Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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PROCESSES FOR MAKING A GRAN11LAR DETERGENT COMPOSITION
CONTAINING MODIFIED CARBOXY METHYL CELLULOSE
FIELD OF THE INVENTION
The present invention generally relates to processes for producing a granular
detergent
composition. More particularly, the invemion is directed to processes during
which detergent
granules or agglomerates are produced from starting detergent materials, one
of which is a
modified carboxy methyl cellulose.
BACKGROUND OF THE INVENTION
Today's fabrics are made of an increasingly wide variety of materials, and
they come in a
multitude of colors. These various fabric and color combinations present new
and challenging
laundering problems for the consumer. Specifically, consumers want their
clothes and other
fabric articles to retain, for as long as possible the "new" look and feel
that these fabrics have
when they are purchased. But normal laundering processes can slowly degrade
the texture of the
fabrics and vividness of the color. This slow loss of a fabric's luster is
caused in part by the
normal wear and tear associated with the fabric's use, but laundering also
takes it toll on the
appearance of fabrics.
In an effort to appease consumers' desires to slow, or preferably, eliminate
the
degradation of a fabric's appearance, fonmulators have searched for detergent
additives that will
aid in maintaining a fabric's appearance over its normal life cycle. As new
detergent additives
are developed, formulators must find a way to incorporate the additives into
detergent
compositions without adversely affecting the physical or chemical properties
of the existing
composition. That is, an additive that maintains fabric appearance should not
reduce the cleaning
efficacy of the detergent, nor should it cause the detergent to clump or
otherwise have
undesirable physical characteristics in the eyes of the average consumer.
Often, the challenges
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associated with the introduction of a new detergent additive can be met with
adjustments to the
detergent manufacturing process.
Generally, there are two primary types of processes by which detergent
granules or
powders can be prepared. The first type of process involves spray-drying an
aqueous detergent
slurry in a spray-drying tower to produce highly porous detergent granules. In
the second type of
process, the various detergent components are dry mixed after which they are
agglomerated with
a binder such as a nonionic or anionic surfactant. In both processes, the most
important factors
which govern the density of the resulting detergent granules are the density,
porosity and surface
area of the various starting materials and their respective chemical
composition.
Moreover, there has been interest in the art for providing processes which
increase the
density of detergent granules or powders. Particular attention has been given
to densification of
spray-dried granules by post tower treatment. For example, one attempt
involves a batch process
in which spray-dried or granulated detergent powders containing sodium
tripolyphosphate and
sodium sulfate are densified and spheronized in a Marumerizer~. This apparatus
comprises a
substantially horizontal, roughened, rotatable table positioned within and at
the base of a
substantially vertical, smooth walled cylinder. This process, however, is
essentially a batch
process and is therefore less suitable for the large scale production of
detergent powders. More
recently, other processes have developed for increasing the density of "post-
tower" or spray dried
detergent granules. Typically, such processes require a first apparatus which
pulverizes or grinds
the granules and a second apparatus which increases the density of the
pulverized granules by
agglomeration. These processes achieve the desired increase in density by
treating or densifying
"post tower" or spray dried granules. The art is also replete with disclosures
of processes which
entail agglomerating detergent compositions. For example, attempts have been
made to
agglomerate detergent builders by mixing zeolite and/or layered silicates in a
mixer to form free
flowing agglomerates.
Furthermore, it has been long-established practice for detergent formulators
to use
surfactants and combinations thereof in detergent compositions. By way of
example,
various anionic surfactants, especially the alkyl benzene sulfonates, alkyl
sulfates, alkyl alkoxy
sulfates and various nonionic surfactants, such as alkyl ethoxylates and
alkylphenol ethoxylates
are commonly used in detergent formulations. Surfactants have found use as
detergent
components capable of the removal of a wide variety of soils and stains. A
consistent effort,
however, is made by detergent manufacturers to improve detersive properties of
detergent
compositions by providing new and improved surfactants. A problem commonly
associated with
anionic surfactants is their sensitivity to cold water and/or hard water.
Improved cleaning
performance above and beyond current standards, especially for granular
detergent compositions
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to be used under colder wash water conditions and/or in hard water, has been
difficult to attain.
Therefore, it would be desirable to have a process for making a detergent
composition which
exhibits improved cleaning performance over a wide variety of soils and
stains.
Accordingly, there remains a need in the art for a process which produces a
granular
and/or agglomerated detergent composition from starting detergent ingredients
including a
surfactant which exhibits improved fabric appearance protection without any
loss in cleaning
performance. Also, there remains a need for such a process which is more
efficient and
economical to facilitate large-scale production of low dosage or compact
detergents.
BACKGROUND ART
The following references are directed to densifying spray-dried granules:
Appel et al,
U.S. Patent No. 5,133,924 (Lever); Bortolotti et al, U.S. Patent No. 5,160,657
(Lever); Johnson et
al, British patent No. 1,517,713 (Ilnilever); and Curtis, European Patent
Application 451,894.
The following references are directed to producing detergents by
agglomeration: Beerse et al,
U.S. Patent No. 5,108,646 (Procter & Gamble); Hollingsworth et al, European
Patent Application
351,937 (Unilever); Swatling et al, U.S. Patent No. 5,205,958; and Capeci et
al, U.S. Patent No.
5,366,652 (Procter & Gamble).
SUMMARY OF THE INVENTION
The present invention meets the aforementioned needs in the art by providing a
process
for continuously preparing detergent agglomerates comprising the steps of: (A)
continuously
mixing a liquid binder and dry detergent materials into a high speed
mixer/densifier to obtain
detergent agglomerates, wherein the ratio of the liquid binder to the dry
detergent material is
from about 1:10 to about 10:1, wherein the dry detergent materials comprise
modified carboxy
methyl cellulose; (B) optionally mixing the detergent agglomerates in a
moderate speed
mixer/densifier to further densify and agglomerate the detergent agglomerates;
and (C) drying
the detergent agglomerates so as to increase their density. In one preferred
embodiment of this
invention, the dry detergent materials consist essentially of modified carboxy
methyl cellulose.
in another preferred aspect of this invention, the liquid binder comprises
water and a
polymer selected from the group consisting of dye transfer agents, polyamines,
homopolymers
and copolymers of polyacrylates, homopolymers and copolymers of
polyacrylamides,
homopolymers and copolymers of polyvinyl alcohol, homopolymers and copolymers
of
polyvinyl pyrrolidone, polymaleates, aliphatic polyesters, natural proteins,
synthetic non-
crystalline polyaminoacids, water soluble nylons, polyethylene glycol,
polyacrylate and mixtures
thereof. Even more preferably, the liquid binder comprises a polymer selected
from the group
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consisting of a polyvinyl N-Oxide, a copolymer of epichlorohydrin and a cyclic
amine moiety,
and mixtures thereof.
