Note: Descriptions are shown in the official language in which they were submitted.
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1
CATIONIC PARTICLE AND
A PROCESS FOR MAKING THEREOF
10
FIELD
The present invention relates to a cationic surfactant particle, particulate
detergent compositions containing such cationic particle, and a process for
making thereof.
BACKGROUND
Recently, there has been considerable interest within the detergent
industry for laundry detergents which are "compact" and therefore, have low
dosage volumes. To facilitate production of these so-called low dosage
detergents, many attempts have been made to produce high bulk density
2o detergents, for example with a density of 600 g/I or higher. The low dosage
detergents are currently in high demand as they conserve resources and can be
sold in small packages which are more convenient for consumers. However, the
extent to which modern detergent products need to be "compact" in nature
remains unsettled. In fact, many consumers, especially in developing
countries,
2s continue to prefer a higher dosage levels in their respective laundering
operations. Consequently, there is a need in the art of producing modern
detergent compositions for flexibility in the ultimate density of the final
composition.
Currently, the relative amounts and types of materials subjected to
3o processes in the production of detergent granules has been limited. For
example, it has been difficult to attain high levels of surfactant in the
resulting
detergent composition, a feature which facilitates production of detergents in
a
more efficient manner. Cationic surfactants are a common surfactant as well as
co-surfactant for use in detergent compositions and is commonly available in a
35 liquid form. In general, detergent compositions will contain one or more
types of
~
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surfactants which are designed to loosen and remove different types of soils
and stains.
Based on the foregoing, there is a need for a cationic surfactant
material which is in a form that is easily incorporated into particulate
detergent
compositions. None of the existing art provides all of the advantages and
benefits of the present invention.
SUMMARY
The present invention relates to a cationic particle containing an
aqueous cationic surfactant solution adsorbed to a water-insoluble high
absorbing material. A process for making the cationic particle is also
described
herein. These and other features, aspects, and advantages of the present
invention will become evident to those skilled in the art from a reading of
the
present disclosure.
In one particular embodiment there is provided a cationic particle,
comprising an aqueous cationic surfactant solution adsorbed to a water
insoluble high absorbing material, wherein the high absorbing material is
precipitated silica or amorphous silica or both having an oil absorption,
using
di-butyl phthalate, of from about 140 mU100g to about 400 mU100g and
wherein the cationic particle has at least about 30% to about 65% by weight
cationic active.
DETAILED DESCRIPTION
While this specification concludes with claims distinctly pointing out and
particularly claiming that which is regarded as the invention, it is believed
that
the invention can be better understood through a careful reading of the
following detailed description of the invention. In this specification, all
percentages, ratios, and proportions are by weight, all temperatures are
expressed in degrees Celsius, molecular weights are in weight average, and
the decimal is represented by the point (.), unless otherwise indicated.
As used herein, "comprising" means that other steps and other
ingredients which do not affect the end result can be added. This term
encompasses the terms "consisting of" and "consisting essentially of".
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2a
The present invention relates to a cationic particle containing an
aqueous cationic surfactant solution adsorbed to a water-insoluble high
absorbing material. It is beneficial to have the cationic surfactant in a
particulate form for various reasons, since cationic surfactants are commonly
available in liquid solution form. For example, in processing particulate
detergent compositions in non-tower processes, the liquid cationic surfactant
may make the mixture during agglomeration sticky due to the excess moisture.
In addition, the cationic particle can be made a higher active particle, as
compared to its liquid form,
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which provides formula space when formulating a particulate detergent
composition. In addition, the cationic particle of the present invention has
good
dispersion and solubility when used in the wash water.
The present invention also meets the aforementioned needs in the art by
s providing a cationic particle which can be used to produce a particulate
detergent composition for flexibility in the ultimate density of the final
composition.
As used herein, the term "mean residence time" refers to following
definition: "mean residence time (hr) = mass (kg) / flow throughput (kg/hr)".
to Cationic surfactant solution
The cationic particle of the present invention contains an aqueous cationic
surfactant solution. The cationic surfactant solution has at least about 70%
water, preferably from about 40% to about 60%, more preferably from about 50%
to about 60%, by weight of the surfactant solution. The amount of cationic
active
15 in the aqueous cationic surfactant solution is at least about 30%,
preferably from
about 40% to 60%, more preferably from about 40% to 50%.
