate 18.0
C12-13 alkyl ethoxylate (9.0) 2.00
C12-14 glucose amide 3.50
Citric Acid 3.00
C12-14 Fatty Acid 2.00
CHDM 5.00
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WO 01/10993 PCT/US00/21570
MEA to pH 8
Ethanol 3.0
Propanediol 6.0
Dye, Perfume, Brighteners, Enzymes, Preservatives, Suds
Suppressor, Other Minors, Water Balance
100%
ExaMple III
Nonaqueous liquid detergent compositions comprising a surfactant-rich liquid
phase and
a solid phase were prepared as follows:
%, By weight
Composition Composition Composition Composition Composition
A B C D E
NaLAS 14.6 14.9 13.9 13.0 14.9
HLAS 0.0 0.0 1.0 1.9 0.0
Nonionic Surfactant 20.6 20.7 20.7 20.7 20.7
NaCitrate dihydrate 3.3 3.3 3.3 3.3 3.3
Copolymer of Acrylic 2.9 2.9 2.9 2.9 2.9
Acid and Maleic Acid
EDDS 1.2 1.2 1.2 1.2 1.2
Ethoxylated Quaternized 1.3 1.3 1.2 1.3 1.3
amine clay material
Sodium Perborate 11.5 11.5 11.5 11.5 11.5
Bleach Activator 2.9 5.8 2.9 2.9 2.9
Triacetin 12.5 0.0 12.5 12.5 8.7
NaCarbonate 9.6 9.6 9.6 9.6 9.6
BPP Solvent 9.1 17.8 9.1 9.1 12.0
Hydrotrope 3.8 4.8 3.8 3.8 4.8
Acetic acid 0.2 0.0 0.1 0.0 0.0
Protease Enzyme 0.8 0.8 0.8 0.8 0.8
Duramyl Enzyme 0.8 0.4 0.4 0.4 0.4
Mannanase Enzyme 0.2 0.2 0.2 0.2 0.2
Carezyme Enzyme 0.1 0.0 0.0 0.0 0.0
Brightener 0.2 0.2 0.2 0.2 0.2
Titanium Dioxide 0.5 0.5 0.5 0.5 0.5
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PEG 8000 0.5 0.5 0.5 0.5 0.5
Perfume 1.7 1.7 1.7 1.7 1.7
Silicone 0.7 0.7 0.7 0.7 0.7
Silicone surfactant DC 3225 0.3 0.3 0.3 0.3 0.3
Sodium salt of a 0.5 0.5 0.5 0.5 0.5
hydrogenated C 16-18
fatty acid
Miscellaneous BALANCE BALANCE BALANCE BALANCE BALANCE
GRANULAR/POWDER PRODUCT FORMULATION EXAMPLES
Example I
The following compositions are in accordance with the invention.
3 C F G
S ra -dried Granules
AS 10.0 10.0 15.0 5.0 5.0 10.0 -
QAS 1.0 1.0 - - -
TPA, HEDP and/or .3 0.3 0.5 0.3 - - -
DDS
gSO4 0.5 .5 .1 - - - -
Sodium citrate - - - 3.0 5.0 - - -
Sodium carbonate 10.0 10 15 10 7 10 - - -
Sodium sulphate 5.0 5.0 - - 5.0 3.0 - - -
Sodium silicate 1.6R - - - - 2.0 - - -
eolite A 16.0 18.0 20.0 20.0 - - - - -
SKS-6 - - - 3.0 5.0 - - -
A/AA or AA 1.0 2.0 11.0 - - 2.0 - - -
CHDM 0.5 2.0 2.5 1.5 1.0 1.0 - - -
QEA 1.0 - - - 1.0 - - - -
3rightener 0.05 0.05 0.05 - 0.05 - - - -
Silicone oil 0.01 0.01 0.01 - - 0.01 - - -
Agglomerate
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WO 01/10993 PCT/US00/21570
AS - - - 0.2 0.2 .01
C45AS - - - - 2.0 - 1.0
3 - - - - - 1.0 .5
Carbonate - - 1.0 1.0 1.0 1.0 -
Sodium citrate - - - - - 5.0
CFAA - - - - -
Citric acid - - - .0 - 1.0 1.0
QEA - - .0 2.0 1.0 -
SRP - - 1.0 1.0 .2 -
eolite A - - - 15.0 26.0 15.0 16.0
Sodium silicate - - - - - - -
CHDM - - - - - - 3.0 - -
3uilder Agglomerates
SKS-6 6.0 - - - 6.0 3.0 - 7.0 10.0
AS .0 5.0 - - 5.0 3.0 - 10.0 12.0
