Note: Descriptions are shown in the official language in which they were submitted.
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GRANULAR DETERGENT COMPOSITIONS HAVING SURFACTANT PARTICLE WITH
REDUCED ELECTROLYTE CONCENTRATIONS
Technical Field
The present invention relates to granular detergent compositions having
surfactant
particles with reduced electrolyte concentrations, and in particular to
detergent compositions with
surfactant particles of reduced carbonate levels.
Background of the Invention
In recent years, the popularity of liquid detergent compositions has been on
the rise. This
growing popularity is due in large part to superiority in dispersion and
dissolution of liquid
detergents in comparison to their granular counterparts. These dissolution and
dispersion
advantages are particularly apparent in cold water conditions, i.e. less than
30°C where
traditionally, the dissolution of granular detergents has been lacking.
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.
In general, performance of granular detergent compositions depends on depends
on both
dispersion of the granules in the wash water and the dissolution of the
individual granules. In
general, there is an optimal balance between the two properties. Particles
that dissolve well
typically have poor dissolution while particle that disperse well are often
slow to dissolve. While
slow dissolution impacts cleaning performance by limiting the amount of
cleaning agent available
in the wash, it is poor dissolution that may have the greatest consumer
noticeable impact is non-
soluble residues on fabrics.
While not wishing to be bound by theory, it is believed that detergent
residues are due in
large part to the bridging of a gel-like substance between surfactant
granules. This gel like
residue results from the partial dissolution of surfactant to form highly
viscous surfactant paste.
When this gel-like substance "connects" to neighboring particles a much larger
"lump" is formed.
Once formed, these lump-gels are difficult to break-up, disperse and dissolve.
By way of the
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present invention, it has been found that the interaction between electrolytes
present in the
surfactant particles and the class of surfactants based on alcohol sulfates is
particularly
problematic in a detergent composition due to lump-gel formation. On the other
hand, the class
of surfactants based on alkyl benzyl sulphonates have a much lower tendency to
interact with
electrolytes to form lump-gels.
One way to minimize these electrolyte-surfactant interactions is to simply
reduce the
amount of electrolyte in the formulation. However, such a reduction of the
typically alkaline
electrolytes, for example sodium carbonate, will result in a reduction in the
wash water pH and as
a result a reduction in cleaning performance of the detergent composition.
Therefore, it is
desirable to maintain, if not increase, the level of electrolyte in the
formulation.
Accordingly, the need remains to improve the dissolution issues surrounding
granular
detergent compositions to maintain formulation flexibility over liquid
detergent compositions,
particularly dissolution in cold water conditions.
Summary of the Invention
This need is met by the present invention wherein a granular detergent
composition
having surfactant particles with reduced electrolyte levels is provided. In
essence the present
invention involves the formulation of a fully formulated detergent composition
which comprises
a surfactant system having an electrolyte rich surfactant zone and an
electrolyte poor surfactant
zone. The composition may be in the form of a single particle with separate
discrete surfactant
zones or may be in the form of multiple particles wherein each surfactant zone
is represented by a
separate particle. In highly preferred scenarios, the electrolyte poor zone is
an agglomerated
detergent particle and the electrolyte rich zone is a spray-dried detergent
particle. The
composition also includes other detergent adjunct ingredients.
The electrolyte poor surfactant zone comprises less than about 20%, more
preferably less
than about 10%, even more preferably less than about 2% and most preferably
about 0%
electrolyte in conjunction with a surfactant or blend of surfactants selected
from the class of alkyl
sulfate surfactants. Meanwhile, the electrolyte rich surfactant zone comprises
more than about
20%, more preferably more than about 35% and most preferably more than about
45% electrolyte
in conjunction with a surfactant or blend of surfactants selected from an
anionic surfactant which
is not an alkyl sulfate surfactants, preferably alkyl benzene sulfonates.
Thus, via the zone
separation of the present invention wherein the electrolyte is separated from
the proximity of the
alkyl sulfate surfactants, the formation of lump-gel residues is minimized
and/or reduced
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resulting in both superior dissolution and dispersion profiles for the
granular detergent of the
present invention.
