Note: Descriptions are shown in the official language in which they were submitted.
CA 02225562 1997-12-22
WO 9?160938 PCTlUS96/07814i
1
NONAQUEOUS, PARTICULATE-CONTAINING
LIQUID DETERGENT COMPOSITIONS WITH
ALKYL BENZENE SULFONATE SURFACTANT
FIELD OF THE INVENTION
This invention relates to liquid laundry detergent products which are
nonaqueous
in nature and which are in the form of stable dispersions of particulate
material such as
bleaching agents and/or other detergent composition adjuvants.
BACKGROUND OF TFIE INVENTION
Liquid detergent products are often considered to be more convenient to use
than
are dry powdered or particulate detergent products. Liquid detergents have
therefore
found substantial favor with consumers. Such liquid detergent products are
readily
measurable, speedily dissolved in the wash water, capable of being easily
applied in
concentrated solutions or dispersions to soiled areas on garments to be
laundered and are
non-dusting. They also usually occupy less storage space than granular
products.
Additionally, liquid detergents may have incorporated in their formulations
materials
which could not withstand drying operations without deterioration, which
operations are
often employed in the manufacture of particulate or granular detergent
products.
Although liquid detergents have a number of advantages over granular detergent
products, they also inherently possess several disadvantages. In particular,
detergent
composition components which may be compatible with each other in granular
products
may tend to interact or react with each other in a liquid, and especially in
an aqueous
liquid, environment. Thus such components as enzymes, surfactants, perfunrea,
brighteners, solvents and especially bleaches and bleach activators can be
especially
difficult to incorporate into liquid detergent products which have an
acceptable degree of
chemical stability.
CA 02225562 1997-12-22
WO 97/00938 PCT/C1S96/07814
2
One approach for enhancing the chemical compatibility of detergent composition
components in liquid detergent products has been to formulate nonaqueous (or
anhydrous) liquid detergent compositions. In such nonaqueous products, at
least some
of the normally solid detergent composition components tend to remain
insoluble in the
liquid product and hence are less reactive with each other than if they had
been dissolved
in the liquid matrix. Nonaqueous liquid detergent compositions, including
those which
contain reactive materials such as peroxygen bleaching agents, have been
disclosed far
example, in Hepworth et al., U.S. Patent 4,615,820, Issued October 17, 1986;
Schultz ea
al., U.S. Patent 4,929,380, Issued May 29, 1990; Schultz et al., U.S. Patent
5,008,031,
Issued April 16, 1991; Elder et al., EP-A-030,096, Published June 10, 1981;
Hall et al..,
WO 92/09678, Published June 11, 1992 and Sanderson et al., EP-A-565,017,
Published
October 13, 1993.
Even though chemical compatibility of components may be enhanced in
nonaqueous liquid detergent compositions, physical stability of such
compositions may
become a problem. This is because there is a tendency for such products to
phase
separate as dispersed insoluble solid particulate material drops from
suspension and
settles at the bottom of the container holding the liquid detergent product.
As one
consequence of this type of problem, there can also be difficulties associated
with
incorporating enough of the right types and amounts of surfactant materials
into
nonaqueous liquid detergent products. Surfactant materials must, of course, be
selected
such that they are suitable for imparting acceptable fabric cleaning
perfonnance to such
compositions but utilization of such materials must not lead to an
unacceptable degree of
composition phase separation. Phase stabilizers such as thickeners or
viscosity control
agents can be added to such products to enhance the physical stability
thereof. Such
materials, however, can add cost and bulk to the product without contributing
to th.e
Iaundering/cleaning performance of such detergent compositions.
It is also possible to select surfactant systems for such liquid laundry
detergent
products which can actually impart a structure to the liquid phase of the
product and
thereby promote suspension of particulate components dispersed within such a
structured liquid phase. An example of such a product with a structured
surfactant
system is found in van der Hoeven et al.; U.S. Patent 5,389,284; Issued
February l~l,
1995, which utilizes a structured surfactant system based on relatively high
concentrations of alcohol alkoxylate nonionic surfactants and anionic
defloculatin.g '
agents. In products which employ a structured surfactant system, the stwctured
liquid
phase must be viscous enough to prevent settling and phase separation of the
suspended '
particulate material, but not so viscous that the pourability and
dispensability of the
detergent product is adversely affected.
