PATES DETERGENTES STRUCTUREES ET PROCEDE DE PREPARATION DE PARTICULES DETERGENTES A PARTIR DESDITES PATES

STRUCTURED DETERGENT PASTES AND A METHOD FOR MANUFACTURING DETERGENT PARTICLES FROM SUCH PASTES

Abrégé français

Pâte structurée pratiquement exempte de sulfonate de benzène d'alkyle linéaire, qui est appropriée pour être traitée en un détergent granulaire à masse volumique en vrac élevée et fortement actif. Les pâtes de tensioactifs de la présente invention ont une viscosité d'au moins 10 Pa.s (mesurée à 70 ~C et 25 sec.?-1¿) et comprennent de 30 % à 90 % en poids de tensioactif anionique, de 0 % à 50 % en poids de tensioactif non ionique, de 0,5 % à 20 % en poids d'un matériau cationique polymère ou d'un acide aminé polaire et de 1 % à 40 % en poids d'eau.

Abrégé anglais

The present invention provides a structured paste which is substantially free
of LAS and which is suitable for processing into a high bulk density, high
active granular detergent. Surfactant pastes of the present invention have a
viscosity of at least 10 Pa.s (measured at 70 ~C and 25 sec-1) and comprise:
from 30 % to 90 % by weight of anionic surfactant; from 0 % to 50 % by weight
of nonionic surfactant; from 0.5 % to 20 % by weight of either a polymeric
cationic material or a polar amino acid; and from 1 % to 40 % by weight of
water.

Revendications

29
WHAT IS CLAIMED IS:
1. A surfactant paste comprising, by weight:
from 50% to 95% anionic surfactant;
from 0% to 50% nonionic surfactant;
from 1% to 12% of a structuring agent selected from
the group consisting of:
a. amino acids selected from the group consisting
of lysine di-hydrochloride, L-arginine hydrochloride and
mixtures thereof;
b. polymers having from 10 to 1,000,000 cationic
functional groups per polymer, wherein the cationic
functional groups are selected from the group consisting
of carboxylate, amide, pyrrolidone, imidazole,
imidazolinium and mixtures thereof; and
c. mixtures thereof; and
from 3% to 30% water;
wherein the surfactant paste has a viscosity of at least
10 Pa.s at 70°C and 25 sec-1.
2. A surfactant paste according to claim 1, wherein the
structuring agent is a polymer having a molecular weight
of from 5,000 to 100,000,000, and comprising a moiety
with the structure:
<IMG>
wherein n is from 100 to 10,000; R1 is an aliphatic,
aromatic or saccharide group; R2 is an ester, ketone,
amine or a C-C group; R3 is a carboxylate, amide,
pyrrolidone, imidazole or imidazolinium; and wherein R3
is connected to the backbone of the polymer by a C1-10
alkyl or alkylene chain.

30
3. A surfactant paste according to claim 1, wherein the
structuring agent is an amino acid having a molecular
weight of from 5,000 to 100,000,000.
4. A surfactant paste according to claim 1, wherein the
paste has a viscosity of from about 30 to about 70 Pa.s
at 70°C and 25 sec-1.
5. A surfactant paste according to claim 1, comprising
less than 5%, by weight, linear alkyl benzene sulfonate.
6. A surfactant paste according to claim 1, comprising,
by weight:
from 50% to 95% anionic surfactant comprising a C8-18
alkyl sulfate and less than 2%, by weight of the paste,
linear alkyl benzene sulfonate;
from 1% to 12% of a structuring agent selected from
the group consisting of polyquaternium-6,
polyquaternium-28 and mixtures thereof; and
from 5% to 20% water;
wherein the viscosity of the paste is from about 20 to
about 100 Pa.s at 70°C and 25 sec-1.
7. A surfactant paste according to claim 1, wherein the
anionic surfactant is selected from the group consisting
of:
a. water-soluble salts of C8-24 fatty acids;
b. sodium and potassium alkyl sulfates;
c. sodium and potassium alkyl benzene sulfonates;
d. sodium alkyl glyceryl ether sulfonates;
e. sodium coconut oil fatty acid monoglyceride
sulfonates;
f. sodium and potassium salts of alkyl phenol
ethylene oxide ether sulfates;
g. sodium and potassium salts of alkyl ethylene
oxide ether sulfates;

