Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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SUSPENDING LIQUID Dhr~:~GENT COr~OSITIONS
F. de BUZZACCARINI
Technical Field
The invention relates to aqueous built detergent
compositions which are pourable, and have suspending
properties.
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Backqround
Aqueous pourable detergent compositions are well known
in the Art, but it is only recently that C10-C16
alk~en~yl substi~uted succinic acids have been used as
builders in these compositions~ which have been disclosed
in European patent publications EP-A-O Z93 040 and EP-A-O 294 904.
These compositions are very satisfactory in terms of
their cleaning performance, but ingredients in the form of
solid particles could not be stably suspended in these
compositions, and therefore it is recommended to use only
liquid ingredients during their manufacture. Indeed, the
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use of ingredients in the form of solid particles
inevitably leads to sedimentation.
Pourable compositions having such suspending
properti~s have been disclosed for instance in European
patent publications EP-A-o 151 884, EP-A-0 120 638,
EP-A-0 092 363, and in U.S. Patent No. 4,692,271;
all the compositions disclosed in these documents do not
contain C10-cl6 alk(en)yl substituted succinic acids,
and it has been found that said compo~itions would lose
their suspending properties upon incorporation of said
substituted succinic acids.
It is an object of the present invention to provide
aqueous, pourable detergent compositions, which contain
C10-Cl6 alk~en)yl substltuted succinic acids and which
further have suspending properties.
Further, the compositions of the prior art tend to
collapse also if hydrophilic solvents are incorporated in
important amounts; it is another object of the present
invention to provide aqueous, pourable detergent
compositions, which contain ClO-Cl6 alk(en)yl
substituted succinic acids and have suspending properties,
and which may further contain hydrophilic solvents, such as
ethanol.
Summary
It has now been found that aqueous, pourable detergent
composition containing an anionic surfactant and
C10-C16 alk~en)yl substituted succinic acid could
acquire suspending properties by formulating them as neat
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phases, by incorporating at least about 7.5% by weight o~
the total composition of a compound of the form~la
RG(CH2CH20)
wherein :
-R is a ~ alkyl, alkenyl, alkynyl, aryl or alkyl
aryl group
-and n is an integer of from 4 to 22
-and y = O to 4
-and n/y 2 2 if y $ O
Detailed Description of ~he Invention
m e present invention addresses the problem of
formulating an aqueous detexgent composition which contains
C10-C16 alk(en)yl substituted succinic acids, and which
has suspending properties.
It has been found that such composition can be
formulated as a neat phase as foll~ws. In the followiny,
~he expre~sion neat phase (or G-phase) refers to an
essentially lamella-structured or spherulitic composition
in which aqueous layers are separated by double layers of :
hydrophobic materials.
Such a_lamellar structure can be identified by observing
the product through an optical microscope, between crossed
`Nichol prisms.
The neat phases are characterized by specific textures
which are described for instance by F~B. Rosevear, journal
of the American ~il Chemists Society, vol. 3, page 628,
195~.
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The compositions of the invention always contains an
anionic surfactant.
Suitable anionic surfactants can be represented by the
general formula R1So3M wherein Rl represents a
hydrocarkon group selec~ed fxom the group consisting of
straight or branched alkyl radicals containing from about 8
to about 24 carbon atoms and alkyl phenyl radicals
containing from a~ou~ 9 to abou~ 15 carbon atoms in the
alkyl gxoup. M is a salt ~orming cation which typically is
selected from the group consisting of sodium, potassium,
ammonium, and mixtures thereof.
A preferred synthetic anionic surfactant is a
water-soluble salt of an al~ylbenzene sulfonic acid
containing from 9 to 15 carbon atoms in the alkyl group.
Another preferred synthetic anionic surfactant is a
water-soluble salt of an alkyl sulfate or an alkyl
polyethoxylate ether sulfate wherein the alkyl group
contains from about 8 to 24, preferably from about 10 to
about 18 carbon a~oms and there are from about 1 to about
20, preferably from about 1 to about 12 etho~y groups.
Other suitable anionic surfactants are disclosed in US
Patent 4,170,565, Flesher et al., issued October 9, 1979.
Suitable anionic synthetic surface-active salts are
selected from the group of sulfonates and sul~ates.
Preferred anionic synthetic water-soluble sulfonate or
_ ... .
sulfate salts have in their molecular structure an alkyl
radical containing from about 8 to about 22 carbon atoms.
Exemples of such preferred anionic surfactant salts are
the reaction products obtained by sulfating C8-C18
fatty alcohols derived from tallow and coconut oil;
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alkylbenzene sulfonates wherein the alkyl group contains
fro~ abou~ 9 to 15 carbon atoms; sodium alkylglyceryl ether
sulfonates; e~her sulfates of fatty alcohols derived from
tallow and coconut oils; coconut fatty acid monoglyceride
sulfates and sulfonates; and water-soluble salts of
paraffin sul~onates having from about 8 to about 22 carbon
atoms in the alkyl chain. Sulfonated olefin surfactants as
more fully descri~ed in e.g. US Patent Specification
3,332,880 can also be used. The neutralizing cation for
the anionic synthetic sulfonates and/or s-llfates is
represented by conventional cations which are widely used
Ln detergent technology such as sodium and potassium.
