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Patent 2080688 Summary

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(12) Patent: (11) CA 2080688
(54) English Title: LIQUID DETERGENT COMPOSITIONS
(54) French Title: COMPOSITIONS DE DETERGENT LIQUIDE
Status: Deemed expired
Bibliographic Data
(51) International Patent Classification (IPC):
  • C11D 1/14 (2006.01)
  • C11D 3/20 (2006.01)
  • C11D 17/00 (2006.01)
(72) Inventors :
  • DONKER, CORNELIS B. (United Kingdom)
  • MACHIN, DAVID (United Kingdom)
  • SCHEPER, FREDERIK J. (Netherlands (Kingdom of the))
(73) Owners :
  • UNILEVER PLC (United Kingdom)
(71) Applicants :
(74) Agent: BERESKIN & PARR LLP/S.E.N.C.R.L.,S.R.L.
(74) Associate agent:
(45) Issued: 1998-11-03
(86) PCT Filing Date: 1991-04-22
(87) Open to Public Inspection: 1991-10-26
Examination requested: 1997-11-27
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/EP1991/000768
(87) International Publication Number: WO1991/016409
(85) National Entry: 1992-10-15

(30) Application Priority Data:
Application No. Country/Territory Date
90304440.2 European Patent Office (EPO) 1990-04-25
90312402.2 European Patent Office (EPO) 1990-11-14

Abstracts

English Abstract



An aqueous liquid detergent composition comprising a primary alkyl sulphate material, which is present in a non-solid
dispersed phase.


French Abstract

Composition liquide, aqueuse, détergente, renfermant un sulfate d'alkyle primaire, présent dans une phase dispersée non solide.

Claims

Note: Claims are shown in the official language in which they were submitted.



CLAIMS

1. An aqueous liquid detergent composition having a
viscosity of less than 2.5 Pas at 21 s-1 after storage for
two weeks at 25°C and comprising from 0.1 to 40% by weight
of a primary alkyl sulphate material, which is present in a
non-solid dispersed phase, characterized in that

(a) the mole ratio of sodium to other cationic counterions
selected from potassium and ammonium in the composition
is from 10:1 to 1:10; and/or

(b) the primary alkyl sulphate material is a branched alkyl
sulphate wherein at least 20% of the PAS molecules are
branched; and/or

(c) the composition also a soap having iodine value of
greater than 70.

2. An aqueous liquid detergent composition according to
claim 1 comprising from 1 to 70% by weight of detergent
active material.
3. An aqueous liquid detergent composition according to
claims 1-2 comprising from 10 to 40% by weight of detergent
active material.
4. An aqueous liquid detergent composition according to
claims 1-3 being internally structured.
5. An aqueous liquid detergent composition according to
claims 1-4 wherein the alkyl sulphate material is present in
a lamellar droplet phase.


21
6. A composition according to claims 1-5, wherein the alkyl
sulphate material constitutes from 5 to 60 % by weight of
the detergent active materials.

7. Use of a composition according to claims 1-6 for the
washing of fabrics.

8. Method of preparing an aqueous liquid detergent
composition comprising a primary alkyl sulphate material in
a non-solid dispersed phase, by which compositions according
to claims-1-6 are obtainable, said method comprising the
mixing of the primary alkyl sulphate material in water at
elevated temperature, cooling the mixture and optionally
followed by the addition of the remaining temperature
sensitive ingredients, wherein the primary alkyl sulphate
material is added to the compositions as a premix comprising
10-50% of primary alkyl sulphate material, 50-90% of
nonionic surfactant and 0-20% of water.





Description

Note: Descriptions are shown in the official language in which they were submitted.



LIQUID DETERGENT COMPOSITIONS

The present invention is concerned with aqueous liquid
detergent compositions which contain a primary alkyl
sulphate material.

Primary alkyl sulphates are anionic surfactant materials,
which are especially preferred for use in detergent
compositions for environmental reasons.
A problem in the formulating of liquid detergent
compositions comprising a primary alkyl sulphate as
detergent active material is sometimes the occurrence of
high viscosities and/or instability after storage.
It has now been found, that liquid detergent compositions
comprising a primary alkyl sulphate material and having
satisfactory stability and/or viscosity properties can be
obtained by ensuring that the primary alkyl sulphate is
present in a non-solid phase dispersed in the system.