Accordingly, it is an object of the present invention to provide a superior
performing
granular detergent composition which has the solubility profile on par with
liquid detergents. In
is a further object of the present invention to provide this solubility via
zone separation of
electrolytes and certain surfactant ingredients. It is a further object of the
present invention to
provide an electrolyte poor zone or particle having alkyl sulfate surfactant
and an electrolyte rich
zone having an anionic surfactant that is not an alkyl sulfate such as alkyl
benzene sulfonate
surfactants. These and other objects, features and advantages of the present
invention, will be
apparent to one of ordinary skill in the art from the following description
and the appended
claims.
Detailed Description of the Preferred Embodiments
Definitions
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 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. 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. 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 50'" percentile of the cumulative distribution
(DS.~.,~/D;°); See
Gotoh et al, Powder Teclmolog~~ Handbook, pp. 6-1 l, Meral Dekker 1997. .
As used herein, the phrase "builder" means any inorganic material having
"builder"
performance in the detergency context, and specifically, organic or inorganic
material capable of
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removing water hardness from washing solutions. As used herein, the term "bulk
density" refers
to the uncompressed, untapped powder bulk density, as measured by pouring an
excess of powder
sample through a funnel into a smooth metal vessel (e.g., a 500 ml volume
cylinder), scraping off
the excess from the heap above the rim of the vessel, measm°ing the
remaining mass of powder
and dividing the mass by the volume of the vessel.
The present invention involves the design of a granular detergent composition
having
superior solubility via the separation of selected detergent ingredients that
have increased
tendency to form gels of lower solubility during the dispersion and
dissolution of a granular
detergent when in proximity to each other. The detergent ingredients which
have been identified
as having the increased tendency to form lump-gel residues are alkyl sulfate
surfactants and
electrolytes. Electrolytes are commonly present in detergent compositions to
provide such
benefits as alkalinity, building etc. and are typically present as alkali
metal salts such as
carbonate, chloride and sulfate salts. Most typical is sodium carbonate and is
the most preferred
electrolyte according to the present invention.
To take advantage of the present invention, the granular detergents are
divided into
electrolyte poor and electrolyte rich zones. The electrolyte poor zone
contains lower levels of
electrolyte than that present in the electrolyte rich zone. Thus, the alkyl
sulfate surfactants are
concentrated in the electrolyte poor zone thereby minimizing their interaction
with the
electrolytes prior to complete solubility of the surfactants. The electrolyte
poor zone contains
less than about 20% by weight of the particle of electrolyte, preferably less
than about 10% by
weight and most preferably less than about 2% by weight of the particle of the
electrolyte with
levels around 0 being the most preferred. The electrolyte poor zone also
preferably includes at
least about 2%, more preferably about 5% and most preferably about 10% by
weight of the
particle of the alkyl sulfate surfactant.
The electrolyte rich zone contains higher levels of the electrolyte than that
present in the
electrolyte poor zone. Accordingly, anionic surfactants other than the alkyl
sulfates may be
formulated into this electrolyte rich zone. Preferably, the anionic surfactant
in this zone is an
alkyl benzene sulfonate surfactant. The electrolyte rich zone contains more
than about 20% by
weight of the particle of electrolyte, preferably more than about 30%, and
more preferably more
than about 35% by weight of the particle of electrolyte. In addition, the
electrolyte rich zone
contains more than about 0% by weight of the particle of anionic surfactant,
more preferably
more than about 2% and most preferably more than 5% by weight of the particle.
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In preferred embodiments, the electrolyte poor zone and the electrolyte rich
zone
comprise separate particles differing composition as formulated into the
granular detergent. The
particles may be selected from spray-dried, agglomeration, extrusion,
pelletization, compaction
and various other particle making processes as well known in the art. In
preferred examples, one
particle may be a spray-dried particle while the other particle is
agglomerated. Preferably, the
electrolyte rich zone is a spray-dried particle while the preferred
electrolyte poor zone is an
agglomerated particle. Of course, one of ordinary skill in the art will
recognize that other forms
of particles may also be advantageous employed. In an alternate embodiment,
the electrolyte rich
zone and the electrolyte poor zone are separate and distinct zones of the same
particle. For
examples, two separate sub-particles of differing composition may be
agglomerated together to
form single particle having the distinct zones as described herein.
