Note: Descriptions are shown in the official language in which they were submitted.
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Structuring Liquid Nonionic Surfactants
Prior to Granulation Process
Background of the Invention
The present invention relates to improving storage
stability and physical properties of granular detergents
which are rich in nonionic surfactant.
It is most useful with nonionic surfactants which are
liquid at ambient temperature, and are therefore mobile.
Without a suitable structurant, the nonionic surfactant
tends to leak from the powder and soak into the cardboard
container which forms an unsightly stain. Although it is
possible to avoid this problem by using lower levels of
WO 94/25553 PCT/US94/04843
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nonionic surfactant in the composition, or by selecting
nonionic surfactants which have a higher solidification
temperature, this limits the flexibility of formulation. '.
The use of nonionic surfactants in granular detergent ,
applications has been widely discussed in the prior art.
The following references describe various processes and
compositions for making granules which comprise nonionic
surfactants.
US 3 868 336, published 25th February, 1975 discloses the
use of a powder premix comprising perborate,
tripolyphosphate, nonionic surfactant and polyvinyl
alcohol. The premix is dry added to other detergent
components.
GB 2 137 221, published 3rd October, 1984 discloses a
nonionic premix which comprises dissolved polyvinyl
pyrrolidone (PVP) and soil release polymer. The premix is
sprayed on to an absorbant detergent carrier particle. The
PVP is used as a stabiliser for the soil release polymer.
EPA 0 215 637, published on 25th March, 1987 discloses the
use of sugars and derivatives as structurants of spray
dried detergent powders. Although nonionic surfactant may
be present in such powders it is incorporated at relatively
low levels (1.5% - 4o in examples 1 to 5). Furthermore the
spray dried powder has a low bulk density (324 - 574 g/1).
EPA 0 513 824, published 19th November, 1992, describes a
process for granulating nonionic detergent and the use of
a surface coating agent having a particle size of less than '
micrometers to give a powder having a high content of
nonionic surfactant (10-600) and a bulk density of 0.6 to '
1.2 g/ml. The use of polymers including polyethylene
glycol, polyvinyl alcohol, polyvinyl pyrrolidone and
carboxymethyl cellulose is disclosed (page 13, lines 17-
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18). However, the benefits of using any of these polymers
to structure or thicken the nonionic surfactant is not
disclosed.
WO 92 6160, published on 16th April, 1992. This application
describes (example 14) a granular detergent composition
prepared by fine dispersion mixing in an Eirich RV02 mixer
of a paste which comprises N-methyl glucose amide and
nonionic surfactant in the presence of sodium carbonate and
zeolite. There is no suggestion to use polymers as
structuring agents.
One aspect of the present invention is a process for making
granular nonionic detergent agglomerates having a bulk
density of at least 650 g/1 and which comprise higher
levels of nonionic surfactant than those of the prior art,
but do not have problems of mobile nonionic surfactants
(i.e. nonionic surfactants with low solidification
temperatures) leaking from the granules and~soaking into
the carton.
This problem is addressed by structuring the liquid
nonionic surfactant before the dispersion and/or
granulation process. This is done by dissolving a
structuring agent which comprises a polymer in the nonionic
surfactant. Preferred structuring agents are polymers,
especially polymers having more than one functional
hydroxyl group, especially polyvinyl alcohols,
polyhydroxyacrylic acid polymers, and polymers such as
polyvinyl pyrxolidone and PVNO. Also useful as components
of the structuring agent are sugars and artificial
sweeteners and their derivatives.
" It is a further aspect of the present invention to provide
a process for incorporating sticky materials into detergent
granules While still maintaining desirable physical
properties including free-flowing particles which have a
~." 4 ~ ~ A 6 ~ 2
good resistance to caking. Sticky materials if present at
or close to the surface of the granules have a negative
effect on flow properties. These materials also tend to gel
upon contact with water which prevents effective dispensing
of the granules from the dispensing drawer of a washing
machine or from a dispensing device which is added to the
wash with soiled load. In this aspect of the present
invention these problems are overcome by using sticky
materials as structuring agents of the nonionic surfactants
thereby improving the surface properties of the granules.
In a further aspect of the invention, high bulk density
granular detergent compositions and components are provided
which comprise nonionic surfactants and structuring agents.
Summary of the Invention
A process for making a granular laundry detergent component
or composition having a bulk density of at least 650 g/l, by
dissolving a structuring agent in a nonionic surfactant,
said structuring agent comprising a polymer, to form a
pumpable premix and finely dispersing said premix with an
effective amount of powder at a given operating temperature
of from about 15°C to 30°C wherein the premix has a
viscosity of from about 380 to about 23,000 mPas when
measured at said operating temperature at a shear rate of
25s-1. Preferred structurants comprise polymers having more
than one functional hydroxyl group, especially polyvinyl
alcohols, polyhydroxyacrylic acid polymers, and polymers
such as polyvinyl pyrrolidone and PVNO, as well as sugars,
artificial sweeteners and their derivatives. The premix is
then processed into a granular detergent by any suitable
process. Fine dispersion mixing, agglomeration, or spraying
the premix onto a granular base product are preferred.
