Note: Descriptions are shown in the official language in which they were submitted.
WO 95107968 PCT/US94/10062
1
2171528
GRANULAR DETERGENT COMPOSITIONS COMPRISING NONIONIC
SURFACTANT AND PROCESS FOR MAKING SUCH COMPOSITIONS
The present invention is concerned with granular detergent
components or compositions which are rich in high
performance nonionic surfactants. The compositions are
based upon specified surfactant systems and processes which
make it possible to produce very high surfactant active
components.
Nonionic surfactants are important components of current
laundry detergent compositions. Present trends demand
particulate components or compositions which have a high
bulk density and which have a high level of nonionic
surfactant. The particulate must have good physical
characteristics, and must deliver nonionic surfactants
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2
which have' been selected for high performance in to the
wash. Various prior art attempts have been described which
approach these demands from different perspectives. For
example:
EP544492, published on 2nd June, 1993, discloses
particulate high density detergent composition comprising
15 to 50% of a mixed anionic/nonionic surfactant system.
The nonionic surfactants chosen are ethoxylated alcohols
having a peaked ethoxylation distribution with an average
of about 3 to 6.5. Although fatty acid soaps are suggested
as suitable structurants which modify the surfactant
viscosity profile, the resulting granules where soap is
used (in Examples 16 to 19, 24 to 29) have surfactant
activities of 29 to 32.5 %.
W09206160, published on 16th April, 1992, discloses high
performing nonionic surfactant systems based on mixtures of
glucose amides and ethoxylated nonionic surfactants. In one
example (example 20) a component is described which
comprises a nonionic surfactant system which is a mixture
of 20% Dobanol (Trade Mark) E03 and 80% N-methyl glucose
amide in aqueous solution.
EP364881, published on 25th April 1990, describes gels
formed from polyglycol ether derivatives and water in
ratios of from 5:1 to 1:2. The gels are formed into free-
flowing granulates by mixing with finely divided solids.
2171528
3
The problem addressed by the present invention concerns
the need to provide high density particulate laundry
detergent which has a high nonionic surfactant content,
and which does not cake or lump upon storage, even in
hot, humid conditions, and which dissolves and
disperses rapidly upon contact with water, even cold
water, to give a high detergency performance on the
washing load.
Whilst the prior art provides some guidance as to how
each of these objectives might be independently
achieved, there does not appear to be a solution to all
of the aspects of the problem provided by any one
reference.
The present invention provides a nonionic, or mixed
nonionic/anionic, surfactant system having a specific
viscosity profile which can be formed into a solid
particulate which does not cake during storage, which
dissolves rapidly and has an excellent performance
profile .
Summary of the Invention
The present invention is directed to a process for
making granular detergent compositions or components
from a surfactant system which is in the solid phase at
temperatures of 25°C and below, wherein said surfactant
system has a softening point from above 25°C to 100°C
and wherein the surfactant system has a viscosity
profile whereby the viscosity of the surfactant system
is at least about 20,000 cps at a temperature of 10°C
above the softening point, and less than about 10,000
cps at a temperature of 30°C above the softening point,
all viscosities being measured at a shear rate of
25 s-1, said process comprising the steps of: a) pumping
a surfactant system in its low viscosity state, said
..,;
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surfactant system comprising a mixture of polyhydroxy
fatty acid amide and ethoxylated nonionic surfactant;
b) cooling said surfactant system to a temperature
where its viscosity is increased to at least about
20,000 cps; c) granulating the surfactant system in the
presence of a finely divided powder to obtain
agglomerates; and d) cooling said agglomerates, wherein
the agglomerates comprise from about 35o to about 85%
by weight of the surfactant system.
Detailed Description of the Invention
It has now been found that high surfactant activities
can be achieved if an agglomeration "window" exists
within which the surfactant system has a high
viscosity. Typically
WO 95/07968 2 1 7 1 ~ 2 ~ PCT/US94/10062
this may be achieved by appropriate selection of nonionic
surfactants such that there is a "window" of at least 10°C,
the lower limit of which is the softening point of the
surfactant system, within which the system has a viscosity
of at least 2000ocps, preferably 25000 to 50000cps.
However, in order to be able to prepare, handle, store and
transport the surfactant system it should have a viscosity
of less than 10000cps at a temperature of 30°C above the
softening point.
High activities and good caking properties can only be
achieved if the surfactant system has a softening point
above ambient temperature, e.g. above 25°C, preferably
above 40°C.
Good rates of solubility can be correlated with the
softening point of the surfactant system. Surfactant
systems having a softening point of greater than 100°C
(e. g. "pure" C16 N-methyl glucosamide) tend to show poor
rates of solubility. Preferably the softening point of the
surfactant system will be less than 80°C.
It is preferred that the surfactant system of the present
invention has a softening point which lies within the range
of from 40°C to 100°C, and furthermore that the surfactant
system has a viscosity profile whereby the viscosity of the
WO 95/07968 PCT/US94/10062
Q
-Z~ ~ ~ ~~2~
6
surfactant system is from 25000 to 50000 cps at a
temperature of 10°C above the softening point.
The surfactant system may be comprised entirely of nonionic
surfactants or, preferably, it will be a mixed
anionic/nonionic surfactant system. In either case the
surfactant system preferably comprises more than 40% by
weight, and more preferably more than 50% by weight of
nonionic surfactant. Where anionic surfactant is present in
the surfactant system the ratio of anionic to nonionic
surfactant should be from 1:100 to 1:1.
Where the surfactant system is exclusively nonionic
surfactant it is often possible to exclude water
completely. However when anionic surfactants are present
these will often be used in the form of a concentrated
paste, or, more preferably, in the form of a hydrated or
moisture containing powder. The surfactant system should
have a water component of less than 15%, preferably less
than 10% by weight, and most preferably less than 5% by
weight of the surfactant system.
Preferred nonionic surfactants may be selected from the
families of ethoxylated nonionic surfactants, glycerol
ethers, glucosamides, glycerol amides, glycerol esters,
fatty acids, fatty acid esters, fatty amides, alkyl
polyglucosides, alkyl polyglycol ethers, polyethylene
glycols, ethoxylated alkyl phenols and mixtures thereof. A
WO 95/07968 PCT/US94/10062
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highly preferred surfactant system comprises a mixture of
polyhydroxy fatty acid amide and an ethoxylated nonionic
surfactant in the ratio of from 3:7 to 7:3.