A preferred aspect of the invention includes the use of a surfactant paste in
addition to
the polymer-based liquid binder. The paste includes surfactants selected from
branched and
linear avionics, nonionic, zwitterionic, ampholytic and cationic classes and
compatible mixtures
thereof. Even more preferably the surfactant paste is selected from the group
consisting of linear
straight chain alkylbenzene sulfonates in which the average number of carbon
atoms in the alkyl
group is from about I 1 to 13, abbreviated as C11-13 LAS, Sodium
ethoxysulphate based on a
biodegradable C12/14 synthetic or natural primary alcohol ethoxylate made with
a nominal 3
moles of ethylene oxide.
In another embodiment of this invention there is provided a process for
preparing a high
density detergent composition, wherein additional detergent ingredients are
formulated into
separate agglomerates or granules and then admixed with the modified carboxy
methyl cellulose
containing agglomerates defined above. Specifically, second detergent
agglomerates can be
made by a process comprising the steps of (A) continuously mixing a detergent
surfactant paste
and additional dry detergent materials into a high speed mixer/densifier to
obtain second
detergent agglomerates, wherein the ratio of the surfactant paste to the
additional dry detergent
material is from about 1:10 to about 10:1; (B) optionally mixing the second
detergent
agglomerates in a moderate speed mixer/densifier to increase their density;
(C) drying the second
detergent agglomerates to further increase their density. The second detergent
agglomerates can
then be mixed with the first detergent agglomerates to form the high density
detergent
composition. In another aspect of this embodiment, the surfactant paste can be
replaced by, or
supplemented with an acid precursor of an anionic surfactant and additional
dry detergent
materials which contain an alkaline inorganic material capable of neutralizing
the acid precursor.
Moreover, detergent granules can be admixed with the modified carboxy methyl
cellulose containing agglomerates defined above to form a high density
detergent composition.
These granules can be formed by spray drying an aqueous slurry containing
adjunct detergent
ingredients to form spray dried granules. Then the granules and the detergent
agglomerates can
be blended together to form the high density detergent composition.
It has been surprisingly found that certain modified carboxy methyl cellulose
materials
provide fabric appearance benefits. Unfortunately, the modified carboxy methyl
cellulose
materials are sometimes supplied as a sticky powder, which when added to a
detergent
composition can cause the resulting detergent agglomerates to be sticky as
well. Sticky
agglomerates often cause clumps in the detergent composition which is a strong
consumer
negative. In addition to the stickiness we have also found that these modified
carboxy methyl
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cellulose materials are not always dispersed satisfactorily, resulting in
reduced performance and
moreover localised residues of the material in the washing machine and on the
fabrics.
Furthermore, the inventors also found that other detergent ingredients can
become entrapped in
the cellulosic material, causing further residue problems, reduced performance
of these other
ingredients. The stickiness and the poor dispersability of the modified
carboxy methyl cellulose,
and its deleterious effect on the detergent composition, can be counter-acted
by the processing
conditions and constituents defined herein.
Accordingly, it is an object of the present invention to provide a process for
producing a
granular and/or agglomerated detergent composition directly from starting
detergent ingredients
which includes a surfactant and a modified carboxy methyl cellulose having
improved fabric
integrity performance. It is also an object of the invention to provide such a
process which is not
limited by unnecessary process parameters so that large-scale production of
low dosage or
compact detergents is more economical and efficient. These and other objects,
features and
attendant advantages of the present invention will become apparent to those
skilled in the art
from a reading of the following, detailed description of the invention and the
appended claims.
DETAILED DESCRIPTION OF THE INVENTION
The present process is used in the production of detergent compositions
wherein two
separate agglomerates particles are prepared. A first agglomerate is prepared
from using a liquid
binder comprising a mixture of surfactant selected from the group of LAS,
preferably Cl 1-13
LAS or Sodium ethoxysulphate, wherein the ethoxysulate is preferably based on
a biodegradable
C12/14 synthetic or natural primary alcohol ethoxylate made with a nominal 3
moles of ethylene
oxide and mixtures thereof; this liquid binder is used in combination with a
polymer selected
from the group of a copolymer of epichlorohydrin and a cyclic amine moiety or
polyvinyl N-
Oxide, and mixtures thereof in combination with dry detergent materials that
include a modified
carboxy methyl cellulose. A second agglomerate is prepared using a surfactant
paste and dry
starting materials that do not include modified carboxy methyl cellulose. The
two separate
agglomerates are admixed to form a detergent composition that is free flowing.
Moreover, the
separate detergent particles of this invention can be formed by spray drying
techniques which can
include further processing of the "post-tower" detergent granules. By "post-
tower" detergent
granules, it is meant those detergent granules which have been processed
through a conventional
spray-drying tower or similar apparatus.
Drv Detergent Materials
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The compositions of the invention contain, in addition to a modified carboxy
methyl
cellulose material, at least one suitable adjunct dry detergent ingredient is
preferably included in
the detergent composition. The resulting detergent compositions preferably
comprises from
about 0.01% to about 4%, more preferably from about 0.05% to about 2%, and
most preferably
from about 0.1 % to about 1%, by weight of the modified carboxy methyl
cellulose.
The adjunct dry detergent ingredient is preferably selected from the group
consisting of
builders, enzymes, bleaching agents, bleach activators, suds suppressors, soil
release agents,
brighteners, perfumes, hydrotropes, dyes, pigments, polymeric dispersing
agents, pH controlling
agents, chelants, processing aids, crystallization aids, and mixtures thereof.
The following
disclosure of modified carboxy methyl cellulose materials and adjunct
detergent ingredients and
mixtures thereof for use in the compositions herein is representative of the
detergent ingredients,
but is not intended to be limiting.
