Canadian Patents Database / Patent 1269012 Summary

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(12) Patent: (11) CA 1269012
(21) Application Number: 598531
(54) English Title: LIQUID LAUNDRY DETERGENT COMPOSITION
(54) French Title: DETERGENT LIQUIDE DE BUANDERIE
(52) Canadian Patent Classification (CPC):
  • 134/3.11
(51) International Patent Classification (IPC):
  • C07C 69/34 (2006.01)
  • C07C 69/40 (2006.01)
  • C07C 69/60 (2006.01)
  • C07C 69/80 (2006.01)
  • C08G 65/32 (2006.01)
  • C11D 1/06 (2006.01)
  • C11D 1/83 (2006.01)
  • C11D 3/20 (2006.01)
  • C11D 17/00 (2006.01)
(72) Inventors :
  • BROZE, GUY (Belgium)
  • BASTIN, DANIELLE (Belgium)
  • LAITEM, LEOPOLD (Belgium)
(73) Owners :
  • BROZE, GUY (Not Available)
  • BASTIN, DANIELLE (Not Available)
  • LAITEM, LEOPOLD (Not Available)
  • COLGATE-PALMOLIVE (United States of America)
(71) Applicants :
(74) Agent: SMART & BIGGAR
(74) Associate agent:
(45) Issued: 1990-05-15
(22) Filed Date: 1985-04-04
(30) Availability of licence: Yes
(30) Language of filing: English

(30) Application Priority Data:
Application No. Country/Territory Date
597,948 United States of America 1984-04-09

English Abstract






ABSTRACT OF THE INVENTION
A liquid heavy duty laundry detergent composition
comprising a suspension of a builder salt in a liquid nonionic
surfactant, said composition containing also a compound
comprising a polyether nonionic surfactant which has an ester
linkage between a polyether group and a group having a free
COOH.


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


62301-1309D


THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A liquid heavy duty laundry detergent composition
comprising a suspension of a builder salt in a liquid nonionic
surfactant, said composition containing also a compound
comprising a polyether nonionic surfactant which has an ester
linkage between a polyether group and a group having a free
COOH.


2. A composition according to claim 1 in which said
compound is a partial ester of a nonionic surfactant and a
polycarboxylic acid.


3. A composition according to claim 2 in which said
polycarboxylic acid is succinic acid.


4. A composition according to claim 2 in which said
compound is a partial ester of a polycarboxylic acid and a
polyethoxylated higher alkanol.


5. A composition according to claim 1 in which said
builder salt is an alkali metal polyphosphate.


6. A composition according to claim 1 containing also
suspended peroxygen bleaching agent.


7. A composition according to claim 6 in which said
bleaching agent comprises sodium perborate monohydrate and an
activator therefor.




- 14 -

62301-1309D

8. A composition according to claim 6 in which said
activator comprises tetraacetyl ethylene diamine.
- 15 -

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

62301-1309D
~L2~
This application is a divisional of Application No.
478,379 filed on April 4, 1985.
The invention of the parent application relates to a
liquid heavy duty laundry detergent composition comprising a
suspension of builder salt in a liquid nonionic surfactant,
said composition containing sufficient polyether carboxylic
acid wherein an ester linkage is attached to a polyether group
to decrease the temperature at which said surfactant forms a
gel with water.
This divisional application relates to a liquid heavy
duty laundry detergent composition comprising a suspension of a
builder salt in a liquid nonionic surfactantl said composition
containing also a compound comprising a polyether nonionic
surfactant which has an ester linkage between a polyether
group and a group having a free COOH.
A second divisional application relates to a half
ester of (a) a nonionic surfactant which is a polyalkoxylated
higher alkanol and ~b) a dicarboxylic acid.
Liquid nonaqueous heavy duty laundry detergent
compositions are well ~nown in the art. For instance,
compositions of that type may comprise a liquid nonionlc
surfactant in which are dispersed particles of a builder, as
shown for instance in the United States patents Nos. 4,316,812;
3,630,929; 4,264,466, and British patents Nos. 1,205,711 and
1,270,040.
In the ordinary use of European household automatic
washing machines, the user places the laundry detergent
composition in a dispensing unit (e.g., a dispensing drawer) of
the machine. Then during the operation of the machine, the
detergent in a dispenser is subjected to a stream of cold water
to transfer it to the main body of wash solutions. In winter,