Accordingly, the present invention relates to an aqueous
liquid detergent composition comprising a primary alkyl
sulphate material, which is present in a non-solid dispersed
phase.


.




SlJ8~ 11 1 UTE SH~~~'"

~O91/1~09 ~ PCT/EP91/00768
2U806~
Preferably compositions of the invention are structured
liquid detergent compositions. Structuring is especially
preferred for providing physical stability to PAS
containing compositions. Structured compositions
according to the invention may be externally structured
(the structuring is provided by materials other than the
main active materials) or internally structured (the
structuring is provided by main active materials, e.g.
detergent active materials in combination with
electrolytes). Preferably compositions of the invention
are internally structured, more preferably compositions
of the invention comprise an internal structure of
lamellar droplets of detergent active material,
dispersed in the aqueous phase of the composition.
Lamellar droplets are a particular class of surfactant
structures which, inter alia, are already known from a
variety of references, e.g. H.A.Barnes,~'Detergents',
Ch.2. in K.Walters (Ed), 'Rheometry: Industrial
Applications', J. Wiley & Sons, Letchworth 1980.

Such lamellar droplet systems are used to endow proper-
ties such as consumer-preferred flow behaviour and/or
turbid appearance. Many are also capable of suspending
particulate solids such as detergency builders or
abrasive particles. Examples of such structured liquids
without suspended solids are given in US patent 4 244
840, whilst examples where solid particles are suspended
are disclosed in specifications EP-A-160 342;
EP-A-38 101; EP-A-104 452 and also in US 4 244 840.
Others are disclosed in European Patent Specification
EP-A-151 884, where the lamellar droplets are called
'spherulites'.

The presence of lamellar droplets in a liquid detergent
product may be detected by means known to those skilled
in the art, for example optical techniques, various


rheometrical measurem~nts. X-ray or neutron diffraction, and
electron microscopy.

The droplets consist of an onion-like configuration of
concentric bi-layers of surfactant molecules, between which
is trapped water or electrolyte solution (aqueous phase).


The Primary alkYl sulphate
Compositions of the invention comprise as part or all of the
detergent active materials a PAS material, preferably a C~
to C20 PAS, more preferably a Cg to Cl5 PAS, most preferably
a C10 to C14 PAS. Suitable materials can for example be made
by sulphating primary alcohols or are for example available
under the trade names Lial 125 ex Enichem, Dobanol 25 ex
Shell, Empicol LX ex Albright and Wilson and Texapon LS ex
Henkel.

The level of PAS material is from 0.1 to 40% by weight of
the composition, preferably from 3 to 20~, more preferably
from 5 to 15%.

The PAS is present in a non-solid dispersed phase. For the
purpose of the present invention this means that the PAS
material is wholly or predominantly present in a non-solid
dispersed phase. Preferably no or only minor amounts (less
than 10%, more preferably less than 5~) of the PAS are
p~esent in the form of solid crystallites, also preferably
no or-only minor amounts (less than 10~, more preferably
less than 5% ) of the PAS are present in solubilised or
micellar form.

The level of PAS in the form of crystallites can be
estimated by light microscopy, the level of PAS in
solubil~sed or micellar from can be estimated by

SUB~



centrifuging the composition at 7350 m/s2 (750G) for 16
hours and then determining the level of PAS in the clear
layer.

As explained, the PAS is predominantly (for more than 80% by
weight, preferably more than 90%, more preferably more than
95%) incorporated in a non-solid dispersed phase. Examples
of non-solid dispersed phases are liquid crystal structures,
for example lamellar droplet structures. Most preferably the
PAS is part of a lamellar droplet structure either as the
sole surfactant in the droplets, or more preferably in
combination with other surfactant materials.

It is believed that it is well within the ability of the
skilled person to detect the presence of such a non-solid
dispersed phase, for example by light microscopy or electron
microscopy.