31
h. 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; and
i. mixtures thereof; and
wherein the nonionic surfactant is selected from the
group consisting of:
j. polyethylene oxide condensates of alkyl phenols;
k. water-soluble condensation products of aliphatic
alcohols containing from 8 to 22 carbon atoms with from
4 to 25 moles of ethylene oxide per mole alcohol;
l. water-soluble amine oxides containing one alkyl
moiety having from about 10 to 18 carbon atoms and 2
moieties each individually selected from the group
consisting of alkyl groups containing from 1 to 3 carbon
atoms and hydroxyalkyl groups containing from 1 to 3
carbon atoms;
m. water-soluble phosphine oxides containing one
alkyl moiety having about 10 to 18 carbon atoms and 2
moieties each individually selected from the group
consisting of alkyl groups containing from 1 to 3 carbon
atoms and hydroxyalkyl groups containing from 1 to 3
carbon atoms;
n. water-soluble sulfoxides containing one alkyl
moiety having about 10 to 18 carbon atoms and a moiety
selected from the group consisting of alkyl groups
containing from 1 to 3 carbon atoms and hydroxyalkyl
groups containing from 1 to 3 carbon atoms; and
o. mixtures thereof.
8. A method of structuring a surfactant paste
comprising, by weight, from 30% to 95% anionic
surfactant, from 0% to 50% nonionic surfactant and from
1% to 40% water, comprising the step of adding to the
surfactant paste from 0.5% to 20%, by weight, of a
structuring agent selected from the group consisting of:

32
a. amino acids selected from the group consisting
of lysine di-hydrochloride, L-arginine hydrochloride,
and mixtures thereof;
b. polymers having from 10 to 1,000,000 cationic
functional groups per polymer, wherein the cationic
functional groups are selected from the group consisting
of carboxylate, amide, pyrrolidone, imidazole,
imidazolinium and mixtures thereof; and
c. mixtures thereof; and
wherein after structuring the surfactant paste has a
viscosity of at least 10 Pa.s at 70°C and 25 sec-1.
9. A method according to claim 8, wherein the
surfactant paste comprises from 50% to 95%, by weight,
anionic surfactant.
10. A method according to claim 8, wherein after the
step of adding the structuring agent to the paste, the
paste hardness increases at least 50% and the paste
stickiness decreases at least 20%.
11. A method according to claim 10, wherein after the
step of adding the structuring agent to the paste, the
paste hardness increases at least 200% and the paste
stickiness decreases at least 60%, and wherein the
viscosity of the paste is from about 30 to about 70 Pa.s
at 70°C and 25 sec-1.
12. A method according to claim 9, wherein after the
step of adding the structuring agent to the paste, the
paste has a viscosity of from about 20 to about 100 Pa.s
at 70°C and 25 sec-1 and comprises, by weight:
from 50% to 95% anionic surfactant comprising a
C8-18, alkyl sulfate and less than 2%, by weight of the
paste, linear alkyl benzene sulfonate;
from 1% to 12% of a structuring agent selected from
the group consisting of polyquaternium-6,

33
polyquaternium-28 and mixtures thereof; and
from 5% to 20% water.
13. A method of forming a detergent agglomerate
comprising the steps of:
i. forming a structured paste comprising, by
weight, from 50% to 95% anionic surfactant, 1% to 40%
water, and from 0.5% to 20% of a structuring agent
selected from the group consisting of:
a. amino acids selected from the group consisting
of lysine di-hydrochloride, L-arginine hydrochloride and
mixtures thereof;
b. polymers having from 10 to 1,000,000 cationic
functional groups per polymer, wherein the cationic
functional groups are selected from the group consisting
of carboxylate, amide, pyrrolidone, imidazole,
imidazolinium and mixtures thereof; and
c. mixtures thereof; and
ii. granulating the paste to form an agglomerate;
wherein the operating temperature during the step of
forming the structured paste is between 40°C and 90°C,
and wherein the activity of the agglomerate is at least
50%, by weight.
14. A method according to claim 13, wherein the paste
has a viscosity of from about 30 to about 70 Pa.s at
70°C and 25 sec-1.
15. A method according to claim 13, wherein the paste
comprises, by weight:
from 50% to 95% anionic surfactant;
from 0% to 50% nonionic surfactant;
from 1% to 12% structuring agent; and
from 3% to 30% water.
16. A method according to claim 15, wherein the
structuring agent is selected from the group consisting

34
of polyquaternium-6, polyquaternium-28 and mixtures
thereof.
17. A method according to claim 15, wherein the
structuring agent is an amino acid having a molecular
weight of from 5,000 to 100,000,000.
18. A method according to claim 13, wherein the step of
granulating the paste comprises mixing the paste with
dry builder comprising zeolite and carbonate.
19. A method according to claim 18, wherein the weight
ratio of surfactant to dry builder is in the range of
from 1:1 to 10 :1.
20. A method according to claim 13, wherein the anionic
surfactant comprises a C8-18 alkyl sulfate and less than
2%, by weight of the paste, linear alkyl benzene
sulfonate.