Finished laundry detergent compositions may be prepared by
mixing or blending the nonionic containing particles with:
a) a component which comprises at least 40% by weight of
anionic surfactant; and
b) a component which comprises at least 70% by weight of a
builder material.
Preferably each of these major components is present at a
level of from 3% to 40% by weight of the finished
component. More preferably component (b) is present at a
level of from 3% to 20% by weight of the finished
composition.
The nonionic surfactant containing particles of the present
invention may be prepared by:
a) pumping a surfactant system in its low viscosity state;
b) cooling said nonionic surfactant to a temperature where
its viscosity is increased to at least 20000 cps;
c) granulating the surfactant in the presence of a finely
divided powder;
d) cooling said agglomerates.
WO 95/07968 PCT/US94/10062
2 ~ ~ ~ 52~
The cooling step (b) is preferably performed using a high
pressure scraped surface heat exchanger.
The term "surfactant system" as used herein means a mixture
of one or more surfactants comprising nonionic surfactants
alone or a mixed anionic/nonionic surfactant system. Whilst
other components such as water and solvents (e. g. short
chain alcohols) may be present in the surfactant system,
these will generally be minimised and preferably excluded.
The term "softening point" as used herein means the
temperature at which the surfactant system passes between
the solid and mixed solid/liquid phases. The softening
point can be identified by using a differential scanning
calorimetry (DSC) curve. The curve is a plot of true
specific heat capacity against temperature. The softening
point is the temperature at which enthalpy of melting is
greater than zero. This is the temperature at which phase
change begins to occur when the solid surfactant system is
heated.
The term "viscosity" as used herein means the viscosity
measured at a shear rate of 25s-1 . The viscosity can be
measured by rotational analysis (e. g. a rheometer).
Suitable instruments for these measurements are
WO 95/07968 2 1 7 15 2 8 PCT/US94/10062
9
manufactured by Physica Messtechnik, Germany, (supplied by
Thermo Instrument Systems of Breda, Netherlands).
The term "high active" as used herein refers to nonionic
surfactant activities of at least 35% by weight of the
particulate component or composition, preferably greater
than 40% by weight, and more preferably about 50% by
weight.
The various aspects of the invention will now be described
in more detail.
Surfactant Systems
In order to provide a surfactant system which fulfils all
of the physical requirements (ie the viscosity profile) of
the present invention, it will usually be necessary to
blend two or more compatible nonionic surfactants to give
the required properties. For example, a homogeneous mixture
of a high melting point surfactant with a low melting point
surfactant, in suitable proportions, will give a surfactant
system having the desired softening point.
While any nonionic surfactant may be usefully employed in
the present invention, two families of nonionics have been
found to be particularly useful. These are nonionic
WO 95/07968 PCT/US94/10062
,o
2,i ~ 1'~~~~
surfactants based on alkoxylated (especially ethoxylated)
alcohols, and those nonionic surfactants based on amidation
products of fatty acid esters and N-alkyl polyhydroxy
amine. The amidation products of the esters and the amines
are generally referred to herein as polyhydroxy fatty acid
amides. Particularly useful in the present invention are
mixtures comprising two or more nonionic surfactacts
wherein at least one nonionic surfactant is selected from
each of the groups of alkoxylated alcohols and the
polyhydroxy fatty acid amides.
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.
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.
WO 95/07968 2 1 7 15 2 8 PCT/US94/10062
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Preferred nonionics are the water-soluble condensation
products of aliphatic alcohols containing from 8 to 22
carbon atoms, in either straight chain or branched
configuration, with an average of up to 25 moles of
ethylene oxide per more 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.
It is a particularly preferred embodiment of the present
invention that the nonionic surfactant system also includes
a polyhydroxy fatty acid amide component.
Polyhydroxy fatty acid amides may be produced 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, where R1 is typically a alkyl, e.g.
methyl group; and the preferred ester is a C12-C20 fatty
acid methyl ester.
Methods of manufacturing polyhydroxy fatty acid amides have
been described in WO 92 6073, published on 16th April,
WO 95/07968 PCT/US94/10062
~ -, ~~ ~~~ ~'3 ,2
2
1992. This application describes the preparation of
polyhydroxy fatty acid amides in the presence of solvents.
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 can directly yield nonionic surfactant systems
which are preferred in the present invention, such as those
comprising N-methyl glucosamide and C12-C14 alcohols with
an average of 3 ethoxylate groups per molecule.
Nonionic surfactant systems, and granular detergents made
from such systems have been described in WO 92 6160,
published on 16th April, 1992. This application describes
(example 15) a granular detergent composition prepared by
fine dispersion mixing in an Eirich RV02 mixer which
comprises N-methyl glucosamide (10%), nonionic surfactant
(lo%).
Both of these patent applications describe nonionic
surfactant systems together with suitable manufacturing
processes for their synthesis, which have been found to be
suitable for use in the present invention. However, for the
purposes of the present invention is necessary to minimise
(and preferably exclude) the presence of water (or other
WO 95/07968 PCT/US94/10062
.. 2171528
13
solvents) in order to achieve the required viscosity
profile of the surfactant system of the present invention.
Other nonionic surfactants which may be used as components
of the surfactant systems herein include ethoxylated
nonionic surfactants, glycerol ethers, glucosamides,
glycerol amides, glycerol esters, fatty acids, fatty acid
esters, fatty amides, alkyl polyglucosides, alkyl
polyglycol ethers, polyethylene glycols, ethoxylated alkyl
phenols and mixtures thereof.
The surfactant system may also comprise anionic
surfactants, indeed the inclusion of such surfactants may
be of considerable advantage in order to improve the rate
of solubility of the granular surfactant.
Anionic Surfactants
The laundry detergent compositions of the present invention
can contain, in addition to the nonionic surfactant system
of the present invention, one or more anionic surfactants
as described below.
Alkyl Ester Sulfonate Surfactant
WO 95/07968 PCT/US94/10062
'~ i~ t1
14
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
wherein R3 is a C$-C2p 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.