For ensuring that a non-solid dispersed phase comprising the
PAS materials is present, several parameters may be varied,
e.g. one or more of the following conditions is fulfilled
for incorporating the PAS into a non-solid phase:

(a) The mole ratio of sodium to other cationic
counterions such as potassium and/or ammonium in
the composition is from 10 : 1 to 1 : 10, more
preferably from 3 : 1 to 1 : 3, most preferably
from 2 : 1 to 1 : 2;
,,

(b) The PAS material is a branched alkyl sulphate,
wherein at least 20%, more preferably more than
30%, most preferably more than 50% of the PAS
molecules are branched.





WO91/1~09 PCT/EP91/00768
20~0688
(c) The composition comprises a soap as part of the
surfactant system, wherein preferably the soap is
predominantly unsaturated. Especially preferably the
iodine value of the soap is greater than 70, more
preferably greater than 75, most preferably oleate
soaps are used.

With respect to condition (a), it is believed that if
compositions of the invention contain available
counterions for the PAS other than sodium, this will
generally lead to less crystallisation of the PAS and
therefore generally to a lower viscosity and/or
increased stability. Preferably compositions of the
invention contain mixtures of sodium and other
counterions. Preferably the other counterions are
selected from the group of monovalent cations such as
potassium, lithium and ammonium, more preferably the
other counterions are potassium ions. The mole ratio of
sodium to other counterions in the total composition is
preferably from 10 : 1 to 1 : 10, more preferably from
3 : 1 to 1 : 3, most preferably from 2 : 1 to 1 : 2.

With respect to (b) preferably the PAS materials are at
least partly branched, preferably at least 20% of the
PAS molecules are branched, more preferably more than
30%, most preferably more than 50%. Branching is
believed to be advantageous because it generally leads
to less crystallisation of the PAS materials and
therefore to a lower viscosity and/or increased
stability.

The use of unsaturated soaps is believed to be
advantageous, because this possibly provides a reduced
formation of solid complexes of the soap and the PAS
material and therefore results in a reduced viscosity
and/or an increased stability.

J~
, 6

Preferably at least two of the three above mentioned con-
ditions are satisfied, especially conditions (a) and (b),
most preferably all three conditions are
satisfied.
The liquid deterqent product

The compositions of the invention are physically stable. In
the context of the present invention, physical stability for
liquid systems of the invention can be defined in terms of
the maximum separation compatible with most manufacturing
and retail requirements. That is, the 'stable' compositions
will yield no more than 5%, most preferred no more than 2%
by volume phase separation as evidenced by appearance of 2
or more separate phases when stored at 25~C for 21 days from
the time of preparation. Especially preferred are com-
positions which do not yield any phase separation upon
storage for 21 days at 25 ~C.

Preferably, compositions of the invention have a pH of
between 6 and 14, more preferred from 6.5 to 13, especially
preferred from 7 to 12.

Compositions of the invention have a viscosity after storage
for 2 weeks of less than 2,500 mPa.s at 21 s-1, preferably
less than 2,000 mPa.s, more preferably less than 1,500
mPa.s, most preferred between 100 and 1,000 mPa.s at 21 s-1.
Preferably these viscosities are observed after storage for
at least two weeks at 25~C, but more preferably also at 15
~C and most preferably also at 5~C and 0~C.

Compositions of the invention comprise detergent active
materials, preferably at a level of from 1 to 70% by weight
of the composition, more preferred a level of 5
.



SUB~ 4 ~?~--~

W O 91/16409 . PC~r/EP91/00768
20806~8
to 50% by weight, most preferred from 10 to 40% by
weight.

Preferably at least 5% by weight of the detergent active
materials are PAS materials, most preferably more than
10%, most preferably more than 20%. Preferably the PAS
constitutes less than 60~ by weight of the detergent
active materials, more preferred less than 50%, most
preferred less than 40%.
If for lamellar droplet structured liquid detergent
compositions a blend of surfactants is used, the precise
proportions of each component which will result in
lamellar droplets will depend on the type(s) and
amount(s) of the electrolytes, as is the case with
conventional structured liquids.