Preferably the cationic surfactant is selected from the group consisting of
cationic ester surfactants, cationic mono-alkoxylated amine surfactants,
cationic
bis-alkoxylated amine surfactants and mixtures thereof. Preferred quaternary
2o ammonium surfactants are selected from mono C1-C30, preferably Cg-C1g N-
alkyl or alkenyl ammonium surfactants wherein remaining N positions are
substituted by methyl, hydroxyethyl or hydroxypropyl groups.
Useful cationic surfactants include water-soluble quaternary ammonium
compounds of the form R4R5R6R,N+X -, wherein R4 is alkyl having from 10 to 20,
25 preferably from 12-18 carbon atoms, and R5, R6 , and R, are each C, to C,
alkyl
preferably methyl; X- is an anion, e.g. chloride. Examples of such trimethyl
ammonium compounds include C,2_14 alkyl trimethyl ammonium chloride and
cocoalkyl trimethyl ammonium methosulfate.
Cationic surfactants also useful is a cationic choline ester-type quat
3o surfactant which are preferably water dispersible compounds having
surfactant
properties and comprise at least one ester (i.e. -COO-) linkage and at least
one
cationically charged group. Suitable cationic ester surfactants, including
choline
ester surfactants, have for example been disclosed in U.S. Patents Nos.
4,228,042, 4,239,660 and 4,260,529.
35 Preferred cationic ester surfactants are those having the formula:
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RS R2
RUO~(C~nO~b~ a ~u (CH2)m (~~ (CH2)t N ~ R3 M
wherein R1 is a C5-C31 linear or branched alkyl, alkenyl or alkaryl chain or M-
s .N+(RgR7Rg)(CH2)s; X and Y, independently, are selected from the group
consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO
wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO
group; R2, R3, R4, Rg, R7 and Rg are independently selected from the group
consisting of alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl and alkaryl groups
Io having from 1 to 4 carbon atoms; and R5 is independently H or a C1-C3 alkyl
group; wherein the values of m, n, s and t independently lie in the range of
from 0
to 8, the value of b lies in the range from 0 to 20, and the values of a, a
and v
independently are either 0 or 1 with the proviso that at least one of a or v
must be
1; and wherein M is a counter anion.
1s Preferably R2, R3 and R4 are independently selected from CH3 and -
CH2CH20H.
Preferably M is selected from the group consisting of halide, methyl
sulfate, sulfate, and nitrate, more preferably methyl sulfate, chloride,
bromide or
iodide.
2o Preferred water dispersible cationic ester surfactants are the choline
esters having the formula:
O CH3
R1COCH2CH2N ~ CH3 M
CH3
2s wherein R1 is a C11-C1g linear or branched alkyl chain.
Particularly preferred choline esters of this type include the stearoyl
choline ester quaternary methylammonium halides (R1=C17 alkyl), palmitoyl
choline ester quaternary methylammonium halides (R1=C15 alkyl), myristoyl
choline ester quaternary methylammonium halides (R1=C1g alkyl), lauroyl
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choline ester quaternary methylammonium halides (R1=C11 alkyl), cocoyl
choline ester quaternary methylammonium halides (R1=C11-C13 alkyl), tallowyl
choline ester quaternary methylammonium halides (R1=C15-C17 alkyl), and any
mixtures thereof.
s The particularly preferred choline esters, given above, may be prepared
by the direct esterification of a fatty acid of the desired chain length with
dimethylaminoethanol, in the presence of an acid catalyst. The reaction
product
is then quaternized with a methyl halide, preferably in the presence of a
solvent
such as ethanol, propylene glycol or preferably a fatty alcohol ethoxylate
such as
io C10-C1g fatty alcohol ethoxylate having a degree of ethoxylation of from 3
to 50
ethoxy groups per mole forming the desired cationic material. They may also be
prepared by the direct esterification of a long chain fatty acid of the
desired chain
length together with 2-haloethanol, in the presence of an acid catalyst
material.
The reaction product is then quaternized with trimethylamine, forming the
desired
is cationic material.
Other suitable cationic ester surfactants have the structural formulas
below, wherein d may be from 0 to 20.