CA 02225562 2001-05-10
3
Given the foregoing, there is clearly a continuing need to identify and
provide
liquid, particulate-containing detergent compositions in the form of
nonaqueous liquid
products that have a high degree of chemical, e.g., bleach and enzyme,
stability along
with commercially acceptable phase stability, pourability and detergent
composition
laundering, cleaning or bleaching performance. Accordingly, it is an object of
the present
invention to provide nonaqueous, particulate-containing liquid detergent
products which
have such especially desirable chemical and physical stability characteristics
as well as
outstanding pourability and fabric laundering/bleaching performance
characteristics.
SUMMARY OF TAE INVENTION
The present invention provides nonaqueous liquid detergent compositions
comprising a stable suspension of solid, substantially insoluble particulate-
material
dispersed throughout a structured, surfactant-containing liquid phase. Such
compositions comprise A) from about 35% to 99% by weight of the composition of
a
nonaqueous liquid phase; and B) from about 1 % to 65% by weight of the
composition of
one or more types of particulate materials.
The nonaqueous liquid phase itself comprises from about 30% to 65% by weight
of
this liquid phase of a certain type of dissolved anionic surfactant. This
anionic surfactant
component comprises a material selected from the alkali metal salts of C l 0-C
16
alkylbenzene sulfonic acids.
In addition to the anionic surfactant component, the nonaqueous liquid phase
of the
compositions herein also comprises from about 35% to 70% by weight of the
liquid
phase of a nonaqueous liquid diluent. Such a diluent comprises both l) alcohol
alkoxylatea of the formula R1(OCmFi2~OH wherein Rl is a Cg-C16 alkyl group, m
is
from 2 to 4, arid n is from about 2 to 12; and u) a nonaqueous, low-polarity
organic
solvent. These components are present in the nonaqueous liquid diluent in an
alcohol
alkoxylate to organic solvent weight ratio of from about 50:1 to 1:50,
preferably from
about 3:1 to 1:3.
The particulate material suspended in the nonaqueous liquid phase of the
compositions herein ranges in size from about 0.1 to 1500 microns and is
substantially
insoluble in the nonaqueous compositions herein. This insoluble particulate
material
preferably comprises a peroxygen bleaching agent, but may also comprise bleach
activators, ancillary anionic surfactants, inorganic alkalinity sources and
combinations of
these particulate material types.
CA 02225562 2000-04-19
4
DETAILED DESCRIPTION OF THE INVENTION
The nonaqueous liquid detergent compositions of this invention comprise a
surfactant - and
low-polarity solvent-containing liquid phase having dispersed therein as a
solid phase certain types
of particulate materials. The essential and optional components of the liquid
and solid phases of
the detergent compositions herein, as well as composition form, preparation
and use, are described
in greater detail as follows: (All concentrations and ratios are on a weight
basis unless otherwise
specified.)
LIQUID PHASE
The liquid phase will generally comprise from about 35% to 99% by weight of
the
detergent compositions herein. More preferably, the liquid phase will comprise
from about 50% to
95% by weight of the compositions. Most preferably, the liquid phase will
comprise from about
45% to 75% by weight of the compositions herein. The liquid phase of the
detergent compositions
herein essentially contains relatively high concentrations of a certain type
anionic surfactant
combined with a certain type of nonaqueous, liquid diluent.
(A) Essential Anionic Surfactant
The anionic surfactant essentially utilized as an essential component of the
nonaqueous
liquid phase is one selected from the alkali metal salts of alkylbenzene
sulfonic acids in which the
alkyl group contains from about 10 to 16 carbon atoms, in straight chain or
branched chain
configuration. (See U.S. Patents 2,220,099 and 2,477,383.) Especially
preferred are the sodium
and potassium linear straight chain alkylbenzene sulfonates (LAS) in which the
average number of
carbon atoms in the alkyl group is from about 11 to 14. Sodium C1~-C~q LAS is
especially
preferred.
The alkylbenzene sulfonate anionic surfactant will be dissolved in the
nonaqueous liquid
diluent which makes up the second essential component of the nonaqueous phase.
To form the
structured liquid phase required for suitable phase stability and acceptable
rheology, the
alkylbenzene sulfonate anionic surfactant is generally present to the extent
of from about 30% to
65% by weight of the liquid phase. More preferably, the alkylbenzene sulfonate
anionic surfactant
will comprise from about 35% to 50% by weight of the nonaqueous liquid phase
of the
compositions herein. Utilization of this anionic surfactant in these
concentrations corresponds to
an anionic surfactant
CA 02225562 2000-04-19
S
concentration in the total composition of from about 15% to 60% by weight,
more
preferably from about 20% to 40% by weight, of the composition.