WO91/1~09 PCT/EP91/00768
208068~ 8 ~
- In the widest definition the detergent-active material
may, in addition to the PAS material as described above,
comprise one or more other surfactants, which may be
selected from anionic, cationic, nonionic, zwitterionic
and amphoteric species, and (provided mutually
compatible) mixtures thereof. For example, they may be
chosen from any of the classes, sub-classes and specific
materials described in 'Surface Active Agents' Vol.I, by
Schwartz & Perry, Interscience 1949 and 'Surface Active
Agents' Vol.II by Schwartz, Perry & Berch (Interscience
1958), in the current edition of "McCutcheon's
Emulsifiers & Detergents" published by the McCutcheon
division of Manufacturing Confectioners Company or in
'Tensid-Taschenbuch', H.Stache, 2nd Edn., Carl Hanser
Verlag, MUnchen & Wien, 1981.

Suitable nonionic surfactants include, in particular,
the reaction products of compounds having a hydrophobic
group and a reactive hydrogen atom, for example
aliphatic alcohols, acids, amides or alkyl phenols with
alkylene oxides, especially ethylene oxide, either alone
or with propylene oxide. Specific nonionic detergent
compounds are alkyl (C6-C18) primary or secondary linear
or branched alcohols with ethylene oxide, and products
made by condensation of ethylene oxide with the reaction
products of propylene oxide and ethylenediamine. Other
so-called nonionic detergent compounds include long
chain tertiary amine oxides, long-chain tertiary
phospine oxides and dialkyl sulphoxides.
Other preferred nonionic surfactant materials are
glyceryl ethers such as for example disclosed in
GB 1,506,419.

Although compositions of the invention may be free of
nonionic surfactants, generally the level of nonionic
surfactants is more than 1% by weight of the



composition, preferably from 2.0 to 25.0% by weight of
the composition.

Compositions of the present invention may also contain
synthetic anionic surfactant ingredients other than
PAS. These other synthetic anionic surfactants are
preferably used in combination with the above mentioned
nonionic materials. Suitable synthetic anionic surfac-
tants are usually water-soluble alkali metal salts of
organic sulphonates having alkyl radicals containing
from 8 to 22 carbon atoms, the term alkyl being used to
include the alkyl portion of higher acyl radicals.
Examples of suitable synthetic anionic detergent com-
pounds are for example sodium and potassium alkyl
(C9-C20) benzene sulphonates, particularly sodium
linear secondary alkyl (C10-Cl5) benzene sulphonates;
sodium alkyl glyceryl ether sulphates, especially those
ethers of the higher alcohols derived from tallow or
coconut oil and synthetic alcohols derived from
petroleum; sodium coconut oil fatty monoglyceride
sulphates and sulphonates; sodium and potassium salts
of sulphuric acid esters of higher (C8-Cl8) fatty al-
cohol-alkylene oxide, particularly ethylene oxide,
reaction products; the reaction products of fatty acids
such as coconut fatty acids esterified with isethionic
a=cid and neutralized with sodium hydroxide; sodium and
potassium salts of fatty acid amides of methyl taurine;
al~ane monosulphonates such as those derived by reac-
ting alpha-olefins (C8-20) with sodium bisulphite and
those derived from reacting paraffins with S02 and Cl2
and then hydrolyzing with a base to produce a random
sulphonate; and olefin sulphonates, which term is used
to describe the material made by reacting olefins, par-
ticularly C10-C20 alpha-olefins,- with -S03 and then
neutralizing and hydrolyzing the reaction product. The
preferred anionic detergent compounds are sodium
(C11-C15) alkyl benzene sulphonates.

4 ~

WO91/1~09 . PCT/EPgl/00768
2~ fi 8~ lo
- Generally the level of non-soap, non-PAS anionic
surfactant materials is from 0-35% by weight of the
composition, for example from 0.5 to 25%.