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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
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
WO 95/07968 PCT/US94/10062
n
preferably between about 0.5 and about 3, and M is H or a
cation which can be, for example, a metal cation (e. g.,
sodium, potassium, lithium, calcium, magnesium, etc.),
ammonium or substituted-ammonium cation. Alkyl ethoxylated
sulfates as well as alkyl propoxylated sulfates are
contemplated herein. Specific examples of substituted
ammonium cations include methyl-, dimethyl-, trimethyl-
ammonium and quaternary ammonium cations, such as
tetramethyl-ammonium, dimethyl piperdinium and cations
derived from alkanolamines such as ethylamine,
diethylamine, triethylamine, mixtures thereof, and the
like. Exemplary surfactants are C12-C1$ alkyl ether (1.0)
sulfate, C12-Clg alkyl ether (2.25) sulfate, C12-Clg alkyl
ether (3.0) sulfate, and C12-C18 alkyl ether (4.0) sulfate,
wherein the counterion 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
WO 95/07968 PCT/US94/10062
2~ 7 ~5 28
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,
C8-C24 alkylpolyglycolethersulfates (containing up to l0
moles of ethylene oxide); methyl ester sulphonates (MES);
acyl glycerol sulfonates, fatty 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 C8-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
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18
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.
Cationic detersive surfactants suitable for use in the
laundry detergent compositions of the present invention are
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
(R2(OR3)YJ(R4(OR3)Y)2R5N+X-
wherein Rz is an alkyl or alkyl benzyl group having from
about 8 to about 18 carbon atoms in the alkyl chain, each
R3 is selected from the group consisting of -CH2CH2-,
-CH2CH(CHg)-, -CH2CH(CH20H)-, -CH2CH2CH2-, and mixtures
thereof; each R4 is selected from the group consisting of
f, ',
r~,. ,~~
2171528
19
C1-C4 alkyd, C1-Cq hydroxyalkyl, benzyl ring structures
formed by joining the two R4 groups,
-CHZCOH-CHOHCOR6CHOHCH20H wherein R6 is any hexose or
hexose polymer having a molecular weight less than about
1000, and hydrogen when y is not 0; R5 is the same as R4 or
is an alkyl chain wherein the total number of carbon atoms
of R2 plus R5 is not more than about 18; each y is from 0
to about 10 and the sum of the y values is from 0 to about
15; and X is any compatible anion.
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 % to
about 25 %, preferably from about 3 % to about 15 % 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-
'i-.-
21 7 15 28
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 form 0 % to
about 15 %, preferably from about 1 % 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
phosphonium or tertiary sulfonium 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 from 0 % to
about 15 %, preferably from about 1 % to about 10 % by
weight of such zwitterionic surfactants.
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2,
Semi-polar~nonionic surfactants are a special category of
nonionic surfactants which include water-soluble amine
oxides containing one alkyl moiety of from about l0 to
about 18 carbon atoms and 2 moieties selected from the
group consisting of alkyl groups and hydroxyalkyl groups
containing from about 1 to about 3 carbon atoms; water-
soluble phosphine 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
hydroxyalkyl groups containing from about 1 to about 3
carbon atoms.
Semi-polar nonionic detergent surfactants include the amine
oxide surfactants having the formula
O
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 from 0 to about 3; and each R5 is an alkyl or
hydroxyalkyl group containing from 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
can be attached to each other, e.g., through an oxygen or
nitrogen atom, to form a ring structure.
WO 95/07968 PCT/US94/10062
22 2171528
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.
Normally the granular components and compositions will also
contain other optional ingredients, such as builders,
chelants (including phosphonic acids, succinic acids and
their salts), bleaches, bleach activators (such as
tetraacetylethylene diamine), polymers and co-polymers.
Examples of such ingredients which are commonly used in
detergents are given in more detail hereinbelow.
The detergent compositions herein can contain crystalline
aluminosilicate ion exchange material of the formula
Naz[(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
WO 95/07968 PCT/US94/10062
23 21 7 15 28
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 5% to
about 28% of water by weight if crystalline, and
potentially even higher amounts of water if amorphous.
Highly preferred crystalline aluminosilicate ion exchange
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 CaC03 water hardness/g of aluminosilicate,
calculated on an anhydrous basis, and which generally is in
2171528
24
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.
CaCOg/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).
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
WO 95/07968 PCT/US94/10062
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exchange materials useful herein are available under the
designations Zeolite A, Zeolite B, and Zeolite X. In an
especially preferred embodiment, the crystalline
aluminosilicate ion exchange material has the formula
Nal2((A102)12(Si02)12)'xH20
wherein x is from about 20 to about 30, especially about 27
and has a particle size generally less than about 5
microns.
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 and alkaline earth
metal, and especially sodium and magnesium, 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, 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.
2171528
26
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 polyhydroxysulfonates. Preferred
are the alkali metal, especially sodium, salts of the
above.
Specific examples of inorganic phosphate builders are
sodium and potassium tripolyphosphate, pyrophosphate,
polymeric metaphosphate having a degree of polymerization
of from about 6 to 21, and 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-diphosphonic 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.
Suitable silicates are those having an Si02:Na2o ratio in
the range from 1.6 to 3.4, the so-called amorphous
WO 95/07968 ''CT/US94/10062
2~ 21 7 15 28
silicates of Si02 . Na20 ratios from 2.0 to 2.8 being
preferred. These materials can be added at various points
of the manufacturing process, such as in the form of an
aqueous solution serving as an agglomerating agent for
other solid components, or, where the silicates are
themselves in particulate form, as solids to the other
particulate components of the composition.
Within the silicate class, highly preferred materials are
crystalline layered sodium silicates of general formula
NaMSix02x+1~yH2~
wherein M is sodium or hydrogen, x is a number from 1.9 to
4 and y is a number from 0 to 20. Crystalline layered
sodium silicates of this type are disclosed in EP-A-
0164514 and methods for their preparation are disclosed in
DE-A-3417649 and DE-A-3742043. For the purposes of the
present invention, x in the general formula above has a
value of 2, 3 or 4 and is preferably 2. More preferably M
is sodium and y is 0 and preferred examples of this
formula comprise the y and 8 forms of Na2Si205. These
materials are available from Hoechst AG FRG as
respectively NaSKS-il and NaSKS-6. The most preferred
material is b -Na2Si205, (NaSKS-6). Crystalline layered
silicates are incorporated either as dry mixed solids, or
as solid components of agglomerates with other components.
