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Patent 1109355 Summary

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(12) Patent: (11) CA 1109355
(21) Application Number: 1109355
(54) English Title: LIQUID DETERGENT COMPOSITION
(54) French Title: DETERGENT LIQUIDE
Status: Term Expired - Post Grant
Bibliographic Data
(51) International Patent Classification (IPC):
  • C11D 1/86 (2006.01)
  • C11D 1/29 (2006.01)
  • C11D 1/66 (2006.01)
  • C11D 1/72 (2006.01)
  • C11D 3/30 (2006.01)
  • C11D 9/00 (2006.01)
  • C11D 10/04 (2006.01)
  • C11D 17/00 (2006.01)
(72) Inventors :
  • RUSSELL, PETER J. (United Kingdom)
  • AUGUSTIJN, GOVERT J.P.
  • VAN DE GRIEND, JACOB A.
(73) Owners :
  • UNILEVER LIMITED
(71) Applicants :
  • UNILEVER LIMITED (United Kingdom)
(74) Agent: SMART & BIGGAR LP
(74) Associate agent:
(45) Issued: 1981-09-22
(22) Filed Date: 1978-05-05
Availability of licence: N/A
Dedicated to the Public: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): No

(30) Application Priority Data:
Application No. Country/Territory Date
19,119/77 (United Kingdom) 1977-05-06
29,729/77 (United Kingdom) 1977-07-15

Abstracts

English Abstract


Abstract of the Disclosure
A liquid detergent composition, particularly suitable
for use in the underbuilt region of dosages, comprises at
least 10 % by weight of a sodium soap, at least 1 % by
weight of an organic synthetic detergent, the wieght ratio
of soap to synthetic detergent being 10:1 to 1:1, and at
least 0.1 % by weight of a buffering agent.


Claims

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


THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An aqueous liquid detergent composition comprising
(a) from 10-60 % by weight of a sodium soap of a fatty acid having
from 8 to 24 carbon atoms in its alkyl residue;
(b) from 1-50 % by weight of an anionic, nonionic, cationic,
zwitterionic or amphoteric organic synthetic detergent, whereby
the weight ratio of (a):(b) is from 10:1 to 1:1; and
(c) from 0.1-20 % by weight of an organic buffering agent selected
from the group consisting of the ethanol-,propanol- and iso-
propanol amines.
2. A composition according to claim 1, comprising
15-50 % by weight of (a)
5-40 % by weight of (b)
and 1-15 % by weight of (c).
3. A composition according to claim 2, comprising
20-35 % by weight of (a)
9-30 % by weight of (b)
and 2-10 % by weight of (c).
4. A composition according to claim 1, wherein the weight
ratio of (a):(b) is from 3:1 to 1:1.
5. A composition according to claim 1, wherein (a) is
selected from the group consisting of sodium oleate, sodium salt of
coconut fatty acids and mixtures thereof, (b) is selected from the
group consisting of nonionic synthetic detergents and alkylether-
sulphates, and (c) is selected from the group consisting of triethan-
olamine and monoisopropanolamine.
6. A composition according to claim 1, further comprising
18

from 1-35 % of a water-soluble organic or inorganic builder material.
7. In a process for making an aqueous liquid detergent
composition according to claim 1, the step forming the soap last,
by in situ neutralization of the fatty acid.
19