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PCT/US94/04843
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Another aspect of the present invention is components or
compositions comprising nonionic surfactant and structuring
agents.
Detailed Description of the Invention
The process aspect of the present invention comprises two
essential steps. The first process step is the formation of
a nonionic surfactant premix which comprises a structuring
agent. The second process step is the processing of the
surfactant premix into the form of a granular detergent
having the desired physical properties of bulk density,
flow properties and storage characteristics.
The first process step of the invention is the preparation
of a structured nonionic surfactant premix. This premix
comprises two essential components which will be described
in more detail below. These components are the nonionic
surfactant and the structuring agent. In the first process
step the structuring agent is dissolved in the nonionic
surfactant.
The second process step may be based upon any of the
techniques of forming granules which are known to the man
skilled in the art. However, the most preferred granulation
techniques for use in the present invention are fine
dispersion of the structured nonionic surfactant paste in
the presence of powders. One example of such a process is
to pump or spray the surfactant paste into a high shear
mixer. The high shear conditions in the mixer break up the
surfactant paste into small droplets and distribute those
droplets onto and around the powder. The process is often
described as "agglomeration".
Another example of such a process is to spray the
surfactant paste onto a powder under low shear conditions
(such as a rotating drum). In this case the energy to break
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WO 94/25553 PCT/US94/04843
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the paste into fine droplets comes at the spray nozzle, and
in the low shear mixer the droplets are absorbed on to the
surface, or into the pores of the powder. Preferred '.
granulation processes are described in more detail below.
For the purposes of the invention described herein, the
term structuring has been used to mean thickening or
raising the solidification point of the nonionic
surfactant, or both of these. It is an essential feature of
the present invention that the viscosity of the premix is
greater than 350 mPas when measured at the operating
temperature and at a shear rate of 25s-1.
The operating temperature, as defined herein, is the
temperature of the surfactant paste at the point which is
sprayed or dispersed onto the powders during the
granulation step of the process.
A pumpable paste is defined herein to mean a paste which
has a viscosity of less than 100 000 mPas when measured at
25s-1 at the required operating temperature. Preferably the
viscosity of the paste will be less than 60 000 mPas, and
even more preferably less than 40 000 mPas.
Nonionic Surfactant
Suitable nonionic surfactants include compounds produced by
the condensation of alkylene oxide groups (hydrophilic in
nature) with an organic hydrophobic compound, which may be
aliphatic or alkyl aromatic in nature. The length of the
polyoxyalkylene group which is condensed with any
particular hydrophobic group can be readily adjusted to
yield a water-soluble compound having the desired degree of
balance between hydrophilic and hydrophobic elements.
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7
Particularly preferred for use in the present invention are
nonionic surfactants such as the polyethylene oxide
condensates of alkyl phenols, e.g., the condensation
products of alkyl phenols having an alkyl group containing
from about 6 to 16 carbon atoms, in either a straight chain
or branched chain configuration, with from about 4 to 25
moles of ethylene oxide per mole of alkyl phenol.
Preferred nonionics are the water-soluble condensation
products of aliphatic alcohols containing from 8 to 20
carbon atoms, in either straight chain or branched
configuration, with an average of from 1 to 25 moles of
ethylene oxide per mole of alcohol. Particularly preferred
are the condensation products of alcohols having an alkyl
group containing from about 9 to 15 carbon atoms with from
about 2 to 10 moles of ethylene oxide per mole of alcohol;
and condensation products of propylene glycol with ethylene
oxide. Most preferred are condensation products of alcohols
having an alkyl group containing from about 12 to 15 carbon
atoms with an average of about 3 moles of ethylene oxide
per mole of alcohol.
Many of the nonionic surfactants which fall within the
definitions given above have are liquid at temperatures
below 40°C (that is to say the solidification temperature
is below 40°C). The present invention has been found to be
particularly useful for such nonionic surfactants.
Structuring Agent
Although any structuring agent may be chosen which has the
effect of raising the viscosity or "stickiness" of the
surfactant premix to the required operating window and / or
increasing the solidification temperature of the premix, it
has been found that structuring agents which comprise at
least one polymer are particularly useful.
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Preferably at least one of the components of the
structuring agent is a polymer having an average molecular ',
weight of at least 2000, and preferably at least 10000.
The group of polymers useful as structuring agents in the
present invention includes the group of polymers which are
derived from monomers having at least one hydroxyl
functional group such as polyvinyl alcohols, polyethylene
glycol and polyhydroxyacrylic acid polymers and mixtures
and derivatives of these. Other polymers which are useful
components of the strucuring agent include polyvinyl
pyrollidone, PVNO.
The structuring agent may also comprise other ingredients.
One group of such ingredients which have been found to be
particularly useful comprises the group of sugars and
artificial sweeteners and their derivatives.
The group of sugars useful in the present invention
includes fructose, lactose, dextrose, sucrose, saccharin
and sorbitol.