It is also possible, and sometimes preferred, to include
an alkali metal soap of a mono- or di-carboxylic acid,
especially a soap of an acid having from 12 to 18 carbon
atoms, for example oleic acid, ricinoleic acid, and
fatty acids derived from castor oil, rapeseed oil,
groundnut oil,coconut oil, palmkernel oil, alk(en)yl
succinates e.g. dodecyl succinate or mixtures thereof.
The sodium or potassium soaps of these acids are
preferably used. Preferably the level of soap in
compositions of the invention is from 0-40% by weight of
the composition, more preferred from 5-25%.

As stated above, preferably the soap material is
predominantly unsaturated and has a iodine va~ue of at
least 70 more preferably more than 75, most preferably
the soap consists for at least 70% by weight of
unsaturated soap materials such as oleate.

Preferably the weight ratio of anionic surfactants
(including the PAS material and the soap material) to
the above mentioned nonionic surfactant materials is
from 10 : 1 to l : 10, more preferred from 5 : 1 to l :
2, most preferred from 4 : 1 to 1 : 2.

Also possible is the use of salting out resistant active
materials such as for example described in EP 328 177,
especially the use of alkyl poly glycoside surfactants
such as for example disclosed in EP 70 074. Also alkyl
mono glucosides may be used. Preferred levels of these
materials are from 0-20% by weight, more preferably from
1 to 15%.

WO91/1~09 PCT/EP91/00768
~ 11 20806~8
The compositions optionally also contain electrolyte,
preferably in an amount sufficient to bring about
lamellar droplet structuring of the detergent-active
material. Preferably the compositions contain from 1% to
60%, especially from 2 to 45% of a salting-out
electrolyte. Salting-out electrolyte has the meaning
ascribed to in specification EP-A-79 646. Optionally,
some salting-in electrolyte (as defined in the latter
specification) may also be included. In selecting the
appropriate level of salting-out electrolyte it is
sometimes preferred to use relatively low amounts of
salting-out electrolytes, say from 2-10% by weight.
These levels are generally sufficiently high to provide
structuring of the composition, and do not provide
viscosity problems.

In any event, it is preferred that compositions
according to the present invention include detergency
builder material, some or all of which may be
electrolyte. In this context it should be noted that
some detergent active materials such as for example
soaps, also have builder properties.

Examples of phosphorous-containing inorganic deter-
gency builders include the water-soluble salts,
especially alkali metalpyrophosphates, orthophosphates,
polyphosphates and phosphonates. Specific examples of
inorganic phosphate builders include sodium and
potassium tripolyphosphates, phosphates and
hexametaphosphates. Phosphonate sequestrant builders may
also be used. Sometimes it is however preferred to
minimise the amount of phosphate builders.

Examples of non-phosphorus-containing inorganic
detergency builders, when present, include water-soluble
alkali metal carbonates, bicarbonates, silicates and
crystalline and amorphous aluminosilicates. Specific

WO91/1~09 PCT/EP91/00768

2080~8~ 12
- examples include sodium carbonate (with or without
calcite seeds), potassium carbonate, sodium and
potassium bicarbonates, silicates and zeolites.

Examples of organic detergency builders, when present,
include the alkaline metal, ammonium and substituted
ammonium polyacetates, carboxylates, polycarboxylates,
polyacetyl carboxylates and polyhydroxysulphonates.
Specific examples include sodium, potassium, lithium,
ammonium and substituted ammonium salts of
ethylenediaminetetraacetic acid, nitrilitriacetic
acid, oxydisuccinic acid, melitic acid, benzene
polycarboxylic acids, CMOS, tartrate mono succinate,
tartrate di succinate and citric acid. Citric acids or
salts thereof are preferred builder materials for use in
compositions of the invention.

Preferably the level of non-soap builder material is
from 5-40% by weight of the composition, more preferred
from 5 to 25% by weight of the composition.

In the context of organic builders, it is also desirable
to incorporate polymers which are only partly dissolved,
in the aqueous continuous phase as described in
EP 301.882. Typical levels are from 0.5 to 4.5% by
weight.

It is further possible to include in the compositions of
the present invention, alternatively, or in addition to
the partly dissolved polymer, yet another polymer which
is substantially totally soluble in the aqueous phase.
Use of such polymers is generally described in our EP
301,883. Typical levels are from 0.5 to 4.S% by weight.