Description

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


C 55L~/B 225 (~)
The present invention relates to an aqueous liquid
detergent composition comprising a mixture of a soap
detergent and a non-soap detergent.
Aqueous liquid detergents are well~known in the art.
Usually such compositions contain one or more synthetic
organic detergents, solvents, and, in the case of built
aqueous liquid detergent compositions, inorganic and/or
organic builder salts. Frequently, such compositions also
contain hydrotropes, enabling the incorporation of
sufficient quantities of detergent material and builder
salts to attain the desired physical properties, as well as
satisfactory detergency performance.
In formulating such aqueous liquid detergent
compositions, physical properties like storage stability,
clarity, viscosity, pourability etc. play an important role,
as well as the detergency and foaming performance at a
required volume usage of the composition. Thus, for example,
while a particular composition may give satisfactory
detergency and foaming performance at a given dosage, often
a significant decline in performance is seen when lower
dosages are used. This is particularly true in such
situations where the dosage is insufficient to render the
water-hardness ions inactive, i.e. in so-called "under-
built" situations. From an ecological standpoint, the
reduction of the amount of phosphate builder salts could
bedesirable~ but such reduction causes a reduction in
detergency performance, particularly in an underbuilt
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situation.
It has already been proposed in the art to formulate
so-called unbuilt liquid detergent compositions~ which are
compositions which are free from builder salts. Thus,
UK Patent Specification 1,370,402 discloses unbuilt liquid
detergent compositions comprising a nonionic surfactant, an
anionic surfactant which is an alkanolamine salt of Cg-Cl5
alkylbenzene sulphonic acid or o~ C8-C24 fatty aci.ds, further-
more a free C8-C2L~ fatty acid and a solubilizing agent.
UK Patent Specification 1,365,46LI descrlbes unbuilt
liquid detergents comprising a nonionic surfactant, a mixture
of an alkanolamine salt of Cg-Cl5 alkylbenzene sulphonic acid
and of C8-C24 ratty acids, and free ethanolamine.
These attempts are, however, not entirely satisfactory,
as the attainment of one or more desirable characteristics
frequently involves a significant reduction of other
desirable properties. Thus, the above formulations may
suffer from a too low foaming capacity, or from an inferior
detergency at a higher dosage.
Furthermore, these formulations are directed to
mixtures, in which the soap component is an alkanolamine
salt, which is better soluble than the more readily available
sodium soaps. The present invention is, however, directed to
soap-based liquid detergent compositions, in which the soap
component is or comprises a sodium soap.
Liquid detergent compositions, which may comprise a
sodium soap, have indeed been proposed in the art. For
example, US Patent Specification 2,875,153 discloses a
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-~ C 551l/~ 225 (R)
liquid detergent composition in gel forrn, which contains a
water-soluble soap and a nonionic detergent. The water-
soluble soap can be a sodium soap. However, this product is
a gel, which makes it unsuitable as a liquid detergent
5 composition in view of its viscosity and pourability
characteristics.
US Patent Specification 2, 543,744 discloses a low-
foaming dishwashing composition comprising an alkali metal
soap, and a nonionic sur~actant. These formulations contain,
when in the form o~ an aqueous liquld with a sodium soap,
up to 7.5% of the latter.
Numerous other proposals have been made for liquid
detergents containin~ a soap component. Thus
US Patent Specification 3,723,328 refers to compositions
15 which may contain up to 16.2% of a sodium soap, and US
Patent Specification 3,707,503 discloses built compositions
which may contain up to 4.5% of a sodium soap.
UK Patent Specification 1,415,719 discloses liquid
compositions containing a liquid nonionic and fatty acids,
which may be partially neutralized to form sodium soaps,
and UK Patent Specification 1,081,556 discloses liquid
detergent compositions in which part o~ the soap component
may be a sodium soap.
Dutch Patent ~pplication 7413265 and ~erman Patent
Application 2,411,528 relate to liquid compositions
comprising a mixture of sodium soaps of C8-C14 saturated
and C16-C22 unsaturated fatty acids, together with other,
synthetic detergents and possibly builder salts.
-4 -
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C 55ll / B 225 (R)
Dutch Patent Application 740600ll discloses a liquid
composition which contains up to 8% of an alkali metal soap,
and up to 60% of a mixture of nonionic surfactants, and
US Patent Specification 2,560,839 discloses a liquid
composition containing up to 10% of an alkali metal soap, up
to 30% of a nonioniG surfactant and up to 30% of a pyro-
phosphate builder salk. Although all these attempts yield
products which are suitable for certain launderinK purposes,
they are less so for other cleaning operations, parkicularly
at different dosages and/or in underbuilt situations.
It has now been found that satisfactory liquid
detergent compositions can be obtained, which are isotropic,
contain ecologically acceptable components, which are
particularly suitable in the underbuilt region of dosages,
but also show, at higher dosages, the superior detergency
characteristics of built products over conventional unbuilt
liquid composi'tions.
The discovery of such versatile compositions has been
made possible by the use of high levels of fatty acid
sodium soaps coupled with the incorporation of suitable
levels of synthetic detergent and certain buffering agents
enhancing the detergency performance of these liquid soap
compositions.
The present invention therefore relates to an aqueous
liquid detergent composition comprising, as essential
ingredients:
a) at least 10% by weight of the composikion of a sodium
soap of a straight- or branched chain C8-C24 fatty acid;
: :