As discussed above, certain modified carboxy methyl cellulose materials, which
are in
the form of cellulosic based polymers or oligomers, can provide substantive
and unexpected
cleaning benefits when added to a laundry composition. But these materials can
also pose certain
processing problems for granular detergent formulators. The modified carboxy
methyl cellulose
materials that are suitable for use in laundry operations and provide the
desired fabric appearance
and integrity benefits can be characterized by the following general formula:
R
O
R
O. . R
O O O
O
0 0 ~ -O
R R O
R
wherein each R is selected from the group consisting of R2, R~, and
CH2 CH O RH
R2 x
wherein:
- each R2 is independently selected from the group consisting of H and C1-C4
alkyl;
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O
I I
eachR~is ~CHZ)y'-'-C-OZ
wherein each Z is independently selected from the group consisting of M, R2,
R~, and R";
each RN is independently selected from the group consisting of CS -C20 alkyl,
CS-C7
cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl,
hydroxyalkyl, C1-C20
alkoxy-2-hydroxyalkyl, C7-C20 alkylaryloxy-2-hydroxyalkyl, {R4)2N-alkyl,
(R4)2N-2-
hydroxyalkyl, (R4)3 N-alkyl, (R4)3 N-2-hydroxyalkyl, C6-C 12 aryloxy-2-
hydroxyalkyl,
O RS O R; O RS O
-C CH C CHZ -C CH2 CH C-OM~ and
O RS O
-C-CH-CH2-C-OM
- each R4 is independently selected from the group consisting of H, C1-C20
alkyl, CS-C7
cycloalkyl, C7-C20 alkylaryl, C7-C2p arylalkyl, aminoalkyl, alkylaminoalkyl,
dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and
hydroxyalkyl;
- each RS is independently selected from the group consisting of H, C 1 -C20
alkyl, CS-C7
cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl,
hydroxyalkyl,
(R4)2N-alkyl, and (R4)3 N-alkyl:
wherein:
M is a suitable cation selected from the group consisting of Na, K, 1/2Ca, and
1/2Mg;
each x is from 0 to about 5;
each y is from about 1 to about S; and
provided that:
- the Degree of Substitution for group RH is between about 0.001 and 0.1, more
preferably
between about 0.005 and 0.05, and most preferably between about 0.01 and 0.05;
- the Degree of Substitution for group R~ wherein Z is H or M is between about
0.2 and 2.0,
more preferably between about 0.3 and 1.0, and most preferably between about
0.4 and
0.7;
- if any RH bears a positive charge, it is balanced by a suitable anion; and
- two R4's on the same nitrogen can together form a ring structure selected
from the group
consisting of piperidine and morpholine.
Preferably the carboxy methyl cellulose is modified with an ester linkage,
ether linkage or
combinations thereof. Modified carboxy methyl cellulose materials suitable for
use in this
invention are described in greater detail in two co-pending applications
entitled "Laundry
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Detergent Compositions With Cellulosic Based Polymers to Provide Appearance
and Integrity
Benefits to Fabrics Laundered Therewith", PCT Ser. No. PCT/US98/19139 and PCT
Ser. No.
PCT/US98/19142. Both of these applications were filed in the PCT on September
15, 1998, in
the name of Jennifer A. Leupin et al., and they claim the benefit of U.S.
provisional application
60/058,892, filed on September 15, 1997. The entire disclosures of PCT Ser.
No.
PCT/L1S98/19139 and PCT Ser. No. PCT/US98/19142 are incorporated herein by
reference.
One or more builders can be used to further improve the perfonmance of the
compositions described herein. For example, the builder can be selected from
the group
consisting of aluminosilicates, crystalline layered silicates, MAP zeolites,
citrates, amorphous
silicates, polycarboxylates, sodium carbonates and mixtures thereof. The
sodium carbonate
ingredient can serve as the inorganic alkaline material when a liquid acid
precursor of the mid-
chain branched surfactant is used. Other suitable auxiliary builders are
described hereinafter.
Preferred builders include aluminosilicate ion exchange materials and sodium
carbonate.
The aluminosilicate ion exchange materials used herein as a detergent builder
preferably have
both a high calcium ion exchange capacity and a high exchange rate. Without
intending to be
limited by theory, it is believed that such high calcium ion exchange rate and
capacity are a
function of several interrelated factors which derive from the method by which
the
aluminosilicate ion exchange material is produced. In that regard, the
aluminosilicate ion
exchange materials used herein are preferably produced in accordance with
Corkill et al, U.S.
Patent No. 4,605,509 (Procter & Gamble), the disclosure of which is
incorporated herein by
reference.
Preferably, the aluminosilicate ion exchange material is in "sodium" form
since the
potassium and hydrogen forms of the instant aluminosilicate do not exhibit as
high of an
exchange rate and capacity as provided by the sodium form. Additionally, the
aiuminosilicate
ion exchange material preferably is in over dried form so as to facilitate
production of crisp
detergent aggiomerates as described herein. The aluminosilicate ion exchange
materials used
herein preferably have particle size diameters which optimize their
effectiveness as detergent
builders. The term "particle size diameter" as used herein represents the
average particle size
diameter of a given aluminosilicate ion exchange material as determined by
conventional
analytical techniques, such as microscopic determination and scanning electron
microscope
(SEM). The preferred particle size diameter of the aluminosilicate is from
about 0.1 micron to
about 10 microns, more preferably from about 0.5 microns to about 9 microns.
Most preferably,
the particle size diameter is from about 1 microns to about 8 microns.
Preferably, the aluminosilicate ion exchange material has the formula
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Naz[(A102)z.(Si02)y]xH20
wherein z and y are integers of at least 6, the molar ratio of z to y is from
about 1 to about 5 and
x is from about 10 to about 264. More preferably, the aluminosilicate has the
formula
Nal2[(A102)12.(Si02)12]~20
wherein x is from about 20 to about 30, preferably about 27. These preferred
aluminosilicates
are available commercially, for example under designations Zeolite A, Zeolite
B and Zeolite X.
Alternatively, naturally-occurring or synthetically derived aluminosilicate
ion exchange
materials suitable for use herein can be made as described in Krummel et al,
U.S. Patent No.
3,985,669, the disclosure of which is incorporated herein by reference.
The aluminosilicates used herein are further characterized by their ion
exchange capacity
which is at least about 200 mg equivalent of CaC03 hardness/gram, calculated
on an anhydrous
basis, and which is preferably in a range from about 300 to 352 mg equivalent
of CaC03
hardness/gram. Additionally, the instant aluminosilicate ion exchange
materials are still further
characterized by their calcium ion exchange rate which is at least about 2
grains
I S Ca++/gallon/minute/-gram/gallon, and more preferably in a range from about
2 grains
Ca++/gallon/minute/-gram/gallon to about 6 grains Ca++/gallon/minute/-
gram/gallon .