WO 95/07968 PCT/iJS94/10062
28
3
As mentioned above powders normally used in detergents such
as zeolite, carbonate, silica, silicate, citrate,
phosphate, perborate, percarbonate etc. and process acids
such as starch and sugars, can be used in preferred
embodiments of the present invention. Optionally, other
components may be added at any one of the stages of the
process of the present invention, or they may be mixed with
or sprayed on to the granular detergents of the present
invention.
Polymers which are particularly useful in the present
invention include 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), polyvinyl pyrrolidone, polyethylene glycol,
polyaspartate, 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.
Most preferred are polymeric polycarboxyate 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.
WO 95/07968 PCT/US94/10062
29 2171528
Another optional detergent composition ingredient is a
suds suppressor, exemplified by silicones, and silica-
silicone mixtures. Silicones can be generally represented
by alkylated polysiloxane materials while silica is
normally used in finely divided forms, exemplified by
silica aerogels and xerogels and hydrophobic silicas of
various types. These materials can be incorporated as
particulates in which the suds suppressor is advantageously
releasably incorporated in a water-soluble or water-
dispersible, substantially non-surface-active detergent-
impermeable carrier. Alternatively the suds suppressor can
be dissolved or dispersed in a liquid carrier and applied
by spraying on to one or more of the other components.
As mentioned above, useful silicone suds controlling agents
can comprise a mixture of an alkylated siloxane, of the
type referred to hereinbefore, and solid silica. Such
mixtures are prepared by affixing the silicone to the
surface of the solid silica. A preferred silicone suds
controlling agent is represented by a hydrophobic silanated
(most preferably trimethyl-silanated) silica having a
particle size in the range from 10 nanometers to 20
nanometers and a specific surface area above 50 m2/g,
intimately admixed with dimethyl silicone fluid having a
molecular weight in the range from about 500 to about
2171528
200,000 at a weight ratio of silicone to silanated silica
of from about 1:1 to about 1:2.
A preferred silicone suds controlling agent is disclosed in
Bartollota et al. US Patent 3,933,672. Other particularly
useful suds suppressors are the self-emulsifying silicone "
suds suppressors, described in German Patent Application
DTOS 2,646,126 published April 28, 1977. An example of
such a compound is DC0544Th', commercially available from
Dow Corning, which is a siloxane/glycol copolymer.
The suds suppressors described above are normally employed
at levels of from 0.001% to 0.5% by weight of the
composition, preferably from 0.01% to 0.1% by weight.
The preferred methods of incorporation comprise either
application of the suds suppressors in liquid form by
spray-on to one or more of the major components of the
composition or alternatively the formation of the suds
suppressors into separate particulates that can then be
mixed with the other solid components of the composition.
The incorporation of the suds modifiers as separate
_ particulates also permits the inclusion therein of other
suds controlling materials such as C20-C24 fatty acids,
microcrystalline waxes and high MWt copolymers of ethylene
oxide and propylene. oxide which would otherwise adversely
affect the dispersibility of the matrix. Techniques for
forming such suds modifying particulates are disclosed in
~v
WO 95/07968 PCTIUS94/10062
3' 2171528 .
the previously mentioned Bartolotta et al US Patent No.
3,933,672.
Another optional ingredient useful in the present invention
is one or more enzymes.
Preferred enzymatic materials include the commercially
available amylases, neutral and alkaline proteases,
lipases, esterases and cellulases conventionally
incorporated into detergent compositions. Suitable enzymes
are discussed in US Patents 3,519,570 and 3,533,139.
Finished product compositions
The nonionic containing particles of the present invention
can be effectively combined with other ingredients to form
a multi-purpose granular detergent. In particular, the
finished detergent composition should include detergent
ingredients such as those described above. In finishing a
product, the nonionic surfactant particles can be simply
mixed with the rest of the ingredients that are in
particulate form or in turn may be subjected to further
process steps of spraying liquids and coating with fine
powders.
WO 95107968 PCT/US94/10062
GJ23 32
21
While the performance of the particles described in the
present invention remains excellent, independently of the
rest of the product matrix, it is advantageous to finish
the granular detergent composition in a way that maximises
performance and permits high flexibility to the formulation
of a wide variety of products without major process
changes. This can be achieved by taking a modular approach
to the building of the finished product matrix.
The modular approach is based on the manufacturing of
particles highly specific in one or at most two ingredients
of the formulation which are then mixed at the desired
ratios to form the finished products. These particles,
being highly specific in the ingredient they are to
deliver, can be used in a wide range of products without
need to be modified. These particles can be prepared with
an optimal combination of ingredients that maximize their
properties independently of full finished product
formulations.
In particular, the nonionic surfactant particles described
in the present invention, can be suitably complemented with
one high activity anionic surfactant particle and at least
one builder particle.
The ability to manufacture high activity nonionic and
anionic particles separately allows their use at different
ratios in different formulations. The high activity of
these particles allow their preparation with a minimum
WO 95/07968 PCT/US94/10062
_. 33 21 7 15 2 8
amount of process aids, which are typically inorganic
builders such as zeolites, carbonates, silicates, etc.
Therefore, in a typical household granular detergent
composition, there is room to be able to incorporate one or
more highly specific builder particles by dry mixing. The
presence of builder particles that dissolve independently
from the surfactants, and which preferably have a more
rapid rate of solution than the principle particles which
contain the surfactants, is preferred. This improves the
rate of alkalinity release to the wash and reduces the
potential precipitation of the surfactants with salts of
calcium or magnesium present in hard water.
Processing
The nonionic surfactant containing particles of the present
invention may be prepared by:
a) pumping a surfactant system in its low viscosity state;
b) cooling said nonionic surfactant to a temperature where
its viscosity is increased to at least 20000 cps;
c) granulating the surfactant in the presence of a finely
divided powder;
d) cooling said agglomerates.