~0~ C 55L~/ B 225 (R)
b) at least l~o by weight of the composltion of an orgarlic synthetic
- detergent, the weight ratio of' the soc~ um soap to the organic
synthetic detergent being from 10:1 to 1:1;
c) at least 0.1% by weight of the composition of a buf'fering agent as
5 . hereina~ter defined.
Such aqueous liquid detergent compositions are effective at lower
dosages in underbuilt situations, and are superior to other conventional
unbuilt liquid compositions at higher dosages, where they may even behave
as built liquids. The compositions of the inventlon have a superior
performance at lower dosages when compared w:ith conventional built
liquids at lower dosap,es.
The essential ingredients of the composition accordlng to the
invention are discussed in detail below.
a. The soap component
The soap component is or comprises a sodium soap of straight- or
branched chain fatty acids with 8-24 carbon atoms in the alkyl
residue. These fatty acids include saturated and unsatured natural
fatty acids, as well as synthetic fatty acids. The latter may show
some degree of branching in the alkyl residue, e.g. up to 20% methyl
groups in the ~-position of the alkyl residue. Typical examples of
suitable f'atty acids include ~aprilic-,capric-, lauric-, myristic-,
palnitic-, stearic-, oleic-, linoleic-, behenic acid as well as
mixtures of such fatty acids. Fatty acids, obtained from natural
faks and oils are also suitable, such as coconut oil fatty acids,
palm- and palm-kernel oil fatty acids, fatty acids derived f'rom soy~
bean oil, safflower oil, tall oil, tallow, ~ish oil, grease lard,
groundnut oil, castor oil, and the like. Examples of synthetic fatty
acids include those obtained by petroleum oxidation or by hydrogen-
ation of carbon monoxide according to the Fischer Tropsch process.
The pre.erred, diu~ soaps are eodium oleate, sodium sa t o~
.
,
,
.... :-., ., ~ . .. .

~ ~ S C 55LI/ B 225 (R)
coconut fatty acids and mixtures thereof. In the latter case,theweight
ratioofthetwocomponents variesfrom 9:1 to 1:9, preferably4:1tol:4.
The minimum amount of the sodium soap to be present
in the composition is about 10% by we;ght; the present
invention enables the incorporation of high levels of
sodium soap, i.e. up to 60% by weight of the sodium soap
can be incorporated. In general, for most practical purposes
the amount of thé sodium soap wi]l be from 15-50,
particularly from 2~-35% by we~ight ofthecomposition.
Other soaps with a different; cation, such as
potassium soaps, and alkanolamine soaps may also be
incorporated, as long as the amount of sodium soap is
within the ranges as given above.
The sodium soaps can be added to the compositions as
such, or they can be formed in situ by neutralization of
the corresponding fatty acids in the composition by means
of the addition of a suitable sodium salt forming alkaline
; material, such as caustic lye and caustic soda. The same
applies to the possibly co-used soaps with another
cation.
b. The organic synthetic detergent.
This ingredient can be selected from the group consisting
of anionic, nonionic, cationic, zwitterionic and amphoteric
organic synthetic detergents. The anionic synthetic
detergents (which term excludes salts of natural or
synthetic fatty acids) are basically compounds with a
hydrophobic radical and a solubilizing, salt forming
anion, such as the sulphate, sulphonate, and phosphate
anion.
~'' ' ' ' '
., ~ , . ,