Liquid Binder
To form the desired agglomerates of the present invention, the dry starting
materials are
mixed with a liquid binder. A binder is added for purposes of enhancing
agglomeration by
providing a "binding" or "sticking" agent for the detergent components. The
preferred liquid
binder for use in this invention comprises water, surfactant paste and a
polymer. The paste
includes surfactants selected from branched and linear anionics, nonionic,
zwitterionic,
ampholytic and cationic classes and compatible mixtures thereof. The
viscosity, rheology and
chemical composition of the surfactant pastes are described in more detail
below. The polymer
is selected from the group consisting of dye transfer agents, polyamines,
homopolymers and
copolymers of polyacrylates, homopolymers and copolymers of polyacrylamides,
homopolymers
and copolymers of polyvinyl alcohol, homopolymers and copolymers of polyvinyl
pyrrolidone,
polymaleates, aliphatic polyesters, natural proteins, synthetic non-
crystalline polyaminoacids,
water soluble nylons, polyethylene glycol, polyacrylate and mixtures thereof.
Detergent
compositions made with the agglomerates of this invention preferably comprise
from about
0.01% to about 4%, more preferably from about 0.05% to about 2%, and most
preferably from
about 0.1% to about 1%, by weight of the liquid binder.
Preferably the surfactant paste is selected from the group consisting of
linear straight
chain alkylbenzene sulfonates, preferably linear straight chain alkylbenzene
sulfonates in which
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the average number of carbon atoms in the alkyl group is from about 11 to 13
(abbreviated as
C11-13 LAS), sodium ethoxysulphate, preferably based on a biodegradable C12/14
synthetic or
natural primary alcohol ethoxylate made with a nominal 3 moles of ethylene
oxide, and mixtures
thereof.
Preferably the dye transfer agent is a polyvinyl N-Oxide such as poly(4-
vinylpyridine-N-
oxide) "PVNO". Copolymers of N-vinylpyrrolidone and N-vinylimidazole are also
acceptable
for use herein. Polyvinyl N-oxide materials are disclosed in U.S. Patent No.
5,804,543, which
issued on September 8, 1998, to Wertz and Panandiker. The entire disclosure of
U.S. Patent No.
5,804,543 is incorporated herein by reference.
Additionally preferred liquid binders for use in this invention are
polyamines, and even
more preferred are copolymers of epichlorohydrin and a cyclic amine moiety.
Descriptions and
example of the preferred polyamines for use in this invention can be found in
the following PCT
Patent Applications: PCT/LIS98/19143, PCT/US98/19141, and PCT/US98/19144, all
three of
these applications were filed internationally on September 15, 1998 and they
all claim the benefit
of U.S Provisional Application No. 60/058,931, which was filed on September
15, 1997. The
entire disclosures of PCT/US98/19143, PCT/US98/19141, and PCT/US98/19144 are
incorporated herein by reference. Moreover, U.S. Provisional Application No.
60/103,978, .
which was filed on October 13, 1998, discloses a detergent composition
comprising copolymers
of epichlorohydrin and a cyclic amine moiety with modified carboxy methyl
cellulose materials.
The entire disclosure of U.S. Provisional Application No. 60/103,978 is
incorporated herein by
reference.
Optionally, the process comprises the step of spraying an additional binder in
one or both
of the mixer/densifiers. The additional binder is preferably selected from the
group consisting of
water, anionic surfactants, nonionic surfactants, polyethylene glycol,
polyvinyl pyrrolidone
polyacrylates, citric acid and mixtures thereof. Other suitable binder
materials including those
listed herein are described in Beerse et al, U.S. Patent No. 5,108,646
(Procter & Gamble Co.), the
disclosure of which is incorporated herein by reference.
Surfactant Paste
The viscoelastic surfactant paste used herein has viscoelastic fluid
properties which can
be described by a commonly used mathematical model that accounts for the shear
thinning nature of the
paste. The mathematical model is called the Power Law Model and is described
by the following
relation:
a = Kyn
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where a = Shear Stress (dynes/cm2), K = Consistency (Poise~secn-1 ), y = Shear
Rate (sec-1 ), and n =
Rate Index (dimensionless). The rate index n varies from 0 to 1. The closer n
is to 0, the more shear
thinning the fluid. The closer n is to 1, the closer it is to simple Newtonian
behavior, i.e. constant
viscosity behavior. K can be interpreted as the apparent viscosity at a shear
rate of 1 sec-l .
In this context, the viscoelastic surfactant paste used in the process has a
consistency K at 70°C
of from about 50,000 to about 450,000 cPoise~secn-1 (500 to 2,500 Poise~secn-
1), more preferably from
about 100,000 to about 195,000 cPoise~secn-1 (1.000 to 1,950 Poise~secn-1),
and most preferably from
about 120,000 to about 180,000 cPoise~secn-1 (1,200 to 1,800 Poise~secn-1).
Preferably, the surfactant
paste has a shear index n of from about 0.05 to about 0.25, more preferably
from about 0.08 to about 0.20
and most preferably from about 0.10 to about 0.15.
The paste includes surfactants selected from branched and linear anionics,
nonionic,
zwitterionic, ampholytic and cationic classes and compatible mixtures thereof.
Detergent
surfactants useful herein are described in U.S. Patent 3,664,961, Norris,
issued May 23, 1972,
and in U.S. Patent 3,919,678, Laughlin et al., issued December 30, 1975, both
of which are
incorporated herein by reference. Useful cationic surfactants also include
those described in U.S.
Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent
4,239,659, Murphy,
issued December 16, 1980, both of which are also incorporated herein by
reference.
The following are representative examples of detergent surfactants useful in
the present
surfactant paste. Water-soluble salts of the higher fatty acids, i.e.,
"soaps", are useful anionic
surfactants in the compositions herein. This includes alkali metal soaps such
as the sodium,
potassium, ammonium, and alkylolammonium salts of higher fatty acids
containing from about 8
to about 24 carbon atoms, and preferably from about 12 to about 18 carbon
atoms. Soaps can be
made by direct saponification of fats and oils or by the neutralization of
free fatty acids.
Particularly useful are the sodium and potassium salts of the mixtures of
fatty acids derived from
coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
Additional anionic surfactants that are suitable for use herein include the
water-soluble
salts, preferably the alkali metal, ammonium and alkylolammonium salts, of
organic sulfuric
reaction products having in their molecular structure a straight-chain alkyl
group containing from
about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester
group. (Included in
the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group
of synthetic
surfactants are the sodium and potassium alkyl sulfates, especially those
obtained by sulfating the
higher alcohols (C8-18 carbon atoms) such as those produced by reducing the
glycerides of
tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in
which the alkyl
group contains from about 9 to about 15 carbon atoms, in straight chain, e.g.,
those of the type
described in U.S. Patents 2,220,099 and 2,477,383. Especially valuable are
linear straight chain
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alkylbenzene sulfonates in which the average number of carbon atoms in the
alkyl group is from
about 11 to 13, abbreviated as C11-13 LAS.