A particularly preferred anionic synthetic surfactant
component herein is represented by the water-soluble salts
of an alkylbenzene sulfonic acid, preferably sodium
alkylbenzene sulfonates having from about 10 to 13 carbon
atoms in ~he ~lkyl group.
The compositions of the in~ention may additionally
contain zwitterionic surfactants which include derivati~es
of aliphatic quaternary ammonium, phosphonium, and
sulphonium compounds in which the aliphatic moiety can be
straight or branched chain and wherein one of the aliphatic
substituents contains from about 8 to about 24 carbon atoms
and another substituent contains, at least, an anionic
water-solubilizing group. Particularly preferred
zwitterionic materials are the ethoxylated ammonium
sulfonates and sulfates disclosed in US Patents 3,925,262,
Laughlin et al., issued December 9, 1975 and 3,929,678,
Laughiin et al., issued Dece~ber 30, 1975.
Th2 compositions may also contain small amount~, i.e.
below about 1% by weight of the total composition, o~
cationic
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surfactants. Examples of suitable cationic surfactants
include quaternary ammonium compounds of the formula
RlR2R3R4N+X , wherein Rl is C12 C20 alk~l
or hydroxyalkyl; R2 is Cl-C4 alkyl or C12-C20
alkyl or hydroxyalkyl or Cl-C4 hydroxyalkyl; R3 and
R4 are each Cl-C4 alkyl or hydroxyalkyl, or C6-C8
aryl or alkylaryl; and X~ is halogen. Preferred are
mono-long chain quaternary ammonium compounds (i.e.,
compounds of tha above formula wherein R2 is C1-C4
alkyl or hydroxyalkyl).
The total amount of ~urfactant in the compositions i5
of from about 5% to about 60%, preferably about 15% to
about 40% by weight of the total composition.
The compositions of the invention additionally contain
at least a~out 7,5% of a compound of the formula
R0(CH2CH20)
wherein
R is a Cn alkyl, alkenyl, alkynyl, aryl or alkyl
aryl group
- n is an integer of from 4 to 22
- y = 0 to 4
- and n/y ~ 2 if y $ 0
or mixtures thereof.
Preferred compounds according to ~his definition are
condensation products of ethylene oxide with a fatty
alcohol in the presence o~ an acidic or basic catalyst.
Pxe~erably, fatty alcohols having from 13 to 15 carbon
atoms are used to make such cond~nsation product.
Also pxeferred are such solvents as butanol,
butoxyethanol, benzylalcohol, hexyl diglycol ether, butyl
diglycolether, and mixtures thereo~.
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The compounds are present in the compositions of the
invention in an amount of at least about 7,5~ by weight o~
the total composition, preferably from about 8% to about
15% by weight.
The compositions of the invention also contain as a
builder system, from about 5~ to about 20% by weight of the
total compositicn of a C10 C16 alk(en~yl substituted
succinic acid, preferably ~rom about 8% to about 15% by
weight of the total composition. m e pre~erred builder ~or
use herein is dodecen~l substituted succinic acid.
Importantly, the compositions of the invention contain
water, in an amount of from about ZO% to about 60~ by
weight of the composition.
All the hereinbefore mentioned ingredients are mixed
together so as to obtain a compositon which is structured
as a neat phase.
Optionally, ~he compositions of the in~ention may
contain an electrolyte such as sodium bromide, chloride,
iodide, nitrate or acetate, preferably sodium chloride.
Cther optionals include detergent enzymes. Suita~le
enzymes include the detergent proteases, amylases, lipases
and cellulases. Enzymatic stabilizing agents for use in
aqueaus liquid detergents which are well known, can also be
used herein; preferred is a ~alt of formic acid, e.g.,
sodiu~ ~ormate. The amount of this stabilizing agent
typically ranges from about 0.5% to about 2%.
.
Examples of organic builders are represented by
polyacids such as citric acid, nitrilotriacetic acid, and
mixtures of tartrate monosuccinate with tartrate
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disu~cinate. Preferred builders for use herei~ are citric
acid. Polymeric carboxylate builders inclusive of
polyacrylates, polydydroxy acrylates and polyacrylates/
polymaleates copolymers can also be used.