(8) Nonaq_ueous Liauid Diluen~
To fonm the liquid phase of the detergent compositions, the hereinbefore
described
alkylbenzene sulfonate anionic surfactant is combined with a nonaqueous liquid
diluent
which contains two essential components. These two components are a liquid
alcohol
alkoxylate material and a nonaqueous, low-polarity organic solvent.
i) Alcohol Alkoxvlates
One essential component of the liquid diluent used to form the compositions
herein comprises an alkoxylated fatty alcohol material. Such materials are
themselves
also nonionic surfactants. Such materials correspond to the general formula:
R 1 (CmH2m0)nOH
wherein Rl is a Cg - 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 component of the liquid diluent 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.
Examples of fatty alcohol alkoxylates useful as one of the essential
components of
the nonaqueous liquid diluent in 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
Neodol 25-7 and Neodol 23-6.5 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; Neodol 23-9, an ethoxylated
primary C 12 -
C 13 alcohol having about 9 moles of ethylene oxide and Neodol 91-10, an
ethoxylated
Cg - C 11 primary alcohol having about 10 moles of ethylene oxide. Alcohol
ethoxylates
of this type have also been marketed by Shell Chemical Comparry under the
Dobanol
trademark . Dobanol 91-5 is an ethoxylated Cg-C 11 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.
CA 02225562 2000-04-19
6
TM
Other examples of suitable ethoxylated alcohols include Tergito) 15-S-7 and
Tergitol 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 C 11 to C 15 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.
The alcohol alkoxylate component which is essentially utilized as part of the
liquid
diluent in the nonaqueous compositions herein will generally be present to the
extent of
from about 1% to 60% of the 4quid phase composition. More preferably, the
alcohol
alkoxylate component will comprise about 5% to 40% of the liquid phase. Most
preferably, the essentially utilized alcohol alkoxylate component will
comprise from
about 5% to 30% of the detergent composition 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.
ii) Nonaauenus I ~,~._polaritv ~~:~ e"h,_...
A second essential component of the liquid diluent which forms part of the
liquid phase of the detergent compositions herein comprises nonaqucous, low-
polarity
organic solvem(s). The teem "solvent" is used herein to connote the non-
surface active
carrier or diluent portion of the liquid phase of the composition. While some
of the
essential and/or optional components of the compositions herein may actually
dissolve in
~ "solvent'-co~aining liquid phase, other components will be present as
particulate
material dispa~sed within the "solvent"-containing liquid phase. Thus the term
"solvent"
is not mgt to require that the solvent material be capable of actually
dissolving all of
the detergent composition components added thereto.
?he nonaqueous organic materials which are employed as solvents herein are
those
which are fiquids of tow 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
should not be utilized. Suitable types of low-polarity solvents useful in the
nonaqueous
CA 02225562 2000-04-19
7
liquid detergent compositions herein do include non-vicinal C4-Cg alkylene
glycols,
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 nonaqueous, low-polarity solvent for use in the
compositions
herein comprises the non-vicinal C4-Cg branched or straight chain alkylene
glycols.
Materials of this type include hexylene glycol (4-methyl-2,4-pentanediol), 1,6-
hexanediol, 1,3-butylene glycol and 1,4-butylene glycol. Hexylene glycol is
the most
preferred.
Another preferred type of nonaqueous, 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 and
dipropylene
glycol monobutyl ether are especially preferred. Compounds of the type have
been
commercially marketed under the trademarks Dowanol, Carbitol, and Cellosolve.
Another preferred type of nonaqueous, 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, nonaqueous solvent comprises lower
molecular weight methyl esters. Such materials are those of the general
formula: R1-
C(O~OCH3 wherein Ri ranges from 1 to about 18. Examples of suitable lower
molecular weight methyl esters include methyl acetate, methyl propionate,
methyl
oetanoate, and methyl dodecanoate.
The nonaqueous, low-polarity organic solvents) 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
will gena~slly be utilized in an amount of from about i% to 70% by weight of
the liquid
phase. More preferably, the nonaqueous, low-polarity organic solvent will
comprise
from about 10% to 60'/o by weight of the liquid phase, most preferably from
about 20%
to 50% by weight, of the liquid phase of the composition. Utilization of this
organic
solvent in these concentrations in the liquid phase corresponds to a solvent
concentration
in th_e total composition of from about 1% to 50% by weight, more preferably
from
about 5% to 40% by weight, and most preferably from about 1 0% to 30% by
weight, of
the composition.