Other anionic surfactants suitable for use herein are the sodium alkyl
glyceryl ether
sulfonates, especially those ethers of higher alcohols derived from tallow and
coconut oil;
sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or
potassium of
ethylene oxide per molecule and wherein the alkyl groups contain from about 8
to about 12
carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether
sulfates containing
about 1 to about I O units of ethylene oxide per molecule and wherein the
alkyl group contains
from about i0 to about 20 carbon atoms.
In addition, suitable anionic surfactants include the water-soluble salts of
esters of
alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the
fatty acid group
and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of
2-acyloxyalkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in
the acyl group
and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether
sulfates containing
from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30
moles of ethylene
oxide; water-soluble salts of olefin and paraffin sulfonates containing from
about 12 to 20 carbon
atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon
atoms in the .
alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
Preferred adjunct anionic surfactants are C10-18 linear alkylbenzene sulfonate
and
C10-18 alkyl sulfate. If desired, low moisture (less than about 25% water)
alkyl sulfate paste can
be the sole ingredient in the surfactant paste. Most preferred are CIO-18
alkyl sulfates, linear or
branched, and any of primary, secondary or tertiary. A preferred embodiment of
the present
invention is wherein the surfactant paste comprises from about 20% to about
40% of a mixture of
sodium C10-13 linear alkylbenzene sulfonate and sodium C12-16 alkyl sulfate in
a weight ratio
of about 2:1 to 1:2. Another preferred embodiment of the detergent composition
includes a
mixture of CIO-lg alkyl sulfate and C10-18 alkyl ethoxy sulfate in a weight
ratio of about 80:20.
Water-soluble nonionic surfactants are also useful in the instant invention.
Such
nonionic materials 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.
Suitable nonionic surfactants include the polyethylene oxide condensates of
alkyl
phenols, e.g., the condensation products of alkyl phenols having an alkyl
group containing from
about 6 to 15 carbon atoms, in either a straight chain or branched chain
configuration, with from
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about 3 to 12 moles of ethylene oxide per mole of alkyl phenol. Included are
the water-soluble
and water-dispersible condensation products of aliphatic alcohols containing
from 8 to 22 carbon
atoms, in either straight chain or branched configuration, with from 3 to 12
moles of ethylene
oxide per mole of alcohol.
An additional group of nonionics suitable for use herein are semi-polar
nonionic
surfactants which include water-soluble amine oxides containing one alkyl
moiety of from abut
to 18 carbon atoms and two moieties selected from the group of alkyl and
hydroxyalkyl
moieties of from about 1 to about 3 carbon atoms; water-soluble phosphine
oxides containing one
alkyl moiety of about 10 to 18 carbon atoms and two moieties selected from the
group consisting
10 of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon
atoms; and
water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18
carbon atoms and a
moiety selected from the group consisting of alkyl and hydroxyalkyl moieties
of from about 1 to
3 carbon atoms.
Preferred nonionic surfactants are of the formula R1(OC2H4)nOH, wherein Rl is
a
C10-C16 alkyl group or a C8-C12 alkyl phenyl group, and n is from 3 to about
80. Particularly
preferred are condensation products of C 12-C 15 alcohols with from about 5 to
about 20 moles of
ethylene oxide per mole of alcohol, e.g., C 12-C 13 alcohol condensed with
about 6.5 moles of
ethylene oxide per mole of alcohol.
Additional suitable nonionic surfactants include polyhydroxy fatty acid
amides. Examples
are N-methyl N-1-deoxyglucityl cocoamide and N-methyl N-1-deoxyglucityl
oleamide. Processes
for making polyhydroxy fatty acid amides are known and can be found in Wilson,
U.S. Patent No.
2,965,576 and Schwartz, U.S. Patent No. 2,703,798, the disclosures of which
are incorporated herein
by reference.
Ampholytic surfactants include derivatives of aliphatic or aliphatic
derivatives of
heterocyclic secondary and tertiary amines in which the aliphatic moiety can
be straight chain or
branched and wherein one of the aliphatic substituents contains from about 8
to 18 carbon atoms
and at least one aliphatic substituent contains an anionic water-solubilizing
group.
Zwitterionic surfactants include derivatives of aliphatic, quaternary,
ammonium,
phosphonium, and sulfonium compounds in which one of the aliphatic
substituents contains from
about 8 to 18 carbon atoms.
Cationic surfactants can also be included in the present invention. Cationic
surfactants
comprise a wide variety of compounds characterized by one or more organic
hydrophobic groups
in the cation and generally by a quaternary nitrogen associated with an acid
radical. Pentavalent
nitrogen ring compounds are also considered quaternary nitrogen compounds.
Suitable anions
are halides, methyl sulfate and hydroxide. Tertiary amines can have
characteristics similar to
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cationic surfactants at washing solution pH values less than about 8.5. A more
complete
disclosure of these and other cationic surfactants useful herein can be found
in U.S. Patent
4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference.
Cationic surfactants are often used in detergent compositions to provide
fabric softening
and/or antistatic benefits. Antistatic agents which provide some softening
benefit and which are
preferred herein are the quaternary ammonium salts described in U.S. Patent
3,936,537,
Baskerville, Jr. et al., issued February 3, 1976, the disclosure of which is
incorporated herein by
reference.
A~elomeration Process
As used herein, the term "agglomerates" refers to particles formed by build-up
agglomeration of starting detergent ingredients (particles) which typically
have a smaller median
particle size than the formed agglomerates. All percentages and ratios used
herein are expressed
as percentages by weight (anhydrous basis) unless otherwise indicated. All
documents are
incorporated herein by reference. All viscosities referenced herein are
measured at 70°C (t5°C)
and at shear rates of about 10 to 100 sec-1
In the first step of the process, the invention entails continuously mixing
into a high .
speed mixer/densifier several streams of starting detergent ingredients which
include a liquid
binder comprising a mix of a liquid polymer and asurfactant paste. Dry
detergent materials,
which may include a modified carboxy methyl cellulose material, are also added
continuously
into the high speed mixer/densifier.
In one embodiment of the process the dry starting detergent material comprises
from
about 10% to about 50%, preferably from about 15% to about 45% and, most
preferably from
about 20% to about 40% of an aluminosilicate or zeolite builder and from about
10% to about
40%, preferably from about 15% to about 30% and, most preferably from about
15% to about
25% of a sodium carbonate. It should be understood that additional starting
detergent ingredients
several of which are described hereinafter may be mixed into high speed
mixer/densifier without
departing from the scope of the invention.