One particularly preferred group of structuring agents is
the derivatives of sugars such as polyhydroxy fatty acid
amides. Such derivatives may be prepared by reacting a
fatty acid ester and an N-alkyl polyhydroxy amine. The
preferred amine for use in the present invention is N-(R1)-
CH2(CH20H)4-CH2-OH and the preferred ester is a C12-C20
fatty acid methyl ester. Most preferred is the reaction
product of N-methyl glucamine (which may be derived from
glucose) with C12-C20 fatty acid methyl ester.
Methods of manufacturing polyhydroxy fatty acid amides have
been described in WO 92 6073, published on 16th April,
1992. This application describes the preparation of
polyhydroxy fatty acid amides in the presence of solvents.
~'O 94/25553 66'~ PCT/L1S94/04843
9
In a highly preferred embodiment of the invention N-methyl
glucamine is reacted with a C12-C20 methyl ester. It also
says that the formulator of granular detergent compositions
may find it convenient to run the amidation reaction in the
presence of solvents which comprise alkoxylated, especially
ethoxylated (EO 3-8) C12-C14 alcohols (page 15, lines 22-
27). This directly yields nonionic surfactant systems which
are preferred in the present invention, such as those
comprising N-methyl glucamide and C12-C14 alcohols with an
average of 3 ethoxylate groups per molecule.
Polyhydroxy fatty acid amides are also active in the
washing process as surfactants in their own right.
Other ingredients which have been found to be useful as
components of the structuring agent include phthalimide,
para-toluene sulphonamide, and maleimide.
The ratio of nonionic surfactant to structuring agent will
vary according to exactly which nonionic surfactant and
which structurant is chosen. Any ratio may be used in the
present invention provided that a premix having a viscosity
of at least 350 mPas when measured at the operating
temperature and a shear rate of 25s-1 is produced.
Typically ratios of nonionic surfactant to structuring
agent in the range of 20:1 to 1:1 have been found to be
particularly suitable, and preferably from 5:1 to 2:1.
Normally the detergent compositions made according to the
present invention may include a wide range of other
ingredients and components which are known to the man
skilled in the art to have a function in the washing
process. Typical examples of such ingredients which may be
used in detergent compositions are given below.
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WO 94/25553 PCT/US94I04843
Granulation Processes
An essential step of the present invention is the process
of forming granules which comprise the surfactant premix
described above. Many processes for granulating surfactant
pastes are known to the man skilled in the art. One of
these processes is spray drying of a slurry containing the
surfactant. However, this is not a preferred process in the
present invention because it does not generally yield a
powder with a high bulk density, and further processing is
needed in order to increase the bulk density.
A process which is more suited to the present invention is
that of fine dispersion mixing or agglomeration. In this
process a powder having a relatively small particle size is
mixed with a finely dispersed paste which causes the powder
to stick together (or agglomerate). The result is a
granular composition which generally has a particle size
distribution in the range of 250 to 1200 micrometers and
has a bulk density of at least 650 g/1. In the present
invention the surfactant premix is used as the paste which
is finely dispersed with an effective amount of powder in a
suitable mixer. Suitable mixers for carrying out the fine
dispersion mixing are described in more detail below. Any
suitable powder may be chosen by mixing one or more of the
ingredients listed below which may be conveniently handled
in powder form. Powders comprising zeolite, carbonate,
silica, silicate, sulphate, phosphate, citrate, citric acid
and mixtures of these are particularly preferred.
It has further been found that a particularly preferred
embodiment of the present invention is to spray water on to
the detergent granules after the granulation step. In this
embodiment of the invention at least one of the powders
used should be an anhydrous powder which may be fully or
partially hydrated when it comes into contact with water. A
similar process has been described in GB 2 113 707,
published on 10th August 1983. This application describes a
process in which anhydrous powders such as phosphate,
carbonate, borate or sulphate are metered into a high shear
mixer (a K-G Schugi [Trade Mark) Blender- Agglomerator)
together with a liquid surfactant and water.The amount of
water added is sufficient to completely hydrate the
hydratable salts. The resulting agglomerates are fed into a
low shear mixer having a longer residence time in order for
the hydration reaction to proceed.
In the process of the present invention, in contrast, it is
highly preferred to add the water into the low shear mixer,
after the agglomerates have been formed. Without wishing to
be bound by theory, it is believed that adding the water
after the initial formation of the agglomerates promotes
hydration at the surface of the agglomerates which gives
rise to the desired physical characteristics.
Most preferred in the process of the present invention is
the use of anhydrous .sodium carbonate, or anhydrous sodium
citrate, or mixtures of these. The anhydrous salts are
agglomerated in the presence of a structured nonionic
surfactant premix and then water is sprayed on to the
resulting agglomerates in a low shear mixer. The
agglomerates are finally dried in a fluid bed dryer.