H3
O O
R10C(CH2)dCOCH2CH2N-CH3 M
CH3
~H3
CH3 O O
M CH3-N CH2CH20C(CH2)dCOCH2CH2N-CH3 M
CH3 CH3
In a preferred aspect these cationic ester surfactant are hydrolysable under
the
conditions of a laundry wash method.
2s Cationic surfactants useful herein also include alkoxylated quaternary
ammonium (AQA) surfactant compounds (referred to hereinafter as "AQA
compounds") having the formula:
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R1 /ApR3
I ~N+ X -
wherein R1 is a linear or branched alkyl or alkenyl moiety containing from
about
8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most
s preferably from about 10 to about 14 carbon atoms; R2 is an alkyl group
containing from one to three carbon atoms, preferably methyl; R3 and R4 can
vary independently and are selected from hydrogen (preferred), methyl and
ethyl;
X- is an anion such as chloride, bromide, methylsulfate, sulfate, or the like,
sufficient to provide electrical neutrality. A and A' can vary independently
and
1o are each selected from C1-C4 alkoxy, especially ethoxy (i.e., -CH2CH20-),
propoxy, butoxy and mixed ethoxy/propoxy; p is from 0 to about 30, preferably
1
to about 4 and q is from 0 to about 30, preferably 1 to about 4, and most
preferably to about 4; preferably both p and q are 1. See also: EP 2,084,
published May 30, 1979, by The Procter & Gamble Company, which describes
1s cationic surfactants of this type which are also useful herein..
AQA compounds wherein the hydrocarbyl substituent R1 is Cg-C11,
especially C10, enhance the rate of dissolution of laundry granules,
especially
under cold water conditions, as compared with the higher chain length
materials.
Accordingly, the Cg-C11 AQA surfactants may be preferred by some formulators.
2o The levels of the AQA surfactants used to prepare finished laundry
detergent
compositions can range from about 0.1 % to about 5%, typically from about
0.45% to about 2.5%, by weight.
According to the foregoing, the following are nonlimiting, specific
illustrations of AQA surfactants used herein. It is to be understood that the
2s degree of alkoxylation noted herein for the AQA surfactants is reported as
an
average, following common practice for conventional ethoxylated nonionic
surfactants. This is because the ethoxylation reactions typically yield
mixtures of
materials with differing degrees of ethoxylation. Thus, it is not uncommon to
report total EO values other than as whole numbers, e.g., "E02.5", "E03.5",
and
3o the like.
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Designation R1 R2 A~R3 A'aR4
AQA-1 C12-C14 CH3 E O EO
(also referred
to as
Coco Methyl E02)
AQA-2 C12-C1g CH3 (EO)2 EO
AQA-3 C12-C14 CH3 (EO)2 (EO)2
(Coco Methyl E04)
AQA-4 C12 CH3 EO EO
to
AQA-5 C12-C14 CH3 (EO)2 (EO)3
AQA-6 C12-C14 CH3 (EO)2 (EO)3
AQA-7 Cg-C1g CH3 (EO)3 (EO)2
AQA-8 C12-C14 CH3 (EO)4 (EO)4
AQA-9 C12-C14 C2H5 (EO)3 (EO)3
AQA-10 C12-C18 C3H7 (EO)3 (EO)4
AQA-11 C12-C1g CH3 (propoxy) (EO)3
2s AQA-12 C10-C1 g C2H5 (iso-propoxy)2
(EO)3
AQA-13 C10-C1g CH3 (EO/PO)2 (EO)3
AQA-14 Cg-C1g CH3 (EO)15* (EO)15*
AQA-15 C1p CH3 EO EO
AQA-16 Cg-C12 CH3 EO EO
AQA-17 Cg-C11 CH3 - EO 3.5 Avg.
-
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AQA-18 C12 CH3 - EO 3.5 -
Avg.
AQA-19 CS-C14 ~H3 {EO)10 {EO)10
s
AQA-20 C10 C2H5 {EO)2 {EO)3
AQA-21 C12-C14 C2H5 {EO)5 {EO)3
to AQA-22 C12-C1g C3H7 Bu {EO)2
AQA-23 C8-C10 CH3 CH3 CH2 CH20H
*Ethoxy, optionally end-capped with methyl or ethyl.