Apart from the ingredients already mentioned, a number
of optional ingredients may also be present, for
example lather boosters such as alkanolamides,

13
particularly the monoethanolamides derived from palm
kernel fatty acids and coconut fatty acids, lather
depressants, oxygen-releasing bleaching agents such as
sodium perborate and sodium percarbonate, peracid bleach
precursors, qhlorine-releasing bleaching agents such as
trichloroisocyanuric acid, inorganic salts such as sodium
sulphate, and,-usually present in very minor amounts,
fluorescent agents, perfumes, enzymes such as proteases,
amylases and lipases (including Lipolase (Trade Mark) ex
Novo), anti-redeposition agents, germicides and colourants.

A preferred further ingredient -which is especially
preferred for incorporation in internally structured
compositions according to the invention- is a deflocculating
polymer e.g one having a hydrophilic backbone and at least
one hydrophobic side chain. Such polymers are described in
our copending patent applications W0/91/06622 (published 16
May 1991), W0/91/06623 (published 16 May 1991) and GB
2,237,813 (published on 15 May 1991) and in our European
patent application EP 346 995. Typical levels of these
ingredients are from 0.5 to 4.5 % by weight.

Compositions of the invention may be prepared by any conven-
tional method for the preparation of liquid detergent com-
positions. A preferred method involves the dispersing of theelectrolyte ingredient -if any- together with the minor
ingredients except for the temperature sensitive ingredients
-if any- in water of elevated temperature, followed by the
addition of the builder material - if any-, the detergent
active materials (preferably as a non-aqueous premix
containing the PAS in acid-form) under stirring and
thereafter cooling the mixture and adding any temperature
sensitive minor ingredients such as enzymes perfumes etc.
The deflocculating polymer -if any- may advantageously be



S~,~BS~ l r~ S~

14 7 ~
added after the electrolyte ingredients, the builder
ingredients or just before cooling.

A particularly preferred method of making an aqueous liquid
detergent composition which contains a PAS material is to
use a premix of PAS with nonionic surfactants, said premix
containing little or no water. Preferred premixes contain 10
to 50% by weight more preferrably 15 to 40% most preferably
20 to 35% of PAS, and 50 to 90% more preferably 60 to 80% of
nonionic surfactant. The water level is preferably less than
20% by weight, more preferably less than 10% most preferably
the premix is substantially free of water. The PAS in the
premix may be present in acid form, but generally the PAS
will be present in salt form for example in its sodium salt
form.

The premixes can easily be handled and do not suffer from
high viscosities. They can for example be supplied as a
feedback raw material from as sulphonation or sulphation
plant.

In use the detergent compositions of the invention will be
diluted with wash water to form a wash liquor for instance
for use in a washing machine. The concentration of liquid
detergent composition in the wash liquor is preferably from
0.05 to 10%, more preferred from 0.1 to 3% by weight.

The invention will now be illustrated by way of the
following Examples.

.




l~BS ~ ~ ~


EXAMPLE I

The following compositions were made by adding the
ingredients in the listed order to the water at a
temperature of 40 ~C.

COMPOSITION ~ wt A B C D E F
Sodium citrate.2H2O l0 l0 l0 l0 l0 5
Glycerol 5 5 5 5 5 5
Borax 3.53.5 3.5 3.5 3.5 3.5
Fluorescer 0.l 0.l0.l 0.l 0.l 0.l
NaOH 2.82.8 - 2.8 2.8 - ~
~OH ~~ ~~ 3'9 ~~ ~~ 3'9
polymer 1) l.0l.0 l.0 l.0 l.0 l.0
Synperonic A720 20 20 20 20 20
oleic acid 6 6 6 6 l0 l0
Coconut fatty acid 4 4 4 4 -- --
Dobanol 9l PAS2)l0 -- -- -- -- --
Lial 145 PAS3) -- l0 l0 -- l0 l0
Empicol PAS4) -- -- -- l0 -- --
Perfume 0.40.4 0.4 0.4 0.4 0.4
Antifoam (DBl00)0.l 0.l 0.l 0.l 0.l 0.l
water < balancc >




notes:

1) polymer A-11 as described in EP 346 995 (100%)
2) A Cg-Cll linear PAS ex Shell (as 100%, sodium salt)
3) A C14-C15 PAS being 60% branched ex Enichem (as 100%,
sodium salt)
4)-A-coconut PAS ex A&W (as lO0~ ammonium salt).