Still another process which is suited to the present
invention is that of preparing a granular detergent powder
and spraying the surfactant premix onto that powder. The
base powder may be made by any one of the processes known
to the man skilled in the art, including spray drying,
granulation,. (including agglomeration). Preferably
different processes which are suited to the preparation of
different components will be used, and then the components
will be mixed together, for example by dry mixing in a
rotating drum or a low shear mixer. In a preferred
embodiment of the invention the surfactant premix is
sprayed onto the base powder in the rotating drum or low
shear mixer.
WO 94125553 PCT/US94/04843
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Suitable pieces of equipment in which to carry out the fine .
dispersion mixing or granulation of the present invention
are mixers of the FukaeR FS-G series manufactured by Fukae
Powtech Kogyo Co., Japan; this apparatus is essentially in
the form of a bowl-shaped vessel accessible via a top port,
provided near its base with a stirrer having a
substantially vertical axis, and a cutter positioned on a
side wall. The stirrer and cutter may be operated
independently of one another and at separately variable
speeds. The vessel can be fitted with a cooling jacket or,
if necessary, a cryogenic unit.
Other similar mixers found to be suitable for use in
the process of the invention include DiosnaR V series ex
Dierks & Sohne, Germany; and the Pharma MatrixR ex T K
Fielder Ltd., England. Other mixers believed to be
suitable for use in the process of the invention are the
FujiR VG-C series ex Fuji Sangyo Co., Japan; and the RotoR
ex Zanchetta & Co srl, Italy.
Other preferred suitable equipment can include
EirichR, series RV, manufactured by Gustau Eirich Hardheim,
Germany; LodigeR, series FM for batch mixing, series Baud
KM for continuous mixing/agglomeration, manufactured by
Lodige Machinenbau GmbH, Paderborn Germany; DraisR T160
series, manufactured by Drais Werke GmbH, Mannheim Germany;
and WinkworthR RT 25 series, manufactured by Winkworth
Machinery Ltd., Berkshire, England.
The Littleford Mixer, Model #FM-130-D-12, with
internal chopping blades and the Cuisinart Food Processor,
Model #DCX-Plus, with 7.75 inch (19.7 cm) blades are two
examples of suitable mixers. Any other mixer with fine
dispersion mixing and granulation capability and having a
residence time in the order of 0.1 to 10 minutes can be
used. The "turbine-type" impeller mixer, having several
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blades on an axis of rotation, is preferred. The invention
can be practiced as a batch or a continuous process.
Further Processing Steps
The granular components or compositions described above may
be suitable for use directly, or they may be treated by
additional process steps. Commonly used process steps
include drying, cooling and/or dusting the granules with a
finely divided flow aid. In addition the granules may be
blended with other components in order to provide a
composition suitable for the desired end use.
Any type of mixer or dryer (such as fluid bed dryers) may
be found to be suitable for this purpose.
The finely divided flow aid, if used, may be chosen from a
wide variety of suitable ingredients such as zeolite,
silica, talc, clay or mixtures of these.
Compositions
Another aspect of the present invention is the composition
of detergent components comprising nonionic surfactant.
Components having a bulk density of greater than 650 g/1
and comprising from 10% to 50% by weight of nonionic
surfactant and from 5% to 30% by weight of one of the
structuring agents listed above fall within the scope of
the present invention. The ratio of nonionic surfactant to
structuring-agent will vary according to exactly which
nonionic surfactant and which structurant is chosen. Any
ratio may be used in the present invention provided that a
premix having a viscosity of at least 350 mPas when
measured at the operating temperature and a shear rate of
25s-1 is produced. Typically ratios of nonionic surfactant
to structuring agent in the range of 20:1 to 1:1 have been
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PCT/US94/04843
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found to be particularly suitable, and preferably from 5:1
to 2:1.
Other ingredients which may be used in making the
compositions of the present invention will be described
below.
Normally the granular detergent will also contain other
optional ingredients. Examples of such ingredients which
are commonly used in detergents are given in more detail
hereinbelow
Anionic Surfactants
Alkyl Ester Sulfonate Surfactant
Alkyl Ester sulfonate surfactants hereof include linear
esters of Cg-C2p carboxylic acids (i.e. fatty acids) which
are 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 oil, etc.
The preferred alkyl ester sulfonate surfactant, especially
for laundry applications, comprises alkyl ester sulfonate
surfactants of the structural formula:
O
R3 - CH - C - OR4
S03M
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wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or
combination thereof, R4 is a C1-C6 hydrocarbyl, preferably
an alkyl, or combination thereof, and M is a cation which
forms a water soluble salt with the alkyl ester sulfonate.
Suitable salt-forming cations include metals such as
sodium, potassium, and lithium, and substituted or
unsubstituted ammonium cations, such as monoethanolamine,
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 C14-C16 alkyl.