In another embodiment of the process, the dry starting detergent material
comprises from
about 10% to about 50%, preferably from about 15% to about 45% and, most
preferably from
about 20% to about 40% of an aluminosilicate or zeolite builder and from about
10% to about
40%, preferably from about 15% to about 30% and, most preferably from about
15% to about
25% of an ester modified carboxy methyl cellulose. It should be understood
that additional
starting detergent ingredients several of which are described hereinafter may
be mixed into high
speed mixer/densifier without departing from the scope of the invention.
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However, it has been found that when the liquid binder comprising of liquid
polymer and
surfactant paste and the dry starting detergent material are continuously
mixed within the ratio
ranges described herein the desired free flowing, crisp, high density
detergent composition are
produced. Preferably, the ratio of the surfactant paste or liquid binder to
the dry starting detergent
material is from about 1:10 to about 10:1, more preferably from about 1:4 to
about 4:1 and, most
preferably from about 2:1 to about 2:3.
Also, it has been found that the first processing step can be successfully
completed,
under the process parameters described herein, in a high speed mixer/densifier
which preferably
is a Lbdige CB mixer or similar brand mixer. These types of mixers essentially
consist of a
horizontal, hollow static cylinder having a centrally mounted rotating shaft
around which several
plough-shaped blades are attached. Preferably, the shaft rotates at a speed of
from about 300 rpm
to about 2500 rpm, more preferably from about 400 rpm to about 1600 rpm.
Preferably, the
mean residence time of the detergent ingredients in the high speed
mixer/densifier is preferably
in range from about 2 seconds to about 45 seconds, and most preferably from
about 5 seconds to
about 15 seconds. The mean residence time can be conveniently and accurately
measured by
dividing the tear weight of the mixer/densifier by the throughput (e.g.,
kg/hr).
The resulting detergent agglomerates formed in the high speed mixer/densifier
are then
fed into a lower or moderate speed mixer/densifier during which further
agglomeration and
densification is carried forth. This particular moderate speed mixer/densifier
used in the present
process should include liquid distribution and agglomeration tools so that
both techniques can be
carried forth simultaneously. It is preferable to have the moderate speed
mixer/densifier to be, for
example, a Lodige KM (Ploughshare) mixer, Drais~ K-T 160 mixer or similar
brand mixer. The
main centrally rotating shaft speed is from about 30 to about 160 rpm, more
preferably from
about 50 to about 100 rpm. The mean residence time in the moderate speed
mixer/densifier is
preferably from about 0.25 minutes to about 15 minutes, most preferably the
residence time is
about 0.5 to about 10 minutes. This mean residence time also can be
conveniently and accurately
measured by dividing the tear weight of the mixer/densifier at steady state by
the throughput
(e.g., kg/hr). The liquid distribution is accomplished by cutters, generally
smaller in size than the
rotating shaft, which preferably operate at about 3600 rpm.
In accordance with the present process, the high speed mixer/densifier and
moderate
speed mixer/densifier in combination preferably impart a requisite amount of
energy to form the
desired agglomerates. More particularly, the instant process imparts from
about 5 x 1010 erg/kg
to about 2 x 1012 erg/kg at a rate of from about 3 x 108 erg/kg-sec to about 3
x 109 erg/kg-sec to
forth free flowing high density detergent agglomerates. The energy input and
rate of input can be
determined by calculations from power readings to the moderate speed
mixer/densifier with and
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without granules, residence time of the granules in the mixer/densifier, and
the mass of the
granules in the mixer/densifier. Such calculations are clearly within the
scope of the skilled
artisan.
Thereafter, the detergent agglomerates are dried in a fluid bed dryer or
similar apparatus.
The density of the resulting detergent agglomerates exiting the fluid bed
dryer is at least 400 g/1,
more preferably from about 500 g/1 to about 600 g/l.
The particle porosity of the resulting detergent agglomerates of the
composition is
preferably in a range from about 5% to about 20%, more preferably at about
10%. As those
skilled in the art will readily appreciate. a low porosity detergent
agglomerate provides a dense or
low dosage detergent product, to which the present process is primarily
directed. In addition, an
attribute of dense or densified detergent agglomerates is the relative
particle size. The present
process typically provides agglomerates having a median particle size of from
about 400 microns
to about 700 microns, and more preferably from about 475 microns to about 600
microns. As
used herein, the phrase "median particle size" refers to individual
agglomerates and not
individual particles or detergent granules. The combination of the above-
referenced porosity and
particle size results in agglomerates having density values of 600 g/1 and
higher. Such a feature
is especially useful in the production of low dosage laundry detergents as
well as other granular
compositions such as dishwashing compositions.
Optional Process Steps
In an optional step of the present process, the detergent agglomerates exiting
the fluid
bed dryer are further conditioned by cooling the agglomerates in a fluid bed
cooler or similar
apparatus as are well known in the art. Another optional process step involves
adding a coating
agent to improve flowability and/or minimize over agglomeration of the
detergent composition in
one or more of the following locations of the instant process: (1) the coating
agent can be added
directly after the fluid bed cooler; (2) the coating agent may be added
between the fluid bed dryer
and the fluid bed cooler; (3) the coating agent may be added between the fluid
bed dryer and the
moderate speed mixer/densifier; and/or (4) the coating agent may be added
directly to the
moderate speed mixer/densifier and the fluid bed dryer. It should be
understood that the coating
agent can be added in any one or a combination of streams, see Capeci et al,
U.S. Patent
5,516,448, issued May 14, 1996 and Capeci et al, U.S. Patent 5,489,392, issued
February 6, 1996.
The coating agent is preferably selected from the group consisting of
aluminosilicates,
silicates, carbonates and mixtures thereof. However, the coating agent may be
one or more
combinations of the builder material, aluminosilicates, carbonates, silicates
and the like. The
coating agent not only enhances the free flowability of the resulting
detergent composition which
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is desirable by consumers in that it permits easy scooping of detergent during
use, but also serves
to control agglomeration by preventing or minimizing over agglomeration,
especially when
added directly to the moderate speed mixerldensifier. As those skilled in the
art are well aware,
over agglomeration can lead to very undesirable flow properties and aesthetics
of the final
detergent product.
Other optional steps contemplated by the present process include screening the
oversized
detergent agglomerates in a screening apparatus which can take a variety of
forms including but
not limited to conventional screens chosen for the desired particle size of
the finished detergent
product. Other optional steps include conditioning of the detergent
agglomerates by subjecting
the agglomerates to additional drying.