Each of these process steps will now be described in more
detail.
WO 95/07968 PCT/US94/10062
. "y
34
L
The surfactant system may be pumped using any conventional
pumping means. However one preferred means of pumping is to
use an extruder. The extruder fulfils the functions of
pumping and mixing the surfactant system on a continuous
basis. A basic extruder consists of a barrel with a smooth
inner cylindrical surface. Mounted within this barrel is
the extruder screw. There is an inlet port for the
surfactant system which, when the screw is rotated, causes
the surfactant system to be moved along the length of the
barrel.
The detailed design of the extruder allows various
functions to be carried out. Additional ports in the barrel
may allow other ingredients, including co-surfactants
and/or chemical structuring agents to be added directly
into the barrel. Secondly means for heating or cooling may
be installed in the wall of the barrel for temperature
control. Thirdly, careful design of the extruder screw
promotes mixing of the paste both with itself and with
other additives.
A preferred extruder is the twin screw extruder. This type
of extruder has two screws mounted in parallel within the
same barrel, which are made to rotate either in the same
direction (co-rotation) or in opposite directions (counter-
rotation). The co-rotating twin screw extruder is the most
preferred piece of equipment for use in this invention.
An extruder is particularly useful in this invention
because the paste can be effectively cooled by adding
liquid nitrogen or solid carbon dioxide into the barrel
2171528 .~i
and at the same time pumps the increasingly viscous
(colder) paste out of the extruder.
Suitable twin screw extruders for use in the present
invention include those supplied by : APV Haker, (CP
series); Werner and Pfleiderer, (Continua Series); Wenger,
(TF Series); Leistritz, (ZSE Series); and Buss, (LR
Series) .
The surfactant system is transferred from the pumping means
into a cooling means. The means for cooling may be any type
of conventional heat exchanger. The surfactant system is
introduced into the heat exchanger at a temperature above
its softening point, and then cooled to a temperature close
to, or even below its softening point with a resulting
sharp increase in viscosity.
The cooling step (b) is preferably performed using a high
pressure scraped surface heat exchanger. Such a piece of
equipment is the Chemetator (Trade Mark), manufactured by
Crown Chemtech Ltd., Reading, England; and the Fryma (Trade
Mark), manufactured by Fryma Maschinen AG, Reinfelden,
Switzerland.
If a very short residence time is achieved in the heat
exchanger (less than 60 seconds, preferably less than 30
seconds), shock cooling or supercooling can be achieved. In
this way the paste stays in a liquid form even at
temperatures below its softening point for a short period
WO 95/07968 21 7 1 5 2 8 PCT/US94/10062
36
of time. The allows very high active agglomerates to be
produced.
The viscous surfactant system is then granulated with
suitable powders (step (c)). Many processes for granulating
surfactant pastes are known to the man skilled in the art.
A process which is suited to the present invention is that
of fine dispersion mixing or agglomeration. In this process
a finely dispersed viscous surfactant system is contacted
with a finely divided powder which causes the powder to
stick together (or agglomerate). Normally a blend of
powders is present in the granulation step, in which case
not all of the powders need to be finely divided. 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 viscous surfactant system 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 above 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.
°~"T/US94/10062
__ w0 95/07968 217 15 2 8
37
The transfer of the viscous surfactant system from the
heat exchanger into the mixer can be done in many ways,
from simply pouring to high pressure pumping through small
holes at the end of the pipe, before the entrance to the
mixer. While all these ways are viable to manufacture
agglomerates with good physical properties, it has been
found that in a preferred embodiment of the present
invention the extrusion of the paste through a die results
in a better distribution in the mixer which improves the
yield of particles with the desired size.
Preferred operating temperatures should also be as low as
possible since this leads to a higher surfactant
concentration in the finished particle. Preferably the
temperature during the agglomeration is less than 80°C,
more preferably between 0°C and 70°C, even more preferably
between 10 and 60°C and most preferably between 20 and
50°C. Lower operating temperatures useful in the process of
the present invention may be achieved by a variety of
methods known in the art such as nitrogen cooling, cold
water jacketing of the equipment, addition of solid C02,
and the like; with a preferred method being solid C02, and
a most preferred method being nitrogen cooling.
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
2~ ~ X528
38
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 LittlefordT"' 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
'm WO 95/07968 21 7 15 2 8 PCT/US94/10062
39
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
blades on an axis of rotation, is preferred. The invention
can be practiced as a batch or a continuous process.
The granulated surfactant particles are then allowed to
cool to ambient temperatures. This may be most effectively
achieved in a fluid bed cooler.
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 as has been
described above.
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.
2171528
40
Examples
In the following examples the abbreviation .
C25E3 stands for a C12-C15 primary alcohol condensed with
an average of 3 moles of ethylene oxide;
C28AS stands for alkyl sulphate with a carbon chain length
principally from C12 to C18. PEG4000 stands for
polyethylene glycol having an average molecular weight of
4000.
Example 1
High active nonionic surfactant particulate compositions
were prepared in batch mode using a pilot plant scale high
shear mixer, an EirichT''' RV02.The mixer was first charged
with a mixture of powders, namely, Zeolite A , Alkyl
Sulphate powder (having a carbon chain length distribution
of C12 to C18), finely divided sodium carbonate and
PEG4000. A surfactant system in the form of a nonionic
surfactant paste consisting of a homogeneous mixture of 1
part ethoxylated nonionic surfactant and 1 part polyhydroxy
fatty acid amide (Palm Glucosamide), was then added on top
of the powder mixture while the mixer was being operated at
1600rpm. Paste was added until discrete granules were
formed in the mixer. The agglomerates where then
transferred to a rotating drum mixer and dusted for 1-2
minutes with a flow aid at a level of 3 % by weight of the
WO 95/07968 2 ~ 7 ~ 5 2 8 PCT/US94/10062
41
granular detergent. The flow aid was a blend of 30 parts
zeolite with 1 part hydrophobic silica. The compositions of
the agglomerates are given below in Table 1.