Description

WO 96100279 PCT/US95108794
~193d5p
STRUCTURED DETERGENT PASTES AND A METHOD FOR MANUFACTURING
DETERGENT PARTICLES FROM SUCH PASTES
The present invention relates to structured surfactant
pastes, and to processes for making a high bulk density
detergent component by forming a structured surfactant
paste, and subsequently granulating the paste to form free-
flowing particles having a bulk density of at least 650
g/1.
In recent years there has been a trend towards making
granular detergents having a higher bulk density than
before. Various techniques of making dense granular
detergents, and of processing low density granular
detergents in such a way that the bulk density is
increased, have been described. One example of a suitable
techniques for making dense granular detergents is known as
"agglomeration". This term describes any process in which
small particles of the components are processed in such a
way that they are built-up (or "agglomerated") to form
suitable granular components.
The ideal detergent agglomerate should have a high bulk
density and a high surfactant content and yet still have
good solubility and dispersion properties. It should also
be possible to use a manufacturing process which is both
efficient and versatile.
SUBSTITUTE SHEET (RULE 261

i i i i i i i '. r
WO 96100279 PCT/LTS95/08794
2~936Sp
The general use of quaternary ammonium compounds as
cationic surfactants as components of surfactant
agglomerates is disclosed in patent application, EP510746,
published on October 28th, 1992. However the cationic
surfactants described generally have a low structuring
effect, if indeed they have any structuring effect at all.
EP508543 also published on October 28th, 1992 discloses
various means for structuring a surfactant paste. It is
disclosed that anionic surfactant pastes are preferably
structured (i.e. physically/chemically brought into a
specific crystalline phase having a high viscosity) prior
to high active paste agglomeration. Such a structuring or
"conditioning" step enables granulation of the paste to be
carried out resulting in very high active surfactant
particles. The conditioning step minimises or eliminates
problems such as caking and poor rate of solubility.
However whilst the conditioning steps described are
particularly effective with certain compositions of
surfactant pastes. they are less effective with other
surfactant compositions.
It is an objective of the present invention to provide
structured pastes which are highly suitable for subsequent
granulation.
SUBSTITUTE SHEET (RULE 261

",~", WO 96/00279 PCT/US95/08794
~i 9.~6~0
3
This has been achieved by incorporating polymeric cationic
compounds, or polar amino acids into surfactant pastes.
Polymeric cationic compounds are known as components of
compositions for textile conditioning and hair
conditioning. Typical disclosures are US4179382 and
US5116543 which are discussed below. However in neither of
these applications is a high active (greater than 35$
active by weight) anionic surfactant paste disclosed which
is effectively structured by the polymeric cationic
compound.
US4179382, published on December 18th, 1979, discloses
textile conditioning compositions containing polymeric
cationic materials. In addition to the polymeric cationic
material, the compositions comprise cationic surfactant and
optionally nonionic surfactant. There is no mention of
anionic surfactants.
Many compositions of the prior art disclose polymeric
cationic materials as active hair conditioning agents. One
such example is .
US5116593, published on May 26th, 1992 describes a paste
comprising an anionic surfactant, a skin conditioner, a
SUBSTITUTE SHEET (RULE.261

~, 21965~
4
hair conditioner (polymeric cationic material) and a
preservative. The paste is for bathing with a small
quantity of water in microgravity conditions. Preferred
pastes are very viscous and comprise from 15-25% of
anionic surfactant and 0.1-30 of polymeric cationic
material.
In particular, the present invention offers a method of
structuring pastes which have a low amount (or zero) of
linear alkyl benzene sulphonate (LAS). LAS has
previously been a common surfactant in laundry
detergents and methods of effectively structuring LAS
have been discussed in the prior art (mentioned above).
Now there is a tendency to reduce the level of LAS in
favour of other anionic surfactants. Consequently the
present invention provides a structured paste which is
substantially free of LAS and which is suitable for
processing into a high bulk density, high active
granular detergent.
Summary of the Invention
In one preferred embodiment there is provided a
surfactant paste comprising, by weight: from 50o to 95%
anionic surfactant; from 0% to 50o nonionic surfactant;
from 1% to 12% of a structuring agent selected from the
group consisting of: a. amino acids selected from the
group consisting of lysine di-hydrochloride, L-arginine
hydrochloride and mixtures thereof; b. polymers having
from 10 to 1,000,000 cationic functional groups per
polymer, wherein the cationic functional groups are
selected from the group consisting of carboxylate,
amide, pyrrolidone, imidazole, imidazolinium and
mixtures thereof; and c. mixtures thereof; and from 3%
to 30% water; wherein the surfactant paste has a
viscosity of at least 10 Pa.s at 70°C and 25 sec-1.
B