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 adkoxy 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
formidability in liquid detergent
formulations are water soluble salts or acids of the formula ROS03M wherein R
preferably is a
C 10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10-C20
alkyl component,
more preferably a C12-C18 alkyl or hydroxyalkyl, and M is I-I or a canon,
e.g., an alkali (Group
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IA) metal canon (e.g., sodium, potassium, lithium), substituted or
unsubstituted ammonium
canons such as methyl-, dimethyl-, and trimethyl ammonium and quaternary
ammonium cations,
e.g., tetramethyl-ammonium and dimethyl piperdinium, and canons derived from
alkanolamines
such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof,
and the like.
Typically, alkyl chains of C 12-16 are preferred for lower wash temperatures
(e.g., below about
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:
IOS03 M+ IOSO3 1VI+
CH3(CHZ)X(CH)CH3 or CH3(CH2)y(CH)CH2CH3
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 each incorporated herein by reference;
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)mS03M 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.~ and about 3,
and M is H or a
cation which can be, for example, a metal canon (e.g., sodium, potassium,
lithium, etc.),
ammonium or substituted-ammonium canon. 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 ammonium
cations, such
as tetramethyl-ammonium, dimethyl piperidinium and canons 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, C 12-C 18 alkyl polyethoxylate (3.0) sulfate, and C 12-C 18 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
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alkyl sulfates and alkyl ether sulfates derived from conventional alcohol
sources, e.g., natural
alcohols, synthetic alcohols such as those sold under the trade name of
NEODOLT"", ALFOLT"",
LIALTM, LUTENSOLT"" and the like. Alkyl ether sulfates are also known as alkyl
polyethoxylate
sulfates.
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' RZ
CH3CH2(CHZ)WCH(CHZ)XCH(CH2)yCH(CHZ)~(EO/PO)",OH
mid-chain branched alkyl sulfates having the formula:
R R~ RZ
CH3CH2(CH2)WCH(CHZ)XCH(CHZ)yCH(CHZ)ZOS03M
and mid-chain branched alkyl alkoxy sulfates having the formula:
R R~ R2
CH3CH2(CHZ),~,CH(CHZ),~CH(CHZ)yCH(CHZ)Z(EO/PO)",OS03M
wherein the total number of carbon atoms in the branched primacy alkyl moiety
of these formulae
(including the R, RI, 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 I S to about
17); R, RI, and R2 are each independently selected from hydrogen, CI-C3 alkyl,
and mixtures
thereof, preferably methyl; provided R, RI, and R2 are not all hydrogen and,
when z is I, at least
R or RI is not hydrogen. M is a water soluble canon and may comprises more
than one type of
canon, 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. E0 and PO represent ethyleneoxy units and
propyleneoxy units having
the formula:
~ H3 ( H3
CHCHZO- or -CHZCHO-
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.
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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
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:
i H3
CH3(CHZ)aCH(CHZ)bCH2(EO/PO)r"OS03M
or the formula:
H3 I H3
CH3(CHZ)dCH(CHZ)eCHCH2(EO/PO)r"OS03M
wherein a, b, d, and a are integers such that a + b is from 10 to 16 and d + a
is from 8 to 14; M is
selected from sodium, potassium, magnesium, armnonium 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 U.S. Patent Application No.
60/061,971,
Attorney docket No 6881P October 14, 1997, No. 60/061,975, Attorney docket No
6882P
October 14, 1997, No. 60/062,086, Attorney docket No 6883P October 14, 1997,
No. 60/061,916,
s
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Attorney docket No 68S4P October 14, 1997, No. 60/061,970, Attorney docket No
6885P
October 14, 1997, No. 60/062,407, Attorney docket No 6886P October 14, 1997,.
Other suitable
mid-chain branched surfactants can be found in U.S. Patent applications Serial
Nos. 60/032,035
(Docket No. 6401P), 60/031,845 (Docket No. 6402P), 60/031,916 (Docket No.
6403P),
60/031,917 (Docket No. 6404P), 60/031,761 (Docket No. 6405P), 60/031,762
(Docket No.
6406P) and 60/031,844 (Docket No. 6409P). 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 stmctural formula:
O
R3CHCOR4
I
S03M
wherein R3 is a C8-C20 hydrocarbyl, preferably an allyl, or combination
thereof, R4 is a C1-C6
hydrocarbyl, preferably an allyl, or combination thereof, and M is a soluble
salt-forming canon.
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 ammonium
cations, e.g. tetramethyl-ammonium and dimethyl piperdinium, and cations
derived from
alkanolamines, e.g. monoethanol-amine, diethanolamine, and triethanolamine.