Alkyl Sulfate Surfactant
Alkyl sulfate surfactants hereof are water soluble salts or
acids or the formula ROS03M wherein R preferably is a C10-
C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having
a C10-C20 alkyl component, more preferably a C12-C18 alkyl
or hydroxyalkyl, and M is H or a cation, e.g., an alkali
metal cation (e.g., sodium, potassium, lithium), or
ammonium or substituted ammonium (e.g., methyl-, dimethyl-,
and trimethyl ammonium cations and quaternary ammonium
cations, such as tetramethyl-ammonium and dimethyl
piperdinium cations and quarternary ammonium cations
derived from alkylamines such as ethylamine, diethylamine,
triethylamine, and mixtures thereof, and the like).
Typically, alkyl chains of C12-16 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) .
Alkyl Alkoxylated Sulfate Surfactant
Alkyl alkoxylated sulfate surfactants hereof are
water soluble salts or acids 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
~.
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WO 94/Z5553 PCT/US94/04843
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C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl or
hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater
than zero, typically between about 0.5 and about 6, more
preferably between about 0.5 and about 3, and M is H or a
ration which can be, for example, a metal ration (e. g.,
sodium, potassium, lithium, calcium, magnesium, etc.),
ammonium or substituted-ammonium ration. Alkyl ethoxylated
sulfates as well as alkyl propoxylated sulfates are
contemplated herein. Specific examples of substituted
ammonium rations include methyl-, dimethyl-, trimethyl-
ammonium and quaternary ammonium rations, such as
tetramethyl-ammonium, dimethyl piperdinium and rations
derived from alkanolamines such as ethylamine,
diethylamine, triethylamine, mixtures thereof, and the
like. Exemplary surfactants are C12-C18 alkyl
polyethoxylate (1.0) sulfate, C12-C18E(1.0)M), C12-C18
alkyl polyethoxylate (2.25) sulfate, C12-C18E(2.25)M), C12-
C18 alkyl polyethoxylate (3.0) sulfate C12-C18E(3.0), and
C12 C18 alkyl polyethoxylate (4.0) sulfate C12-C18E(4.0)M),
wherein M is conveniently selected from sodium and
potassium.
Other Anionic Surfactants
Other anionic surfactants useful for detersive
purposes can also be included in the laundry detergent
compositions of the present invention. These can include
salts (including, for example, sodium, potassium, ammonium,
and substituted ammonium salts such as mono-, di- and
triethanolamine salts) of soap, C9-C20 linear
alkylbenzenesulphonates, 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,
Cg-C24 alkylpolyglycolethersulfates (containing up to 10
moles of ethylene oxide); aryl glycerol sulfonates, fatty
~~
17
oleyl glycerol sulfates, alkyl phenol ethylene oxide ether
sulfates, paraffin sulfonates, alkyl phosphates,
isethionates such as the acyl isethionates, N-acyl
taurates, alkyl succinamates and sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and
unsaturated C12-C18 monoesters) diesters of sulfosuccinate
(especially saturated and unsaturated C6-C14 diesters),
acyl sarcosinates, sulfates of alkylpolysaccharides such as
the sulfates of alkylpolyglucoside, branched primary alkyl
sulfates,.alkyl polyethoxy carboxylates such as those of
the formula RO(CH2CH20)kCH2C00-M+ wherein R is a C$-C22
alkyl, k~is an integer from 0 to 10, and M is a soluble
salt-forming cation. 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 Column 29, line 23.
When included therein, the laundry detergent compositions
of the present~invention typically comprise from about 1
to about 40 %, preferably from about 3 % to about 20 % by
weight of such anionic surfactants.
Other Surfactants
The laundry detergent compositions of the present invention
may also contain cationic, ampholytic, zwitterionic, and
semi-polar surfactants, as well as nonionic surfactants
other than those already described herein, including the
semi-polar nonionic amine oxides described below.
Cationic detersive surfactants suitable for use in the
laundry detergent compositions of the present invention are
. s~ T~ '1.- n.
WO 94/25553 ~'~f' ~A~ ~~66'~ PCT/US94/04843."y
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those having one long-chain hydrocarbyl group. Examples of
such cationic surfactants include the ammonium surfactants
such as alkyldimethylammonium halogenides, and those
surfactants having the formula .
R1R2R3R4N+X-
wherein R1 is an alkyl or alkyl benzyl group having from
about 8 to_ about 18 carbon atoms in the alkyl chain, each
of R2, R3, R4 is independently C1-C4 alkyl, C1-C4 hydroxy
alkyl, benzyl, and -(C2H4)xH where x has a value from 2 to
5, and X- is an anion. Not more than one of R2~ R3, R4
should be benzyl.
The preferred alkyl chain length for R1 is C12-C15,
particularly where the alkyl group is a mixture of chain
lengths derived from coconut or palm kernel fat, or is
derived synthetically by olefin build up or OXO alcohols
synthesis. Preferred groups for R2, R3, R4 are methyl and
hydroxyethyl groups, and the anion X may be selected from
halide, methosulphate, acetate and phosphate ions.