-- 1 --

~ 2~ ~f~ ~ 62301-1309D

when the detergent composition and the water fed to the
dispenser are cold, there can be problems in that some of the
composition is not flushed completely off the dispenser during
operation of the machine, and a deposit of the composition
builds up with repeated wash cycles, so that it may become
necessary for the user to flush the dispenser with hot water.
One reason for this problem involves the behaviour of
the nonionic surfactant when mixed with cold water. Its
viscosity increases markedly and a gel is formed. As a result,
the detergent composition does not flow readily or completely
from the dispenser.
It has now been found that the flow from the
di~pen~er can be improved considerably by including in the
liquid detergent composition sufficient polyether carboxylic
acid wherein an ester linkage is attached to a polyether group
to decrease the temperature at which the suractant Eorms a gel
wlth water. Such a compound may be formed, for instance, by
reacting a nonionic surfactant with a polycarboxylic acid
anhydride, such as succinic anhydride, to form a partial ester
of the polycarboxylic acid. The resulting acidic compound will
react, in the wash bath, with the alkalinity of the detergent
composition and acts as an effective anionic surfactant.
Preferably the polyether carboxylic acid is soluble
in the nonionic surfactant and the composition is substantially
nonaqueous.
A preferred embodiment of the other divisional appli-
cation provides a half ester o (a) a nonionic surfactant which
i~ a polyoxyethylated higher alkanol and (b) a dicarboxylic
acid.
The inventions of this application and the divisional
applications are illustrated further by the following examples:

62301-1309D
~Z69~i 2
EXAMPLE 1
400 g. of a nonionic surfactant which is a C13 to C15
alkanol which has been alkoxylated to introduce 6 ethylene
oxide and 3 propylene oxide units per alkanol unit is mixed
with 32 g. of succinic anhydride and heated for 7 hours at
100C. The mixture is then cooled and filtered to remove
unreacted succinic materi.al. Infrared analysis indicates that
about one half of the nonionic surfactant has been converted
to the acidic half ester thereof. Viscosities and gel tempera-
tures of the product as compared to the unmodlfied nonionic
~urfactant are given below:




-- 3 --

lZ69~



Product Unmodified Nonionic
Surfactant_


Viscoslty at 20C 138 cps 60 cps

Cel temperature of
a 40/60 mlxture wlth
water (l.e. mlxture con-
talnlng 60Z water) 7C 20C

Vl~co~ity of the 40/60
mlxture wlth water
at 25C 60 cp~ 189 cps
at 20C 100 cps 445 cp~


It will be ~een that even though the product (which,
au previou~ly lndica~ed, 1~ a mlxture of about equal parts of
un~odlf~ed nonionic surfactant and acidic half ester thereof)
ha~ a hlgher vlscoslty than the unmodifled ~urfactant, its
vlscosity on dllution with wster i~ conslderably lower, a~ is
lt~ gelllng temperature.



_AMPLE 2
522 g. of the nonlonic fiurfactant known as Dobanol*
25-7 (the product of ethoxylation of a C12 to C15 alkanol,
whlch protuct has about 7 ethyleneoxlde units per molecule of
slkanol2 iB m$xed with 100 g. of ~uccinic anhydrlde and 0.1 g.
of pyrldine (which acts as an e~terification catalyst here~ and
heated at 60C for 2 hour~, cooled and filtered to remove un-

reacted succlnic materlal. Infrared analy~is indlcates that
~ubstsntlally all the free hytroxyls of the surfactant have re-
acted.
Other e~teriflcation catalyst~, such a8 an alksli metal
slkoxlde (e.g. ~odlum methoxide) may be used ln place of, or in
admlxture with, the pyrldine.

* Trademark

$~ -


EXAMPLE 3
Exsmple 2 is repeated using 1000 g. of Dobanol*91-5
~the product of ethoxylation of a Cg to Cll alkanol, which
product haR about 5 ethylene oxlde units per molecule of alkanol)
and 265 g. succin~c anhydrlde.



EXAMPLE 4
A llquld nonsqueou6 heavy duty laundry detergent i6
formulated from the following ingredients, ln the proportlons
~peclfled.
3SX nonlonlc surfactant comprlslng a mlxture of equal
part~ of:
(8) a relatlvely water ~oluble nonionlc ~urfactant
whlch form3 a gel wnen mixed wlth water at 25~C, ~peclfically
a C13 to ClS alkanol whlch has been alkoxylated to lntroduce
10 ethylene oxlde and 5 propylene oxlde unlts per alkanol unlt and
(b) a less water-~oluble nonionlc ~urfactant, ~peciflc-
ally a C13 to C15 alksnol whlch has been alkoxylated to lntroduce
4 ethylene oxlde and 7 propylene oxlde unlt6 per alkanol unlt.
12% of the product of Example 3.
31.2% sodium tripolypho~phate.
9X 60dlu~ perborate monohydrate.
4.5% tetraacetyl ethylene diamine; thi~ 18 an activator
for the sotium perborate.
4Z copolymer of about equal molee of methacrylic acld
and malelc anhydride, completely neutrallzed to form the sodium
sslt thereof (Sokalan*CP5); thl~ serve~ to inhlblt lncru~tatlon
(-B from formation of dlcalcium phosphate).