Preferably, R3 is
C10-C16 alkyl, and R4 is methyl, ethyl or isopropyl. Especially preferred are
the methyl ester
sulfonates wherein R3 is C 14-C 16 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., AlCI~, or made using acidic
silica/alumina or
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made from chlorinated hydrocarbons, such as C9-C20 linear alkylbenzene
sulfonates, particularly
sodium linear alkyl Clp-C15 benzene sulfonate. These surfactants are water
soluble salts or
acids typically of the formula RAS03M wherein R is a branched or linear CIO-
C24 alkyl group,
preferably a C 10-C20 alkyl, more preferably C 10-C 18 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
example, a metal canon (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:
R1RZL R3
CM a +~
b
SO3
a
wherein L is an acyclic hydrocarbyl moiety comprising from 6 to 18 carbon
atoms; R', R'', and R
are each independently hydrogen or C,-C3 alkyl, provided R' and R' are not
attached at the
terminus of the L unit; M is a water soluble canon having charge q wherein a
and b are taken
together to satisfy charge neutrality.
These and other suitable MLAS surfactants are further described in copending
U.S. Patent
applications No. 60/053,319 Attorney docket No 6766P filed on July 21 st,
1997, No. 60/053,318,
Attorney docket No 6767P filed on July 21st, 1997, No. 60/053,321, Attorney
docket No 6768P
filed on July 21st, 1997, No. 60/053,209, Attorney docket No 6769P filed on
July 21st, 1997, No.
60/053,328, Attorney docket No 6770P filed on July 21 st, 1997, No.
60/053,186, Attorney docket
No 6771P filed on July 21st, 1997, No. 60/105,017 Attorney docket No 7303P
filed on October
20th, 1998, No. 60/104,962 Attorney docket No 7304P filed on October 20th,
1998, and No.
60/144,519 Attorney docket No 7663P filed on July 19th, 1999. 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.
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Examples of suitable anionic surfactants are given in "Surface Active Agents
and
Detergents" (Vol. I and II by Schwartz, Periy 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,
ammonium, and substituted ammonium 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 methyl tauride, alkyl succinamates and
sulfosuccinates, monoesters
of sulfosuccinate (especially saturated and unsaturated C 12-C 18 monoesters)
diesters of
sulfosuccinate (especially saturated and unsaturated C6-C 14 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(CH2CH20)kCH2C00-M+
wherein R
is a C8-C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-
forming canon, 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 Colunm 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 copending U.S. Serial
No. 60/020,503
(Docket No. 6160P), 60/020,772 (Docket No. 6161P), 60/020,928 (Docket No.
6158P),
60/020,832 (Docket No. 6159P) and 60/020,773 (Docket No. 6162P) all filed on
June 28, 1996,
and 60/023,539 (Docket No. 6192P), 60/023493 (Docket No. 6194P), 60/023,540
(Docket No.
6193P) and 60/023,527 (Docket No. 6195P) riled on August 8th, 1996, the
disclosures of which
are incorporated herein by reference.
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DETERGENT COMPONENTS
The detergent composition can, and preferably does, include a detergent
builder.
Builders are generally selected from the various water-soluble, alkali metal,
ammonium or
substituted ammonium phosphates, polyphosphates, phosphonates,
polyphosphonates,
carbonates, silicates, borates, polyhydroxy sulfonates, polyacetates,
carboxylates, and
polycarboxylates. Preferred are the alkali metal, especially sodium, salts of
the above. Preferred
for use herein are the phosphates, carbonates, silicates, C10-18 fatty acids,
polycarboxylates, and
mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium
pyrophosphate,
citrate, tarh-ate mono- and di-succinates, sodium silicate, and mixtures
thereof (see below).
Specific examples of inorganic phosphate builders are sodium and potassium
tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of
polymerization of
from about 6 to 21, and orthophosphates. Examples of polyphosphonate builders
are the sodium
and potassium salts of ethylene diphosphonic acid, the sodium and potassium
salts of ethane
1-hydroxy-1, 1-diphosphonic acid and the sodium and potassium salts of ethane,
1,1,2-triphosphonic acid. Other phosphorus builder compounds are disclosed in
U.S. Patents
3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, all of
which are
incorporated herein by reference.