Table 1: Composition lA Composition iB
% by weight % by weight
Polyhydroxy fatty acid amide 18 19
Nonionic surfactant (C25E3) 18 19
Sodium Alkyl Sulphate 18 20
Sodium Carbonate 27 21
Zeolite 8 18
Poly ethylene glycol (MW=4000) 8
Flow aid (Zeolite/Hydrophobic
silica) 3 3
The resulting agglomerates were made with a total
surfactant activity of 54% and 58% respectively and showed
good cake strength and compression values, and dissolved
rapidly in water.
Example 2
The process of example 1 was repeated to provide the
following composition (see table 2):
WO 95/07968 PCT/US94/10062
~~ ~
?1
V
42
Table 2:
% by weiqht
Polyhydroxy fatty acid amide 20
Nonionic surfactant (C25E3) 20
Sodium Carbonate 30
Zeolite 2~
Flow aid (Zeolite/Hydrophobic silica) 3
The resulting agglomerates were made with a total
surfactant activity of 40% and showed good cake strength
and compression value. Although the rate of dissolution in
water was still acceptable, it was not as rapid as the
composition of example 1 under comparable conditions.
Comparative example 3
This example describes the process in batch mode in a pilot
plant scale high shear mixer as used in example 1. The
mixer was first charged with a mixture of powders namely
Zeolite A and finely divided sodium carbonate. A surfactant
system in the form of a nonionic surfactant paste
consisting of a homogeneous mixture of 1 part ethoxylated
nonionic surfactant and 3 parts of polyhydroxy fatty acid
amides (Tallow Glucosamide), was then added on top of the
" WO 95/07968 21 7 15 2 8 PCT/US94/10062
43
powder mixture while the mixer was being operated at
1600rpm.The following composition was made (see table 3):
The surfactant system has a high softening point, greater
than 100°C.
Table 3:
~y weiqht
Polyhydroxy fatty acid amide 30
Nonionic surfactant (C25E3) 10
Sodium Carbonate 30
Zeolite 27
Flow aid (Zeolite/Hydrophobic silica) 3
The resulting agglomerates were made with a total
surfactant activity of 40% and showed good cake strength
and compression values. However the rate of dissolution of
this composition was considerably slower than either of
examples 1 or 2.
Comparative example 4
This example describes the process in batch mode in a pilot
plant scale high shear mixer as used in example 1. The
mixer was first charged with a mixture of powders to be
used, namely Zeolite A and finely divided sodium carbonate.
A surfactant system in the form of a nonionic surfactant
paste consisting of a homogeneous mixture of 3 parts
WO 95/07968 PCT/US94/10062
44
ethoxylated nonionic surfactant and 1 part polyhydroxy
fatty acid amides (Tallow Glucosamide), was then added on
top of the powder mixture while the mixer was being
operated at 1600rpm. The surfactant system had a softening
point of 40°C and a viscosity of only 13000 cps at a
temperature just above that softening point (viscosity
measured at a shear rate of 25s-1). The following
composition was made (see table 4):
Table 4:
% by weight
Polyhydroxy fatty acid amide 7
Nonionic surfactant (C25E3) 21
Sodium Carbonate 35
Zeolite 34
Flow aid (Zeolite/Hydrophobic silica) 3
The resulting agglomerates were made with a total
surfactant activity of 28% and showed higher cake strength
and compression values. Although this composition has a
rapid rate of dissolution, the total surfactant activity
achieved is lower than either of examples 1 or 2.
Comparative example 5
This example describes the process in batch mode in a pilot
plant scale high shear mixer as used in example 1. The
~ WO 95/07968 21 7 15 2 8 _ PCT/US94/10062
mixer was first filled with a mixture of powders to be
used, in this particular case Zeolite A and fine sodium
carbonate. A nonionic surfactant paste of polyhydroxy
fatty acid amides (Tallow Glucosamide) with a softening
point of 148°C (in this case the softening point is a true
melting point), was then added on top of the powder
mixture while the mixer was being operated at 1600rpm.The
following composition was made (see table 5):
Table 5:
% by we ig,~t
Polyhydroxy fatty acid amide 40
Sodium Carbonate 30
Zeolite
Flow aid (Zeolite/Hydrophobic silica) 3
The resulting agglomerates were made with a total
surfactant activity of 40% and showed high cake strength
and compression values. However the rate of dissolution of
this composition was considerably slower than either of
examples 1 or 2.
Example 6
This example describes the process in batch mode in a
pilot plant scale high shear mixer as used in example 1.
The mixer was first charged with a mixture of powders to be
WO 95!07968 PCT/US94/10062
~Z~~1'~L~ 46
used, namely Zeolite A, finely divided citrate and finely
divided sodium carbonate. Anionic surfactant agglomerates
were separately prepared by granulating a 78% active
surfactant paste (4 parts alkyl sulphate, C14-C15 and 1
part alkyl ether sulphate, C13-C15 with an average of 3
ether groups per molecule) with a powder mixture of
zeolite, carbonate, CMC, acrylic-malefic co-polymer. 22
parts of surfactant paste, 11 parts of zeolite, 9 parts of
carbonate, 1 part of CMC and 5 parts of co-polymer were
used and the resulting agglomerates were ground and sieved
through mesh 250 microns. These fine anionic surfactant
agglomerates were then added together with a surfactant
system in the form of nonionic surfactant paste on top of
the powder mixture while the mixer was operating at
1600rpm. The nonionic surfactant paste consisting of 1 part
ethoxylated nonionic surfactant and 1 part polyhydroxy
fatty acid amides (Palm Stearine Glucosamide). The nonionic
surfactant paste was cooled from 70 to 55 °C and extruded
from a high pressure scraped surface heat exchanger. The
following composition was made (see table 6):
WO 95/07968 PCT/US94/10062
47
Table 6
% by weight
Polyhydroxy fatty acid amide 19
Nonionic surfactant (C25E3) 19
Sodium Carbonate 13
Zeolite 13
Citrate 13
Fine anionic agglomerates 20
Flow aid (Zeolite/Fiydrophobic silica) 3
The agglomerates show excellent handling properties and
rate of surfactant release.
Example 7
A surfactant system was prepared by thorough mixing of two
nonionic surfactants; namely, 50% by weight palm stearine
(C16-C18) glucosamide (GA) with 50% by weight of C12-C15
alkyl ether sulphate (having an average of 3 ether groups
per mole), C25E3.