The preferred bis-ethoxylated cationic surfactants herein are available
~s under the trade mark ETHOQUAD from Akzo Nobel Chemicals Company.
Highly preferred bis-AQA compounds for use herein are of the formula
R\ +/CHZCH20H
N X
CH / \CH2CH20H
3
wherein R1 is C1p-C1g hydrocarbyl and mixtures thereof, preferably C10, C12
C14 alkyl and mixtures thereof, and X is any convenient anion to provide
charge
2o balance, preferably chloride. With reference to the general AQA structure
noted
above, since in a preferred compound R1 is derived from coconut (C12-C14
alkyl) fraction fatty acids, R2 is methyl and ApR3 and A'qR4 are each
monoethoxy, this preferred type of compound is referred to herein as
"CocoMeE02" or "AQA-1" in the above list.
25 Other preferred AQA compounds herein include compounds of the
formula:
R~ ~(CH2CH20)pH
N+ X
RZ~ ~(CH2CH20)qH
wherein R1 is C1p-C1g hydrocarbyl, preferably C10-C14 alkyl, independently p
is
1 to about 3 and q is 1 to about 3, R2 is C1-C3 alkyl, preferably methyl, and
X is
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an anion, especially chloride.
Other compounds of the foregoing type include those wherein the ethoxy
(CH2CH20) units (EO) are replaced by butoxy (Bu), isopropoxy [CH(CH3)CH20]
and [CH2CH(CH30] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO
and/or
s Pr and/or i-Pr units.
Additional cationic surfactants are described, for example, in the
"Surfactant Science Series, Volume 4, Cationic Surfactants" or in the
"Industrial
Surfactants Handbook". Classes of useful cationic surfactants described in
TM TM
these references include amide quMts (i.e., Lexquat AMG & Schercoquat C MS),
io gtycidyl ether quats (i.e., Cyostat 609), hydroxyalkyl quats (i.e.,
Dehyquart E),
TM TM
alkoxypropyl quats (i.e., Tomah Q-17-2), polypropoxy quats (Emcol CC-9),
cyclic
alkylammonium compounds (i.e., pyridinium or imidazolinium quats), and/or
benzalkonium quats.
High absorbin4 material
1s The cationic particle of the present invention also contains a water-
insoluble high absorbing material. The water-insoluble high absorbing material
is
a material having an oil absorption (using di-butyl phthalate) of preferably
from
about 140 mU100g to about 400 mU100g, even more preferably from about 200
mU100g to about 300 mU100g.
2o Preferably, the high absorbing material is selected from the group
consisting of aluminosilicate, precipitated silica, amorphous silica, talc,
and
mixtures thereof.
Especially preferred are sodium aluminosilicates and amorphous
precipitated silica. An example of an amorphous precipitated silica is a
porous
2s hydrophyllic silica (trademark SIPERNAT 22S) available by DeGussa. Another
example of a precipitated silica is a white carbon, such as calcium silicate
synthetic amorphous silica, (trademark Carplex) available by Shionogi and
Company ftd.
In a preferred cationic particle, the ratio of the high absorbing material to
3o the cationic surfactant active when forming the particle is from about 1:3
to about
1:1, even more preferably from about 1:2 to about 1:1. Absorption here means
that the high absorbing material is coated with the cationic surfactant
solution,
and/or that the high absorbing material is impregnated with the cationic
surfactant solution.
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The finished cationic particle preferably has a mean particle size of
greater than about 100 microns, and more preferably from about 100 microns to
about 1000 microns, even more preferably from about 150 microns to about 650
microns.
s A preferred finished cationic particle has the following composition, by
weight percent of the cationic particle: cationic surfactant active from about
30%
to about 65%; moisture content of from about 3% to about 15%; and the
balance, the high absorbing material. Optionally filler and anionic surfactant
may
be included.
to One embodiment for the cationic particle contain in addition, some anionic
surfactant. If included, the ratio of anionic surfactant active to cationic
surfactant
active is from about 1:10 to about 1:30, preferably from about 1:15 to about
1:25.