Another optional step of the instant process entails finishing the resulting
detergent
agglomerates by a variety of processes including spraying and/or admixing
other conventional
detergent ingredients. For example, this step encompasses spraying perfumes,
brighteners and
enzymes onto the finished agglomerates to provide a more complete detergent
composition.
Such techniques and ingredients are well known in the art.
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Spra~rvine Process
One or more spray drying techniques can be used alone, or in combination with
the
aforementioned agglomeration processes, to make detergent compositions in
accordance with the
instant invention. One or more spray-drying towers may be employed to
manufacture granular
laundry detergents which often have a density of about 500 g/1 or less. In
this procedure, an
aqueous slunry of various heat-stable ingredients in the final detergent
composition are formed
into homogeneous granules by passage through a spray-drying tower, using
conventional
techniques, at temperatures of about 175°C to about 225°C. If
spray drying is used as part of the
overall process herein, additional process steps as described herein can be
optionally used to
obtain the level of density (i.e., > 650 g/1) required by modem compact, low
dosage detergent
products.
For example, spray-dried granules from a tower can be densified further by
loading a
liquid such as water or a nonionic surfactant into the pores of the granules
and/or subjecting them
to one or more high speed mixer/densifiers. A suitable high speed
mixer/densifier for this
process is the aforementioned "Lodige CB 30" or "Lddige CB 30 Recycler" which
comprises a
static 'cylindrical mixing drum having a central rotating shaft with
mixing/cutting blades mounted
thereon. In use, the ingredients for the detergent composition are introduced
into the drum and
the shaftlblade assembly is rotated at speeds in the range of 100-2500 rpm to
provide thorough
mixing/densification. See Jacobs et al, U.S. Patent 5,149,455, issued
September 22, 1992. Other
such apparatus includes the devices marketed under the trade name "Shugi
Granulator" and under
the tradename "Drais K-TTP 80).
Another process step which can be used to densify further spray-dried granules
involves
grinding and agglomerating or deforming the spray-dried granules in a moderate
speed
mixer/densifier so as to obtain particles having lower porosity. Equipment
such as the
aforementioned "Lddige KM" (Series 300 or 600) or "Ltidige Ploughshare"
mixer/densifiers are
suitable for this process step. Other useful equipment includes the device
which is available
under the tradename "Drais K-T 160". This process step which employs a
moderate speed
mixer/densifier (e.g. Lodige KM) can be used by itself or sequentially with
the aforementioned
high speed mixer/densifier (e.g. Lodige CB) to achieve the desired density.
Other types of
granules manufacturing apparatus useful herein include the apparatus disclosed
in U.S. Patent
2,306,898, to G. L. Heller, December 29, 1942.
While it may be more suitable to use the high speed mixer/densifier followed
by the low
speed mixer/densifier, the reverse sequential mixer/densifier configuration is
also contemplated
by the invention. One or a combination of various parameters including
residence times in the
mixer/densifiers, operating temperatures of the equipment, temperature and/or
composition of the
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granules, the use of adjunct ingredients such as liquid binders and flow aids,
can be used to
optimize densification of the spray-dried granules in the process of the
invention. By way of
example, see the processes in Appel et al, U.S. Patent 5,133,924, issued July
28, 1992 (spray-
dried granules are brought into a deformable state prior to densification);
Delwel et al, U.S.
Patent 4,637,891, issued January 20, 1987 (granulating spray-dried granules
with a liquid binder
and aluminosilicate); Kruse et al, U.S. Patent 4,726,908, issued February 23,
1988 (granulating
spray-dried granules with a liquid binder and aluminosilicate); and,
Bortolotti et al, U.S. Patent
5,160,657, issued November 3, 1992 (coating densified spray-dried granules
with a liquid binder
and aluminosilicate).
Admixin;a Process
Specifically, other aspects of the process invention include admixing
additional detergent
materials with the various agglomerates, spray dried granules and combinations
thereof. This
admixing step may be enhanced by combining the agglomerates, granules, or
combinations
thereof with additional detergent materials and a liquid binder in a mixing
drum or other similar
device. Optionally, the additional detergent materials may be coated with a
nonionic surfactant
or other liquid binder as described previously before the admixing step so as
to preclude any .
deleterious interaction with the other detergent ingredients (e.g. anionic
surfactants) prior to
immersion in the washing solution (i.e. during processing and storage). This
liquid binder or
nonionic surfactant coating also improves the flow properties of the detergent
composition in
which the builder material is included.
Other Processes
In yet another process embodiment, the high density detergent composition can
be
produced by feeding a liquid acid precursor of an anionic surfactant, an
alkaline inorganic
material (e.g. sodium carbonate) and optionally other detergent ingredients
into a high speed
mixer/densifier (residence time 5-30 seconds) so as to form agglomerates
containing a partially
or totally neutralized anionic surfactant salt and the other starting
detergent ingredients.
Subsequently, the contents in the high speed mixer/densifier can be sent to a
moderate speed
mixer/densifier (e.g. Lodige KM) for further agglomeration resulting in the
finished high density
detergent composition. In another process embodiment, the surfactant paste is
premixed or
extruded in a mixing or extruding apparatus such as a twin-screw extruder
(e.g., Wetner and
Pfleiderer, Continua Series) to structure the paste for easier agglomeration.
Additionally,
structuring agents such as polymers, sodium hydroxide, sodium chloride,
postassium hydroxide
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silicates and the like can be used to render the paste more suitable for
loading higher amounts of
surfactant. See Aouad et al, U.S. Patent 5,451,354, issued September 19, 1995.
Optionally, high density detergent compositions can be produced by blending
conventional or densified spray-dried detergent granules with detergent
agglomerates in various
proportions (e.g. a 60:40 weight ratio of granules to agglomerates) produced
by one or a
combination of the processes discussed herein. Additional adjunct ingredients
such as enzymes,
perfumes, brighteners and the like can be sprayed or admixed with the
agglomerates, granules or
mixtures thereof produced by the processes discussed herein.
Another process of the invention involves cooling a molten surfactant paste
and
forming flakes on a chill roll, after which the flakes are ground to the
desired particle size. The
cooled flakes can be dried further using a rotary drum dryer.
In order to make the present invention more readily understood, reference is
made to the
following examples, which are intended to be illustrative only and not
intended to be limiting in
scope.