The surfactant system had a softening point at 50°C, and
viscosities of 25000 cps at 60°C, and 100 cps at 70°C.
WO 95107968 PCT/US94/10062
- ~ n 48
~_~ ~ 1 '~ ~;~
The surfactant system was cooled from 70°C to 60°C and then
granulated with a mixture of particulate materials to give
the following composition:
% by weight
Nonionic surfactant (GA/C25E3) 40
C12-C28 alkyl sulphate powder 10
Zeolite A 20
Citrate 20
Polyethylene glycol (MW=4000) 5
Water and miscellaneous 5
Example 8
Example 7 was repeated replacing the palm stearine
glucosamide by tallow stearine glucosamide.
The surfactant system had a softening point at 65°C, and
viscosities of 25000 cps at 75°C, and 100 cps at 85°C.
The surfactant system was cooled from 85°C to 45°C using a
high pressure scraped surface heat exchanger. The short
residence time (10 seconds) in the heat exchanger results
in the surfactant system remaining liquid for a short
period of time even below the solidification point.
Granulation was then carried out with a mixture of
particulate materials in a Braun food processor to give the
following compositions:
W0 95/07968 2 ~ 7 ~ 5 2 g ' PCT/US94/10062
49
Ex. 8A Ex. 8B
% by weight % by weight
Nonionic surfactant (GA/C25E3) 50 50
C12-C28 alkyl sulphate powder - 15
Zeolite A 25 20
Carbonate 25 15
Example 9
The process of example 8 was repeated using a die at he
outlet of the heat exchanger to form noodles or extrudates
of the surfactant system. The following composition was
produced:
% by weight
Nonionic surfactant (GA/C25E3) 60
C12-C28 alkyl sulphate powder 20
Zeolite A 10
Carbonate 10
The compositions of examples 7 to 9 showed good cake
strength and compression values, and dissolved rapidly in
water.
WO 95/07968 ~ t~ PCT/US94/10062
Example 10
High active nonionic surfactant particulate compositions
were prepared in a batch mode using a pilot plant scale
mixer, an Eirich RV02. The mixer was charged with a mixture
of powders, namely zeolite A , Alkyl Sulphate powder, and
finely divided sodium carbonate. Molten dodecyl glycerol
ether was added on top of the powder while the mixer was
being operated at 1200 rpm. The nonionic surfactant was
added until discrete granules were formed. This viscosity
of the dodecyl glycerol ether was 20,000 cps at 60°C but
4000 cps at 80°C.
The composition was:
% by weight
Dodecyl Glycerol Ether 40%
Alkyl Sulphate 10%
Sodium Carbonate 25%
Zeolite 25%
The agglomerates had a total surfactant activity of 50 %
and showed good cake strength and compression values.
2171528
51
Example 11~
A finished laundry detergent was put together by blending
the following components:
~ by weight
a)Nonionic surfactant agglomerate 13.4
b)Anionic surfactant agglomerate 32.5
c)Layered Silicate compacted granule 10.1
d)Granular Percarbonate 22.7
e)Tetraacetylethylene diamine agglomerate 7.8
f)Suds Suppressor Agglomerate 6.5
g)Perfume encapsulate 0.1
h)Granular Soil Release Polymer 0.4
i)Granular Sodium Citrate dihydrate 3.5
j)Enzymes 3.0
Component a) was prepared according to the composition and
process described in Example lA above.
Component b) was prepared from an anionic surfactant paste
having the following composition, the separate ingredients
being mixed in aqueous form and subsequently dried to the
required water level:
21 7 1528 ~
52
alkyl, sulphate (C14-C15) 57.2
alkyl ether sulphate (C13-C15 with 3E0) 14.3
acrylic-malefic copolymer 16
sodium ethylenediamine-N,N'-disuccinic acid 1.5
water 11
The anionic surfactant paste was maintained at 60°C and
added to an Eirich RV02 mixer, operating at 1600 rpm with
the following powder composition:
zeolite A 14
light soda ash 75
Carboxymethyl cellulose 4
Magnesium sulphate 4
Water g
Sufficient surfactant paste was added to the mixer until
discrete particles, having an average particle size of
about 500 micrometers were obtained. The particles were
then dried in a fluid bed dryer to an equilibrium relative
humidity of 10~ at 20°C.
The final particulate composition of component b) contained
53~ anionic surfactant and had a bulk density of 710 g/1.
Component c), the layered silicate compact granule, was
prepared from powder layered silicate 2.0 ratio (SKS-6
trade mark ex Hoechst), powder citric acid and ethoxylated
s;,~ >.
2~~~528
53
tallow alcohol, TAE50 (average of 50 ether groups). The
SKS-6 and the citric acid, both with an average particle
size of about 150 microns were mixed together while sprayed
with TAE50 in a rotating spray drum at the following
composition
77% SKS-6
21% anhydrous citric acid
2% TAE50
The mixture was then passed to the feed hopper of a roll
compactor and was compacted into a flake. The flake was
ground up to 600 microns average particle size. The
oversize fraction was recycled back to the grinder and the
fines fraction back to the compactor.
The particle prepared via this. process reaches its maximum
calcium exchange capacity at the pH of the wash in less
than 2 minutes.
Components d) to j) were obtained from the following
commercially available sources:
d) supplied by Interox; e) supplied by Warwick
International; f) prepared according to US3,933,672; g)
supplied by Haarman & Reimer; h) supplied by Hoescht;
i) supplied by Jungbunzlauer; j) supplied by Novo Nordisk.
WO 95/07968 PCT/US94/10062
54
2~ 7 128 .
The finished composition was made by placing components a)
to j) in a 120 litre rotating drum operating at 15 rpm. A
mixture of nonionic surfactant and a 20% aqueous solution
of optical brightener at ratios of 14:1 were sprayed at
55°C on to the granular mixture to a level of 5% by weight
of the finished product. The nonionic surfactant used
consisted of a mixture of 7 parts of nonionic surfactant
(C25E3) with 3 parts of palm stearine glucosamide.