C 554/B 225 (R)
Typical examples are C8-C18 straight- or branched
chain alkylaryl sulphonates~ C~-C22 primary or secondary
alkyl sulpha~es, C8-C22 primary or secondary alkane
sulphonates, C8-C24 ~-olefin sulphonates, C8-C22 primary
or secondary alkylether sulphates, containing from 1-15 moles
o~ ethylene oxide, propylene oxide, butylene oxide or mixtures
thereof, sulphonated fatty acids or fatty acid esters,
C8-C24 acyltaurides, C8-C24 acylisethionates, C8-C18 alkyl-
or alkylaryl phosphates or -ether phosphates with 1-10
moles of ethylene oxide, propylene oxide or mixtures thereof'.
Alkyl polyglycol ether carboxylic acid salts are a]so
embraced by the term anionic synthetic detergents. Further
examples of anionic synthetic detergents are described in
standard text books, such as SchwartZ, Perry and Berch
"Surface-active Agents and Detergents", Vol. I (~949) and
Vol. II (1958). These anionics are used in the f'orm of their
sodium-, potassium-, ammonium- or alkanolamine salt.
The nonionic synthetic detergents broadly embrace
compounds having a hydrophobic radical and a water-
solubilizing group which does not ionize. Normally this
water-solubilization is effected by ethoxylation and/or
propoxylation of a hydrophobic molecule, containing a
removable proton.
Typical examples are the ethoxylation and/or
propoxylation products of linear or branched-chain, primary
or secondary, natural or synthetic alcohols having 8-24
carbon atoms in their alkyl chain, of mono- or dialkyl
phenols having from 8-18 carbon atoms in their alkyl chain,
-8-
: . , ` . - - ' : ~ -
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'

C 55l~/B 225 (~)
o~ C8-C22 f'atty acids (as defined f'or the sodium soaps
herebefore), of polyethylene- or polypropyleneglycols, o~
C8-C22 fatty amines, f'atty am:ides or fatty alkylolamides
etc. Further examples are given in the standard text book
referred to above. By the non:ionic detergents are also to
be understood the tertiary amine oxides having one alkyl
chain with 8-18 carbon atoms and two alkyl chains with 1-5 carbon
atoms, which may be substituted or ethoxylated; as well as sucrose esters.
Typical examples of cationic synthetic detergents are
quaternary ammonium compounds such as the (di) higher alkyl
di (lower) alkyl ammonium chlorides. Further examples are
again given by the standard text book referred to above.
Zwitterionic synthetic detergents are for example the
sulphobetaines such as alkyl dimethyl ammoniumpropane
sulphonate, and amphoteric synthetic detergents are for
example the mono- or dialkyl ~-amino carboxylic acids.
Examples of zwitterionic or amphoteric synthetic
detergents are also disclosed in the standard text book
ref'erred to above. Their salt forming cation may be a
sodium, potassiurn, ammonium or an alkanolamine cation.
Naturally, mixtures of these synthetic organic
detergents~ either of the same class or of a different
class, may be used, e.g. a mixture of two diff'erent anionic
or nonionic synthetic detergents, or a mixture of an anionic
and a nonionic detergent. In general, at least 1% of the
synthetic organic detergent should be present in the
; liquid composition. The maximum level can be as high as
50' by weight, and for most practical purposes the amount
_g_

~ C 55LI/B225 (R)
varies from 5-40%, preferably f'rom 9-30% by weight.
The preferred synthetic detergents are the calcium-
insensitive synthetic detergents, which have lime-soap
dispersing properties, such as nonionics and alkylether-
sulphates.
In general, the weight rat:io of the sodium soap to
synthetic organic detergent is from 10:1 to 1:1 and,
preferably~from 3:1 to 1:1.
c. The buffering agent.
The buffering agent of the invention can be an organic
and/or inorganic source of alkalinity, exerting a buf'f'ering
capacity to provide and maintain the wash liquor, prepared
from the liquid detergent composition, at the appropriate
pH-value, which i5 normally within the range from 7-11,
preferably 8-10. The buffering agent can be a substance,
which is simultaneously used to neutralize particular acid
substances in the composition, and in that case an excess
of the buffering agent should be used so as to provide for
the minimum level of 0.1% by weight of free buffering agent
to be present in the liquid composition.
The buffering agent can be an inorganic alkaline
material such as NaOH, alkaline silicates, carbonates and
metacarbonates, but preferab~y the buffering agent is an
organic base such as morpholine, piperazine, and the alkanol-
amines such as the mono-, di- and triethanolamines, the
mono-, di-, and tripropanolamines and the mono-, di- and
triisopropanol amines. Of these, the alkanolamines are
preferred.Tri--ethanolamine is preferred for a low pH buffer,
' ' ' i . ' ~ ' '