The following product forms were obtained after storage
for 2 weeks at the temperature indicated (L=liquid
indicates a viscosity at 21 s _1 of less than 2,500
mPa.s, P = Paste indicates a viscosity of more than
2,500 mPa-.s at 21 s~1)~


16

COMPOSITION A B C D E F
at 25 ~C L L L L L L
at 15 ~CL/P P L L L L
5 at 5 ~C P P P P P L
at 0 ~C P P P P P L




This example illustrates that PAS containing com-
positions of satisfactory viscosity after storage at
25 ~C can be obtained by using a Dobanol 91 or Lial 145
PAS (compositions A and B). Further viscosity benefits
can be obtained by using mixed counterions
~Compositions C and D) or by using unsaturated soap
materials (Composition E), especially advantageous
results can be obtained by using mixed counterions in
combination with unsaturated soaps (Composition F).

EXAMPLE II
The following compositions were made as in example I
COMPOSITION % wt A B C D
Glycerol 5 5 s 5
Borax 3,5 3.5 3,5 3.5
Pluorescer 0.1 0.1 0.1 0.1
25 Nacitrate.2aq -- -- -- 10
Citric acid.laq 7.1 7.1 7.1 --
NaO~ 4.7 2.4 -- --
KO~ 3.3 6.6 10 --
po}ymer 1~ 1.0 1.0 1.0 1.0
30 Synperonic A7 20 20 20 16
oleic acid 10 10 10 --
LiaI 1453) 10 10 -'10 24
water . < balancc >




1) polymer A-11 as described in EP 346 995 (100%)
. 3) A C14-C15 PAS being 60% branched ex Enichem (as 100%,
sodiu~ salt)

17

The ~ollowing product forms were obtained after storage
for 2 weeks at the temperature indicated (L=liquid
indicates a viscosity at 21 5-1 of less than 2,500
mPas, P = Paste indicates a viscosity of more than
2,500 mPas at 21 5-1):

COMPOSITION A B C D
at 20 ~C L L L L
at 4 ~C L L L P
at O ~C P L L P

This example illustrates that the viscosity after
storage is less, when more potassium counterions are
present (Compositions A-C). From composition D it
follows that higher levels of PAS may cause viscosity
problems after storage.

EXAMPLE III
The compositions were made in the following way:
A premix of PAS with nonionic sufactants was made. This
premix had a water content of about 6%. Oleic acid was
mixed with the premix.
Borax and citric acid and KOH were added to water under
stirring followed by the addition of the Zeolite,
porymer, antifoam, the above active mix and the
remaining ingredients. Oleic acid could equally well be
added sperately after addition of the blends.




S~ ,5j s ~ ~ ~E ~~~--T

18

COMPOSITION ~ wt A B C
Glycerol 4.1 4.1 4.1
Borax ~10 aq) 2.8 . 2.8 2.8
F~uorescer 0.1 0.1 0.1
Nacitrate (anh.) 6.7 6.7 6.7
NaOH 1.2 1.2 1.2
KOH 4.2 4.2 4.2
Zeolite (4A type) 15.0 15.0 15.0
Polymer 1) 0.8 0.8 0.8
Antifoam 0.2 0.2 0.2
Nonionic 5) - 17.2 15.4 11.6
Llal 123 6) 4.6 6.4 10.1
Oleic acid 6.3 6.3 6.3
Perfume 0.3 0.3 0.3
Water < balance >




l) polymer A-11 as described in EP 346 995 (100%).
5) Syperonic A7 and Syperonic A3 ex ICI in a 50 : 50
weight ratio mixture.
6) A C12-C13 PAS being 60g~ branched ex Enichem.