,2193fi50
The polymeric cationic material where present is
preferably at a level of from 1% to 12% by weight.
The polymeric cationic material preferably has a
molecular weight of from 5,000 to 100,000,000,
preferably 10,000 to 10,000,000, and most preferably
1,000,000 to 10,000,000. The average number of cationic
functional groups per molecule of polymer is preferably
at least 2, and more preferably from 10 to 1,000,000.
The cationic functional groups may be selected from the
group consisting of carboxylate, amide, pyrrolidone,
imidazole, imidazolinium and mixtures thereof.
The polar amino acid where present is preferably at a
level of from 1°s to 12% by weight. The polar amino acid
preferably being selected from the group consisting of
lysine di-hydrochloride, L-arginine hydrochloride, and
mixtures thereof.
The polar amino acid preferably has a molecular weight
of from 5,000 to 100,000,000, preferably 10,000 to
10,000,000, and most preferably 1,000,000 to 10,000,000.
The polar amino acid preferably has at least 2
functional groups selected from the group consisting of
amine, quaternary amine and mixtures thereof.
It is further preferred that the surfactant paste
includes a total level of alkyl benzene sulphonate
surfactant which is less than 5%, preferably less than
2% by weight of the paste.
In another preferred embodiment there is provided a
method of structuring a surfactant paste comprising, by
weight, from 30% to 95o anionic surfactant, from 0% to
50% nonionic surfactant and from to to 40% water,
comprising the step of adding to the surfactant paste
B

. 2193650
6
from 0.5% to 20%, by weight, of a structuring agent
selected from the group consisting of: a. amino acids
selected from the group consisting of lysine
di-hydrochloride, L-arginine hydrochloride, and mixtures
thereof; b. polymers having from 10 to 1,000,000
cationic functional groups per polymer, wherein the
cationic functional groups are selected from the group
consisting of carboxylate, amide, pyrrolidone,
imidazole, imidazolinium and mixtures thereof; and
c. mixtures thereof; and wherein after structuring the
surfactant paste has a viscosity of at least 10 Pa.s at
70°C and 25 sec-1.
A further embodiment of the invention is a granular
detergent composition or component having a bulk density
of at least 650 g/1, comprising:
(a) from 35% to 70% by weight of surfactant; and
(b) from 0.1% to 20% by weight of either a
polymeric cationic material or a polar amino acid
(preferably chosen from those polymeric cationic
materials and/or polar amino acids described above).
B

WO 96100279 PCT/LTS95108794
193~5~
Detailed Description of the Invention
Structuring of a paste means the modifying its physical
characteristics. This may be done in order to form higher
active agglomerates which otherwise are not easily
obtainable under normal operating conditions. The present
invention is particularly applicable to all neutralized
aqueous alkyl sulphate pastes. In one embodiment of the
present invention, the anionic surfactant is formed into an
aqueous, highly concentrated solution of its salt,
preferably its sodium salt. These high active (and,
preferably, low moisture) surfactant pastes are of a high
viscosity but remain pumpable at temperatures at which the
surfactants are stable. In the present invention cationic
polymers and/or polar amino acids that alter the physical
structure and/or physical characteristics of the surfactant
paste are added to the paste. It has been found that the
addition to the surfactant paste reduces the stickiness of
the paste, increases its viscosity and increases its
softening point. This allows for more paste to be added
during the agglomeration process thus leading to higher
active agglomerates i.e. more than 35$, preferably more
, than 50~. This method of structuring (or "conditioning")
the surfactant paste can be performed batchwise and
continuously, preferably continuously.
SUBSTITUTE SHEET (RULE 261

.2193650
a
Structuring cf the paste, as defined herein, means: a)
increasing hardness, b) reducing stickiness and c)
increasing elasticity. The hardness and stickiness of the
paste can be measured using a Texture Analyer/Penetrometer
(e. g. Stevens Texture analyser QTS25TM). If the paste
hardness measured by this technique increases by at least
50$, preferably 100$, more preferably 200$; and the
stickiness of the paste, as measured by the same instument
decreases by 20$, preferably 40$, more preferably 60$, then
the paste is considered to have been structured within the
meaning of the present invention.
A preferred paste useful for this invention consists of at
least 40$ by weight of salts of anionic surfactants, which
has a viscosity of at least 10 Pa.s when measured at 70°C
and a shear rate of 25s-1.
~ The Polymeric Cationic and Polar Amino Acid Structuring
A ents
In general terms polymeric cationic structuring agents
useful in the present invention are .
( -- - R2 ) ( -- R1 - R2 -- )
R1 --
( I ) or ( ~ / )
( R3 ) n ( R3 ) n
B