C 55L~/B 225 (R)
and mono-isopropanolamine for a high pH buffer.
At least 0.1% by weight of the buffering agent should
be present, and the maximum level is about 20% by weight.
Normally from 1-15, and particuLarly from 2-10% by weight
will be required for optimum properties.
The compositions Or the invention may furthermore
comprise a number of non-essential, but often desirable,
optional ingredients.
Thus, the compositions may comprise a solvent or a
hydrotrope system. Such systems a1d in improving the
physical properties of the composition, such as clarity,
viscosity and phase stability. Solvents include the lower
aliphatic alcohols, glycols and mono- or dialkylglycol-
ethers, hydrocarbons, tetrahydrofurfuryl alcohol, and so
on. The hydrotropes include sodium-, potassium-, ammonium-
or alkylolamine salts of xylene-, toluene- and cumene-
sulphonic acid, urea, mono alkane phosphonates and the
like. Mixtures of solvents and hydrotropes may also
be used.
In general, the amount of solvent or hydrotrope ranges
from 0-10% by weight of the composition.
The composition may furthermore contain foam boosters
such as the fatty acid alkylolamides, foam depressors such
as sillcones, preservatives, anti-oxidantsg chelating agents,
perfumes, fluorescers, colouring agents, germicides, bac-
tericides, enzymes and enzyme-stabilisers, soil-suspending
agents, anti-redeposition agents, opacifiers, electrolyte
salts, such as alkali metal chlorides, -sulphates, -acetates

C 55LI/B 225 (R)
and the like.
All these further ingredients are normally used in
minor amounts, e.g. in the order of 0.1~2% by weight.
As stated before, the liquid detergent compositions of
~he invention can be formulated into an unbuilt formulation,
which ls preferred, but it is also possible to include
builder salts therein. Any of the conventional organic
and/or inorganic builder salts may be used, such as the phos-
phate-type builder salts like sodium or potassium ortho-,
pyro- or tripolyphosphate, furthermore salts of carboxy-
methyloxysuccinate, calciumcarbonate, citrates, nitrilotri-
acetic acid, sodiumaluminosilicates of the molecular sieve
types, and other well-known builder salts. If builder salts
are incorporated, the amount thereof may vary from 1-35%,
and preferably 5-30% by weight of` the composition. In this
respect it has also been found, that already small amounts
of` a builder in these compositions give an improved detergency
effect on cotton at 60C.
The compositions of the invention are particularly
suitable for fabric washing, particularly of polyester/
cotton mixed fabrics, and they have shown to possess
extremely good rinsing properties. They are isotropic
liquids, having excellent physical stability under freeze/
thaw conditions.
The products of the invention can be made in any
suitable manner, but it has been found advantageous to add
the ingredients in such a sequential order that the sodium
soaps are formed last, by in-situ neutralization. Thusg
- 12 -
,-
.' ~ " .

~ C 55ll/B 225 (R)
3~5i
a preferred process consists of the following steps:
Add sequentially:
1. the fatty acids and melt these;
2. the fluorescer~ prePerably pre-dispersed in a
nonionic surPactant;
3. preservatives;
Il. balance oP nonionic surfactant;
5. buPPer;
6. hydrotrope:
7. neutralizing agent as an aqueous solution;
8. water and perfume, iP desired.
The invention will now be Purther illustrated by
way of Example.
Example I
The Pollowing clear isotropic liquid composition was prepared:
% by weight
sodium oleate 17
sodium salt of coconut fatty acids 13
: C13-C15 primary alcohol, condensed with 7
moles of ethylene oxide 22
monoisopropanolamine 3
industrial methylated spirit 10
coconut Patty acid ethanolamide 2
fluorescer 1.0
ethylenediaminetetraacetic acid 0.1
ethanehydroxydiphosphonic acid 0.1
perfume 0.12
water balance
This liquid was an isotropic liquid, having a freezing
point o~ 3-4C.
Example II
, An isotropic liquid was prepared of the following composition:
- 13 -