Of the above formulations the initial viscosity and the
viscosity after 2 weeks was measured in mPa.s at 21 5-
at ambient temperature was measured, the softeningtemperature was measured and the Mole ratio of potassium
to sodium was calculated. The following results were
obtained:
_
COMPOSITION A B C
NI /-PAS ratio 3.7/12.4/1 1.15/1
Mole ratio (R / Na) 1.23/11.12/1 0.95/l
Softening temperature (~C) ~ 0 < 0 < 0
Initial viscosity (mPa.s, 21 s 1) 815 770 1150
Viscosity after 2 weeks of
storage at 20~C 790 630 695




This example indicates that satisfactory viscosities of
PAS-containing compositions can be obtained by using
mixtures of non-ionics with PAS in different ratios,
together with Zeolite.


19
EXAMPLE IV

The compositions were made in the following way:
The ingredients were mixed in the listed order, with PAS
added as the last active, followed by 20 minutes mixing.

COMPOSITION ~ wt A B
Glycerol 5 5
Borax 3.5 3~5
Citric acid 6.4 6.4
Fluorescer - 0.1 0.1
NaOH 1.1 1.1
~OH 4'9 4'9
Polymer 1.O 1.O
Syperonic A7 20 20
Oleic acid I0 10
PAS 7) 4 6
Perfume 0.4 0.4
Water <------balance----->

7) Empicol LXV, a sodium coconut PAS ex A&W.

COMPOSITION A 8
NI/PAS ratio 5 3.7
~ole ratio (~/Na) 1.26 1.15
Softening temperature (~C) < 0 5
Initial viscosity
(mPa.s, 21 s 1) 240 270
Viscosity after 2 weeks of
storage at 20~C 195 195

This example shows that also with using a natural
derived material, satisfactory compositions can be
obtained.


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Administrative Status

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Administrative Status

Title Date
Forecasted Issue Date 1998-11-03
(86) PCT Filing Date 1991-04-22
(87) PCT Publication Date 1991-10-26
(85) National Entry 1992-10-15
Examination Requested 1997-11-27
(45) Issued 1998-11-03
Deemed Expired 2004-04-22

Abandonment History

There is no abandonment history.

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $0.00 1992-10-15
Maintenance Fee - Application - New Act 2 1993-04-22 $100.00 1993-03-18
Registration of a document - section 124 $0.00 1993-11-30
Maintenance Fee - Application - New Act 3 1994-04-22 $100.00 1994-03-15
Maintenance Fee - Application - New Act 4 1995-04-24 $100.00 1995-03-15
Maintenance Fee - Application - New Act 5 1996-04-22 $150.00 1996-03-15
Maintenance Fee - Application - New Act 6 1997-04-22 $150.00 1997-03-17
Request for Examination $400.00 1997-11-27
Maintenance Fee - Application - New Act 7 1998-04-22 $150.00 1998-03-16
Final Fee $300.00 1998-06-22
Maintenance Fee - Patent - New Act 8 1999-04-22 $150.00 1999-03-17
Maintenance Fee - Patent - New Act 9 2000-04-24 $150.00 2000-03-15
Maintenance Fee - Patent - New Act 10 2001-04-23 $200.00 2001-03-14
Maintenance Fee - Patent - New Act 11 2002-04-22 $200.00 2002-03-13
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
UNILEVER PLC
Past Owners on Record
DONKER, CORNELIS B.
MACHIN, DAVID
SCHEPER, FREDERIK J.
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Cover Page 1998-10-19 1 20
Description 1998-04-08 19 729
Claims 1998-04-08 2 58
Claims 1994-05-28 2 53
Description 1994-05-28 19 686
Abstract 1995-08-17 1 54
Cover Page 1994-05-28 1 15
Correspondence 1998-06-22 1 53
International Preliminary Examination Report 1992-10-15 22 729
Office Letter 1995-12-15 1 45
Prosecution Correspondence 1995-11-27 1 48
Office Letter 1993-04-28 1 52
Fees 1997-03-17 1 61
Fees 1996-03-15 2 54
Fees 1995-03-15 1 44
Fees 1994-03-15 2 49