EXAMPLE I
This Example illustrates the process of the invention which produces free
flowing, crisp,
high density detergent composition. Two feed streams of various detergent
starting ingredients
are continuously fed, at a rate of 2800 kg/hr, into a Lddige CB-30
rnixer/densifier. One stream
comprises a liquid binder containing water and PVNO the other stream
containing dry detergent
materials containing an ester modified carboxy methyl cellulose,
aluminosilicate and sodium
carbonate. The rotational speed of the shaft in the Lbdige CB-30
mixer/densifier is about 1400
rpm and the mean residence time is about 10 seconds. The contents from the
Lbdige CB-30
mixer/densifer are continuously fed into a Lodige KM 600 mixer/densifer for
further
agglomeration during which the mean residence time is about 30 seconds. The
resulting
detergent agglomerates are then fed to a fluid bed dryer and then to a fluid
bed cooler, the mean
residence time being about 10 minutes and 15 minutes, respectively. A coating
agent,
aluminosilicate, is fed after the Lodige KM 600 mixer/densifier to control and
prevent over
agglomeration. The detergent agglomerates are then screened with conventional
screening
apparatus resulting in a uniform particle size distribution. The composition
of the detergent
agglomerate mixture exiting the fluid bed cooler for three process runs are
set forth in Table I
below:
TABLE I
Com vent % Weight of Total Feed
A B C
Ester Modified Carboxy Methyl Cellulose 5.0 5.0 3.0
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PEG 36.0 41.0 22.0
Aluminosilicate 25.4 24.0 34.0
Sodium carbonate 26.3 24.0 34.0
Polyethylene glycol (MW 1.1 1.7 2.0
4000)
Misc. (water, etc.) 6-22 4.3 5.0
100.0 100.0 100.0
EXAMPLE II-V
Several detergent compositions made in accordance with the invention and
specifically
for top-loading washing machines are exemplified below. The base granule is
prepared by a
conventional spray drying process in which the starting ingredients are formed
into a slurry and
passed though a spray drying tower having a counter current stream of hot air
(200-300°C)
resulting in the formation of porous granules. The admixed agglomerates are
formed from two
feed streams of various starting detergent ingredients which are continuously
fed, at a rate of
1400 kg/hr, into a Schugi high shear granulator ( 1000-4000 RPM) or a Ltidige
CB-30
mixer/densifier, one of which comprises a liquid binder containing either: 1 )
PVNO and water or
2) a coploymer of epichlorohydrin and a cyclic amine moiety (IME) and water or
3) the IME
material, alkyl ethoxy sulfate surfactant paste and water; and the other
stream containing starting
dry detergent containing a premixed mixture of either: 1) an ester modified
carboxy methyl
cellulose, aluminosilicate and sodium carbonate or 2) ester modified carboxy
methyl cellulose
and aluminosilicate. The rotational speed of the shaft in the Ltidige CB-30
mixer/densifier is
about 1400 rpm and the median residence time is about 5-10 seconds. The
contents from the
Lodige CB-30 mixer/densifier are continuously fed into a Lbdige KM-600
mixer/densifier for
further agglomeration during which the mean residence time is about 1-2
minutes. The resulting
detergent agglomerates are then fed to a fluid bed dryer and to a fluid bed
cooler before being
admixed with the spray dried granules. These agglomerates are then admixed
with agglomerates
made with a surfactant paste that contains surfactant and water and dry
detergent ingredients
containing dry detergent material containing aluminosilicate and sodium
carbonate. The
remaining adjunct detergent ingredients are sprayed on or dry added to the
blend of agglomerates
and granules.
II III IV V
Base Granule
C 16.5 alkyl sulfate, Na 6.0 19.0 6.0 6.0
Aluminosilicate i 5.0 2.0 15.0 15.0
Sodium sulfate 10.0 10.0 10.0 10.0
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Sodium polyacrylate polymer 3.0 3.0 3.0 3.0
PolyethyleneGlycol (MW=4000) 2.0 2.0 2.0 2.0
C12-13 linear alkylbenzene 6.0 6.0 6.0 6.0
sulfonate, Na
C14-15 alkyl ethoxylated sulfate,3.0 3.0 3.0 3.0
Na
Sodium silicate 1.0 1.0 1.0 1.0
Brightener 246 0.3 0.3 0.3 0.3
Sodium carbonate 7.0 7.0 7.0 7.0
DTPA 1 0.5 0.5 0.5 0.5
Admixed Agglomerates
Ester Modified Carboxy Methyl0.4 0.4 2.3 2.0
Cellulose
AE3S8
___
-__ ___ 0.7
PVNO 1.9 1.9 _-_ ___
Aluminosilicate 1.3 1.3 2.3 2.1
Sodium Carbonate 1.3 1.3 --- -__
PolyethyleneGlycol (MW=4000) 0.1 0.1 --- __-
IME ~
--- --- 0.2 0.2
Sodium Polyacrylate (MW=4500)--- --- 0.2 ---
Admix
C12-15 alkyl ethoxylate (EO 2.0 2.0 2.0 2.0
= 7)
Perfume 0.3 0.3 0.3 0.3
Polyvinylpyrnlidone 0.5 0.5
0.5 0.5
Polyvinylpyridine N-oxide 0.5 0.5 0.5 0.5
Polyvinylpyrrolidone-polyvinylimidazole0.5 0.5 0.5 0.5
Distearylamine & Cumene sulfonic2.0 2.0 2.0 2.0
acid
Soil Release Polymer 2 0.5 0.5 0.5 0.5
Lipolase Lipase ( 100.000 0.5 0.5 0.5 0.5
LU/I)4
Termamyl amylase (60 KNU/g)5 0.3 0.3 0.3 0.3
CAREZI'ME~ cellulase (1000 0.3 0.3 0.3 0.3
CEW/g)4
Protease (40mg/g)5 0.5 0.5 0.5 0.5
NOBS 3 5.0 5.0 5.0 5.0
Sodium Percarbonate 12.0 12.0 2.0 2.0
Polydimethylsiloxane 0.3 0.3 0.3 0.3
Miscellaneous (water, etc.) alance balance
balance balance
Total 100.0 100.0 100.0 100.0
1 Diethylene Triamine Pentaacetic
Acid
2 Made according to U.S. Patentssued
5,415,807, i May
16,
1995
to Gosselink
et al
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3 Nonanoyloxybenzenesulfonate
4 Purchased from Novo Nordisk A/S
Purchased from Genencor
6 Purchased from Ciba-Geigy
5 7 Copolymer of epichlorohydrin and a cyclic amine moiety
Alkyl Ethoxy Sulphate
Having thus described the invention in detail, it will be clear to those
skilled in the art
that various changes may be made without departing from the scope of the
invention and the
invention is not to be considered limited to what is described in the
specification.