219650
9
where n represents a number of basic units which are
') combined as eit!~er homopolymers or copolymers.
n is preferably from 10 to 1 000 000, preferably from 100
to 10 000.
R1 is aliphatic, aromatic or saccharide unit, R2 is ester,
ketone, amine units or a C-C linkage, and R3 is a cationic
functional group which is connected to the backbone of the
polymer by means of a C1 to C10 alkyl or alkylene chain.
The cationic functional group of R3 is selected from the
group consisting of carboxylate, amide, pyrrolidone,
imidazol and imidazolinium. In the case of co-polymers some
of the R3 units may be anionic or nonionic functional
groups.
Specific examples of suitable polymeric cationics are given
in US4179382. Most preferred for use in the present
invention are polyquaternium-6, polyquaternium-28, such as
those sold under the Trade Mark Merquat~ and Gafquat~.
Other structuring agents are polar amino acids having at
least 2 functional groups selected from the group
consisting of amine, quaternary amine and mixtures thereof.
Particularly preferred polar amino acids are lysine di-
hydrochloride, L-arginine hydrochloride, and mixtures
thereof.
B

WO 96/00279 PCT/US95/08794
~' 9~6so
,o
The Pastes
One or various aqueous pastes of the salts of anionic
surfactants is preferred for use in the present invention,
preferably the sodium salt of the anionic surfactant. In a
preferred embodiment, the anionic surfactant is preferably
as concentrated as possible, (that is, with the lowest
possible moisture content that allows it to flow in the
manner of a liquid) so that it can be pumped at
temperatures at which it remains stable. While granulation
using various pure or mixed surfactants is known, for the
present invention to be of practical use in industry and to
result in particles of adequate physical properties to be
incorporated into granular detergents, an anionic
surfactant must be part of the paste in a concentration of
above 30$, preferably from 30-95$, more preferably from 40-
95$, and most preferably from 50~-95~.
It is preferred that the moisture in the surfactant
aqueous paste is as low as possible, while maintaining
paste fluidity, since low moisture leads to a higher
concentration of the surfactant in the finished particle.
Preferably the paste contains between 1$ and 40$ water,
more preferably between 5 and 30~ water and most preferably
between 5~ and 20~ water.
SUBSTITUTE SKEET (RULE 261

WO 96/00279 PCT/US95108794
2~93~50
It is preferable to use high active surfactant pastes
to minimize the total water level in the system during
mixing, granulating and drying. Lower water levels allow
for: (1) a higher active surfactant to builder ratio, e.g.,
1:1 and above; (2) higher levels of other liquids in the
formula without causing dough or granular stickiness: (3)
less cooling, due to higher allowable granulation
temperatures; and (4) less granular drying to meet final
moisture limits.
Two important parameters of the surfactant pastes
which can affect the mixing and granulation step are the
paste temperature and viscosity. Viscosity is a function,
among others, of concentration and temperature, with a
range in this application from about 10 Pa.s to 10,000
Pa. s. Preferably, the viscosity of the conditioned paste
is from about 20 to about 100 Pa.s and more preferably from
about 30 to about 70 Pa.s. The viscosity of the paste of
this invention is measured at a temperature of 70°C and a
shear rate of 25s-1.
The paste can be introduced into the mixer (or the
first of a series of mixers) at an initial temperature
between its softening point (generally in the range of 40-
60°C) and its degradation point (depending on the chemical
nature of the paste, e.g. alkyl sulphate pastes tend to
degrade above 75-85°C). High temperatures reduce viscosity
SUBSTITUTE SHEET (RULE 26)

WO 96100279 PCTIUS95/08794
2~936~0
,2
simplifying the pumping of the paste but result in lower
active agglomerates. In the present invention, the activity
of the agglomerates is maintained high due to the
elimination of moisture.
High Active Surfactant Paste
The aqueous surfactant paste contains an organic surfactant
selected from the group consisting of anionic, nonionic,
zwitterionic, ampholytic and cationic surfactants, and
mixtures thereof. Anionic surfactants are preferred.
Surfactants useful herein are listed in U.S. Pat. No.
3,664,961, Norris, issued May 23, 1972, and in U.S. Pat.
No. 3,919,678, Laughlin et al., issued Dec. 30, 1975.
Useful cationic surfactants also include those described in
U.S. Pat. No. 9,222,905, Cockrell, issued Sept. 16, 1980,
and in U.S. Pat. 4,239,659, Murphy, issued Dec. 16, 1980.
The following are representative examples of surfactants
useful in the present compositions.
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 alkylammonium salts of
higher fatty acids containing from about 8 to about 24
SUBSTITUTE SHEET (RULE 2fi1