Immediately afterwards, perfume was sprayed on at a level
of 0.5%. Finally, without stopping the rotating drum,
zeolite was slowly added to the drum to a level of 5% by
weight of the finished product. The mixer was then
continued for a further 30 seconds, and the product then
discharged.
After two days of ageing the finished composition had a
bulk density of 850 g/1. The particle size distribution
was:
Tyler Sieve no. Micrometers % by weight
of product on sieve
14 1180 1~
20 850 39
35 425 88
65 212 99
100 150 99.5
WO 95/07968 2 1 7 1 5 2 8 PCT/US94/10062
The mean particle size of the finished product composition
was about 720 micrometers.
The product prepared according to this example exhibits
very high rates of dissolution of both anionic and nonionic
surfactants. Furthermore the rate of alkalinity release
(principally due to component c) was excellent.
Example 12
A homogeneous mixture of 2 parts polyhydroxy fatty acid
amide (Palm Stearine Glucosamide) with 3 parts ethoxylated
nonionic surfactant (C25E5) at 85°C was mixed with a
copolymer of acrylic-malefic acid. The paste was then cooled
from 85 to 45 °C using a high pressure scraped surface heat
exchanger. The viscosity of the cooled paste was greater
than 20 000 cps. The cooled paste was immediately
agglomerated with detergent powders in a Braun food
processor. In this example the powders were alkyl sulphate,
sodium carbonate and zeolite A. The resulting agglomerates
had the following composition:
WO 95/07968 PCT/US94/10062
56
by weight
Polyhydroxy fatty acid amide 16
Nonionic surfactant 24
Zeolite A (hydrated) 20
Carbonate 15
Sodium alkyl sulphate 15
Copolymer of acrylic-malefic acid 10
The composition shows good cake strength and compression
values and a high rate of surfactant release in water.
Example 13
This example describes the same process as used in example
12 but now some of the alkyl sulphate powder was premixed
with the mixture of nonionic surfactants prior to cooling.
A die was used at the outlet of the heat exchanger and
therefore the paste was coming out as noodles or
extrudates. The cooled paste was immediately agglomerated
with detergent powders including a copolymer of acrylic-
malefic acid in a Braun food processor. In this case the
powders are Alkyl sulphate (C28AS)~ sodium carbonate and
zeolite A.
WO 95/07968 2 1 7 1 5 2 8 pCT/US94/10062
57
by weictht
Polyhydroxy fatty acid amide 20
Nonionic surfactant 30
Alkyl Sulphate 20
Zeolite A (hydrated) 10
Carbonate 10
Copolymer of acrylic-malefic acid 10
Example 14
This example describes the same process as used in example
13 but a cooled twin screw extruder was used to premix the
alkyl sulphate with the nonionic surfactant instead of a
scraped surface heat exchanger.
Example 15
This example describes the process in batch mode in a pilot
plant scale high shear mixer, an Eirich RV02, to produce
high active nonionic detergent agglomerates. The mixer was
first charged with a mixture of powders to be used, in this
example Zeolite A , Alkyl Sulphate (C28AS), fine citrate
and fine sodium carbonate. A nonionic surfactant paste
comprising a mixture of 1 part polyhydroxy fatty acid
amides (Palm Stearine Glucosamide) with 2 parts ethoxylated
nonionic surfactant (C25E5) was mixed with
WO 95/07968 PCT/U594/10062
58
polyethyleneoxide (molecular weight = 100 000). The paste
was then added to the high shear mixer containing the
powder mixture while the mixer was being operated at
1600rpm. Enough paste was added until the granulation was
achieved. The agglomerates were then transferred to a
rotating drum mixer and dusted for 1-2 minutes with a flow
aid at a level of 3 ~ by weight of the granular detergent.
The composition of the agglomerates is given below.
~ by weight
Polyhydroxy fatty acid amide 12
Nonionic surfactant (C25E5) 24
Alkyl Sulphate 20
Sodium Carbonate 14
Zeolite A 10
Fine citrate 10
Polyethyleneoxide
Flow aid (ZeoliteA /Zeolite DAY) 3
The resulting agglomerates were made with a total
surfactant activity of 57 $ and showed good cake strength
and compression values. The rate of nonionic surfactant
release in water is comparable to example 12.
WO 95/07968 ~ ~ ~ 15 2 a PCT/US94110062
59
Example 16
A homogeneous mixture of 1 part Palm Stearine Glucosamide
with 1 part ethoxylated nonionic surfactant (C25E5) at 90°C
was mixed with a molten Palmitic Acid, PEG 4000 and zeolite
in a jacketed tank fitted with a mixing screw. The
resultant mixture was fed into a continuous belt cooler and
produced into flakes. The flakes had the following
composition:
by weight
Polyhydroxy fatty acid amide 20
Nonionic surfactant 20
Palmitic Acid 10
Zeolite 30
PEG 4000 10
Alkyl Sulphate 10
The resulting flakes were ground up to average particle
size of 200 microns in a pin disk mill using 5 o zeoliteA
as a flow aid. The resulting powders showed good cake
strength and compression values. The rate of nonionic
surfactant release in water is comparable to example 12.
Example 17
A homogeneous mixture of 3 parts Palm stearine Glucoseamide
and 7 parts ethoxylated nonionic surfactant (C25E5) was
WO 95/07968 PCT/US94/10062
2~ l ~ J2u
cooled in a Scraped Wall Cooler (Chemitator~) to 45°C and
mixed with powdered Alkyl Polyglucoside in a twin screw
extruder. The resulting mixture had a viscosity of greater
than 20.000 cps. The mixture was the agglomerated in batch
mode in a pilot plant scale high shear mixer, an Eirich
RV02. The mixer was first charged with a mixture of powders
to be used, in this particular case Zeolite P, fine
citrate and water as a binder, and then the surfactant
mixture was added to the mixture to produce nonionic
detergent agglomerates.
~ by weight
Polyhydroxy fatty acid amide 10
Nonionic surfactant 23
APG 12
Zeolite P 25
Citrate 25
moisture 5
The resulting agglomerates were made with a total detergent
activity of 45$ and showed good cake strength and
compression values. The rate of nonionic surfactant release
in water is comparable to example 12.