~ h2 compositio~s of the invention may also contain
chelants, such as ethylenediaminotetracetic acid,
diethylenetriaminopentacetic acid, ethylenediamino
disuccinic acid or the water-soluble alkali metals
thereof. Other additives include organo-phosphonic acids;
particularly preferred are e~hylenediamino
tetramethylenephosphonic acid, hexamethylenediamino
tetramethylenephosphonic acid, diethylenetriamino
pentamethylenephosphonic acid, aminotrimethylene-
phosphonic acid and hydroxyethylidene 1,1 diphosphonic
acid.
m e compositions herein can contain further optional
ingredients which are mostly used in additive levels,
usually below about 5%. Examples of the like additives
include : Suds regulants, opacifiers, agents to improve
the machine compatibility in relation to enamel-coated
surfaces, bactericides, dyes, perfumes, brighteners and the
like.
m e b~neficial utilization of the claimed compositions
under various usage conditions can require the utilization
of a suds regulant like polysiloxanes such as
dimethylpolysiloxane, also frequently termed silicones~
These silicones are frequently used in a level not
exc~eding about 1.5%, most preferably between about 0.1%
and about 1.0%.
It can also be desirable to utilize opacifiers inasmuch
a3 they contribute to create a unifQrm appearance of ~he
.
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concentrated liquid detergent compositions. Examples of
suitable opacifiers include : polystyrene commercially
known as LYTRON~621 manufactured by MONSAN~O CHEMICAL
CORPORATION. The opacifiers are frequently used in an
amount from about 0.3% to about 1.5%.
It can further be desirable to add from about 0.1% to
about 5~ of known antiredeposition and/or compatibilizing
agents.
Examples of the like additives include : sodium carboxy-
methylcellulose; hydroxy-Cl_6-alkylcellulose;
polycarboxylic homo or copolymeric ingredients, such as :
polymaleic acid; a copolymer of maleic anhydride and
methylvinylether in a molar ratio of 2:1 to 1:2; and a
copolymer of an ethylenically unsaturated monocarboxylic
acid monomer, having not more than 5, preferably 3 or 4
carbon atoms, for example (meth)acrylic acid, and an
ethylenically unsaturated dicarboxylic acid monomer having
not more than 6, preferably 4 carbon atoms, whereby the
molar ratio of the monomers is in the range from 1:4 to
4:1, said copolvmer being described in more detail in
EUROPEAN Patent Publication No. 0,066,915.
Since the c~mpositions of the invention have acquired
suspending properties, due to the formulation as a neat
phase, it is possible to use ingredients which are in the
form of solid particles. There is no restriction as to the
natura of the ingredient, but these ingredients are
preferably in the form of solid particles having an average
diameter size in the range o~ from about 1 micrometer to
about 350 micrometers.
Such ingredients can be zeolites, clays, suds
suppressors such as silica waxes, any encapsulated
material, and a highly preferred ingredient to be suspended
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in the compositions are solid, water-soluble peroxygen
bleach mg compounds, preferably per~orates, persulfates,
peroxydisulfates, perphosphates and the crystalline
peroxyhydrates formed by reacting hydrogen peroxide wi~h
sodium carbonate or urea. Preferred are sodium perborate,
monohydrate and tetrahydrate, and sodium percarbonate.
If a peroxygen bleaching compound is used, the
compositions preferably contain water miscible organic
solvents including ethanol, n-propanol, isopropanol
polyethylene glycol, dipropylene glycol, hexylene glycol,
methoxyethanol, ethoxyethanol, ethyldiglycolether, and
mixtures thereof. Preferably, the compositions will contain
from 4% to 10% of the total composition of ethanol, as a
stabilizing system for the peroxygen compounds.
Also, in such a case, the pH as is of the compositions
should be in the range of from about 8 to about 12,
preferably about 9 to about 11.
The following examples will illustrate and facilitate
the understanding of ~he invention, but ar~ not meant to
restrict its scope.
Examples
The following composition are obtained by mixing
together the listed ingredients in the listed proportions
(LAS stands for linear alkyl benzene suphonate, CnAS
stands for coconut alkyl sulfate, TAS stands for tallow
alkyl sulfate and DTMPA stands for diethylene triamine
pentamethylene ~hosphonic acid.)
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The order in which the ingredients are mixed plays no
role in the achievement of the neat phase structure; it is ~.
however particularly convenient to proceed a~ follows,
re~erring to example IV.
A premix which is made with water, DTMPA and citric
acid is neutralized to pH 7 with sodium hydroxide. The
solvents (ethanol and hexyl diglycolether) are then
added.The linear alkyl benzene sulfonate and ~he dadecenyl
substituted succinic acid are added while cooling the
mixture; the pH is then trLmmed to 10 with sodium
hydroxide. The composition at this point is not yet a neat
phase, but an isotropic solu~ion characterized by its low
viscosity and transparency. The neat phase which is formed
on adding the C14alcohol 3 times ethoxylated can be
identified by a higher viscosity and a translucent
appearance; to confirm the formation of the neat phase
structure, the composition can be examined with an optical
microscope, between crossed Nichol prisms.
m e sodium chloride and all minor ingredients are
finally incorporated in the composition.
If an ingredient in the ~orm of solid particles is to
be incorp~rated, it is preferable to do so before the
formation o~ the neat phase, in order to facilitate the
mixing.
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