PCT/US95108794
WO 96100279
X193650
13
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.
Useful anionic surfactants also include the water-
soluble salts, preferably the alkali metal, ammonium and
alkylolammonium salts, of organic .sulfuric reaction
products having in their molecular structure an 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 (Cg-Clg carbon
atoms) such as those produced by reducing the glycerides of
tallow or coconut oil; and the sodium and potassium alkyl
benzene sulfonates in which the alkyl group contains from
about 9 to about 15 carbon atoms, in straight or branched
chain configuration, e.g., those of the type described in
U.S. Pat. Nos. 2,220,099 and 2,477,383. Especially
valuable are linear straight chain alkyl benzene sulfonates
in which the average number of carbon atoms in the alkyl
group is from about 11 to 13, abbreviated as C11-C13 ~~
SUBSTITUTE SHEET (RULE 261

WO 96100279 PCTlUS95/08794
2~y3650
14
Other anionic surfactants 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 salts of alkyl phenol
ethylene oxide ether sulfates containing from about 1 to
about 10 units 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 from about 1 to about 10
units of ethylene oxide per molecule and wherein the alkyl
group contains from about 10 to about 20 carbon atoms.
Other useful anionic surfactants herein 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-acyloxy-alkane-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; watersoluble salts
of olefin sulfonates containing from about 12 to 24 carbon
atoms; and beta-alkyloxy alkane sulfonates containing from
about 1 to 3 carbon atoms in the alkyl group and from about
SU9STITUTE SHEET RULE 26)

", WO 96100279 PCTlUS95108794
2~9365a
8 to about 20 carbon atoms in the alkane moiety. Although
the acid salts are typically discussed and used, the acid
neutralization cam be performed as part of the fine
dispersion mixing step.
The preferred anionic surfactant pastes are mixtures
of linear or branched alkylbenzene sulfonates having an
alkyl of 10-16 carbon atoms and alkyl sulfates having an
alkyl of 10-18 carbon atoms. These pastes are usually
produced by reacting a liquid organic material with sulfur
trioxide to produce a sulfonic or sulfuric acid and then
neutralizing the acid to produce a salt of that acid. The
salt is the surfactant paste discussed throughout this
document. The sodium salt is preferred due to end
performance benefits and cost of NaOH vs. other
neutralizing agents, but is not required as other agents
such as KOH may be used.
Water-soluble nonionic surfactants are also useful as
surfactants in the compositions of the invention. Indeed,
preferred processes use anionic/nonionic blends. A
particularly preferred paste comprises a blend of nonionic
and anionic surfactants having a ratio of from about 0.01:1
to about 3:1, more preferably about 0.1:1 to 1:1. Such
nonionic materials include compounds produced by the
condensation of alkylene oxide groups (hydrophilic in
nature) with an organic hydrophobic compound, which may be
SUBSTITUTE SHEET (RULE 26)

WO 96/00279 PCT/US95/08794
293650
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 16 carbon atoms, in either a straight chain
or branched chain configuration, with from about 0.8 to 25
moles of ethylene oxide per mole of alkyl phenol.
Preferred nonionics are the water-soluble condensation
products of aliphatic alcohols containing from 8 to 22
carbon atoms, in either straight chain or branched
configuration, with from 4 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
4 to 25 moles of ethylene oxide per mole of alcohol; and
condensation products of propylene glycol with ethylene
oxide.
Semi-polar nonionic surfactants include water-soluble
amine oxides containing one alkyl moiety of from about 10
to 18 carbon atoms and 2 moieties selected from the group
SUBSTITUTE SNEET (RULE 26)

,, WO 96100279 PCT/US95108794
~ 1 y .~ 6 .~ U
consisting of alkyl groups and hydroxyalkyl groups
containing from 1 to about 3 carbon atoms; water-soluble
phosphine oxides containing one alkyl moiety of about 10 to
18 carbon atoms and 2 moieties selected from the group
consisting 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:
Ampholytic surfactants include derivatives of
aliphatic or aliphatic derivatives of heterocyclic
secondary and tertiary amines in which the aliphatic moiety
can be either straight or branched chain 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.
Particularly preferred surfactants herein include
coconut and tallow alkyl sulfates; coconutalkyl glyceryl
ether sulfonates; alkyl ether sulfates wherein the alkyl
SUBSTITUTE SHEET (RULE 261