* Trademark

-
-




lZ sodium salt of diethylene triamine p~ntamethylene
pho~phonic acid (DTP~P),
1% Proteolytlc enzyme slur~y ~in non~onic surfactant)
(Esperase)
lX mixture of sodium carboxymet~ylcellulose and
hydroxymethylcelluloqe ~an antiredeposition agent) (Relatin*
DM4096).
0.5% perfume
0.5% opticnl brightener (of stilbene 4 type)
0.3% partial ester of phoephorlc acld and a C16 to C18
alkanol (Empiphos*5632, ln which there is about 1/3 monoester and
2/3 die~ter)
The ingredientfi are mlxed together, w$th the phosphoric
ester and then the ~odium tripolyphosphate belng preferably added
last, and pas~ed through a collold mill to reduce the particle
size of the ~olld materials to le&s than 100 microns ~e.g. to
about 40 microsn). The mixture is then sub~ected to ginding to
reduce the ~izes of the suspended ~olid partlclee to lesa thsn 10
mlcrons (e.g. to in the range of abou~ 2 to lO microns wlth less
than about 10% of the solids hsving psrtlcle size8 sbove sbout
10 microns).
The ingredlents and conditions are chosen so that the
total unbound water content of the compoeition iB leea than 2%,
preferably less than lX, such as about ~% or les~.

* Trademark

~2~ 62301-1309D

The mixture has a high viscosity, but dispenses
readily with cold water in the automatic washing machine. Its
specific gravity is about 1.25. It gives excellent washing
when used at a dosage of about 100 grams per wash load (as
compared with 170 grams per wash load for the usual heavy duty
laundry detergent powders) in conventional European home
laundry machines (which employ ahout 20 liters of water for the
washing hath~.
In the foregoing Examples/ there is a carboxylic acid
moiety joined to the residue of the nonionic surfactant by a
carboxylic ester linkage. Instead of a succinic acid moiety,
othex polycarboxylic acid moieties may be used, e.g., maleic,
glutaric, malonic, phthalic, citric, etc. Other linkages may
be used, such as ether, thioether or urethane linkages, formed
by conventional reactions. For instance, to form an ether
linkage, the nonionlc surfactant may be treated with a strong
~ase (to convert its OH group to an ONa group for instance) and
then reacted with a halocarboxylic acid such as chloroacetic
acid or chloropropionic acid or the corresponding bromo compound.
Thus the resulting carboxylic acid may have the formula
R-Y-ZCOOH where R is the residue of a nonlonic surfactant (on
removal of a terminal OH), Y is oxygen or sulfur and Z
represents an organic linkage such as a hydrocarbon group of
say, one to ten carbon atoms which may be attached to the
oxygen (or sulfur) of the formula directly or by means of an
intervening linkage such as an oxygen-containing linkage, e.g.,a
C O
Il 11
-C- or -C-NH-, (i.e., carbonyl or carboximido, respectively).

The carboxylic acid may be produced from a polyether


:30 which is not a nonionic surfactant, e.g., it may be made by

reaction with a polyalkoxy compound such as polyethylene glycol

62301-1309D
;5

or a monoester ~ monoether thereof which does not have the long
alkyl chain characteristic of the nonionic surfactants. Thus,
R may have the formula R (OCH-CH2)n - where R is hydrogen or
R2




methyl, Rl is alkylphenyl or alkyl or other chain terminating
group and "n" is at least 3 such as 5 to 25. When the alkyl of
Rl is a higher alkyl, R is a residue of a nonionic surfactant.
~s indlcated above Rl may instead be hydrogen or lower alkyl
(e.g., methyl, ethyl, propyl, butyl) or lower acyl (e.g.,
acetyl, etc.). The acidic polyether compound is preferably
present, in the detergent composition, as a solution in the
nonionic surfactant.
The carboxylic used may also be a polyalkoxy-
carboxylate or N-acyl sarcosinate as described and listed in
Kirk-Othmer, "Encyclopedia of Chemical Technology", 3rd Edition,
Vol. 22 (1983), Pages 348-349.
As is ~ell known, the nonionic synthetic organic
detergents are characterized by the presence of an organic
hydrophobic group and an organic hydrophilic group and are
typically produced by the condensation of an organic aliphatic
or alkyl aromatic hydrophobic compound with ethylene oxide
(hydrophilic in nature). Practically any hydrophobic compound
having a carboxy, hydroxy, amido or amino group with a free

hydrogen attached to the nitrogen can be condensed with
ethylene ox~de or with the polyhydration product thereof,
polyethylene glycol, to form a nonionic detergent. The length
of the hydrophilic or polyoxy ethylene chain can be readily
adjusted to achieve the desired balance between the hydrophobic
and hydrophilic groups. Typical suitable nonionic surfactants
are those disclosed in United States patents 4,316,812 and