Examples of nonphosphorus, inorganic builders are sodium and potassium
carbonate,
bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a
weight ratio of Si02
to alkali metal oxide of from about 0.5 to about 4.0, preferably from about
1.0 to about 2.4.
Water-soluble, nonphosphorus organic builders useful herein include the
various alkali metal,
ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates
and
polyhydroxy sulfonates. Examples of polyacetate and polycarboxylate builders
are the sodium,
potassium, lithium, ammonium and substituted ammonium salts of ethylene
diamine tetraacetic
acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene
polycarboxylic acids, and
citric acid.
Polymeric polycarboxylate builders are set forth in U.S. Patent 3,308,067,
Diehl, issued
March 7, 1967, the disclosure of which is incorporated herein by reference.
Such materials
include the water-soluble salts of homo- and copolymers of aliphatic
carboxylic acids such as
malefic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid,
citraconic acid and
methylenemalonic acid. Some of these materials are useful as the water-soluble
anionic polymer
as hereinafter described, but only if in intimate admixture with the nonsoap
anionic surfactant.
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Other suitable polycarboxylates for use herein are the polyacetal carboxylates
described
in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al., and
U.S. Patent 4,246,495,
issued March 27, 1979 to Crutchfield et al., both of which are incorporated
herein by reference.
These polyacetal carboxylates can be prepared by bringing together under
polymerization
conditions an ester of glyoxylic acid and a polymerization initiator. The
resulting polyacetal
carboxylate ester is then attached to chemically stable end groups to
stabilize the polyacetal
carboxylate against rapid depolymerization in alkaline solution, converted to
the corresponding
salt, and added to a detergent composition. Particularly preferred
polycarboxylate builders are
the ether carboxylate builder compositions comprising a combination of tarnate
monosuccinate
and tartrate disuccinate described in U.S. Patent 4,663,071, Bush et al.,
issued May 5, 1987, the
disclosure of which is incorporated herein by reference.
Water-soluble silicate solids represented by the formula Si02~M20, M being an
alkali
metal, and having a Si02:M20 weight ratio of from about 0.5 to about 4.0, are
useful salts in the
detergent granules of the invention at levels of from about 2% to about 15% on
an anhydrous
weight basis, preferably from about 3% to about 8%. Anhydrous or hydrated
particulate silicate
can be utilized, as well.
Any number of additional ingredients can also be included as components in the
granular
detergent composition. These include other detergency builders, bleaches,
bleach activators, suds
boosters or suds suppressors, anti-tarnish and anti-corrosion agents, soil
suspending agents, soil
release agents, germicides, pH adjusting agents, nonbuilder alkalinity
sources, chelating agents,
smectite clays, enzymes, enzyme-stabilizing agents and perfumes. See U.S.
Patent 3,936,537,
issued February 3, 1976 to Baskerville, Jr. et al., incorporated herein by
reference.
Bleaching agents and activators are described in U.S. Patent 4,412,934, Chung
et al.,
issued November 1, 1983, and in U.S. Patent 4,483,781, Hartman, issued
November 20, 1984,
both of which are incorporated herein by reference. Chelating agents are also
described in U.S.
Patent 4,663,071, Bush et al., from Column 17, line 54 through Column 18, line
68, incorporated
herein by reference. Suds modifiers are also optional ingredients and are
described in U.S.
Patents 3,933,672, issued January 20, 1976 to Bartoletta et al., and
4,136,045, issued January 23,
1979 to Gault et al., both incorporated herein by reference.
Suitable smectite clays for use herein are described in U.S. Patent 4,762,645,
Tucker et
al., issued August 9, 1988, Column 6, line 3 through Column 7, line 24,
incorporated herein by
reference. Suitable additional detergency builders for use herein are
enumerated in the
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Baskerville patent, Column 13, line 54 through Column 16, line 16, and in U.S.
Patent 4,663,071,
Bush et al., issued May S, 1987, both incorporated herein by reference.
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 . R2.N+(CH3)2(C2H40H) 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
Nal2(AlO2Si02)12.27H20 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 8- Na2Si2O5
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 (Si02:Na20 = 2.0:1)
Sulfate . Anhydrous sodium sulfate
Mg sulfate : Anhydrous magnesium sulfate
Citrate . Tri-sodium citrate dehydrate of activity 86.4% with a particle size
distribution between 425pm and 850pm
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
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CMC . Sodium carboxymethyl cellulose
Protease Proteolytic enzyme. having 4% by weight of active
: enzyme, as described
in WO 95/10591, sold by Genencor Int. lnc.