C 55~/B 225 (R)
% by wei~ht
sodium oleate 8
sodium salt of coconut fatty acids 12
C13-C15 primary alcohol, condensed with
7 moles of ethylene oxide plus propylene
oxide (weight ratio of Eo:Po=92:8) 15
triethanolamine 10
monoethyleneglycol 10
fluorescer ~ dye o L~
water balance
This liquid was clear and re~ained stable over prolonged periods
of storage at temperatures between -5 and-~50C.
Example III
The following isotropic liquid was prepared:
% by weight
sodium oleate 12.5
sodium salt of coconut fatty acids 12.5
secondary linear Cll-C15 alcohol, condensed
wlth 9 moles of ethylene oxide 20
C16-C18 linear primary alcohol, condensed
with 3 moles of ethylene oxide, sulphated
(sodium salt) 5
monoethylene glycol 10
triethanolamine, ethanol . 5
water balance
-14-

C 554/B 225 (R)
A~,~,,,,r~
Examp e IV
The ~ollowing built liquid was prepared:
_ ht
sodium oleate
sodium salt o~ coconut ~atty acids 6
C12-C15 alcohol, condensed with 9 moles o~ ethylene oxide 5
sodium linear C12 alkylbenzenesulphonate 9
tetrapotassiumpyrophosphate 14
tetrasodiumpyrophosphate
monoethanolamine 2
water balance
Example V
: The ~ollowing unbullt liquid detergents were prepared:
. ~ by weight
A B C D
sodium oleate 22.7 17 17 10
sodium salt ofcoconut ~atty acids 17.3 13 13 10
C13-C15 alcohol, condensed with 7
moles of ethylene oxide 5 ~ 14 14
sodium alkylether sulphate - 9
sodium alkylbenzene sulphonate - - 8
sodium C14_15 alkylSulPhate - ~ 6
~ triethanolamine 5 5 - 5
: monoisopropanolamine - 3 3
industrial methylated spirit 15 10 10 10
~luorescer
preservative 0.2 0.2
water balance balance balance balance
-15-

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rl ~ ~ \ r
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r1 ~ ~ ~ r~ ~r~ O ~_~ rl
a~ S L~-\ S S ~1 ~ O
r~ E~ ~3 E3 ~ L~ 3 ~ ~ S X r1
~QI rl rl V V V ~ ~5 a) aO) ~ Q ~ I rl a.
t~l ~ r~, rl ~ ~ ~ ~
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C 554/B 225 (R)
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Example VII
-
The liquid of Example I was compared in Tergotometer
washing experiments with a product according to UK Patent
Specification 1,365,464, containing 33% of a nonionic,
12% of an anionic and 10. 5% triethanol amine as the basic
system. The washes were carried out in water of 6FH at about
25C, using 1 kg of 50% soi~dloads for 8 minutes, folIowed
by three rinses. The detergency was measured using ERTC 41 A
and AS 12 test pieces, and fluorescence and redeposition
were measured using non-fluorescent cotton pieces. The
products were used at concentrations oE 0.7, l.o, 1.5 and 2.0 g/l.
The detergency results (reflectancy) were as follows:
ct conc. 0.7 l.o 1.5 2.0 I
test cloth ~ Ex.1 Contr. Ex.1 Contr. Ex.1 Contr. Ex.1 Contr.
. . ,
ERTC 41 A 67.5 68 7o 7o 73~5 71 74 5 71.5
`~ AS 12 52 52 56 53.5 60 56 63 56 L
~; The product of Example 1 was superior especially at
higher dosages.
~:
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Administrative Status

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Event History

Description Date
Inactive: IPC from MCD 2006-03-11
Inactive: IPC from MCD 2006-03-11
Inactive: IPC from MCD 2006-03-11
Inactive: IPC from MCD 2006-03-11
Inactive: IPC from MCD 2006-03-11
Inactive: Expired (old Act Patent) latest possible expiry date 1998-09-22
Grant by Issuance 1981-09-22

Abandonment History

There is no abandonment history.

Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
UNILEVER LIMITED
Past Owners on Record
GOVERT J.P. AUGUSTIJN
JACOB A. VAN DE GRIEND
PETER J. RUSSELL
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) 
Claims 1994-03-18 2 43
Abstract 1994-03-18 1 13
Cover Page 1994-03-18 1 15
Drawings 1994-03-18 1 14
Descriptions 1994-03-18 16 539