Dry-add particulate
com onents
alic 8.0 - 10.0 1.0 - 8.0 - - 1.0
acid/carbonate/bicarbonate
(40:20:40)
QEA - - - 0.2 0.5 - - - -
ACAOBS 3.0 - - 1.5 - - - 2.5 -
OBS - 3.0 3.0 - - - - - 5.0
AED 2.5 - - 1.5 2.5 6.5 - 1.5 -
AS (flake) 10.0 10.0 - - - - - 8.0 -
S ra -on
3rightener 0.2 0.2 .3 0.1 0.2 0.1 - 0.6 -
ye - - - 0.3 0.05 0.1 - - -
7 - - - - - 0.5 - 0.7 -
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erfume - - - .8 - .5 - .5 -
Dry-add
Citrate - 20.0 1.0 - 5.0 15.0 - 5.0
ercarbonate 15.0 3.0 6.0 10.0 - - 18.0 5.0
erborate - - - 6.0 18.0 - - -
hotobleach .02 0.02 .02 .1 .05 - 0.3 - 0.03
nzymes (cellulase, 1.3 0.3 .5 .5 0.8 2.0 0.5 0.16 0.2
amylase, protease, lipase)
Carbonate .0 10.0 - - 5.0 8.0 10.0 5.0
erfume (encapsulated) 0.6 0.5 .5 - .3 0.5 0.2 0.1 0.6
Suds suppressor 1.0 .6 .3 - 0.10 0.5 1.0 .3 1.2
Soap 0.5 0.2 .3 3.0 .5 - - .3 -
Citric acid - - 6.0 6.0 - - - 5.0
yed carbonate (blue, .5 .5 1.0 2.0 - 0.5 .5 .5 1.0
green)
SKS-6 - - - .0 - - - 6.0 -
illers up to 100%
The compositions exemplified above have at least 90% by weight of particles
having a geometric
mean particle diameter of from about 850 microns with a geometric standard
deviation of from
about 1.2. Unexpectedly, the compositions have improved aesthetics,
flowability and solubility.
TABLET PRODUCT FORMULATION EXAMPLES
Example 1 a
i) A detergent base powder of composition A (see table 1) was prepared as
follows: all the
particulate materials of base composition A were mixed together in a mixing
drum to form a
homogenous particulate mixture.
ii) 1 part of polyethyleneglycol was sprayed onto 99 parts of base powder of
composition A
while mixing.
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iii) Tablets were then made the following way. 54 g of the mixture was
introduced into a mould
of circular shape with a diameter of 5.5 cm and compressed at a force of 2.OkN
with an
Instron 4464 press. The tablet tensile strength (or diametrical fracture
stress) obtained at this
force was 19.2kPa. Means to assess tablet strength (also referred to as
diametrical fracture
stress) are given in Pharmaceutical dosage forms : tablets volume 1 Ed. H.A.
Lieberman et al,
published in 1989.
Example lb
i) The same composition A was prepared following the same process as in
example la.
ii) 0.9 parts of polyethyleneglycol and 0.1 part of 1,4 cyclohexanedimethanol
were mixed
together and sprayed onto 99 parts of base powder of composition A while
mixing.
iii) Tablets were then made following the same way as described in example la.
. The tablet
tensile strength (or diametrical fracture stress) obtained at a force of 2.OkN
was 23.6kPa.
Examples 2a-3b were prepared in an analogous fashion to the process described
above
and according to the formulation compositions detailed below.