Examples of suitable quaternary ammonium compounds for use
herein are:
coconut trimethyl ammonium chloride or bromide
coconut methyl dihydroxyethyl ammonium chloride or
bromide
decyl triethyl ammonium chloride or bromide
decyl dimethyl hydroxyethyl ammonium chloride or
bromide
C12-14 dimethyl hydroxyethyl ammonium chloride or
bromide
myristyl trimethyl ammonium methyl sulphate
lauryl dimethyl benzyl ammonium chloride or bromide
lauryl methyl (ethenoxy)4 ammonium chloride or
bromide
The above water-soluble cationic components of the
compositions of the present invention, are capable of
CA 02160662 1999-04-15
19
existing in cationic form in a O.lo aqueous solution at
pHlO.
Other cationic surfactants useful herein are also described
in US Patent 4,228,044, Cambre, issued October 14, 1980.
When included therein, the laundry detergent compositions of
the present invention typically comprise from 0 o to about
25 %, preferably from about 3 o to about 15 o by weight of
such cationic surfactants.
Ampholytic surfactants are also suitable for use in the
laundry detergent compositions of the present invention.
These surfactants can be broadly described as aliphatic
derivatives of secondary or tertiary amines, or aliphatic
derivatives of heterocyclic secondary and tertiary amines in
which the aliphatic radical can be straight- or branched
chain. One of the aliphatic substituents contains at least
8 carbon atoms, typically from about 8 to about 18 carbon
atoms, and at least one contains an anionic water-
solubilizing group e.g. carboxy, sulfonate, sulfate. See
U.S. Patent No. 3,929,678 to Laughlin et al., issued
December 30, 1975 at column 19, lines 18-35 for examples of
ampholytic surfactants.
When included therein, the laundry detergent compositions of
the present invention typically comprise from 0 o to about
15 0, preferably from about 1 o to about 10 % by weight of
such ampholytic surfactants.
Zwitterionic surfactants are also suitable for use in
laundry detergent compositions. These surfactants can be
broadly described as derivatives of secondary and tertiary
amines, derivatives of heterocyclic secondary and tertiary
amines, or derivatives of quaternary ammonium, quarternary
20
ohosphonium or tertiary sulfvnium compounds. See U.S.
Patent No. 3,929,678 to Laughlin et al., issued December
30, 1975 at columns 19, line 38 through column 22, line 48
for examples of zwitterionic surfactants.
when included therein, the laundry detergent compositions
of the present invention typically comprise form 0 % to
about 15 %, preferably from about 1 % to about 10 % by
weight of such zwitterionic surfactants.
Semi-po ur nonionic surfactants are a special category of
nonionic surfactants which include water-soluble amine
oxides containing one alkyl moiety of from about 10 to
about 18 carbon atoms and 2 moieties selected from the
group consisting of alkyl groups and hydrocyalkyl groups
containing form about 1 to about 3 carbon atoms; water-
soluble phosphine oxides containing one alkyl moiety of
form about l0 to about 18 carbon atoms and 2 moieties
selected form the group consisting of alkyl groups and
hydroxyalkyl groups containing from about 1 to about 3
carbon atoms.
Semi-polar nonionic detergent surfactants include the amine
oxide surfactants having the formula .
0
R3(OR4)xN(R5)2
wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group
or mixtures thereof containing from about 8 to about 22
carbon atoms; R4 is an alkylene or hydroxyalkylene group
containing from about 2 to about 3 carbon atoms or mixtures
thereof; x is form 0 to about 3; and each R5 is an alkyl or
hydroxyalkyl group containing form about 1 to about 3
carbon atoms or a polyethylene oxide group containing from
about 1 to about 3 ethylene oxide groups. The R5 groups
.e
,r. 0 94/25553 ,~ PCT/US94/04843
21
can be attached to each other, e.g., through an oxygen or
nitrogen atom, to form a ring structure.
There amine oxide surfactants in particular include C10-C18
alkyl dimenthyl amine oxides and Cg-C12 alkoxy ethyl
dihydroxy ethyl amine oxides.
When included therein, the laundry detergent compositions
of the present invention typically comprise form 0 % to
about 15 %, preferably from about 1 % to about 10 % by
weight of such semi-polar nonionic surfactants.
Builders and Other Optional Ingredients
Sodium aluminosilicate may take many forms. One example is
crystalline aluminosilicate ion exchange material of the
formula
NazL(A102)z~(Si02)y]~xH20
wherein z and y are at least about 6, the molar ratio of z
to y is from about 1.0 to about 0.4 and z is from about 10
to about 264. Amorphous hydrated aluminosilicate materials
useful herein have the empirical formula
Mz(zA102-ySi02)
wherein M is sodium, potassium, ammonium or substituted
ammonium, z is from about 0.5 to about 2 and y is 1, said
material having a magnesium ion exchange capacity of at
least about 50 milligram equivalents of CaC03 hardness per
gram of anhydrous aluminosilicate. Hydrated sodium Zeolite
A with a particle size of from about 1 to 10 microns is
preferred.
The aluminosilicate ion exchange builder materials
herein are in hydrated form and contain from about 10% to
about 28% of water by weight if crystalline, and
potentially even higher amounts of water if amorphous.