-- 8 --

~LZ6~ 6 2 301 -1 3 0 9D


3,630,929, as well as those described and listed in the
discussion on nonionic surfactants in Kirk-Othmer "Encyclopedia
of Chemical Technology",3rd Edition, Vol. 22 (1983), Pages
360-379.
The compositions preferably contain fine particles
of a detergent builder dispersed in the nonionic surfactant.
Among the suitable builders are inorganic and organic builder
salts such as the phosphates, carbonates, silicates,
phosphonates, polyhydroxysulfonates, polycarboxylates and the
like. Typical suitable builders are those disclosed in United
States patents 4,316,812; 4,264,466; and 3,630,929.
Since, as indicated in Example 4, the compositions
may be used at relatively low dosages, it is desirable to
supplement any phosphate builder (such as sodium tripoly-
phosphate) with an auxiliary builder such as a polymeric
carboxylic acid having high calcium binding capacity, in amount
in the range, for instance, of about 1 to 10% of the composition,
to inhibit incrustation which could otherwise be caused by
formation of an insoluble calcium phosphate. Such auxiliary
builders are well known in the art.
The composition preferably compri~es a psroxygen
bleaching agent. This may be a peroxygen compound, such as an
alkali metal perborate, percarbonate or perphosphate; a
particularly suitable material is sodium perborate monohydrate.
The peroxygen compound is preferably used in admixture with an
activator therefor. Suitable activators are those disclosed in
United States patent 4,264,466 or in column 1 of United States
patent 4,430,244~ Polyacylated compounds are




_ g _

~L2G~2



preferred activators; among ehese, co~pounds such as tetraacetyl
ethylene diamlne ("TAED") and pentaacetyl glucose are part~cularly
~referred.
The activator usually interacts with the peroxygen
compound to form a peroxyacld bleaching agent in the wash water.
It i8 preferred to lnclude a sequestering agent of high complexing
power to lnhlblt any unde~ired reaction between such peroxyscld
and hydrogen peroxlde in the wash solution in the presence of
metal ions. Such a seque~tering agent ls an organic compound
whlch 1~ able to form a complex with Cu2+ ion6, ~uch that the
8tablllty con~tant (pK) of the complexation ls equal to or greater
than 6, at 25C, in water, of an ionic strength of 0.1 molelliter,
pK belng conventionally defined by the formula: pK~-log K where
K repre~ents the equllibrium constant. Thus, for example, the
pK values for complexatlon of copper ion with NTA and EDTA at
the ~tated condltions are lZ.7 and 18.8, respectlvely. Suitable
~equestering agents include the sodium ~alts of nitrilotriacetic
scid (NTA); ethylene dlamine tetraacetlc acid (EDTA); diethylene
trlsmine pentaacetlc acid (DETPA); diethylene triamlne penta-
~thylene phocphonic acid (DTPMP); and ethylene dlamine tetrs-
methylene phosphonic acit ~EDITEMPA).
Other ingredients which may be included in the compo-
~ltlon are enzymes (e.g. protea~e~, amylases or l$pases or
mixturec thereof), optical brightener~, antiredepositlon agents,
colorante (e.g. pigment~ or dye~) etc.