CA 02225562 1997-12-22
PCT/US96/078I4
WO 97/00938
8
iii) Alcohol Alkoxvlate To Solvent Ratio
The ratio of alcohol alkoxylate to organic solvent within the liquid
diluent can be used to vary the rheological properties of the detergent
compositions
eventually formed. Generally, the weight ratio of alcohol alkoxylate to
organic solvent
will range from about 50:1 to 1:50. More preferably, this ratio will range
from about 3:1
to 1:3.
iv) Liquid Diluent Concentration
As with the concentration of the alkylbenzene sulfonate anionic surfactant
mixture, the amount of total liquid diluent in the nonaqueous liquid phase
herein will be
determined by the type and amounts of other composition components and by the
desired
composition properties. Generally, the liquid diluent will comprise from about
35% to
70% of the nonaqueous liquid phase of the compositions herein. More
preferably, the
liquid diluent will comprise from about 50% to 65% of the nonaqueous liquid
phase.
This corresponds to a nonaqueous liquid diluent concentration in the total
composition.
of from about 15% to 70% by weight, more preferably from about 20% to 50% by
weight, of the composition.
SOLID PHASE
The nonaqueous detergent compositions herein also essentially comprise from
about 1% to 65% by weight, more preferably from about 5% to 50% by weight, of
a
solid phase of 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 such material will range in size from about 5 to 200
microns.
The particulate material utilized herein can comprise one or more types of
detergent composition components which in particulate form are substantially
insoluble
in the nonaqueous liquid phase of the composition. The types of particulate
materials
which can be utilized are described in detail as follows:
(A) Peroxv~en Bleachinr~ Aeent With Optional Bleach Activators
The most preferred type of particulate material useful for forming the solid
phase of
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.
CA 02225562 2000-04-19
9
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 metachloro perbenzoic
acid, 4-
nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such
bleaching
agents are disclosed in U.S. Patent 4,483,781, Hartman, Issued November 20,
1984;
European Patent Application EP-A-133,354, Hanks 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 (NAppA) 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 prefer
ed. 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 paoxylhydrate, 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, Solway 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/bieaching) 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 nonanoyloxybenzate sulfonate (HOBS) 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.
Other useful amido-derived bleach activators are those of the formulae:
R1N(RS)C(O)R2C(O)L or R1C(O)N(RS)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms,
R2 is an
alkylene containing from 1 to about 6 carbon atoms, RS is H or alkyl, aryl, or
alkaryl
containing from about 1 to about 10 carbon atoms, and L is any suitable
leaving group.
CA 02225562 2000-04-19
A leaving group is any group that is displaced from the bleach activator as a
consequence
of the nucleophilic attack on the bleach activator by the perhydrolysis anion.
A preferred
leaving group is phenol sulfonate.
Preferred examples of bleach activators of the above formulae include (6-
octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)
oxybenzenesulfonate,
(6-decanamido-caproyl)oxybenzenesulfonate and mixtures thereof as described in
the
hereinbefore referenced U.S. Patent 4,634,551. Such mixtures are characterized
herein
as (6-Cg-C10 alkanudo-caproyl)oxybenzenesulfonate.
Another class of useful bleach activators comprises the benzoxazin-type
activators
disclosed by Hodge et al. in U.S. Patent 4,966, 723, Issued October 30, 1990.
A highly preferred activator of the benzoxazin-type is:
O
I
~O
yC
N
Still another class of useful bleach activators includes the acyl lactam
activators,
especially acyl caprolactams and aryl valerolactams of the formulae:
O C CH2-~CH2 O O-~CH~-CH
R6~-N \ Rs ~ I I _
H --C-N
2
~CH2--CH2~ ~CH2--CH2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing
from 1 to about
12 carbon atoms. Highly preferred lactam activators include benzoyl
caprolactam,
octanoyl caprolactam, 3,5,5-trimethyihexanoyl caprolactam, nonanoyl
caprolactam,
decanoyl caprolactatn, undecenoyl caprolactam, benzoyl valerolactam, octanoyl
valerolaaam, daanoyl valerolactant, undecenoyl valerolactam, 3,5,5-
trimethylhexanoyl
vaterolactam utd mixtures thereof. See also U.S. Patent 4,545,784, Issued to
Sanderson, October 8, 1985, which discloses acyl ~pro~]uding benzoyl
caprolactarn, adsorbed into sodium perborate.