WO 96100279 PCT/US95108794
2 ~ 936'0
,8
moiety contains from about 14 to 18 carbon atoms and
wherein the average degree of ethoxylation is from about 1
to 4; olefin or paraffin sulfonates containing from about
14 to 16 carbon atoms; alkyldimethylamine oxides wherein
the alkyl group contains from about 11 to 16 carbon atoms;
alkyldimethylammonio propane sulfonates and
alkyldimethylammonio hydroxy propane sulfonates wherein the
alkyl group contains from about 14 to 18 carbon atoms;
soaps of higher fatty acids containing from about 12 to 18
carbon atoms; condensation products of C9-C15 alcohols with
from about 3 to 8 moles of ethylene oxide, and mixtures
thereof.
Useful cationic surfactants include water-soluble
quaternary ammonium compounds of the form R4R5R6R~N+X-,
wherein R4 is alkyl having from 10 to 20, preferably from
12-18 carbon atoms, and R5, Rg and R~ are each C1 to C~
alkyl preferably methyl; X- is an anion, e.g. chloride.
Examples of such trimethyl ammonium compounds include 012-
14 alkyl trimethyl ammonium chloride and cocalkyl trimethyl
ammonium methosulfate.
The ratio of the surfactant active to dry detergent
builder or powder ranges from 0.1 to 19:1, preferably from
1:1 to 10:1, and more preferably from 1.5:1 to 5:1.
SUBSTITUTE SHEET (RULE 261
r t....~.~._-_.'..w"r_~ , , ~ T~ _ ., _.._

", WO 96/00279 PCT/US95/08794
2193650
19
Processing and Processing Equipment
In a preferred embodiment of the invention an extruder is
used to structure or "condition" the paste. The extruder is
a versatile piece of equipment which enables two or more
pastes to be mixed and/or the chemical structuring agents
to be added to, and mixed with the viscous paste.
Furthermore it enables moisture to be removed under vacuum,
and it enables control of paste temperature.
In an alternative embodiment of the invention a Discotherm
~ is used to structure the paste. The Discotherm ~, like
the extruder, enables two or more pastes to be mixed and/or
the chemical structuring agents to be added to, and mixed
with the viscous paste, and it enables moisture to be
removed under vacuum. It is possible to dry the paste in
the Discotherm ~ to low levels of moisture, and to directly
form the surfactant contaning particles in that piece of
equipment which can be directly mixed with other granular
components to form the finished product.
Also useful in the present invention is a thin film
evaporator. However this piece of eqipment may not be
suitable for handling the high viscosity materials which
are preferred in the present invention, because high
viscosity materials do not easily form a thin film.
SUBSTITUTE SHEET ~RUIf 261

WO 96/00279 PCT/US95108794
2i936~0
Moreover the thin film evaporator does not allow intimate
mixing, and simultaneously structuring and drying.
The high active surfactant paste of the present invention
may, after the structuring step, be granulated in further
processing steps. Alternatively if the granulation of the
high active paste has already been started simultaneously
with the structuring step, then further processing steps
may be used to complete granulation. Granulation may be
carried out in a mixer.
Especially preferred are mixers of the FukaeR FS-G series
manufactured by Fukae Powtech Kogyo Co., Japan; this
apparatus is essentially in the form of a bowl-shaped
vessel accessible via a top port, provided near its base
with a stirrer having a substantially vertical axis, and a
cutter positioned on a side wall. The stirrer and cutter
may be operated independently of one another and at
separately variable speeds. The vessel can be fitted with
a cooling jacket or, if necessary, a cryogenic unit.
Other similar mixers found to be suitable for use in
the process of the invention inlcude 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
SUBSTITUTE SHEET (RULE 26)

~. 21 ~~6~0
2i
FujiR VG-C series ex Fuji Sangyo Co., Japan' and the RotoR
ex Zanchetta & Co srl, Italy.
r ~.~
Other preferred suitable equipment can include
EirichR, series RV, manufactured by Gustau Eirich Hardheim,
Germany: LodigeR, series CB and FQ~t in series for continuous
mixing/agglomeration, manufactured by Lodige Machinenbau
GmbH, Paderborn Germany; DraisR T160 series, manufactured
by Drais Werke GmbH, Mannheim Germany: and WinkworthR R~ 25
series, manufactured by Winkworth Machinery Ltd., Bershire,
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
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 granules may be subjected to a further drying step if
the moisture level is to be further reduced. A conventional
fluidised bed dryer is suitable for this.
Processing Conditions
B

WO 96100279 PCT/US95108794
2~9~650
Preferred operating temperatures for paste structuring and
granulation 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 100°C, more preferably between
40 and 90°C, and most preferably between 60 and 80°C.
Examples
Example 1
Structured Paste: Parts by weight:
a. Sodium Alkyl Sulphate 40
b. Polyquaternium-6 1
c. Water and 15
miscellaneous
56
d. Sodium aluminosilicate 20
(anh.)
e. Water (bound to 4
aluminosilicate)
f. Sodium carbonate 24
SUBSTITUTE SHEET (RULE 26)
_..._..._".~,..~._.,r..__ .."..._ t .,~ . r r ..,.f__.~..._.,~,.. _. ~
_...~....__ ......