By weight percentage of the finished cationic particle, the content of anionic
surfactant is preferably from about 1 % to about 5%. Of course, the anionic
surfactant may in addition be included as an additional cleaning component for
the final detergent composition. Although not wanting to be limited by theory,
it
is believed that the addition of small quantities of anionic surfactant in the
cationic particle provides free flow characteristics to the cationic particle
and
provides a less sticky surface on the cationic particle.
2o The cationic particle optionally also contains a filler, such as soda ash,
other silicate, and/or sulfate.
Additional Detergent Composition Components
The cationic particle may be formulated in detergent compositions. Such
detergent compositions herein may optionally comprise other known detergent
2s cleaning components including alkoxylated polycarboxylates, bleaching
compounds, brighteners, chelating agents, clay soil removal / anti-
redeposition
agents, dye transfer inhibiting agents, enzymes, enzyme stabilizing systems,
fabric softeners, polymeric soil release agents, polymeric dispersing agents,
suds suppressors. The detergent composition may also comprise other
3o ingredients including carriers, hydrotropes, processing aids, dyes or
pigments.
The preferred detergent compositions have a wide range of density, e.g., from
about 300 g/I to about 1000 g/I, especially for high dense detergent
agglomerates e.g., from about 600 g/I to about 850 g/I.
The cationic particle can be used to formulate detergent compositions. In
3s such detergent compositions, the amount of cationic particle, by weight of
the
~
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1~
final detergent composition is preferably from about 0.5% to about 30%, more
preferably from about 0.5% to about 10%.
P
Preferred examples of the process of making the cationic particle of the
s present invention is described below. In one method of making the cationic
particle via a spray drying process, the cationic surfactant solution, high
absorbing material, and optionally anionic surfactant and a filler, are mixed
and
agitated to form a substantially homogenous mixture. The mixture is then
sprayed into a tower, wherein cationic particles are formed. In another method
of
making the cationic particle via an agglomeration process, the cationic
surfactant
solution is added to the high absorbing material and agitated in a mixer to
form a
moist granular powder, or agglomerate. The powder is then dried, such as in a
fluid bed dryer, to form the finished cationic particle.
EXAMPLES
~5 The following examples further describe and demonstrate embodiments
within the scope of the present invention. The examples are given solely for
the
purpose of illustration and are not to be construed as limitations of the
present
invention, as many variations thereof are possible without departing from the
spirit and scope of the invention.
2o In one embodiment, cationic surtactant solution (30-70% active),
amorphous precipitated silica, optionally sodium carbonate, optionally sodium
linear alkyl benzene sulfonate and water, are mixed in a crutcher tank mix.
The
mixture is then fed into the spray tower and cationic particles having about
150
microns are formed. The spray tower's drying temperature is about 160°C
to
25 170°C.
In another embodiment, 100 kg/hr of amorphous precipitated silica is fed
into a mixer, such as a Loedige KM mixer, and 250 kg/hr of cationic surfactant
solution is added to the mixer at one or more points while mixing takes place.
The calculated mean residence time in the mixer of the silica is about 1-10
3o minutes. The moist granules from the mixer are then fed to a fluid bed
dryer,
where the moisture is removed by warm air at about 100°C to
150°C, preferably
about 115°C to 130°C. The resultant cationic particles have a
mean particle size
of about 100 to 1000 microns, preferably 350 to 650 microns. The finished
agglomerate particle is free-flowing without the need for additional
ingredients.
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The following examples show cationic particle compositions of the present
invention
Example Ex.1 Ex.2 Ex.3 Ex.4 Ex.5
Cationic surfactant 50 50 50 - -
A (%)
Cationic surfactant - - - 50 50
B (%)
SIPERNAT 22S (%) 35 - 35 40 35
Carplex 80D (%) - 40 - - -
NaLAS (%) 2 - - - 2
Soda Ash (%) 8 5 10 - 8
Water (%) 5 5 5 10 5
Cationic surfactant A = C12-14 Dimethyl Hydroxyethyl Ammonium
Chloride Solution
Cationic surfactant B = C8-10 Dimethyl Hydroxyethyl Ammonium
Chloride Solution
It is understood that the examples and embodiments described herein are
for illustrative purposes only and that various modifications or changes in
light
thereof will be suggested to one skilled in the art without departing from its
spirit
to and scope.