If peroxygen bleaching agents are used as all or part of the essentially
present
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 3% to 15% by weight of the composition.
If
utilized, bleach activators can comprise from about 0.5% to 20%, more
preferably from
about 1% to 10%, by weight of the composition. Frequently, activators are
employed
CA 02225562 1997-12-22
WO 97/00938 PCT/US96/078141
11
such that the molar ratio of bleaching agent to activator ranges from about
1:1 to 1U:1,
more preferably from about 1.5:1 to 5:1.
In addition, it has been found that bleach activators, when agglomerated with
certain
' acids such as citric acid, are more chemically stable.
(B) Ancillary Anionic Surfactants
Another possible type of particulate material which can be suspended in the
nonaqueous liquid detergent compositions herein includes ancillary anionic
surfactants
which are fully or partially insoluble in the nonaqueous liquid phase. The
most common
type of anionic surfactant with such solubility properties comprises primary
or secondary
alkyl sulfate anionic surfactants. Such surfactants are those produced by the
sulfation of
higher Cg-C2p fatty alcohols.
Conventional primary alkyl sulfate surfactants have the general formula
ROS03-M+
wherein R is typically a linear Cg - C2p hydrocarbyl group, which may be
straight chain
or branched chain, and M is a water-solubilizing cation. Preferably R is a C
10 - C'.14
alkyl, and M is alkali metal. Most preferably R is about C 12 and M is sodium.
Conventional secondary alkyl sulfates may also be utilized as the essential
anionic
surfactant component of the solid phase of the compositions herein.
Conventional
secondary alkyl sulfate surfactants are those materials which have the sulfate
moiety
distributed randomly along the hydrocarbyl "backbone" of the molecule. Such
materials
may be depicted by the structure:
CH3(CH2)n(CHOS03'M+) (CH2)mCH3
wherein m and n are integers of 2 or greater and the sum of m + n is typically
about 9 to
15, and M is a water-solubilizing cation.
If utilized as all or part of the requisite particulate material, ancillary
aniooc
surfactants such as alkyl sulfates will generally comprise from about 1% to
10% by
weight of the composition, more preferably from about 1% to 5% by weight of
the
composition. Alkyl sulfate used as all or part of the particulate material is
prepared and
added to the compositions herein separately from the unalkoxylated alkyl
sulfate material
which may form part of the alkyl ether sulfate surfactant component
essentially utilized
as part of the liquid phase herein.
(C) Orstanic Builder Material
Another possible type of particulate material which can be suspended in the
nonaqueous liquid detergent compositions herein comprises an organic detergent
builder
material which serves to counteract the effects of calcium, or other ion,
water hardness
CA 02225562 2000-04-19
12
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 bequest 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.
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
cart be made by direct sagoni&cation of fats and oils or by the neud~alization
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 requisite 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.
IAlkalinitv ources
Another possible type of particulate material which can be suspended in the
nonadueous 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
~°~~ b~~nates. borates, silicates and metasilicatcs. 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.
CA 02225562 1997-12-22
WO 97!00938 PC'T/US96/07814
13
The alkalinity source, if in the form of a hydratable salt, may also serve as
a
desiccant in the nonaqueous liquid detergent compositions herein. The presence
of aw
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 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
nonaqueous detergent compositions herein. Thus such materials will generally
hoe
dispersed in the nonaqueous liquid phase in the form of discrete particles.
OPTIONAL COMPOSITION COMPONENTS
In addition to the essential composition liquid and solid phase components as
hereinbefore described, the detergent compositions herein can, and preferably
will,
contain various optional components. Such optional components may be in either
liquid
or solid form. The optional components may either dissolve in the liquid phase
or may
be dispersed within the liquid phase in the form of fine particles or
droplets. Some of th.e
materials which may optionally be utilized in the compositions herein are
described in
greater detail as follows:
(a) Optional Surfactants
Besides the essentially utilized alkylbenzene sulfonate surfactant materials
and the
alcohol alkoxylate component of the liquid diluent, the detergent compositions
herein
may, in addition to the optional alkyl sulfates hereinbefore described, also
contain other
types of surfactant materials. Such additional optional surfactants must, of
course, be
compatible with other composition components and must not substantially
adversely
affect composition rhe;ology, stability or performance. Optional surfactants
can be of the
anionic, nonionic, cationic, and/or amphoteric type. If employed, optional
surfactants
will generally comprise from about 1% to 20% by weight of the compositions
herein,
more preferably from about 5% to 10% by weight of the compositions herein.