WO 96100279 PCT/US95/08794
23 2 i ~365~
104
a = Sodium alkyl sulphate having an average carbon
chain length of C12 to C15
b = Merquat O
d = Zeolite 4A
f = finely divided; having a mean particle size of 114
micrometers
A structured paste was prepared by mixing a high active
sodium alkyl sulphate paste (the paste comprising 20~ by
weight of water and not more than 4o by weight of
impurities, typically sulphate and unreacted alcohol), with
a 40$ aqueous solution of Merquat ~. The mixing was carried
out in a lab scale mixer at 60°C for 10 minutes. The
hardness of the paste during the structuring step inreased
by 200$.
A dry blend of zeolite and carbonate was then added to a
high shear mixer (a food processor) to give the finished
composition. Upon addition of the zeolite/carbonate mix,
discrete granules were formed having a mean particle size
of 500 micrometers !95$ by weight of the particles having a
particle size of between 300 and 800 micrometers).
SUBSTITUTE SHEET (RULE 261

WO 96/00279 PCTIUS95/08794
2~~365U
24
The particles were subsequently dried in a fluidised bed
for 10 minutes in air at 60°C to attain a free moisture
level of 40, and a surfactant activity of 40~ by weight.
SUBSTITUTE SHEET (RULE 26~
T. _.»r... ~... r.. ~ ......._.. .~

WO 96100279 PCT/US95108794
. - 2193550
Example 2
Structured Paste: Parts by weight:
a. Sodium Alkyl Sulphate 40
b. Polyquaternium-28 2
c. Water and 20
miscellaneous
62
d. Sodium aluminosilicate 17
(anh.)
e. Water (bound to 4
aluminosilicate)
f. Sodium carbonate 22
105
b = Gafquat
A structured paste was prepared by mixing a high active
sodium alkyl sulphate paste (the paste comprising 20~ by
weight of water and not more than 4~ by weight of
impurities, typically sulphate and unreacted alcohol), with
a 22~ aqueous solution of Gafquat ~. The mixing was carried
out in a twin screw extruder at a rate of 100 kg/h. Mixing
of the paste and structuring agent takes place continuously
at the kneading block of the extruder. The structured paste
exits the extruder at 50°C.
SUBSTITUTE SHEET (RULE 261

WO 96/00279 PCT/US95108794
2~~36~0
26
A sample of the paste was then granulated in lab scale high
shear mixer with a dry blend of zeolite and carbonate as in
example 1.
The particles were subsequently dried in a fluidised bed
for 10 minutes in air at 60°C to attain a free moisture
level of 40, and a surfactant activity of 40~ by weight.
Example 3
Structured Paste: Parts by weight:
a. Sodium Alkyl Sulphate 60
b. Polyquaternium-6 6
c. Water and 4
miscellaneous
67
d. Sodium aluminosilicate 12
(anh.)
e. Water (bound to 3
aluminosilicate)
f. Sodium carbonate 15
100
SUBSTITUTE SHEET (RULE 261

",~.,n WO 96/00279 PCT/L1S95108794
2, 2 ~ 9.~~50
A structured paste was prepared by mixing a high active
sodium alkyl sulphate paste (the paste comprising 20$ by
weight of water and not more than 4o by weight of
impurities, typically sulphate and unreacted alcohol), with
a 40~ aqueous solution of Merquat ~. The mixing was carried
out in a Discotherm ~ and a vacuum of 40-100 mbar was
applied for 1 hour to reduce the paste moisture level to
5~. The structured paste was removed from the Discotherm O
at a temperature of 70°C.
A sample of the paste was then granulated in lab scale high
shear mixer with a dry blend of zeolite and carbonate as in
example 1.
Example 4
Structured Paste: Parts by weight:
a. Sodium Alkyl Sulphate 50
bl. Polyquaternium-6 5
b2. Co-polymer of malefic & 10
acrylic acid
c. Water and 10
miscellaneous
SUBSTITUTE SHEET (RULE 26)

W O 96!00279
PCTIUS95/08794
28
d. Sodium aluminosilicate 10
(anh.)
e. Water (bound to 2.5
aluminosilicate)
f. Sodium carbonate 12.5
100
A structured paste was prepared by mixing a high acive
sodium alkyl sulphate paste !the paste comprising 20~ by
weight of water and not more than 4$ by weight of
impurities, typically sulpha-to and unreacted alcohol), with
a 40~ aqueous solution of Merquat ~ and a 25o aqueous
solution of the copolymer. The mixing was carried out in a
Discotherm ~ and a vacuum of 40-100 mbar was applied for 1
hour to reduce the paste moisture level to 10~. The
structured paste was removed from the Discotherm ~ at a
temperature of 70°C.
A sample of the paste was then granulated in lab scale high
shear mixer with a dry blend of zeolite and carbonate as in
example 1.
SUBSTITUTE SHEET (RULE 26)