Cellulase Cellulytic enzyme, having 0.23% by weight of active
: enzyme, sold by
NOVO Industries A/S under the tradename Carezyme
Amylase : Amylolytic enzyme, having 1.G% by weight of active
enzyme, sold by
NOVO Industries A/S under the tradename Termamyl
120T
Lipase : Lipolytic enzyme, having 2.0% by weight of active
enzyme, sold by
NOVO Industries A/S under the tradename Lipolase
Perborate Sodium perborate
:
PercarbonateSodium 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.
PhotoactivatedSulfonated zinc phthlocyanine encapsulated in
: bleach ( 1 ) dextrin soluble
polymer
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((C2H50)(C2H40)n)(CH3) -N+-C6H12-N+-(CH3)
bis((C2H50)-
(C2H4 O))n, wherein n = from 20 to 30
SRP . Diethoxylated poly (1, 2 propylene terephtalate)
short block polymer
Silicone antifoam : Polydimethylsiloxane foam controller with siloxane-
oxyalkylene
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:
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Example I
The following compositions are in accordance with the invention.
B C F G
S ra -dried Granules
LAS 10.0 10.0 15.0 5.0 5.0 10.0
QAS 1.0 1.0
DTPA, HEDP and/or0.3 0.3 0.5 0.3
EDDS
MgS04 0.5 0.5 0.1
Sodium citrate 3.0 5.0
Sodium carbonate10.0 10 15 10 7 10
Sodium sulphate 5.0 5.0 5.0 3.0
Sodium silicate .0
1.6R
eolite A 16.0 18.0 20.0 20.0
SKS-6 3.0 5.0
MA/AA or AA 1.0 .0 11.0 2.0
PEG 4000 .0 1.0 1.0
QEA 1.0 1.0
rightener 0.05 0.05 0.05 0.05
Silicone oil 0.01 0.01 0.01 0.01
A lomerate
LAS 0.2 .2 0.01
C45AS .0 1.0
3 1.0 0.5
Carbonate .0 1.0 1.0 1.0
Sodium citrate 5.0
FAA
Citric acid .0 1.0 1.0
EA 2.0 .0 1.0
SRP 1.0 1.0 0.2
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Zeolite A 15.0 6.0 15.0 16.0
Sodium silicate
PEG .0
Builder A lomerates
SKS-6 6.0 6.0 3.0 7.0 10.0
LAS .0 5.0 5.0 3.0 10.0 12.0
D -add articulate
com onents
Malic 8.0 10.0 .0 8.0 .0
acid/carbonate/bicarbonat
a
(40:20:40)
QEA 0.2 0.5
NACAOBS 3.0 1.5 .5
OBS 3.0 3.0 5.0
AED 2.5 1.5 .5 6.5 1.5
LAS (flake) 10.0 10.0 8.0
S ra -on
Brightener 0.2 0.2 0.3 0.1 0.2 0.1 .6
ye 0.3 0.05 0.1
E7 0.5 0.7
Perfume 0.8 0.5 .5
D -add
Citrate 20.0 .0 5.0 15.0 5.0
Percarbonate 15.0 3.0 6.0 10.0 18.0 5.0
Perborate 6.0 18.0
Photobleach 0.02 0.02 0.02 0.1 0.05 0.3 0.03
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Enzymes (cellulase,1.3 0.3 0.5 0.5 0.8 2.0 0.5 0.16 0.2
amylase, protease,
lipase)
Carbonate 0.0 10.0 5.0 8.0 10.0 5.0
Perfume (encapsulated)O.G 0.5 0.5 0.3 0.5 0.2 0.1 0.6
Suds suppressor 1.0 0.6 0.3 0.10 0.5 1.0 0.3 1.2
Soap 0.5 0.2 0.3 3.0 0.5 0.3
Citric acid 6.0 6.0 5.0
Dyed carbonate 0.5 0.5 1.0 .0 0.5 0.5 0.5 1.0
(blue,
green)
SKS-6 .0 6.0
Fillers 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.
Having thus described the invention in detail, it will be obvious 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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