One common type of anionic surfactant material which may be optionally added
to
the detergent compositions herein 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
CA 02225562 2000-04-19
14
R2-O-(CmH2m0)n-S03M
wherein R2 is a C i0-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 C 12-C 1 g 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 C 12-C 16, m is 2, n is from about 1 to 6, and M is
sodium.
Ammonium, alkylammonium and alkanolammonium counterions are preferably avoided
when the solid phase materials used in the compositions herein include a
peroxygen
bleaching agent.
Another common type of anionic surfactant material which may be optionally
added to the detergent compositions herein comprises carboxylate-type
anionics.
Carboxylate-type avionics include. the C l0-C l g alkyl alkoxy carboxylates
(especially the
EO 1 to 5 ethoxycarboxylates) and the C l p-C 1 g sarcosinates, especially
oleoyl
sarcosinate. Another common type of anionic surfactant material which may be
optionally employed comprises other sulfonated anionic surfactants such as the
Cg-C 1 g
para»n sulfonates and the Cg-C 1 g olefin suifonates.
A preferred type of optional nonionic surfactant comprises surfactants which
are
ethylene oxide (E0) - propylene oxide (PO) block polymers. Materials of this
type are
well known 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 M~lwidsky; Synthetic Detergents. 7th Ed ;
Longman
Scientific and Technical (1987) at pp. 34-36 and pp. 189-19i and in U.S.
Patents
2,674,619 and 2,677,700. These Pluronic type nonionic surfactants are believed
to
function as effective suspending agents for the particulate material which is
dispersed in
the liquid phase of the detergent impositions herein.
Another preferred type of optional nonionic surfactant for use in the
compositions
herein comprises polyhydroxy fatty acid amide surfactants. Materials of this
type of
nonionic stufactant are those which conform to the formula:
O CpHzp+1
R-C-N-Z
wherein R is a Cg-17 alkyl or alkenyl, p is from l to 6, and Z is glycityl
derived from a
reduced sugar or alkoxylated derivative thereof. Such materials include the
C12-C18 N-
methyl glucamides. Examples are N-methyl N-1-deoxyglucityl cocoanude and N-
methyl
CA 02225562 2000-04-19
N-1-deoxyglucityl oleamide. Processes for making polyhydroxy fatty acid,
amides are known 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.
(b) Optional Inorganic Deter~yent 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.
(c) Optional Enzymes
The detergent compositions herein may also optionally contain one or more
types of
detergent enzymes. Such enzymes can include proteases, amylases, cellulases
and lipases. Such
materials are known in the art and are commercially available. They may be
incorporated into the
nonaqueous liquid detergent compositions herein in the form of suspensions,
"marumes" or
"prills". Another suitable type of enzyme comprises those in the form of
slurries of enzymes in
nonionic surfactants, e.g., the enzymes marketed by Novo Nordisk under the
trademark "SL" or
the microencapsulated enzymes marketed by Novo Nordisk under the trademark
"LDP".
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
nonaqueous 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 terms 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.
CA 02225562 1997-12-22
WO 97/00938 PCT/US96/07814
16
If employed, enzymes will normally be incorporated into the nonaqueous liquid
compositions herein at levels sufficient to provide up to about 10 mg by
weight, more
typically from about 0.01 mg to about 5 mg, of active enzyme per gram of the -
composition. Stated otherwise, the nonaqueous liquid detergent compositions
herein
will typically comprise from about 0.001% to 5%, preferably from about 0.01%
to 1°/~ .
by weight, of a commercial enzyme preparation. Protease enzymes, for example,
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.
(d) Optional Chelating_Ag_ents
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
nonaqueous
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 nuxtures thereof.
Amino carboxylates useful as optional chelating agents include:
ethylenediaminetetraacetates, N-hydroxyethyl-ethylenediaminetriacetates,
nitrilotriacetates, ethylene-diamine tetrapropionates,
triethylenetetraaminehexacetates,
diethylenetr-iaminepentaacetates, ethylenediaminedisucci-nates and
ethanoldiglycines.