Highly preferred crystalline aluminosilicate ion exchange
' r .~ ", .,.
WO 94125553 PCTIUS94/04843 "~)
22
materials contain from about 18% to about 22% water in
their crystal matrix. The crystalline aluminosilicate ion
exchange materials are further characterized by a particle
size diameter of from about 0.1 micron to about 10 microns.
Amorphous materials are often smaller, e.g., down to less
than about 0.01 micron. Preferred ion exchange materials
have a particle size diameter of from about 0.2 micron to
about 4 microns. The term "particle size diameter" herein
represents the average particle size diameter by weight of
a given ion exchange material as determined by conventional
analytical techniques such as, for example, microscopic
determination utilizing a scanning electron microscope.
The crystalline aluminosilicate ion exchange materials
herein are usually further characterized by their calcium
ion exchange capacity, which is at least about 200 mg
equivalent of CaCO3 water hardness/g of aluminosilicate,
calculated on an anhydrous basis, and which generally is in
the range of from about 300 mg eq./g to about 352 mg eq./g.
The aluminosilicate ion exchange materials herein are still
further characterized by their calcium ion exchange rate
which is at least about 2 grains
Ca++/gallon/minute/gram/gallon of aluminosilicate
(anhydrous basis), and generally lies within the range of
from about 2 grains/gallon/minute/gram/gallon to about 6
grains/gallon/minute/gram/gallon, based on calcium ion
hardness. Optimum aluminosilicate for builder purposes
exhibit a calcium ion exchange rate of at least about 4
grains/gallon/minute/gram/gallon.
The amorphous aluminosilicate ion exchange materials
usually have a Mg++ exchange of at least about 50 mg eq.
CaC03/g (12 mg Mg++/g) and a Mg++ exchange rate of at least
about 1 grain/gallon/minute/gram/gallon. Amorphous
materials do not exhibit an observable diffraction pattern
when examined by Cu radiation (1.54 Angstrom Units).
23
Aluminosilicate ion exchange materials useful in the
practice of this invention are commercially available. The
aluminosilicates useful in this invention can be crystalline
or amorphous in structure and can be naturally occurring
aluminosilicates or synthetically derived. A method for
producing aluminosilicate ion exchange materials is
discussed in U.S. Pat. No. 3,985,669, Krummel et al., issued
Oct. 12, 1976. Preferred synthetic crystalline
aluminosilicate ion exchange materials useful herein are
available under the designations Zeolite A, Zeolite B,
Zeolite M and Zeolite X. In an especially preferred
embodiment, the crystalline aluminosilicate ion exchange
material has the formula
Nal2 [ (AlOz) 12 (Si02) 1z] -xH20
wherein x is from about 20 to about 30, especially about 27
and has a particle size generally less than about 5 microns.
Other ingredients which are known for use in the
components and compositions may also be used as optional
ingredients in the present invention.
The granular detergents of the present invention can
contain neutral or alkaline salts which have a pH in
solution of seven or greater, and can be either organic or
inorganic in nature. The builder salt assists in providing
the desired density and bulk to the detergent granules
herein. While some of the salts are inert, many of them
also function as detergency builder materials in the
laundering solution.
Examples of neutral water-soluble salts include the
alkali metal, ammonium or substituted ammonium chlorides,
fluorides and sulfates. The alkali metal, and especially
sodium, salts of the above are preferred. Sodium sulfate is
typically used in detergent granules and is a particularly
preferred salt. Citric acid and, in general,
.itt
"~
24
any other organic or inorganic acid may be incorporated
into the granular detergents of the present invention as
long as it is chemically compatible with the rest of the
agglomerate composition.
Other useful water-soluble salts include the compounds
commonly known as detergent builder materials. Builders
are generally selected from the various water-soluble,
alkali metal, ammonium or substituted ammonium phosphates,
polyphosphates, phosphonates, polyphosphonates, carbonates,
silicates, borates, and polyhyroxysulfonates. Preferred
are the~alkali metal, especially sodium, salts of the
above.
Specific examples of inorganic phosphate builders are
sodium and potassium tripolyphosphate, pyrophosphate,
polymeric metaphosp~ate having a degree of polymerization
of from about 6 to 21, and orthophosphate. 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-diphosphcnic acid and the
sodium and potassium salts of ethane, 1,1,2-triphosphonic
acid. Other phosphorus builder compounds are disclosed in
U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137;
3,400,176 and 3,400,148.
Examples of nonphosphorus, inorganic builders are
sodium and potassium carbonate, bicarbonate,
sesquicarbonate, tetraborate decahydrate, and silicate
having a molar ratio of Sio2 to alkali metal oxide of from
about 0.5 to about 4.0, preferably from about 1.0 to about
2.4.
As mentioned. above powders normally used in detergents
such as zeolite, carbonate, silica, silicate, citrate,
phosphate, perborate, etc. and process acids such as
v
PCT/US94/04843
"~"~IO 94125553
starch, can be used in preferred embodiments of the present
invention.