-- 10 --

~26~ 62301-1309D

The composition may also contain an inorganic
insoluble thickening agent or dispersant of very high surface
area such as finely divided silica o~ extremely fine particle
size le.g., of 5-100 millimicrons diameter such as sold under
the name Aerosil*) or the other highly voluminous inorganic
carrier materials disclosed in United States patent 3,630~929,
in proportions of 0.1-10%, e.g., 1 to 5%. It is preferable,
however, that compositions which form peroxyacids in the wash
bath (e.g., compositions containing peroxygen compound and
activator therefor) be substantially free of such compounds and
of other silicates; lt has been found, for instance, that
6ilica and silicates promote the undesired decomposition of the
peroxyacid.
Preferably the mixture of liquid nonionic surfactant
and solid ingredients is subjected to an attrition type of mill
in which the particle sizes of the solid ingredients are
reduced to less than about 10 microns, e.g., to an average
particle size of 2 to 10 microns or even lower (e.g., 1 micron).
Compositions whose dispersed particles are of such small size
have improved stability against separation or settling on
storage. It is found that the acidic polyether compound can
decrease the yield stress of such dispersions, aiding in their
dispensibility, without a corresponding decrease in their
stability against settling.
l'he mixture may contain anti-settling ingredients such
as a partial ester of phosphoric acid and a higher alkanol,
present in small amounts such as less than 1%, e.g., below 1/2%,
during the grinding. Other phosphate ester surfactants may be
used instead such as those described and listed in Kirk-Othmer
"Encyclopedia of Chemical Technology", 3rd Edition, Vol. 22(1983),
Pages 359-361.


*Trade Mark
-- 11 --

~g~6~3~ ~ 2
62301-1309D

In the grinding operation it is preferred that the
proportion of solid ingredients be high enough (e.g., at least
about 40% such as about 50%) that the solid particles are in
contact with each other and are not substantially shielded from
one another by the nonionic surfactant liquid. Mills which
employ grinding balls (ball mills) or similar mobile grinding
elements have given very good results. Thus, one may use a
laboratory batch attritor having 8 mm diameter steatite grind-
ing balls. For larger scale work a continuously operating mill
in which there are 1 mm or 1.5 mm diameter grinding balls
working in a very small gap between a stator and a rotor
operating at a relatively high speed (e.g., a CoBall mill) may
b~ employed; when using such a mill, it is desirable to pass
the blend of nonionic surfactant and solids first through a
mill which does not effect such fine grinding (e.g., a colloid
mill) to reduce the particle size to less than 100 microns
(e.g., to abo~t 40 microns) prior to the step of grinding to an
average particle diameter below about 10 microns in the
continuous ball mill.
In the compositions typical proportions of the
ingredients are as follows:
Suspended detergent builder, within the range of about
10 to 60~ such as about 20 to 50%, e.g., about 25 to 40%;
li~uid phase comprising nonionic surfactants and
dissolved carboxylic acid gel-inhibiting compound, within the
range of about 30 to 70%, such as about 40 to 60%; this phase
may also lnclude a diluent such as a glycol, e.g., polyethylene
glycol (e.g., "PEG 400") or hexylene glycol.




- 12 -

` - -
6~



Carboxylic ac$d gel-inhibit~ng compound, an amount
to ~upply ln the range of about 0.5 to 10 part~ (e.g., about 1
to 6 part# ~uch as about 2 to 5 parts) of -COOH (M.W. 45) per
100 part~ of blend of such acid compound and nonionlc ~urfact-
ant. (In Example 4 there are about 3 part~ of COOH per 100
psrts of such blend). Typlcally, the amount of the carboxyllc
acld compound 18 in the ran8e of about 0.01 to 1 part per part
of nonlolc surfactant, such as about 0.05 to 0.6 part, e.g.,
sbout 0.2 to 0.5 part;
Peroxygen compound (such as sodium perborate monohydrate)
ln the ran8e of about 2 to 15%, such as about 4 to 10%;
Acti~ator, ln the range of about 1 to 8%, such a6
about 3 to 6%.
A sequestering agent of high complexing power, in the
rsnge o sbour ~ to 3%, 8UC~ as about ~ to 2%.
In this application all proportlons are by welght un-
le~ other wlse indlcated. In the Examples, atmospherlc pre~-
uure is used unless other wl~e indlcated.
It is understood that the foregoing detailed descrlptlon
18 given merely by way of illustration and that variatlons may
be ~ade thereln without departlng irom the spirlt o f the inventlon.




_ 13 ~

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Title Date
Forecasted Issue Date 1990-05-15
(22) Filed 1985-04-04
(45) Issued 1990-05-15
Lapsed 1995-11-15

Abandonment History

There is no abandonment history.

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Registration of Documents $0.00 1985-09-27
Filing $0.00 1989-05-02
Maintenance Fee - Patent - Old Act 2 1992-05-15 $100.00 1992-01-27
Maintenance Fee - Patent - Old Act 3 1993-05-17 $100.00 1993-01-27
Maintenance Fee - Patent - Old Act 4 1994-05-16 $100.00 1994-04-06
Current owners on record shown in alphabetical order.
Current Owners on Record
BROZE, GUY
BASTIN, DANIELLE
LAITEM, LEOPOLD
COLGATE-PALMOLIVE
Past owners on record shown in alphabetical order.
Past Owners on Record
None
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.

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