The alkali metal salts of these materials are preferred.
Anuno 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 compositions, and include ethylenedianunetetrakis (methylene-
phosphonates) as DEQLJEST. 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 (I~DP),
diethylene triamine penta acetic acid (DTPA), ethylenediamine disuccinic acid
(EDDS)
and dipicolinic acid (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 frown
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.
CA 02225562 1997-12-22
WO 97/00938 PCT/US96/07814
17
(e) Optional Thickening. Viscosity Control and/or
Dispersing A ents
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
polyvnylpyrrolidone
(PVP).
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, malefic acid (or malefic 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 10,000, 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.
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% lby
weight. More preferably, such materials can comprise from about 0.5% to 2% by
weight
of the detergents compositions herein.
(~ Optional 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 tlhe
nonaqueous liquid phase of the detergent compositions herein. One such liquid
bleach
activator is acetyl triethyl citrate (ATC). Other examples include glycerol
triacetate and
CA 02225562 1997-12-22
WO 97/00938 PCTlUS96/07814
18
nonanoyl valerolactam. Liquid bleach activators can be dissolved in the
nonaqueous
liquid phase of the compositions herein.
(g) Optional Brighteners. Suds Suppressors. Dves and/or Perfumes
The detergent compositions herein may also optionally contain conventions;l
brighteners, suds suppressors, silicone oils, bleach catalysts, dyes and/or
perfume
materials. Such brighteners, suds suppressors, silicone oils, bleach
catalysts, dyes and
perfumes must, of course, be compatible and non-reactive with the other
composition
components in a nonaqueous environment. If present, brighteners suds
suppressors, dyes
and/or perfumes will typically comprise from about 0.0001% to 2% by weight of
the
compositions herein. Suitable bleach catalysts include the manganese based
complexes
disclosed in US 5,246,621, US 5,244,594, US 5,114,606 and US 5,114,611.
COMPOSITION FORM
As indicated, the nonaqueous liquid detergent compositions herein are in the
fornn
of bleaching agent and/or other materials in particulate form as a solid phase
suspended
in and dispersed throughout a nonaqueous liquid phase. Generally, the
nonaqueous liquid
phase will comprise from about 35% to 99%, more preferably from about 50% to
95°/.,
by weight of the composition with the dispersed solid phase comprising from
about 1°io
to 65%, more preferably from about 5% to 50%, by weight of the composition.
The particulate-containing liquid detergent compositions of this invention ane
substantially nonaqueous (or anhydrous) in character. While very smalll
amounts of
water may be incorporated into such compositions as an impurity in the
essential or
optional components, the amount of water should in no event exceed about S%
b;y
weight of the compositions herein. More preferably, water content of the
nonaqueous
detergent compositions herein will comprise less than about 1% by weight.
The particulate-containing nonaqueous 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 5,000 cps, more preferably from about 500 to 3,000 cps. For
purposes of
this invention, viscosity is measured with a Brookfield Viscometer using a 1ZV
#5 spindle
at 50 rpm.
CA 02225562 1997-12-22
WO 97/00938 PCT/US96/078I4
19
COMPOSITION PREPARATION AND USE
The nonaqueous liquid detergent compositions herein can be prepared by
' combining the essential and optional components thereof in any convenient
order and by
mixing, e.g., agitating, the resulting component combination to form the phase
stable
' compositions herein. In a typical process for preparing such compositions,
essential and
certain preferred optional components will be combined in a particular order
and under
certain conditions.
In the first step of such a typical preparation process, an admixture of the
alkylbenzene sulfonate anionic surfactant and the two essential components of
the
nonaqueous diluent is formed by heating a combination of these materials to a
temperature from about 30°C to 100°C.
In a second process step, the heated admixture formed as hereinbefore
described is
maintained under shear agitation at a temperature from about 40°C to
100°C for a period
of from about 2 minutes to ZO hours. Optionally, a vaccuum can be applied to
the
admixture at this point. This second process step serves to completely
dissolve the
anionic surfactant in the nonaqueous liquid phase.
In a third process step, this liquid phase combination of materials is cooled
to a
temperature of from about 0°C to 35°C. This cooling step serves
to fonm a structured,
surfactant-containing liquid base into which the particulate material of the
detergent
compositions herein can be added and dispersed.
Particulate material is added in a fourth process step by combining the
particulate
material with the liquid base which is maintained under conditions of shear
agitation.