Polymers
Also useful are various organic polymers, some of
which also may function as builders to improve detergency.
Included among such polymers may be mentioned sodium
carboxy-lower alkyl celluloses, sodium lower alkyl
celluloses and sodium hydroxy-lower alkyl celluloses, such
as sodium carboxymethyl cellulose, sodium methyl cellulose
and sodium hydroxypropyl cellulose, polyvinyl alcohols
(which often also include some polyvinyl acetate),
polyacrylamides, polyacrylates and various copolymers, such
as those of malefic and acrylic acids. Molecular weights
for such polymers vary widely but most are within the range
of 2,000 to 100,000;
Polymeric polycarboxylate builders are set forth in
U.S. Patent 3,308,067, Diehl, issued March 7, 1967. 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.
Other Optionals Ingredients
Other ingredients commonly used in detergent
compositions can be included in the components and
compositions of the present invention. These include color
speckles, bleaching agents and bleach activators, suds
boosters or suds suppressors, antitarnish and anticorrosion
agents, soil suspending agents, soil release agents, dyes,
fillers, optical brighteners, germicides, pH adjusting
agents, nonbuilder alkalinity sources, hydrotropes,
enzymes, enzyme-stabilizing agents, and perfumes.
PCT/US94/04843 ""~,,
WO 94125553
26
Examples
In these examples the following abbreviations have been
used:
C25E3: C12-15 alkyl ethoxylate, with an average of 3
ethoxy groups per molecule
GA: N-methyl glucamide
C25AS: C12-15 alkyl sulphate
C45AS: C14-15 alkyl sulphate
C25AE3S: C12-15 alkyl ethoxy sulphate, with an average
of 3 ethoxy groups per molecule
pVp: Polyvinyl Pyrrolidone
PVNO: Polyvinyl Pyrridine N oxide
216066
~O 94/25553 ' ~ . PCT/US94/04843
27
TABLE 1
Ex 1 2 3 4 5 6 7
C25E3 80 75 67 67 46 46 46
PVP 20 25 33 33
PVNO 13 13 13
lactose 11
dextrose il
sucrose 11
water 30 30 30
Operating 30 30 15 15 20 20 20
Temp.(C)
Viscosity 900 1300 2000 2000 23000 23000 23000
(mPas)
8 9 10 A
C25E3 75 67 86 97.5
GA 12.5 11
PVP 22 14 2.5
PVNO 12.5
Operating 40 40 20 20
Temp.(C)
Viscosity 24000 15000 380 50
(mPas)
,,
".~.,-
28
Example 1
The C25E3/PVP paste defined in Table 1 was sprayed into a
Loedige CB mixer (Trade Mark] at a rate of 1120 kg/hr and
at a temperature of 30°C. At the same time zeolite A was
added to the mixer at a rate of 1340 kg/hr, as well as
anhydrous carbonate 1340 kg/hr.
Dispersion of the paste premix and high intensity mixing of
the premix and the powders occurred in the Loedige mixer.
The residence time was approximately eight seconds.
The resulting mixture was fed into a Loedige HIri mixer
(Trade Name] and distinct agglomerates were formed. Two
high speed choppers in the first half of the Loedige HI~i
mixer prevented a high proportion of oversize agglomerates
being formed.
In the second half of the Loedige IQ~i mixer water was
sprayed on to the agglomerates at a rate of 225 kg/hr
promoting the hydration of the carbonate in the
agglomerate.
After the water spray on, a mixture of zeolite and silica
was added at a rate of 160 kg/hr.
The agglomerates leaving the Loedige ~Qri mixer were then
passed through a fluid bed cooler / elutriator
The resulting agglomerates had excellent physical
properties including flowability, and were found to be
physically stable under stressed storage conditions.
Example 2
The process~of example 1 was repeated using the components
listed in Table 1.
Example 3
The process of example 1 was repeated using the components
listed in Table 1 and at an operating temperature of the
paste premix of 15°C.
29
Example 4
The process of example 3 was repeated using the components
listed in Table 1, with the Zeolite A being replaced by
anhydrous citrate, and the rate of water addition being
increased to 190 kg /hr.
Example 5
The C25E3/PVNO/lactose paste defined in Table 1 was sprayed
into a Loedige CB mixer [Trade Mark] at a rate of 1400
kg/hr and at a temperature of 20°C. At the same time
zeolite A_was added to the mixer at a rate of 1200 kg/hr,
as well as anhydrous carbonate 1200 kg/hr.
The remainder of the process was carried out as in examcle
1 with water being sprayed on to the agglomerates at a rate
of 200 kg/hr.
Examples 6-10
The process of example 5 was repeated using the components
listed in Table 1.
In each of the examples 2 to I0, a free flowing granular
products were produced which were found to be physically
_ stable under stressed storage conditions.
Comparative Example A
The process of example 5 was repeated using the components
listed in Table 1. Due to the lower viscosity of the
surfactant premix it was not possible to make granules
having the desired particle size or physical properties.