Table 1
Composition Composition Composition
A B C
Anionic agglomerates' 34 34 34
Nonionic agglomerates2 9.57 9.57 9.57
Layered silicate3 2.7 1.5 1.5
Sodium percarbonate 12.43 12.43 12.43
Bleach activator agglomerates4 6.48 6.48 6.48
Sodium carbonate 19.01 18.96 18.46
EDDS/Sulphate particle5 0.50 0.50 0.50
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Tetrasodium salt of Hydroxyethane Diphosphonic 0.8 0.8 0.8
acid
Fluorescer 0.11 0.11 0.11
Zinc Phthalocyanine sulphonate encapsulate6 0.027 0.027 0.027
Soap powder 1.49 0.74 0.74
Suds suppressor' 1.8 1.8 1.8
Citric acid 7.51 7.51 7.51
Protease 0.8 0.8 0.8
Cellulase 0.16 0.16 0.16
Amylase 0.61 0.61 0.61
Polyethylene glycol MW of 4000 flakes - 1.5 1.5
Sodium salt of Linear Alkyl Benzene Sulphonate / 1 1 1.5
DiIsoPropylBenzeneSulphonateg
1: Anionic agglomerates comprise 37% anionic surfactant, 2% cationic
surfactant, 22%
layered silicate, 10% acetate, 6% carbonate and 23% zeolite.
2: Nonionic agglomerates comprise of 24% nonionic surfactant, 6% ethoxylated
hexamethylene diaminequat, 40% acetate/zeolite mix, 20% carbonate and 10%
zeolite.
3: Layered silicate comprises of 95% SKS 6 and 5% silicate.
4: Bleach activator agglomerates comprise of 81% TAED, 17% acrylic/maleic
copolymer
(acid form) and 2% water.
5: Ethylene diamine N,N-disuccinic acid sodium salt/Sulphate particle comprise
of 58% of
Ethylene diamine N,N-disuccinic acid sodium salt, 23% of sulphate and 19%
water.
6: Zinc phthalocyanine sulphonate encapsulates are 10% active.
7: Suds suppressor comprises of 11.5% silicone oil (ex Dow Corning); 59% of
zeolite and
29.5% of water.
8: Sodium salt of Linear Alkyl Benzene Sulphonate /
DilsoPropylBenzeneSulphonate
comprises of 67% Linear Alkyl Benzene Sulphonate and 33%
DilsoPropylBenzeneSulphonate.
A tablet binder composition was sprayed onto the above detergent base powders
according to the following compositions:
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Table 2
Example Example Example Example Example Example
la lb 2a 2b 3a 3b
Powder A 99% 99%
Powder B 98.5% 98.5%
Powder C 98.5% 98.5%
Polyethyleneglycol 1% 0.9% 1.50% 1.35% 1.5% 1.3%
1,4 0.1% 0.15% 0.2%
cyclohexanedimethanol
The strength of the tablets was then tested as has been described above in
step iii) and
elsewhere in the present invention:
Table 3
Example Example Example Example Example Example
la lb 2a 2b 3a 3b
Tablet tensile 19.2 23.6 12.4 14.7 16 19
strength (kPa)
The tensile strength of the tablet samples which contained CHDM were greater
than the
CHDM tablet samples of virtually identical composition, but which contained no
CHDM.
The operating window was also assessed:
Table 4
Example 3a Example 3b
Density at a tablet hardness of 1035 1010
5.5kP
Density at a tablet dispensing of 1052 1035
15%
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The operating window of the tablet samples which contained CHDM (width = 25
g/liter) was
broader than the operating window of the tablet samples which contained no
CHDM (width = 17
g/liter).
The amount of dispensing of a detergent tablet as tabulated above in table 4
can be
determined through an experimental test which measures the amount of detergent
product
dispensed during an automatic wash process in the following way:
l. Two tablets, nominally 50 grams each, are weighed, and then placed in the
dispenser of a Baucknecht WA9850 washing machine. The water supply to the
washing machine is set to a temperature of 20 C and a hardness of 21 grains
per
gallon, the dispenser water inlet flow-rate being set to 8 1/min.
2. The level of tablet residues left in the dispenser is checked by switching
the
washing on and the wash cycle set to wash program 4 (white/colors, short
cycle).
3. The dispensing percentage residue is then determined as follows:
% dispensing = residue weight x 100 / original tablet weight
The level of residues is determined by repeating the procedure 10 times and an
average
residue level is calculated based on the ten individual measurements.
Having thus described the invention in detail, it will be clear to those
skilled in the art
that various changes may be made without departing from the scope of the
invention and the
invention is not to be considered limited to what is described in the
specification.
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