When more than one type of particulate material is to be added, it is
preferred that a
certaun order of addition be observed. For example, while shear agitation is
maintained,
essentially all of any optional surfactants in solid particulate form can be
added in tlhe
form of particles ranging in size from about 0.2 to 1,000 microns. After
addition of any
optional surfactant particles, particles of substantially all of an organic
builder, e.g.,
citrate and/or fatty acid, and/or an alkalinity source, e.g., sodium
carbonate, can be
added while continuing to maintain this admixture of composition components
under
shear agitation. Other solid form optional ingredients can then be added to
the
composition at this point. Agitation of the mixture is continued, and if
necessary, can he
increased at this point to form a uniform dispersion of insoluble solid phase
particulat~es
within the liquid phase.
After some or all of the foregoing solid materials have been added to this
agitated
mixture, the particles of the highly preferred peroxygen bleaching agent can
be added to
the composition, again while the mixture is maintained under shear agitation.
By adding
CA 02225562 1997-12-22
WO 97/00938 PC:T/US96l078i4
the peroxygen bleaching agent material last, or after all or most of the other
components,
and especially after alkalinity source particles, have been added, desirable
stability
benefits for the peroxygen bleach can be realized. If enzyme prills are
incorporated, they .,
are preferably added to the nonaqueous liquid matrix last.
As a final process step, after addition of all of the particulate material,
agitation of
the mixture is continued for a period of time sufficient to form compositions
having the
requisite viscosity and phase stability characteristics. Frequently this will
involve
agitation for a period of from about 1 to 30 minutes.
As a variation of the composition preparation procedure hereinbefore
described,
one or more of the solid components may be added to the agitated mixture as a
slurry of
particles premixed with a minor portion of one or more of the liquid
components. Thus
a premix of a small fraction of the alcohol alkoxylate and/or nonaqueous, low-
polarity
solvent with particles of the organic builder material and/or the particles of
the inorganic
alkalinity source and/or particles of a bleach activator may be separately
formed and
added as a slurry to the agitated mixture of composition components. Addition
of such
slurry premixes should precede addition of peroxygen bleaching agent and/or
enzymie
particles which may themselves be part of a premix slurry formed in analogous
fashion.
The compositions of this invention, prepared as hereinbefore described, can be
used
to form aqueous washing solutions for use in the laundering and bleaching of
fabrics.
Generally, an effective amount of such compositions is added to water,
preferably in a
conventional fabric laundering automatic washing machine, to form such aqueous
laundering/bleaching solutions. The aqueous washing/bleaching solution so
formed is
then contacted, preferably under agitation, with the fabrics to be laundered
and bleached
therewith.
An effective amount of the liquid detergent compositions herein added to water
to
form aqueous laundering/bleaching solutions can comprise amounts suflncient to
form
from about 500 to 7,000 ppm of composition in aqueous solution. More
preferably,
from about 800 to 3,000 ppm of the detergent compositions herein will be
provided in
aqueous washing/bleaching solution.
CA 02225562 1997-12-22
WO 97/00938 PCT/US96/07814
21
EXAMPLE
The following example illustrates the compositions of the present invention,
but are
'' not necessarily meant to limit or otherwise define the scope of the
invention herein.
A bleach-containing nonaqueous liquid laundry detergent is prepared having
f.he
composition as set forth in Table I.
Table I
Component Wt.
~,icLuid Phase
Na C 12 Linear allcylbenzene sulfonate (LAS) 27.3
C12-14~ EO=5 alcohol ethoxylate 13.6
Hexylene glycol 27.3
Perfume 0.4
ii s
Protease enzyme 0.4
Na3 Citrate, anhydrous 4.3
Sodium perborate 3.4
Sodium nonanoyloxybenzene sulfonate 8.0
(HOBS)
Sodium carbonate 13.9
Diethyl triamine pentaacetic acid 0.9
(DTPA)
Brightener 0.4
Suds Suppressor 0.1
Minors 0-44
100%
Such a composition is prepared by mixing the LAS, hexylene glycol and alcohol
ethoxylate together at 54°C (130°F) for 1/2 hour. This mixture
is then cooled to 29°C
(85°F) whereupon the remaining components are added. The resulting
composition is
then stirred at 29°C (85°F) for another 1/2 hour.
The resulting composition is a stable anhydrous heavy duty liquid laundry
detergent
which provides excellent stain and soil removal performance when used in
normal fabric
laundering operations.
